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Key Concepts Organic
Key Concepts Organic
1. Inductive effect
1.7 Resonating structure with more number of covalent bond, non polar with complete octet are more stable.
1.8 Stability order by resonance:
Extended conjugation > cross conjugation > less conjugation
3. Mesomeric effect
Order of +M effect : (Tentative order)
O– > NR2 > NH2 > OH > NH – C – R > O – C – R > Ph > CH ≡ CH > F > Cl > Br > I
O O
Order of –M effect :
NO2 > CN > C – H > – C – R > – C – OH > – C – OR > –C – NH2
O O O O O
4. Hyper conjugation
Due to presence of α − H in carbocation or π electron system, σ bond delocalisation of C–H bond
+ H effect → alkyl group ∝ no. of αH
– H effect → –CX3 group (decrease e– density)
or
G G
G G G Acidic strength Basic strength
Carbonation Free Carboanion (ka) (kb)
stability radical stability
Steric inhibition of resonance caused by ortho group affect acidic strength, basic strength, bond length, etc.
properties.
••
7. Aromatic Compound
Essential conditions
→ 4n + 2π electron
→ Cyclic delocalization
→ Planar molecule
Stability order : for similar unsaturated system
Aromatic > Non Aromatic > Anti aromatic
(4nπ electron)
Properties of Intermediate
Carbocation Free radical Carbanion Carbene
⊕
Θ
•
8. Carbocation
Positively charged 'C' atom as reaction intermediate is called carbocation. Generally it contains only six
electrons in three bonds.
8.1 Structure and Hybridisation:
Classical carbocation (carbenium ion) are sp2 hybridised and of planar structure.
Unhybridised vacant 'p' orbital lies below and above the plane.
+ C
120º
sp2
9. Carbanion
A carbon intermediate which contain three bond pair and a negative charge on it, is called carbanion.
Ex: ΘCH
3, Methyl carbanion
sp2
C
C
Unhybridised pure
‘p’ orbital
C
120º
C C
11. Carbene
Carbenes are neutral species containing a carbon atom with two bonds and two non-bonded electrons:
i.e. –C–
(carbene)
11.1 Types of Carbene: Carbenes are classified into two classes.
Cl –
OH Cl
Cl C–H Cl C–
Cl –H2O Cl
(v) CCl4 + Li-R → R–Cl + Li-CCl3
12. Benzyne
Benzyne may be defined as a neutral highly reactive intermediate in which the aromatic character is not
disturbed.
Benzyne can be represented as
or
(ii) Side way poor overlapping of sp2 orbitals forms π bonds outside the ring and out of the plane of π
system of the ring.
12.2 Generation of Benzyne:
(i) From chlorobenzene
(ii) From chloro bromo benzene
O
C–OΘ
(iii) From:
+
N2
12.3 Reactions of Benzyne :
(i) Benzynes are too unstable to be isolated and react with any nucleophile present in the solution.
NH2 NH2 O–CH3 O–CH3
– –
NH2 NH2
H–NH2
(a) (b) NaNH2
NH3
NH2
CH3 CH3
OH
(c) NaOH
H–OH
13. Nitrene
Nitrene may be defined as the electron deficient species in which nitrogen has a sextet of electrons. Nitrenes
are analogues of carbene also known as unidogen, azene, unene i.e.
·· ··
H – N· · or R – N· · are nitrene.
13.1 Generation of Nitrene:
ν
(i) R – N3 h
··
→ N2 + R – N· ·
O O
ν
(ii) R – C – N3 h
··
→ N2 + R – C – N· ·
ν
(iii) H – N = C = O h
··
→ CO + H – N· ·
13.2 Reactions of Nitrene:
(i) Addition to Olefin:
(ii) Rearrangement reaction:
(a) Hofmann rearrangement
(b) Curtius rearrangement
(iii) Insertion Reaction
(iv) Recombination of Two Nitrenes
Addition by
Molecular attack
Addition Addition by
Reaction Anionic attack
Addition by
free radical attack
Addition by
Carbene attack
14.1.2 Addition by cationic attack
(Electrophilic addition)
14.1.3 Addition by free radical attack
14.1.4 Addition by anionic attack
(Nucleophilic addition)
14.1.5 Addition by carbene attack
14.1.6 Addition by nitrene attack
14.1.7 Addition by molecular attack
14.1.8 Classification based on fashion of addition
Addition Reaction
Addition Addition on
Via cyclic machanism the surface of the
catalyst
Cis Addition: If the group AB adds to – C = C < in such a way that both of A and B attack from same side
H Cl H Cl
HCl
CH2 – CH–CH=CH2 + CH2–CH=CH–CH2
H H H H
H2
CH2 – CH–CH=CH2 + CH2–CH=CH–CH2
Catalyst
14.2 Substitution reaction
Compound pKa
+
CH 3 C ≡ N H – 10.1
HI –10
HBr –9
+O H
|| –8
CH3CH
HCl –7
+
CH 3 S H 2 – 6.8
Compound pKa
H2SO4 –5
H
CH 3CH 2 OCH 2 CH 3 – 3.6
+
H
CH 3CH 2 OH –2.4
+
H3O+ –1.7
HNO3 – 1.3
CH3SO3H –1.2
+OH
||
0.0
CH 3 CNH 2
O
||
0.2
F3 CCOH
O 0.64
||
Cl 3 CCOH
+ 0.79
N–OH
+
O2N NH3 1.0
N
1.0
N
+
H
O
||
1.3
Cl 2 CHCOH
HSO −4 2.0
H3PO4 2.1
O
||
2.7
FCH 2 COH
O
||
2.8
ClCH 2 COH
O
||
2.9
BrCH 2 COH
O
||
3.2
ICH 2 COH
Compound pKa
HF 3.2
HNO2 3.4
O
O2N COH 3.4
O
||
3.8
HCOH
+
Br NH3 3.9
O
Br COH 4.0
O
COH 4.2
O
CH3 COH 4.3
O
CH3O COH 4.5
4.6
+
NH3
O
||
4.8
CH 3 COH
4.9
N+
H
+
CH3 NH3 5.1
N+ 5.2
H
+
CH3O NH3 5.3
+
CH 3 C = N HCH 3
5.5
|
CH 3
O O
|| ||
5.9
CH 3 CCH 2 CH
Compound pKa
H2CO3 6.4
HN
+
NH 6.8
H2S 7.0
O2N OH 7.1
H 2 PO −4 7.2
SH 7.8
N 8.0
+
H H
+
H2 N N H3 8.1
O 8.2
||
CH 3COOH
CH3CH2NO2 8.6
O O
|| || 8.9
CH 3CCH 2 CCH 3
HC ≡ N 9.1
O
9.3
+ N
H H
Cl OH 9.4
+
HOCH 2 CH 2 N H 3 9.5
O
+
|| 9.8
H 3 N CH 2 CO −
OH 10.0
CH3 OH 10.2
HCO 3− 10.2
CH3NO2 10.2
Compound pKa
H2N OH 10.3
CH3CH2SH 10.5
O O
|| ||
10.7
CH 3 CCH 2 COEt
10.7
+
NH3
+
CH 3 CH 2 N H 3 10.7
11.1
+ N
H H
CF3CH2OH 12.4
O O
|| || 13.3
EtOCCH 2 COEt
HC ≡ CCH2OH 13.5
O
||
13.7
H 2 NCNH 2
CH 3
+|
CH 3 NCH 2 CH 2 OH 13.9
|
CH 3
N NH 14.4
CH3OH 15.5
H2O 15.7
CH3CH2OH 16.0
O
||
16
CH 3CNH 2
Compound pKa
O
CCH3 16.0
~ 17
N
H
O 17
||
CH 3CH
(CH3)3COH 18
O
||
20
CH 3CCH 3
O
||
CH 3COEt 24.5
HC ≡ CH 25
CH3C ≡ N 25
O
||
CH 3CN (CH 3 ) 2 30
ALKANE
1. General Introduction :
• These are the hydrocarbons in which Carbon - Carbon contains single bond (Saturated hydrocarbon).
• These are also called as ‘Paraffin’ (Parum + Affinis i.e. less reactive).
• In alkane if chiral carbon or unsymmetrical carbon is present, then it shows optical isomerism.
• General reagents such as dil. and conc. HCl, dil. and conc. H2SO4, dil. and conc. HNO3, acidic and basic
KMnO4 and K2Cr2O7 usually do not react with alkane.
• Number of bond angle in methane are six, while in ethane are twelve.
H H H
H 4
3 1 2
1 6 5
2 5
3 6
2
H 1 3
4 5 4
H 6 H H H H
Methane Ethane
• C–C bond energy is 84 kcal/ mole while C–H bond energy is 98 kcal /mole.
• First three member methane, ethane and propane do not exhibit any isomerism, while butane and
pentane shows only chain isomerism.
H
|
H– C –H CH3–CH3 CH3–CH2–CH3
|
H
n-Butane Iso-butane
CH3
|
CH3–CH2–CH2–CH2–CH3 CH3–CH –CH2–CH3 CH3–C–CH3
| |
CH3 CH3
CH3
CH3–CH2–CH2–CH2–CH2–CH3 CH3–CH2–CH–CH2–CH3 CH3–CH–CH2–CH3
CH3 CH3
CH3–CH–CH2–CH2–CH3 CH3–CH–CH–CH3
CH3 CH3 CH3
• The molecules of alkanes are angular, so carbon chains in these molecules are zig- zag type (not
straight) which may be branched or unbranched as shown below.
(Unbranched) (Branched) (Branched)
2. Physical Properties
• Alkanes are colourless, odourless and tasteless.
• Physical state:
C1–→ C4 Gaseous state
• Graphical representation:
[Irregular or zig-zag graph]
B.P. [regular graph] M.P.
Halogenation
R–X
X2/hν or UV light
(F2 > Cl2> Br2 > I2)
O
Nitration
R–N
HNO3/400ºC
O
Sulphonation
R–SO3H
H2S2O7
Reed reaction
R–SO2Cl
SO2 + Cl2/hν
R–H
Isomerisation
or Branched alkane
R–R AlCl3/HCl
Pyrolysis
Alkenes + CH4 or C2H6
500–700ºC
Cr or Mo or V oxide
Aromatic compound
+Al2O3/500ºC
CH2N2/∆
Higher alkane
step up reaction
O2
CO2 + H2O
combustion
O2 / Cu R–CH2OH
Catalytic MoO
R–CHO
Oxidation (AcO)2 Mn
R–COOH
4. Preparation methods of Alkane
NaOH + CaO/∆
RCOOH
Soda lime
Kolbe's electrolysis
RCOONa
Na / ether
R–X
Wurtz reaction
Zn / Ether
R–X
Frankland's reaction
R–H
Zn/HCl or LiAlH4 or Red P/HI
R–X or
Reduction
R–R
HOH or ROH
R–Mg–X
or NH3 or RNH 2
HI / red P / 140ºC
RCOOH or ROH or R–C–R or RCHO
Reduction
O
Zn–Hg/HCl
R–C–R or R–C–H
Clemmenson's reduction
O O
H2N–NH2 / KOH
R–C=O or R–C=O
Wolff Kishner reduction
R H
200–300ºC, H2/Ni
R–C≡CH or R–CH=CH2
Sabatier Senderen's reaction
5. Special Points
• LPG is called as liquefied petroleum gas or kitchen gas which is a mixture of propane and butane.
• A mixture of n-butane and isobutane is called as Calore gas.
• Methane reacts with ozone to make formaldehyde.
• When methane is heated (at about 1500º C) in presence of nickel it makes acetylene.
• Sabatier Senderen's reaction:
Ni/200ºC
CO + 3H2 CH4 + H2O
Ni/200ºC
CO2 + 3H2 CH4 + 2H2O
ALKENE
1. General Introduction :
• These are the acyclic hydrocarbons in which unsaturation (C=C) is present.
• These are also known as olefins (i.e. oleum, oil + fines, forming) because lower alkene react with
halogens to form oily substances.
• General formula is CnH2n (n = 2, 3, 4, 5..........).
(iii) Functional isomers (ring chain isomerism) → CH3–CH2–CH=CH2 and CH2– CH2
| |
CH2– CH2
(iv) Geometrical isomers → CH3–C–H and CH3–C–H
|| ||
CH3–C–H H–C–CH3
(cis -2-butene) (trans-2-butene)
*
(v) Optical isomerism → CH3CH2–CH–CH=CH2
CH3
NOTE: Cumulated polyene can exhibit geometrical as well as optical isomerism.
CH3 H
C=C=C
H CH3
This molecule is simplest example of cumulated polyene which can exhibit optical isomerism because
this is a chiral molecule. Similarly suitably substituted polyene containing odd no. of double bond can
exhibit geometrical isomerism as this is a planar molecule.
CH3 CH3
C=C=C=C
H H
a
• Cumulated polyene having even no. of double bonds which has = C system at the both end can
b
exhibit optical isomerism but cannot exhibit geometrical isomerism.
a
• Cumulated polyene having odd no. double bonds which have = C system at both end can exhibit
b
geometrical isomerism but cannot exhibit optical isomerism.
2. Physical Properties
• Physical state:
Molecular weight
Boiling and Melting point ∝
No. of branches
Name Formula B.P.(ºC) M.P.(ºC)
Ethylene CH2 =CH2 –102 –169
Propylene CH3 –CH=CH2 –48 –185
1-Butene CH3 CH2 –CH=CH2 –6.5 –171
cis-2-Butene cis–CH3 –CH=CH–CH3 4 –139
trans-2-Butene trans–CH3 –CH=CH–CH3 1 –106
Isobutylene (CH3 )2 C=CH2 –7 –141
• The melting points of cis isomers are lower than trans isomers because isomer is less symmetrical than
trans. Thus trans packs more tightly in the crystal lattice and hence has a higher melting point.
• The boiling points of cis isomers are higher than trans isomers because cis–alkenes has greater polarity
(Dipole moment) than trans one.
HBr/Peroxide X
R–CH2–CH2Br
X2
R–CH–CH2X
HOCl X
R–CH–CH2Cl
OH
dil. H2SO4
R–CH–CH3
OH
(i) (AcO)2Hg (ii) H2O
R–CH2–CH2–OH
(iii) NaBH4 H2O/H⊕
R–CH2CH3
Hydrolysis
BH3
(RCH2CH2)3B
Hydroboration
H2O2/OH
H2/Ni R–CH2CH2–OH
R–CH2–CH3 Oxidation
200–300ºC
OsO4/H3O⊕
R–CH–––CH2
OH OH
OH
Baeyer reagent
R–CH=CH2 R–CH–––CH2
1% alkaline KMnO4
OH OH
OH
per acid H3O⊕
R–CH–––CH2 R–CH–––CH2
Prelischave's reaction
O OH OH
OH
O3 + H2O + Zn
R–CHO + HCHO
ozonolysis
O3 + H2O
RCOOH + HCOOH
ozonolysis
Strong oxidant
RCOOH + CO2 + H2O
KMnO4/H⊕
O2
CO2 + H2O
combustion
Cl2
Allylic substitution product (Cl–H2C–CH=CH2)
500ºC
NBS/∆
Allylic substitution product (Br–H2C–CH=CH2)
Al2(SO4)3
Isomerisation
200–300ºC
alc. KOH
R–CH2–CH2–X
–HX
NaNH2
R–CH2–CH2–X
–HX
Zn dust
R–CH–CH2
–X2 R–CH=CH2
X X or CnH2n
H2
R–C≡CH
Pd + BaSO4/CaCO3
Kolbe's electrolysis
R–CH–COOK
R–CH–COOK
R R
⊕ ∆
N OH
R CH2–CH2–R Pyrolysis
∆
R–C–O–CH2–CH2–R
Pyrolysis
O
R
R–N O ∆
Pyrolysis
CH2–CH2–R
4. Special Points
• Ethene is used in the artificial ripening of fruits.
• Water solution of sodium or potassium salt of succinic acid on electrolysis gives ethene at anode.
• Ethene react with sulphur monochloride (S2Cl2) to form poisonous mustard gas (β, β-dichloro diethyl
sulphide). Gas is used as a war gas. (Used in 1st world war)
CH2N2/∆ (Cyclopropane)
N2O3
O2N–CH2–CH2–N=O (Ethylene nitrosite)
N2O4
CH2=CH2 O2N–CH2–CH2–NO2 (Ethylene nitrosate)
CH3COCl/AlCl3
CH3–C–CH2–CH2–Cl
CH3 O
CH3–C–Cl/AlCl3
CH3
CH3
CH3–C–CH2–CH2–Cl
CH3
CH3–O–CH2–Cl/AlCl3
CH3–O–CH2–CH2–CH2–Cl
CO + H2
CH3–CH2–CHO
CO + H2O
CH3–CH2–COOH
ALKYNE
1. General Introduction :
• These are the acyclic hydrocarbons in which unsaturation (C≡C) is present.
• Hybridisation state of triple bonded carbon in alkyne is sp.
• Geometry of unsaturated carbon is linear in alkynes.
• Bond angle in alkyne on sp carbon atom is 180º.
• Their general formula is CnH2n–2 (n = 2, 3, 4, 5 ..........................)
• C–C triple bond length is 1.20 Å.
• C–H bond length is 1.08 Å.
• C–C triple bond energy is 200 kcal/mol.
• C–H bond energy is 121 kcal/mol.
• Alkyne shows chain, position and functional isomerism. They are functional isomer with cycloalkene
and alkadiene.
ex.: Isomers of C4H6 are:
CH3–C≡C–CH3 CH3–CH2–C≡CH CH3–CH=C=CH2 CH2=CH–CH=CH2
CH3 CH2
CH3
1-Methyl cyclopropene 3-Methyl cyclopropene Methylidene cyclopropane Bicyclobutane
2. Physical Properties
• Alkynes are colourless, odourless and tasteless.
• Lower alkynes are partially soluble in H2O. (It is due to its polarizability).
• Higher alkynes are insoluble in water due to more % of covalent character.
• Completely soluble in organic solvents.
• Melting point and boiling point increases with molecular mass and decreases with number of
branches.
• Physical state:
C2–C4 → Gaseous C5–C11 → Liquids C12 & above → Solids
Molecular weight
Boiling point and Melting point ∝
No. of branches
Name Formula B.P. (ºC) M.P. (ºC)
Acetylene HC ≡ CH –75 –82
Propyne CH3 –C≡CH –23 –101.5
1-Butyne CH3 CH2 –C≡CH 9 –122
2-Butyne CH3 –C≡C–CH2 27 –24
3. Chemical properties of alkyne
Br
HBr
R–C–CH3
Br
HBr/Peroxide
R–CH–CH2–Br
Br
Cl Cl
Cl2
R–C––CH
Cl Cl
HOCl Cl
R–C–CH
Cl
O
BH3/H2O2/OH
R–CH2–CHO
H2/Ni
R–CH2–CH3
H2/Pd–BaSO4
R–CH=CH2
CH3OH OCH3
R–CH (Methylal)
(BF3–HgO) OCH3
HCN/Ba(CN)2 CN
R–C≡CH R–CH2–CH
CN
CH3COOH/Hg+2 OCOCH3
R–CH2–CH
OCOCH3
NaNH2
R–C≡C–Na
AgNO3 + NH4OH
R–C≡C–Ag
(Tollen's Reagent)
Cu2Cl2+ NH4OH
R–C≡C–Cu
Baeyer Reagent
R–C–CHO
O
+2
H2O/Hg
R–C–CH3
O
O3/H2O/Zn
R–C–C–H
ozonolysis
O O
KMnO4/H⊕
R–COOH + CO2 + H2O
Strong oxidant
Combustion
CO2 + H2O
4. Preparation methods of Alkyne
alc KOH or NaNH2
CH2–CH2
Br Br
Br Br Zn dust HC≡CH
CH–CH or
Br Br CH3–C≡C–R
Zn dust
Br–CH=CH–Br
HC–COONa
(i) Na
CH3–C≡CH
(ii) R–X
(i) CH3MgI
CH3–C≡CH
(ii) R–X
5. Special Points
• Ethyne is used in oxy-acetylene flame (2800-3200ºC) which is used for cutting and welding of metal.
• Ethyne is used in carbide lamps for lightning (is an illuminating agent in hawker's lamp)
• When electric arc is passed in atmosphere of hydrogen between carbon electrode, ethyne is formed
(Berthelot Method).
• Mixture of ethyne and nitrogen in electric spark converted into HCN.
• Ethyne burns with sooty flame due to presence of high % of carbon.
• Acetylene is used in artificial ripening of fruits.
• Pure acetylene (NARCYLENE) is odourless and impure acetylene has odour like garlic. It is due to
impurities of Arsine (AsH3) & Phosphine (PH3).
• Acetylene & 1- alkyne are acidic in nature. It is due to greater electronegativity of sp hybridised
carbon.
• Acetylene has two acidic hydrogen atoms. It can neutralise two equivalents of base at the same time.
So it is also called as dibasic acid. But the base should be very stronger as NH2 or CH3etc.
• Some other reactions of acetylene are.
Cl AsCl2
AsCl3
HC=CH (Lewisite)
CO + H2
CH2=CH–CHO
Hydroformylation
CO + ROH
CH2=CH–COOR
CO + H2O
CH2=CH–COOH
(Hydrocarboxylation)
H2O/Hg+2
HC≡CH CH3–CHO
Kuchrov's reaction
Dimerisation
CH2=CH–C≡CH
Cu2Cl2 + NH4Cl/∆
Trimerisation
Red hot Fe tube
Tetramerisation
Ni(CN)2
OH SH SH
1. Preparation methods of benzene :
NaOH + CaO / ∆
COOH Sodalime
H2O / ∆
SO3H
H 2O
Mg – Br
Zn Benzene
OH
reduction
Cr2O3 + Al2O3
500ºC
CH2
(i) CH2 = CH2
HC
(ii) Platforming
HC
CH2
2. Chemical properties of benzene
Cl2/AlCl3
Cl
Halogenation
HNO3+ H2SO4
NO2
Nitration
H2SO4
SO3H
Sulphonation
CH3CH2–Cl/AlCl3
CH2CH3
Friedal-Craft alkylation
O
O
CH3–C–Cl/AlCl3
C–CH3
Friedal-Craft acetylation
(CO + HCl)/AlCl3
CHO
Gattermann-Koch reaction
O3/H2O/Zn CHO
Ozonolysis (Glyoxal)
CHO
Cl Cl
Cl2/sunlight
Cl Cl (BHC or 666)
Benzene Cl Cl
H2/Pd or Pt or Ni
H.T.P.
Na/liq. NH3
Birch reduction
V2O5/300ºC
OH (Phenol)
Oxidation
O O
V2O5/400º-500ºC OH – H2O
O (maleic anhydride)
Oxidation OH
O O
Combustion
6CO2 + 3H2O
3. Aromaticity
Benzene and other organic compounds which resemble benzene in certain characteristics properties are called
aromatic compounds. These characteristic properties constitute what is commonly known as aromatic
character or Aromaticity.
Such Important properties are summarised below.
(i) Unusual stability
(ii) Substitution rather than addition reaction.
(iii) Resistant to oxidation
(iv) C=C bond length value
(v) Ring current.
Note: According to modern concepts aromaticity can now be defined as the ability to sustain an induced
current.
In general aromatic compounds are those which are
(i) Cyclic (ii) Planar
(iii) Containing a total of (4n + 2) π electrons where n may be 0, 1, 2, 3, ...........
Third condition is well known as Huckel rule.
ex. :
(i) (ii)
4n + 2 = 6 4n + 2 = 10
n=1 n=2
∴ Aromatic ∴ Aromatic
(iii) (iv)
4n + 2 = 10 4n + 2 = 10
n=3 n = 3/2
∴ aromatic ∴ Not aromatic
H H sp3
sp2
⊕
(v) (vi)
(vii) (viii)
4n + 2 = 0 4n + 2 = 2
n = 1/2 n=0 4n + 2 = 2 4n + 2 = 4
∴ Anti aromatic It is not aromatic because it n=0 n = 1/2
is not planar and does not
∴ Aromatic ∴ Anti aromatic
have cyclic resonance
(Because it is planar)
H H sp3
(v) (vi)
4n + 2 = 0 4n + 2 = 2 O
n = 1/2 n=0
⊕
∴ Anti aromatic It should be aromatic but is (ix) (x)
not, because it is not planar ⊕
and does not have cyclic 4n + 2 = 2 4n + 2 = 2
resonance n=0 n=0
sp2
⊕
∴ Aromatic ∴ Aromatic
⊕
(vii) (viii)
(xi) (xii)
4n + 2 = 2 4n + 2 = 4
n=0 n = 1/2 4n + 2 = 4 4n + 2 = 6
∴ Aromatic ∴ Anti aromatic n = 1/2 n=1
(Because it is planar) ∴ Aromatic
∴ Anti aromatic
4n + 2 = 6 4n + 2 = 6 4n + 2 = 6 4n + 2 = 6
n=1 n=1 n=1 n=1
∴ Aromatic ∴ Aromatic ∴ Aromatic ∴ Aromatic
sp3
(xvii) (xx)
(xviii)
4n + 2 = 6 4n + 2 = 8 Aromatic
n=1 n = 3/2
∴ not ∴ but anti
i aromatic (xxi)
sp2
⊕
(xix)
4n + 2 = 6 It is Aromatic because
n=1 only peripheral p electrons
∴ Aromatic should be considered
(xxiv)
4n + 2 = 10
n=2
But not aromatic because
not planar
(xxv)
O O 4n + 2 = 10
⊕ n=2
(xxii)
∴ Aromatic
(Tropone)
(because it is planar also)
This compound is aromatic
This compound is partly
aromatic and partly non
aromatic which can be explained
on the basis of resonance (xxvi)
(xxiii)
(Azulene) 4n + 2 = 18
4n + 2 = 10 n=4
n=2 [18] Anulene
∴ Aromatic It is an
Note : Despite the wide utility of the Huckel's rule a number of systems are known which do not contain (4n + 2) p
electrons but are still aromatic. Well-known examples of these anomalous cases are heptalene,
acenaphthene, etc., and they posses considerable delocalization energies.
heptalene acenaphthen
4. Do yourself
Suggest the product (On the concept of aromaticity)
O
(i) + HBr → ?
H5C6 O – C4H9
(ii) HCl
→
H 5C 6 C 6H 5
Cl
(iii) + SbCl5 → ?
Ph C−Cl
(iv) 3 → ?
5. Miscellaneous examples
CH3 CH3 O=C–CH3
OH NH2
SO3H SO3H
H 2SO Oleum
←4 →
80 C H 2S2O7 SO3H
Benzenesulphonic acid Benzene m-Benzenedisulphonic acid
So for sulphonation, it must be hot and conc. H2SO4 and the attacking species is SO3.
(B) Acylation (Reaction with acid chloride or acid anhydride)
Aromatic ketones are formed.
R–C=O
S
+S +S δ+ S
+S
– δ−
– δ−
≡
– δ−
S S
δ+ S E
δ− δ− Orthoattack
+
Para
→ E →
attack
δ− E
ortho product para product
The above mechanism is followed when S is
– OH, – NH2, – Cl2, – Br, – I, – OR etc.
Ιn methyl or alkyl group, the +I effect of the methyl group or alkyl group initiates the resonance effect.
Thus methyl or alkyl group directs all electrophiles to ortho and para positions.
7. Meta directing
The substituent ‘S’ withdraws electrons from ortho and para positions. Thus m– position becomes a point of
relatively high electron density and further substitution by electrophile occurs at meta position.For example,
–NO2 group is a meta directing (electron withdrawing). Its mechanism can be explained as:
Θ Θ Θ Θ
Θ Θ
O ⊕ O O ⊕ O– O ⊕ OΘ O ⊕
N
O O ⊕
N
O
N N N
⊕
⊕
All meta-directing groups have either a partial positive charge or a full positive charge on the atom directly
attached to the ring.
1. Chemical Properties of Halo-alkane
(Wurtz reaction) Na/dry ether
R–R
(Frankland reaction) Zn/dry ether
R–R
Corey-House reaction
R–R′
(i) Li (ii) CuX (iii) R′–X
Reduction
R–H
LiAlH4 or NaBH4 or Ph3SnH
RCOONa or RCOOAg
R–COOR
••
N H3 ••
R– N H 2
••
R– N H 2 ••
R– N H –R
••
R– N H –R ••
R3 N
••
R3 N ⊕
R4 N X
KCN/(Ionic)
R–C≡N
AgCN (covalent)
R–N = C
KO–N=O (Ionic)
R–O–N=O
Ag–O–N=O (covalent) O
R–N
O
2. Preparation Methods of Halo-alkane
X2/hν
R–H
HX
Alkene
HBr/Peroxide
Alkene
Cl–N=O
R–NH2
(Tilden reagent)
Darzen reaction
R–OH
SOCl2/Pyridine
R–X
PCl3 or PCl5
R–OH
HI or HBr or
R–OH
NaBr + H2SO4
HCl + ZnCl2
R–OH
(Lucas reagent)
Br2/CCl4
R–C–OAg
Hunsdiecker reaction
O
3. Chemical properties & preparation methods of dihalides
aq. NaOH CH 2 − OH
|
CH 2 − OH
OH
aq. NaOH –H2O
2HCl CH3–CH CH3–CHO
HC≡CH
(Unstable) OH
alc. KOH/∆
HC≡CH
or NaNH2
Cl
PCl5
CH3–CH=O CH3–CH
Cl
Zn
CH3–CH=CH–CH3
Gem dihalide
PCl5
CH2CH2CH2CH2 alc. KOH or
CH2=CH–CH=CH2
OH OH NaNH2
CH2CH2CH2CH2
Cl Cl
α,ω−dihalide Zn
Cl2/hν
O
Lab. Method aq. NaOH
CH3– CH − CH3 H–C–ONa (salt)
| (CaOCl 2 + H2O)/∆ (excess)
OH
O
OH
CH3–C–CH3
Ind. Method CH3–C–CH3 Chloretone
CH 3 − CH − H (Hyprotic)
| aq. NaCl/electrolysis Cl CCl3
OH H–C Cl
Cl Cl
NaOH HO–NO2/∆
O2N–C Cl +H2O Chloropicrin or
H – C – CCl 3 Chloroform (–H2O)
|| Cl Nitro chloroform
O (Tear Gas)
(Chloral)
(i) alc. KOH
R–N = C
3Cl2/hν ••
CH4 (ii) R–NH2
air & light
COCl2 + HCl
(Oxidation) Phosgene (Poisonous)
Zn+HCl
CH2Cl2
Reduction (–HCl)
Zn+H2O
CH4
(–3HCl)
Ag/∆
HC≡CH
5. Chemical Properties & preparation methods of carbon tetra chloride
aq. NaOH
Na2CO3
Cl2/hν (excess)
CHCl3 (salt)
(–HCl)
3Cl2/AlCl3 2HF/SbCl5
CS2 Cl Cl CF2Cl2+ 2HCl
(–S2Cl2)
C (Freon-012)
Cl Cl
9Cl2/500ºC
CH3–CH2–CH3 Reduction
(–C2Cl6) CHCl3
Fe/H2O
(–8HCl)
ALCOHOL
H2O/H⊕
CH2 = CH2
Θ
BH3/H2O2/OH
CH2 = CH2
(AcO)2 Hg/H2O/NaBH4
CH2 = CH2
aq. NaOH
CH3CH2–Cl
CH3MgBr/H3O⊕
H–C–H
||
O
H2/Pd or LiAlH4/H⊕
CH3–CH=O
reduction
LiAlH4/H⊕
CH3–C–Cl CH3CH2OH
|| reduction
O Ethyl alcohol
LiAlH4/H⊕
CH3–C–OCH2CH3
|| reduction
O
NaOH
CH3–C–OCH2CH3
||
O
H 3O ⊕
CH3–C–OCH2CH3
|| reversible reaction
O
NaNO2 + HCl
CH3CH2–NH2
or HNO2
dil. H2SO4
CH3CH2–O–CH2CH3
∆
2. Chemical reactions of alcohol
PCl3 or PCl5 or SOCl2
R–Cl
Lucas reagent
R–Cl
(H–Cl + ZnCl2)
H–NH2/Al2O3/∆
R–NH2
(–H2O)
H–O–NO2/100ºC
R–O–NO2 (Alkyl nitrate)
(–H2O)
H2SO4/100ºC
R–HSO4 (Alkyl hydrogen sulphate)
(–H2O)
O
O
R'–C–OH/H⊕
R'–C–OR
(–H2O)
O
O
CH3–C–Cl
CH3–C–OR'
(–HCl)
CH2=C=O
CH3–C–OR
Ketene
O
HN=C=O
H2N–C–OR
Isocyanic acid
O
R'MgX
R'–H
Grignard reagent
O
O
Ph–C–Cl
Ph–C–OR
Schotten-Baumann reaction
HI + red P
R–H
reduction
CH2N2/∆
R–O–CH3
H2SO4/170ºC
Alkene
H2SO4/140ºC
R–O–R
Oxidation [O]
aldehyde/ketone Carboxylic acid
3. Formation of ethanol by fermentation
(2) grain
→ Starch → maltose
Diastase
→ glucose
Maltase
→ EtOH
Zymase
HOH hydrolysis
ETHER
dry Ag2O
(1) C2H5I
C2H5ONa
(2) C2H5I
Williamson ether synthesis
Cl2–CH2–O–CH2–CH3
(4) C2H5–Mg–Br
Lower ether
Al2O3
(5) C2H5OH
180-200ºC
2. Chemical reactions
H2SO4 ⊕
[CH3CH2–OH–CH
•• 2CH3] HSO4
BF3 CH3CH2 O
••
BF3
CH3CH2
••
CH3CH2 – O –CH2CH3
RMgX
R–Mg–X
Grignard reagent
CH3CH2–O–CH
•• 2CH3
HF ⊕
[CH3CH2–OH–CH
•• 2CH3] F
HCl ⊕
[CH3CH2–OH–CH
•• 2CH3] Cl
HI or HBr
CH3CH2I + CH3CH2OH (Ziesel reaction)
(Cold and conc.)
•• HI or HBr
CH3CH2 –O– 2 CH3CH2I + H2O
•• CH2CH3 (Hot and cond.)
Diethyl ether
BCl3
3 CH3CH2–Cl + (CH3CH2)3BO3
PCl5 / ∆
2 CH3CH2–Cl + POCl3
CH3COCl /AlCl3
CH3CH2–Cl + CH3–C–OCH2CH3
O
CO / BF3 / HgO / ∆ CH3CH2–C–O–CH2CH3
O
dil.H2SO4 / ∆
2 CH3CH2–OH
Cl2 / dark
CH3–CH–O–CH–CH3 (α,α'-dichloro ether)
Cl Cl
Cl2 / sunlight
CCl3–CCl2–O–CCl2–CCl3 (Per chloro ether)
3. General reactions
air
(1) Et-O-CH(CH3)-O-O-H
Cl2, 20ºC
(5) α, α'- Dichloro ether
dark, ∆
Cl2
(6) (C2Cl5)2O penta chloro eth
hν, sunlight
••
CH3CH2 –O–
••
CH2CH3
Diethyl ether
Conc. H2SO4
(7) Oxonium salt
BF3
(8) (Et)2O→BF3
CO, 150ºC
(9) Et–COOEt
H2O & BF3, 500 atm
CH3COCl
(10) CH3COOC2H5
anhy ZnCl2
Al2O3
(11) CH2=CH2
380ºC
dil. H2SO4
(12) EtOH
PHENOL
OH
Zn HNO3
O2N NO2
H2SO4
Reduction
Cl NO2
PCl5 OH
+ Ph3PO4 25ºC SO3H
(Major) Sulphonation
O H2SO4 OH
HO OH CH3–C–CH3 / H2SO4 100ºC
OH OH
FeCl3
Voilet colour (i) HCN + HCl / AlCl3 CHO
Neutral +
(ii) H3O⊕
OH Gattermann Reaction CHO
O CH2OH
ALDEHYDES AND KETONES
O3/ H2O / Zn
C=C
H2O / HgSO4
—C≡C—
Θ
BH3 / H2O2 / OH
—C≡C—
Cl ar. NaOH
(Gemdihalide) C=C
Cl
C=O
oxidation
(1º/2º-alcohol) CH–OH Aldehyde
PCC or collin's
reagent or
Ketone
H 3O ⊕
Oxime C=N–OH
OR H3O⊕
acetal / Ketal C
OR
(i) RMgX
R–C≡N (ii) H3O⊕
O
H2 /Pd + BaSO4
R–C–Cl
Rosenmund
reduction
2. Chemical properties of carbonyl compounds
Θ
H–CN / OH cat. OH
C (Cyanohydrin)
CN
(i) R–MgX OH
C
(ii) H3O ⊕
(alcohols)
R
Θ⊕
OH
(i) R–C≡C Na (Acetylinic alcohol)
C
(ii) H⊕ C ≡ C–R
OH
NaHSO3 (White Crystal)
C
SO3Na
H2O / H⊕ OH
C (Unstable)
OH
2 RO–H / H⊕ OR
(Acetal or Ketal)
C
(–H2O) OR
C=O
Aldehyde 2 RS–H / H⊕ SR
Thioacetal or Thioketal
C
or (–H2O) SR
Ketone
H–O–CH2
⊕ O–CH2
H–O–CH2 H
C (Cyclic acetal or ketal)
(–H2O) O–CH2
aldol reaction
β–Hydroxy aldehyde / Ketone
dil. NaOH
COOR
(i) H2C Pyridine
COOR
C = CH–COOH (Knoevenagel reaction)
(ii) H3O⊕ / ∆
H2N–Z / H⊕ C = N–Z
(–H2O )
Witting reaction
C = CH2 + Ph3P=O
Ph3P= CH2
H2 / Pd or LiAlH4 / H⊕ CH–OH
Zn – Hg / HCl Reduction
CH2
NH2–NH2 / KOH
CH2
∆
3. Special points
Coloured Coloured
1 Brady reagent / DNP Coloured Crystal
crystal crystal
Corrosive sublimate
5 Black Black ×
(HgCl2)
Legal test
9 (Sod. nitropruside / × Red Red
NaOH)
m-dinitrobenzaldehyde
10 × × Blue
test
Preparation methods of carboxylic acid
Cl
aq. NaOH
R–C Cl
Cl
H2O/H⊕
R–C–Cl
O
H2O/H⊕
R–C–OR′
O
R–C–OH
COOH
H 2C ∆ O
(–CO2)
COOH Carboxylic acid
or CnH2nO2
H2O/H⊕
R–C≡N
⊕
R–C–H KMnO4/H /∆
oxidation
O
KMnO4/H⊕/∆
R–CH2OH oxidation
(AcO)2Mn
CH3–CH3 oxidation
O3/H2O
R–CH=CH2
O3/H2O
R–C≡CH
CO H2O
RONa RCOONa
High temp.
H3PO4
R–CH=CH2 CO + H2O
High temp. & Pres.
Chemical properties of carboxylic acid
Sodalime Na 1
R–H ∆ R–C–ONa + H2 ↑
|| 2
O
(i) NaOH NaOH
R–R R–C–ONa + H2O
(ii) electrolysis ||
O
NaHCO3
R–C–ONa + H2O + CO2 ↑
||
(i) AgOH O
H
R–Br
OO
(ii) Br2/CCl4 Na2CO3
R–C–ONa + H2O + CO2 ↑
C
of
||
-H
O
e to
Ca(OH)2 CH2N2
Du
R–C–R ∆ R–C–OCH3 + N2 ↑
||
O O O
||
R′–C–Cl
R–C–OH R–C–O–C–R′ + HCl
MnO || || ||
R–C–R O
300°C O O
O
Carboxylic acid CH2=C=O
R–C–O–C–CH3
|| ||
O O
GR
Alkane
p
l grou
R′OH/H⊕
R–C–OR′
f Alky
(–H2O) ||
H
Due to -O
O
α-H o
Due to
PCl3/PCl5/SOCl2
R–C–Cl
||
O
P2O5/∆
(–H2O)
R–C–O– C–R
H.V.Z Reaction || ||
R–CH–COOH Br2/red P/∆ O O
|
Br ●●
NH3 ⊕ ∆
R–C–ONH4 R–C–NH2
(–H2O) ||
||
α-Halogenation product O
O
is obtained by Hell-Volhard-
Zelinsky reaction HI/red P/∆
reduction
R–CH3
LiAlH4/H⊕
reduction
R–CH2OH
1. Preparation methods of acid chloride
HCl
CH2=C=O
PCl5/PCl3/SOCl2
CH3–C–OH CH3–C–Cl
∆
O O
or Acetyl
Chloride
(CH3CO)2O
PCl5/PCl3/SOCl2
CH3–C–ONa ∆
O
O
||
CH3–C–O
H–OCH2CH3
O
(–CH3COOH)
CH3–C–O
||
O
H–OCH2CH3
CH3–C–OCH2CH3
CH3–C–Cl ||
(–HCl) O
||
O Ethyl acetate
CH3CHO
CH3–C–OAg
|| (–AgBr)
O
Tischenko reaction
2CH3–CH=O
(Al(OEt)3
O NaBH4/H2O
No reaction
NH3 Reduction
CH3– C –NH2
–C2H5OH
Ethanamide
O O
CH3–NH2 LiAlH4/H2O
CH3– C –NHCH3 + C2H5OH CH3– C –OC2H5 2C2H5OH
Reduction
N-Methyl Ethanamide Ethyl ethanoate Ethanol
O ⊕ Na/C2H5OH
C2H5ONa
CH3– C –CH2COOC2H5 + C2H5OH Bouveault 2C2H5OH
Ethyl aceto acetate (β-ketoester)
Claisen Blanc reduction Ethanol
condensation
O PCl5/∆
C3H7–O–H/Alkoxide CH3COCl + C2H5Cl
CH3– C –O–C3H7 –POCl3
Trans esterification Ethanoyl chloride
Propyl ethanoate
H2N – OH
CH3– C –NH–OH
OH Hydroxyl amine
CH3MgBr/H3O⊕ O
CH3–C–CH3 N-Hydroxy ethanamide
Grignard reagent
CH3 NH2–NH2
Tert. Butyl alcohol CH3– C –NH–NH2
Hydrazine
O
5. Preparation methods of acid anhydride
CH3COOH
CH2=C=O
O O
|| ||
CH3–C–ONa
CH3–C–OH
(–NaCl)
O
||
O O CH3–C
|| || O
CH3–C–OH/Pyridine CH3–C
CH3–C–Cl (–HCl) ||
O O
|| P2O5/∆
2CH3–C–OH Acetic
(–H2O)
anhydride
O
||
O–C–CH3 Distillation/∆
CH3–CH (–CH3CHO)
O–C–CH3
||
O
O O O O O
2NH3 PCl5
CH3–C–NH2 + CH3–C–ONH4 CH3 – C –O– C –CH3 2CH3–C–Cl + POCl3
Ammonolysis Acetyl chloride
Ethanamide Amm.acetate Acetic O O
O O anhydride N–O–N O
Cl2/hν O O O
CH3–C–Cl + ClCH2–C–OH 2CH3–C–O–N
Nitrogen pentaoxide
Acetylchloride Monochloro acetic acid Acetyl nitrate O
O O
O
Dry HCl
C2H5NH2 CH3C–Cl + CH3–C–OH
CH3–C–Cl–NHC2H5 + CH3COOH Acetyl chloride Acetic acid
N-Ethyl ethanamide Acetic acid
O
O CH3CHO/AlCl3
CH3 C–OCH3
Acetaldeyde C
C–CH3 + CH3COOH H C–OCH3
/AlCl3
Anhy. AlCl3 O
Acetophenone (Friedal Craft Acylation) Ethylidene acetate
Perkin reaction
–CH=CH–COOH
–CHO/CH3COONa Cinnamic acid
7. Preparation methods of acid amide
••
NH3
CH3–C–Cl
|| (–HCl)
O
••
NH3
CH3–C–OCH3
|| (–CH3OH)
O
H2O/OH CH3–C–NH2
CH3–C≡N ||
Partial hydrolysis
O
Acetamide
⊕ ∆
CH3–C–ONH4 (–H2O)
||
O
P2O5/∆ H2O/H⊕
CH3–C≡N CH3–C–OH + NH3↑
(–H2O)
O
CH3–C–NH2
Reduction NaOH
CH3–CH2–CH2 O CH3–C–ONa + NH3↑
Na/EtOH
or LiAlH4/H⊕ Acetamide O
(1) CO2+H2O+2Ag+Ag2O
Tollen's Reagent
+Hg2Cl2
(a) 2HCl + CO2 + 2Hg
black ppt.
Fehling Solution
(3) Cu2O + H2O + CO2
+2CuO (red ppt.)
acidic. dichromate
(4)
2 KHSO4 + Cr2(SO4)3 + 2H2O + 3CO2
200ºC H2SO4 green + K2Cr2O7+ 5H2SO4 (Orange)
CO + NaOH
6-10 atm.HCOONa –Na2SO4 Acidic permangnate
(5)
+2MnSO4 + 2KHSO4 + 5CO2 + 8H2O
BF3 200-300ºC HCOOH
CO + H2O +2KMnO4 + 3H2SO4 (Colour less)
20-25 atm. Formic acid
alkaline permaganate
(6)
Oxid. 2MnO2 + 3K2CO3 + 5H2O + 2KMnO4+
CH3OH Oxid. HCHO 4KOH (brown ppt.) pink
160º, ∆ H2O + CO
(7)
conc. H2SO4
(8)
H2O + CO
Oxid.
(9)
CO2 + H2O
Na-Salt
(10)
COONa
360º C
+ H2
COONa
10. Method of preparation & Chemical properties of benzoic acid
Distillation of
(4) (C6H5)2C = O
CO2, H2O Ca salt
(3) C6H5MgBr Benzophenone
C6H5COOH
(m-directing)
CaCl2/AlCl3 PCl3,PCl5, SOCl2
(4) C6H6 (5) C6H5COCl
H 2O
(5) HO–C6H4–COOH
Zn/∆ (6) Hunsdiecker reac. C6H5Br
(o, m, p) Ag-salt+Br2
P 2O 5
(6) C6H5–CH3 Side-chain Oxidation (7) (C6H5CO)2O
MnO −4 /OH –H2O
KOH, Fe C2H5OH
(7) C6H5 CCl3 (8) C6H5COOC2H5
HOH LiAlH4
(8) C6H5–CN (9) C6H5CH2OH
oxid. oxid.
(9) C6H5–CH2OH C6H5CHO Cl2/FeCl3
(10)
m-chloro benzoic acid
Conc. H2SO4
(11)
m-sulphobenzoic acid
COOH COOH
nitration 140ºC
(12)
30ºC
NO2 NO2 NO2
O
|| (i) KOH (ii) R–X (iii) H3O⊕
C N–H
C Gabriel phthalimide reaction
||
O
Cl–NH2 R–NH2
R–MgCl (–MgCl2) Alkyl amine
NH3/∆
R–X or R–OH
H3O⊕
R–N C
Complete hydrolysis
2KOH
R–N=C=O
Wurtz reaction
O
|| LiAlH4/H2O
R–C–NH2 Reduction
LiAlH4/H2O
R–C≡N
Reduction
O LiAlH4/H2O
R–N O
Reduction
O
||
⊕ H 2O Cl–C–Cl R–N=C=O
R–NH3 OH (–2 HCl) (Alkyl isocyanate)
O
O ||
⊕ || CH3–C–OH CHCl3+alc.KOH
RNH3 O–C–CH3 R–N C
Hoffmann
n (Pungent smell)
Carbyl amine rx
⊕
HCl CH3–CH=O/H⊕ CH –CH=N–R
R–NH3 Cl 3
(Schiff's Base)
⊕
R–NH3 HAuCl4 HAuCl4 Cl–N=O
R–NH2 R–Cl
Tilden reagent
NO2
⊕
Na(Metal) 1
NO2 HO NO2 R–NHNa + H 2↑
⊕ 2
NO2
R–NH3 O NO2
Picric acid R–X
NO2 R–NH–R → R3N
(–HX)
2° amine 3° amine
O
⊕ –2 || O
H2SO4 CH3–C–Cl ||
R–NH3 2 SO 4 R–NH–C–CH3
(–HCl)
O O
|| ||
⊕ –2 Ph–C–Cl
∆ H2PtCl6 R–NH–C–Ph
Pt metal RNH3 PtCl6 (–HCl)
Schotten Bauman reaction
CH3MgCl Cl
CH4 + Mg
NHR
Br2 + KOH
Halogenation R–NH–Br
CS2 , HgCl2
RNCS
Hoffmann's
mustard oil reac.
C6H5 – SO2Cl
R–NH–SO2–C6H5
Hinsberg reagent
HNO2
R–OH
3. Preparation methods of aniline
Br2+KOH
C–NH2 (excess)
O
N3H/H⊕
C–OH
(i) NaNH2
Cl Aniline
(ii) NH3(liq.)
H 3O ⊕
N C
2 KOH
N=C=O
O Sn/HCl
N Reduction
O
Cl – NH2
C6H5MgBr
NH3
OH
ZnCl2, 300°C
[B] Reactions due to NH2 group :
⊕
NH3Cl
HCl
••
NH–R
R–X
–HX
O O
C –Cl ••
NH–C
•• –HCl
NH2
⊕
O=CH /H ••
Aniline N=CH
(–H2O)
Cl ••
C=O N=C=O
Cl
(–2HCl)
N C
CHCl3/alc. KOH
RMgX
C6H6
Hofmann
Mustard oil reaction
C6H5NCS
Hinsberg reagent
C6H5 – NH – SO2C6H5
C6H5SO2Cl2
Na
C6H5NH–Na+ + H2
NOCl
NO reaction
[C] Reactions due to ring :
CH3COCl
o- & p- Nitro aniline + H2O
then nitration mix
Direct nitration
o- & p- Nitro aniline
Exception
CH3COCl
o- & p- Bromo aniline
then Br2/CCl4 + H2O
Br2/H2O
2,4,6-Tribromo aniline (white ppt)
Test
NH2 NH2
Fuming-H2SO4
180º C Rearrangement
Aniline
SO2OH
Sulphanilic Acid
C6H5N2Cl
p- amino azo benzene
Ni/H2
Ni/H2 C6H11NH2
Cyclohexylamine test
NH2
NaOCl Light
Voilet colour
Na2Cr2O7
Aniline black
Conc. H2SO4
Na2Cr2O7
O= =O
dil. H2SO4
p-benzo quinone
* BENZENE DIAZONIUM CHLORIDE IS USED IN SYNTHESIS OF FOLLOWING AROMATIC COMPOUNDS :
H3PO2 or C2H5OH
reduction
CuCl Cl
CuCN/∆
CN
KI
I
NaBF4
∆
F (Beltz-Schiemann reaction)
Cu/HCl
Cl
Cu/HBr
Br Gattermann reaction
⊕ Cu/HNO2
N2Cl NO2
H2O
OH
Benzene
diazonium
chloride R–OH
O–R
N=N
OH
N=N OH
NH2
(Orange dye)
N=N NH2
Coupling reaction (ESR)
Me (yellow dye)
N
Me
Me
N=N N
Me
(yellow dye)
OH N=N
OH
(Red dye)
β-Naphthol
4. Preparation Methods and chemical properties of nitro benzene
NO2 NO2
Conc. HNO3 HNO3
∆
NO2 NO2 NO2
E.S.R NO2
Fuming H2SO4
SO3H
NO2
Cl2/AlCl3
Cl NO2 NO2
HNO3 NaNH2 NH2 +
H2SO4
O
NH2
CH3–C–O–NO2/∆ NO2 NO2
NO2
(–CH3COOH) N.S.R OH
NaOH +
NH2
Nitro Benzene OH
CF3CO3H
Oxidation NO2 NO2
⊕ CH3ONa OCH3 +
Reduction
N2Cl
Sn/HCl
HNO2/Cu NH2
or LiAlH4/H2O OCH3
Gattermann reaction or H2/Pd
Fe/H2O
N= O
dil.H2SO4
NH2
Electrolysis
rearranged
Conc.H2SO4 NH–OH HO NH2
O
Na3AsO3 or
N=N (Azoxy benzene)
CH3OH/NaOH
or glucose/NaOH
Na2SnO3 or
N=N (Azobenzene)
CH3OH/NaOH/Zn
H2O/NaOH/Zn
NH–NH (Hydrazobenzene)
5. Preparation methods and chemical properties of nitroalkane
Sn/HCl
CH3CH2–NH2
H2/Pd
CH3CH2–NH2
Na/EtOH
CH3CH2–NH2
⊕
LiAlH4/H
CH3CH2–NH2
Zn/NH4Cl
CH3CH2–NH–OH
AgNO2 H2O/H⊕
CH3CH2–Cl CH3–CHO
O Nef reaction
CH3CH2–N
O NO2
Fuming HNO3 O==N–OH
CH3–CH3 colourless CH3–C N–OH (Nitrolic acid)
600°C
sweet
smelling
∆ liquid Tautomerism O
(aci-nitro form)
CH3–CH–COOH CH3–CH=N
| (–CO2) OH
NO2 CH3MgBr
CH4
(α-Nitro acid)
CH3
CH3CHO |
CH3–CH–CH–NO2 (Nitro-alcohol)
|
OH
Cl2/NaOH
CH3–CH–NO2
(–HCl)
Cl
∆
CO2↑ + N2↑ + H2O
Pyrolysis
6. Preparation methods and chemical properties of Alkyl cyanide
KCN H2/Pd
CH3–Cl reduction CH3CH2–NH2
Na/EtOH
CH3CH2–NH2
reduction
LiAlH4/H⊕
P2O5/∆ CH3CH2–NH2
CH3–C–NH2 reduction
|| (–H2O)
O SnCl2/HCl H3O⊕
CH3–C ≡ N Stephen reduction
CH3–CH=NH CH3–CHO
Methyl cyanide
(i) CH3MgBr CH3–C–CH3
P2O5/∆ (ii) H3O⊕ ||
CH3–CH==N–OH O
(–H2O) (i) ROH
CH3–C–OR
(ii) H3O⊕ ||
O
H2O/OH
CH3–C–NH2
||
O
Cl–CN H2O/H⊕
CH3MgBr CH3–C–OH
||
O
AgCN H3O⊕
CH3–Cl CH3NH2 + HCOOH
H2/Pd
CH3–NH–CH3
reduction
CH3–N C
P2O5 Na/EtOH
CH3–NH–C–H Methyl CH3–NH–CH3
|| ∆ reduction
isocyanide
O
O3/∆
CH3–N=C=O + O2↑
CHCl3 2HgO
CH3–NH2 CH3–N=C=O + Hg2O
alc. KOH
(MIC)
Carbohydrate
Nut shell classification of Carbohydrates
Polysaccharides
Monosaccharides Oligosaccharides
Triose Disaccharide
(Glyceraldehyde (sucrose, Maltose, Homopolysaccharide Hetropolysaccharide
Dihydroxyacetone) Lactose) (Starch, cellulose, glycogen (Hygluronic acid, chondritin sulphate,
Trisaccharide chitin, dextrin, insulin) heparin, pectine, hemicellulose)
Tetrose
(raffnose)
D-Erythrose
Pentose Tetrasaccharide etc.
(D-Ribose)
Hexose
Aldohexose Ketohexose
(Glucose) (Fructose)
Glucose
Preparation of glucose
CHO CH = N – OH
NH2OH
(CHOH)4 (CHOH)4
CH2OH CH2OH
OH
CH
HCN CN
(CHOH)4
CH2OH
COOH
Br2/H2O
(CHOH)4
CH2OH
Gluconic acid
Ac2O
Penta Acetate
COOH
HNO3
Saccharic acid (CHOH)4
O
H – C – OH H –C 1 HO – C – H
H OH H 2
OH H OH
O O
HO H HO 3 H HO H
H OH H 4
OH H OH
H H 5
OH H
CH2OH 6 CH2OH
CH2OH
α - D - (+) Glucose β - D - (+) - Glucose
Pyran H OH H OH
Structure of fructose
CH2OH
HOCH2 – C – OH C=O HO – C – CH2OH
HO H HO H HO H
O
O
H OH H OH H OH
H H OH H
Amylopectin →
α - D - glucose (C1 – C4)
glucosidic linkage→ Branched
Protein
Proteins are the most abundant biomolecules of the living system. Chief sources of proteins are milk, cheese,
pulses, peanuts, fish, meat, etc. They occur in every part of the body and form the fundamental basis of
structure and functions of life. They are also required for growth and maintenance of body. The word protein is
derived from Greek word, ‘‘Proteios’’ which means primary or of prime importance. All proteins are polymers
of α-amino acids.
Amino Acids :-
Amino acids contains amino (–NH2) and carboxyl (–COOH) functional groups. Depending upon the relative
position of amino group with respect to carboxyl group, the amino acids can be classified as α, β, γ, δ and so on.
Only α-amino acids are obtained on hydrolysis of proteins. They may contain other functional groups also.
R – CH – COOH
NH2
α-amino acid (R = side chain)
All α-amino acids have trivial names, which usually reflect the property of that compound or its source. Glycine
is so named since it has sweet taste (in Greek glykos means sweet) and tyrosine was first obtained from cheese
(In Greek, tyros means cheese). Amino acids are generally represented by a three letter symbol, sometimes one
letter symbol is also used. Structures of some commonly occurring amino acids along with their 3-letter and 1-
letter symbols are given in Table
COOH
Natural Amino Acids H2N H
R
N
H
H 2C
19. Histidine* NH His H
N
COOHa
20. Proline HN H Pro P
CH2
R – CH – C – O – H R – CH – C – O–
+
:NH2 NH3
(Zwitter ion)
In zwitter ionic form, amino acids show amphoteric behaviour as they react both with acids and bases.
Except glycine, all other naturally occurring α-amino acids are optically active, since the α-carbon atom is
asymmetric. These exist both in ‘D’ and ‘L’ forms. Most naturally occurring amino acids have L-configuration. L-
Aminoacids are represented by writing the –NH2 group on left hand side.
Structure of Proteins :-
You have already read that proteins are the polymers of α-amino acids and they are connected to each other by
Peptide bond or peptide linkage. Chemically, peptide linkage is an amide formed between –COOH group and –
NH2 group. The reaction between two molecules of similar or different amino acids, proceeds through the
combination of the amino group of one molecule with the carboxyl group of the other. This results in the
elimination of a water molecule and formation of peptide bond –CO–NH–. The product of the reaction is called
a dipeptide because it is made up of two amino acids. For example, when carboxyl group of glycine combines
with the amino group of alanine we get a dipeptide, glycylalanine.
CH3
Peptide linkage
Glycylalanine (Gly-Ala)
If a third amino acid combines to a dipeptide, the product is called a tripeptide. A tripeptide contains three
amino acids linked by two peptide linkages. Similarly when four, five or six amino acids are linked, the
respective products are known as tetrapeptide, pentapeptide or hexapeptide, respectively. When the number
of such amino acids is more than ten, then the products are called polypeptides. A polypeptide with more than
hundred amino acid residues, having molecular mass higher than 10,000 u is called a protein. However, the
distinction between a polypeptide and a protein is not very sharp. Polypeptides with fewer amino acids are
likely to be called proteins if they ordinarily have a well defined conformation of a protein such as insulin which
contains 51 amino acids.
Proteins can be classified into two types on the basis of their molecular shape.
(a) Fibrous proteins
When the polypeptide chains run parallel and are held together by hydrogen and disulphide bonds, then
fibre-like structure is formed. Such proteins are generally insoluble in water. Some common examples are
keratin (present in hair, wool, silk) and myosin (present in muscles), etc.
(b) Globular proteins
This structure results when the chains of polypeptides coil around to give a spherical shape. These are
usually soluble in water. Insulin and albumins are the common examples of globular proteins.
Structure and shape of proteins can be studied at four different levels, i.e., primary, secondary, tertiary
and quaternary, each level being more complex than the previous one.
(i) Primary structure of proteins : Proteins may have one or more polypeptide chains. Each polypeptide in
a protein has amino acids linked with each other in a specific sequence and it is this sequence of amino
acids that is said to be the primary structure of that protein. Any change in this primary structure i.e.,
the sequence of amino acids creates a different protein.
(ii) Secondary structure of proteins: The secondary structure of protein refers to the shape in which a long
polypeptide chain can exist. They are found to exist in two different types of structures viz. α-helix and
β-pleated sheet structure. These structures arise due to the regular folding of the backbone of the
O
polypeptide chain due to hydrogen bonding between –C– and –NH– groups of the peptide bond.
α-Helix is one of the most common ways in which a polypeptide chain forms all possible hydrogen
bonds by twisting into a right handed screw (helix) with the –NH group of each amino acid residue
hydrogen bonded to the C= O of an adjacent turn of the helix as shown in figure.
α-Helix structure of proteins
In β-structure all peptide chains are stretched out to nearly maximum extension and then laid side by
side which are held together by intermolecular hydrogen bonds. The structure resembles the pleated
folds of drapery and therefore is known as β-pleated sheet.
N N N
(iii) Tertiary structure of proteins: The tertiary structure of proteins represents overall folding of the
polypeptide chains i.e., further folding of the secondary structure. It gives rise to two major molecular
shapes viz. fibrous and globular. The main forces which stabilize the 2° and 3° structures of proteins are
hydrogen bonds, disulphide linkages, van der Waals and electrostatic forces of attraction.
(iv) Quaternary structure of proteins: Some of the proteins are composed of two or more polypeptide
chains referred to as sub-units. The spatial arrangement of these subunits with respect to each other is
known as quaternary structure.
A diagrammatic representation of all these four structures is given in figure where each coloured ball
represents an amino acid.
Figure : Primary, (a) Primary (b) Secondary (c) Tertiary (d) Quaternary
secondary, tertiary structure structure structure structure
and quaternary
structures of C N R groups
haemoglobin H O Haeme group
Denaturation of Proteins :-
Protein found in a biological system with a unique three-dimensional structure and biological activity is called a
native protein. When a protein in its native form, is subjected to physical change like change in temperature or
chemical change like change in pH, the hydrogen bonds are disturbed. Due to this, globules unfold and helix get
uncoiled and protein loses its biological activity. This is called denaturation of protein. During denaturation
2° and 3° structures are destroyed but 1° structure remains intact. The coagulation of egg white on boiling is a
common example of denaturation. Another example is curdling of milk which is caused due to the formation of
lactic acid by the bacteria present in milk.
POLYMERS
H2C = CHCl Vinyl chloride Polyvinyl Chloride(PVC) Raincoats, pipes, floor tiles etc.
utensils
Polyvinyl chloride (PVC) CH2 = CHCl ( Vinyl Chloride) Electrical insulation, water
proof clothing
(Perspex)
Structure of Polymer/
Monomer(s) Common uses
Name of Polymer
[ CH2–C=C–CH2 ]n
CH2=C–CH=CH2
1 G
G Branched chain
polymer
G = –CH3
[ CH2–C=C–CH2 ]n
CH2=C–CH=CH2
2 CH3 Natural rubber
CH3 Polyisoprene
(Isoprene)
G = Cl
[ CH2–C=C–CH2 ]n
CH2=C–CH=CH2
3 Cl Synthetic rubber
Cl
Polychloroprene or Neoprene
(Chloroprene)
House ware, containers, bottles,
[ CH–CH2 ]n
4 CH2=CH2 (ethylene) toys, polyethylene sheets, and
Polyethene
films for packaging
n
Glyptal
O O
13 N–H [ NH–(CH2)5–C ]n Fiber, rope, plastic
Caprolactum Nylon-6
NH2–(CH2)6–NH2
O O
Hexamethyl diamine + Adipic
14 [NH–(CH2)6–NH–C–(CH2)4–C]n Fiber, parachutes
acid
Nylon–66
COOH–(CH2)4–COOH
O
15 Urea + HCHO [NH–C–NH–(CH2]n Fiber, unbreakable cups & plates
Urea formaldehyde resin
NH2 N NH2–CH2
H2N N NH2
N N
N N + H–C–H NH
16 Plastic sheets
NH2 O
Melamine Melamine
formaldehyde resin
OH OH
OH
Insulating material for electrical
17
+ HCHO n goods thermosetting plastic
Bakellite
[ CH2–CH ]n Synthetic carpets, automobile
CH2 =CH–CH3
18 CH3 parts, packaging, toys, and house
(Propylene)
Polypropylene ware
[ CH2–CH ]n
CH2=CH–OCOCH3
19 OCOCH3 Adhesives, as binder for paints
(Vinyl acetate)
Polyvinyl acetate
[ CH2–CH ]n
CH2=CH–CO2CH3
20 COOCH3 As a substitute of glass
(methyl methacrylate)
Polymethyl methacrylate
(Plexiglass, Lucite)
Cl Air and water proof packaging
CH2=CCl2 [ CH2–C ]n films. Its copolymer with vinyl
21 [Vinylidine chloride] Cl chloride is used for making
(1, 1-dichloroethene) Polyvinylidine conveyer belts and acid proof
chloride
(Saran) ropes.
CH3
As lining and insulators for cables
CH2=C(CH3)2 [ CH2–C ]n
22 Its copolymer with isoprene is
(Isobutene) CH3
used for manufacturing tyres.
Polyisobutene
Electrical switches, lamination,
23 Phenol and formaldehyde Bakelite
etc.
Ion-exchange resin, adhesives,
24 Urea and formaldehyde Urea-formaldehyde resin electrical fittings grease resisting
textile, foams, lamination,
Kitchen ware (melamine
crockery), furniture, laminates,
25 Melamine and formaldehyde Melamine-formaldehyde resin
electrical insulators, adhesives,
fabric and paper treatment.
Adipic acid and Hexa-
26 Nylon 6, 6 Synthetic fiber
methylenediamine
27 Caprolactam Nylon 6 Synthetic fiber
Synthetic fiber of high tensile
Terphthalic acid and Ethylene
28 Polyester (Terylene, Dacron) strength with anti-wrinkle
glycol (or its ester)
properties
Used extensively in automobile
industry, table cutlery, as
Bis-phenol A and Carbonic acid
29 Polycarbonate protective covering, compact disc
derivative
(CD), as bullet proof sheets, safety
glasses, etc.
As adhesive in shoe soles, tyres,
30 Diisocyanates Diols Polyurethanes and foam surface coating in paints
and varnishes.
1. Qualitative analysis
The qualitative analysis of an organic compound involves the detection of all the elements present in
it.
2.1 Detection of Carbon and Hydrogen : A small amount of the dry and powdered substance is mixed
with about double the amount of pure and dry copper oxide. The mixture is heated in a well dried
hard glass tube (fig) delivery tube is packed with glass wool containing anhydrous copper sulphate
(white) . When the mixture is heated , the carbon present in the compound is oxidised to carbon
dioxide which turns lime water milky. The hydrogen present in the organic compound is oxidised to
water which turns anhydrous copper sulphate in the bulb to blue.
Anhydrous copper sulphate
Organic compounds
+
Copper oxide Lime water
C + 2CuO Heat
→ CO2 + 2Cu
from organic compound
CO2 + Ca(OH)2 → CaCO3 + H2O
lime water milky
2H + CuO Heat
→ H2O + Cu
from organic compound
CuSO4 + 5H2O → CuSO4 . 5H2O
anhydrous hydrated copper sulphate
copper sulphate (blue)
(white)
This method is known as copper oxide test.
2.2 Detection of Nitrogen : Nitrogen in an organic compound is detected by the following tests :
(a) Soda lime test. A pinch of an organic compound is heated strongly with soda lime (NaOH + CaO)
in a test tube. If ammonia gas evolves, it indicates nitrogen.
CH3CONH2 + NaOH CaO
→ CH3COONa + NH3
acetamide
Limitation : This method has a limitation. A large number of organic compounds such as nitro and
diazo compounds do not liberated ammonia on heating with sodalime.
(b) Lassaigne’s method : A small piece of a dry sodium metal is heated gently in a fusion tube till it
melts to a shining globule. Then , a small amount of organic substance is added and the tube is
heated strongly till it becomes red hot. The red hot tube is then cooled and filtered. The filtered
liquid is known as sodium extract or Lassaigne’s extract.
The Lassaigne’s extract is usually alkaline. If not, it may be made alkaline by adding a few drops of a
dilute solution of sodium hydroxide added to a part of sodium extract a small amount of a freshly
prepared ferrous sulphate solution is and the contents are warmed. A few drops of ferric chloride
solution are then added to the contents and the resulting solution is acidified with dilute hydrochloric
acid. The appearance of a bluish green or a blue colouration confirms the presence of nitrogen in the
organic compound.
The following chemical reactions occur during the test :
Na + C + N –––––→ NaCN
from organic compound
FeSO4 + 2NaCN –––––→ Fe(CN)2 + Na2SO4
Fe(CN)2 + 4NaCN –––––→ Na4[Fe(CN)6]
sodium ferrocyanide
3Na4[Fe(CN)6] + 4FeCl3 ––→ Fe4[Fe(CN)6]3 + 12NaCl
ferric ferrocyanide
(blue colour)
2.3 Detection of Sulphur : The sulphur in the compound reacts with sodium metal to form sodium
sulphide.
2Na + S –––––→ Na2S
from organic compound
The Lassaigne’s extract is divided into two parts and following tests are performed.
(i) Sodium nitroprusside test. The one portion of the extract, a few drops of sodium nitroprusside
are added. The appearance of violet colouration indicates sulphur.
Na2S + Na2 [Fe(CN)5NO] –––––→ Na4[Fe(CN)5NO.S]
sod.nitroprusside violet colouration
(ii) Lead acetate test : The other part of the Lassaigne’s extract is acidified with acetic acid and then
lead acetate solution is added. Formation of black precipitate confirms the presence of sulphur.
Na2S + Pb(CH3COO)2 –––––→ PbS + 2CH3COONa
lead acetate black
2.4 Detection of Halogens : Lassaigne’s test. Sodium extract is prepared as already. During fusion,
sodium will combine with the halogen (from the organic compound) to form sodium halide
→ NaX (X = Cl , Br, I)
Na + X Fusion
(i) A white precipitate soluble in ammonium hydroxide solution indicates the presence of chlorine
in the organic compound
NaCl + AgNO3 –––––→ AgCl + NaNO3
white ppt.
(ii) A dull yellow precipitate partially soluble in ammonium hydroxide solution indicates the presence
of bromine in the organic compound.
NaBr + AgNO3 –––––→ AgBr + NaNO3
dull yellow ppt.
(iii) A bright yellow precipitate, completely insoluble in ammonium hydroxide solution, indicates the
presence of iodine in the organic compound.
NaI + AgNO3 –––––→ AgI + NaNO3
bright yellow ppt
Special test for bromine and iodine.
2NaBr + Cl2 –––––→ 2NaCl + Br2
(turns CS2 layer orange)
2NaI + Cl2 ––––––→ 2NaCl + I2
(turns CS2 layer violet)
Example
based on Qualitative Analysis
Ex.1 In Lassaigne’s test when both N and S are present, blood red colour obtained is due to the
formation of –
(A) Ferric ferrocyanide
(B) Ferric sulphocyanide
(C) Ferric cyanide
(D) None Ans.(B)
Sol. 3 NaCNS + FeCl3 ––––→ Fe(CNS)3 + 3NaCI
(Red)
Ex.2 Lassaigne’s test for the detection of nitrogen will fail in case of –
(A) NH2CONH2
(B) H2NCONHNH2 . HCI
(C) H2N . NH2 . 2HCl
(D) C6 H5NHNH2 . 2HCl Ans.(C)
Sol. For Lassaigne’s test of N, compound must contain N in addition to carbon, so that NaCN can be
formed in sodium extract.
2. Quantitative analysis
2H + O HNO
3 → H2O
S + H2O + 3O HNO
3 → H2SO4
Calculations :
Let the mass of organic compound be w g
Mass of silver halide formed = a g
Now , AgX = X
108 + X parts by weight of silver halide contains X parts by weight of halogen
(X is its atomic mass)
(108 + X) g of silver halide give halogen = X
a g of silver halide will give halogen
X
= ×ag
(108+ X)
∴ Percentage of halogen
Mass of ha logen
= × 100
Mass of organic compound
X×a 100
= ×
(108 + X) w
Here X is the atomic mass of halogen, ex.
Cl = 35.5, Br = 80 (79.9 exact), I = 127
(126.9 exact)
Percentage of halogen =
Atomic mass of halogen × Mass of silver halide
× 100
(108 + At. mass of halogen ) × Mass of org. subs tan ce
S + H2O + 3O HNO
3 → H2SO4
H2SO4 + BaCl2 → BaSO4
ppt.
Calculations :
Let the mass of organic compound = w g
Mass of BaSO4 formed = a g
BaSO4 ≡ S
137 + 32 + 64 = 32
= 233
233 g of BaSO4 contain sulphur = 32 g
32 × a
a g of BaSO4 will contain sulphur = g
233
Percentage of sulphur
Mass of sulphur
= × 100
Mass of organic compound
32a 100
= ×
233 w
Example
based on Quantitative Analysis
Ex.3 0.2475g of an organic compound gave on combustion 0.4950g of carbon dioxide and 0.2025 g of
water. The percentage of carbon and hydrogen are–
(A) 54.54, 9.09 (B) 52.54, 8.09
(C) 120 , 5.8 (D) None Ans. (A)
Sol. Wt. of organic compound = 0.2475 g
Wt. of CO2 produced = 0.4950 g
Wt. of H2O produced = 0.2025 g
Percentage of carbon
12 Wt. of CO 2
= × × 100
44 Wt. of compound
12 0.4950
= × × 100 = 54.54
44 0.2475
Percentage of hydrogen
2 Wt. of H 2 O
= × × 100
18 Wt. of compound
2 0.2025
= × × 100 = 9.09
18 0.2475
Ex.4 In a Dumas nitrogen estimation 0.3 g of an organic compound gave 50 cm3 of nitrogen collected at
300 K and 715 mm pressure. The percentage of nitrogen in the compound (vapour pressure of
water at 300K is 15 mm) is
(A) 15.46 (B) 17.46
(C) 50 (D) 70 Ans. (B)
Sol. Vapour pressure of gas = 715 - 15 = 700 mm
To calculate the volume of N2 at S.T.P.
V1 = 50 cm3 V2 = ?
P1 = 700 mm P2 = 760 mm
T1 = 300 K T2 = 273 K
P1V1 PV
Applying = 2 2 or
T1 T2
P1V1T2
V2 =
P2 T1
700 × 50 × 273
∴ V2 = = 41.9 cm3
760 × 300
22400 cm3 of nitrogen at S.T.P. weigh= 28 g
41.9 cm3 of nitrogen at S.T.P weight
28 × 41.9
= = 0.0524g
22400
0.0524
Percentage of nitrogen = × 100
0.3
= 17.46%
Ex.5 0.257 g of an organic substance was heated with conc H2SO4 and then distilled with excess of
strong alkali. The ammonia gas evolved was absorbed in 50 ml of N/10 HCl which required 23.2
ml of N/10 NaOH for neutralisation at the end of the process. The percentage of nitrogen in the
compound is–
(A) 14.6 (B) 18.0
(C) 17.0 (D) 15.5 Ans.(A)
N
Sol. Volume of HCl taken = 50ml
10
N
Volume of NaOH used for neutralisation of unused acid = 23.2 ml
10
Now N1 V1(NaOH) = N2V2(HCl)
N N
23.2 ml of NaOH ≡ 23.2 ml of HCl
10 10
N
∴ Volume of HCl unused = 23.2 ml
10
∴ Volume of N/10 HCl required for neutralization of NH3 = 50 - 23.2 = 26.8 ml
N
26.8 ml of HCl = 26.8 ml of N/10 NH3
10
1000 ml of 1N NH3 solution contains nitrogen = 14 g
26.8 ml of NH3 solution contains nitrogen
14 × 26.8
=
10 × 1000
14 × 26.8 × 100
Percentage of nitrogen =
10 × 1000 × 0.257
= 14.6%
Ex.6 0.15 g of an organic compound gave 0.12 g of AgBr by Carius method. The percentage of
bromine in the compound is
(A) 43 (B) 54
(C) 34 (D) 66 Ans. (C)
Sol. Mass of AgBr formed = 0.12 g
AgBr ≡ Br
188 g of AgBr contain bromine = 80 g
0.12 g of AgBr will contain bromine
80 × 0.12
= = 0.051 g
188
0.051
Percentage of bromine = × 100 = 34%
0.15
Ex.7 0.395 g of an organic compound by Carius method for the estimiation of sulphur gave 0.582 g of
BaSO4. The percentage of sulphur in the compound is–
(A) 20.24 (B) 35
(C) 40 (D) 45 Ans. (A)
Sol. Mass BaSO4 = 0.582 g
We know BaSO4 ≡S
233 32
233 g of BaSO4 contain sulphur = 32 g
0.582 g of BaSO4 contains sulphur
32
= × 0.582
233
Percentage of sulphur
Wt. of sulphur
= × 100
Wt. of compound
32 × 0.582
= × 100 = 20.24 %
233 × 0.395
(i) All organic compound are grouped into smaller number, each group exhibits similar chemical
properties.
(ii) This means that all the compounds of the group must have something common, this common
feature is known as functional group or reactive functional group.
(iii) It is defined as the group which largely determine the properties of a compound ex., CH3OH
C2H5OH, C3H7OH are all collectively called alcohol as the common reactive group in all is – OH.
(iv) Some common and important functional group usually encountered in organic compounds are
given in following table.
Some common Functional groups
Name of Functional group Example
the family
or group
Alkene C=C CH2 = CH2
Alkyne –C≡C– HC ≡ CH
Note :-
(1) Apply both tests, since some compounds react slowly with bromine.
(2) Enols (–OH group containing compounds) are also found to decolourise bromine as well as
permanganate solution. but the type of reaction which takes place with bromine is somewhat
different in this case than with unsaturated compounds. Enols are substituted by bromine and an
equivalent of HBr is evolved. So during the reaction white fumes will come, when a glass rod
moistened with concentrated ammonia solution is held near the mouth of the test tube.
HBr + NH3 → NH4Br
4.1.2 Test for Terminal Alkyne
Acetylene and other terminal alkyne (1 – alkyne) are weakly acidic in character. They react with
ammonical solution of cuprous chloride and silver nitrate to form the corresponding copper and
silver alkynide.
R – C ≡ C – H + 2 [CuCNH3)2] Cl → Cu C ≡ C Cu + 2NH4Cl + 2NH3
Diammine copper (Ι) chloride Dicopper acetylide (red ppt)
R – C ≡ C – H + 2 [Ag (NH3)2] → AgC ≡ C Ag + 2 NH4NO3 + 2NH3
Diamine silver (Ι) nitrate Disilver acetylide (white ppt)
Note :- Non terminal Alkynes will not give this test
CH3C ≡ CCH3 + 2 [Ag(NH3)2] NO2 → No reaction
4.1.3 Tests for Alcoholic (–OH) group
(i) – OH group is called alcoholic or hydroxy group, but it is different from the hydroxy group of
inorganic compounds.
(ii) For example, – OH group of sodium hydroxyide and methanol have entirely different properties.
Sodium hydroxide is a base and turns red litmus blue but methanol does not give this test.
(A) Sodium metal test or Xanthate test :-
(i) Take compound in an absolutely, dry test tube. Acid a small quantity of anhydrans calcium
chloride to absorb moisture, decant it into another test tube.
(ii) Add a small piece of dry sodium metal to it (sodium should be handled with (are) . Efferuescence
with the evolution of hydrogen gas indicate the presence of alcoholic group in the
compounds.
1
C2H5OH() + Na(s) → C2H5ONa + H2 (g)
2
Ethanol Sodium Sodium Ethoxide Hydrogen
Note : -
(i) Test tube & alcohol should not contain even trace of moisture as water also reacts with sodium
metal to evolve hydrogen gas.
(ii) Cerric ammonium nitrate test :- To about 1 ml. of the substance in test tube add a few drops a
cerric ammonium nitrate solution. Appearance of red colour indicate the presence of
alcohols.
CH3OH + (NH4)2 Ce(NO3)6 →(CH3OH)2 Ce (NO3)4 + 2NH4NO3
(colourless) Cerric ammonium nitrate (Red) (colourless)
(Yellow)
(iii) Ester test :-
When alcohol is treated with acetic acid in the presence of conc. H2SO4, a characteristic fruity
smell due to the formation of ester indicates the presence of alcohol.
C
C
O O NaOH
→
C C
O O
Phenolphthalein(colourless)
O –
O Na +
COO–Na+
Sodium salt of Phenophlhatein (Pink)
(d) Liebermann’s reaction :-
To a small amount of substance in as test tube add few crystals of solid sodium nitrite and then
few drops of conc. H2SO4.
A green or blue colour is obtained which change to red on dilution and again turn blue or green
an making the solution alkaline with NaOH.
Note : -
(i) Nitrophenols and p-substituted phenol do not give this test.
(ii) This test is also shown by o-cresol.
(e) Cerric Ammonium nitrate test :-
To Cerric Ammonium nitrate add a pinch of given compound.Appearance of green or brown
precipitates indicate the presence of phenolic group in the given compound.
4.1.5 Test for Carboxylic (– COOH ) group
Compound containing this group behave like acid and almost all the tests meant for acids can be
applied for testing this group.
(i) Litmus test :-
Place a small quantity of the organic substance an a piece of moist blue litmus paper, or in a blue
litmus solution. If the colour change to red, carboxylic group may be present.
(ii) Sodium bicarbonate test : -
Take 5 ml of dilute solution of sodium bicarbonate in a test tube and add a small quantity of
substance to it strong effervescence with the evolution of carbon dioxide gas indicate the
presence of carboxylic acid.
CH3COOH + NaHCO3 → CH3COOHNa + CO2↑ + H2O
(iii) Ester test :-
To a small quantity of substance add 5 drops of ethyl alcohol and two drops of conc. H2SO4.
warm the tube an water both. A fruity small of ester indicate the presence of
– COOH group.
CH3COOH + C2H5OH Conc
→
. H 2SO 4
CH3COOC2H5 + H2O
Ethyl acetate
(iv) To a mixture of about 3 ml 0.1% acriflavine solution and 3 ml 1% potassium chromate solution
add a few drops of aqueous solution of substance (if it is liquid then it may be added as such).
Appearance of a yellow or brown-yellow precipitate confirms the presence of carboxylic acid.
4.1.6 Test for Aldehydes :-
To 2 ml of substance, if it is liquid or to its 2 mole cold aqueous solution add 2ml Schiff’s reagent*
(Rosaniline decolourised with SO2) and shake for 2 minutes. Do not heat or warm. A deep
violet-red or red colour indicates the presence of aldehydic group.
R CH.SO2NH
H.SO2NH OH C NH
C NH2
→ R CH.SO2NH
2 R .CHO
− H 2SO 3
H.SO2NH
SO2 OH
Schiff’s reagent (colourless) Violet-red
(ii) Fehling’s test - In a test tube mix 1 ml each of Fehling A (CuSO4 in water with few drops of acetic
acid) and Fehling B (Rochelle salt and NaOH solution) solutions when a deep blue colour appears.
To this add 0.1gm or 2-3 drops of substance and boil for 5 minutes. The blue colour of Fehling’s
solution slowly fades away and a reddish-brown precipitate of Cu2O is obtained indicating the
presence of aldehydic group.
CH C O–
O O CHOH.COO–
∆
2 Cu + R.CHO + 2H2O
→ 2 + R.COOH + Cu2O ↓
O O CHOH.COO–
CH C O–
Tartrato-cuprate anion (blue) cuprous oxide (Red)
(Fehling’s solution)
(iii) Tollen’s test -To 2 ml Tollen’s reagent in a test tube (To 1 ml ANO3 solution add few drops of
NaOH solution add few drops of NaOH solution and dissolve the precipitate of silver oxide by
adding excess NH4OH) add 2-3 drops or 0.1 gm of substance. Keep the test tube in boiling water
without disturbing for 5 minutes when a shining silver mirror deposits on the walls of test tube
indicating the presence of aldehydic group.
2Ag (NH3)2OH + R.CHO + H2O → R.COONH4 + NH3 + 2NH4OH + 2Ag ↓
Tollen’s reagent
4.1.7 Test for Ketones :-
If the tests for aldehydes are negative perform following tests for ketones.
(a) To a solution of 0.5 gm or 0.5 ml substance in 5 ml dilute HCl add 2 ml of solution of
2, 4-dinitrophenylhydrazine in dilute HCl. Cool and allow to stand for 2 minutes when a yellow,
orange or red coloured crystalline precipitate (in case Schiff’s test is negative) indicates the
presence of kentonic group.
(b) To 2-3 drops of substances add 1 ml freshly prepared sodium nitroprusside solution and then
NaOH solution drop by drop. A wine red or orange red colour confirms the presence of ketonic
group.
4.1.8 Test for Esters and Lactones :-
(a) Dissolve about 0.5 gm or 0.5 ml substance in 10 ml alcohol, add a drop of phenolphthalein and
few drops of NaOH solution. A pink colour is produced by phenolphthalein in alkaline medium
Heat the reaction mixture for 5 minutes when NaOH solution is used up in the hydrolysis of ester
or lactone and the pink colour of phenolphthalein disappears.
R.COOR’ + NaOH → R.COONa + R’OH
(b) To 3-4 drops or 0.2 gm of substance add 0.2 gm solid hydroxylamine hydrochloride and 5m 10%
NaOH solution. Boil the solution gently for 2 minutes, cool and acidify the solution with dilute
HCl. Then add 2-3 drops of FeCl3 solution when a violet or deep red brown colour due to
formation of ferric complex of hydroxamic acid, indicates the presence of ester group.
∆
R.CO.OR’ + NH2OH
→ R.CO.NHR’OH + R’OH
Coloured Complex
4.1.9 Test for Ethers :-
If the compound responds to none of the above tests then the presence of ether group may be
confirmed by following tests.
(a) Feigl’s test - Take 2 ml of substance in a boiling tube and cover the mouth of the tube with a
filter paper moistened with a mixture of cupric acetate and benzidine hydrochloride. Heat the
tube or 3-5 minutes when a deep blue colour appears on filter paper due to formation of
benzidine blue, confirming the presence of ether group.
R
R.O.R’ + O (from air) → O→O
R'
Ether Ether peroxide
R
O→O + Cu++ → R.OR + CuO2
R'
Cupric peroxide
Benzidine hydrochloride
H 2N NH2.NH =
Benzidine blue
NH . HCl
Diazonium salt
4.1.11 Test for secondary amines :-
Dissolve a small amount of substance in 2 ml HCl, dilute it with 3-4 ml water and add 2 ml of 2%
NaNO2 solution. If white or yellow oily emulsion is obtained or a low melting solid separates the
compound is a secondary amine.
Ar. NH.R + HNO2 → Ar. N(NO). CH3 + H2O
Nitrosamine
4.1.12 Test for tertiary amines :-
Most of the aromatic tertiary amines respond to following test :
On adding 2 ml of 2% NaNO2 solution to a solution of substance in dilute HCI, if a yellow or yellow-
green colour is produced which turns dark greenish on making the solution alkaline then the
compound may be an aromatic tertiary amine. Refer to Section G.
Methanol Formaldehyde
CH3CH2OH Oxidation
→ CH3CHO
Ethanol Acetaldehyde
As acetaldehyde forms iodoform with Ι1 and alkali, therefore, iodoform test can be employed to
distinguish ethanol from methanol.
CH3CH2OH Ι → CHI3
2 / NaOH
Iodoform
CH3OH Ι →
2 / NaOH
No iodoform
Ex.10 The aqueous solution of a nitrogen and chlorine containing organic compound (A) is acidic to
litmus. (A) on treatment with aqueous NaOH gives a compound (B) containing nitrogen, but not
chlorine. Compound (B) on treatment with C6H5SO2Cl in the presence of NaOH gives an insoluble
product(C), C13H13NO2S. Give structures of (A) and (B)
Sol. Since the compound B reacts with C6H5SO2Cl in presence of NaOH to give insoluble product C, B
must be secondary amine.
Ex.11 An organic compound (A) reacts with ethanol to give (B) and (C). On acid hydrolysis, (C) yields (B)
and (D). Oxidation of (D) gives (B). (B) is an acid and forms a salt with Ca (OH)2 which on dry
distillation gives (E), C3H6O. Give structures of (A) to (E) with proper reasoning.
Sol. Summary of the given reactions.
(i) A + C2H5OH → B + C
+
(ii) C H→ B + D
.→ B
(iii) D oxi
B
(iv) ( → E
i ) Ca ( OH ) 2
(Acid) ( ii ) dry distil
Reaction (iv) indicates that the acid B is acetic acid. Further formation of B by acidic hydrolysis of
C indicates that C should be an ester of acetic acid. Oxidation of D
(an alcohol) to give B (CH3COOH) indicates that D is C2H5OH. hence C must be ethyl acetate, and
thus finally A must be acetic anhydride (anhydrides on treatment with alcohol give acids and
ester).
CH3CO
O + C2H5OH →
CH3CO
[A] CH3COOH + CH3COOC2H5
[B] [C]
+
CH3COOC2H5 H→ CH3CH3COOH +C2H5OH
[C] [B] [D]
2CH3COOH Ca
( OH
)2
→ (CH3COO)2Ca dry → CH3COCH3
distil
[B] [E]