The Synthetic Use of Metals in Organic Chemistry

THE S Y N T H E T I C U S E IN O K G A N I C C H E M I S T E Y O F M E T A L S
A R T H U R J. H A L E , B.SC.(LOND.), A.I.O.
FELLOW OF THE OHKMIOAL SOOU'lTY; LHOTURKK, A . T S T ) IN CHicariaTRy AT T H K crrY AND G U I L D S TEOi COLLKGI', l^
LONDON J . & A . C H U K C H I L L
7, a R E A . T
MARLBOKOUail
STREET
Q<
P K E F A C E
THE student of Organic Chemistry will probably be impressed at an early stage with the importance of metallic sodium and its compounds in synthetic work, and will subsequently mark the value of such substances as acetoacetic-, malonic-, and cyanaceticester and their sodium compounds. He will notice the use of aluminium chloride in the preparation of various aromatic compounds, will hear the story of the discovery of the zinc alkyls, and will possibly be attracted by those interesting bodies, the organo-rnetals. Various metals arid metallic derivatives have been utilised in the development of Organic Chemistry, and during recent years, much attention has been given to the use of magnesium in the Grrignard reaction and to the value of the carbides iu the fixation of atmospheric nitrogen, wliilo tlio reduction and synthesis of organic compounds in tlio presence of reduced nickel and other metals has, by development, led to the discovery of numerous catalytic changes in the presence of certain metallic oxides.
VI
PREFACE
In this volume an attempt has been made to present an account of the uses to which the metals and certain of their compounds have Tbeen put, and the work is based upon a course of lectures, on this subject, recently given by the author to the advanced students of Finsbury Technical College. Each chapter is supplemented by an appendix of practical work exemplifying the methods mentioned in the text. Most of the preparations have been carried out in the College laboratories, and in connection with fthis part of the work the author desires to acknowledge the valuable assistance of two advanced students, Messrs. T. McLachlan and E. Mendoza. He is also indebted to Mr. F. W. Streatfeild, F.LC., Senior Demonstrator, for help during the reading of the proofs. A. J. H.
LONDON;
February, 1914
C O N T E N T S
CHAPTER I. S O D I U MA N D POTASSIUM. Synthetic Use of the MetalsSodium ethylateSodamide Sodium hydroxidePotassium cyanidePotassium "bisulphatePotassium hydroxide Potassium nifcrato Potassium and sodium disulphates . . . . CHAPTER II. C O P P E RA N D SILVHXt. Use of the MetalsCopper acetylene derivativesSilver cyanideSilver hydroxide CHAPTER III. M A G N E S I U M ,C A L C I U MA N D BARIUM. Applications of the Grignard reagentCarbides of Calcium and BariumNitrogen fixationCalcium and Magnesium nitridesHydroxides of the metals . . . CHAPTER IV. Z I N OA N D MERCURY. Metallic ZincZinc chlorideMercuric oxidoMetallic mercury 42 35
V1U
CONTENTS CHAPTER V. ALUMINIUM, TIN A N D LEAD.
Aluminium chlorideAluminium-mercury coupleTin and lead organo-metallie compoundsTin tetrachloride Lead oxideAntimony and the chlorides of antimony Vanadium pentoxidc CHAPTER VI. IRON, NICKEL A N D PLATINUM. Ferrous sulphateFerrous potassium oxalateIron and ferric chlorideReduction by reduced iron, nickel or cobalt
P A G E 11
88
APPENDIX I. P R A C T I C A L WORK: SODIUMPOTASSIUM. Ethyl benzeneAnisoleBenzoic anhydrideHexamethyleneTrimethylene dicarboxylic acidChlorof ormic esterCarbonyl chloride Ethyl benzoateToluic ethyl esterAeetoacetic esterEthyl acetoacotic ethyl ester Aceto-succinic esterMalonic esterEthyl malonic esterDiaceto-succinic esterEthane tetra-carboxylic ester Acetyl-acetoacetic esterAntipy rineMethyl succinic esterSuccino-succinic esterTin tetraphenyl Lead tetraphenylMercury diphenylSilicon tetraphenylOxalyl-acetic esterHydroxy-methylene camphorAcetyl-acetophenoneEthyl acetophenoneFurfurol acroleinCinnamyl-vinyl-methyl ketoneAcetic anhydride Benzoin Desyl-acetophenone Phonanthroxylene-acetoacetic ester 104 APPENDIX II. P R A C T I C A LW O R K : COPP1RSILVER. AcroleinAcrylic acid/3-Iodopropionic acidAdipic acid Carbazoleo-Nitrophenyl-propiolic acidDi-o-nitrophenyl-diacetylene o-Chlor -toluene o-Chlor-benzoio acidjp-Chlor-tolueneFormaldehyde . . . . 128
CONTENTS APPENDIX III. P R A C T I C A L WORK: M A G N E S I U M C A L C I U M .
IX
P A O K Benzoic acidPhenyl-ethyl-carbinolTrimethyl carbinol Triphenyl carbinolCamphoric anhydrideHomo-camphoric acidCamphorPentamethyleneCyanamide . 137 APPENDIX IV. P R A C T I C A LW O R K :Z I N C M E R C U R Y . Citric acidUse of Zinc alkyl iodideNaphthaleneIsoquinolineITuoresceinMalachite greenAcridine a-Methyl-indolePropyl chloridea-Ethoxy-quinoline Phthalic acid 144 APPENDIX V. PRACTICAL WORK: ALUMINIUMTINLEAD. Dimethyl-aniline-phosphor-chloride jp-Tolxiic-aldehyde Diphenyl-methanea-HydrindoneTriphenyl-methane Acetophenoneo-Benzoyl-benzoic acidAnthraquinone Hydrolysis of anisoleTolueneDiphenyl Oxalic acid 153 APPENDIX VI. P R A C T I C A L WORK: IRONNICKEL. o-Amino-benzaldehydeo-Amino-cinnamic acidMannose HexahydrobenzeneHexahydrophenol . . .162 INDEX 167
ABBREVIATIONS
USED
IN
THE
BIBLIOGRAPHY.
Ann. Ann. Ch. Phys. Ber.
= Liebig*s Annalen der Chemie. Annales de Chimie et de Physique. = Berichte der deutsohen chemischen G-esellschaft. Bull. Soc. chim. = Bulletin de la Soci6t6 chimique de Paris. Chein. Centr. = Chemisches Centralblatt. Chem. Zeit. = Chemiker-Zeitung. Compt. rend. ~ Comptes rendus de TAcad&nie des Sciences. D.R.P. German Patent. J. Am. Chem. Soc ~ Journal of the American Chemical Society. J. Soc. Chem. Ind. = Journal of the Society of Chemical Industry. J. prakt. Chem. = Journal fur praktische Chemie. Monats. Monatshefte fur Chemie. Phil. Trans. = Philosophical Transactions. Proc. = Proceedings of the Chemical Sooiety. Rec. Trav. Chim. Recueil des travaux chimiques dos PaywBas. Trans. = Transactions of the Chemical Society. Zeit. ang-ew. Chem. = Zeitschrift fur angewandte Chomio. Zeit. phys. Chem. Zeitschrift fur physikalische Chomie.
THE
SYNTHETIC IN ORGANIC
USE
OF
METALS
CHEMTSTRY
CHAPTERS I SODIUM AND POTASSIUM ALMOST the first metal to Tbe used for organic synthesis, sodium continues to hold a foremost positk/Ai among all the metals utilised as synthetic agents in organic chemistry. Although potassium was tho first used, being applied by Frankland and Kolbe in 1848 to the preparation of hydrocarbons by heating the metal with alkyl nitriles^ yet sodium has always received a far wider application. Twentythree parts by weight of sodium suffice to bring about a chemical change which would require tho use of thirty-nine parts of potassium^ and thin fact, together with the lower price of sodium, gives tho metal an economic advantage. Another reason for the priority of this metal is that in many cases the more electro-positive and nioro chemically active potassium proves to be too violent
SYNTHETIC USE OF METALS
in its action, and renders the control of the reaction difficult. After the investigation of Frankland and Kolbe mentioned above, Frankland in the following year heated metallic zinc with alkyl iodides, and besides preparing paraffin hydrocarbons in this way, he also discovered the zinc alkyl s, the first of the organo-metallic compounds. 1 In 1850, Williamson prepared certain ethers by the interaction of alkyl iodides and sodium ethoxide, a method of preparation which rendered evident the constitution of these bodies : C2H5I + C2H6O]Sra = ]STaI + C2H5.O.C2H5. In 1855, Wurtz emphasised the importance of sodium for preparing the paraffin hydrocarbons, and prepared di-isobutyl, by the action of the metal upon isobutyl iodide 3 : 2(CHa)2CH.CH2I + 2Na - (CH3)2CH.CHo.CH2.CH(CH3)3 + 2NaI. A few years later, Fittig applied this reaction to the synthesis of aromatic hydrocarbons by condensing aryl and alkyl radicles. The following reactions will indicate the usefulness of this method 8 : C6H6Br + CH3Br + 2Na = C6HB*CH3 + 2NaBr. Brombenzene. Methyl Methyl benzene bromide. (toluene). CBH4Br2 + 2C2HfiI + 4Na - C6H4(CaH6)a + 2NaI + 2NaBr Dibrom-benzene. Ethyl iodide. Diethyl-benssene. In these changes the alkyl groups take up the positions occupied by the halogens in the benzene nucleus. After 1850, various compounds were prepared by
SODIUM AND POTASSIUM
the agency o sodium and potassium, and tho following are examples of some of tho best known roaotionn oC tills class: Phenol and other formation : <yrfi.o.on3 . Nai AUIHOIO (methyl phonyI othor). Tho samo exchango in offoctod by uning an alkyl sulphate or an alkyl liydrogon Hulphato: CaH4OK + c a ir B nso 4 car&.o.<uifi f - KHHO, Ethyl hydrogon sulphato. 2C 2 II 5 OK + (<nr3)3so4 r- 2cyr&.o.air3 + Kao4 Mothyl Htilphato. Ethyl xnoihyl othor. Tho following aro chai*actoriHtic roacjtionn of alkyl potassium sulphates: When hoatod alone they yield olofiuo.s :
(lf)
oir,i
Sodium phonato.
When boiled with water Utoy yic^ltl alcoliols: oaiiftKso4 n a o i cyiftOH - KHHO4. When treated with Kl, KC5N, K^S, KHH, ilusy yield alkyl iodidos, nitrih^H, thio-ethern and morcaptans respectively: 2UKS<)4 + KM K.H.R -^ akjH()4 KKHOt + KBU K.S.U. 4 K9HO4. When heated with tho alkali HHIIH of organic u<*itlN; esters are obtained ; RKSOj + OH8COOK t CirsCOOR 4 K.HO,
Sodium b(aizoato.
SYNTHETIC USB OF METALS
Acid anhydrides are produced by distilling a mixture of the acid chloride with an alkali salt of the acid : CH3COC1 + CH3COONa = (CH3CO)X> + NaCl Acetyl chloride. Acetic anhydride. C6H5COC1 + C6H5COOK - (CCH5CO)2O + KC1 Benzoyl chloride. Benzoic anhydride. Numerous hydrocarbons can be prepared by the action of sodium upon halogen substitution products. In addition to those already mentioned, unsaturated hydrocarbons can be synthesised in this way: 2CH2: CH.CH2I + 2Na CH2: CH.CH2.CH2.CH: CH2 + 2NaI Allyl iodide. Diallyl. 2CH2: CHBr + 2Na = CH-: CH.CH: OIL + 2NaBr Vinyl bromide. Divinyl. Sodium has played an important role in the preparation of many polymethylene hydrocarbons and their derivatives. The first member of this series of hydrocarbons was prepared by Freund (1882), by allowing sodium to act upon trimethylene bromide 4 : yCH2Br y CIL OH/ + 2Na = = Oil/ I " + 2NaBr. \CH2Br "\CH 3 The same method was used in 1888, for preparingmethyl tetra-methylene from 1 : 4-dibrompentane 5 : CH3.CH. . CH C2 2 I + + 2NaBr, | I .CH CH2 .CH 2 2 and again in 1894 for preparing hexamethylene from the corresponding dibromide : CH3.CHBr.CHo.CHfl.CH2Br + 2Na
SODIUM AND POTASSIUM CH3.CH2.CH2Br | + 2Na OH2.CH2.CH2Br CH2.CH2.CHS | | + 2NaBr. OH2.CH2.OH2 Cyclohexane.
Many polymethylene carboxylic acids can bo propared by the aid of di-sodium malonato : CIl.Br /COOC.JIs CIIjV /OOOO0II5 + 2NaBr OH2Br \COOCaH5 OHo/ \COOCaUs Triinetliylene dicarboxylio oatoir.
The condensation product when hydrolysod given the corresponding acid and the latter on heating, passes to a monocarboxyl compound : CHo\ yCOOH Heat CPL>\ I " NCX -> I " NCn.CO0H -i- COo. CH 2 / \COOH OIL/ Similar compounds are formed by using triinothylenc dibvomide and pentamothyloiio dibromido. 0 Numerous acids may bo prcparod by tlie action of carbon dioxide upon aromatic halogen compouudsj in the presence of sodium. This method was first used by Kekule iu 18G0 for preparing benzoic and toluic acids from brombonzouo and bromtoluene: CoHfiBr + CO3 + 2Na = = C(5HftCOONa + NaBr /OH3 .Qll, C6H4< + COo + 2Na = C()II4< + NaBv. x Br XiOONa Magnesium is now used instoad of sodium for this type of reaction (see later). Wurtz, by the aid of chloroformic ester, prepared the corresponding esters of these itcids: O6H5Br + 2N"a + CICOOC-II5 CoU^COOC^ -I- NaCl + Kalir.
SYNTHETIC T T S J E OF METALS USES OF ACETO-ACETIC ESTEB.
This useful reagent was discovered by G-euther in 1863, who pi*epared it by the action of sodium upon ethyl acetate. About the same time Frankland and Duppa, using the same reaction, discovered that the hydrogen atoms of the raethylene group are replaceable by sodium and various organic radicles. G-euther represented the substance as OH 3 .C(OH) : CH.COOC2H6, that is /3-hydroxycrotonic ester, but Frankland and Duppa preferred the keto formula OHg.CO.OHg.OOOOgHg, and represented it as acetoacetic ester.7 The formation of the substance may be represented thus: CH3.COOC2H5 + CH3.COOC2H5 = CH3.CO.CH2.COOC3H6 + CaH6On Wislicenus had by 1877, investigated the substance and shown that other substances contained methylene groups, the hydrogen of which could be replaced by sodium.9 A few years later, Conrad showed that an alcoholic solution of sodium ethoxide would suffice, in place of metallic sodium or the dry ethoxide, for this type of reaction; he applied his method in particular to the preparation of alkyl malonic esters. 10 Not only does condensation take place between two molecules of an ester such as acetic ester, but also between an ester and a ketonc. Acetyl acetone can be prepared, for example, from acetic oster and acetone : OH3.COOC2H5 + CH3.CO.CH3 CH3.CO.CH2.CO.CH3 + C2H5OH. Propionic and butyric esters undergo the same type of condensation:
SODIUM AND POTASSIUM 2CH3.CH2.COOC2H5 CH3.CH2.CO.CH.COOC2H6 + C2H6OH
CH3 Propio-propionic oster. 2C,HB.CHa.COOC3Hs = = C,Hfi.CHa.CO.CH.CO0CaH5 + GftOH C2H5 Butyrobutyric ester. Iii both cases the carboxyl group of one molecule of the oster attaches itself to the a-carbon atom of the other. The yields in both cases are lower than that obtained with acetic ester, which is about 25 per cent, of that calculated. Isobutyric and isovaleric esters were found by Hantzsch 1 1 to follow a different course. The compound which might be expected when using isobutyric ester could not be isolated, and was apparently reduced by the sodium present to ethoxycaprylic oster, while simultaneously some of it becamo hydroiysed to hydroxycaprylic acid thus : (CHa)2CII.C(OH)(OC2H6).C(CH3)2.COOC2Hs Not isolated. Partly reduced to (CH3)2CH.CH.(OC2H6).C(CHJ)l,COOC2H6 Etlioxycaprylic ester. Partly hydroiysed to (CH3)2CH.CH(OH).C(Cir8)2.COOH Hydroxycaprylic acid. Similar changes occurred when using isovaleric ester and are represented by the following oquations : 2(CH3)2CH.CH2.COOC2H5 - (CH3)2CH.CH.vC(OH) (OC2H6) .CILC3H7.COOR Not isolated. (CXr3)2CH.CHo.CH(OC2H6).CILC3H7.COOCoH5 Ethoxycapvic ester. (CH8)2CH.CH2.CH(OH).CH.C3H7.COOH llydroxycapric acid. Acetoacetic ester was tho first of those compounds to be studied, which contain the grouping00
CH2CO , the hydrogen of the methylene group (CH2) being replaceable, entirely or in part, by sodium. Around its constitution and principal reactions much controversy was destined to take place, and even now the last word has not been heard concerning this important and interesting substance. Geuther, endeavouring to show that a second hydrogen atom of acetic acid could be replaced by sodium, caused the metal to act upon acetic ester. Hydrogen was evolved, sodium ethoxide was formed, and a solid sodium compound was isolated, having the composition C0H9O3Na, which on acidifying yielded an oil capable of forming salts with bases. Geuther also proved that by the action of alkyl iodides the sodium was replaced by alky], and this fact was confirmed shortly after by Frankland and Duppa. Wislicenus next showed that the product under discussion was acetoacetic ester and that two hydrogen atoms were replaceable by sodium in two stages. He represented the reactions in the following manner, adopting the formula of Frankland: (i) CHa.CO.CHNa.COOCaH8 + C3H6I CHs.CO.CH(C2H6).COOC2H6 + Nal (ii) CH8.CO.CNa(C2H6).COOC2H5 + C2H5I = CH8.CO.C(C2H5)2.COOC2H5 + Nal Geuther ascribed the enolic or hydroxylic formula CH 3 .C(OH):OH.COOC 2 H 6 to the substance, maintaining that it explained better its chemical nature. 12 Claisen was the first to propose an important explanation of its mode of formation, and offered a view which is still regarded with favour.13 This view is, that the condensation of acetic ester, and other con-
densations of this type, take place through tho formation and subsequent decomposition of an intermediate addition compound, in the formation of which sodium ethylato plays an important role. Tho stages of the reaction may therefore be represented t h u s : .ONa CH3.OOOCvHfi + CJHsONa = Cl3.C-OCallfi (Intoraodiato comc n 3 . c - o c y i , + c1i3.cooc.jir5 CH3.C(ONa): C1LOOOC.2H6 + 2CaiI5OJI. Sodium dorivative. The sodium derivative is decomposed by weak acids yielding acetoacetic ester, for which reason tho derivative is frequently represented with sodium linked to carbon directly and the liberation of tho ester is then represented thus : CHj.CO.CHffa.COOC2H6 + HC1 - CH,.CO.CHa.0OOU3Ub 4- NaCl The abovo intermediate compound has not boon isolated; but by tho interaction of bouzoic inolhylostor and sodium benzylate an analogous compound has been produced and separated.
/ 2r)
O6H5.COOCH3 + C0H6.CIL,ONa - CUHB.C Other compounds containing a motliyleno group ; the hydrogen of which is replaceable by sodium ai)d by alkyl groups, are : Acetyl acetone CJrjCO.ClI3.OOOH, Malonic esior 0.JUi,OOC.OH..OO()C<2llA Acetono clicarboxylio estor C2llo000.(!ll2.C0,Cn340o0CaJI,, Cyanacotio oator NC.CJTs.OC>OCaH6 Benzyl cyaixido Deoxybenzoin
10
A few applications illustrating the value of tliese sodium derivatives may now be outlined. The sodium derivative of acetoacetic ester, prepared by treating the ester with an alcoholic solution of sodium ethylate, is convorted into an alkyl substituted ester by boiling with any alkyl iodide: CH3.CO.CH2.COOaH5 -> CH3.CO.CII]Sra.COOC2H5 -* CH3.CO.CHR.COOC2H6 A second radicle II 1 may be caused to replace the second hydrogen of the methylene group, by repeating the treatment with sodium ethylate and an alkyl iodide E a I. CH3.CO.CHRCOOC0H5 - CH3.CO.CNaR.COOC2H5 - These substituted esters, like aceto-acetic ester itself, can be hydrolysed in two different ways and thus yield a variety of ketones and acids of the acetic series. 14 Boiling with dilute acid or dilute alkali brings about ketonic hydrolysis chiefly : R CH3.CO.C.COOCaH6 + Sift = CH3.CO.CHRR1 + CO2 + C2H6OH, I Kotone while boiling with strong alkali favours acid hydrolysis : R CH3.CO.C.COOCoH + 2H2O- C1I3COOH + CHRR^COOII + C2H3OH. - 5 I1 Acid R Malonic ester in particular can be used for preparing higher acids of the acetic series by first
11
replacing one or both of the methylene hydrogens by an alkyl group : yCOOC2H5 /COOC2H5 yCOOC3H6 CH2; -* CHRX or C&R1 ( \COOC2H5 \COOC2H5 \COOC2H5 On hydrolysis these substituted malonic esters give the corresponding acids and the latter on being heated to 200 lose carbon dioxide : yCOOH /COOH CHEf -B.CH,.CO0H; CKBF - ERlCH.COOH \COOH " \COOH The monosodium derivative of aceto-acetic ester on treatment with iodine undergoes condensation to a dibasic ester (diaceto-succinic ester). CH3.CO.CHNa.COOC,H5 CH3.CO.CH.COOC2H5 + I2 | + 2NaI CH:j.CO.CHN*a.COOC2H5 CH3.CO.CH.COOC2H6 The mono-sodium compound of malonic ester gives a tetra-carboxylic ester when similarly treated (ethane tetra-carboxylic ester): OC2H5 CH(COOC2H6)2 + Io = =| + 2NaI OC3H6 " OH(COOC2H6)2 Acetyl aceto-acetic ester is prepared by the action of acetyl chloride upon the compound 0H s .0O.0H Na.COO0 3 H 5 , and on hydrolysis gives acetic and aceto-acetic acids : CH3.CO.OH.COOC3HB I + 2H2O = COCH, CH3.COOH + CH3.C6.CH3.COOH + O2HCOH In a similar manner, by using a-monochloracetone, the y-diketone, acetonyl acetone, is obtained after hydrolysis 15 :
12
SYNTHETIC USE OF METALS CHg.CO.CHN'a.COOCHg + CICHa.CO.CH,, = CHa.CO.CH.COOC3H5 + NaCl OHo.COOH,
H e a t i n g with water a t 160 is sufficient to h y d r o lyso t h e substitution compound a n d eliminate carbon dioxide : CUj.CO,Cn.COOH I | c1i3.co.cuj cn s .co.ciij c n / c o . c i r , OIL co.cir, + co 3 Acetonyl acetone affords a means ol passing to i'urf urane, thiophone, a n d pyrrol derivatives. H e a t e d with d e h y d r a t i n g a g e n t s such as zinc chloride or phosphorus p e n t oxide, i t yields dimethyl furfurane, a change which is sometimes explained b y t h e following s t e p s : /Oil, c n : c ciio.co.cnj \nT, ca: o v .01 ij I ^ 011 " I > .cir, C Heated with phosphorus pentasulphide it yields the corresponding thiophene compound, whilo the action of alcoholic ammonia solution foims a pyrrol compound: SB* 0U:0 CH C< ' \ - J /CHj L / ' ^ CH:C/.CH, dimothyl-pyrrol u diniothyl-tliiopheno
S O D U IM A N DP O T A S S U IM 1 T h e behaviour o fs o d i u m ethyl aceto-acetate towards chloracetic ester a n d chloroformic ester respe tive! jy indicates that the c o m p o u n d exhibits dyna isomerism because in the first reaction it be asthough s o d i u mw e r e directlyunitedto carbon, a n in the s e c o n d reaction as though the s o d i u mw e r e united to o x y g e n: C H C .O C .H N a C .O O a T j5 + C 1 C H C .O O C H r C H C .:O C .H C .O O C 3 2 2 5= } C H C . O O C H ? 2 5 A c e t o s u c c i n i c est e r ,O C O G f t C H C .O N a:C H C .O O C H ,5 + C 1 C O O C H H C .O 3 2S = C 3 ^ C H C .O O C H 2 if / 3 c a r b e t h o x y c r o t o n i c est e r F r o m acetyl-acetone a series o f j3- or 1: 3-diketones can be obtained b y treating the m o n o s o d i u m c o m p o u n d with alkvl iodides : I3C C H J Ea = C H C .O C .H ( C 2 H C ) .O .+ H l 3 B 3+N Treatment o f the s o d i u m derivative with iodine gives tetra-acetyl ethane : C H 3 C .O C .H N a C .O C .H 3 C H C .O C .H C .O C .H 3 3 + C H C . C .H N a C .O C .H H C .O C .H C .O C .H aO 3 *" C 3 f Aceto-acetic ester is technically valuable inthe preparation o f antipyrine. T h eester isfirstallowed to react with phenyl-hydrazine, and the ring c o m p o u n df o r m e d is then convex'ted into antipyrin b y methyl iodide and s o d i u m: C n C .O C .H C .O O C H 3 3 s5
14
SYNTHETIC USE OF METALS forms
The hydrazone then loses C 2 H 5 OH and l-phenyl-3-rnethyl pyrazolon : CH3.C : CH.CO "L-J.Q.B.
which then passes to 1 : 2 : 3-phenyl dimethyl-pyrazolon. From benzyl cyanide and deoxy benzoin alkyl derivatives can be formed by the action of sodium and alkyl halides: C6H5.CH3.COCflH5 -> CCH5.CHR.COCGH6 The preparation of dimethyl succinic ester will illustrate the use of cyanacetic ester. 16 The sodium compound is condensed with a-brompropionic ester to form cyauo-methyl succinic ester : CN CHa CN CH3 CHNa + Br.CH CH CH + NaBr
1 1 1 T COOC2H5 COOCJHB COO2IIfi COOC2H5 This substance is then treated with ISTaOEt and OH3I and the product hydrolysed with loss of carbon dioxide: C N CH, C N CII, I I C O O C o H r C O C " + CH8I C.CH8 CH + Nal COOC2H5 6OOC2H5 C O O C a H a COOC2H5 Hydrolysis C O O H CH3 -CO2 CH3 CH3 "* 6.CH3 CH ~ > CH CH COOC2H5 COOC2H6 COOC2H5 COOCjHs The synthesis of S-keto-hexahydrobenzoic acid further illustrates the use of cyanacetic ester.17
15
The di-sodium derivative is condensed with /3-iodopropionic ester to form y-cyanopentane-a-ye-tricarboxylic ester :
C2H5OOC.C(CN)NA2 + 2CH 2 I.CH 2 .COOC 2 H 5 /CI1 2 .CH 2 .COOC 2 II, = C2H5OOC.C(CN) + 2TSM \CH 2 .CH 2 .COOC 2 H 5
Hydrolysis of this cyano-ester gives pentane-ayctricarboxylic acid, which on digestion with acetic anhydride and subsequent distillation yields S-ketohexahydro-benzoic acid: ,CH2.CH2.COOH ,CH2.CH2 HOOC.CH = HOOC.CH NcO + CO2 + H2O. \CH2.CH2.COOII \C Further examples of the synthesis of cyclic compounds are : The formation of butane tetra-carboxylic ester from ethylene dibromide and mono-sodium-malonic ester: OHjBr CH(Na) (COOC2H6)2 CH2.CH(COOC2H6)2 I + I =| + 2NaBr CI !H2Br CH(lSra) (COOC2H5)2 CH2.CH(COOC2H5)2 When the sodium derivative of butane tetracarboxylic ester is acted upon by bromine, the resulting product is tetramethylene-1 : 2-tetracarboxylic ester: CH2.CNa(COOC2H6)2 CH2.C(COOC2H5)2 CH2.CNa(COOC2H5)2
+
^ " CH2.C(COOC2H5)2
The use of trimethylene bromide with sodium
16
malonic ester will make the following reactions possible: . CH2.CH(COOC2H5)2 y CH2.C(COOC2H5)2 CH2 - OHo J \ CH2.CH(COOC2Hr,)a \ CH2.C(COOC2H6).2 Pentametliylene-tetracarboxy] ic ester Using methylene iodide instead of bromine, a cyclohexane-tetracarboxylic ester results:
CHj + CH a I 2 \cH 2 .CISra(COOC 2 H B ) 2 / CH 2 .C(COOC 2 H 5 ) 2 CH 2 \cH 2 .d(COOC 2 H f i ) 2
Succino-succinic e s t e r is f o r m e d b y t h e c o n d e n s a t i o n of s u c c i n i c e s t e r i n t h e p r e s e n c e of s o d i u m : 1 S C2H6OOC.CH2.CHo.COOC2H5 , C2HfiOOC.CH2.CH;.COOC2l-I5 * CJELfiOC.CE/ OC

2
\ C O + 2O,II 5 OH CH.COOC2K5
and this on oxidation is converted into 2 : 5-dihydroxyterephthalic ester:

C-COOC a TT 6
HC ^ C . O H II I HO.C CH
C--COOC2H5 Succino-succinic ester can also be prepared by the action of sodium upon a-bromaceto-acetic ester. 19
SODIUM AND POTASSIUM CH3.CO.CHBr.COOCoH5

+
17 \ CH.COOC2H6 CH2
/ H2C C2H5OOC.HC
CO
C2H5OOC.CHBi\CO.CHa
CO When hydrolysed with sodiam hydroxide the ester passes to the corresponding acid ; and this is decomposed when heated to 200 into >-diketohexaniethylene and carbon dioxide : CO CO H,C CH.COOH H2C CH2 I I -> I I + CO2 HOOC.HC CH2 H2C CH2 v v The latter substance was used by Baeyer in preparing dihydro-, tetrahydro-, and hexahydrobenzene. 20 Succino-succinic ester was also used by Baeyer for synthesising the terpene hydrocarbon p-menthadiene. 2 1 Succino-succinic ester, like phloroglucin, exhibits dynamic isomerism (tautomerism), behaving under some conditions as a keto-body ; and under other conditions as a hydroxylic, or phenolic body having this structure: C.OH II2C C.COOC2H6 C.OH A furthor example oJ' ester and ketone condenaa-
18
SYNTHETIC USB OP METALS
tion is afforded by the syntliesis of acetyl-pyroracemic ester, from acetone and oxalic ester : COOC2H5 CH3.CO.CH3 + j = CH3.CO.CH3.CO.COOC2H5 + C3H6OH iooc3H5 cc By using mesityl oxide and oxalic ester the condensation product is mesityl-oxide-oxalic ester : CH3V COOC2H5 >C : CH.CO.CH3 + I CK/ COOC3H5 CH3 C : CH,CO.CH2.CO.COOC2H6 + C3H8OH CH3 A case of internal condensation similar to that of succinic ester^ is the formation of keto-pentamethylene carboxylic ester from 1 : 4-butane dicarboxylic ester: CH3- CH2COOC3H5 CH 2 - CH.COOC2H6 = | NCO + C2H5OH CH2- CH2COOC3H5 CH 2 - CH3 Sometimes condensation products are formed by the elimination of water. For example: C6H6.CHO + CH3.COOC2H6 = C6H5.CH: CH.C0OCaH6 + H2O Benzaldehyde Acetic ester Cinnamic ester
+ H8 C6H5.CHO + CH2 C6H5CH : o / X ^COOCjjHfi COOC3H5 Cyanacetio ester Benzylidene cyanacetic ester Sodium has been widely used in the synthesis of various organo-metals and organo-metalloids, by causing the halides of the elements to react with organic halogen compounds. The following are examples of this type of reaction :23
19
S21CI4 + 4C6H5Br + 8Na = Sn(C6H5)4 + 4NaBr + 4Na01 SiCl4 + 4C6H6Br + 8Na = > Si(CcH5)4 + 4NaBr + 4NaCl. Sometimes the sodium alloy of the metal is utilised, as in the preparation of tin, lead, and mercury compounds, by means of tin-sodium, lead-sodium, and sodium amalgam respectively :33 Pb + 4Na + 4O3H7I = Pb(C3H7)4 + 4NaI Sn + 4Na + 4C6H5Br = Sn(C6H6)4 + 4NaBr I t is advisable to accelerate these reactions by means of a small quantity of acetic ester.
SODIUM BTHYLATE.
The value of this sodium derivative was first extensively illustrated by Claisen.2* I t may be used for condensing esters and ketones, and esters by themselves as well as with aldehydes, in much the same manner as sodium itself. Benzoic ester and acetone yield benzoyl-acetone. C6H5.COOC2H6 + CH3.CO.CH3 = C6Hfi.CO.CH2.CO.CH3 + C2H6OH Sucoinio ester and acetone yield teraconic ester. CH3.COOC2H5 (CH3)2C: C.COOC2H5
co+ 1 I +H 2 O
CH2.COOC2H5 CH2.COOC2H8 Benzoic ester with acetic ester yields benzoyl-acetic ester, while with acetophenone it gives dibenzoylmethane : 06115.00.0^.0000^5 +C2H5OH C6H6.CO.CH2.CO.O0H6 + C2H6OH. By condensing formic ester with other monocarboxylic esters, aldehyde esters result, while by using oxalic ester, ketonic dibasic esters are formed:
20
HCOOC2H5 + CH3.COOC.2H6 = HCO.CH.2.COOC2HS + C3H6OH Formyl acetic ester. COOC,H5 CHaCOOC,H5 CO.CH2.COOC2H5 | " + - | + 2C2H5OH OOOC.2H6 CH3GOOC2II5 CO.CH2.COOC2II5 Diacetyl dicarboxylic ester. Pormyl acetone may be prepared by using formic ester and acetone: HCOOC2H5 + CH3.CO.CH3 = HCO.CHj.CO.CH3 + C2H5OII This substance can be farther condensed by acetic acid to triacetyl-benzeno: CH /CHO H CH,.CO.CH8 CHaCO.C C.COCH3 I -> II I +3H2O OHO OHO HC CH CHg.CO.CH3 C COCH3 Similarly acetophenouo and formic ester yield formyl-acetophenone, which may bo condensed further to tribenzoyl benzone. Bing condensations with oxalic ester are : Diketocyclopentane dicarboxylic ester from oxalic and glutaric esters :25 COOC2II5 CH2COOC.J-I5 00CHC \ \ oir2 oir2 +20 2 H 5 OH. COOC2H5 OILCOOO2H5 0 0 - OH COOO2Hh By using /3j3-dimethyl glutaric ester, Konnnpa obtained diketo-apocamphoric ester which was used for the synthesis of camphoric acid :26 OOO02H5 CH2.OOOC.2H6 COOH.COOC2ir6 O(CII3)2 OHo.OOOC2H5 ere: (0Ha)2 000H.0O002H6
SODIUM AND POTASSTUM
21
A methyl group was introduced into the latter compound by the aid of sodium and methyl iodide, and the resultant compound reduced and then hydrolysed to dihydroxy-camphoric acid: CH3 CH, COCC00O>H5 C(CH3)2 COCHCOOCUH5 -> CHOHCCOOH C(CH3)2 CHOHCHCOOH
On boiling the last product with phosphorus and hydrogen iodide, the result was dehydrocamphoric acid, which was then combined with hydrogen bromide to form j3-brom-camphoric acid. The last named substance was reduced by zinc dust and acetic acid to racemic camphoric acid : CH-, CH3 CH3 I I I CHCCOOH CH2CCOOH CH>0COOIt C(CH:{)2 - C CHCHCOOH CHBrCHCOOH CH2CHCOOII Sometimes the oxalic ester only undergoes lialfcondensation as in the formation of oxalyl acetic ester: COOCJI5 CO.CIL,.COOC2Hr) + CH3.COOCjH6 = COOC2H5 COOCaH6 + C2ITr,OII.
By means of sodium ethylate or sodium, Claisen prepared hydroxymethylene camphor by condensing camphor with amyl formate :27
22
SYNTHRTJC USE OF METALS

en. + Hcooc5Hn C.CHOH
-i- Cf>lInOH. CO CO This substance is strongly acid, forming salts and esters, in which the hydroxyl hydrogen is replaced by metals and by organic radicles respectively. The reaction led to the discovery of many other hydroxymethylene bodies possessing similar properties. Olaisen also obtained nitroso-ketones by the use of amyl nitrite in tho presence of sodium ethylate : CflH5.CO.CH3 + CfiH^.O.NO * CC1I5.CO.CH: NOH + C6HnOH An examplo of this elimination of water is cinnamic nitrile, from nitrile: C(1H, C(!H6.CHO + | CIT2.CN class of condensation with the formation of a-phenylbenzaldehyde and benzyl CCH5.CTI: C.CJI, I + ILO. CN \ \
SODAMIDB AS A SYNTHETIC AGENT. This substance was utilised by Claisen in 1905, for alky latin g ketones and for preparing 1 :3-diketones. Its action seems to bo quieter and more regular than that of sodium or sodium ethylate. 28 One or two ethyl groups may be introduced into acetophenone by using ethyl iodide with sodamide : CflH5.CO.CH3 + C2H6I - C0H5.CO.CH2.C2H6 + HI CflH6.CO.CH3 + 2C2H6I - CflH^CO.CHCGft).* + 2HI. By using benzyl chloride the benzyl group can be introduced: f C6H5.CO.CH3 + C6H6.CH2C1 ~ C6Hfi.CO.CH2.(CH2CfiHB) + HC1.
23
1 : 3-Diketones are prepared by condensing ketones with esters. Acetyl acetone from acetic ester and acetone: CH3.COOC2H5 + OH8.CO.CH3 = CH8.CO.CH2.CO.CH3 + GftOH. Benzoyl acetone from acetic ester and acetophenone: CH3.COOC0H5 + CH3.CO.CCH5 = CH3.CO.CH2.CO.OGH5 + C2H5OH. The powdered sodamide is added gradually to the mixed substances, cooled in ice, and after standing for some time, the mixture is treated Avith ice-cold water and the product precipitated by acidifying with acetic acid. Hydroxymethylene ketones are formed by using formic ester: CH3.CO.CH3 + HCOOR = CH3.CO.CH : CHOH + EOH. Sodamide has been technically applied in at least two instances, namely, the production of cyanide by Castner's process and also the production of indigo. I n the preparation of cyanide, the sodamide is mixed with carbon and the mixture subjected to a dull red heat, when the following reaction takes place: NaNH2 + C = NaCN + H2 Indigo can be synthesised according to the German Patent 158,089, by heating sodamide with tho diethyl ester, or the diamido-derivative, of phenyl-glycocoll-carbonic acid, in benzene solution : .NH.CH2.COOH .NHV -> CflH4< >CH2 + H.>0 + COo. 4< XJOOH MX)' Indoxyl The indoxyl formed is converted into indigo by exposure to air.
24
Metallic sodium has recently received important application as a polymerising agent in tho transformation of isoprene into artificial rubber. 29 The steps in this important synthesis, starting from starch, are as follows : The starch is fermented to fusel oil and acetone, and from tho former liquid, isoamyl alcohol is separated. By treatment with hydrogen chloride, isoamyl alcohol is converted to the monochloride, and the vapour of this when acted upon by chlorine gas leads to the formation of three isoamyl dichloindes : (CH:02CH.CK,CH2OH + HC1 = (CII:l)oCH.CHo.CH2Cl + H3O S (CH:))2CH.CHC1.CH2C1 + IIC1 (CH.))3CH.CHn.CH2Cl + C l ^ ^
:<N >CH.CHo.CH2Cl + HC1 CHoCK
These isoamyl dichlorides, when heated with lime, lose hydrogen chloride and pass to isoprene (methyl divinyl) : *\c.CH : CH2 CH/' Isoprene on standing for some time with metallic sodium becomes converted into synthetic rubber.
SODIUM HYDROXTDE.
This sodium derivative is generally utilised in aqueous solution for condensation work, the concentration often being 10 per cent. Schmidt30 was the first to use the reagent, in 10
SODIUM AND POTAflSTUM
25
per cent, aqueous solution, for condensing together furfurol and acetaldehyde : >CHO .CH : CH.CHO CH : c<( CH : | J>0 + CH3.CHO = fan : dH Furfurol acrolein. Claisen, in the following year, used 10 per cent, aqueous sodium hydroxide to condense furfurol with acetone and thus obtained mono-furfurylidene acetone :81 C4II:iO.CIIO + CHn.CO.CH3 = C4H3O.CH : CH.OO.C1I3 + HUO. Using benzaldehyde and acetone, ho obtained mono- and di-benzylidene acetone. Further examples of condensation of this class ai-e the formation of indigo from o-nifcrobenzaldehyde and acetone, and the formation of quinoline from o-aminobenzaldehyde and acetaldehyde: .Clio vGHOH.CH.CO.cn
C H C O C H - C0H4<
o-nitrophenyl-lactic acid kotono. This product is then decomposed by the excess of sodium hydroxide : yCHOH.CHo.CO.CH3 \NO2 .CO v .CO x C(5H4< > C : C< > C(1Ht + 2HO + 2CHSCOOH: \NH/ \ m ' Baryta or ammonium hydroxide may also be used for this reaction. 82 Quinoline and quinoline derivatives are obtained by using o-amino-benzaldehyde :8S
26 CH
C.COH CH2.H I +| C.NHo CHO CH o-amino-benzaldeliyde.
HC | HC
HC I
C I I
CH I + 2H3O I CH
CH quinoline.
By substituting aceto-acetic ester for acetaldebyde, a quinoline derivative is obtained : CH CH CH /' \ ^ \ / N HC C.COH Cm.COOailfi HC C C.COOOJI5 I I I + I - I I J " +2H2O HC C.NIL CO.CIT, 1IC C C.CH3 CH CH N rt-metliyl-q[xiinoliiie-/3-carboxylic ostev. Fischer made use of 1 per cent, sodium hydroxide solution to polymerise a mixture of glyceric aldehyde and hydix)xy-acetone, in the formation of a-acrose. After allowing the mixture to stand for four or five days the transformation was complete :u CH2OH CH2OH CH2OH ~ CHOH CH2OH CO CHOH + CO
CHO CH2OH CHOH OHOH (Q-lycerose). a-acrose (inactive fructoso). By the same method ; glycollie aldehyde has been polymerised to erythrose : CH2OH CHO CHO CH2OH CH2OH CHO CHOH - CHOH
Cinnamic aldehyde can be formed from benzal-
A N DP O T A S S T T J M
27
dehyde **11 ^ c e t a l d e h y d e , and the product can be again ctX(*nBecl w i t h acetaldehyde or acetone : C o ll" < j n -+ OIT3.CHO = C6H5.CH : CH.CHO + H2O : CH.CHO + CH3.CHO = : CH.CH: CH.CHO + H 2 O Cinnamyl acrolein. :: CH.CHO + CHVCO.CH, ^ : CH.CH: CH.CO.CH> + H2O Oinnamyl-vinyl-methyl ketone. If tv^ c> l u l o c u l a r quantities of cinnamic aldehyde beusodj ^ J ^ u i n t K e last case di-cinnamyl-vinyl ketone results. Anot>l*ai* c n s o of quinoline formation is the con^ T ^ e n z o y l acetone and aniline, resulting in C H C.C6Hr,
j. HC
,L...
CH
* CO.CH.
ii
C.CH,
+ 2II2O
It w ^ ^ n h o w n by V. Meyer, that solid sodium hydroxi<lu i b e t t e r than sodium ethylato for condensing1 b e n z y l nitrile with methyl iodide :36 Î.i(JN .^- CH a I + NaOH = CcH5.CHCISr + Nal + HaO. CH8 Quitu>tios c a n be prepared by condensing 1: 2diketonc^H by rtquoous sodium hydroxide.30 In ill o tivnij p l a c e an unsaturated 1 : 2 : 5-triketone is formed wliich. Tby further condensation passes to a quinom*# Diixcetjl gives first dimethyl-quinogen and then jM-x
28
SYNTHETIC USE OF METALS CO
CH3.CO.CO.CH, -> CH3.CO.CO.CH3
CH3.CCO.CH3 *I I ' -> CH.CO.CO.Cir,
CHVC ' I HC
Oil I I O.CH,
Acetyl-propionyl condenses in this way, forming duroquinone : CO CH.}.CO.CO.CH>.CH, OHn.CHo.CO.CO.CH.{ CH,.C 0.CH, ' I I I CTT,.C O.CTT, ' Y + 2TI>0.
The reaction may be expi*essed in a general wa}r thus : CO X.CHo.CO.CO.Y - Y.CO.CO.CHo.X X.C.CO.CO.Y XC CY I I -> I I I Y.C.CO.CH..X YC CX
A further example of condensation by sodium hydroxide is afforded by ionone, used as a substitute for essence of violets, -which is formed from citral and acetone.37 Pseudo-ionone is the first product, and this is then converted to a mixture of a- and j3-ionone by boiling with dilute sulphuric acid : (CH3)2C:CH.CH2.CH2.C(CH3):CH.CHO + CH3.CO.CH8 (CH8)2C:CH.CH2.CH2.C(CH3):CH.CH:CH.CO.CH3 + H30. The next stage is explained by the scheme: following
SODIUM AND POTASSIUM CH3 CH3 / HC I c CH.CH: CH.CO.CH3 +2H3O
29
H.c
> H,C CH2.CH : CH.CO.CH3 | | XH3
CH3 CH3 < > H /X

V CH2
0H
I to
0 CH.CH: C H . C O . C H 3 ( C C . C H 3 a-ionone
H2C C.CH: CH.CO.CH3 H 2 C C . C H 3 C H o /3-ionone.
POTASSIUM COMPOUNDS.
Potassium itself is rarely used in synthetic work, but the cyanide, acid sulphate, and hydroxide are often made use of. A commercial process in which potassium may be rogarded as a synthetic agent is Beilby's process for preparing cyanide, by heating a mixture of potassium carbonate and carbon in ammonia. Potassamide is probably an intermediate compound, and the method corresponds to Castner's cyanide process: KaCO8 + 2NH3 + 2 C - 2KNH2 2 C
30
While the action of carbon monoxide upon heated potassium results in the formation of the carbonyl, moist carbon dioxide reacts with the metal to form carbonate and formate : 0K + 6CO K6(CO)0 2K + H2O + 2CO2 = KHCO3 + H.COOK 4K + H3O + 3CO2 = K2CO3 + 2H.C00K
POTASSIUM CYANIDE is especially useful for con-
densing aromatic aldehydes (benzoin condensation) , 38 Benzoin is formed from benzaldehyde: 2CCH5.CHO = C6H5.CHOH.CO.CCH5 Acetophenone condenses with benzoin in the presence of alcoholic cyanide, giving desylacetophenone : C6H5.CHOH C6H5.CH.CH2.CO.C6H6 I + CH3.CO.C0H5 . I + H3O. CO.CflH5 CO.C6H6 Mandelo-nitrile and benzyl cyanide condense in the presence of aqueous potassium cyanide, giving di-phenyl-succinic nitrile : C6H5.CHOH CH2.C6H5 C6H5.CH-~CH.C6H8 I + I I I +H2O ON CN ON CN I t has been suggested that cyanhydrin formation is an intermediate stage in this class of condensation, and benzoin formation is represented by the following scheme :89 C6H6.CHO + KCN - C6H5.CHOK C N " C6H5.CHOK 4 C6H6.CHO -> C0H5.COKCH0H.CflH5 CN CN KON is then eliminated C6H5.CO.CHOH.CflH6 + KCN.

ACID POTASSIUM SULPHATE may be used for
31
the
following condensations. The leuco-base of malachite green from benzaldehyde and dimethyl-aniline: C6H5.N-(CH3)2 /C6H4.N(CH3)2 = CgH5.CH C6H5.CHO + C0H5.CH' +HjO C6H6.N(CH3)2 \C6H4.N(CH3)3 The resultant tetra-methyl-diamino-triphenyl methane is then oxidised to the carbinol, which is converted to malachite green by hydrogen chloride:
/ \ H C I C
6
<
+H2O
\C6H4.N(CH3)2 \CCH4:N(CH3)2C1 Aromatic aldehydes condense with phenols, e. g. benzaldehyde and naphthol give hydroxy-dinaphthylphenyl methane: CCH5.CHO + 2C10H7.OH = C6H5.CH(C10H6OH)3 + H2O. Pyruvic acid is formed by the removal of the elements of water from either tartaric or glyceric acids : CH0H.COOH I = CH-{.CO.COOH + CO3 + H2O CHOH.COOH CH2OH CHOH - CH3.CO.COOH + HaO. COOH By a similar elimination of water, glycerin yields acrolein and terpineol passes to dipentene: CH2OH.CHOH.CH2OH - CH2: CH.CHO + 2H2O OH CH3.C* \CHjCH,/ \CH 3
8
32

POTASSIUM HYDROXIDE can often be used for the
same syntheses as sodium hydroxide, as for example, in condensing diketones with mono-ketones : Phenanthraquinone condenses with either acetoacetic ester or acetone :40 C6H4.CO CO.CH3 C0H4.CO I I + I - I I /COCH3 + H2O CHo.COOC2HB C6II4.C< 4.0O
2 6
Plienanthroxylene acetoacetic ester. C6H4.CO CH3.CO.CH3 C8H4.C(OH).CH2.CO.CH3 C6H4.CO+ CH3.CO.CH3 ~ C6H4.C(OH).CH2.CO.CH3 Diacetone-phenanthraquinone. Potassium hydroxide, when heated in aqueous solution with aromatic aldehydes, converts these in part to acids and in part to alcohols : 2C6H5.CHO + KOH = CcH6.C0OK + C6H5.CH2OH Certain aliphatic aldehydes undergo a similar change. Isobutyric aldehyde, for example, is converted to isobutyric acid and di-isopropyl glycol: 3(CH3)2CH.CHO + KOH = (CH3)2CH.COOK + (CH3)2CH.CHOH (CH3)2CH.CHOH This is a method for obtaining di-secondary glycols from certain aldehydes by means of alcoholic potassium hydroxide solution.41 Potassium nitrate may be used for the preparation of acid anhydrides from acid chlorides, by distilling the latter after mixing with the alkaline nitrate. 43 Potassium and sodium disulphate bring about condensation with elimination of water. The following examples illustrate the use of this method: ^ Triphenyl benzene from acetophenone, benzal
33
aniline from benzaldehyde and aniline,, benzal malonic acid from bonzaldehyde and malonic acid, benzal acotophenone from benzaldehyde and acetophenone.
BIBLIOGRAPHY.
Ann., 1853, 85, 329. Ann., 1855, 96, 365. 3 Ann., 1863,131, 301. 4 Monats., 1882, 3, 625. 5 Trans., 1888, 53, 201. R Ber., 1902, 35, 2091. ' Ann., 1866,138, 204, 328. 8 Phil. Trans., 1866,156,37. Ann., 1877,186,163; 190, 257. Ann., 1880, 204,127. 11 Ann., 1889, 249, 54. 12 Ann., 1883, 219,123. 13 Ber., 1887, 20, 646 w Ann., 1877,190, 276. 1 5 Ber., 1885,18, 58. l f i Trans., 1899, 75, 839. w Trans., 1904, 85, 416. w Ann., 1882, 211, 306. 19 Ann., 1888, 245, 74. 2 Ber., 1894, 27, 229. 21 Ber., 1893, 26, 232. 22 Ber., 1886,19, 1012. 23 Ann., 1864,130,1055 Bor., 1889,22, 2917. 24 Ber., 1887, 20, 655. 25 Ber., 1897, 30, 1470. 26 Ber., 1903, 36, 4332. =7 Ann., 1897, 297,1. Ber., 1905, 38, 693. a X Soc. Chem. Ind., 1912, 31, 622. 3 Ber., 1880,13, 2342. Ber., 1881,14, 2468. 3 2 Ber., 1882, 15, 2856. 33 Ber., 1882, 15, 2574.
2
34
SYNTHETIC USJfl OF METALS
Ber., 1888, 21,1417. v Ber., 1898, 31, 808. 38 Ber., 1892, 25, 293; Her., 1893, 26, G O . 39 Trans., 1903, 83, 995. 40 Ber., 1883,16, 276. 41 Ber., 1896, Ref., 350. 42 Ber., 1911, M, 3333. 43 J. Amer. Chem. Soc, 1913, 35, 81.
34 Ber., 1887, 20, 3386. 35 Ann., 1899, 250, 123. 36
CHAPTER
II
COPPER AND SILVER BOTH these metals bring about condensation by the removal of halogens, for which they havo considerable affinity, and so function in this respect as sodium, but the reactions are not so vigorous. The formation of butane from ethyl bromido and of ethylene from methylene iodide are examples of this condensation : 2C2H5Br + Cu = CuBr2 + C2H5.C3H6 2CH2I2 + 4Cu 2Cu.2I3 + C2H4 Copper or silver can be used to condense /3-iodopropionic acid to adipic acid, and also for condensing a-brom-propionic ester to dimethyl succinic ester :l CHo.CH3.COOH 2CHoI.CHo,COOH + 2Ag = | + 2AgI CH2.CH2.COOH 2CH3.CHBr.COOR + 2Ag = | + 2AgBr. CH3,CH.COOR Other examples in which finely divided silvor is used, are, the preparation of suberic ester from y-brom-butyric ester, and di-isopropyl succinic ester from a-brom-isovaleric ester :2
36
CH2.CH2.CH2.COOK 2CH3Br.CH3.CHc.COOR + 2Ag = I + 2AgBr. CH3.CH3.CH3.COOE (CH,)20H.CH.COOR 2(CH3)2CH.CHBr.COOR + 2Ag | + 2AgBr. (CH3)2CH.CH.COOR Copper has been used to facilitate the removal of hydrogen chloride and potassium chloride in the following condensations. 3 Anthranilic acid from o-chlorbenzoic acid and ammonia:
2 + HC1, XJOOH phenyl anthranilic acid is obtained if anilino bo used in place of ammonia: yCl yNH.C6H5 C6H4< + C6H5.NH2 = C6H4< + HCL \COOH \COOH Further examples of the same class are : y Cl yOC6H5 C6H4< + C6H5OH = C6H4< + HC1 \COOH \COOH o-chlor-benzoic acid plienol phenyl-salicylic acid. /Cl /SO2.CGH5 CfiH4< + C6H5.SO2K CGH4< + KC1 \COOK \COOK o-chlor-benzoie potassium phenyl-srilphi-benzoic acid phenyl sulphinate acid. CH
NH3 =
C6H/'
HC^ C.C1 CH3O.C C.COOH

+
l-dilor-4-methoxymeth.oxy.phenylbenzoic acid salicylic acid. C6H5OK + C0H6Br - C6B[5.O.C6H5 + KBr Diphenyl ether.
C O P P E RA N D S L IV E T f 37 Copper is sometimes used to effect condensation by combining with sulphur. The two following syntheses o f methane illustrate this reaction : C S H S+8 C u = CII4 + 4 C u S 2+ 2 a 2 C S + 2 H O + 6 C u = C f + 2 C I T S + 2 C u O . 2 2 2 4 Carbazole is formed w h e n thio-diphonylamino is m i x e d with copper powder and the mixture distilled in carbon dioxide :
/C0H4v C0H#1v S< >NH + Cu = I >NH + CuS. In a similar way j3-dinaphthyl carbazolo is formed from thio-j3-dinaphthylaraine : 4 Sv CjoHbCWIT(5 >C1UHC + Cu = \ / + CuS. The action of potassium ferricyanido upon copper acetylene derivatives is interesting. Diacotylonodicarboxylic acid is obtained from tlio copper derivative of propiolic acid by troatment with forricyanido :r> C : C.COOII yC : C.COOH \ C : C.COOH C; C.COOII If the acid sodium salt of this bo digested with water, carbon dioxide is liberated and tlio sodium salt of diacetylene-monocarboxylic acid is formed : C; C.COOH C:CH I - 1' + CO,. C;C.COONa CjC.COONa The copper derivative of this compound can nlso be condensed in the presence of foiTicyamdo, nud tetr-acetylene-dicarboxylic acid r e s u l t s : C : CO : 0.000 II yC i C.C: C.COOII
<
<
' -> r ' Ci0.C:C.C00ir C C.C ' C.COoll
38
SYNTHETIC FSB OF METALS
In using this method, the copper derivative (1. mol.) is added to a solution of potassium ferri cyanide (1 mol.) containing potassium hydroxide (1 mol.), and tho mixture is allowed to stand some hours. 0 By the same process it is possible to prepare diphenyl-diacetylene from the copper derivative of phenyl-acetylene : CCH5.C j C.Cu.C i C.CJ-I-, -> CBHfi.C i C.C C.CflH5. Diphenyl-diacetylene is the parent hydrocarbon of indigo blue, and the dye itself can be prepared by means of this reaction; starting with o-nitro-phenylpropiolic acid. By loss of carbon dioxide the acid becomes o-nitro-phenyl-acetylene, the copper derivative of which passes to di-ortho-nilrophcnyl-diacetylene : CGH4<( * N T O 3 O j C.Cu.C ; Cv -> C e l l / * -> N N T O a yC C.C : Cv
\NO2 ^0/ \NOo NO./ The last substance is changed to the isomcric di-isatogen by alkalis and this becomes indigo when reduced:
C6H/ \ c. c / \c f l n 4 -> C ( ; H / C \ C :
)>C 8 H 4 -> O J T /
\C 8 TT 4
The use of copper salts and of copper itself for the replacement of the diazo-group of aromatic compounds, by chlorine, bromine, cyanogen, etc., is important. Halogen substitution products of benzene were first prepared by the aid of copper salts in 1884,
COPPER AND SILVER
39
when Sandmeycr discovered the reaction which is still named after him :7 CCH5.N:N.C1 -> C6H5C1 + N2. G-attermann,8 in 1890, showed that the same reaction could be carried out, using copper powder instead of the salts of that metal, and the method was applied in substituting by, -01, -Br, -ON, - N 0 2 and -CNS groups. The yields by this method were superior to those obtained by the Sandmeyer method, probably because the copper powder was added to the diazonium solution in the cold, whereas Sandmeyer recommended adding the diazonium solution to a hot solution of the copper salt. Later, Erdman, also Armstrong and Wynne (1892 93) used cold solutions of the copper salts and found the yiolds by Sandmeyer's method very much improved. 9 Erdman also showed that there was a definite optimum temperature at which, by Sandmeyer's method, the maximum yield of halogen compound was formod, the optimum temperature referring to the temperature of the copper salt solution when the diazonium salt was added. Heller (1910) states that by increasing sufficiently the amount of hydrochloric acid used, quantitative yields of chlor-compounds are possible by Sandmeyer's method. 10 Somotimes condensation takes place in the presence of cuprous chloride, simultaneously with halogenation by Sandmoycr\s method. When, for example, onitranilino is diazotised and treated with cuprous
40
SYNTHETIC USB OF MKTALS
chloride a considerable quantity of Dinitro-diphenyl results as well as o-chlor-nitro-bonzeno. 11 Heated metallic copper acts as a catalyst in tho oxidation of primary alcohols to aldehydes by air or oxygen, but ifc has also been shown by Sabatior, that moderately heated copper in a finely divided stato effects the dehydrogenation of primary and secondary alcohols, yielding aldehydes and ketones respectively. Powdered silver was found by Gomberg to yield results when sodium failed, in preparing the peculiar and interesting substance called by him triphonylmethyl. Both triphenyl brom-methane and triphenyl chlor-methane were used to effect the following change: 2(C6H5)3C.Br + 2Ag = (C6H5)3O.C(C()H5), + 2AgBr. The hexaphenyl ethane obtained was far more reactive than was to be expected, and on account of its properties Gromberg named it triphonyl methyl. Since then much work and discussion have centred around this substance, which is now gonorally regarded as being hexaphenyl-ethane. Various constitutional formula have been suggested and the molecular structure of the hydrocarbon is still in dispute, but opinion appoars to give preference to a formula which ascribes a quinonoid structure to one or two of the phenyl rings. 12 Silver cyanide seems capable of acting in the same way as molecular silver. For example, it brings about the condensation of iodo-acetoacetic ester forming diaceto-succinic ester :13 CH8.CO.CH.COOC2Hr, I Cir .CO.CHI.COOC H CH .CO.CH,COOC ir
3 2 6 8 2 6
COPPER AND SILVER
41
Silver hydroxide is used in exhaustive methylation, a process often utilised in order to obtain an unsaturated cyclic hydrocarbon from an amino by treating it with methyl iodide and silver hydroxide; the trimethyl-ammonium hydroxide obtained is then decomposed by distillation. Cyclo-butylamine, for example, is converted to cyclo-butyl-ammonium hydroxide, and this on distilling is decomposed into cyclo-butylene, trimethylamine and water : 1 4
CH/ ; C H . N H , -> CH/ ;CH.N(CH 3 ) 8 OH
/OH CHo
OH + N(CH3)3 + ILO.
Silver oxide suspended in water receives limited application as a hydrolysing agent, and in alkaline solution it is used as an oxidising agent, especially for converting aldehydes into a c i d s . u Ann., 1869, 1*9, 220;- Ber., 1895, 28, Kof. 4m. 2 Bor., 1880, 13, 473; Ber., 1889, 22, 48. 3 Ber., 1904, 37, 853. < Bor., 1886,19, 2243. 5 Ber., 1885,18, G78, 2269. 6 Ber., 1882,18, 57. 7 Ber., 1884, 17, 1633. 8 Ber., 1890, 2$ 1218. 9 Trans., 1892,&*, 1072. 10 Zeit. angow. Oliom., 1910, 23, 389. Ber., 1901, 3*, 3802. 15 J. Amer. Chem. Soc, 22, 957; Bor., 1900, 33, 3150; Bor., 1901, 3S, 3818. ' 14 Ann., 1889, 253, 182. Ber., 1882,18, 1830.
1
BIBLIOGRAPHY.
CHAPTER MAGNESIUM.
III BAEIUM
CALCIUM.
THE great value of magnesium as a synthetic reagent was'indicated in 1900, when Grignard showed how various hydrocarbons and alcohols could be prepared from the confounds obtained by allowing the metal to react with alkyl halides in the presence of dry ether. 1 I n the previous year Barbior had! shown that by the interaction of methyl hoptcnonc, magnesium, and methyl iodide in ether, and subsequent decomposition of the resulting product by dilute acid, a tertiary alcohol was obtained, dimethyl heptenol :3 (CH,)2C: CH.CH3.Cir2.CO.GH:{ -> (CH3)3C: CH.CH2CH2.C(Oir)(Cir:,)o The metal has to a great extent replaced zinc, which was used in 1849 by Frankland in tho preparation of paraffin hydrocarbons and the zinc alkyls, and subsequently by Wagner for preparing secondary alcohol from aldehydes, by Saytzeff in preparing tertiary alcohols from ketones, and by Butlerow in the preparation of both ketones and tertiary alcohols from acid chlorides. The advantage of magnesium over zinc depends
MAGNESIUM.
CALCIUM.
BATJIUJff
43
upon the fact that the organo-magnesium compounds are not spontaneously inflammable; it is not essential that they should be isolated during syntheses, while they are more readily prepared than the corresponding zinc compounds, and they are more reactive, and therefore capable of much wider application. I n practice, tho metal in the form of ribbon or borings is added gradually to a solution of well dried alkyl or aryl halide in dry ether; a brisk reaction usually takes place, owing to the formation of the magnesium compound of type E.Mg.X (X=01,Br,I). When all the magnesium has been added and a clear solution obtained, the organic compound to be used in the synthesis (ketone, ester, etc.) is added gradually, and the mixture cooled in ice to modify the reaction if necessary. When the vigorous roaction has subsided, it may be completed by heating on the water-bath for half an hour, or it may bo allowed to stand over-night. The next stago is to add ico-cold dilute acid to tho reaction mixture gradually, to decompose the complex intermediate compound formed, and tho end-product is thon isolated by suitable means. If magnesium ribbon is used, it must be first well cleaned with emery-paper, while borings muat be washed first with alcohol and then with ether to remove all oil, and then thoroughly dried. All the reagents used must bo woll dried, and the roaction should be conducted under a reflux condenser fitted with a top tube containing calcium chloride to prevent access of moisture, and some soda-lime to keep out carbon dioxide. The ether used should be
44
SYNTH HTIC USE OP ]\l RTAI/3
purified by treatment with powdered potassium permanganate, followed by treatment with solid potash to remove aldehyde, alcohol, and most of the water. The ether is then allowed to stand over calcium chloride for two days, and finally over sodium wire for about a week. Traces of moisture arc very harmful, and the presence of moisture is indicated by a turbidity which appears when the magnesium is first added. W h e n the magnesium albyl compound does not form readily, i. e. in using aryl halides, a crystal of iodine is often added to start the reaction. Other solvents than ether have been used, i. e. anisolc, phenyl amyl ether, and dimethyl-aniline. The solvent apparently combines with the compound MgRX forming intermediate products R 2 O.MgllX and BoN.MgllX, and acts as a catalyst, since it has boon found that the reactions proceed in benzene or xylene provided a small amount of ether or dimethyl-aniline be added. The constitution of these compounds is represented, according to the suggestion of Bacyer and Villiger, 3 by an oxoninm formula with the halogen directly attached to quadrivalent oxygen, a suggestion supported by Blaise. The dhneUiyl-aniline compound is similarly represented: CHr-N Although the formation of the compound MgRX is the normal course, there is a tendency for the magnesium to form a hydrocarbon by the removal of
]MA<JNILSH!M.
CALCIUM.
BARIUM
15
halogen from two molecules of RX, which is more marked as the molecular magnitude of R increases. When working with brom-benzene and benzyl chloride a considerable quantity of diphenyl and dibenzyl result, but this may be ayoided by adopting Barbier's original method of omitting the first stage (preparation of MgRX) and mixing all the reagents at once. This fact was emphasized by Kipping recently, and the method has also been used with allyl bromide and iodide syntheses with success, although the allyl halides do not form a compound of the type MgRX in the presence of ether.* The following syntheses wero carried out by means of zinc, prior to 1900, and are now more conveniently accomplished by the aid of magnesium:
PARAFFIN HYDROCARBONS.
MgK3 + 2H2O = 2EII + Mg(OII)2 EMgX + II2O = EII + MgX(OII)" EMgX + ENH2 = E.E + MgXNH2 = 2E,C "
SECONDAUY ALCOHOLS FROM ALDEHYDES.
/O.M*r.X + E.CIIO + R'.Mg.X -> R.CE' \IX IIC
J>C1IOII + MgXCl. E'/
If formaldehyde be used, a primary alcohol results :5 yOMg.X 1I.CHO + E.Mg.X -> II.CE
+nC1
> E.CHoOII + Mg-XCl.
46
SYN'LLIETIO U f c i K OF METALS
TERTIARY ALCOHOLS FROM KETONE>S.
X)MgX E.CO.E + E'.Mg.X -> E.CE
1IC1
> EoR'COlI + M-^
KETONES AND TiflliTIAliY ALCOHOLS lîOM ACID

CHLORIDES.
K.COC1 + E'.Mg.X -> E.CCl
-> E.CO.14' + MgXOJ
With a second molecule of Mgli'X the following change takes place : />MgX ,x /OMgX E.C.E'
TERTIARY ALCOHOLS FROM ESTERS.
+ E;/.Mg.X -> B < c o R /
"LjfJt
E.CI
E.CE;/
> EE7/2COn + MgXCl.
With formic ester a secondary alcohol is obtained : /OMgX vOMgX H.COOE + E'.Mg.X -> II.COE -> H.CE' ~> E'aCHOII.
\E
7
\E/
A dicarboxylic ester like oxalic ester may have only one carboxyl group acted upon at a time :
MAGNIUfcJJUM.
CALCIUM.
B A H HIM
-17
COOK COOK
yOMgX ,/ N&' COOE
Mg /\,, SR' COOE
R'3C.OII OOOE Dialkyl glycollic ostor.
Since 1900 various syntheses have been added, of wliicli the following are typical examples :
TIIJBTIARY ALCOHOLS VROM OAKBONYL CuLorjDjyj.
COC], + 3E.Mg.X = KjCOMg-X + 2MgXCl R3C0MgX + IIC1 = R3C.OH + MgXCl.

ALDEHYDES PKOM FORMIC AND ORTUO-POUMIC ESTEUS.
/OM-X + 1I.COOE -1- li'.Mg.X -> H.COli / 0 K +R'MgX / 0 E 11,0011 > II.COH
HCI
> R'CIIO + EOH + MgXCl. + ILO --> E'.CHO + 2K0II.
KBTONES PROM CYANOGEN, JSTITRILES, AND AMIDES. 0
^NMgX +M-EX 7/NMgX N -. C.C i N + ll.Mg.X - N: C.C\ > R.cf Cyanogon R Mi .NMgX + 11,0 + IIC1 : E.CT > E.CO.E + NiL< + MgXOl. \E ^ g + IJ.,0 + IfCl R.CN + ti'MgX ^> ll.Cf '* > X Niirile E' ; E.C0.E + NIL, + MgXCl. + 2E'M^X-> E.C U' + It'll
48
SYM'IIKTK! UriK O K + NIL, + 2MgXCl.
DIAZO-AMINO COMPOUNDS FROM AZOIMIBES.
+ K/Mg-X ~ > E.N(MgX)N: N.R'
ANILIDES FROM AKYL OABBIMIDES.
.OMgX CoHa-N: CO ~> C6HVN : C< -> C0H3.NH.COK.

HYDEOXYLAMINB DERIVATIVES FROM ABIYL NITRITE.
C5HU.O.NO + 2MgEX = Eo^TOMgX + MgOC5H13X + HC1 = iySTOH + MgXCl. Esters of the type R.COOK aro obtained by the action of MgRX upon esters of meta-carbonic acid : .OMgX ô CO(OEt)k> + EMgX -> (EtO)oC<; -> EtO.C< Triplienyl methyl chloride in benzene solution reacts with an ether solution of RMgCl thus : 7 (C6H5)3C.C1 + RMgCl = (CGH6)3C.E Hydrocarbons are formed by the action of methyl sulphate upon E M g X : (CH3)3SOi + EBTgX = B.CII3 + CII3(MgX)SO4. Unsaturated hydrocarbons may be obtained from aromatic aldehydes via the carbinols, which on distillation sometimes decompose, as phenyl-benzyl-carbinol does; into stilbene and water :8
MAGNESIUM.
CALOIUM. BARIUM
C6H5.CHO + CflH5.CHj.MgBr - CoH5.C Sometimes the unsaturated hydrocarbon is formed directly, as with benzyl chloride and anisic aldehyde : MgC6H6CHoCl + CoHX -> CGH5CH: CH.C6H4.OCH.,.
Benzyl alcohol may be obtained from benzyl chloride by the action of oxygen: CcH6CH2.MgCl + O - CflH6CHs.O.MgCl - C6H6CH2OH + Mg(OH)Cl. Tertiary alcohols and ketones result from acid anhydrides: R.CO K.CO \ o -> No -> E.COOH + B.CO.E + Mg(OH)X. R.CO R.COMgX
\R P r o m succinic a n h y d r i d e a ditertiary glycol results: CH2.CO CH2.CR2OH
CH0.CR0OH From phthalic anhydride similai^ly dimethyl-^ diethyl-, and dipropyl-phthalide are obtained: >CO >CB2 CCH4 No + 2EMgX -> C6H, ÔH - C6H4 \CO ^COOH
Camphoric anhydride with benzyl chloride two isomeric campholides: .00
V
CH2,CO ,
gives
X(CH 2 C 6 H r) ) 2 " ~~
V
.CO and CdHM No
50
SYNTHETIC USE OP METALS
a-Diketoncs give ditertiary glycols, as in the case of benzil to tetraplienyl glycol: CfiH5.CO C6H5.CO C((H5C(OH)K C,lTr)C(OH)K
If only one carbonyl group be attacked, phony] benzoin results: C(JH5CO.CEOH.CGHf, Acids are formed by the action of carlbon dioxide upon E.Mg.X: MgX + HC1 > R.COOH + MgXCl. Many organo-rnetallic compounds can be preparod by digesting- an etliereal solution of tlio magnesium^ alkyl or aryl halide with the metallic lialogon com- - pound. The following compounds have been preparod in tin's way: Sn(C2H5)45 Sn(CflHG)4, Pb(C0H5)4, Pb(CHr{)4, I^(OuH0)^ and an optically active silicon compound in which four different radicles are present, Si(C3HG) (C3II7) (OflH6)(OH2CfiH5)-9 Pivalic (trimethylacetic) acid is formed from tertiary butyl chloride and magnesium (yield, 30 por cent.) : + Mg + CO2 /O (CH3)3C.C1 > (CH3)3C.Mg.Cl > (CHa),CC<
<
Tetramethyl-methylene-glycol from succinic estor:
MAGNESIUM.
CALCIUM.
BARIUM
51
.OMgX CH2.COOR CH2.C^-R + 2MgRX \OR + 2R.Mg.X OMgX ,OMgX CH2.COOR CH2.Cc-R CH2.C^-: + 2HC1 CH2.CR2.OH
2 2
(A ditertiary glycol is also obtained from oxalic ester.) By the same reaction this can be obtained from acetonyl acetone: CH2.CO.CH3 ,CO.CH3 CH2.C^R CH2.C(CH3)R.OH X CH3 .OMgX * CH2.C^-R CH2.C(CH3)R.OH X CH3
+ 2MgXCl .c .OH k.CE
The ketonic group of a-tetonic esters is attacked in preference to the carboxyl group. Prom pyruvic ester is obtained a-methyl lactic ester: yOMgX CPI3.CO.COOR + MeMgX -> CH3.C^COOR -> Nvte CH3.C(Me)(OH).COOR y-Ketonic esters, such as laevulinic ester ; behave in the same way: OH CH3.CO.CH2.CHo.COOR -> CH3.C^-CH2.CH2.COOR X R j3-Ketonic esters, such as acetoacetic ester, show a somewhat different behaviour. The ethyl and menthyl esters both react with MgRX as if possessed of an enolic structure, and the magnesium compound fox'med
52
SYNTHETIC T T S E OF METALS
is decomposed by dilute acid, giving the original acetoacetic ester : 10 CH3.C(OH) :CH.COOE + E'MgX = CH3.C(OMgX): CH.COOE + E'H CH3C(OMgX):CH.COOE + HCl CH3.CO.CH2.COOE + MgXCl When, however, enolisation is retarded by an alkyl substituent in the methylene group, the reaction follows the same course as a- and y-ketonic esters : CH3.CO.CHE.COOE - CH3.CE'(OH).CHE.COOE If the carboxyl group be next attacked by MgR'X, the following change takes place, resulting in a substituted trimefchylene glycol: CH3.CE'.CHE.COOE CH3.CE'.CHE.CE'2 OH ~* OH OH The tendency to form organo-metallic compounds, seen in the metals of group 1 (alkali metals) reaches a maximum in the metals of group 2 ; it diminishes on passing through groups 3, 4 and 5, and none of the metals in groups 6 and 7 combines with organic radicles. The property reappears in group 8, which contains the transitional elements. Aluminium, thallium, indium and lithium form complexes with alkyl or aryl halides, which are decomposed by water, with the formation of hydrocarbons. These compounds are not produced in the presence of ether, but by heating the halogen derivatives with the metal. 11 Two important applications of the Grignard reagent to synthesis in the terpene series may be mentioned. The formation of dipentene from S-keto-hexahydrobenzoic acid (see p. 14) by Perkin involved the
CALCIUM.
UAlilUM
53
following stages : Tho ester was troalod with magnosium methyl bromido, and tlio addition compound gave on hydrolysis S-liydroxy-lioxahydro-p-toluic ostor: yCiia.cii3v xjjT8.cxrav xOii KOOC.CII CO -> ROOC.OH C This ostor was then converted into -brom-hoxaliydro-_2>toluiocstoi% by tlio action of hydrogen bromido, and from this, by romoval ot II Br with alkali or pyridino, A R -tetra-hydro-y-toluic ostor was obtained; >CII2.CILjV y\\t yCili.CiL EOOC.CII C -> KOOCJ.CII C.OU3 Troatmonb oi: this ostor with 2MgMoBr gave tcrpinool, which was converted into dipontono by dehydration with acid potassium sulphate : oir,\ /Oi / 1 ;c(on).ou " e c u , -> " . e c u coir, Tho synthesis of A :J:B(0) -2^monthadiono from ethylA 8 -totrahydro-j>-toluato involved tho following stages: OIL, CLT3 0HH on ii a c Clio
>
on u^' ojr2
v
ctn nBo on.
n a c on *" ua<! e n "" nô on \<s \ \ 0 0 C OOOR 0 0 / I \ Oil CUaCIIj <ifia on a
54
CALCIUM AND BABIUM.
These metals, so alike chemically and physically, have been closely associated together in the solving of the problem of atmospheric nitrogen fixation. Calcium has received some application in organic synthesis similar to that of magnesium; alkyl and aryl compounds, CaR 2; have been prepared, and it seems likely that many of the magnesium syntheses, already mentioned, could be accomplished by the use of calcium. The compounds of calcium and barium, instrumental in bringing about nitrogen fixation, are the carbides, the preparation of which has been rendered possible by the advent of the electric furnace. This means of attaining very high temperatures came into general use during the eighties of last century, and rendered possible the preparation, on a largo scale, of many new and useful substances. In 1895, Erank and Caro found that when barium carbide was heated to redness in air the main product was barium cyanide, but simultaneously a cortain amount of barium cyanamide was formed. These two reactions, therefore, proceeded side by side: Ba(CN)3 ; BaC2 + N2 = BaN.CN + C These workers subsequently found that when calcium carbide was used the cyanamide was the main product, while the cyanide became the by-product. These efforts to prepare a nitrogenous land fertilizer promised success, since the cyanamido decoin-
MAGNESIUM.
OALCJUM.
J3AKJUM
55
posed easily in the presence of water, yielding ammonia and lime : CaN.CN + 3H3O CaCO3 + 2NH3 Later work has shown that cyanamide o lime is not only a valuablo fertilizer product, but that it can be used for a variety of purposes and transformed into various useful products. Eleven European factories were making the substance in 1909, and their yearly output was estimated at 166,000 tons, while in the same year the American Cyanamide Company erected at Niagara, plant capable of yielding 20,000 tons per annum. The substance is sold for agricultural uses under the name of nitrogen lime (Gorman, Kalkstickstoff), and has been shown to be equal in value to an equivalent of calcium nitrate. Since 1901 it has boon found unnecessary to prepare the carbide itself in tho first place, and necessary to exclude oxygen, so that now the process involves the heating together, in an electric furnace, of lime and carbon in atmospheric nitrogen, when the following change takes place: CaO + 2C + N3 = CaN.CN + CO. The complete decomposition of the cyanamide into calcium carbonate and ammonia may be accomplished in stages by suitably arranging the conditions, so that the first substance to bo formed is cyanamide itself, which is then transformed into urea, and the third stage involves the hydrolysis of urea into carbon dioxide and ammonia :
56
SYNTH KTIC USE Ol1 MKTALS CaN.ON + 2II3O = Ca(OH)s + NH2.CN NHS.CN + H3O - CO(NH2)2 CO(NH8)4 + H3O = CO2 + 2NH3
Under ordinary soil conditions all tlio above stages are realised, but by heating with, water under pressure, complete decomposition into calcium carbonate and ammonia takes place. The chief uses of calcium cyanamide are as follows : (1) By decomposition with steam it is used for preparing ammonia and ammonium salts. (2) When fused with sodium carbonate, or chloride, and carbon it yields sodium cyanide : CaN.CN + Na.2CO3 + C = CaCO3 + 2NaCN. Hundreds of tons of cyanido arc manufactured annually in this way in Europe, and in Mexico it is made in the mining districts. (3) It roceives some application in the caso-hardoning of steel. (4) By the action of dilute acids, dicyanamido is formed : 2CaN.CN + 4.11*0 = 2Ca(OH)2 + (CN.NH2)a Dicyanamide is used in largo quantities by dyers and explosive manufacturers. Its presence in gunpowder tends to lower the temperature of the gunbarrel. (5) Artificial urea made from cyanamido is used in large quantities for certain pharmaceutical preparations : CaN.CN + 31LO Ca(OII)2 + CO(N1I2)2 (6) Large quantities of guanidino are made from cyanamide. Two methods aro available for this
MAQNHSJLUM.
CALCIUM.
BARIUM
57
preparation ; either the cyan amide may bo treated with ammonia, or it may bo reduced with zinc and hydrochloric acid. In the latter method, mcthylamine is produced at the same time by reduction of the hydrogen cyanide formed : CN.NII, + NUj ~ II .NIL, 2C3ST.NII2 + II) = UN: C< + IICN NNH3 HCN + 2H3 - CHj.NII2. (7) Creatino is prepared by combining cyanamide with sarcosino (methyl glycine) at 100 0. : CN.NH2 + ClIy.NH.CIL COOH = \c.N(CH3).CH3.COOH.
(8) Another method for proparing cyanide depends upon the heating of dicyanamide with alkaline carbonate and carbon. Ammonia is formed at tho same time and is generally absorbed in sulphuric acid. 2(CN.NII2)2 + 2K2COa + 4C = 4.KCN + 2NHa + II3 + 6CO + N2 A process patented in 1903 by the Amp&re ElectroChemical Co. (U.S. patent 71922C) for tho preparation of barium cyanide and acetone is as follows: Barium hydroxide and carbonate are heated with coke in a revolving electric furnace. Tho barium carbide formed, rolls down into a cooler region and there comes into contact with a stream of atmospheric nitrogen, and the resulting cyanide is withdrawn :
58
SYNTHETIC USE OJi1 METALS
Tho cyanide is next treated with acetic acid to liberate the hydrogen cyanide, which is then passed into alkali: Ba(CN)3 + 2Cn3COOH = (CII3COO)2Ba + 2HOT The acotato is thon submitted to distillation, whereby acetone is formed,, and the barium carbonate is usod. over again : (CH3C00)aBa = CHj.CO.CH3 + BaCO3 The "by-product of the first stage, barium cyanamide, is separated from the cyanide and converted into alkali cyanido by fusion with carbonate : BaN.CN + Na2CO3 + C = BaCO3 + 2NaCN\ The preparation of nitrides from atmospheric nitrogen making use of calcium or magnesium, has boon the subject o much investigation and o many pat outs. Tho nitrides are easily decomposed by the weakest acids, oven by carbonic acid, liberating ammonia, and often they can bo decomposed by water. Some processes depend on the fact that the oxide of a nitride-forming metal is reduced to the metallic condition, when heated in the electric furnace with carbon in tho requisite quantity, and if a stream of nitrogen be thon blown through the fused mass, nitride is formed. Magnosium has, for example, been utilised in this way: 23%O + C - 2Mg + CO2 j 6Mg- + 3N3 = 2Mg3N2 Mgstfa + 6H2O - 8Mg(OH)2 + 2N"H3 The French Patent, 350966, depends upon the production of calcium hydride which is formed by
MAGNESIUM.
CALCIUM.
B A 1 U U M
59
heating tlio metal in hydrogen ; the hydride is next converted into the nitride by a stream of nitrogen, ammonia being formed at the same time : Ca + II2 CaH2 ; 3CaH2 + 2N2 - CaJST2 + 2NHj CagNs + 6H2 = 3CaH2 + 2NH:{ The nitride is then heated in hydrogen to decompose it in the manner indicatod above; the method is one., therefore, of continually fixing atmospheric nitrogen and converting it into ammonia. In developing this method it has been found that either calcium or magnesium may be used, or a mixture of the two metals ; also that it is immaterial whether the hydrogen and nitrogen pass over the metal separately or together ; and instead of hydrogen it is possible to use water-gas. The reaction may, therefore, be regarded as a synthesis of ammonia from its elements in the presence of magnesium or calcium. Another process for the fixation of atmospheric nitrogen is the subject of an English Patont, 1894, 13315. A heated air-blast is passed into the bottom of a vertical furnace containing a mixture of alkaline carbonate and coal (the carbonate may be replaced by or mixed with oxide, hydrate or nitrate), whereby a cyanide results, which is carried up in the form of a fume and at a suitable height is decomposed by a jet of steam, into carbonate and ammonia, the latter being collected in condensers : IC3CO:, + 40 + Ns = 2KCN + 300 KOT + 2H2O = H0ONII2 + K01I HCONiJ2 = CO + NIL, 00 + O COjj 5 G02 + 2K01I 'K 3 COJ' h 1I2O.
60
SYNTHETIC U8K OF METALS
Tlio K 2 0O 3 is allowed to fall down to the "bottom of the furnace and the process is repeated. The entire reaction may be represented by the following equation : 2KCN + 3H2O + O2 - K2CO3 + 2NH3 + CO2 This process may evidently be used to yiold ammonia and formic acid if the reaction is rogulated to bring about the following change : 13 KCN + 2H2O = HCOOK + NH3 Two applications of the calcium and barium salts of various organic acids are common and of great importance. Firstly, the calcium and barium salts of organic acid are frequently used in the preparation of the acids themselves, by treatmont with mineral acids such as sulphuric, hydrochloric or phosphoric. This method was first utilised by the Swedish chemist, Scheele (about 1770), who discovered by this means tartaric, citric, malic and oxalic acids. Secondly, by the dry distillation of the calcium and barium salts of organic acids, ketones are formed: (CH3COO)aCa = CaCO, + CH8.CO.CH3 If the salt of formic acid be mixed in molecular quantity with the other salt then an aldehyde is produced: (HCOO)2Ca + (CHjCOO)aCa = 2CH3.CHO + 2CaCOy Certain cyclic ketones have been formed in this way, and from them, the cyclic hydrocarbons. For example, the calcium salt of adipic acid yields on distillation, adipoketone (keto-pentamethylone),
M A G N E S U IM .C A L C U IM .B A R U IM 6 1 a n d this b y reduction a n ds u b s e q u e n tu s eo fh y d r o g e n i o d i d e gives pentamethylene: +H I H C H o C .H o C .O O C H C .H d u c eC 2 C H 2 2 r( j 2 1 Sco C H C . H C . O O H C .H C H ~ C H 2 2 2 2 2 2 ( C H C . H 3 H o C .C H ^ 2 2 > rH r o c l u c> " ) C H 2 \ O I C H C .H C H C .H 2 3 2 2 In a similar m a n n e rh e x a m e t h y l e n ec a nb e prep a r o df r o m pimelic acid, a n dh e p t a m e t h y l e n ef r o m suberic a c i d: C .H 2 C .H 2 C .O O C .H C .H C .H C H 2 2 C I L \ca >C H S c O C H 3 2 C \H C .H C .O O \ C H C .H 2 2 2 2 C H C .H C .H C .2O O C H C .H C .H 2 2 2 2 2 2 \ S I \c C I L , . C I I , . C I I . 2 C . O O " 2C H C .H C .H 2 2 2
CH2.CH2.CH2 By means of this reaction Haller obtained camphor from camphoric acid. 13 The complete process was as follows; camphoric anhydride from camphoric acid was reduced with sodium amalgam to campholide, and this combined with potassium cyanide gave homocamphoric nitrile. The nitrile was hydrolysed, and the calcium salt of the resulting homocamphoric acid, on heating, gave camphor :
62
SYNTHETIC USE OF METALS II > O .coon " 0,11,/ -> C \coon hydrolyse >CHo.ON
cy*,/ "
reduced
+T C C N
/CII..COOH
-
/CT-L
-> CSITU<; i -
-> cbnn<;
XI00K XJOOH \ CO The Lydroxides of magnesium, calcium and barium, liavo played an important part in the synthesis of sugars. In 1801, Butlorow digested an-aqueous solution of calcium hydroxide with trioxy methyl one (a polymer of formaldehyde) and obtained a sweet yellowish syrup. 14 In 188G, Loow prepared a syrup which he termed formoso, by shaking a 4 per cent, solution of formaldehyde with milk of lime and then filtering. After standing for live or six days, the solution was evaporated and a syrup obtainod.15 A few years lator (1889) ho used magnesium hydroxide, and by the same method obtained a sweet syrup which was fermentable and which ho termed mothosc.10 The above throe syrups all appear to have contained a-acrose, which Emi] Fischer isolated in a pure state in 1887, by the action of baryta water upon acrolein bromide, when a mixture of a- and /3-acrose was obtained. 17 SCjHiOBra + 2Ba(OII)2 = C(5ir]20(, + 2BaBr2 Fischer subsequently obtained a-acrose alone, by tho polymerising influence of one per cent, sodium hydroxide uponj^glycerose, an oxidation product of glycerol. 18
MAGNFSIUM.
CILOII CH,OII
CALCIUM.
cn>on
BARIUM
CB\OII
63
I I CHOH + CO CHO
I -v CHO1I CIIOH
I * CO CHOTI
CHoOH
BIBLIOGRAPHY
1 Compt. rend., 1900, 130, 1322. 2 Compt. rend, 1899, 123, 110. { Ball. Soc. Chim, 1907 (iv), 1, 610 4 Bei\, 1909, 52, 435. r > Compt rend., 1902,134, 107. G
Compt. rend., 1901,133, 299. ~' Ber., 1906, 39,1461. 8 Ber., 1904, 37, 453. q Trans., 1901, 79, 451; Proe, 1903, 290; Trans., 1907, 91, 209 10 Trans., 1906, 89, 380.
Ber., 1905, 38, 905; J. prakt. Chom., 1908 (ii), 78, 97. Zeit. angew. C h e m , 1912, 25,12G8 >3 Compt. rend., 1896,122, 446. 4 Ann., 1861,120, 295. 11 J. prakt. Chem., 1844, 33, 321. 1 ( ' Ber., 1889, 22, 475. V Ber, 1887,20,1093, 2566, 3384 ; 1890, 23, 2125 1 S Ber, 1891, 27, 3190.
12 11
CHAPTER
IV
ZINC AND MERCURY TEE use of zinc for preparing ketones and tertiary alcohols from acid chlorides, has received wider application since Michael showed how it might be used in a similar manner to magnesium, without isolating spontaneously inflammable organo-zinc compounds. It has been used largely by Blaise and his co-workers in synthesizing ketones and cyclo-acetals ; it is less reactive than magnesium, and is, therefore, complementary to that motal in synthetic work. The zinc organo-halide is prepared for use by heating together the zinc-copper couple, the alkyl or aryl halide, ethyl acetate, and toluene for about an hour, the reaction being started if necessary with a crystal of iodine. All the roagonts must be well dried, and the colourless viscous liquid which results is utilised by adding to it the acid chloride dissolved in toluene, and when the required amount has been added the intermediate zinc complex is decomposed by the addition of dilute sulphuric acid. 1 Blaise synthesised aj3-unsaturated ketones, and ketone-alcohoLs as follows: A |3-liydroxy-aliphatic ester is prepared by condensing a kctone with an
ZINC AND MKBOTRY
65
a-halogen substituted ester by means of zinc (lieforniatsky's reaction) : R.CHBr COOR The j3-hydroxy-aliphatic acid is then acetylated and converted to the acid chloride by thionyl chloride,, after which the acid chloride reacts with ZnRX, to produce an acetoxy-kctone which is liydrolysod to an a/3-unsaturated ketone : HO.CHR.CHE'.COOH -> A.cO.CIIE.CIIir.COCl ->" - AcO.CHR.CHE'.GOE" -> RCH: CR'.COR'' If however, there is no hydrogen atom in tho a-position, a saturated koto-alcohol results: AcO.CHjj.CRo.COR" ~> HO.CH2.CE2.COE'7 )3-hydroxy-a-dimetl]yl propionyl chloride, for example, changes in this manner. 2 The semi-acid chlorides of succiuic and glutaric acids yield keto-acids by treatment witli Z n R l : CHo.COOE CHo.COOE CIL.COO1I OII2.COC1 CJIo.COB cna.COR Diketones are obtained from tho acid chlorides of adipic acid and higher acids of tho scries : /COC1 (0Ha)< -> This change is not applicable to saccinic and glutaric acids. 3 Compounds of tho type E.CO.O.CLILl.COC] give cyclo-acetals, probably by the following change : /OC<K ZnIO.CRa.O.CHRCOCl -> lUlS
66
These cyclo-acetals may be hydrolysed, forming hydroxy-acid and aldehyde :4
nru_o ^>CHR' + H2O = KCHO + R'CHOH.COOH.
The use of zinc in those syntheses which are now generally carried out by the aid of magnesium, has already been mentioned, p. 45. A further application of zinc is seen in a reaction first carried out by Reformatsky in 1887, in which halogen substituted esters are condensed with ketones or with ketonic esters. An example is afforded by the production of j3-hydroxy-isovaleric ester from acetone and iodo-acetic ester; a zinc addition compound is probably formed; and on the addition of dilute acids is decomposed. This reaction is therefore represented in the following manner: CHav /I CHjv yOZnL >CO + CH< -> >C< CEL/ " XJOOCgH* CIV XCH2.C0OaH5 CHav .OZnl CH3v /OH >C< + HC1 >C< 4 ZnlCl. CH,/ \CI-L.COOGoH5 CH/ \C Citric ester has been synthesised in this way from broni-acetic ester and oxalyl-acetic ester :5 CH.,Br COOC.2H3 CO.COOCH, CH3.C00C0H5 CH, OOOCoHs C(OH) CH, COOC0H5 COOC2H3
Another esamplo is camphoronic acid (aa/3-triniethyl-tricarballylic acid), an oxidation product ol camphoric acid, which can be synthesised from a-broin-isobutyric ester and acetoacetic ester.5
ZINC AND MERCURY (CH3)oC.Br "| COOC2H3 (CH8)3C CO.CH3 + 1 -> OHo-COOUjlI,, C.CH, CH2
67
COOC3H3 OH COOC2H3 The liydroxyl group of this hydroxy-trimethyl glutaric ester is replaced by chlorine, this again by cyanogen, and the nitrile gives the required acid on hydrolysis, dl-camphoronic acid: (CH3),C C.OH3 CJrL I I I I I -> COOCH C CN COOG li 2 5 (CH ),C C.CII3 GIL
3
(JOOH
COOII
COOH
Magnesium has been used in place of zinc for this type of synthesis. 0 Zinc is frequently used for bringing about condensation by the elimination of halogen or of hydrogen lialide. For the preparation of hydrocarbons it may replace sodium in the Wurtz-Fittig reaction : 2GoHrjI + Zn = Znl> + CHu,. Ill reactions where hydrogen halide is eliminated, zinc plays a somewhat similar role to that of aluminium or aluminium chloride in the Friedel-Crafts reaction (Chapter V). Naphthyl-phcnyl-ketone is obtained from naphthalene and benzoyl chloride, in the presence of zinc :7 C1()LL3 + O(,HdCOGl =- eiulJr.OO.C()Ll, -1- Jit1]. Phenyl-tolyl-metluino L'rom bouzyl chloride and toluene is another example : C6H6.CII2CI + cji.,.01^ =- c0uo.0Ji3.0(,ii1.ciitl \ u n .
68
A recent and interesting use of zinc is found in the preparation of keten, the simplest of the ketides, from brom-acetyl bromide. 8 After an unsuccessful attempt to remove the chlorine from chlor-acetyl chloride, it was found possible to remove the bromine from brom-acetyl bromide by treatment with zinc turnings, in ethereal solution. Tor this purpose the brom-acety] bromide (50 gms.) was dissolved in ether (250 gms.) or in acetic ester (200 c.cm.), and the mixture was then dropped on to zinc turnings, in a distillation flask. A vigorous reaction took place and the product was allowed to distil over, in a current of hydrogen gas. The keten was isolated by passing the mixed vapours through a vessol immersed in liquid air and was found to be a gas at ordinary temperatures, which liquefied when cooled to 56 and solidified at151: CII.Br.COBr + Zn = CH3: CO + ZnBr2. Methyl and ethyl keten can be prepared by tho same method using a-brom-propionyl bromide and a-brom-butyryl bromide respectively, but the yields are smaller than with keten itself : CH3.CHBr.COBr + Zn - CII,.CII: CO + ZnUr8 C2H5.CHBr.COBr + Zn = C2H5.CH: CO + ZnBr3. Carbon suboxide (03O3) may be regarded as keten in which the two hydrogens of the methylene group have been replaced by the carbonyl group : H2C : CO CO : C : CO Keten Carbon suboxide. This substance was prepared in 1906, by heating malonic acid with phosphorus pentoxide at 300 under
ZINC AND MERCUKY
69
reduced pressure (12 mm.). Carbon suboxide is a colourless gas at ordinary temperatures, its boiling point is + 7 and the melting point of the solid is 108. It is to be regarded as malonic anhydride, since it is formed by the removal of two molecules of water from malonic acid and because it recombines with water, forming malonic acid :9 XJOOII CH< " XX)0II = >;CO C, + 2H,O. CO
This oxide of carbon can also be prepared by the action of zinc turnings upon di-brom-malonyl bromide: .COBr -CO CBi\< + 2Zn = O{ + 2ZnBr,. ^C ^ Zinc is a valuable reducing agent in acid, alkaline, or neutral solution, and in the dry state it is used to remove oxygen from phenols and other oxygencontaining bodies. By mixing alizarin with zinc dust, and heating the mixture, Graebe and Liebermann in 1886, reduced the dye-substance to its parent hydrocarbon^ anthracene. In effecting the reduction of oxygen compounds by this method, zinc dust ii mixed with the substance to bo reduced, and the mixture is then heated in a combustion tube. The reduction is often facilitated by passing a stream of hydrogen or carbon dioxide through tho heated mixture : C0I-I5OH + Zn = C,,Hb + ZnO ; C10H7OH + Zn = C,OHS + ZnO. By this method succinimide can bo converted to pyrrol, and hoino-phthalimide to isoquinoline :
70 CH2.00 OIL CO ,/PI, 00 \

T I
CH: CII N OHrCIL ^ + 2r/n = r.,11, | 2Zn
2ZnO
+ 2ZnO.
Homophthalimidc itself is produced by reducing phthalic anhydride and then hj r drolising the cyanonddition product; the ammonium salt of the acid formed is then heated : CO CTI2 + I C 0 N CH2CN (^H,^ j>0 -v C()Tl/ V ) > C([T, -> CO CO N'OOIC .CH,.COOJI CIL.COONIT, i^ CHj.CO \NI-T + Nfla + 211,0. Ct(II(.CO
ZINC
This substance is used to effect condensation by the elimination of water, ammonia, or hydrogen chloride. It was used by Groves in 1874, to prepare ethyl chloride by the interaction oF ethyl alcohol and hydrogen chloride : ] 0 CÔII + HC1 = 0,11,01 + II2O. Illustrative of the power of zinc chloride to eliminate the elements of water, is the fact that many of the higher primary alcohols when heated with this reagent, become converted into olefine hydrocarbons.
ZINC A N DM T U K O i m Y
71
Homologues of the phenols can be prepared by heating a mixture of the phenol with a primary alcohol and zinc chloride at 200; thus, from phenol and isobutyl alcohol is obtained isobutyl-phenol, while from cresol tho analogous isobutyl-crcsol results :11
CV,H5OII + (cn:,)2cH.rH3on (CF:i):tc.o,H4.oir + TT.,O.
CH, I
OIL, + HoO.
I + (CH3)2CH.CILOII = I
Alkyl ethers of the phenols are formed simultaneously. The production of phthaleins by zinc chloride is exemplified by the condensation of phthalic anhydride and dimethyl-aniline : CfiH4.N(CTT3)a ttO + 2O H .N(CH ) = | | \C,,H .
G 5 3a 4
co . o The leuco-base of malachite green is formed by condensing benzaldehyde with dimethyl-aniline in the presence of zinc chloride: CCIT5.CHO + 2C(1Hri.N(CH3).. = C6\Lt.CE<( + IIaO. \onNcr Acid chlorides condense with acid anydrides, hydrogen chloride being eliminated in tho presence of zinc chloride : ^ CV,H5.COC1 CGH5.CO Q.lira.CO.C,1H4CO + ^>O = N o + 2HO1. Cfin5.COCl CfiHB.CO QHB.CO.CTlIT.iCO Acvidine and its homologues are fomned by heating
72
the acidyl derivatives of diphenylamine with zinc chloride : 13 cao XJH^ The method of Groves for preparing alkyl chlorides has been improved by Delm and Davis, who recommend the use of phosphorus trichloride instead of hydrogen chloride. The reaction is represented by the following equation : 14 PC13 + ZnCl2 + 3C3H7On = 3C3H7C1 + 2HC1 + ZnHPO3. While the maximum yield by Groves' method, using hydrogen chloride, was 28 per cent., they obtained by the above modification a yield of 90 per cent, of propyl chloride, and with isobutyl and isoamyl chlorides tho yields were 60 and 70 per cent, respectively. Many condensations are brought about with the elimination of ammonia, by zinc chloride. Naphthylamine and methyl alcohol yield naphthylmethyl-cther: C1()1I7.NII2 + CIT3OII - CJ0II7.O.CH, + NII3. Phenyl-hydrazoncs of aldehydes and ketones lose ammonia and form indol derivatives. 15 Acetono phenyl-hydrazone gives a-metliyl-indole, whilo tho hydrazone of propaldehyde gives j3-methylindole : O(lII6.NTI.N : C( = CcH/ )C.CH3
/C.cn 3 v \ NH /
ZINC AND MERCURY
73
Zinc chloride may bo used to assist the introduction of acetyl groups by means of acetic anhydride,10 A saturated alcoholic solution of tlie chloride may sometimes be used instead of the solid itself. For example, by warming o-amino-cinnamic ester in an alcoholic solution saturated with the chloride, water is eliminated and n-ethoxy-quinoline results :17 / /CH:CH.COOaH5 / " = cyau' CH | + ir8o. coaii
Metallic zinc may be used as an oxidising catalyst. When the vapour of alcohol, mixed with air, is passed through a tube containing heated zinc, a yield of aldehyde amounting to 80 per cent, may be obtained.
MERCURY AND MKRCURY COMPOUNDS.
The use of mercury and its compounds is confined to the substitution of halogens and to oxidation. The aluminium-mercury couple (prepared by immersing aluminium foil in mercuric chloride solution) is a halogen carrier of some value, and is used to facilitate substitution in. the aromatic series of compounds, by chlorine and bromine. For this purpose the hydrocarbon or the body in (,o which it is desired to introduce bromine is placed in a flask and a few pieces of the couple added ; the bromine is then added slowly and the substitution is accompanied by a vigorous reaction.18 Mercuric oxide is utilised when iodino is to be
74
SYNTHETIC USE OF M T S T A L S
introduced ; the easily reducible oxide forms mercuric iodide with the liberated hydrogen iodide which it is essential to remove from the sphere of action. The following avo examples of this method : Phenol is converted to iodo- and di-iodo-phenolby adding gradually, iodine and mercuric oxide to an alcoholic solution of phenol and agitating :10 2CfiHr,0I-I + IlgO + 2L = 2CJT.1(OH)I + Hg-r, + R,0 20(.H:)OH + 2HgO + 4I - 2C{5Ha(OH)I2 + 2HgI3 + 2IIX>. lodo-dnrene is obtained by adding iodine and mercuric oxide to durene dissolved in petroleum d,lier; and allowing the mixture to stand some time."0 As an oxidantj mercury may be used in the presence of sulphuric acid. One of the most important examples of this is the oxidation of naphthalene to phthalic acid ; used on the large scale in the firststage of the process for preparing indigo from the* hydrocarbon. The phthalic acid is next converted into anthranilic aoid; and this is condensed with chloracetic acid ; the stages are indicated by the following formula?: .COOH clon8 -> c f i H/ COOH /CO XJO " "' COOH
N
/CONJL >COOII
<
.NH.CH3.COOH
COOJI
The phenyl-glycine-carbonic acid is fused with caustic soda and the aqueous extract from the fused mass oxidised by air.
Z T N O ANT) M B R C T T f l Y
75
The use of mercuric oxide as a ruild oxidant is shown in tlie following examples. Salts of phenyl-hydrazino are oxidised to the corresponding diazo-eomponnds : (OCM5.NH.NH2)2 H2SO4 + 2O2 (OCH> N : N)2 SO, + 4ir2O. Di-ethyl-hydrazine is oxidised to tetra-ethyl-tetrnzone : 2(CoHr,)2N.NHo + O2 = (CJI-,): N.N : N.N(CJI3)3 + 2JLO. This action differs from that of Fehling's solution, which in the first case gives benzene and in the second case diethylamine : 2OflH:,.NH.NTr2 + O2 .-- 2CJl{] + 2N2 + 2IT2O 4(Coirr,)>N.NIL, + 0.2 ~ ^(ailOiNTT + 2N2 + 2EL.O. The addition oC the elements of water io various acetylenes takes place in the presence of mercuric bromide and other mercury salts. 21 Acetylene is converted to acetaldehyde, allylene to acetone, and valerylene also to a ketone : C.TL + TLO -r CTT3.CnO; CH,.C : CH + lT3O-CH3.rO.CJT.,. BlBLIOGRAPnT.
Bull. See. Chim., 1911 (iv), 9 (i-xxv). 2 Compt. rend., 11)07, 1$5, 73. : < Compt. rend., 1909, 148, 489. 4 Compt. rend., 1912, 154, 596. r > Trans., 1897, 71, 457. ( ( Bor., 1902, 35, 2140 j J. prakt. Chom., 1908 (ii), 78, 97. " Ann., 1888, 247, 1807. 8 Ber., 1908, 41, 59 i, 906. ' ' Ber., 1906,39,689. 1 ( 1 Ann., 1874, 174, 372. 11 Bov., 1881, 14, 1842 ; BLT., 1894, 27, 1(>14.
1
76
12 13
Ber., 1881,14, 648. Ber., 1884, 17, 101. 14 J. Amer.Cliem. Soc, 1907, 29, 1328. 15 Ber., 1886, 19, 1503. 1G Ber., 1889, 22, 1465. V Ber., 1882, 15, 2103. 13 Trans., 1899, 75, 893. w Chem. Contr., 1870, 63. 20 Ber., 1892, 25, 1522. 21 Ber., 1881,1$, 1542; Ber., 1884,17, 28.
CHAPTER
V ANTIMONY.
ALUMINIUM. TIN. LEAD. VANADIUM
The use of aluminium chloride for bringing about condensation by the elimination of hydrogen chloride was first made known by Friedel and Crafts in 1877, ?/ho applied it to the preparation of benzene hydrocarbons by the treatment of benzene with alkyl chlorides, in the presence of anhydrous aluminium chloride : C,H6 + CH3CI = CfllI5.CH:{ + 1101 C6II6 + C2H5Br = CGH5.C2H3 + HBr. Its nse has been greatly extended^ and aromatic ketones may be prepared by using acid chlorides and benzene hydrocarbons. For example, benzene with acetyl chloride gives acetophenone, while benzene with carbonyl chloride gives benzophenone: C6Hf) + CH3.COCI = C6H6.CO.CII3 + HC1 2cGi-rG + c6ci a = cGn5.co.cGH5 + 2HC1. Aluminium chloride condensations aro effected by mixing tho reagents in a suitable solvent (carbon
78
bisulphide, petroleum ether, etc.) and gradually adding powdered, dry, and freshly prepared aluminium chloride. If desired the procedure may bo altered by placing the whole amount of aluminium chloride in the solvent and then adding the reacting substances gradually. The reaction, which is vigorous, is completed by heating the mixture on the water-bullJ, smd then pouring the contents into cold water previous to extracting the end-product with benzene, ether or other suitable solvent. Acids can be prepared by using carbonyl chloride or carbamic chloride; in the formor case an acid chloride is obtained in the first instance, and in ilio latter case an amide :l C6H0 + COCLj = CbH3.COCl + 1101 CGHG + CICONH* = C6H3.CO.NH3 + HOI. Aldehydes of phenols and of phenol-ethers can be obtained by passing gaseous hydrogen chloride a n d hydrogen cyanide into the phenolic substance, mixed with aluminium chloride :2 OCH, CbH5.O.CH3 + C1CH: NH = CbH< + 1101. Xtti: Nil The intermediate imino-compound is acidified and distilled with steam :
N
Ci : JNH
CI1O
Aldehydes can be formed by acting upon aromatic hydrocarbons with a gaseous mixture of carbon monoxide and hydrogen chloride :3
ALUMINIUM. TIN.
LEAD. ANTIMONY. VANADIUM 79
Q,uo.cn, + cicon = C ( I H / + HOI. \0HO The following are examples of internal condensation brought about by A1013 :'A Plienyl propionyl chloride - hydrindone : / ' \ coci/
GH 2
>CHo + HOI.
Plienyl valeryl chloride -> pheno-keto-heptamethylone : > GILOHo v jCKrCH-v " >CH, -> Q H / " >CHo + HOI. COClCIV " ^COCHX yimilarly phenyl-butyryl chloride passes to -ketoLolrahydro-naphthalenc. Sometimes direct combination of two molecules '"results without any elimination taking place, as for cxaurplo, in the union of phthalic anhydride and benzene to form o-benzoyl benzoic acid : 5
\ /
\COOH
Auotlior example is the formation of benzaniliclc from plionyl carbimide and benzene: C0H6 + CGH5N : CO = CbH3.NH.CO.CClH5. />Diketones (1 : 8-diketones) may be obtained Fi'oiu acid chlorides, and here again, an intermediate addition compound appears to bo formed and then decomposed !>y treatment with water. The formation oi% acetyl acetone from acetyl chloride will serve to illustrate this typo of synthesis :
80
SYNTHETIC USB OF METALS 3CH3COC1 + AICI3 = CH3COV >CH.CClo.O.AlCl2 + 2HC1 CH3CCK
CRfiO'
>CH.COOII + 1IC1 +
CH3CO.CH2.COCH3 + COo. Benzene is converted into benzene snlpliinic acid by sulphur dioxide, in the prcsonce of anhydrous aluminium chloride, while oxygen will bring about the formation of phenol :(5 c()n() + sex, -= c,,irvso,u 2C,,irb + O3 = 2C()[15OII. When substances containing hydroxyl g]*oups arc used with aluminium chloride, it is necosary to protect theso groups from attack by the metallic chloride and this is accomplished by estoritying them. For example di-benzoyl-quinol is prepared by the action of benzoyl chloride upon quinol dibenzoato and subsequent hydrolysis of the product: cjitCO.co.cyir,). + 2Cbiir,.ooci -= (cl)n)(JO)o<j(,ir,(o.co.cl>fi))l> % 21 LCI. (CcII5CO),C()IL(O.C0.06n5)o + 21LO - (C,,lI>CO)Cflir(011)o + 2CUI5.COOU. The function of aluminium chlorido in these various condensations appears to be catalytic. 7 Sometimos relatively small quantities of tho chloride are sufficient to coinplete the reactions and
ALUMINIUM. TIN. LEAD. ANTIMONY. VANADIUM 81 at other times larger quantities are necessary; complex compounds are generally formed and thus the chloride is removed from the sphere of action. Anhydrous ferric chloride, which brings about the same kind of condensation, does not exhibit tho same tendency to form complex intermediate compounds and therefore acts as a catalyst. The following are examples of the complex intermediate compounds which have been isolated : 8 ALJClG.CbHG; Al2Clfi.CfiH3(CH3)3.6Ct>nG; AI,Cl,.CaTI],.6C0ir,. Compounds of oxygen-containing bodies have also been isolated : With ether C4H10O.A1C13 ; with anisolo C 7 H 8 O.A1C1 3 ; with ethyl benzoate C 9 H 10 Oo.AlCi 3 . All of these are crystalline solids. A study of the reaction between anisole and benzyl chloride indicates that the change is unimolecular and that the chloride of aluminium acts as a catalyst, since the velocity of reaction is proportional to its concentration. 9 The formation of aromatic kofconos has been explained as proceeding in tho following stops : 10 R.COC1 + AICI3 - R.COCI.AICI3 R.COC1.A1C13 + I1B' = RCCR'Alda + 1TO1 K.CO.K/.AICI3 + uiloO = E.CO.R' + AICI.JIHOO. Anhydrous zinc chloride as well as forric chlorido can often be used instead of aluminium chloride in these condensations. I t is interesting that the rovorsc reaction can bo accomplished in the case of the alkylation of benzene. All the hydrogen atoms of the hydrocarbon can bo replaced by methyl groups, and conversely hoxamethyl-benzene can be converted into benzene. n
82
SYNTHETIC U S T O OF METALS
The alkyl groups can also be made to pass from one hydrocarbon to another, toluene in the presence of aluminium chloride yielding both benzene and meta- and yara-xylene. The fact that small quantities of the aluminiummercury couple can bring about similar condensations, indicates that the chloride acts as a catalyst; the formation of diphenyl-methane from benzyl chloride and benzene is an example of this. 12 Inorganic radicles may be condensed with hydrocarbons as in the formation of antimony triphenyl and dimethyl-amino-phenyl-phosphine-dichloride : 13 SbCl3 + 3CfiHG = Sb(CflH6), + 3HC1 PC13 + CGH5.N(CH3)2 = PCla.CcH4.tf(CH3)2 + HC1. Aluminium trichloride can be used for hydrolysing the alkyl ethers of phenol and its derivatives :14' qHs.O.CH3 + HC1 = C(5H5.OH + CH3C1 + CH3C1
TIN AND LEAD.
Both metals form compounds with organic radicles, in which the metals themselves are tetravalent. These compounds are prepared by treating the sodium alloy of the metal with the required halogen compound, and in the case of tin two other methods are available,namely, the treatment of tin tetrachloride with sodium in the presence of the halogen organic compound, and the action of organo-magnesium compounds upon tin tetrachloride. These reactions may be represented by the following equations (X represents 01, Br or I) :
ALUMINIUM. TIN. LEAD. ANTTMONY. VANADIUM 83 Sn + 4Na + 4RX = SnE4 + 4NaX S11CI4 + 8Na + 4RX = SnR4 + 4NaCl + 4NaX SnC]4 + 2MgRX SnRaCl2 + MgX2 + MgCl2. By the action of iodine upon the tetra-alkyl compounds one or more alkyl radicles can be replaced : PbR4 + I2 = PbR3I + El. Compounds of the type PbR 3 I and SnR 3 I are converted into the corresponding hydroxides by treatment with the hydroxides of silver or sodium : PbR3I + AgOH = PbR3OH + Agl. The stannonium and plumbonium hydroxides are strongly basic crystalline substances which form salts with acids. Optically active tin compounds have been prepared by combining the metal with four different groups and then resolving the racemic compound produced. The following scheme will indicate the method adopted by Pope and Peachy in separating active methylethyl-propyl tin iodide : 16 2Sn(CH3)aI + Zn(C2H5)2 = 2Sn(CH3)3(CaH5) + Znl2 Sn(CH3)3(CaH5) + Ia = Sn(CH8)9(CaH5)I + CH3I 2Sn(CH3)a(Cya6)I + Zn(C3H7)a = 2Sn(CH3)a(CaH5)(C3H7) + Znla Sn(CH3)2(CaH5)(C3H7) + Ia - Sn(CH3)(CaH5)(C3H7)I + CH3I (Faint yellow oil, b.p. 270.) Resolution was effected by treatment with the silver salt of d-camphor-sulphonic acid and subsequent decomposition of the camphor-sulphonate formed, by means of potassium iodide : Sn(CH3)(CaH6)(C3H7)I + C]0H]6OSO3Ag Sn(CH3)(C2H5)(C3H7)SO3OCltiH16 + Agl Sn(CH8)(CaH5)(C3H7)SO3OC10H16 + KI - Sn(CH3)(C2H6)(C3H7)I + C10H16OSO8K
84
Tin is used as a reducing agent in acid or alkaline solution, and after reduction the metal may be separated from the solution as sulphide by hydrogen sulphide, or if the reduced compound be a base, caustic soda may be added in excess and the base then extracted by some suitable solvent. When using stannous chloride and hydrochloric acid for reduction, the usual proportions are 40 parts SnCl 2 and 100 parts HC1 (1*17). This mixture may be used in alcoholic solution since stannous chloride is soluble in alcohol. 16 Alkaline stannous chloride is largely used in preparing azo-compounds and particularly for transforming diazo-compounds into hydrocarbons :17 C0H5N: N.OH + H2 CttHc + N2 + H3O The entire reaction may be represented thus : C6H5N:NC1 + SnCl, + H20 = C6H6 + Na + SnOCl2 + IIC1 Tin tetrachloride is very efficient in bringing about the formation of phthaleins; for this purpose the chloride is heated with the reacting substances to about 120. The formation of phenol-phthalein and of salicylphenol will serve to illustrate this method : 18
2C6H6OH HO.C6H4.COOH + C6H5OH HO.C6H4.CO.C6H4.OH + H2O The separation of organic acids by means of the lead salt which is subsequently decomposed by
ALUMINIUM. TIN. LEAD. ANTIMONY. VANADIUM 85 hydrogen sulphide, is a method much used, and may be illustrated by reference to formic acid : (HCOO)2Pb + H2S - PbS + 2H.C00H Lead monoxide, like silver oxide, may be used in the presence of water, for hydrolysis. Fats, for example, are saponified (hydrolysed) by boiling them with water containing PbO in suspension ; the resulting products are glycerol and a lead soap : 2(C15H31COO)3C3H6 + 3PbO + 3HaO 3(CI6H31COO)aPb + Palmitin. Load palmitato. 2C8H5(OH)3 G-lycerol. Lead monoxide is also used as an oxidant, generally by mixing it with the compound to be oxidised and heating, or passing the vapour of the compound over heated lead oxide. By this method benzil is oxidised to bonzophenone, acenaphthene to acenaphthylene, and o-aininodiphenyl-methane is converted into acridino : 10 CaH5.CO,CO.C0H6 + PbO = C0II5.CO.CJT5 4- CO2 + Pb OH2 y Cli + PbO - CXOHZ|| + H2O + Pb OH6< I CH2 ^CH 0F T H5 + 2PbO * C 6 H 4 / I \COH4 + 2HaO + 2Pb Lead peroxide is used for oxidising leuco-bodies. For example, leuco-malachite groon (obtained by condensing bonzaldehyde with dimethyl-anilino) is converted to the base of malachite groon by lioating1 with P b O 2 : C0H6.CH/ 6 *' *a -> C0H6.C(OII)/ * "2 N \C6H4.N"(CH8)a C0H4.N(CII3).i
86
The peroxide is utilised on the large scale for this purpose. [Germ. Patent 50782.]
ANTIMONY.
The chief use of antimony and its chlorides is for accelerating the chlorination of organic compounds. Chlorination is also accelerated by the chlorides of iron, aluminium, molybdenum or thallium, and the metals themselves may be used. Just as the trichloride and pentachloride of antimony are suitable, so also are the two chlorides of molybdenum, MoCl 3 and Mo01 5 , and the two chlorides of thallium, T1C1 and T1O13.20 Nitrobenzene is converted intom-chlor-nitrobenzene by chlorine in the presence of antimony trichloride. 21 According to the German Patent 32564, phthalic anhydride is converted into the tetra-chlor-derivative by passing chlorine into a mixture of the anhydride and antimony pentachloride heated to a temperature of 200: .CO yCO >O + 4C12 = CeCl4/ No + 4HC1 30 X!O Antimony trichloride is used to facilitate pyro-condensations such as that of dinaphthyl from naphthalene. Only a small quantity of the product is obtained by passing naphthalene alone through a red-hot tube, but the yield is very much improved by mixing the vapour of antimony trichloride with the vaporised hydrocarbon : 6C10H8 + 2SI)C13 = 2Sb + 6H01 + 8Cl0H7.CloH7
ALUMINIUM. TIN. LEAD. ANTIMONY. VANADIUM 87 The vapour of stannic chloride appears to be still more efficient in this type of condensation. By its means a good yield of diphenyl is obtained from benzene.
VANADIUM PENTOXIDE has received limited applica-
tion as an oxygen carrier. Its presence accelerates the oxidation of ethyl alcohol to aldehyde and acetic acid, when effected by air or by oxygen. The oxidation of cane-sugar to oxalic acid by concentrated nitric acid is facilitated by the presence of a small quantity of vanadium pentoxide. 32
BlBLIOGBAPHY.
Ann., 1888, 244, 50. Ann., 1906, 347, 347; Ann., 1907, 357, 320. 3 Ber., 1897, 30, 1622. 4 Trans., 1894, 65, 484; 1899, 75, 144; 1901, 79, (502. 5 J. prakt. Oheni., 1890,149, 147, 301. 6 Ann. Ch. Pliys. (6), 14, 433. 7 Trans., 1903, 83, 1470. 8 Compt. rend., 1903,136, 1065; Trans., 1904, 83, HOG. 8 Zeit. phys. Chem., 1904, 48, 430. l Rec. Trav. Chim., 1900,19,19. 11 Ber., 1885,18, 339, 657. 12 Trans., 1895, 67, 826. 13 Ber., 1888, 21, 1497. 14 Ber., 1892, 25, 3531. 1& Proa, 16, 42,116. l B Ann., 1891, 264, 131 ; Her., 1882, 15, 1422. V Ber., 1885,18, 29J2. 18 Ann., 1880, 202, 68 ; Ber., 1883,16, 2298. 19 Ber., 1883,16, 502 ; Ber., 1893, 26, 3085. 20 Ann., 1884, 225, 199. al Ann., 1876,182,102. 22 J. prakt. Chem., 1907, 75,146.
2
OHAPTEE IEON. NICKEL.
VI PALLADIUM
PLATINUM.
THESE metals have all been used as catalysts, particularly in oxidation and reduction processes, and in this connection the value of nickel and platinum is well known. Certain iron compounds have been used for reduction. Ferrous sulphate in aqueous solution, with ammonia, baryta, or sodium hydroxide, may be used for reducing, as also may ferrous potassium oxalate in neutral, alkaline, or weakly acid solution. The following are examples of the reduction of nitro-compounds by ferrous sulphate : nitro-phenyl propiolic acid1 and nitro-dichlor-benzaldehyde 2 ; the method has been used to reduce several nitro-acids to the corresponding amino-acids. s Ferrous potassium oxalate can be utilised in these cases with good results. 4 The value of iron and of ferric chloride as halogen carriers is well known. Ferric chloride or ferric hydroxide may be used for oxidising purposes, the oxidant being in each case reduced to the ferrous condition.
IRON.
NICKEL.
PLATINUM.
PALLADIUM
89
The oxidation of ethyl indoxylate to ethyl indoxanthinate 5 and of naphthol to dinaphthol 6 may be accomplished by ferric chloride : 2C10H7OH + 2FeCl3 = C2()H12(OH)o + 2HC1 + 2FeCl2 Ferric hydroxide is sometimes used for oxidising leuco-bases. 7 The oxidising action of hydrogen peroxide in the presence of ferrous sulphate, was first used by Fenton and applied by him in the conversion of the polyhydric alcohols to the corresponding aldehydes. I n the first instance, the reagent was used to prepare di-hydroxy-maleic acid from tartaric acid : CH(OH).C00H C(OH).COOH 2| + Oa - 2 || + 2H3O CH(OH).COOH C(OH) .COOH Glycerol, erythrite and mannitol can be converted to the corresponding aldoses by this oxidant: 8 The first indication of the value of reduced nickel for accelerating the reduction of organic compounds by hydrogen, was obtained by Sabatier and Senderens in 1897, when studying the compounds obtained by passing acetylene or ethylene over heated reduced nickel. I t was subsequently shown that many organic substances could be reduced in this manner, the chief factors which determined the success of the reaction being, the temperature at which the nickel was first prepared from the oxido by hydrogon, and the temperature at which the mixture of tho substance and hydrogen was allowed to pass over tho metallic nickel. Generally, the catalyst (nickel) is prepared by heating pumice, impregnated with nickel oxide, in a
90
current of dry hydrogen at about 300. When reduction is complete the temperature is allowed to fall to between 160 and 200, and the mixture of the substance to be reduced, with hydrogen, is passed through the reduced nickel. The following is a brief summary of the results hitherto obtained by this method, and a collection of references to the original papers will be found at the end of the chapter. I t will be seen that although nickel is the metal most used and the one which generally yields the best results, yet other metals, namely, copper, cobalt, iron and platinum, ' have been utilised. In 1897 it was found that by passing ethylene over reduced nickel at about 325, a gaseous mixture was obtained consisting of 10 vols. of hydrogen, 60 vols. of ethane and 30 vols. of methane. At higher temperatures the volume of ethane was diminished, and the nickel was found to be most active when the nickel oxide was reduced at 300. A mixture of ethylene and hydrogen at a temperature of 150 gave a quantitative yiold of ethane. In 1899 and during subsequent investigations, it was shown that when acetylene and hydrogen are passed over reduced nickel at ordinary temperatures the gases combine, a rise in temperature takes place spontaneously, and ethane is the chief product, but the composition of the product depends upon the temperature, the proportion of acetylene to hydrogen, and the velocity of the gas current. Olefines, paraffins and benzene are found in the product and the liquid constituents increase with rise of temperature, while
IKON.
NICKEL.
PLATINUM.
PALLADIUM
91
a diminution of hydrogen also favours the formation of liquid hydrocarbons, especially benzene compounds. Metallic iron, copper and cobalt behave in a similar way, and the formation of liquid hydrocarbons supports the idea that petroleum may have been formed naturally, by the gases evolved from the action of water upon carbides of the alkalis and alkaline earths, passing through layers of heated metals in the earth's interior. The metals copper, iron and cobalt produce the following changes in mixtures of acetylene and hydrogen on the one hand, and mixtures of ethylene and hydrogen on the other hand. If acetylene be passed over copper at 180-250, a mixture of hydrogen, unchanged acetylene, and volatile hydrocarbons results; the copper swells up, owing to a deposit of yellowish highly condensed hydrocarbon of composition (C 7 H 6 ) n which has been named ciiprene. If the acetylene bo first mixed with excess of hydrogen and the temperature 200, the mixture resulting, contains 3 per cent, of define (ethylene) and 18 per cent, of ethane; a more compact form of copper at 170 causes the define content to increase ninefold while the ethane is reduced in quantity. If the mixture contains half its volume of acetylene and the reaction proceeds at 150 the amount of ethylone in the product is still further increased and tho cthano decreased. Reduced iron at ordinary temperatures docs not affect a mixture of acotylene and hydrogen, but above 180 ethane, ethyleno (and higher olofines),
92
and a small amount of benzene hydiôcarbons r e sult. Reduced cobalt accelerates the reduction of acetylene to ethane by hydrogen above 180, a t x d some liquid paraffins result at the same t i m o Evidently those three metals bring about different* rosults under similar conditions. While copper favours ethylene formation, i r o i * and cobalt, when a sufficently high temperature i s reached, favour ethane formation accompanied in o a case by benzene hydrocarbons and in the other c a s o by liquid paraffins. As regards mixtures of ethylene and hydrogen.^ the reaction, 0 2 H 4 + H 2 = O3H6, is not induced b y copper below 180, but between 180-300 this is t h e main reaction. Metallic iron has no effect on t h p mixture at ordinary temperatures, and when heatecL to 180 the reaction soon ceases owing to the meta/1 becoming carburised. Reduced cobalt induces the reaction, C^H^ + H 3 = O2H6, at first and the metal becomes spontaneously heated, but it soon becomes carburised and inactive. If heated to 100150 the reaction proceeds, yielding* ethane mixed with unchanged ethylene and hydrogen, together with traces of higher acetylenes. At 3 0 0 much unchanged ethylene and hydrogen are found with ethane, together with small amounts of methano and liquid hydrocarbons; the cobalt still becomes carburised and its activity declines. The reaction between ethylene and hydrogen is only temporary in the presence of platinum black a t ordinary temperatures, but at 100120 slow com-
IRON.
NICKEL.
PLATINUM.
PALLADIUM
93
bination takes place, and at 185 the yield of ethane is almost quantitative. Spongy platinum behaves in a similar manner at 180. Acetylene with excess of hydrogen, in the presence of platinum, black at ordinary temperatures gives only ethane, but if acetylene is in excess then ethylene is also formed, while at 180 some liquid hydrocarbons also result. The passage of acetylene alone, over the metals nickel, platinum, cobalt and iron gives the following results. A rapid current of acetylene when passed over reduced nickel causes intumescence, and this is apparently due to occluded hydrogen in the metal, because when displaced by a stream of nitrogen gas no reaction is observed below 180. At higher temperatures no intumescence is observed if the acetylene current be sufficiently slow, and the products are hydrogen, ethane, ethylene and liquid hydrocarbons containing benzene with higher olefines. A. rapid stream of gas gives rise to intumescence, and the issuing gas is made up of hydrogen 51*4 per cent., ethane 36 f 3 per cent., ethylene 2 per cent., benzene and homologues 10*3 per cent.; at the same time a liquid condenses which contains unsaturated hydrocarbons. Finely divided platinum induces no effect with acetylene at ordinary temperatures, but above 150 intumescence is observed, and the gas is partly decomposed into carbon, ethylene, benzene, ethane, and hydrogen, the last three in small quantity. Cobalt free from nickel has no action upon acety-
94
lene at ordinary temperatures, but above 200 the gas is almost completely decomposed into hydrogen, ethane and carbon while small quantities of benzono and its homologues are formed. Iron behaves similarly but much loss ethane results, while olefines and benzone accompany the gases. Ethylene is not affected by finely divided platinum or copper below 400, but cobalt above 300, partly decomposes the gas into ethane, methane, hydrogen and carbon, no acetylene being formed. Iron above 350 has less action, but decomposes some of the gas into ethane, hydrogen and carbon. The following are some of the results obtained by reducing aromatic substances in this manner: Benzene and its homologues are reduced by hydrogen in the presence of nickel at 180-200 yielding the corresponding cyclohexanes. If the side-chafa be long, then a certain amount of disruption accompanies the reduction, and lower homologues are produced as well as the normal cyclohexane. At a higher temperature, decomposition of the reduced products may occur; cyclohexane itself, for example, is decomposed if the temperature is 300, into methane and carbon. The hydrogenation of benzene seems peculiar to nickel, since cobalt and platinum black have only a transitory effect, while spongy platinum, iron and copper are quite inert. Limonene, sylvestrene and terpinene are all reduced to l-methyl-4-isopropyl-cyclohexane by this method, naphthalene gives tetrahydro-naphthalene, and acenaphthene behaves similarly. Nitrobenzene, o- and m-nitrotoluene, are all re-
IRON.
NICKEL.
PLATINUM.
PALLADIUM
95
duced to the corresponding amino-compounds in the presence of copper at 300-400, and the reducing action of platinum black is similar. Reduced nickel acts more vigorously and reduction takes place normally at 200, but at 250 the products obtained from nitrobenzene are benzene, cyclohexane and ammonia, as well as aniline, while at 300 benzene is the chief product. Reduced iron and cobalt act in a similar manner to nickel when heated to 450500. Reduced copper does not effect hydrogenation in hydrocarbons unless at least one unsubstituted (:0H 2 ) group is present; styrene is reduced to ethyl benzene, and limonene O 10 H 16 passes to C 10 H 18 , but limonene becomes still further reduced by nickel to liexahydrocymene C 10 H 20 . " * Hydrogen in the presence of reduced nickel converts phenol into cyclohexanol and cyclohexane. Poly-phenols are affected similarly, while aniline and its homologaes become reduced to cyclohexylamines; quinones are reduced to quinols and nitriles to amines. The catalyst remains active in continual use, often for a month, but is poisoned by halogens or sulphur and also by the decomposition of carbonaceous matter when working at too high a temperature. The following reactions are also important : Carbon monoxide (1 vol.) and hydrogen (8 vols.) react in the presence of nickel at 250 to fonn methane and steam, CO + 3H 2 = CH 4 + H 2 O. Carbon dioxide is also reduced at a higher temperature, CO2 + 4H S = CH 4 + 2H S O. Hydrocarbons of the ethylene series up to a carbon
96
content of C8, are reduced to the corresponding paraffins; below 160 the product is practically pure, but above 200 partial decomposition takes place and hydrocarbons of lower molecular weight result. The liquid product obtained from acetylene and hydrogen at temperatures not above 200 is fluorescent, not attacked appreciably by a mixture of sulphuric and nitric acids, and presents the characteristics of American petroleum. Acetylene alone, yields a green-coloured liquid which resembles Russian petroleum. Dehydrogenation takes place when the vapour of primary alcohols is passed over reduced copperat250 300 and aldehydes result, while secondary alcohols are converted by the same method into ketones. Nickel and cobalt effect the same changes, but in too vigorous a manner generally. Tertiary alcohols are decomposed into defines and water by the agency of reduced nickel and copper. For the catalytic reduction of aldehydes, nickel reduced at as low a temperature as possible is most efficient; a quantitative yield of alcohol from acetaldehyde is obtained at 140, while the optimum temperature for reducing formaldehyde is 90 and for propaldehyde 102-140. Eeduced cobalt, platinum sponge, and copper are not suitable for aldehyde reduction. The reduction of oleic acid to stearic acid by this method is of technical importance and is one example of the reduction of unsaturated aliphatic acids to the corresponding saturated acids. Iron, nickel, zinc or lead may be used, according
UtON.
NICKEL.
PLATINUM.
PALLADIUM
97
to the German Patent 185932,, for reducing formic acid to formaldehyde by hydrogen at 300. Sabatier and Maihle have studied the catalytic action of various metallic oxides upon the vapours of certain organic compounds. They find that alcohols are oxidised to aldehydes by manganous oxide and that they are dehydrated by alumina, thoria or the blue oxide of tungsten, with the formation of olefincs and ethers. Those changes arc explained in the case of thoria by the following equations : ThO2 + 2Cnn2n+i.OH = ThO(OOnn.jn+i)a + H,0 Below 300 ThO(OCnHto+1)a = ThO2 + (CuHou+T)20 Above 300 ThO(OCnH2n+I)a = ThO, + H2O + 2CnH2n. The rosults obtained by passing the vapour of primary alcohols over various heated metallic oxides have been summarised, and the oxides used have been *arranged in four classes as follows : (1) Tho oxidation is limited to the formation of aldehyde and wator; tho metallic oxide used has no effect upon tho aldehyde and the metal or lower oxide which results has no catalytic powor. To this class belong Sb 2 O 3 and Bi2O3. (2) The aldehyde formed may be partly oxidisod either to the corresponding acid, or with the formation of carbon dioxide and water. Mercuric oxide at 150 oxidises alcohol to acctaldehydo with the simultaneous formation of carbon dioxide, but no acetic acid is produced. Manganese dioxide at 200 oxidises alcohol to aldohyde and is itself roduccd to Mn 2 O 3 ; at 250 the Mn 2 O 3 brings about further oxidation and tho products are acetaldohyde, carbon dioxide, and acetic acid. 7
98
SYNTHETIC USE OF MKTALS
(3) The oxides catalytically dehydrate the alcohol, and ethylene is the chief result. To this class belong Fe 2 O 3; A12O3, and ThO 2 . (4) The largest class consists of those oxides which are reduced to the metal, or a lower oxide, capable of producing a catalytic effect which is superposed upon the initial oxidation. The oxides of nickel and cobalt, of lead (PbO2, P b ^ , PbO), of copper (CuO, Cu 2 O), at 350 belong to this class; the reduced metals in these cases have a dehydrogenating effect upon the alcohol, and aldehyde results. Mn 2 O 3 is reduced at 350 to pale green MnO, which converts the alcohol to aldehyde by dehydrogenation. Tungstic oxide at 350 is reduced to a blue oxide which has a dehydrating effect and ethylene results as well as aldehyde and acetic acid. The oxides TJO3 and V 2 O 5 are reduced to UO 2 and V 2 O 3 respectively, aldehyde and carbon dioxide resulting. The further action of UO 2 or V 2 O 3 gives aldehyde, hydrogen, ethylene and water. Mixed ethers result when alcohols and phenols are used with thoria at 390420 and esterification takes place when alcohol and acid interact at 350-400. Esfcerification10 is more complete in the presence of titanic oxide at 280300. One molecule of acid is used with twelve molecules of alcohol, and in this way methyl, ethyl, propyl, butyl, and benzyl esters have been prepared from acetic,propionic and butyric acids. In the case of formic acid it is necessary to work at 150 with titanium oxide and at 200 with thoria to avoid decomposition of the acid.
IKON.
NIOKia.
PLATINUM.
PALLADIUM
99
Hydrolysis is effectod under similar conditions if the ester and oxcess of steam are passed over these catalysts. defines are obtainod by passing the vapour of paraffin monohalides over reduced nickel or copper, heated to 250; the resulting products are the olefine and the haloid acid, which are prevented from recombining by passing them through potash. The chlorine derivatives decompose thus below 260, but a higher temperature is required for bromo- and iodo-compounds. 11 The bivalent chlorides of nickel, cobalt, cadmium, iron, lead and barium produce the same effect at 300; barium chloride is the most efficient catalyst. Chlorides of univalont metals are not able to bring about this change, and the following equations possibly represent the reaction in the case of the bivalent chlorides: (1) MCI, + CnnJn+lCl = * MCl.CnllonCl + HOI. (2) MCl.CnHonCl = OnHon + MCL. Tho reduction of nitrilos by hydrogen in the presence of reduced nickel or copper usually gives primary, secondary and tertiary amines together with ammonia, and the changes aro probably represented by the following equations :12 Q) K.CN + 2Hs = K.CHaNIIa (2) 2R.CHjNH9 - (R.CH,)9NH + Nil, (3) 3R.CH2NH2 (Jft.CHa)3N + 2NH3. Aldoximes are reduced to amines by hydrogen at 180220 in the presence of reduced nickel or copper; with benzaldoxime, however, the chief product is benzaldeliyde when copper is used, and toluene when nickel is used. 13
100
SYNTHETIC (JSK 01' M K T A L S
Primary alcohols are converted into primary, se dary and tertiary amines, by ammonia, in the presoncM * of heated tungstic oxide or thoria. A mixture of reduced nickel and alumina may l>t* used to effect reduction by hydrogen and tlio simul" taneous fission of water ; thus fenchenol is converted "by this method into fenchane and bornool is t r a n ^ formed into iso-caniphane :1<J; CJ0H17OH > CIOH]0 -> C]0H18. PLATINUM is not only suitable for accelerating reduction processes, "but is also an excellent catalyst who** oxidation is effected by air or oxygen. Formaldehyde was first prepared by passing the vapour ol methyl alcohol and air over a heated platinum spiral. 15 Later, copper gauze was found equally effectives and formaldehyde is now manufactured by passing* the vapour of wood spirit mixed with air, over finely divided platinum or copper distributed over an earthenware surface. The following processes fur manufacturing ammonia and nitrates or nitritort (substances essential for the synthesis of the highly complex plant and animal bodies), depend largely upon the use of platinum as a catalytic agent. Ammonia is formed when nitric oxide and hydrogen are mixed and passed over platinum sponge at 80. The hydrogen used may be that present in Dowson-gas or water-gas and the reaction involved is indicated by the following equation : 16 2NO + 5H2 = 2NH3 + 2H2O. If ammonia and air be passed over red-hot finely
IRON.
NICKEL.
PLATINUM.
PALLADIUM
101
divided platinum (or one of the platinum metals), onitric acid is formed, 17 and nitrous acid is produced i n the same way if ferric oxide at 700 be substituted f o r platinum. 18 Ammonia is now made by the Badische Anilin und Sodafabrik, by passing nitrogen and hydrogen o v e r heated platinum at a temperature of 80 ; under ct pressuro of about thirty atmospheres. Other catalysts used in the process are manganoso, uranium a n d osmium. Keten has been prepared from acetic anhydride, "by exposing the vapour of the anhydride to the <~lehydrating influence of a white-hot platinum wire :1(J CI-T3.CO No = 2cn2:co + ir a o. CH3.CO Platinum and palladium in colloidal solution arc used for effecting the Uydrogonalion of substances* in aqueous or alcoholic solution. llydrogon is passed through the solutions and it is often advantageous to work under slightly increased pressure; the colloidal metals are obtained from palladious chloride or potassium platinichlorido, in tho presence of gum arabic. By this method unsaturated aldehydes and ketones n r e converted into the corresponding Hat united compounds, while benzene, toluene and benzoic acid may "bo converted into cyclohcxane, methyl-cyclohexnno a n d cyclo-hexanc-carboxylic acid respectively. 20 Tho reduction of nitro-compoumls in solution by spongy copper depends upon tho precipitation of tho copper from copper wulplinte solui-ion )>y sodium
102
R Y N T T T B J T T C U R T C OF METALS
hypophospliite and tho simultaneous decomposition of water, with evolution of hydrogen. 21 The nitro-compound is usually dissolved in alcohol, spongy copper added^ and an aqueous solution of hypophosphito is gradually run into the mixture. Tlio presence of halogen or hydroxyl groups in the nitro-compound is no disadvantage and good yields are obtained.
I Ber., 1882,15, 214.7. - Bor., 1884,17, 75-1. 3 Bor., 1879,12,1946. * Monats., 1880,1, 1137. r ' Bor., 1882,13, 775. c Ber., 1888, 21, 728. 7 D.E.P. 19484. 8 Trans., 1899, 73, 1. 9 Conipt. rend., 1908,147, 16. 1(1 Compt. rend., 1911,152, 358, 494,1044. Chom. Zoit., 1906, 30, 37. la Chom. Zoit., 1900, 30, 458. I1 Compt. rend., 1905,150, 3091. 1 ' Bor., 1912, 45, 3205. " Ann., 1868,145, 358. " > D.R.]?., 1572876. 17 Eng. Patent, 1903, 698. ' Proncli Patent, 1903, 335220. 1 { ) Trans., 1907, 91, 1941. 2() Ber., 1912,45, 3579. 21 Bull. Soc. Chim., 1910 (iv), 7, 952.
References to the papers of 8dbaticr and Scnderens in * Gotnptes rcnd%B do VAcademie des Sciences/ Paris. 1897,124, 616, 1358; 1899,128,1173 j 1900, 130, 250, 1559, 1701, 1028 j 1900,131,40, 187,207;
IRON.
NICKEL.
PLATINUM.
PALLADIUM
103
1901, 132, 210, 566, 1254; 133, 321; 1902,134, 514, 1127, 689, 1185 ; 135, 87, 225 j 1903,136, 738, 921, 983 ; 137, 301, 1025,1904,138, 457, 1257 ; 1905, 140, 482; 1906, 142, 1394; 1908, 146, 457, 1193 ; 147, 106 ; 1909,148, 898, 1734; 1910,130, 823 ; 1911,152, 358, 494, 669, 1212s Also 'Ann. Qhim. Pliys.,' 1905,4, 319, 433 ; 1909, 16, 70.
APPENDIX PEACTICAL WOEK:
T POTASSIUM
SODIUM
ETHYL BENZENE from brom-benzene and ethyl bromide. [Ann., 1864,131, ,304 Ann., 1869,149, 342 ] The brom-benzene (60 gms.) and ethyl bromide (50 gms.) are mixed in a 1-htro flask fitted with a reflux condenser, and double the volume of dry ether added. The sodium (18 gms.), in small piccos, or in the form of wire, is added gradually, and a few drops of acetic ethyl ester may bo added to accelerate the reaction. When all the sodium has been added the mixture should stand for four or five hours (preferably overnight), and then be boiled on the water-bath for half an hour. After cooling, the liquid is decanted from the sodium bromide and the residue washed twice with dry ether. The washings are addod to the original liquid, and after distilling off the other the residual oil is fractionated. That fraction is collected which distils between 132-135, Yield, about 20 gms.
PRACTICAL WORK : SODIUM. POTASSIUM
105
ANISOLE from sodium phenate and methyl iodide. [Ann., 1851, 78, 226^ Sodium (5 gms.) in small pieces is dissolved in methyl alcohol (100 c.cm.) contained in a ^-litre flask fitted with a reflux condenser. When the sodium has all dissolved, phenol (20 gms.) and methyl iodide (40 gms.) are added, and the mixture heated on the water-bath until it gives no alkaline reaction (about three hours). The alcohol is then distilled off and water added to the residue to precipitate the anisole, which is extracted with ether. After drying the ethereal extract over calcium chloride, the ether is distilled off and the residual oil fractionated, that fraction being collected which boils between 150155. Yield, about 16 gms. of a colourless oil with agcoablc odour, b.p. 154. BKNZOTC ANITYPKIDK from sodium bonzoale and benzoyl chloride. Bonzoyl chloride (10 gms.) is added to powdered sodium benzoato (10 gms.) in a small retort and tho mixture is heated strongly. The distillate, which is collected in a receiver, solidifies and may be recrystallised from bonzene, and the odour of bcnzoyl chloride may be removed from tho crystals of benzoic anhydride by placing them in a desiccator over solid potassium hydroxide for a few hours. Yield, about 12 gms. Rhombic prisms; m.p. 42, b.p. 360.
106
SYNTHTSITC USE 01? METALS
HEXAMETHYLENE from the dibromide. [Trans., 1894, 65, 599.] The preparation of hexametltyleno dibromide from oK^-cliloro-brom-propane, which is itself prepared from allyl chloride, is as follows: Allyl alcohol may be converted into allyl chloride by heating with cone, hydrochloric acid in a sealed tube at 100 for several hours. Allyl chloride is then converted to chloro-brompropane by heating in a sealed tube with a slight excess of cone, hydrogen bromide solution at 100 for seven to eight hours. The mixture is then washed, dried and fractionated. The boiling point of the product is 140142. Chloro-brom-propane (1 mol.) is next dissolved in a little methyl alcohol; and the calculated amount of sodium (1 atom in twelve times its weight of methyl alcohol) is added in three portions, the mixture being boiled after each addition. As soon as the vigorous action ceases the product is cooled and mixed with twice its volume of water, the oily layer extracted with ether and the ethereal solution washed with water to remove alcohol. After drying the extract over calcium chloride it is distilled with a fractionating column: the portion boiling at 115-118 is chlor-methoxy-propane, yield 50-60 per cent. Chlor-methoxy-propane (20 gms.) is next dissolved in 60 c.c. of light petroleum (b.p. 50-60) and heated to boiling under a long reflux condenser.
PEACTTCAL W O K K : SODIUM.
POTASSIUM
107
The flame is removed and small pieces of potassium added gradually, the very violent action after each addition being allowed to subside before adding another piece. The mixture soon thickens owing to the separation of potassium chloride, and when the metal is no longer acted upon the whole is boiled for half an hour, any unchanged metal being removed by alcohol. The product is then poured into water, the oily layer separated and dried over calcium chloride before fractionating. Most of the liquid distils between 100150 and is unchanged chlor-methoxypropane, while the liquid boiling above 150 is chiefly di-methoxy-hexane, which is next digested under a reflux condenser for three hours with fuming hydrobromic acid. The dark-coloured product is poured into water, the oily layer extracted with ether, and after removing the ether from the dried extract, the residue is heated in a sealed tube with hydrobromic acid for two hours at 150160. The product is poured into water, extracted with ether, and the dark-coloured hexamethylene dibromide fractionated under reduced pressure (20 mm.). That portion is collected which boils between 125 and 140. The heavy colourless dibromide (30 gms.) is now mixed with meta-xyloiiQ (30 gms.), and added through a funnel drop by drop to a mixture of sodium (15 gms.) in small pieces, and 70 c.c. of m-xylene. The reaction is vigorous, and if a condenser be fitted to the side-tube of the reaefcion-flask, the resulting hexamethylene distils over between 70 and 100; this may be refractionatcd over sodium and that part
108
SYNTHETIC USE OF M K T A L R Yield about
collected which distils at 77 n -80. 10 gms.
TRIMBTTIYLENE DlCAKBOXYLtC ACID. [Bor.,1884.,17,61..] Di-sodium malonic ester is prepared by dissolving sodium (13*5 gins.) in alcohol (150 gms.) and adding malonic ester (45 gms.) gradually. Ethylene dibromide (54 gms.) is then slowly added, and the solid mass which forms is thon heated under a reflux condenser to 100 for twenty hours; the mass becomes liquid soon after heating, and at the end of this time should be no longer alkaline to litmus. The excess of alcohol is next distilled over and the residue mixed with water to dissolve sodium bromide, after which it is extracted with ether and the extract dried over calcium chloride. The dried extract is now freed from ether by distillation, and the residual yellow-coloured oil fractionally distilled in a flask with a long neck and the fraction collected which distils between 195~225. This fraction should again be distilled and the portion boiling at 203~210 collected. To separate malonic ester still present and which amounts to 15 to 20 per cent, it must be converted into the higher boiling derivative, benzyl-malonic ester. For this purpose half a gram of sodium in alcohol is added to every 20 gms. of the oil collected, and to this mixture 2*5 gms. of benzyl chloride is added and the whole heated until neutral. Water is then added and the esters extracted with
PRACTICAL WOltK : SODIUM. POTASSIUM
109
ether, and after removing the ether the remaining oil is fractionatod. Benzyl-malonic ester boils at 300, so that tho frrimethylene ester may be separated by collecting the distillate which passes over at 206 210 b . The ester is hydrolysed by boiling with alcoholic potash for three hours, and after boiling off all alcohol tho residue is dissolved in water, and -on acidifying with sulphuric acid the trhnothyleno dicarboxylic acid is extracted with ether. Crystalline solid, m.p. 140. By heating to 200 carbon dioxide is evolved and tho mono-carboxylic acid results, which is a liquid, b.p. 188 o -190.
CHLOROFORMIC ESTER.
[UOI\, 1885, 18,1177.]
Liquid carbonyl chloz'ide is placed in a flask which is immersed in a freezing mixture. The flask is fitted with a reflux condenser through which a stream of ice-cold water circulates. The upper end of the condonser is closed by a cork through which passes a calcium chloride tube, and into which is fixed a dropping funnel. The calculated quantity of methyl alcohol is slowly added from the dropping funnel; a vigorous reaction follows the fall of each drop and hydrogen chloride is evolved and passes out through the calcium chloride tube. When tho addition of alcohol produces no further action the ester is poured into water, washed with soda carb. solution, separated and dried over calcium chloride; b.p. 70.
r . n n ii' i .i
MI
i \i
iJtt., I MM, 20, m*o. For tlii;* ]tir{tt.ii* Milphur friovide i allowed tourt mvhuu tt-f ruchl<>rttlt*. ( V I , i *JS< \ C!<K* 1 The pyroMtlphur^ I eh!rido !'ofiuf<l traeL't with the sulphuric acid present I hits : N ^ M ' I , f J|(4S()^ Tho ntrlnu flu* \\atcr*lmt!i utut^r n ( j y <r having thrrp or l'ur lnilh* <tt the iimor luhi'), with a nitlr-ttthn i'u vtl inft tin* lp part, ami it dropping fumu*l ititvil in Ihrupi u n u l , thmu^h which *() c.c\ fittuuijjr Milphtirit* arit! (M) pt*r cut. M\\) v\ (lnppi*<l .4tnvly. Tlu* vaptu*.M which u ccutl flu* cundctthpr pav;s <ut throti^h IIu* adc-iubc ittitl am wanhctt hy pa.iîn|( through rtiuc. sulphuric uc-id (well coolctl) ; they then pa:n inin a n r o i v r r iittmrn oil in a. fnH'zin^ xuiHturo when* tin* carhtmyl chturicl^ {*tUoc*t. \Va:4tiu^ through cnr. ^tilphuric ncUl HVVVVH io rentnvt* HO:l nnd HS^sVl^ from flu* vapours. Wluni all the? hunting sulphuric acitl ha;i heen intihul the ila^k may \H\ warmed l'tr Iivt* minuteii over the Ilium* to drive out nil (*<)t'l,. Weight <! ermle product i\ lia IH) gun, Thi* tuny In* purilied by redistilling thnai^h rotu f . sulphuric acitl, tlit* warmth of the hand being MiiHrii*ttt t<* product* boilitig, h,p. j Hf\
PRACTICAL WORK: F>O]>JUM.
POTASSIUM
111
METHYL BENZOATE.
[Ann., Suppl. 7, 125.] Brom-benzenc (30 gms.) and chloroformic ester (20 gms.) are mixed with 1 per cent, sodium amalgam (1200 gms.) and heated for several days at 110 under a reflux condenser. Tho mercury is then poured off, tho residue extracted with ether and tho extract fractionally distilled. B. p. of methyl benzoate is 199.
TOLUIC ETHYL ESTEI?.
This may be prepared in the same manner as methyl benzoate, using brom-toluene (34 gms.) ; chloroformic ethyl ester (20 gms.), and 1 per cent, ^sodium amalgam (1500 gms). ACETOACETIC ESTER. [Ann., 1877,186,101.] Acetic ester (200 gms.) is placed in a round flask and sodium in thin slices (20 gms.) is quickly added. After this a reflux condenser is fitted to the flask, and if the reaction becomes too vigorous the latter must be immersed in cold water. When the reaction subsides the mixturo is boiled on the water-bath until no sodium remains, and after cooling, the mixture is made acid by adding 50 per cont. acetic acid (about 100 c.c.); an equal volume of saturated brine is then added to salt out any acetic ostor, which collects at the top with acetoacetic ester. This layer is placed in a distilling flask and distilled over wire
112
SYNTHETIC X T S K Ol1 METALS
gauze until the temperature reaches 100, to remove all acetic ester. The remaining liquid is distilled under reduced pressure to avoid decomposition of the acetoacetic ester. Tho boiling points under various pressures are as follows : 88 at 29 mm. . . 97 at 59 mm. 94 45 . . 100 80 The yield is about 35 gms. ; b.p. 181.
ETHYL ACETOACETIC ETHYL ESTER.
[Ann., 1878,192, 153.1 Aceio-acotic ester (32 gms.) is added to a solution of sodium (5'5 gms.) in alcohol (70 gms.), and to this mixture is gradually added ethyl iodide (40 gms.). The mixture is then heated on the water-bath till it gives no alkaline reaction with litmus (about 2 hours). Most of the alcohol is then distilled off, tho residue is mixed with water to dissolve the sodium iodide and then extracted with other. After drying the ethereal extract over calcium chloride, tho ethor is distilled off and tho ronminiug oil fractionally distilled. Yield about 25 gms., b.p. 198. Tho yield may bo improved by distilling under reducod pressure. B. p. at 140 mm. pressure is 140, at 100 mm. 127, at 40 mm. 106. Acid hydrolysis of the ester by concentrated potash. [Ann., 1877,190, 270.] The ester (20 gms.) is boiled with 22 per cent, alcoholic potash (made by dissolving 20 gms. of
PRACTICAL WORK: SODIUM.
POTASSIUM
113
potash in 90 c.c. of alcohol) for four hours under a reflux condenser. When cool, it is extracted with other to remove any ketone formed, and then again extracted after acidifying with sulphuric acid, to remove butyric acid. After drying the extoact over calcium chloride the ether is distilled off. Yield of butyric acid about 8 gms., b.p. 163. of the ester by dilute sulphuric acid. CHaCO.CI-LCOOC2H5 + H3O = CH3CO.CHa.CaH5 + CO2 + C2H5OII. C9H5 The ester (20 gms.) is boiled with 200 c.c. of dilute sulphuric acid (1 part acid to 2 parts water) for three hours under a reflux condenser. The cooled mixture is then extracted with ether, and after drying the extract over calcium chloride, the ether is distilled off and the remaining oil fractionally distilled. Yield about 10 gms. B.p. of propyl-methyl-ketone is 102.
ACETO-SUCCINIC ETHYL ESTER.
Ketonic
hydrolysis
A mixture of aceto-acetic ester (33 gms.) with sodium (5 gms.) dissolved in alcohol (70 gms.) is treated with mono-chlor-acetic ester (32 gms.) which is added gradually. The mixturo is then boiled on the water-bath until no alkaline reaction is shown (about two hours), afbor which it is treated with water to dissolve sodium chloride, extracted with other*, and the ethereal extract dried over calcium chloride and distilled. Yield 1215 gms. of a pale yellow oil, b.p. 256. ft
114
SYNTHETIC U R KO K MKTAI.H MALONIt' [Ann., IHHO, 204, 120. |
Jti this preparation ehlor-ucotic acid is converted info potassium cyanaeotato, which is then hydrolysed and ostoriliod in one operation : t K(1N ^ < ) ICHSO, h (NH,)HHOt. (Jhloracoiic acid (*t() f(inH.) tnixod with water (80 (\c.) is hoatud to 50(K)n wltilo potass, carh. (U2 is addcnl until tho licpiid in noutral and elTorv CCMISOH. Powdcnnl poiassium eyanido (*^2 fifniH.) in now added and tho whole wcll wtinvd. AI*UT tlu iirsl redaction iw over the niasH in carefully heated till tho temporal tiro reaches Itf5n and then allowed to cool. rV\n\ Holid is then broken up, and tho oyanncetafo ]>r(^sont is himultaneounly hydrolynod and eHierilied by ilrnt mixing with 10 c.e. of alcohol, and then adding a mixture of alcohol (05 c.e.) and cone, sulphuric acid (05 c.e.) gradually, during Urn minuter. f Pho flask in tlwxi Incited on the water-bath for ono hour tinder a roflux condenHtvi', after which tho cool mixture is treated with HO c.e. of wator, filtered from insoluble matt.cn', and tho filtrate extracted several times with other, Tho ethereal extract is washed with sodium carbonate solution and then dried over calcium chloride. After dintilling off tho other, tho remaining oster is distilled under reduced pressure. B.p. at ordinary pressure is J95. B.p. at 80 mm. is 12?; at 00 mm. 120, at SO mm. 108, Colourless liquid, Yield, *i54*0 gms.
PRACTICAL WORK : SODIUM.
POTASSIUM
115
MONO-ETHYL MALONIC ESTER.
Malonic ethyl ester (20 gms.) is added gradually to a solution of sodium (3 gms.) in ethyl alcohol (40 c.c.). The solid sodium salt separates out, and when all the malonic ester has been added the solid mass is mixed with ethyl iodide (25 gms.), which is added gradually and which causes the mass to become liquid. The mixture is then heated on a water-bath for one and a half hours, by which time sodium iodide has separated out and no alkaline reaction is obtained. The alcohol is next distilled off, water added, and the mixture extracted with ether. After drying the extract over calcium chloride, the ether is removed and that portion of the remaining oil collected which distils at 206-208. Yield, 10-15 gms. Hydrolysis and Conversion to Butyric Acid.
The ethyl malonic ester (10 gms.) is hydro!ysed by boiling for an hour on the water-bath with strong aqueous potash containing 15 gms. of potash. The product is treated with moderately strong hydrochloric acid till neutral, and the acid is then precipitated as the calcium salt by adding a concentrated solution of calcium chloride. The salt is filtered and decomposed by strong hydrochloric acid and the free ethyl malonic acid extracted with ether. The ether extract deposits crystals on evaporation, and these may be recrystallised from a small quantity of boiling water. Colourless prisms, m.p. 111*5. Yield, about 5 gms.
116
If some of the acid be heated over a small flame, carbon dioxide is liberated and butyric acid remains. /COOH C,H5.CH< = C3H7.COOH + CO2 XIOOH
DrAOETO-suociNic ESTER.
[Ann., 1880, 201, 142.] Solid sodium acetoacetic ester is first prepared by dissolving 5 gms. of sodium in 40 gms. of alcohol, and after adding an equal volume of dry ether, acetoacetic ester (28 gms.) diluted with its own volume of ether, is gradually added with shaking. To the mixture 1 c.c. of water is then added and the whole well stirred; this causes the sodium compound to separate, and it is filtered and drained on the pump. Yield, 20-25 gms. The sodium compound is mixed into a thin paste with ether, and an ethereal solution of iodine then added till no more sodium iodide precipitates. The mixture is allowed to stand some hours and then filtered. The ethereal solution is shaken with mercury to remove iodine, after which it is crystallised from dilute alcohol or 50 per cent, acetic acid. White crystals, m.p. 78. Yield, 10 gms.
ETHANE TETRA-CAKBOXYLIC ESTER.
[Ber., 1884,17, 2781.] Sodium (2*3 gms.) is dissolved in alcohol (30 gms.) 3 and to the cold solution is added malonic ethyl ester (16 gms.). To the clear mixture, ether is added till a turbidity appears, and then iodine (12'7 gms.),
POTASSIUM
117
dissolved in ethor, is added gradually with shaking. After standing a short time, wator is added to dissolve sodium iodido,and the separated ethereal layer shaken with thiosulphate solution to decolorise it. After separating and drying over calcium chloride, the ether is removed and tho remaining oil solidifies on cooling. Oolourloss prisms, m.p. 76. Yield, about 8 gms. ACBTYL ACETOACETIC ESTER. [Ber., 1884,17, Eef. 604.] Dry sodium acetoacetic ester (20 gms.), which is prepared according to the method given under diacoto-succinic ester, is dissolved in ether, and acetylchlorido (12 gms.) is added slowly. A vigorous reaction takes place, which may be completed by warming, after which a little water is added to dissolve sodium chloride, and the ethereal layer separated. After removal of the ether tho remaining oil is distilled under reduced pressure. B.p. at 50 mm. is 122-124. Yield, about 20 gms.
ANTIPYRINE.
[Ann., 1887, 238, 147,160.] [Ber., 1883,16, 2597.] IDEP. 20429.] Phcnyl hydrazino (10 gms.) is added to acotoacctic ethyl ester (12*5 gms.) and well shaken; much heat is evolved, and when the reaction is over tho oily product is separated from tho water formed, and heated on the water-bath till a samplo poured into water becomes solid (2 hours). Tho whole is poured whilo fetill warm into ether, tho white precipitate
118
collected, well w a s h e d w i t h e t h e r , a n d thon d r i e d recrystallised from alcohol. The p h e n y l - m e t h y l - p y r a z o l o n is t h e n methyl, b y heating w i t h t h e calculated a m o u n t of m e iodide in m e t h y l alcohol a t 100ISO0, in a scaled 1 for one or two h o u r s . T h e hydriodido of a n t i p y p r e s e n t in t h e c o n t e n t s , is decomposed b y aqu potash, and t h e a n t i p y r i n e obtained is t h e n cry* Used from toluene or e t h e r . M.p. 114. Y i a b o u t 10 g m s .
MONO-METHYL SUCCINIC E S T E R .
[Trans., 1899, 75,839.] (3-Mothyl-cyano-succinic ester is first p r e p a r e d m i x i n g cyan-acetic ester (28*5 gms.) with 5*7 g m s sodium dissolved in 70 g m s . of alcohol, a n d t a d d i n g very carefully t o t h e thick p a s t e , 4 2 g m s a-brom-propionic ester. T h e sodium compo dissolves with evolution of heat, a n d sodium b r o n separates. After a n h o u r on t h e w a t e r - b a t h , n e u t r a l liquid is cooled a n d p o u r e d into w a t e r , : t h e oil which s e p a r a t e s is e x t r a c t e d w i t h ether. ' e t h e r extract is w a s h e d w i t h dilute sodium c a r b o r solution a n d t h e n with w a t e r , a n d after d r y i n g o calcium chloride t h e e t h e r is distilled off; t h e maining yellow oil is fractionated u n d e r 24 r pressure. T h e g r e a t e r p o r t i o n distilling befcw 1 4 0 - l 65 is collected a n d refractionated u n d e r 1 7 n pressure, a n d t h a t p a r t collected which passes ovoi 160-165. Yield, 60 p e r cent. T h e cyano-succinic ester t h u s obtained, is h y d lysed by boiling w i t h six times its volume of co
POTASSIUM
119
hydrochloric acid under a reflux condenser for five hours. Any acid which scparatos on cooling is filtered, the liquid is made alkaline with ammonia, and boiled with 25 per cent, calcium chloride to precipitate the calcium salt of tho acid, which is filtered and treated with hydrochloric acid to separate tho methyl succinic acid.
SUCCINO-SUCCINXC EsTEJt.
^-DlKETO-HBXAMKTUYLKNK.
[Ann., 1882, 211, 308.] [Ann., 1885, 229, 45.] [Ber., 1889, 22, 2168.] Sodium (10 gms.), cut into small pieces, is added to succinic ester (38 gms.) containing two or three drops of alcohol. The mixture soon becomes semisolid, and is allowed to stand for ten days with occasional shaking. At tho end of this time the mass is brokon up, acidified with dilute hydrochloric acid, and tho insoluble ester is then filtered and recryatallised from alcohol. Colourless crystals, m.p. ]26. Yield, about 20 gms. N.B.A smaller quantity can be obtained in less time if a little ether be added to the mass, and tho mixture be heated on the water-bath for about twenty hours, during throo days. To obtain p-dikoto-hexamethyleiic, tho ester is hydrolysed with sodium hydroxide, and the acid (succino-Hiiccinic) precipitated by acidifying. This acid is then heated to 200, when it loses carbon dioxide and the diketo-body remains; ni.p. 78 \ Another method is to hydrolyao the ester with con-
120
bYNTRimC USE OF METALS
centrated sulphuric acid, when it loses carbon dioxide and passes directly to p-diketo-hoxamethylene.
TIN TETRAPHENYL.
[Ber., 1889, 22, 2917.] Twenty-five gms. of tin-sodium alloy (25 per cent, sodium) is prepared by adding sodium in small piccos to strongly heated molten tin, in an iron crucible. Tho alloy when cold is broken up into small pieces and mixed with 30 gms. of brombenzeno in a flask, and 1 to 2 gms. of acetic ester added. Tho mixture is then boiled under a reflux condonser in an oil-bath for ton hours. Tho brown semi-solid mass is next extracted with benzene and the extract crybtallised. Colourless prisms; m.p. 226. Yield, 1015 gms.
LEAD TETKAPHENYL.
[Ber., 1887, 20, 710.] This is prepared in the same manner as tin tetraphonyl, using 25 gms. of powdered lead-sodium (8 per cent, sodium) and tho same quantity of broxnbenzene. The mixture should be boiled for fifteen hours and then extracted with benzene. Pale yellow noodles; m.p. 224. Yield, about 18 gms.
MERCURY DIPHENYL.
[Ann., 1870,153, 93.] Brombenzene (31*5 gms.) is dissolved in an equal volume of xylene, and heated with 400 gms. of sodium amalgam (2 per cent, sodium) at 160 in an oil-bath. A small amount of acetic e&ter (about 1 gin.)
I'KACTh'AL W O R K : MUHUM.
POTASSIUM
121
accelerates tlio reaction and boiling* is continued during four hours. rI1ho clear liquid is then filtered hot, and tho crystalline substance which separates from tho jcylono on cooling is reorystallisod from benzene. Colourless needles; ni.p. 120. Yield about 15 gins. tfu.U'ON TWTKANIKNM,. [H<n-., IHHf), 18, inu.| I Nor., lHhtt, 19, IO1 ^J Silicon tolraolilorido (20 gins,) is mixed with dilorbon/jono (56 gins.) and four MimiH tho volumo of dry ctht'i^ nnd a Hnui.ll (iiumtidy of acolic cisUir (I to 2 gtns.) addod. rPho iln.sk i h > attachort to a rollux coudonsor, and iilum sodium (2^ gms.) in small piocos is gradually added. A vigorous reaction follows and tho flask should bo repeatedly shaken. When Mm reaction is completed, water is addod to remove any unattaekod sodium, and thon enough to dissolve tho sodium chloride, after which the mixture in extracted with hot bonzono. White crystals separate from the benzene solution, m.p. 22H.
\\Uw.y lhH(i, 19, iil^f). 1 Oxalic ester (20 gins.) M mixed with ether (100 gms.) anil sodium Q) gms.) in thin slices. Acetic ester (12 gms.) in then added From adroppingrunnel, slowly, nnd nflcu" tw(*lvre hours tlu^ mass which has solidified is treated in the mime way as
122
SYNTHETIC! USE OF WKTALS
for tlio separation of acetoacciic osier (see p. 111). Yield, 50 to 60 per cent. A colourless oil, which crystallises with difficulty. Method 2. [Ann., 1893, 277, 375.] Sodium ethoxido (9 gms.) is prepared by dissolving 3 grm. of sodium in a small quantity of etliyl alcohol and then distilling off the latter in a stream of dry hydrogen gas. The distillation should be conducted in an oil-bath and the temperature allowed to rise to 200 in order to drive off all alcohol. Oxalic ester (20 gms.) is then added and enough ether to give a clear solution; acetic ester (12 gms.) is next added, and the whole is boiled under a reflux condenser for one hour. After this, the cool mixture is decomposed with cold dilute sulphuric acid, the ester is extracted with ether, and after drying over calcium chloride the ethereal solution is allowed to crystallise. Yield, about 50 per cent.
HYDROXYMETHYLENE-GAMPHOR.
[Ann., 1894.., 281, 328.] In a litre-flask, dry ether (20 c.c.) is mixed with sodium (8 gms.) in thin slices. The flask is attached to a reflux condenser fitted with a dropping-funnel, and camphor (50 gms.), dissolved in 200 c.c. of dry ether, is added to the ether and sodium, after which amyl formate (45 gms.) is added gradually from the dropping-funnelto the well cooled mixture in the flask.
PRACTICAL W O I M C : SODIUM.
POTASSIUM
123
Tlio reaction is allowed to moderate after each addition of 4 or 5 gms. of the formate, and tho flask is shaken occasionally. About half an hour is taken to add all the formate, and the mixture is then allowed to stand for two hours, by the end of which time most of tho sodium will have dissolved and the mixture will be semi-fluid and brown. After standing another four hours to allow the sodium salt to separate, the wholo is poured into 200 c.c. of iced water. The yellow aqueous layer is extracted twice with ether to remove any camphor or borneol in it, and finally air is blown through it to remove all ether. The aqueous solution is then treated with ice-cold acetic acid (30 per cent.) until the deposition of oil ceases, and after an hour, when the oil has solidified, it is filtered and dried. Yield, about 20 gms.; m.p., 70-76: yC: CHONa 2Cl0IIIbO + 2Na + IICOOC.Hn-CsH.Z | + CluHi70Na + c B n n 0H ACISTYL ACETOPHENONE. [Bor., 1905, 38, C95.] [D.R.P. 49642.] Acetic osier (19 gms.) and acotophenono (24 gms,) are mixed with 150 gms. of dry ether and tho mixture cooled in ico, whilo powdered sodamido (16 gms.) is gradually added. When tlio sodauiide has all been added, the mixture is allowed to stand for a day, during which time a thick paste < > C sodium salt separates. At tho end of thin period ice-water is added; the aqueous layer is separated from the ether, aud nil
124
SYNTHETIC U S K OF METALS
traces of ether blown out of i t ; it is then acidified with acetic acid, and the precipitated ketone filteiêd off. Crystals; m.p., 60~61; yield, about 25 gms. Preparation of Sodamide. [Trans., 1894, 65, 504.] Ammonia gas is passed over sodium heated in a glass tube to a temperature of 300~400. Since the glass is attacked, the sodium should rest in a trough of nickel foil. When powdering the sodamide, it should first be moistened with benzene, since it is very hygroscopic.
ETHYL ACETOPIIENONE.
[Ber., 1905, 38, 698.] Acetophenone and ethyl iodide in molecular quantities are mixed, and sufficient dry ether added to dissolve them (several volumes). One molecular quantity of sodamide is then added gradually with cooling, and after a while ammonia gas is evolved and the ether boils. After standing twenty-four hours, ice-water is added and the ethereal layer separated. This contains acetophenone, together with mono- and di-ethyl derivatives, which are separated by fractional distillation. B.p. of ethyl acetophenono, 227-233. FURFUROL ACJROLEIN. [Ber., 1880,13, 2342.] Furfurol (1 part) is mixed with acotaldehyde (2 parts), water (100 parts), and 10 per cent, sodium hydroxide (5 parts).
PEACTICAL WOEK : SODIUM.
POTASSIUM
125
By gradually heating the mixture to 5060 a yellow oil first separates, passing to a brown solid, and when the latter appears, the liquid is neutralised with sulphuric acid. The liquid is next distilled, and the distillate (containing needle-crystals) is extracted with ether, the ethereal extract distilled, and when the temperature has reached 210 the residual oil is allowed to solidify. The brown needles of furfurol acrolein are recrystallised from Tboiling water. Pale yellow needles; m.p. 51; yield, about 60 per cent, of furfurol used. ClNNAMYL-VINYL-METHYL IClSTONE. [Bor., 1885,18, 2320.] Acetone (30gms.) is shaken with water (3600 grns.) till dissolved, and then cinnamic aldehyde (40 grns.) is added and shaking continued till a white emulsion is obtained. Sodium hydroxide (40 gms. of 10 per cent. aqueous solution) is then added,, and the whole is allowed to stand forty-eight hours, with occasional agitation. At tho end of this time the kotono will have completely crystallised. I t may bo recrystallised from ether. Rhombic plates; m.p. 08.
ACETIC ANHYDKIDE.
[Bor., 1911, U, 3333.] Acetyl chloride (40 gms.) is mixed with potassium nitrate (7 gms.) in a flask attached to an upright condenser, which is closed by a calcium, chloride tubo. A vigorous reaction is accompanied by tho evolution of chlorine and nitrosyl chloride, and after standing
126
SYNTHETIC USE OF MKTALS
for half an hour, the mixture is heated on a waterbath and gradually raised to boiling temperature, at which it is maintained for two hours. The colourless liquid mass is then extracted with other to romovo the potassium chloride, and the othoroal extract fractionally distilled. Yiold, 15 to 20 gins.; l).p., 138.
PROM BENZALDEHYDE.
[Ann., 1840, 34, 186.] Bonzaldohydo (25 gms.) mixed with potassium cyanide (5 gms. in 20 c.c. of water) and absolute alcohol (50 c.c), is heatod on a water-bath under a reflux condenser for half an hour. At the end of this time tho benzoin crystallises out and may be filtered, washed with a little alcoliol and rocrystallised from spirit. Oolourloss prisms, m.p. 137. Yiold about 20 gms.
DESYL-ACBTOHIHNONE.
[Trans., 1890, 57, 644.] Acetophonono (18 gms.) is mixed with benzoin (31 gms.), potassium cyanide (4 gms.), water (75 gms.) and alcohol (75 gms.). The mixture is boiled on tho water-bath and if necessary a little more alcohol may bo added to dissolve tho benzoin. After half an hour, dosyl-acetophonone separatos as an oil, and after 1^ hours, tho boiling is stopped, and the oil?allowed to settle and separate. On cooling, the oil solidifies, and after draining on a plate is recrystallised from alcohol. Pale-yellow crystals; m.p. 126. Yield, about 18 gms.
PRACTICAL WOEK : SODIUM.
POTASSIUM
127
PHENANTHROXYLENE ACETOACETIC ESTER.
[Ber., 1883,16, 21Q.~] Finely powdered phenanthraquinone (33 gms.) is mixed in a flask with acetoacetic ester (30 gms.) and 150 c.c. of potassium hydroxide solution (one part K O H to six parts water) added. The mixture is gently warmed with continual shaking, heat is evolved, and the red colour of phenanthraquinone gives place to the light grey of the crude product. This is boiled with water, washed with alcohol and recrystallised from benzene. Yield, about 30 gms. White silky needles, which blacken and decompose at 185.
APPENDIX PEACTICAL
II SILVEE
W O E S : COPPEK AND
ACJIOLEIN -> /3-IODOPROPIONIC ACID. Acrolein is prepared from glycerol by mixing the latter substance with twice its weight of powdered acid potassium sulphate, and after standing two days, distilling the mixture in a retort; two layers collect in the receiver, the upper of which is acrolein. This aqueous distillate is shaken up with powdered litharge until no more lead sulphite is produced, and it is then distilled on a water-bath. The moist acrolein which collects, is allowed to stand over calcium chloride for two hours and then redistilled. B.p. 52. Yield, about 35 per cent. The acrolein is next oxidised to acrylic acid as follows : An alkaline silver oxide solution is prepared by dissolving silver nitrate (1 part) in water (10 parts), and mixing with sodium hydroxide (1 part), also dissolved in water (10 parts)."* Ammonia solution is then added gradually till the precipitated silver hydroxide just dissolves. A quantity of this solution, sufficient to oxidise the acrolein taken, is warmed to 6070 on the water-hath, and * These quantities should not "be departed from and the solution should not be allowed to evaporate, otherwise silver fulminate may be formed and a dangerous explosion may result.
PRACTICAL WORK: COPPER AND SILVER
129
the acrolein, dissolved in the minimum amount of water, is added gradually; when all has been added the heating is continued for half an hour, with occasional shaking. After this the mixture is acidified with hydrochloric acid and the acrylic acid separated by distillation with steam. The acid distillate is neutralised with lead carbonate, heated and filtered, after which, the dry lead salt is decomposed by heating it in an inclined tube, through which passes a current of dry hydrogen sulphide. B.p. 140. 2CH2:CH.CHO + 3Ag2O = 2CH2:CH.COOAg + 4Ag + H2O The acrylic acid is now dissolved in the minimum quantity of water, and the calculated amount of concentrated hydrogen iodide solution gradually added, shaking well after each addition. When all has been added, the mixture is warmed on the waterbath for one hour and then evaporated to crystallisation ; the resulting /3-iodopropionic acid melts at 82.
ADIPIC ACID.
[Ann., 1869,149,220.] /3-Iodopropionic acid is melted in a small flask with finely divided silver in slight excess of that calculated from the equation : 2CH2I.CH2.C00H + 2Ag = 2AffI + (CH2)4(COOH)a. The silver is prepared by suspending silver iodide or silver chloride in water, and adding the necessary amount of zinc dust. The precipitated silver is filtered, washed with diluto hydrochloric acid to
130
remove any zinc, and then dried by heating gradually to 150. The molten mixture of iodo-acid and silver is maintained at 100120 until it thickens and the temperature is then raised to 150-160, After remaining at this temperature for two or tliree hours the mixture is cooled and then extracted with boiling water. The aqueous extract, on evaporation, deposits a considerable crust of adipic acid which is separated. A further quantity of adipic acid is obtained by evaporating the mother-liquor, and the whole may be recrystallised from hot water. Colourless crystals; m.p. 148-149. Adipic acid is more conveniently prepared by the following method, from ^y-chlorobutyronitrile (C1.CH2. CH 2 .CH 2 .CN), which is itself prepared from trimethylene chlorobrornide as follows: To a hot solution of potassium cyanide (80 gms.) dissolved in 125 gms. of water, hot 96 per cent, alcohol is added (500 c.c), and to thi clear, hot mixture, trimethylene chlorobromide (200 gms.) is added; the whole is then boiled for 1\ hours on the water-bath under a reflux condenser. The alcohol is next distilled off, and carries with it most of the unchangedtrimethylene chlorobromide. Water is then added to the residue in the flask to dissolve potassium salts, and the oily layer is distilled after drying over calcium chloride. After two or three fractionations the portion boiling at 192205 is taken as y-chlorobutyronitrile. B.p. 195-197. Yield, 50 per cent. [Ber., 1890,23,1771.] [Trans., 1901,79,130.]
PRACTICAL WORK : COPPER AND SILVER
131
The nitrile, prepared as above, is next digested with the calculated amount of sodium malonic ethyl ester, on the water-bath, till no alkaline reaction is obtained. After removal of the alcohol and sodium chloride, the cyano-propyl-malonic ethyl ester is fractionally distilled under reduced pressure. B.p. 170-175 at 40 mm. This substance, CNXH 2 .CH S .CH 3 .CH(COOO S H B ) 2 , is then boiled with dilute sulphuric acid (1:2) for five h o u r s ; the resulting adipic acid is extracted with ether and purified by recrystallising from water.
CARBAZOLB FROM THIO-DIPHENYLAMINE.
[Ber., 1886,19, 2243.] Thio-diphenylamine is prepared by heating a mixture of diphenylamine (30 gms.) and sulphur (12 gms.), at a temperature of 250280 for one hour or until hydrogen sulphide is no longer evolved. The mixture is then distilled (in a retort) ; any unchanged diphenylamine boils at 310, while thiodiphenylamine distils at 370. The distillate may be crystallised from alcohol. Yellow plates; m.p. 180. Yield, over 50 per cent. To prepare carbazole, the thio-diphenylamine is mixed in a retort with excess of copper powdor and distilled in a stream of carbon dioxide. If the distillate has a yellow colour (due to thio-diphenylamine) it should be again mixed with copper powder and distilled. Colourless crystals, m.p. 238; b.p. 355. Yield, C0-70 per cent.
132
Dl-ORTIIONJTROPHENYL-DIACTCTYLENE. [Ber., 1882,15, 50.] It is necessary to prepare first, o-nitro-phenylpropiolic acid, which is itself obtained from o-nitrocinnamic acid. Cinnamic ester (50 gms.) is nitrated by pouring gradually into cooled nitric acid (sp. g. 1-5). After completing the nitration by warming on the water-bath for twenty minutes, the mixture is poured into water, and the mixed o- and j9-nitro-esters separated by digestion with a little alcohol, in which only the ortho-compound dissolves. The substance may then be obtained in a pure state by pouring the alcoholic solution into cold water and filtering. Bromination of o-Nitro-cinnamic Ester. [Ann., 1882, 212,125.] The ester (20 gms.) dissolved in carbon bisulphide (300 gms.) under a reflux condenser, is treated gradually with bromine (15 gms.) and warmed. The bromine soon disappears, and if the 0S 2 be quite dry, no hydrogen bromide will be evolved. After warming a short time, part of the 0S 2 is distilled off and the remainder evaporated. Pale yellow crystals will separate; m.p. 71. Yield, 30 gms. The ester is next treated with alcoholic potash as follows: Di-brom-o-nitrocinnamic ester (12 gms.) is dissolved in alcohol, and potash (6 gms.), also dissolved in alcohol, is added slowly. Potassium bromide at
VHA.CTICAL W O I U C : COPPER AND SlLVEti
133
once separates, and when all the potash has been added tho liquid is filtered from bromide, part o the alcohol distilled off, and the romainder evaporated over sulphuric acid. The dark brown liquid deposits crystals (mixed with resin), which are poured into water and extracted with ether to remove impurities, after which the nitro-phenyl-propiolic acid is precipitated by sulphuric acid fractionally. A brown precipitate is first thrown down and removed, further addition of sulphuric acid throws down nitro-phenyl-propiolic acid, and more is obtained by extraction with ether. The slightly red crystals melt at 157, and when subjected to a steam distillation give nitro-phenylacetylene. The last-named compound is converted into the copper derivative by dissolving it in much alcohol and adding an ammoniacal solution of cuprous chloride. The rosulting precipitate is washed with ammonia, then beaten to a pulp and air bubbled through it to remove ammonia; it may be recrystallised from chloroform. I n the final stage of the process this copper compound (1 part) is addod to a solution of potassium ferricyanide (2 parts) and potassium hydroxide (0*4 part) in water (9 p a r t s ) ; this mixturo is allowed to stand till the red colour of the copper compound disappears (24 hours). The green-brown rcsiduo is separated and after drying, extracted with chloroform; the di-phenyl-diacetylene uitro-compound crystallises in yellow needles.
13-i
SYNTJ1KT1C USE OF M W T A L K
O-CllLOE-TOLUENE. [Zoit. angow. Chem., 1910, 23, 389.] o-Toluidine (53 gms.) is dissolved in a mixture of 170 gms. of 23 per cent, hydrochloric acid and 500 gms. of ice-cold watei\ It is diazotised by adding gradually, sodium nitrite (37 gms.) dissolved in water (80 gms.). The ice-cold diazo-solution is then added to a solution of cuprous chloride (50 gms.) in 23 per cent, hydrochloric acid (380 gms.) diluted with water (830 gms.). The temperature of the copper solution should be kept at + 5 during the mixing, and tho process should occupy fifteen minutes. After standing a short time, the mixture is heated on the waterbath to drive off nitrogen and is then stoam-distillod. The distillate is extracted with chloroform, tho extract dried over calcium chloride, and after removal of chloroform the oil is distilled. B.p. 157. Yiold, about 50 gms.
O-CHLOR-BENZOIC ACID.
o-Chlor-tolacne is boiled in a flask under a reflux condenser, with a solution of potassium permanganato containing a weight of the oxidant equal to that of the chlor-toluene used. The time required is about ten to twelve hours and the permanganato solution may be added gradually. When the liquid has cooled two methods of treatment aro possible : Either it may be filtered from precipitated manganese oxide and then acidified with hydrochloric acid to precipitate chlor-benzoic acid, or sulphur dioxide may be passed in straight away without filtering. The latter
PRACTICAL WORK : COPPER AND SILVER
135
process will dissolve the oxide of manganese and at the same time precipitate the chlor-benzoic acid. Colourless crystals ; m.p. 137. Yield, nearly quantitative. (G-attermann). [Ber., 1890, 23, 1218.] p-Toluidino (36 gms.), dissolved in a mixture of 40 per cent, hydrochloric acid (225 gms.) and water (150 gms.), is diazotised by 25 gms. of sodium nitrite dissolved in 100 c.c. of water. Copper powder (40 gms.) is then made into a paste with water and added gradually to the above diazo-solution during half an hour. After standing a short time the mixture is steam-distilled and the _p-chlor-toluene separated by extraction with chloroform. B.p. 160. Yield, about 35 gms.
FORMALDEHYDE.
[J. Eaiss. Phys. Chora. Soc, 1913, 53, 286.] Methyl alcohol (100 c.c.) is placed in a flask which is kept at a temperature of 40, and connected to a horizontal combustion tube in which a roll of copper foil (5 cm. long) is placed. The other end of the combustion tube is connected to a condenser and a well cooled receiver. A stream of air is driven through the alcohol causing a mixture of air and alcohol vapour to pass through the copper coil, which should bo hoated until it just glows. The reaction will proceed without further heating and a solution of formaldehyde in methyl alcohol will collect in the receiver.
136
Small explosions on t h e copper do no liarm ; b u t t h e t e m p e r a t u r e should n o t exceed a dull r e d h e a t or some of tho a l d e h y d o will b e decomposed. A much i m p r o v e d yield (about 80 p e r cent.) m a y b e obtained b y s u b s t i t u t i n g pumice, coated w i t h a mixture of silver a n d c o p p e r , for t h e roll of copper foil. F o r a m e t h o d of e s t i m a t i n g the p e r c o n t a g e of formaldehyde obtained, see c Volumetric A n a l y s i s / b y Sutton.
APPENDIX
III CALCIUM
PRACTICAL WORK: MAGNESIUM.

BENZOIC ACID.
A solution of magnesium phenyl bromide in ether is proparod by mixing Ibrombenzene (16 gms.) with dry ether (50 c.c.) and gradually adding magnesium r i b b o n (2*4 gms.). The reaction, which is fairly vigorous, may require to be started by the addition of a crystal of iodine. When all the magnesium lias dissolved, the solution is cooled in iced water and a atroam of well dried carbon dioxide passed through it for about three hours, at the end of which time t h o flask contains a solid mass of the addition prod u c t C c H 5 .COO.MgBr. Tho solid mass is treated with 50 c.c. of ice-water w i t h shaking, and then 40 gms. of cold 20 per cent. hydrochloric acid is added gradually. This process liberates bonzoic acid, which may then be extracted w i t h other and crystallised. Yield, about 10 gms.
138
SYNTHETIC USE OF METALS PHENYL-ETHYL-CARBINOL.
[Compt. rend., 1900,130,1322.] Magnesium ethyl iodide is prepared by mixing ethyl iodide (40 gms.) with dry ether (100 c.c.) and then adding magnesium ribbon (6 gms.). When all the magnesium has dissolved, the solution is cooled in ice, and benzaldehyde (25 gms.) in 50 c.c. of dry ether added gradually. The solid magnesium compound which separates is allowed to stand overnight and then ice-cold water (200 c.c.) is added, followed by sufficient hydrochloric acid (1 :1) to just dissolve the magnesia. The ethereal layer is removed and washed, first with sodium carbonate solution, and then with sodium bisulphite to remove iodine, after which it is dried over potassium carbonate. The ether is distilled off and the phenyl-ethyl-carbinol distilled under reduced pressure. Yield, about 20
TRIMETHYL CARBINOL.
Magnesium methyl iodide is prepared from methyl iodide (25 gms.), and magnesium (4 gms.) in dry ether (15 c.c). To this solution is added, gradually, acetone (10 gms.) in an equal quantity of ether, and the mixture is allowed to stand over-night. After this, dilute acid is added and the two layers which result are separated. The ether is distilled from the ethereal layer and the trimethyl carbinol which remains is added to the acid aqueous solution ; this is distilled with steam
PRACTICAL W O K K : MAGNESIUM.
CALCIUM
139
until the addition of solid potassium carbonate ceases to " s a l t o u t " the carbinol. From tlio aqueous distillate the carbinol is salted out with potassium carbonato, separated, and dried over lime or barium oxide. Yield, about 60 per cent.; b.p. 83.
TUIPHENYL CARBINOL.
Magnesium phonyl bromide is prepared by dissolving brom-benzeno (16 gms.) in ether (80 c.c.) and adding gradually magnesium ribbon (2*4 gms.). The solution when ready, is treated with benzophenone (18 gms.) in ether (50 c.c), and when the main reaction is over it is completed by boiling on the water-bath for half an hour. A few lumps of ice arc then added to the well cooled liquid, followed by diluto sulphuric acid. The ethereal layer is separated, washed with sodium carbonate solution and then dried over potassium carbonate, after which the ether is distilled off and tho solid rccrystallised from benzene. Yield, about 20 gms. ; m.p. 159.
CAMPHOR FKOM CAMPHORIC ACID.
[Compt. rend., 1896, 122, 293, 448.] Camphoric Anhydride -> Campholide -> Homocamp] i or ic Acid.
Camphoric anhydride is proparcd by mixing camphoric acid (100 gms.) with acetic anhydride
140
SYNTHETIC T T 8 J M OF MKTALfl
(70 gins.) and acotyl chloride (11 gins.) and boil the mixture under a reflux condenser for half hour. After cooling, the anhydride is washed w wator and rocrystallisod from alcohol. Yield, 90 per cent. ; in.p. 221. The camphoric anhydride is dissolved in alco and an excess of 5 per cent, sodium amalgam ado gradually during 3 days, keeping the mixturo 1 and continually acid by addition o cone, sulphu acid. Tlio resulting campholide may bo rocryst lised from benzene. M.p. 21G. The campholide is next heated in a scaled tu with the calculated amount of potassium cyanide 230 for six hours. When cold, the mass is trai ferred from the tubo to water, in which unchang campholido is insoluble, and the aqueous solution extracted with other to remove traces of catnpholi* at'lor which it is acidified with sulphuric acid precipitate homocamplioric nitrilo. This substai is colloctcd, rocrystalliwod from alcohol or other a hydrolysod by boiling with 30 per cont. potash i ammonia is no longer ovolved. Tho mixture is th acidified and tho precipitate of homocainphoric ac filtered. M.p. 234. Homocamplioric acid is now neutralised with so solution and precipitated with load acetate ; tho le salt of tho acid is collected, dried, and thon pack into a long combustion tubo and hoatod gont Camphor sublimes and may be collected.
CAMPHORIC ACID is proparcd from camphor
heating 50 gms. with a inixtu.ro of 400 gms. niti acid (1*4) and 260 c.c. of wator for twenty hours
PRACTICAL WOBK: MAGNESIUM.
CALCIUM
141
a boiling water-bath. The mixture should be in a litre-flask, with a boiling tube, which contains cold water, fitted in the neck. At the end of this time the mixture is well cooled, and the camphoric acid which separates is filtered offabout 30 gms. The mother-liquor, about 600 c.c., is mixed with a further 80 c.c. of cone, nitric acid and camphor (50 gms.) added, and after heating for a further twenty hours, camphoric acid is separated as before (about 40 gms.). The mother-liquor is again treated with 130 c.c. of cone, acid and 60 gms. of camphor, and after a further twenty hours' heating, about 40 gms. more of camphoric acid is separated. In this way from 160 gms. of camphor, about 110 gms. of camphoric acid will be obtained70 per cent, yield [Amer. Chem. Journ., 1894, 16, 500].
PENTAMETHYLENE.
[Ann., 1893, 275, 312.] Adipo-ketone is produced by distilling the calcium salt of adipic acid in an iron or glass tube. The distillate is re-distilled, and that portion collected which boils at 128-132. The ketone is then reduced by mixing it with an equal volume of ether in a flask fitted with a reflux condenser; an equal volume of water is then added and sodium in small pieces dropped in. When the required amount of sodium has been introduced, the ethereal layer is removed, dried over potassium hydroxide and the ether distilled off. The remaining
142
SYNTHETIC USE 01 METALS
oil is fractionated and the portion collected which boils at 135145; this is refractionated. The resulting cyclo-pentanol boils at 139. The alcohol is next cooled to 0 and saturated with hydrogen iodide; after standing ovor-night the liquid is shaken with dilute sodium hydroxide. A colourless oil separates, which can be distilled with little decomposition in a current of carbon dioxide at 164-165. The iodide is now reduced to pentamethylene by mixing it with five times its weight of alcohol and some granulated zinc in a flask fitted with reflux condenser. Fuming hydrochloric acid is added drop by drop, and after some time the solution becomes turbid and an oil separates, which, after standing during some hours with the zinc and acid, is separated, and any iodide present removed by shaking with a mixture of concentrated sulphuric and nitric acids. The liquid after separation is dried and distilled. B.p. 50.
CYANAMIDE; G-UANIDINE.
[J. angew. Cliom., 1910, 23, 2405.] Sodium cyanamide (50 gins.). is gradually added to concentrated hydrochloric acid (1'19), 74 gms. while well cooled, and the water is then removed by distillation in vacuo. The residue, which solidifies on cooling, is extracted with ether, and the ether evaporated; the cyanamide solidifies when cooled. Yield, about 10 gms. M.p. 40.
PRACTICAL WORK : MAGNESIUM.
CALCIUM
143
From calcium cyanamide the procedure is as follows : The calcium compound is dissolved in water and the calculated amount of aluminium sulphate added in solution; this liberates cyanamide^ and a precipitate of calcium sulphate and a]umina is formed. The filtrate is evaporated in vacuo and the cyanamide crystallised from ether. By this method about 20 gms. of cyanamide is obtained from 200 gms. of the calcium compound. A good yield of guanidine nitrate is obtained by treating dicyanamide (obtained by heating cyanamidej with a mixture containing 25 per cent, of hydrochloric acid (1 ]9) and 35 per cent, of nitric acid (1*38), in water.
APPENDIX PEACTICAL WOEK:
IV MEBCURY
ZINC.
OITRTC ACID.
[Trans., 1897, 71, 457.] Oxalyl-acetic ester (20 gms.) is mixed with monobromacetic ester (17 gms.) in a flask of 300 c.c. capacity, fitted with an air-condenser. Enough zinc turnings to cover the end of a spatula are added and the mixture becomes brown, while the temperature quickly reaches 50 and the zinc dissolves. Addition of a second portion of zinc is attended by boiling and the reaction is moderated by cooling; the metal is added in excess, and the mixture is then heated on the water-bath for a short time. After cooling, the mixture is treated with cold dilute sulphuric acid and ether, well shaken to get a clear solution, and the ethereal layer removed, washed with dilute sodium carbonate and dried over calcium chloride. The ether is next distilled and the remaining oil fractionated under reduced pressure; most of it passes over below 200 at 35 mm. That portion taken as citric ester (b.p. 212~216) is hydrolysed
W O K K : /INC.
M I C U C U R Y
145
l)y alcoholic potash. From tho neutral solution calcium citrate is precipitated. Yield, about 5 gins.
KETONTBS OU THRTIARY ALCOHOLS FROTH ACID CHLORIDES.
[Bull. Soc. Claim., 1911 (iv), 9, i-xxv.] Tho zinc alkyl reagent is prepared as follows: Twice the amount of zinc-copper couple theoretically required, is mixed with the alkyl iodide (1 rnoh), ethyl acetate ($ niol.), and dry toluene equal to twice tho weight of ethyl acetate used. This mixture is heated under a reflux condenser at 100, and the reaction started, if necessary, by adding a crystal of iodine. About forty-five minutes' heating is required, and towards the end, the temperature may be raised to 110; the flask should be occasionally shaken. When refluxing has stopped, the contents of the flask are cooled, an amount of toluene equal to that first used is added, and the viscous liquid is decanted into a dry flask or bottle. Yield, about 80 per cent. For use with acid chlorides the procedure is as follows : An amount of the above reagent (zinc-alkyl-iodido) is taken (25 per cent, in excess of tho calculated amount), and while cooled to 0, the acid chloride dissolved in dry toluene is added drop by drop with shaking. When all the acid chloride has been run in, the mixture is cooled and dilute sulphuric acid added. Tho toluene layer contains the required product, and often a * small quantity of zinc which may "be removed by shaking with ammonia. After this the 10
IU)
SYNTHETIC USE C W MlflTALK
toluene solution is washed with NallCC^ and also with thiosulphate; it is then dried over sodium sulphate before separating the ketone or tertiary alcohol.
NAPHTHALENE PROM JS-OKTAFHTHOL.
A combustion tube is half filled with a mixture of zinc dust and /3-naplithol (10 gins.). The remainder of the tube is filled with granulated pumice impregnated with zinc dust, and this (the front end) is connected to a receiver. The other end of the tube is connected to a generator for providing a stream of dry hydrogen. The combustion tube should be between 50 and 60 cm. long, and rest in a furnace. When all air has been expelled by hydrogen, the zincpumice is heated to redness and then the naphthol mixture is heated. In the receiver, naphthalene and water collect, and when the distillation is complete, the aqueous distillate is extracted with ether and the ethereal solution dried over calcium chloride. On evaporating the ether, naphthalene remains. ISOQUINOLINE. [Ber., 1888, 21, 2299.] [Ber., 1884,17, 2178.] Phthalic Anhydride - Fhthalide - Ilomophthalimide. Phthalic anhydride (200 gins.) is dissolved in glacial acetic acid (1 kilo.), and while heated on the water-bath, zinc dust (300 gms.) is gradually added.
P R A C T I C A LW O l H v : ZINC. M E R C U R Y
147
Tho zinc dissolves rapidly with evolution of hoat and when the reaction becomes sluggish; heat is applied. Needles of diphthalyl
x
which deposit on cooling are filtered oil, and on diluting the mother-liquor a mixturo of hydrodiphthalyl and hydrodiphthal-lactonic acid is precipitated. After filtering these off, the phthalide is extracted from the mothor-liquor with ether. Prisms; m.p. 73. Yield, about 30 per cent. The phthalide is next converted to cyanotoluic acid by heating it in a scaled tube with the calculated amount of potassium cyanide at 230-240, for five or six hours. Tho contents of tho tube are then transferred to water, filterod from any insolublo matter, and tho nitrilo precipitated by sulphuric acid. When filtered, it is hydrolyscd by boiling with 30 por cent, potash till no more ammonia is evolved, after which homophthalic acid is precipitated by sulphuric acid. M.p. 175. Homojohthalic Acid - Homophthalimide. [Ber., 1886,19, 1653.] The ammonium salt is preparod by neutralisation with ammonia, and then distilled, when it decomposes into homophthalimide, wator and ammonia. The two latter substances pass over first, and leavo behind homophthalimido, which melts at 223. The homophthalimide is then mixed with zinc dust
148
SYNTHETIC T J B i S OP METALS
in a combustion tube and heated in a stream of hydrogen, at a dark red heat. A deep-brown liquid distils over which smells of isoquinoline, and this is saturated with hydrogen chloride, the hydrochloride of the base filtered and dried, and it may then bo decomposed by aqueous potash. The isoquinolino, which may be obtained by extraction of the alkaline liquor with ethor, or distillation with steam, may fc0 furthor purified by formation of the picrate and its subsequent decomposition. M.p. 23. B.p. 241.
[Ann., 1876,183, 3.] Rosorcinol (7 parts) i s m i x c ( j w i t h phthalic anhydride (5 parts), and powdered anhydrous zinc chloride (3 parts) is gradually added to tho mixture, with stirring, at a temperature of 180. When all the zinc chloride has been added, the mass is heatod to 210 for two hours. The cooled mass is then pulverised and boiled with dilute hydrochloric acid for ten minutes, after which the solid fluorescein is filtered and washed. It m&y be purified by recrystallising from alcohol. Yield, about 80 por cent.
MALACHITE GREEN.
[Ann., 1881, 206,122.] Dimethylaniline (5 parts) is mixed with benzaldehyde (2 parts) and powdered anhydrous zinc chloride (4 parts).
PRACTICAL WORK : ZINC.
MERCURY
149
This mixture is heated on the water-bath, in a basin, until it no longor smells of benzaldehyde (four to five hours). The product is then transferred to a large flask and distilled with steam to remove unchanged dimethyl-anilino; the leuco-base is filtered when cool and recrystallised from alcohol. Almost a quantitative yield is obtained. The zinc chloride double salt of the dye is prepared as follows : Ten. gms. of the base is dissolved in diluto hydrochloric acid containing 2*7 gms. of H O I ; the liquid is diluted with 800 c.c. of water and 10 gms. of 40 per cent, acetic acid added; it is then cooled with ice, and a thin paste of 7"5 gms. of lead peroxide added gradually with shaking. After standing a few minutes, the lead is precipitated by adding 20 per cent, sodium sulphate, and to the filtrate from lead sulphate is added 8 gms. of zinc chloride dissolved in a little water. The dye is then salted out by addition of common salt. Yield, about 7 gms. ACRIDINE. [Ber., 1884,17, 101.] Diphonylamino (1 part) is mixed with chloroform (1 part), zinc chloride (1 part), and zinc oxide (J a part). The mixture is placed in a sealed tube and heated to 200210 for seven to eight hours. The mixture is then digested with cone, hydrochloric acid and the filtered solution poured into water to precipitate any unchanged diphcnylamine, the hyclrochlorido of which is dissociated by water. Prom the
150
filtered solution, acridine is precipitated by sodium hydroxide, and may be recrystallised from hot water after separating by steam distillation. Fine leaflets. M.p. 110. Yield, about 50 per cent. a-MsTHYL-INDOLE. [Ber., 1886,19,1563.] Acetone phenyl-hydrazone is first prepared by mixing phenyl-hydrazine (30 gms.) with, acetone (18 gms.). The mixture becomes warm and water separates; it is then heated on the water-bath for half an hour, and at the end of this time heated in a dish on the water-bath, to drive off acetone and steam. The hydrazone is then mixed with five times its weight of anhydrous zinc chloride, and heated under a reflux condenser in an oil-bath at 180. A vigorous reaction takes place, and when completed, the dark-coloured mass is distilled with steam. The a-methyl-indole collects in the receiver and soon solidifies to a pale yellow mass. It may be purified by recrystallising from ligroin. M.p. 59. Yiold is over 60 per cent, of that calculated.
PBOPYL CHLOEIDE.
[J. Am. Chem. Soc, 1907, 29,1328.] Anhydrous zinc chloride (30 gms.) is melted in a round flask (-litre), which is rotated so that the cooled chloride forms a layer inside, with a large surface exposed. The flask is fitted with a threeholed cork through which pass two dropping funnels and a fractionating column ; the last is fitted with a
PRACTICAL W O K K : ZTNC.
MRRCUEY
151
thermometer and the side tube passes into a vertical spiral condenser. Through a second hole at the top of the condenser, a tube is passed for dropping cold water, so that hydrogen chloride may be absorbed. Propyl alcohol (54 gras.) is required and phosphorus trichloride (30 gms.). One half of the trichloride is run in from the funnel which reaches to the bottom of the flask, and while heating gently, one third of the alcohol is admitted drop by drop through tho second funnel which reaches just above the level of the mixture. When this portion has been added the remaining phosphorus trichloride and alcohol are added simultaneously and at the same rate. Propyl chloride distils over, mixed with hydrogen chloride continuously, but the latter is provcnted from escaping into the air, by dropping water at a suitable rate into the condenser. The distillation (hitherto conducted on a water-bath) is finished over a flame, and the propyl chloride separated and driod over calcium chloride. Yield, 80-90 per cent. B.p. 44<. a-ETJTOXY-QUINOLINK. [Bcr., 1882,13, 2103.J o-Aanino-cinnamic ester (20 gms.), prepared by reducing o-nitro-cinnamic acid and then esterifying the resulting ammo-acid (see p. 162), is warmed with a saturated alcoholic solution of zinc chloride for some hours at 8090. The mixture is then made alkaline and distilled with steam, when the quinoline derivative passes over and may bo extracted from
152
the distillate with other. After drying the extract over potassium carbonate and removing the ethor, the remaining oil is distilled, B.p. 256.
PHTUALIC ACID.
[D.R.P. 91202.] Naphthalene (20 gins.) is mixed with mercuric sulphate (10 gins.) and concentrated sulphimc acid (300 gms.) in a retort which is fixed upright, and warmed until the naphthalene has dissolved. The retort is then turned, connected with an air-condenser and heated strongly. Eeaction commences at 200250 and becomes vigorous at 300, while the products distilling over, consist of phtlialic acid, sulphophthalic acid, naphthalene, and water, accompanied by sulphur dioxide and carbon dioxide. The distillate is collected in 250 c.c. of cold water and hoating continued till the retort is nearly dry, after which the distillate is filtered. The precipitate is washed with water and then dissolved in sodium hydroxide, filtered from unchanged naphthalene, and the phtlialic acid re-precipitated by hydrochloric acid. It may be recvystallised from water or alcohol. Yield, about 70 per cent.
153
APPENDIX
V TIN. LEAP
PRACTICAL WORK: ALUMINIUM.
DlMTDTHYL-ANILINE-PKOSPHOR-CTILOKTDE [Bor., 1888, 21, 1407.] Phosphorus trichloride (33 gms.) is mixed with dimethyl-aniline (23 gms.) in a. flask fitted with a reflux condenser. Anhydrous aluminium chloride (7 gms.) is tlion added, through the condenser, a little at a tinio whereby a vigorous reaction ensues. W h e n n.11 the chloride has been added, the flask is hoatotl on a water-bath for three hours, and then when cool, Lho oily liquid is extracted two or throe tinws with petroleum ether (until the residue in tlio flask is nearly solid). On distilling the clear extract over a water-bath, the petroleum ether is removed, and the residue on cooling separates in tables. I t may be purified by recrystallisation from ether or benzene. Yellow crystals; m.p. 06. Yield, about 50 per
154
SYNTHETIC USK OF METALS
J0-TOLUIC-ALDEIIYDE. [Ber., 1897, 30, 1622.] Toluene (30 gms.) is mixed with anhydrous aluminium chloride (45 gms.) and cuprous chloride (4 gms.) in a flask, and into the mixture a stream of carbon monoxide and hydrogen chloride gases is passed; while the flask is continually shaken and tho tomperature maintained at 20-25. Tho carbon monoxide may be stored in a 10-litre bottle and is enough to pass steadily for about three hours. The hydrogen chloride should pass at half the rate of the carbon monoxide. The escaping gases may be collected in a second bottle and used over again. At the end of three hours the reaction-product is poured into ice-water; an oily layer separates, and the mixture is distilled with steam to remove toluene and toluic aldehyde. The aqueous distillate is shaken with saturated sodium bisulphite, and undissolved toluene separated from the aqueous layer. If the aldehyde bisulphite separates at this stage it must be dissolved by adding more water. Finally, the separated aqueous solution is made alkaline with sodium hydroxide and distilled with steam; the aqueous distillate is then extracted with ether, and after drying over calcium chloride tho ether is removed by distillation. Yield, about 20 gms. of oil; b.p., 204.
DIPHENYL METHANE.
[Trans., 1895, 67,826.]. Benzene (60 gms.) is placed in a flask under a reflux condenser and half a gram of aluminium-
PRACTICAL WORK : ALUMINIUM.
TIN.
LEAD
155
mercury couple added in strips. The couple is prepared by immersing aluminium foil in concentrated mercuric chloride solution for a minute ; the mercurycoated strips are first washed with water, then with alcohol, and lastly with benzene, and dropped quickly into the benzene in the flask. Benzyl chloride (30 gins.) is then added slowly, from a tap-funnel in the top of the condenser, during one hour. Effervescence is caused by the evolution of hydrogen chloride, and when all has been added the flask is heated for a short time on the water-bath (quarter of an hour). The liquid is then shaken up with dilute sodium hydroxide solution, the benzene layer separated and fractionally distilled. When the temperature reaches 100, the distillation is continued under diminished pressure (80 mm.) and the fraction collected which passes over at 170-176. On cooling, this forms a mass of colourless needles (diplienyl methane). M.p. 25. Yield, about 14 gms.
O-HYDRINDONH.
[Trans., 1894, 65, 484.] Hydrocinnamic Acid -> fi-Phenyl-propionyl Chloride,
Cinnamic acid (1 part) is mixed with water (10 parts) and neutralised with sodium hydroxide. To this solution, 2 percent, sodium amalgam (17*parts) is gradually added with shaking, after which the liquid is poured off from the mercury, and the
156
hydrocinnainic acid precipitated by hydrochloric acid. Yield, 80-90 per cent.; m.p. 47* The acid chloride is prepared by treating the acid (50 gnis.) in a flask, gradually, with phosphorus pentachloride (69 gnis.) ; the reaction may bo completed by warming on the water-bath. To remove phosphorus oxychloride, the liquid is distilled under diminished pressure; subsequently the pressure is reduced to below 35 mm. boforo the /3-phenylpropionyl chloride can be distilled without decomposition. B.p. 125-135 at 33 mm. and 117-119 under 13 mm. Yield, about 90 per cent. /3-Phenyl-propionyl chloride (25 gms.) is dissolved in petroleum ether (b.p. 6070); and after adding anhydrous aluminium chloride (25 gms.) the mixture is heated gently, under a reflux condenser, on the water-bath, till the mixture boils and a vigorous evolution of hydrogen chloride takes place; the flask is then removed till the reaction subsides. This heating on the water-bath and subsequent cooling, is repeated until the evolution of hydrogen chloride is small (20-30 mins.). After treatment with ice-cold water the mixture is steam distilled, and the hydrindone in the receiver is extracted with petroleum ether, washed with sodium carbonate and crystallised. Colourless crystals; m.p. 41. Yield,about 10 gms.
TKIPIIENYL-METHANE.
[Bor, 1893, 26, 1961.] Dry benzene (160 gms.) is mixed with dry chloroform (32 gms.) in a flask connected with a reflux
PRACTICAL WORK : ALUMINIUM.
TIN.
LEAD
157
condenser, and powdered aluminium chloride (25 gms.) is added gradually; with shaking. Hydrogen chloride is evolved, and when all the aluminium chloride has been added, the flask is heated to boiling for half an hour. When cold, the mixture is added to an equal volumo of cold water, and tho upper benzene layer which contains the triphenyl-methane, is separated and dried over calcium chloride. Benzene is then distilled off and tho temperature finally raised to 200, aftor which any diphenyl-mcthano is removed by di&tilling under 80 mm. pressure. B.p. 175. When the thermometer rises above 180, tho distillation is stopped and the residue, when cool, extracted with warm benzene. Tho crystals obtainod from this liquid contain benzene of crystallisation which is removed by heating on tho water-bath; the triphcnyl-mothanc may bo rocrystallised from alcohol. Colourless plates; m.p. 92. Yield, 20-25 gms. ACETOHIENONE. Aluminium chlorido (60 gms.) is powdered, and covered with benzene (36 gins.) in a half-litro flask fitted with a reflux condonser, and acotyl chlorido (42 gms.) is gradually added to tho well cooled mixture through a tap-funnel. A vigorous ovolution of hydrogen chloride takes place and the mixture is allowed to stand for an hour, after which it is stirred and poured into 300 c.c. of ice-cold water. The aluminium compound decomposes with evolution of
158
SYNTHETIC USE OV METALS
heat, and the dark oil which separates is extracted with benzene. The benzene extract, after washing with dilute caustic soda and then with water, is dried over calcium chloride and distilled. Benzene passes over first and the thermometer then rises rapidly to 190; that portion is collected as acetophenone which distils at 195200. The pale yellow oil solidifies on cooling. Yield, about 25 gins. Colourless plates ; m.p. 20, b.p. 202.
O-BENZOYL-BINZOIC ACID.
[Ber., 1880,13,1612.] Phthalic anhydride (25 gras.) is dissolved in warm benzene (250 gms,), and dry aluminium chloride (40 gms,) is gradually added during three quarters of an hour* After standing for a short time the cooled benzene layer is poured off and decomposed by dilute hydrochloric acid, when a yellow mass separates, which, is washed with water and then treated with warm sodium carbonate solution, whereby most of the solid dissolves. The acid (benzoyl-benzoic) is reprecipitated by acidifying the solution of the sodium salt, and may be recrystallised from xylene. Yields about 15 gms. Phenyl-benzoyl-benzoic acid
4
\X>OH
may be prepared similarly, using diphenyl and phthalic anhydride. [J. Prakt. Chem., 1890,1*9,147.]
PRACTICAL WOKK : ALUMINIUM.
TIN.
LEAD
159*
Benzoyl-benzoic Acid ~> Anthraquinone. The acid is dissolved in cone, sulphuric acid and heated to 100 for half an hour. On pouring into water, a white precipitate of crude anthraquinone is formed, which is washed with water and then with sodium hydroxide solution. I t is then recrystalliscd from glacial acetic acid and further purified by sublimation. Yellow needles; m.p. 275.
HYDROLYSIS OF ANISOLE BY A1C]3.
[Bei\, 1892, 23, 3531.] Anisole (10 gms.) is mixed gradually with powdered anhydrous aluminium chloride (15 gms.), A vigorous reaction ensues, and crystals of aluminium double compound separate; the flask is then heated in an oil-bath to 120 for three hours, when methyl chloride is steadily ovolvod. At the end of this time the aluminium phenolate is decomposed by cold water acidified with hydrochloric acid, and the phenol extracted with ether. Unchanged anisole is removed from the phenol thus obtained, by dissolving the' latter in sodium hydroxide and re-precipitating with acid, and again extracting with ether. Yield, about 5 gms.
TOLUENE PROM ^-TOLUIDINE.
[Ber., 1889, 22, 587.] p-Toluidine (15 gms.) is dissolved in 45 c.c. cone, hydrochloric acid diluted with 90 c.c. of water, and
160
1 SYNTHETIC I F . S KO H METALS
diazofciscd with sodium nitrite (10*5 gms.). The diazonium solution is poured into caustic soda solution made by dissolving 22 gms. of sodium liydroxide in 75 c.c. of water, and the mixture is kopt below 10 all the time. This alkaline mixture containing the diazonium salt is next added slowly, through a condenser, to alkaline stannous chloride solution, in a flask which is immersed in ice. The alkalino tin solution is prepared by dissolving tin chloride (45 gms.) in water (110 gins.), and adding 50 por cent, caustic soda solution till the precipitated tin hydroxide almost dissolves. A vigorous evolution of nitrogen takes place after each addition of the diazo-solution and impure toluono separates; this is removed by steam distillation, and the toluone in the distillate separated and dried over calcium chloride. Yield, about 8 gms. DlPHJENYL. [Bor., 1870, 9, 407.] Benzene (100 gms.) is boiled and the vapour passed through an iron or glass combustion tube 1 metre long, which is filled with granulated pumice and heated to redness in a furnace. The vapours issuing from the combustion tube (consisting of diphenyl, unchanged benzene, and hydrogen) are passed through a condenser so arranged as to bring the diphenyl, etc., back to the flask o boiling benzene. A glass tube fused into the lower end of the condenser serves for the escape of hydrogen which is liberated during the reaction. By this
PEACTICAL WORK : ALUMINIUM.
TIN.
LEAD
161
arrangement, the vapours pass repeatedly through the red-hot pumice, and after two hours, the contents of the flask may be distilled and that portion boiling below 150 rejected. The remainder, in the distilling flask, solidifies on cooling and may be re crystallised from alcohol. M.p., 71.
OXALIC ACID.
[J. Prakfc. Chem., 1907, 75, 146.] Concentrated nitric acid (140 c.c.) containing vanadium pentoxide (0*1 grm.) is warmed gently in a litre-flask; it is then placed in a fume-cupboard and powdered cane-sugar (20 gms.) is added. As soon as the reaction becomes vigorous and brown fumes are evolved, the flask is placed in cold water to moderate the reaction. The mixture is allowed to stand for twenty-four hours, by which time the oxalic acid will have crystallised; the crystals are drained and recrystallised from water. Yield, about 16 gms.
11
162
APPENDIX
VI
PRACTICAL WORK: IRON. NICKEL. PLATINUM

O-AMINO-BENZALDEHYDE.
[Ber., 1884,17, 456, 754.] o-Nitro-benzaldehyde (10 gms.) is suspended in a litre of water, containing 100 gms. of ferrous sulphate in solution, and excess of ammonia solution is added. The mixture is then heated to 100 for ten minutes a n d afterwards steam-distilled; the amino-benzaldehyde is extracted from the distillate with ether. M.p. 39.
O-AMINO-CINNAMIC ACID.
[Ber., 1882,15, 2299.] o-Nitro-cinnarnic acid (30 gms.) is reduced by ferrous sulphate (270 gms.) as above. Instead of steamdistilling, it is advisable to filter from ferric hydroxide a n d to precipitate the amino-acid in the cold solution b y adding glacial acetic acid. Bright yellow needles of amino-cinnamic acid separate. Yield, 54 per cent. M.p. 158.
PRACTICAL WORK : IRON.
NICKEL.
PLATINUM
163
MANNOSE FROM MANNITOL.
[Trans., 1899, 75, 9.] Mannitol (40 gms.) is dissolved in water (100 c.c.), and powdered ferrous sulphate (10 gms.) added. When this has dissolved, the clear solution is oxidised by added " 20-volume " hydrogen peroxide (120 c.c.) gradually. After standing for two hours the solution is divided into two parts, one of which is used for isolating the mannose as follows : The solution is treated with excess of barium carbonate and filtered from iron oxide, etc. I t is then distilled under diminished pressure at 50 to remove water, and the syrup obtained is then transferred to a dish and allowed to crystallise. Yield of mannose, 8-10 gms. The second half of the above solution is again divided and one part used for preparing the hydrazone, while the other part serves for preparing the osazone. The hydrazone is prepared by making the solution alkaline with sodium carbonate and then acidifying with acetic acid; to this solution is added phenylhydrazine (5 gms.) which has been dissolved in 25 per cent, acetic acid. After standing for forty-five minutes the hydrazone is filtered off, washed with a very little acetone and recrystallised from water. Pale yellow crystals; m.p. 181. Yield, about 5 gms. The portion used for preparing the osazone is made alkaline with sodium carbonate, then acidified with acetic acid, and phenyl-hydrazine (10 gms.) dissolved in 25 per cent, acetic acid is added together with 10
164
gins, of sodium acetate in a little water. This mixture is digested on the water-bath for three hours, after which the osazone is filtered, washed with water, and recrystallised from alcohol. M.p. 195; yield, about 8 gms.
HEXAHYDRO-BENZENE.
[Compt. rend., 1901,132, 210.] A 50 cm. combustion tube is loosely packed with pumice, which has been previously mixed with an equal weight of nickel oxide and a little water, and gently dried. This is then placed in an air-bath and heated to about 300 while a stream of hydrogen gas is passed through, to reduce the oxide. When no more steam is produced the tube is allowed to cool, and to one end is attached a distilling flask, containing 30 c.c. of benzene, through the neck of which, a glass tube passes connected with a hydrogen-generating apparatus. The hydrogen is allowed to pass through the tube, driving out all air, and is then made to bubble through the benzene warmed to 30, while the nickelpumice is heated to 180190. About six hours is required to pass all the benzene through and to convert it into hexahydro-benzene. Any unchanged benzene is removed by nitrating the distillate. Yield, 80 per cent. B.p. 80-82.
HEXAHYDRO-PHENOL.
[Compt. rend., 1901,132, 210.] About 40 gms. of phenol may be reduced by hydrogen in the presence of reduced nickel, by the
VliAOTXCAh WORK : IKON.
NICKBL,
PLATINUM
165
&o>***e method an hoxahydro-bontfeno in prepared. The t o x n p o r a t u r o of the nickel Rhould bo 160170 and fclxo phenol may bo hoaiod nearly to ita boiling point yyixilo a fairly rapid current of dry hydrogenbubblon h it. Tho diHtillnto ultnnately obtained, IB with oaimtic Hoda nolution to remove unc g phenol, extracted with other, and after d r y i n g tho extract over potaHHiutn carbonate, it is f r a c t i o n a l l y dintillod, B.p. of hoxahydro-phenol in 170.
I N p Acoiio anhydride, J*2, 125 Aootoacotio nht<U\ 0, 111 liydrolyMH of, 10 A colony 1 acetone, 12 Aootophonono, K > 7 AeetoHUceinic out or, 1 1 1 1 Awtyl-acotoacoiio onior, 11, % 117 Aflotyl-aectophouono, 1 SA Acotyl-ncntono, 0, 2<'i Acwtyl'pyroraeomic o.-iter, J8 Acid anhydride format ion, 4, U2, Acid itotiiHhium Miilpliato, i)J Aori(limi,7l, 1 1 U Acrolom, lil, 128 rt-AoroHO, L * < K 02 Aoryliu* acid, liJH Adipuwicid, :m, 00, liii>, 1 U Aiih M y ph 7 82 Aluminium chloride, 77, iri'] oxtdo an ('atalynt, i)7, K K ) Amino-)Mn/,ldohy<l<s 102 Amino-citinnuiic acid, 102 Ammonia, Hynili<Mih of, UX) Aniwdo, !()o, lfi'J Anihranilic acid, JJ<i, 7l< Antimony, M oxido, i>7 Anti|)yrin<*, 13, 11 acid, 1 U 7 anhydride, lor
D U X
H<ui/.o)iluJion<>, 77 H^nzoyl aeotouo, 2tt Utm'Auyl-lnm'/inv acid, 79, 158 UonzyJ ryiuiido, M < BiHnatth oxidtt an catulynt, 97 lhiiano toinusarboxylic OHIOV ji(l<, 02, i;J9 ('amphor, 01, i:tf) ( ( am]lioric acid, 20, (U, I'M) (îinphoronic a.cid, 00 (Wl.azohs Jl7, t.'M (4ar!>idoKT fi'j. Carbon i uhox'uh*, O S Cnrljotiyl chlori<l<\ 101) C'aHincr <'yani<lo prociMH, 2'i ('hloi'bonzoic acid, I .'It (Milorobroui-pt'itpat^s 1 O I 5 (Miloroformic owtcr, fi, 109 o~('lilor(olu(u<i, III I fMiiloHoluono, 1'$5 (1innamic aldehyde, 20 nator, 18 (1iunntuyl-\ inyl-m<lhyl K(i Ciliic <^1(^r, 00, M 1 (4lai n, 8, 19 Coba 11, a,i calaly t, til ^'oppcr an cataly.Û 91 Cynnncotic oHtoi, 1 1 <'yntmmi<l<, T r > , 1 12 Cyclo-iirctnl.i, ( J O Cycl<t-litiiyl<ius 11 I>oxyh(Ui'/tin, 11
168
INDEX Hydrogen peroxide, 89, 163 Hydrolysis by A1C13, 82,159 by catalysts, 99 Hydroxymethylene camphor, 22, 122 ketones, 23 Indigo, 23, 25, 38, 74 p-Iodopropionic acid, 35, 128 Ionone, 28 Isoprene, 24 Isoquinoline, 70,146 Keten, 68, 101 -Keto-hexahy drobenzoic acid, 14, 52 Keto-pentamethylene, 60, 3-41 carboxylic ester, 18 Komppa, 20 Lead monoxide, 85 organo-compounds of, 19, 50, 83,120 peroxide, 85,149 tetraphenyl, 50,120 Magnesium syntheses, 45,137 Malachite green, 31, 71,148 Malonic ester, 11,16, 114 Manganese dioxide, 97 Mannose, 162 Mercury diphenyl, 50,120 Mercuric oxide, 74 ^-Menthadiene, 53 Mesityl-oxide-oxalic ester, 18 Metallic oxides as catalysts, 97 Methane, synthesis of, 37 Methyl benzoate, 111 succinic ester, 118 indole, 72,150 Molybdenum, 86 Naphthalene, 146 Naphthyl-phenyl-ketone, 67 Nickel as catalyst, 89,164 Nitrides, 58 o-Nitro-cinnamic ester, 132 Nitro-compounds, reduction of, 88, 94,101,162
Desyl-acetophenone, 30, 126 Diaceto-succinic ester, 11, 40,116 Diaeetyl-dicarboxylic ester, 20 Diacetylene dicarboxylic acid, 37 Diazo-compounds, 38 Dibenzoyl methane, 19 Di-isatogen, 38 Bi-isopropyl succinic acid, 35 Di-keto-hexamethylene, 17, 119 Diketones by ZnRI, 65 /3-Diketones by A1C13,79 Dimethyl-aniline-phosphor-chloride, 82,153 glutarie ester, 20 succinic ester, 14, 35 Di-o-nitrophenyl-diacetylene, 38, 132 Dipentene, 31, 52 Diphenyl, 160 diacetylene, 38 methane, 154 Di-tertiary glycols, 50 Esterification by catalysts, 98 Ethane tetracarboxylic ester, 11, 116 Ethoxy-quinoline, 73,151 Ethyl acetophenone, 124 Ethyl benzene, 104 Exhaustive methylation, 41 Fats, hydrolysis by PbO, 85 Ferric chloride, 88 Ferrous sulphate, 88, 162 Fluorescein, 148 Formaldehyde, 100,135 Friedel-Crafts' reaction, 77,153 Furfurane, 12 Furfurol acrolein, 25,124 Gattermann, 39,135 Glycerose, 26 Grignard reagent, 41,137 Guanidine, 56,142 Hexahydrophenol, 164 Hexamethylene, 4, 61,106,164 Hexaphenyl ethane, 40 Hydrindone, 79,155
INDEX Nitrogen fixation, 54 Nitroso-ketones, 22 defines from alkyl chlorides, 99 Organo-metals, 19, 50, 52, 82,120 Oxalic acid, 161 Oxalyl-acetic ester, 21,121 Palladium, 101 Pentamethylene, 61,141 Petroleum formation, 91, 96 Phenanthroxylene acetoacetic ester, 32,127 Phenyl-ethyl-carbinol, 138 Phenyl salicylic acid, 36 Phenyi-tolyl-methane, 67 Phloroglucin, 17 Phthalic acid, 74,152 Phthalide, 146 Pivalic acid, 50 Platinum as catalyst, 93 Polymethylenes, 4 Potassium alkyl sulphate, 3 cyanide, 30, 126 ferricyanide, 37, 133 hydroxide, 31,127 nitrate, 32, 125 Propiolic acid, 37 Propyl chloride, 72, 150 Pyrazolon, 14,118 Pyrrol, 12, 69 Pyruvic acid, 31 Quinoline, 25, 27 Quinones, 27 Keformatsky's reaction, 65, 66, 144 Rubber, artificial, 24 Sabatier and Senderens, 89, '" Sandmeyer's reaction, T *
169
Silicon tetraphenyl, 19, 50, 121 Silver cyanide, 40 hydroxide, 41 Sodamide, 22, 124 Sodium cyanide, 23, 57 ethylate, 19, 122 hydroxide, 24, 124 Stannous chloride, 159 Suberic ester, 36 Succino-succinic ester, 16,119 Teraconic ester, 19 Terpineol, 31 Tetra-acetyl ethane, 13 Tetramethylene carboxylic ester, 15 Thiophene, 12 Thoria as catalyst, 98 Tin tetrachloride, 87 Tin tetraphenyl, 19, 50, 82, 120 Toluene, 159 Toluic aldehyde, 154 Triacetyl-benzene, 20 Trimethyl carbinol, 138 Trimethylene, 4 dicarboxylic acid, 109 Triphenyl benzene, 32 carbinol, 139 methane, 156 methyl, 40 Tungstic oxide as catalyst, 98 Vanadium pentoxide, 87,161 Wurtz-Fittig reaction, 2, 104 inxj atkyl syntheses, 64, 145 l ^^ agent, 69, 146
A DL A U DA N D SO.

The Synthetic Use of Metals in Organic Chemistry

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THE S Y N T H E T I C U S E IN O K G A N I C C H E M I S T E Y O F M E T A L S

CONTENTS CHAPTER V. ALUMINIUM, TIN A N D LEAD.

CONTENTS APPENDIX III. P R A C T I C A L WORK: M A G N E S I U M C A L C I U M .

Ann. Ann. Ch. Phys. Ber.

SYNTHETIC USE OF METALS

SODIUM AND POTASSIUM

SYNTHETIC USB OF METALS

SYNTHETIC T T S J E OF METALS USES OF ACETO-ACETIC ESTEB.

SODIUM AND POTASSIUM 2CH3.CH2.COOC2H5 CH3.CH2.CO.CH.COOC2H6 + C2H6OH

SYNTHETIC USE OF METALS

SODIUM AND POTASSIUM

SYNTHETIC USE OF METALS

SODIUM AND POTASSIUM

SYNTHETIC USE OF METALS CHg.CO.CHN'a.COOCHg + CICHa.CO.CH,, = CHa.CO.CH.COOC3H5 + NaCl OHo.COOH,

SYNTHETIC USE OF METALS forms

SODIUM AND POTASSIUM

The use of trimethylene bromide with sodium

SYNTHETIC USE OF METALS

Succino-succinic e s t e r is f o r m e d b y t h e c o n d e n s a t i o n of s u c c i n i c e s t e r i n t h e p r e s e n c e of s o d i u m : 1 S C2H6OOC.CH2.CHo.COOC2H5 , C2HfiOOC.CH2.CH;.COOC2l-I5 * CJELfiOC.CE/ OC

and this on oxidation is converted into 2 : 5-dihydroxyterephthalic ester:

SODIUM AND POTASSIUM CH3.CO.CHBr.COOCoH5

SYNTHETIC USB OP METALS

SODIUM AND POTASSIUM

SYNTHETIC USE OF METALS

SODIUM AND POTASSTUM

SYNTHRTJC USE OF METALS

SODIUM AND POTASSIUM

SYNTHETIC USB OF METALS

SODIUM AND POTAflSTUM

SYNTHETIC USB OF METALS

C.COH CH2.H I +| C.NHo CHO CH o-amino-benzaldeliyde.

Cinnamic aldehyde can be formed from benzal-

SYNTHETIC USE OF METALS CO

CH3.CO.CO.CH, -> CH3.CO.CO.CH3

CH3.CCO.CH3 *I I ' -> CH.CO.CO.Cir,

SODIUM AND POTASSIUM CH3 CH3 / HC I c CH.CH: CH.CO.CH3 +2H3O

> H,C CH2.CH : CH.CO.CH3 | | XH3

CH3 CH3 < > H /X

H2C C.CH: CH.CO.CH3 H 2 C C . C H 3 C H o /3-ionone.

SYNTHETIC USE OF METALS

SODIUM AND POTASSIUM

SYNTHETIC USE OF METALS

SODIUM AND POTASSIUM

SYNTHETIC USJfl OF METALS

34 Ber., 1887, 20, 3386. 35 Ann., 1899, 250, 123. 36

SYNTHETIC USE OF METALS

HC^ C.C1 CH3O.C C.COOH

' -> r ' Ci0.C:C.C00ir C C.C ' C.COoll

SYNTHETIC FSB OF METALS

COPPER AND SILVER

SYNTHETIC USB OF MKTALS

COPPER AND SILVER

SYNTH HTIC USE OP ]\l RTAI/3

J>C1IOII + MgXCl. E'/

> E.CHoOII + Mg-XCl.

X)MgX E.CO.E + E'.Mg.X -> E.CE

> EoR'COlI + M-^

KETONES AND TiflliTIAliY ALCOHOLS l^iOM ACID

K.COC1 + E'.Mg.X -> E.CCl

-> E.CO.14' + MgXOJ

TERTIARY ALCOHOLS FROM ESTERS.

+ E;/.Mg.X -> B < c o R /

> EE7/2COn + MgXCl.