13 - Alcohol, Phynol, Ether (New) PDF
13 - Alcohol, Phynol, Ether (New) PDF
13 - Alcohol, Phynol, Ether (New) PDF
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The prefixes like chloro, bromo et c are added before the name of aromatic hydrocarbons.
In a benzene ring the relative positions of functional groups are 1,2; 1,3 and 1,4 indicated by prefix ortho (o),
meta (m) and para (p) respectively.
Nomenclature of alcoholS
Alcohols are named by replacing e in the name of parent alkane by ol.The position of carbon atom attached to
OH group is specified by a number and its number should be least.
Alcohols with one hydroxy group are known as monohydric alcohols similarly having two-OH groups are
called diols or glycols. Alcohols having three -OH groups are called triols. Names of some alcohols are given
below.
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If a organic compound contains four or more than four hydroxy groups (-OH) they are called polyhydric alcohols.
Alcohols which contain only one hydroxy group are monohydric alcohols , classified as Primary, Secondry and
Tertiary alcohols depending upon whether -OH group is attached to which carbon atom.
Naming of Phenols When -OH group is attached to benzene nucleus it is called phenol.
If benzene ring contains one- OH group it is called monohydric phenol. If benzene ring contains two-OH group
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We have to remember that if -OH group is not attached to benzene ring then it in not phenol but then they are
callled aromatic alcohols. Some aromatic alcohols are as under.
Haloalkanes Preparation
From hydrocarbons Halogens (Cl2, Br2, I2) react with alkanes in the presence of UV light and form
haloalkane
Methane gives a mixture of four products. By fractional distillation we can get pure component.
From alkenes Haloalkenes can be prepared by the additon of halogen acids (HCl, HBr, HI)
Addition of halogen acid takes place in accordance with markownikoffs rule (electronegative group will go to
that carbon atom which is having least hydrogen) For example
However in the presence of peroxides such as Benozoyl peroxide (C6H5 - COO -OOC-C6H5), the addition of
HBr to unsymmetrical olefins (alkenes, alkynes) takes place just opposite to Markowrikoffs rule
=
The above effect is due to presence of peroxide therefore it is called peroxide effect or Kharasch effect.
From alcohols We can get haloalkanes from alcohols due to substitution of the hydroxyl group with a
halogen atom.
CH3 - CH2 - OH + HCl(in ZnCl2) CH3CH2Cl + H2O
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Here anhydrous ZnCl2 is dehydrating agent which will absorb the water molecules. Haloalkanes can also be
obtained by treating the alcohols with NaBr+H2SO4
CH3-CH2-CH2-OH + NaBr + H2SO4 CH3- CH2- CH2- Cl + H2O
1 Propanol + NaHSO 4 React ivit y of halogen acids towards alcohols is as HI > HBr > HCl
HI is more reactive because we will get more and more H+ Reactivity of alcohols towards halogen acid is as
under Tertiary alcohol > Secondry alcohol > Primary alcohol Haloalkenes are also obtained by the reaction of
alcohols with PCl3 or PCl5
(a) 3 CH3 - CH2 - OH + PCl3 3 CH3 - CH2 - Cl + H3PO3
(b) 3 CH3 - CH2 - OH + PCl5 3 CH3 - CH2 - Cl + POCl3 + HCl (P4 + I2)
(c) 3 CH3 - CH2 -CH2- OH + PI3 3 CH3 - CH2 - CH2I + H3PO3
In the above reaction red phorpharo us (P 4) reacts with Iodine to give PI 3 P 4+6I 2 4PI 3
By Darozens procedure we can get pure haloalkanes.In this method alcohols is refluxed with thionyl chloride
(SOCl2) in this presence of a small amount of pyridine pyridine
CH3- CH2 - OH + SOCl2 CH3CH2Cl + SO2 + HCl
Thionyl chloride is preferred because in this process the side products are gases and can be easily expelled
during distillation and we will get chloro alkanes in pure state.
PROPERTIES OF HALOALKANES
Physical Melting point and boiling point of haloalkanes are in the order of RI > RBr > RCl > RF. It is due
to higher molecular mass of Iodoalkanes and also magnitude of vander waals forces of attraction which is
highest. Haloalkanes are polar in nature but they are insoluble in water because they are not able to form
hydrogen bonds . They are soluble in organic solvents. Alkyl fluorides and chlorides are lighter than water but
alkyl bromides and iodides are generally heavier.Order of increasing densities are on as under Fluorides <
Chlorides < Bromide < Iodide
Chemical Haloalkanes are polar in nature
As X is more electronagative, it will attract the bonded electrons toward it self and X will get a slightly negative
charge. Carbon which is bonded with X will get a slightly positive charge (d +).
Presence of partial positive charge (d+) on the carbon atom makes it susceptible to attack by electron rich group
called nucleophiles. When a nucleophil stronger than the halide ion approaches the positively charged carbon
atom of an alkyl halide, the halogen atom along with its bonding electron pair gets displaced and a new bond
with the carbon and the nuclophile is formed.
These reactions are called nucleophilic substitutoin reactions.
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Here from 2 chlorobutane we get 2 Butene which is having two alkyl groups (-CH ) and it is more stable
3
compound. These reactions are known as Dehydrohalogenation. Reaction with metals
Haloalkanes form alkylmagnesium halides (Grignard reagents) when it is treated with Mg in dry ether as
solvent.
R X + Mg R - Mg - X Grignard reagents are highly reactive compounds, they are used for the preparation
of a number of other carbon compounds such as alcohols, aldehydes, ketones and carboxylic acids. Haloalkans
on treatment with sodium metal under go Wurtuz reaction
2 R I + 2Na (dry ether) R- R + 2 NaI
For example
2CH - I + 2Na (dry ether) CH - CH + 2NaI
3
Bromobenzene can also be prepared by above method. For the preparation of Iodobenzene, Iodination is carried
out in the presence of an oxidising agent like HIO or HNO .
3
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PROPERTIES OF HALOARENES
Physical
The boiling points of monohalogen derivatives of benzene follow the order as Idobenzene > Bromobenzene >
Chlorobenzene. The boiling point of Isomeric dihalobenzens are nearly the same but the melting points of these
compounds show a considerable variation. Paraisomers generally have 70 to 100 degrees higher melting point
than the ortho and meta isomers
The higher melting point of paraisomer is due to its symmetry which leads to more close packing of its molecules
in the crystal lattice. Haloarenes are insoluble in water, acids or bases but soluble in organic solvents. Haloarenes
are heavier than water.
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Structure III, IV, V show that C-Cl bond has double bond character. As a result of this the C-X bond in
chlorobezene is shorter and stronger as compared to chloroalkanes. Thus cleaves of C-Cl bond in chlorobenzene
is difficult some chemical reactions are as under
Replacement by - OH group
The reactivity of the haloarenes towards nucleophilic substitution reaciton increases if some electrons with
drawing group such as NO , -CN, -COOH group is attached to the ring.
2
For example
From aldehydes
Aldehyde on reduction gives primary alcohol and ketone gives secondry alcohol. The reducing agents used are
LiAlH , NaBH , Na/C H OH or H with Ni or Pt or Pd as a catalyst
4
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By Oxo process
Alkenes react with CO + H in the presence of [CO(CO) ] as a catalyst and at high temperature and pressure to
2
4 2
give aldehydes. Catalytic hydrogenation of aldehydes gives primary alcohols.
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As oxygen is move electronegative than carbon and hydrogen therefore C-O and O-H bonds in alcohols and
phenols are polar bonds and hence both alcohols and phenols possess a net dipole moment. Due to polar nature,
alcohols and phenols are capable of forming hydrogen bonds.
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In the above reaction H+ ion has attached on oxygen of ethyl alcohol which is having two loan pair of electron
and acting as a base. The order of reactivity of hydrogen halides are as under HI > HBr > Hcl
The order of reactivity of alcohols are as under
Tertiary alcohol > Secondry alcohol > Primary
alcohol Reaction with phosphorous trihalide and thionyl chloride Alcohols are converted to alkyl halide
with Px3 thionyl chlonide reacts with alcohol to give chloroalkenes.
3C2H5OH + PX3 3C2H5X + H3PO3 (X=Cl,Br)
CH3-CH2OH + SOCl2 CH3CH2Cl + SO2 + HCl
Reaction with H2SO4
When excess of alcohol is treated with H2SO4 aat 413K, ether is obtained.
C2H5OH + HO-C2H5 C2H5-O-C2H5+H2O
When alcohol is treated with H2SO4 at 443K alkene is obtained.
Oxidation of alcohol
Alcohols under go oxidaiton with oxidising agents like chromium trioxide (CrO 3), KMnO4, K2Cr2O7, HNO3
Primary alcohol give aldehyde which on further oxidation gives an acid.
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Tertiary alcohols are not oxidised with mild oxidising agents. When oxidisation is carried out under acidic
conditions ,tertiary alcohols first undergo dehydration to form alkene. The alkene formed is then oxidised to
ketone which is finally oxidised to carboxylic acid with lesser number of carbon atoms
than the starting alcohol.
Dehydrogenation Alcohols are oxidised by passing alcohol vapours over heated copper at 573K
CuCH3 - CH2 - OH >
CH3- CHO + H2 573 K
Primary alcohol aldehyde
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Due to above resonating structure, H will go out taking a positive charge and this is the reason that phenol is
acidic in nature.
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Reaction with bromine Phenol react with Bromine in the presence of less polar solvent such as CS2 or CCl4 at
low temperature and give monobromophenol.
Nitration
Phenol react with dilute HNO3 at low temperature
(293K) to give a mixture of ortho and para
nitrophenol.
With conc HNO3 and in the presence of H2SO4 phenol gives 2,4,6, trinitrophenol.( picric acid)
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Sulphonation
Phenols are sulphonated with conc H2SO4
Kolbes reactions
When sodium phenoxide is heated with CO2 at 400K and at 4-7 atomospheric pressure, sodium salicylate is
formed.This on acidfication yields salicylic acid.
Salicylic acid is the st arting material for the manufacture of 2 acetoxybenzoic acid (aspirin).
Reimer-Tiemann reaction
Treatment of phenol with chloroform in the presence of aqueous alkali at 340 K result in the formation of
o-Hydroxy benzaldehyde and p hydroxy benzaldehyde
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If in the above reaction CCl4 is used in place of chloroform ( CHCl3 ), Salicylic acid is obtained as the major
product.
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Phenols are acidic in nature. They turn blue litmus red and react with alkali metal and alkalies to form their
salts.
However phenol is weaker acid than carboxylic acid. Therefore like carboxylic acid it does not react with
Na2CO3 and NaHCO3.
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From propanol
reaction occurs as follows
CaOCl2 + H2O Ca(OH)2 + Cl2
Nitration
Chloroform reacts with conc. HNO3 to form nitro chloroform or chloropicrin.
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( Ethylene glycol )
Preparation
In lab, it is prepared by the action of alkaline solution of KMnO4 on ethene.''
Commercially it is prepared by the oxidation of ethene to epoxy-ethane and then epoxy ethane is hydrolysed
by steam at 473K.
Ethylene glycol on oxidaton with dil HNO3 or alkaline KMnO4 it gives oxalic acid
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Glycerol occurs in nature in oils and fats.Oils and fats are triester of glycerol with higher fatty acids. These
triesters are called glycerides. Thus oils and fats are glycerides. The higher fatty acid may be palmitic and
C15H31COOH or srearic acid (C17H35COOH) a glyceride may be represented by general formula as
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Nitration.
Glycerol reacts with cone HNO3 in the presence of cone H2SO4 at 283-198 K to form glycerol trimate.
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SOLVED PROBLEMS
Q.1
(a)
Ans.
(b) O2NCH2CH2OH
Common name
(b)
(c)
O2NCH2CH2OH
CH3CH(NO2)CH2CH3
Q.2
(a) T. N. T.
CH3CH(NO2)CH2CH3
IUPAC name
(a)
Ans.
(c)
(c)
p nitrotoluene
(2, 4, 6 Trinitrophenol)
(c) p nitrlotoluene
(d) Azoxybenzene
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For facilitating nitration, aromatic amines are converted to amide which after nitration are hydrolyzed back
to amino group.
Q.5
Ans.
Explain what happens when aniline reacts with a mixture of sulphuric acid and nitric acid?
A mixture of conc. H2SO4 and conc. HNO3 acts as a nitrating agent and nitroaniline is formed.
Q.6
Ans.
Q.7
Explain why does nitrobenzene on nitration with nitric acid and sulphuric acid form only m
dinitrobezene?
The NO2 group strongly deactivates the benzene ring towards electrphilic substitution and thus we get m
dinitrobenzene as the only product.
Ans.
Q.8
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Q.9
Ans.
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Q.10 Explain why is nucleophilic substitution of p nitrochlorobenzene easier than that of chlorobenzene?
Ans. The presence of nitro group facilitates nucleophilic substitution in, otherwise unreactive aromatic halides,
by stabilizing the intermediate carbanion.
Q.11
Ans.
Q.14 How is it that a ketone reacts with Grignard reagent to form a tertiary alcohol but in the reaction of
a nitrile with Grignard reagent, a ketone is formed?
Ans. In Grignards reagents (RMgX) the C Mg bond is highly polar and carbon is electronegative relative to
electropositive magnesium.
Tertiary Alcohols are produced by the reaction of Grignards reagents with Ketones.
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In reaction of Nitrile with Grignards reagent, the initially formed imine derivative is hydrolyzed to form a
ketone. This is reaction offer a new route to obtain ketones as esters always react further with Grignards
reagent to form tertiary alcohols.
Q.16 How does an isocyanide react with an electrophile and a nucleophile at the same isocyanide carbon?
Give an example.
Ans. In an isocyanide, first an electrophile and then a ncleophile add at the carbon to form a species which
usually undergoes further
transformations.
RN+ C + E+ RN+ CE Nu
RN C (Nu) E
Q.17 How will you convert benzonitrile to acetophenone (C6H5COCH3)?
Ans.
Q.18 Draw structures for the following compounds.
(a) N isopropylaniline
(b) p toluidien
Ans.
(c)
t butylamine.
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Q.21 How will you convert an alkyl halide into a primary amine having one more carbon than the alkyl
halide used?
Ans. By Action With Alc. KCN
RX + Alc. KCN RCN [H] RCH2NH2
Q.22 How can a carboxylic acid be converted to an amine having one carbon atom less than the carboxylic
acid used?
Ans. By Hofmann Bromadide Reaciton
RCOOH + NH3 RCONH2
RCONH4 + Br2 + 4NaOH
RNH2 + 2NaBr + Na2CO3 + 2H2O
Q.23 Explain the observed Kb order : Et2NH > Et3N > EtNH2, in aqueous solution.
Ans. Et2NH
> E3N
> EtNH2
10 104
> 5.6 104 > 5.1 104
The Kb value of Et2NH
> Et3N and E2NH2.
It is because, in solution ammonium cations are stabilized not only by electron releasing effect of the alkyl
groups but also by solvation through their hydrogen bond donation to the solvent. It is evident that due to
the number of hydrogen atoms present on the nitrogen and thereby similar number of hydrogen bonds, the
stability of aliphatic ammonium cations and also the basic strength will be in the order primary > secondary
> tertiary amine which is opposite to the electron releasing effect based basic strength (i.e. tertiary > secondary
> primary). There could also be some steric repulsion to H bonding in cations derived from tertiary
amines. Due to a combination of all these effects (i.e., electron releasing,
H bonding, steric) the stability of carbonium cation in solution and thereby the resulting basic strength
order of aliphatic amines is
secondary
>
tertiary
>
primary.
It explains the observed Kb values.
Q.24 What will be the basic strength order of EtNH2, Et2NH, Et3N in gas phase? Explain.
Ans. In gas phase the trend is as expected i.e., tertiary amine > secondary amine > primary amine > ammonia.
It is because, the solvent effect is missing in gas phase.
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Q.31 How do aliphatic primary and secondary amines react with nitrous acid?
Ans.
If however, the temperature rises above 273 K, the initially formed fiazonium salt decomposes to form
phenol.
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Q.32 Explain how does the presence or absence of hydrogen on N of amines affect the modes of their
reactions with nitrous acid?
Ans. When N is attached with 2 hydrogen atoms (i.e., a primary amine) then on reaction with HONO we get an
alcohol and nitrogen gas.
If N is attached with 1 hydrogen atom (i.e., a secondary amine), then on reaction with HONO we get an
oily compound (i.e., Nitrosoamine).
If N is not attached with hydrogen (i.e., a tertiary amine) then protonation will occur to form a salt soluble
in water.
Q.33 How will you prepare ethyl amine from acetaldehyde?
Ans. CH3CHO (Acetaldehyde) LiAlH4 CH3CH2OH + NH3 Al2O3 / heat CH3CH2NH2
(Ethylamine) + H2O
Q.34 Amino group is o, p directing for aromatic electrophilic substitution. Why does aniline on nitration
gives a substantial amount of m nitroaniline?
Ans. It is due to protonation of aniline to form C6H5N+H3 which is met directing and deactivating.
Q.35 Why does bromination of aniline, even under very mind conditions give 2, 3, 5 tribromoaniline
instantaneously?
Ans.
Yes aniline gets brominated instantaneously even in the absence of a catalyst and even under mild conditions.
It is because NH2 group is electron releasing and so it increases reactivity towards electrophilic substitutions.
Because of this aniline when reacted with bromine gives 2, 4 ,6 tribromoaniline (i.e., all the three o , p
positions get brommiated).
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In amide
group is attached to NH2 which is electron withdrawing group and so the acidic character of
amide increases where as in amine there is alkyl group which is electron releasing and makes it more basic
or less acidic.
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EXERCISE - I
UNSOLVED PROBLEMS
Q.1
Write the structure of allyl alcohol. Also give its IUPAC name.
Q.2
Q.3
Q.4
Draw the structure of sec-butly alcohol and give its IUPAC name.
Q.5
Write the structure of tert-butyl alcohol and give its IUPAC name.
Q.6
Write the structure of isopropyl alcohol and give its IUPAC name.
Q.7
What happens when acetyl chloride reacts with phenol ? Write the chemical equation.
Q.8
Q.9
Q.10
Al2O3
633 K
?+?
Q.11
Q.12
Arrange the following set of compounds in order of their increasing boiling points : Pentan-1-ol, butan-1ol, butan-2-ol, ethanol, propan-1-ol, methanol.
Q.13
Arrange the following compounds in increasing order their acid strength : Propane-1-ol, 2,4,6-trinitrophenol,
3-nitrophenol, 3,5-dinitrophenol, phenol, 4-methylphenol.
Q.14
Arrange the following alcohols in order of increasing reactivity towards Lucas reagent : 2-butanol, 1butanol, 2-methyl-2-propanol.
Q.15
Alcohols react with halogen acids of phosphorus halides to form haloalkanes but phenol does not form
halobenzenes. Explain
Q.16
Q.17
Q.18
Give chemical tests to distinguish between compounds in each of the following pairs.
(i) Phenol and benzyl alcohol
(ii) Butan-2-ol and 2-Methylpropan-2-ol.
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OH
(i)
and
CH2OH
Describe the mechanism of formation of diethyl ether from ethanol in the presence of concentrated sulphuric
acid.
Q.21
A unique method of addition of water to alkenes in a way opposite to the Markownikov's rule was developed
by H.C. Brown in 1959. In this method, alcohol is obtained in excellent yield. Name the method. How can
you use this method to obtain propan-1-ol from propane in excellent yield ?
Q.22
Give the major products that are formed by heating each of the following ethers with HI.
Q.23
Give the structures and IUPAC names of the products experted from the following reactions
(a) Catalytic reduction of butanal.
(b) Hydration of propane in the presence of dilute sulphuric acid.
(c) Reaction of propene with methyl magnesium bromid followed by hydrolysis.
Q.24
Write the structures of the major products expected from the following reactions :
(a) Mononitration of 3-methylphenol
(b) Dinitration of 3-methylphenol.
(c) Mononitration of phenylmethanoate.
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EXERCISE - II
BOARD PROBLEMS
Q.1
Explain why phenols do not undergo substitution of the OH group like alcohols ?
[CBSE 2001]
Q.2
[CBSE 2006]
Q.3
[CBSE 2008]
Q.4
Alcohols react both as nucleophiles as well as electrophiles. Write one reaction of each type and describe its
mechanism.
[CBSE 2008]
Q.5
[CBSE 2008]
Q.6
Q.7
[CBSE 2009]
[CBSE 2011]
[CBSE 2011]
Q.8
Q.9
Q.10
(a)
(b)
(i)
COOH
(ii)
(iii)
C6H5CHOO
CH2
SOCl2
heat
H2NCONHNH2
CHO
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[CBSE 2011]
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[CBSE 2011]
[CBSE 2011]
Q.13
Why is the reactivity of al lte three classes of alcohols with conc. HCl and ZnCl2 (Lucas reagent) different
?
[NCERT Example]
Q.14
Give chemical tests to distinguish between compound in each of the following pairs :
(i)
Phenol and benzyl alcohol
(ii)
Butan -2-ol and 2 Methylpropan-2-ol
[CBSE Sample Paper]
Q.15
You are given benzene, conc. H2SO4 and NaOH. Write the equations for the preparation of phenol using
these reagents.
[CBSE 2011]
Q.16
Q.17
H+
443K
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[CBSE 2013]
[CBSE 2013]