11.alkenes and Alkynesexercise PDF

Chem i str y | 11.
43
Solved Examples
JEE Main/Boards
Example 1: Complete the following reactions:

NBS Alc.KOH (C)
(B)
(a) Me
(A)
Me Br
Alc.KOH
(b) (Y) + (Z)
(X) (Major) (Minor)
Me
H
(c ) (B)
(A)
Cl2 1. Li -B
(B) (C) (D)
o
(d) Me at 500 C 2. CuI
(A)
(e) HO
KHSO4
or (Y)
OH
(X) Al2O3 or P2O5
Allylic Br Br
3 1 3
NBS Alc. KOH
Sol: (a) 4 4
Me Allylic Me 2 -Hbr 2
But-1-ene Substitution 3-Bromo-but-1-ene Buta-1,3-diene
(A)
(b) (Z) is formed by Saytzeff’s elimination, but the product (Y) is formed in major amount because product (Y) is a
more stable conjugate diene than (Z), isolated diene
Me 6 4 2
Br -HBr
5 1
Me 6 2 H at C-3 3
4
5 removed Me
(b)
3 1 5-methly hexa-1,3-diene
Me H H Alk.KOH (Y) Major
4-Bromo-5-methylhex-1-ene
Me 6 4 2
(X)
-HBr
5 3 1
H at C-3
is removed Me
Saytzeff 5-methly hexa-1,4-diene
elimination (Z) Minor
1 1 . 4 4 | Alkenes and Alkynes
(c)
4 1
H H
3 5 -H 2 6
H
(c) H
2 6 3 5
1 4
Less stable More stable
isolated diene conjugated diene
(A) (B)
Cyclohexa-1,4-diene Cyclohexa-1,3-diene
2 o 2 2
Cl2 at 500 1. Li 4
(d) 1 Allylic
3
1 2. Cu
1
Me 3
(d) Corey-House
Allylic
Prop-1-ene substitution Cl
(A) synthesis Diallyl R
3-Chloro-
lithium cuperate
prop-1-ene
(B)
4 4 Cl
6
1 3 5
R’
H
(e)
(e)
HO 2 4
KHSO4
OH Or 1 3
H Al2O3 or P2O5
(X) (Y)
(-H2O)
Butan-1,4-diol Butan-1,3-diene
Example 2: Give the major products (not stereoisomers) of the following:

5
(a 5
(a) 11 44
(a)
22 33
Cyclopenta-1,3-diene
Cyclopenta-1,3-diene
11 mol of
of Br
Br22 1 1mol
mol 1 mol
1 mol 1 mol
1 mol
HBr
HBr+ + HBrHBr H2S +
H2S +
peroxide
peroxide peroxide
peroxide
(b) 5
5
1
(b)
(b) Me 1 4
Me 4
2 3
2 3
1-Ethylcyclopenta-1,3-diene
1-Ethylcyclopenta-1,3-diene
1 mol of Br2 1 mol 1 mol 1 mol
1 mol of Br2 1 mol
HBr + HBr1 mol 1 mol
H2S +
HBr +
peroxide HBr H2S +
peroxide
peroxide peroxide
Chem i str y | 11.45
Sol: 1
(a) (a) 2 5

3 4
(A) All 1,4-addition products
Br2 HBr or H2S+
1,4-Add. HBr+peroxide Peroxide
3 Br 5
H H
2 4 1 4 1 4
1 2 2
5 Br 3 Br 3 SH
3,5-Dibromo- 3-Bromo- Cyclopent-1-
cyclopent-1-ene cyclopent-1-ene ene-3-thiol
(b)
(b) 1
Me 4
2 3
All 1,4-addition products
1 mol of Br2 HBr + peroxide HBr + peroxide H2S + peroxide
Anti-Markonvikov’s Anti-Markonvikov’s Anti-Markonvikov’s
add. add. add.
4 4 4 4
1 5 Br 3 5 Br 1 5H 5 3 SH
Me Br Me H Me Br Me H
2 3 2 1 2 3 1 2
3,5-Dibromo- 5-Bromo-3-ethyl- 3-Bromo- 5-Ethyl cyclo-

3-ethyl-cyclopent-1-ene cyclopent-1-ene 3-ethyl-cyclopent-1-ene pent-1-ene-3-thiol
Example 3: Write all the possible structures and give the structure of the products that are thermodynamically
favoured.
2 4 6
2 4 1 mol of
1 62 Products
Sol: 3 5 Br 1 mol of
1 Products
3
Hexa-1,3-5-triene Br2
5
Hexa-1,3-5-triene
2 4
6
1 3 2 5 4 6
Br
1 Br2 3 5
Br
Br Br2
2 Br 2 6
Br 6 4
4 Br
1 3 5 1 3 5
2 Br
1,4-Addition 2 6
Br 6 4
4
4 Br
Br 1 3 6 5 Br 14 3 5
2 Br 6
1,4-Addition
1 3 5 2
4 1 3 Br5
Br 2 6 Br 1,2-Addition 4
Br 24 2Br 4 2 6 6
1 3 6 5 Br
1 3 5 1 3 Br 5
1 3 5
1,2-Addition
(III)
2 4 1,6-Addition
Br 2 4 6
6 Br
1 3 5 Br
1 3 5 Br
2 4 Br2 2 (III)
6 6
1,6-Addition
1,2-Addition
2 4
Br 2 4 6
6 Br
1 3 5 Br
1 1 . 4 6 | Alkenes and Alkynes 1 3 5 (III)
1,6-Addition
Br
2 4 Br2 2
6 6
Addition of 4
1 3 5 1 3 5
Br2 at C3-C4
double bond
More stable Products (II and III, conjugate dienes) are thermodynamically
2 favoured
4 products than
2 I and4IV (isolated
dienes) (a) 1 and 1
3 5 3 5
Example 4: Distinguish between the given pairs. (A) (B)
3
2 4 2 4 5 4 3 2 1 2
C = C=C COOH and
(a) 1 3
and 1 3 (b) 6 4 1
5 5 COOH
H H
(A) (B) (C) (D)
Sol: (a) Compounds (A) and (B) are distinguished
3 chemically by quantitative catalytic hydrogenation. Since
5 4 3 2 1 2 compound (B) has only one double bond .Compound (A) will require
compound (A) has two double
C = C=C COOH and 4 bond whereas
6
2 moles of H2 for 1 mole of (A) while (B) will1COOH
(b) requires 1 mole of H2 per mole of (B).
H H
(C) (D)
COOH
Me C=C=C
H COOH
(C)
(b) Allene (C) with different groups on each of the double bonds is optically active and can be resolved into its
enantiomers.
Compound (D) is conjugate diene and does not show optical isomerism.
Example 5: Give the major and minor products. CH2 CH2 H

1
CH2
3 2 6
2 HBr
4 o
1 mol HBr at 45 C 3
o 5
at 45 C Br
1 5 4
6 (B) (major)
(A)
3-Bromo-1-methyl-
3-Methylenecyclohex-1-ene
cyclohex-1-ene
Sol: At high temperature (45ºC), 1, 4-addition products is more favourable.
CH2 H CH2
CH2 Br
CH2 1
1
2 2 6
6
HBr HBr
o
at 45 C 3 5
3 5
Br H
(A) 4
4
(B) (major) (C) (major)
3-Bromo-1-methyl- 1-Bromo-1-methyl-
cyclohex-1-ene cyclohex-1-ene
Example 6: Dehydration of (A) with conc. CH2 H Br

2
SO4 gives a compound that exists in two Me H
CH2
isomeric forms. Give the structures of both the isomers.
1
2 6 H OH

HBr (A)
3 5
H
(A) 4
Sol: 5 6
Me H Me 1 H Me
Conc. 4 +
H
H OH H2SO4 H H
(H) H 3 H H
(Z) or cis (E) or trans
4-Methylclohex-1-ene
Example 7: Me
H2 + Lindlar’s Catalyst
(B)
H2SO4
(A)
Me
Sol: Addition of H atom by Lindlar’s catalyst is a syn-addition. It reduces (C ≡ C) bond to
(C = C) bond so the product (B) is H H
Example 8: C10H16(A)
O3/Reduction
C5H8(B)
Not-reslovable Not-resolvable aldehyde
O3/Reduction
C5H8O2(C)
Not-resolvable acid
3 equivalent of H2+Pd
o
at 120 C
(D)
Write all the possible structures of (A), (B) and (C).
Sol: Since the reductive and oxidative ozonolysis products are different, the alkene of the type
H H
is possible
R R
If R = ( ) , the possible structures of (A) can be:
— CH 2 —
R = ( CH2 ( , the possible structures of (A) can be :

5 6
H H H 4 7
3 mol
3 8
of H2
H 2 9
1 (D) 10
Both optically inactive Decane
4 5
O3/Reduction O3/Oxidation
3 6
2 CH = O 2 COOH Me 2 7 Me
(B) (B)
1 8
Optically inactive Optically inactive
(D1)
2,7-Dimethyloctane

2
(D) is obtained when (C1 – C3) bond breaks 1
H
H 3
(D1) is obtained when (C2 – C3) bond

1
2
3

H breaks during hydrogenation of (A).
H
Example 9: Give the number of stereoisomers of (A) in the following reactions.

O3 /oxidation
(a) (A) (C7 H12 ) Acetone + Oxalic acid + Acetic acid
(B) (C) (D)
O3 /oxidation
(b) (A) (C8 H14 ) Butane-2-one + Oxalic acid + Acetic acid
(B) (C) (D)
Sol:
(a) Me
O HOOC - COOH HOOC - Me
Me
(B) (C) (D)
Convert acid
to aldehyde
Me
O O = HC - CH = O O = HC - Me
Me Remove and join
the double bond
to obtain the structure of (A)
Me 1
2 3 4 5 6
CH CH = CH Me
Me
(A) (C7H12)
6
H H Me
Here Compound (A) shows G.I around C4 — C5 H 5
double bond (since the two groups around C-4
4C C5 and
4C C
3 6 3
and C-5 are different) but do not show G.I around CH Me CH H
1 2 1 2
C2 — C3 double bond because the two groups Me Me
around C-2 are the same. (I) Me (II)
Me
Number of stereoisomers for (A) — 2
4Z-2-Methylhexa-2,4-diene 4E-2-Methylhexa-2,4-diene

(b) Proceed in the same manner as in (a)
Me
O HOOC - COOH HOOC - Me
Me
(B) (C)
Convert acid
to aldehyde
Me
O O = HC CH = O O = HC Me
Me
Remove O and join

Me
O O = HC CH = O O = HC Me
Me

Remove O and join
the double bond
to obtain the structure of (A)
Me
5 4 3 2 1
CH CH = CH Me
7 6
Me
(A) (C8H18)
(5-Methylhepta-2,4-diene)
(A) shows geometrical isomers around both (C2 — C3) and (C4 — C5) double bonds (two of the groups around these
double bonds are different)
Me H Me H
Moreover, terminal groups (—CH3) and (—C2H5), around C2 and aroundHC5, respectively, are different.
4 H
5 C 5 C Me
H
Number of G.I. when the terminal groups are different = 2 , where 4n is the number of double bonds C(two
n 3 2 double
C
1
7 C C 7
bonds). Me 6 3 2 Me Me 6
H
1
G.I. = 22 = 4 (I) (II)
(2Z,4Z) (2E,4Z)
Number of stereoisomers of (A) = 4
Me H Me H Me Me H
H 4 H Me 5 4 H 4 H Me
5 C H 5 C C H 5 C
4 3 2 1 2 3 2 1
7 C C 7 C C 7 6 H C C 7 6 C C
Me 6 3 2 Me Me 6 Me 3 Me
H Me H
(I) 1 (II) (III) 1 (IV)
(2Z,4Z) (2E,4Z) (2Z,4E) (2E,4E)
Example
Me 10: Explain the formationMe
of theHproducts giving the structures of the intermediates.
5 4 4 H
(a) C
H
HCl H 5 C Me
2 + 3 2Cl +1other products (D)+(E)

7
Me 6 H OH
C
3
C 7 Cl 6
Me
C C
Me H
(A) (III) 1 (B) (IV)
(2Z,4E) (2E,4E)
Sol:
(a) H -H2O Cl
OH Cl
OH2
(A) (B) (B)

(I)
In this reaction presence of double bond influences the reaction pathway and unusual product may also be formed.
Due to the presence of e–-rich double bond, the intermediate (I) carbocation may also involve intra-molecular
rearrangement to form a three membered cyclic ring as shown below:
1
2 2
Cl Cl
3 3
4 4
(I) (C)
Other products can be obtained due to carbocation (I) rearrangement.

Cl
1
1,2H shift
H Cl Cl
H Cl Me
o Me
o
(1 C ) 2 allyl C
o
(1 allyl C ) (E)
(More stable)
Example 11: Complete the following reaction:

6
5 3
1 (i) B4H6/THF NaOH
(B) (C)
Cl
4 2 (ii) H2O2,OH
(A) Al2O3 or P2O6
Sol: It is an example of hydroboration-oxidation reaction, it is used in the formation of alcohol from an alkene. It
follows anti-Markovnikov’s rule, and the addition of H and OH is syn (cis)(addition of H and BH2 takes place from
the same side)
( (
5 3 1 5 3
B2H6
(A) 2 H2O2/ -OH 2
THF Cl B Cl OH
4 4
H 3 H
(5-Chloropentane-1-ol)
(B)
Cl O
OH
5 1 NaOH
-HCl
4
2 H
3 Dihydropyran
(C)
JEE Advanced/Boards
Example 1: Complete the following reaction with appropriate reagents.

(a) ? ? ?
(B) (C)
(A) (D)
OH Me
D D
? ?
(B) D H
(b) Me Me
H D
Me (A) Me
Me Me
Sol: (a) Compound (D) Contains a (C = C) bond in the ring, Double bond can be obtained by the dehydration of
alcohol.So, (C) is an alcohol.Alcohol (C) is obtained by the reduction of (>C = 0) using reducing agent like LAH.
∴ So (B) contains a keto group (>C = O) , (> C = O) group can be obtained from (A) by ozonolysis.
The different steps are as follows:
O3/Red [H] (Conc.H2SO4)

O OH
LAH -H2O
OO
(A) (B) (C) (D)
(b) Proceeding reverse: (Retrosynthetic approach)

Compound (D) contains one Me and one –OH group. It can be obtained by adding (Cl2+ H2O) (HOCl) to (A).
Thus compound (B) will have one OH and one Cl group; now one Me group can be added to (B) by Corey-House
synthesis or Wurtz reaction of (B).
D D OH Cl
2 Cl2 + H2O CH3Cl + Na + dry ether
1 D D
Me Me Wurtz Reaction
H HO Cl H
Me
Me Me
Me HO Me
(A) (B)
Due to + I effect (CH3)2LiCu D D
Me
Electromeric effect Corey-House H
takes place from synthesis Me
Me (C)
C2C1

Ph Alc. KOH (B) + (C)
(a) Ph Ph and
Alc. KOH (B) + (C)
(a) Ph Br and
(A)
Br
(A) Me
(b) + CHBr3 + Me
Me OK (B)
(b) + CHBr3 + Me
Me OK (B)
(A)
Me
(A) O
O Cl + KOH + MeOH (B)
(c) Ph Cl + KOH + MeOH (B)
(c) Ph
Sol: H Ph H H H
Ph Alc. KOH
(a) and H Ph Ph Ph
Ph H (-HBr) (B) (C)
Br E or trans Z or cis
(More stable)
1,2-Diphenyl ethene
or styrene
Me Br Me
(b) CBr3+ Br
Me O H C Br Me OH + CBr
Dibromo carbene
Me Br Me
3 2
2 Br
4 1 Br -Br 3
+ :CBr2
5 6 Br Ring expansion 4 6
(A) (A)
5
(Bond breaks)
(c) It is an example of -elimination.

O
O
H
Cl
Ph
Ph or OH
H
H H Cl
O
H
H atom are more Ph
acidic due to the presence
of EWG ( C = O group ( O
Cl
Ph C
Example 3: Identify the5 products in the following reactions giving their stereoisomers (if any).
3 Me D2+ Poisoned Pd H2+Pt
(a) (A)Me1 2 5 (B) C (No. of isomers)
1 2 3 4 Me D2+ Poisoned Pd H2+Pt
(a) (A) Me (B) C (No. of isomers)
4
Baeyer’s
(b) (B)(from Problem A) (D) + (E) (Colour of precipitate)
Baeyer’s
reagent
(b) (B)(from Problem A) (D) + (E) (Colour of precipitate)
reagent
PhCO3H +H2O
( c ) (B) (D)
PhCO3H +H2O
( c ) (B) (D)
Na+liq. ND3 + EtOH Alk.KMnO4
(d) (A) (F) (D)
Na+liq. ND3 + EtOH Alk.KMnO
or 4
(d) (A) (F) (D)
OSO4/NaHSO
or 3
OSO
PhCO 4/NaHSO
3H/H2O 3
PhCO3H/H2O
Sol: 1 1
(a) Me 4 Me 4
2 3 H2+Pt 2 3 5
Me D2 +Poisoned 5 * * Me
Me Me Syn-addition
Pd H D
(A) D D D H
( C C ) ( C = C) (B) (C)
2Z-2,3-Dideuteropent-2-ene 2,3-Dideuteropentane
or or
2Z-2,3-Di-d-pent-2-ene 2,3-Di-d-pentane
Since Addition of D2 by (D2+Pd) is a syn addition Compound (B) is a cis compound and the addition of H2 + Pt
is also syn. But (B) has two different (R) groups (Me and Et), so the product (C) will not be Meso but a racemic
compound.
Compound (C) contains two chiral carbon, thus the number of optical isomers will be 22 = 4 (two pairs of enantiomer).
These are:
1 1 1 1
Me Me Me Me
H 2 * D D 2 * H H * D D * H
3 * 3 * * H * D
H D D H D H
4,5 Et Et Et Et
I II III II
Racemate Racemate
Pairs of enantiomers: I and II; III and IV (I, III); (I, IV); (II, III),
Pairs of diastereomers: (II, IV)
1
(b) Me Me 4
Baeyer’s reagent 5
2*
3 *
Me + MnO2
(b) Me (Cold. alk. KMnO4)
D D D (Brown-black ppt)
OH OH D
(B) sys-hydroxylation) (E)
(D)
cis-Compound 2,3-Dideutentropent-2,3-diol
with two different or
R group 2,3-Di-d-pent-2,3-diol
[Two chiral centres; four stereoisomers as in (a)]
(B) PhCO3H +H2O

(c) cis-Compound Anti-hydroxylation (D)
with two different [As in (b)]
R group
Me1 D
Na+liq.ND3 + EtOH 2
Me (D) 3 5
(d) Me
(Anti-addition of two D) D Me
4
(A) (trans or E)
(2E-2,3-Deuteropent-2-ene)
or
2E-2,3-Di-d-pent-2-ene
Alk.KMnO4
or
D [as a in (b)]
F
Trans compound OsO4/NaHSO3
(sys-hydroxylation)
PhCO3H/H2O
Example 4: Identify (A), (B) and (C) in the following reaction.

H2 + Pt
(A) (C7H10) (B) (C7H14)
H2 + Ni2B
No reaction
[O] Acidic KMnO4
2
3 1
COOH
(4-Oxohexan-1,6-dioic acid)
4 COOH or 4-Ketoadipic acid)
O 6
5
(C)
Sol: First of all we have to calculate degree of unsaturation:

(2nC + 2) − nH (7 × 2 + 2) − 10
D.U. in (A) = = = 3º
2 2
(7 × 2 + 2) − 14
D.U. in (B) = = 1º
2
Since (A) does not react with P-2 or Brown catalyst (Ni2B) that reduces alkyne to alkene
Therefore, (A) does not contain (C ≡ C) bond.
As we have calculated, (B) has 1.D.U., it must be a ring (because after hydrogenation of (A) no double bond will be
left)
From the above data it appears that, (A) has one ring and two (C = C) bonds; hence, (A) is a diene.
Total number of C atoms in (A)=7 

 one C atoms is lost as CO2
Total number of C atoms in (C)=6 
Possible structure of (A) are as follows:

i. 2
3 1
COOH
7
CO2 +
4 COOH
O 6
5 Proceeding
reverse
Racemate
2 6
3 1 1
CH 5
CH2 4 CH 4
2
6 H2C
5 3
(I)
(4-Methyl cyclohexene)
ii. Other two possibilities of the combination are as follows:

1 4 7 6
(a) (COOH) Groups combines with ( C ==H) group and CO2 combination with (COOH).
O
1
HOOC 2 CH 2
7 6 O O
CO2+ HOOC
3 7 6 3
4 4
CH2 HC
5 5

1 2
2 3
2' 7 6 3
4 4
1 H2C CH
3' 5
1'
(II) (II)
(Numbering in accordance (Numbering in accordance
with naming) with problem)
1-(prop-2-enyl)cyclobut-1-ene
or
1-Allyl cyclobutene
6 1
(b) (COOH) Groups combines with (C=O) group and CO2 is in combination with (COOH)
2
7 1 7 1
CO3 + HOOC 3 H2C CH 3
4 O 4
5
5 6
6
COOH
(Numbering in accordance
with problem)
4 2
3 1
(Numbering in accordance
with naming)
(4-(Cyclopropenyl)but-1-ene)
Structure III is not possible, because on hydrogenation (A) gives (B) (C7H14), i.e., it absorbs 2 mol of H2, whereas III
will absorb 3 mol of H2.
Because of highly strained ring Structure III is unlikely.
Two possible structures are as :-
5

6 4
1
H2C Me 3
2
(I)
(B)
(C7H14) (1-Methyl cyclohexane)
2 mol H2 3 2
4 1
Me
(II) (B)
1-Propyl-cyclobutane

O
Ph
Ph 4 5 H
1 +
O O (Z) + CO2
Ph 3 2 H Disappearance
Ph
O of purple
(X) Purple colour (Y) colour
2,3,4,5,-Tetraphenyl cyclopenta- Maleic
2,4-dien-1-one anhydride
Sol: It is an example of Diels Alder reaction. The mechanism is a concerted type (bond breaking and bond making
takes place simultaneously)
Ph O Ph O
H
H 1' 5
Ph 4 5 Ph
1 4 1 1'
O O O O
2' 2'
Ph 3 2 H Ph 3
2
H
Ph O Ph O
Ph O Ph O
H
5 Ph
Ph 1
4 1'
O
2'
O O
-CO
Ph 3 2
Ph
H
Ph O Ph O
(Z)
(Colourless
compound)
Example 6: Identify (A) to (H)

(A)
Reagent I II III IV V
100 atm, H2+Ni NH2NH2+O2 Sia2BH+
H2+Ni or
H2+Pt+Al2O3 CH3COOH
35 atm,
(B) (C) (D) + (E) (gas) (F) + (G) (H)
Sol:
(A)
Reagent I II III IV V
100 atm, H2+Ni NH2NH2+O2 Sia2BH+
H2+Ni or
H2+Pt+Al2O3 CH3COOH
35 atm,
(B) (C) (D) + (E) (gas) (F) + (G) (H)
(A)
Reagent I Reagent II Reagent III Reagent IV Reagent V

H
6
5
Me Me Me + Me + Me
4 2
3
(C) (D) (F)
(B)
BSia2
N2(gas) H
(E) H
(G)
(H)
Example 7: Write the product with its mechanism.
Conc. H2SO4
Me
B+H
B+ H2 O
2
O
HO Me
Me
(A)
Sol: 2 2
5 1 6
3
Me
1,2 Me Shift 3
4
4 5
Me Me
Me
2C
o Me Me
3oC
(Numbering in according
with problem for understanding)
7 5 2
6 1
8 4 3
-H
3 4
9 Saytzeff elimination 6
1 5
2 Me Me
10
Me Me Me Me
2,2,3-Trimethyl bicyclo [4.4.0] dec-1-ene
Example 8: Which of the following show G.I.?

Me
Me
Me
(a) (c) N OH
(b)
Me
Me Me O2N
H
(d) N.OH (e) N NH2 (f) N NH NO2
Me H Me
(g) Ph N=N Ph (h)
Me Me
Sol: In order to show geometrical isomerism the alkene must contain different substituents i.e. the substituents on
both the carbon bearing double bond must have different substituents
(a) It shows G.I.
H H H H
or or
H H H H
cis trans
(i) Two atoms on the dotted line (..........................) means that the groups are below the plane of the ring.
(ii) Two atoms on the bold lines (..........................) means that the groups are above the plane of the ring.
(iii) One atom on the dotted line (..........................) means that one group is below and another is above the plane
of the ring.
(b) It shows G.I.
CH3 CH3 CH3 CH3
CH3 CH3 CH3 CH3
or or
cis trans
(c) It does not show G.I.
Me
OH
N
:
Me
Two same groups
Priority of C2H5 > CH3 and OH > LP of e s
Me

N Two higher priority group
on the same side, on two different
OH C atom of the double bond
Me
anti or E
(e) It does not show G.I

H
NH2
N
Two different groups

Two same groups
(f) It does not show G.I

O2N
Me
NH NO2
Me
Two different groups

Two same groups
(g) It shows G.I.
Ph Ph
H3C CH3 H3C Ph H H CH3
N=N
N=N
* * * *
Ph
Two different HTwo different
H H CH3 or CH
anti E 3 H
groups groups
(+) or D (-) or L
Cis has a plane of
(h) It shows G.I.symmetry so O.I.A Trans is optical active
(Meso from)
H3C CH3 H3C H H CH3

Me
* * * * Br
Me Me
HBr H H CH3 CH3 H
(a) (b) (c) Me
(+) or D HO (-) or L Me
Cis hasMe
a plane of Me
symmetry so O.I.A Trans is optical active Me Me
(Meso from) Me Me
Example 9: Give IUPAC name to each of the following using E or Z designations.

Me
Br Me Br
Me (C) Me Me
(A) (B)
Me Me HO Me
Me Me
Me
Sol:
(a) (b) 2'
Me
1
Br Me Br
1' Me
2 3 Me 2 3
Me 4 5 HO
1 4 5
6
Me
Two higher priority groups on opposite side,1E,
1-Bromo-2,3-dimethyl pent-2-ene Priority of (-Br) > (-CH2OH) and [(CH3)2CH-]>(-C3H7).
Two higher priory groups on the same side.
2Z,2-Bromo-3-(1-methyl ethyl) hex-2-en-1-ol
(c)
1 2 5 6

3 4 2'
Me Me
1 1
2 Me
Me Me
Priority of HC C- > (CH3)3C- > CH2=CH-B> (CH3)2CH-

Two higher priority groups on the same side.
3Z,3-(1-methyl ethyl)-4-(1-1-Dimethyl ethyl)-hexa-1,3-dine-5-yne
ALKYNES
1. INTRODUCTION
1.1 Nomenclature
Alkynes are unsaturated hydrocarbons that contain (C≡C) bond. Their general formula is CnH2n–2.
Condensed Stick Bond line IUPAC name Common or trivial name

C2H2 H—C≡C—H 2 1 Ethyne Acetylene
C3H4 H3C—C≡C—H 3 2 1 Propyne Methylacetylene
C4H6 CH3—CH2—C≡CH 4 But-1-yne Ethylacetylene

3 2 1
CH3—C≡C—CH3 But-2-yne Dimethy lacetylene
4 3 2 1
C5H8 CH3—CH2—CH2—C≡C—H 4 3-Methyl-but-1-yne Propylacety lene

3 2 1
5
or 4 3-Methyl-but-1-yne Isopropyl-acetylene
3 2 1
CH3
CH3—CH—C≡C—H
or 5 Pent-2-yne Ethyl methylacetylene

4 3 2 1
CH3—CH2—C≡C—CH3
1.2 Structure
Each carbon atom of ethyne is sp-hybridized. One sp-hybridized orbital of each carbon undergoes head on overlap
with sp-hybrisized orbital of another carbon to form a sp-sp, C-C, σ-bond. The second sp-hybridized orbital of each
carbon overlaps along the internuclear axis with 1 s-orbital of each of the two hydrogen atoms forming two sp-s,
C—H, σ-bonds. Each carbon is now left with two unhybridized p-orbitals (2px and 2py) which are perpendicular to
each other as well as to the plane of the C—C sigma bond.
The two 2px– orbitals, one on each carbon, are parallel to each other and hence overlap sideways to form a π-bond.
Similar overlap between 2py– orbitals, one on each carbon, results in the formation of a second π-bond as shown
in figure.
Sp-s Sp-s
C-H, -bond C-H, -bond
1s sp sp
sp
1s
sp
(a) H C C H
sp-sp, C-C
-bond
In the plane
Below the plane
of the paper
of the paper
2px
(b)
2px
C C

Above the plane In the plane of

of the paper the paper
120 pm 107.9 pm
H C C H
o
180
Carbon-carbon triple bond consists of one strong σ-bond and two weak π-bonds. The total strength of C ≡ C bond
in ethyne is 823 kJ mol–1. It is stronger than the C = C bond of ethane (599 kJ mol–1) and C – H bond of ethane
(348 kJ mole–1). Further, due to the smaller size of sp-orbitals (as compared to sp2 and sp3–) and sideways overlap
of p-orbitals, the carbon-carbon bond length in ethyne is shorter (120 pm) than those of C = C (134 pm) and C–C
(154 pm).
1.3 Isomerism in Alkynes

(i) Position isomerism. The first two members, i.e., ethyne and propyne exist in one form only. However, butyne
and higher alkynes exhibit position isomerism due to the different position of the triple bond on the carbon
chain. For example,
CH3—CH2—C≡CH CH3—C≡C—CH3
But-1-yne But-2-yne
(ii) Chain isomerism. Alkynes having five or more carbon atoms show chain isomerism.
CH3
4 | 2 13
CH3—CH2—CH2—C≡CH CH3—CH—C≡CH
(iii) Functional isomerism: Alkynes are functional isomers of dienes

4 3 3 1 1 2 3 4
CH3 — CH2 — C ≡ CH =
CH2 CH
= — CH CH2

But-1-yne Buta-1,3-diene
(iv) Ring chain isomerism: Alkynes show ring chain isomerism with cycloalkenes. For example,
CH3—C≡CH and are ring chain isomers.

Cyclopropene
Propyne Cyclopropene
2. PREPARATION OF ALKYNES
2.1 From Calcium Carbide

Alkynes are prepared by the following general methods.
1. By the action of water on calcium carbide: Ethyne (acetylene) is prepared in the laboratory as well as on a
commercial scale by the action of water on calcium carbide.
CaC2 + 2H2O → HC≡CH + Ca(OH)2

Calcium carbide Ethyne (Acetylene)
Calcium carbide needed for the purpose is manufactured by heating limestone (calcium carbonate) with
coke in an electric furnace at 2275 K.
2275K
→ CaO + CO2
CaCO3 
CaO + 3C 
2275K
→ CaC2 + CO
2. Procedure: Lumps of calcium carbide are placed on a layer of sand in a conical flask fitted with a dropping
funnel and a delivery tube. The air present in the flask is replaced by oil gas since acetylene forms an explosive
mixture with air. Water is now dropped from the dropping funnel and the acetylene gas thus formed is
collected over water.
3. Purification: Acetylene gas prepared by the above method contains impurities of hydrogen sulphide and
phosphine due to the contamination of CaS and calcium phosphide in calcium carbide. Phosphine is removed
by passing the gas through a suspension of bleaching powder. Pure acetylene is finally collected over water.
2.2 Double Dehydrohalogenation of Dihalides
Double dehydrohalogenation of a geminal dihalide

H X
| |
R—C—C—R’ + 2NaNH2 R—C≡C—R’ + 2NH3 + 2NaX
| |
H X
Geminal dihalide Sodium amide Alkyne Ammonia Sodium halide
Double dehydrohalogenation of a vicinal dihalide

H H
| |
R—C—C—R + 2NaNH2 R—C≡C—R’ + 2NH3 + 2NaX
| |
X X
Vicinal dihalide Sodium amide Alkyne Ammonia Sodium halide
The most frequent application of these procedures are in the preparation of terminal alkynes. Since the terminal
alkyne product is acidic enough to transfer a proton to the amide anion. One equivalent of base in addition to the
two equivalents required for double dehydrohalogenation is needed. Adding water or acid after the reaction is
complete converts the sodium salt to the corresponding alkyne.
2 3NaNH H2O
1. (CH3)3CCH2CHCl2 → (CH3)3CC≡CNa  → (CH3)3 CC≡CH
NH3
1,1-Dichloro-3,3- Sodium salt of alkyne 3,3-Dimethyl-

Dimethylbutane product (not isolated) 1-butyne (56-60%)
2. 3NaNH
CH3(CH2)2CHCH2Br  → CH3(CH2)7C≡CNa 
2 H2O
→ CH3(CH2)7C≡CH
NH
| 3
Br
1,2-Dibromodecane Sodium salt of alkyne 1-Decyne (54%)

Product (not isolated)
Double dehydrohalogenation to form terminal alkynes may also be carried out by heating geminal and vicinal
dihalides with potassium ter-butoxide in dimethyl sulfoxide. By heating with alcoholic solutio`n of KOH
CH2—Br
CH
| +2 KOH (alc.) 
∆
→ ||| + 2KBr + 2H2O
CH2—Br
CH
1,2-Dibromodecane Acetylene
(Ethylene dibromide)
PLANCESS CONCEPTS
Misconception: The reaction, in fact, occurs in two steps and each step involves the loss of a
molecule of HBr as shown below:
∆
BrCH2—CH2Br + KOH (alc.)  → CH2=CHBr + KBr + H2O
Ethylene dibromide Vinyl bromide
∆
CH2=CH—Br + KOH (alc.) → CH≡CH+KBr+H2O
Vinyl bromide Acetylene
Aman Gour (JEE 2012, AIR 230)
Explanation: In ethylene dibromide, Br is present on a saturated carbon atom. Therefore. Like alkyl halides, it is
a reactive molecule. Consequently, on heating with alcoholic KOH, it readily eliminates a molecule of HBr to form
vinyl bromide in good yield. In contrast, due to the presence of Br on a doubly bonded carbon atom, vinyl bromide
is a highly unreactive molecule and hence on heating with alcoholic KOH, it does not easily lose a molecule of HBr
to form acetylene. Thus, with alcoholic KOH, the yield of acetylene is low. Therefore, to obtain acetylene in fairly
good yield from vinyl bromide, a much stronger base than alcoholic KOH such as NaNH2 in liquid NH2 is usually
used. Thus, dehydrohalogeneation of ethylene dibromide to acetylene is preferably carried out in the following
two stages.
H H H
KOH(alc.), NaNH2/liq.NH3
R C C H H C C H H C C H
-HBr -HBr
Br Br Br Acetylene
Vicinal dihalide Vinyl bromide
Θ
With a strong base ( NH2 ), isomerisation also taken place to give terminal alkyne.
:
(i)NaNH2, 400K
Me C C Me Me C C Na
H2O
Me C CH
Prop-1-yne
Dehalogenation of tri/tetra halides
Br
Me1 Br 3 (i) 2(Zn+EtOH) 4 3 2 1

Me C C Me + 2ZnBr2
2 or
(But-2-yne) or
Br Me (ii) 2(Mg+EtOH)
2MgBr2
or
Br or
(iii) 4(NaI in acetone)
4NaBr +2I2
2,2,3,3,-Tetra bromobutane
3. By dehalogenation of tetrahalides.: Tetrahaloalkanes when heated with zinc dust in methanol undergo
dehalogenation to yield alkynes. For example
Br Br
CH3OH
H C C H + 2 Zn H C C H + 2 ZnBr2

Acetylene
Br Br
1,1,2,2-Tetrabromoethane
2.4 Dehalogenation of Haloforms

By dehalogenation of haloforms: Chloroform and iodoform on heating with silver powder undergo dehalogenation
to form ethyne.
∆
CH Cl3 + 6 Ag + Cl3 CH HC CH + 6 AgCl
Chloroform Ethyne
Chloroform
∆
CH l3 + 6 Ag + l3 CH HC CH + 6 AgI
Iodoform Iodoform Ethyne
2.5 Kolbe’s Electrolytic Reaction

Kolbe’s electrolytic reaction: Acetylene can be prepared by electrolysis of a concentrated solution of sodium or
potassium salt of maleic acid or fumaric acid. Thus,
H COOK H COOK
C C Electrolysis CH
+ 2H2O + 2CO2 + H2 + 2KOH

or
C C CH
Acetylene
H COOK KOOC H
Pot. maleate Pot. fumerate
(cis isomer) (trans-isomer)
This reaction is called Kolbe’s electrolytic reaction and is believed to occur by the following steps:
CHCOOK ionaization CHCOO +

2OH- + 2 H
+
+2K ; 2 H2O
CHCOOK CHCOO
CH
CHCOO CHCOO + 2CO2
- 2e-
CH
CHCOO CHCOO
unstable
CHCOOK ionaization CHCOO + Chem i str y | 11.65
2OH- + 2 H
+
+2K ; 2 H2O
CHCOOK CHCOO
CH
At anode: CHCOO CHCOO + 2CO2
- 2e-
CH
CHCOO CHCOO
unstable
At cathode: 2H+ + 2e− →[2H] → H2
2.6 From α-diketo

α- Diketone reacts with hydrazine (NH2 – NH2) to give bis-hydrazone which on oxidation with HgO gives unstable
bis(diazo) compound which decomposes to give alkyne.
O N NH2
4
2 3 Me 2NH2 NH2 Me
1
Me Me
O N NH2
Butan-2,4-dione Bis-hydrazone of (I)
(1)
HgO
N
-N2
Me Me Me
But-2-yne Me
N
Bis-(diazo) of (I)
2.7 Industrial Method

2CH4 ( g) 
→ CH ≡ CH ( g) + 3H2 ( g)
1773 K
The reaction is highly endothermic, yet the optimum time for this reaction is 0.01 second.
∆n = nP – nR = 4 – 2 = 2 mol, and this causes a significant increase in ∆S. At this high temperature, the T∆S term in
the equation ∆G = ∆H – T∆S predominates, making ∆G = –ve , although ∆H = +ve.
But ∆H°f for C2H2 = +227 k mol–1 shows that acetylene is thermodynamically unstable, explodes readily, and gets
converted into its elements.
C2H2(g) → 2C(s) + H2 (g) , ∆H° = – 227 kJ mole–1
2.8 Berthelot Synthesis

Mearcellin Berthelot synthesized acetylene from its elements (carbon and hydrogen) by striking an electric arc
between two electrodes in an atmosphere of H2 gas.
2C + H2 CH CH(g)
Acetylene
2.9 Higher Alkynes from Acetylene

Synthesis of higher alkynes from acetylene: Acetylene is first treated with sodium metal at 475K or with sodamide
in liquid ammonia at 196 K to form sodium acetylide. This upon treatment with alkyl halides gives alkyne.
For example:
Liq.NH ,196K
3 → HC ≡ C−Na+ + NH3
HC ≡ CH + NaNH2 
Ethyne(Acetylene) Sodiumacetylide
HC C-Na+ + CH3 Br HC C CH3 + NaBr

Sod. acetylide Bromomethane Propyne
HC C-Na+ + CH3 CH2 I HC C CH2CH3 + NaI

Sod. acetylide Idoethane But-1-yne
HC C-Na+ + CH3 CH2 CH2 Br HC C CH2CH2CH3 + NaBr

Sod. acetylide 1-Bromopropane Pent-1-yne
(n-propyl bromide)
An analogous sequence usually terminal alkynes as starting material yields alkynes of the type RC = CR’.
N NH
2 3 → (CH ) CHCH C ≡ CNa 
3 →(CH ) CHCH C ≡ CCH CH Br
(CH3 )2 CHCH2C ≡ CH  3 2 2 3 2 2 3
2 −Methy −1 −Pentyne NH3 5 −Methyl−2 −Hexyne −181%
Dialkylation of acetylene can be achieved by carrying out the sequence twice.
3 1.NaOH,NH 3 1.NaOH,NH
HC ≡ CH → HC ≡ CCH2CH3 → CH3C ≡ CCH2CH3
Acety lene 2.CH3CH2Br 2.CH3Br 2 −Pentyne(81%)
3. PROPERTIES OF ALKYNES
(i) No cis-trans isomerism: The sp hybrid orbitals are linear, ruling out cis-trans stereoisomers in which
substituents must be on different sides of the multiple bond.
(ii) Bonds: Bond length decreases in the following order: Alkane > Alkene > Alkyne
Bond length order: −C − H > = C − H > ≡ C − H

sp3 sp2 sp
Bond Strength order: ≡ C − H > = C − H > –C − H

sp sp2 sp3
As a general rule ‘more the s – character of hybrid orbitals used by an atom, closer are the bonding electrons to the
atom and shorter and stronger is any of its σ-bonds’.
(iii) Solubility and Dipole moment
Decreasing solubility in H2O: Alkynes > Alkenes > Alkanes
Alkynes are slightly more soluble in H2O because they are somewhat more polar.
The dipole moment of alkyne is greater than those in alkene because (C — C) sp bond is more polarized
than (C — C) sp2 bond: this is because C with more s character is more electronegative.
Dipole moment of but-1-yne is 0.8 D and that of but-1-ene is 0.3 D.
Due to a slightly high polarity and dipole moment of alkynes than those of alkenes (and of alkenes
higher than alkane) boiling point of alkynes > alkenes > alkanes, with the same number of C atoms.
They go from gases to liquids to solids with increasing molecular weights. There is a little difference in
boiling points of these hydrocarbons with similar C skeletons.
(iv) Smell: All alkynes are odourless except acetylene which has a garlic smell due to the presence of impurity,
phosphine.
(v) Physical state: The first three members are gases, the next eight are liquids, and the rest are solids.
(vi) Melting and Boiling points: The m.p. and b.p. of alkynes are slightly higher than those of the corresponding
alkenes and alkanes. This is probably due to the presence of a triple bond, alkynes have linear structures and
hence their molecules can be more closed packed in the crystal lattice as compared to those of corresponding
alkenes and alkanes.
(vii) Densities: Densities of alkynes like those of alkenes and alkanes increase as the molecular size increases.
However, they are all lighter than water, since densities lie in the range 0.69 – 0.77 g/cm2.
(viii) Stability: Alkynes are less stable than isomeric dienes as is evident from their heat of formation ( ∆H°f ) values.
2 4
1 5 (1,4-Pentadiene) +106.0 kJ mol-1
3
Me 5
1 +129.0 kJ mol-1
Me (Pent-2-yne)
4 3 2
4
2 1
5 H (Pent-2-yne) +144.5 kJ mol-1
Me 3
(ix) Reactivity: However, alkynes are less reactive than the corresponding alkenes towards electrophilic addition
(EA) reaction (except catalytic hydrogenation), even though they contain two π-bonds. This is due to:
(a) Greater EN of sp-hybridised C atom of alkynes than sp2 –hybridised C atom of alkenes which hold the
π - electrons of alkynes more tightly.
(b) Greater delocalisation of π -electrons in alkynes (because of cylindrical nature of their π -electrons
cloud) than in alkenes. As a result, π -electrons of alkynes are less easily available for addition reaction
than those of alkenes. So alkynes are less reactive than alkenes towards electrophilic addition reaction.
Catalytic hydrogenation, however, is an exception: Alkenes are adsorbed on the surface of
catalyst only when the plane of π-bond approaches perpendicularly. In alkynes because of the
cylindrical nature of π-bonds, approach by hydrogen along the axis of the cylinder is more effective
and thus transition state in alkynes is less strained. So alkynes react faster than alkenes with H2.
(x) Acidity of alkynes:
Terminal alkynes are more acidic than alkenes because alkyne C-atoms are sp hybridized and electrons
in an s-orbital are more tightly held than in a p-orbital also s-electrons are closer to the nucleus.
Furthermore, since the sp orbital has more s character (50% s) than sp2 (33% s) or sp2 orbital (25% s), the
electrons in sp orbital are more tightly held by the nucleus than electrons in sp2 or sp3 orbital.
In another words, sp-hybridised C is more EN than sp2, or sp3-hybridised C atom. Due to this greater
EN, the electrons of (C — H) bonds are displaced more towards the C atom than towards the H atom.
Therefore, the H-atom is less tightly held by the C atom and hence can be removed as a proton (H+ ion)
by a strong base and consequently terminal alkynes behave as acids.

R—C C — H + strong base R—C C — Base — H
As a rule, as the s character decreases from sp to sp2 to sp3 hybridised C atom, the acidic character of hydrocarbons
decreases in the following order.
= O ←→ Me − C⊕H − OΘ
Me − HC
4. REACTIONS OF ALKYNES
4.1 Acidic Character

(i) Formation of alkali metal acetylides: Ethyne and other terminal alkynes (Alkynes in which the triple bond
is at the end of the carbon chain) or 1-alkynes react with strong bases such as sodium metal at 475 K or
sodamide in liquid ammonia at 196 K to form sodium acetylides with evolution of H2 gas.
475K
2HC ≡ CH+ 2Na  → 2HC ≡ C−Na+ + H2
Ethyne Monosodiume ethynide
(Acetylene) (monosodiumacetylide)
Liq.NH
3 → R − C ≡ C −Na+ + NH
R − C ≡ CH + NaNH2 
(A ter minalalkyne) 196K
3
(A sod. alkynide)
During these reactions, the acetylenic hydrogen is removed as a proton to form stable carbanions
(acetylide ions) Sodium acetylide is decomposed by water regenerating acetylene. This shows that water
is a stronger acid than acetylene and thus displaces acetylene from sodium acetylide.

HC ≡ C−Na+ + H2O → HC ≡ CH+ NaOH
(Monosodiumacetylide) (Acetylene)
(ii) Formation of heavy metal acetylides: Acetylenic hydrogens of alkynes can also be replaced by heavy metal
ions such as Ag+ and Cu+ ions. For example. When treated with ammoniacal silver nitrate solution (Tollen’s
reagent), alkynes form a white precipitate of silver acetylides.
CH ≡ CH + 2[Ag(NH3 )2 ]+ OH− → AgC

= CAg + 2H2O + 4NH3
Ethyne Tollensreagent Disilver ethynide
R − C ≡ CH + [Ag(NH3 )2 ]+ OH− → R − C ≡ C − Ag+ H2O + 2NH3

(Ter minalkyne) Tollensreagent Silver alkynide
(Whiteppt.)

Similarly, with ammoniacal cuprous chloride solution, terminal alkynes form red ppt. of copper acetylides.

HC ≡ CH + 2[Cu(NH3 )2 ]+ OH− → CuC ≡ CCu + 2H2O + 4NH3
(Ethyne) Dicopper ethynide
R − C ≡ CH + [Cu(NH3 )2 ]+ OH− → R − C ≡ C − Cu + H2O + 2NH3

(Terminal alkyne ) Tollensreagent Monocopper alkynide
(Re dppt.)
Unlike alkali metal acetylides are not decomposed by water. They can however, be decomposed with dilute mineral
acids to regenerate the original alkynes.
AgC ≡ CAg + 2HNO3 → HC ≡ CH + 2AgNO3
(Disilver acetylide) Acetylene
CuC ≡ CCu + 2HCl → HC ≡ CH + 2CuCl

(Dicopper acetylide) Acetylene
(iii) Formation of alkynyl Grignard reagents: Acetylne and other terminal alkynes react with Grignard reagents
to form the corresponding alkynyl Grignard reagents. For example.
Dry
HC ≡ CH + RMgX → HC ≡ CMgX + RH

(Acetylene) Grignardreagent Ether Acetylenic Alkane
Grignard reagent
R '− C ≡ CH + RMgX
Dry
→ R '− C ≡ CMgX
 + RH
Ter minalalkyne Grignardreagent Ether AlkynylGrignard reagent Alkane
Alkynyl Grignard reagents like usual Grignard reagents can be used to prepare a variety of organic compounds.
Importance: The formation of metal acetylides can be used:
(a) For the separation and purification of terminal alkynes from non-terminal alkynes, alkanes and alkenes.
(b) To distinguish terminal alkynes from non-terminal alkynes or alkenes.
4.2 Hydrogenation / Reduction

cat
RC ≡ CR '+ 2H2  → RCH2CH2R ' Catalyst = Pt, Pd, Ni or Rh
Alkene is an intermediate
H2 Pt
CH3CH2 CH2CH3
H2/Pd/BaSO4 H3C CH3

H3C C C CH3 Quinoline C=C
(Lindlar’s catalyst) H H
H3C H
Na, NH3(liq.)
C=C
H CH3
The general case

H H
H2 H2
H3C C C CH3 C=C CH3CH2 CH2CH3
PVC PVC
H3C CH3
The reaction takes place on the surface of Pt or Pd. Since the addition is twice, it is hard to see the syn addition.
But the reaction can be stopped at the alkene stage by using the following reagents.
(a) H2 + Pd + BasO4 + S or quinoline in boiling xylene (called Lindlar’s catalyst). In this case, reaction proceeds
via syn addition of H2.
(b) H2 + P-2 or Brown catalyst (H2 + Ni + B) or (H2 + Ni2B). It also proceeds via syn addition of H2.
(c) Alkali metals (Na, K, Cs) + liq. NH3 and C2H5 OH (It is called Birch reduction). It proceeds via anti-addition of H2.
(d) LiAlH4(LAH). It reduces (C ≡ C) to (C = C) via anti addition of H2; does not reduce (C = C) to (C — C) bond;
reduces (C=C) to (C —C) only when the phenyl group is attached to the -C atom of the double bond.
β α
(E.g. Ph − CH =CH − CH3 to Ph − CH2 − CH2 − CH3 )
Reduction of alkynes to (Z) – alkenes
Lindlar’s catalyst: Pd, quinoline, Pb and CaCO3 poisons the metal catalyst. So that the H2 adds only to the alkyne.
Not reactive enough for alkenes.
H H
H2
CH3(CH2)2 C (CH2)2CH3 C=C
Pd/CaCO3/Pb
CH3(CH2)2 (CH2)2CH3
Lindlar catalyst
96% cis
H (CH2)2CH3
Na/NH3
CH3CH2 C C (CH2)3CH3 C=C
H
CH3CH2
98% trans
H H
H2
CH3(CH2)2 C (CH2)2CH3 C=C
Pd/CaCO3/Pb
CH3(CH2)2 (CH2)2CH3
Lindlar catalyst
96% cis
H (CH2)2CH3
Na/NH3
CH3CH2 C C (CH2)3CH3 C=C
H
CH3CH2
98% trans
Reduction of alkynes to (E) – alkenes. Reaction via Na radical dissolved in liquid NH3.
Na● + NH3 → Na+ + e– [NH3]n
Solvated electron
−33°C
Mechanism of Na/NH3 reductions: Na+  → Na+ + NH3 (e− )
R R H R H R H
Na H NH2 Na NH2 H
R C C R C C C C C C C C
+ -NaNH2 +
Na R R R H R
NaNH2
4.3 Addition of X2
Like alkenes, 1 mol of alkynes adds 2 moles of halogens and proceeds via anti-addition of halogens, and orange or
brown colour of Br2 is discharged (test for unsaturation)
H
Br
H Br- 2 1
+
HBr
(I) HC CH HC=CH H2C CH
Markovnikov’s
(EA) Br
Br 1,1-Dibromo ethane
or Ethylidene bromide
(II)
Me 4
Mechanism: Me 4 Br
2 1 HBr 2 1 HBr 3 2 1
Like alkenes it proceed
3 via the
H: formation of
Markovnikov’sintermediate
3 cyclic
CH2bromonium ion. First, electrophile
Markovnikov’s
Me (Br ⊕ ) add
Θ
and then the addition of nucleophile (EA)
But-1-yne (Br ) from anti-position
Br take place.(EA)That is whyMethis reaction is called EA
4
(electrophilic addition) reaction. The reaction is stereospecific
2-Bromo(attack by electrophile in a specific
Br manner).
2,2-Dibromo
Anti-Markovnikov’s But-1-ene
HBr+ROOR butane
free radical
H
(Peroxide)
addition H H
Br
Br Br Br
HC CH C=C C = C
R.D.S Br H
Me
Slow4 Br Me 4 1
Br Br
3 2 1 HBr+ROOR 3 2
Br H
Br
Br H Br H Br C—C
H C — C H 1,1-Dibromobutane
Br
1-Bromobut-1-ene Br H
Br (Butylidene bromide)
Br
Cl Cl
CCl4 Cl2/CCl4 - HCl
CHCH + Cl3 CH = CH H-C-C-H Cl2C = CHCl
Ba(OH)2
Cl Cl Cl Cl Trichloroethylene
or
Westron or 1,1,2,2,-tetrachloro or westrosol
BaCl2
ethane or acetylene tetrachloride
4.4 Addition of Water
Hydration of alkynes
O
||
H2O/H2SO 4
H3C − C ≡ C − H →
HgSO
H3 C − C − CH3
4
H H
H +
H2O
H3C– C ≡ C–H H3C– C = C – H H3C– C = C – H
+ –H+
s-viniylcation
OH
H an enal
H3C– C = C – H H3C– C = CH3
O O
H Ketone
enol
(Oxymercuration-demercuriation of triple bond)

Hg2+ OH2
Me – C C–H Me — C = C — H
2+
Hg
H2O Attack of H2O on

more substituted C atom
HO H H3O⊕ HO
C = C C = C H
Me H –Hg2+ Me
Hg
Tautomerise
Me – C – Me
4.5 Addition of HX
H Br Br Br
Br H
CH3 CC H C C C C
CH3 CH2 H3C CH3 CH3 CH3 H3C Br CH3

H
H
Br
H Br- 2 1
+
HBr
Markovnikov’s
(EA) Br
(II)
Me 4 Me 4 Br
2 1 HBr 2 1 HBr 3 2 1
H: CH2 Me
3 Markovnikov’s 3 Markovnikov’s
But-1-yne Br 4
(EA) (EA) Me
2-Bromo Br
2,2-Dibromo
HBr+ROOR butane
Br
H Br- 2 1
+
HBr
Markovnikov’s
(EA) Br
(II)
Me 4 Me 4 Br
2 1 HBr 2 1 HBr 3 2 1
H: CH2 Me
3 Markovnikov’s 3 Markovnikov’s
But-1-yne Br 4
(EA) (EA) Me
2-Bromo Br
2,2-Dibromo
HBr+ROOR butane
free radical
(Peroxide) Br
addition
4Me Me 4 1
3 Br
2 1 HBr+ROOR 2
3 Br
H
H H
1,1-Dibromobutane
1-Bromobut-1-ene
(Butylidene bromide)
PLANCESS CONCEPTS
The order of reactivity of HX is HI > HBr > HCl > HF

Aishwarya Karnawat (JEE 2012 AIR 839)
4.6 Addition of Acids

Addition of carboxylic acids: When acetylene is passed into warm acetic acid in presence of mercury salts, first
vinyl acetate and then ethylidene diacetate is formed.
Hg2 +
3 CH COOH
HC ≡ CH + CH3COO − H → H2=
C CH − OCOCH3 
→ CH3 − CH(OCOCH3 )2
Acetylene Acetic acid 353K vinyl acetate Hg2 + Ethylidene discetate
Vinyl acetate is used for the manufacture of vinyl resin. Ethylidene diacetate, when heated rapidly to 573-673K,
gives acetic anhydride and acetaldehyde.
OCOCH3 CH3 CO
573-673K O + CH3CHO
CH3 CH
OCOCH3 CH3 CO Acetaldehyde
Ethylidene diacetate Acetic anhydride
4.7 Addition of HCN

The reaction is nucleophilic addition (NA) initiated by CN– from NaCN.
.. HCN
HC CH + CN CH = CH CH2 = CH CN
+H Vinyl cyanide
CN or
Acrylonitrile
4.8 Addition to Other Compounds

CH2 O CH3
H2SO4
HC CH + Conc. H2SO4 CH2 O S OH CH(OSO3H)2
O
Vinyl hydrogen sulphate Ethylidene hydrogen sulphate
CHCl
HOCl CHCl2 -H2O CHCl2
HC CH + HOCl
Hypochlorous CHOH
CH(OH)2 CH=O
acid 2-chloro Dichloro acetaldehyde
eth-1-en-1-ol or 2,2-Dichloro ehtanal
CH3OH
CH3OK CH2 CH3OK CH3
HC CH + CH3OH
430-470K CH(OCH3)2
CH OCH3
under pressure
Methyl vinyl Ethylidene
ether methoxide
+
Hg
HC CH + Conc. HNO3 CH(NO3)3
oxidative
Nitroform
cleavage
4.9 Ethyne + Methanal

The addition of ethyne to unsaturated link like (>C = O) is called ethinylation. Acetylene or terminal alkyne containing
≡ CH (a methine H-atom) reacts with a carbonyl group (>C = O) in the presence of sodium or potassium alkoxide
(RONa or ROK) or NaNH2 to give alkyndiol with a small amount of alkyneol.

..
CH3O H C CH CH3OH + C CH
.. CH3OH
3 2 1
HC C CH2 = O HC C CH2 O H C C CH2OH
Propargyl alcohol or
Formaldehyde
Prop-2-yn-1-ol
CH3O
..
C C CH3OH
CH2 = O
1 2 3 4
CH3OH
HOCH2 C C CH2OH + CH3O O H2C C C CH2OH
But-2-yn-1,4-diol
4.10 Nucleophilic Addition

Because of the greater electronegativity of the sp-hybridized carbons as compared to sp2 hybridized carbons,
alkynes are more susceptible to nucleophilic addition reactions than alkenes.
For example, when acetylene is passed into methanol at 433-473 K in presence of a small amount (1-2%) of
potassium methoxide under pressure, methyl vinyl ether is formed.
3 CH O−K +
HC ≡ CH + CH3O − H 
→ CH=
2 CH − OCH3
Acety lene Methanol 433− 473K Methyl vinyl ether
CH3O−K +
HC ≡ CH + CH3O − H 
→ CH=
2 CH − OCH3
Acety lene Methanol 433− 473K Methyl vinyl ether
Methyl vinyl ether is used for making polyvinyl ether plastics.

4.11 Propargylic Halogenation

Alkenes undergo allylic substitution with NBS, whereas alkynes undergo propargylic halogenation with NBS, Cl2SO2
(sulfuryl chloride). Me3COCl(t-butyl hypchlorite), and Cl2 at 500°C.
O

4Me NBS+CCl4 4Me 2 1
2 1 3
H H + N-H
3 +h
But-1-yne Br
3-Bromo but-1-yne O
Propargylic
H-atom O-Cl 4Me
3 2 1 OH
H +
+CCl4 + h
Cl
3-Chlorobut-1-yne
Reaction proceeds via free radical mechanism to give propargylic radical, which is stabilized by resonance via
extended π-bonding.
4.12 Hydroxylation of Alkynes

Hydroxylation of alkyne with aqueous or neutral KMnO4 solution (Baeyer’s reagent) test for unsaturation)
Pink colour of KMnO4 is discharged and brown black precipitate of MnO2 is obtained. This reaction converts alkynes
first to enediols and then further gives tetraols, which being unstable lose H2O to give diketones.
OH OH
1 2 3 4 aq. KMnO4 1 2 3 4 OH (But-2-en 2,3 diol)
Me C C Me Me C C Me
OH
OH OH
But-2-yne aq. KMnO4
1 2 3 4 Me Me
Me C C Me -2H2O
HO C C OH
O O
Butan 2,3 dione
OH O H
Unstable
Me C C Me Me C C Me
OO
(Break two bonds and add O O
O atom on both sides)
OH
1 OH
OH 3
OH aq. KMnO4 H
2 H 2 1
3
OO 4
O O
But-1-en-3-yne
3,4-Dihydroxy-2-oxo
butan-1-al
4.13 Oxidation Reactions
4.13.1 Oxidative Cleavage

(a) Alkynes are oxidatively cleaved in alkaline or acidic conditions at higher temperature, as mentioned.
R C R COOH
H C [H COOH] CO2
1
Me 3
(i) 6 Me 3
2 3 4 7 [O] 1 1 4
C C
5 Me 2 COOH + HOOC 2 Me
Hept-3-yne Propanoic Butanoic
acid acid
(ii) Me Me
3
3 2 1 [O] 1
C C H 2 COOH+[HCOOH]
But-1-yne Propanoic
acid CO2
6 3
(iii) Me Me
5 4 3 2 1 [O] 2 1
C C C C Me COOH + [HOOC COOH]
Oxalic acid
Hexa-2,4-diyne Propanoic
acid
+HOOC-Me 2CO2
Ethanoic
acid
CrO3 in CH3COOH oxidizes alkenes but does not affect alkynes
4.14 Ozonolysis of Alkynes

Alkyne form ozonides with O3 and are decomposed by H2O to give diketones, which are then oxidised by H2O2 or
KMnO4/NaIO4 or peracids; given acids, and on reduction with metal / acid, LAH, or NaBH4 give diols.
O
(i) HC CH + O3 H C C H
O O
H2O
H2C CH2 Reduction

H C C H + H2O2
Zn+CH3COOH
OH OH or O O

or HO OH
OH LAH or NaBH4
HO Glyoxal
Glycol H2O2
[O]
2CO2 2HCOOH
Formic or
methanoic acid
Terminal alkynes give HCOOH as one of the products which is further oxidized to CO2
These oxidative cleavage reactions are rarely used for synthesis because alkynes are not readily available. They are
used to locate the position of a triple bond in an alkyne.
4.15 Hydroboration of Alkynes

•• Terminal alkynes of HBO reaction give aldehyde, whereas internal alkynes give ketone.
•• Alkynes react with BH3 or B2H6 complexed with THF (tetrahydrofuran O) to give trivinyl borane, which upon
subsequent treatment with alkaline H2O2 gives alcohols corresponding to anti-Markovnikov’s addition of H2O
to alkynes, which on tautomerisation give corresponding aldehydes or Ketones.
•• If trivinyl borane is treated with acid(CH3COOH), it gives cis-alkene (proceeds via syn-addition of H2).
Me
3Me CC Me 3BH3+THF Me C=C B

But-2-yne
H
n
itio
n - add
Sy H H2O2/OH
COO
CH 3
4 1
Me
Me Me
3 2
C=C Me CH=C
H H OH
Z-But-2-ene
Tautomerise
4 1 2 1
Me CH2 C Me
O
Butan-2-one
4.16 Polymerisation
1. Linear Polymerisation

1
Cu2Cl2 2 3 4 1 2
HC CH + HC CH CH CH + 3 4 5 6
NH4Cl or CH2 = CH C C CH = CH2
1 2 3 4 Cu2Cl2 + NH4Cl or
Cu +O2
2+ 1 6
CH2 = CH C CH 23 4 5
Vinyl acetylene
H C C C C H
But-1-en-3-yne
But-1,3-dyne Divinyl acetylene or
1mol 1mol Hexa-1,5-dien-3-yne
HCl HCl

Cl
Cl
H2 + Ni2B 4 3 2 1 Peroxide/h
HC C C = CH2 CH2 = CH C = CH2
Polymerisation CH2 CH = C CH2
n
Cl
Chloroprene or Neoprene or
2-Chloro-buta-1,3-diene Polycholoropene
2. Cyclic Polymerisation
CH CH 1 2
CH
8 3
CH CH CH CH
Red hot tube Ni(CN)4
or 3 (HC CH) or 4 (HC CH) 4
or THF 7
CH CH CH CH
Hot copper 6 5
Benzene CH CH
HC Cycloocta
1,3,5,7 tetra-ene
Me
3. Propyne Me
CH
CH CH
or 3 (Me C CH) Red hot tube
Me CH C Me
Me Me
HC 1,3,5-Trimethyl benzene or Mesitylene
4.17 Isomerization
When alkynes are heated with NaNH2 in an inert solvent such as kerosene oil or paraffin oil, they undergo
isomerization. i.e. 2-alkynes isomerize to 1-alkynes and vice versa.

Uses of alkynes
(i) Acetylene and its derivatives are widely used in synthetic organic chemistry for synthesis of cis-and trans-
alkenes, methyl ketones etc.
(ii) Oxyacetylene flame is used for cutting and welding of metals.
(iii) Acetylene is used as illuminant in hawker’s lamp and in light houses.
(iv) Acetylene is used for the ripening of fruits and vegetables.
(v) Acetylene is used for manufacture of ethyl alcohol, acetaldehyde, acetic acid, vinyl plastics, synthetic rubbers
such as Buna N and synthetic fibers such as Orlon.
PLANCESS CONCEPTS
Difference between Alkenes and Alkynes
Test Alkene Alkyne

1. Flame observed on comnustion Luminous Smoky
2. Br2/CCl4 solution Orange colour is discharged Orange colour is discharged
3. Cold aq. or alkaline KMnO4 Pink colour is discharged with the Pink colour is discharged with the
solution (Baeyer's reagent) formation of diol compound formation of dicarbonyl compound
4. Ammoniacal AgNO3 solution No action Whote ppt. of silver alkynide (given
[Ag(NH3)2]+ (Tollens reagent) by only terminal alkynes)
5. Ammoniacal CuCl solution No action Red ppt. of copper acetylide (given
by only terminal alkynes)
6. Reactivity towards electrophilic Alkenes are more reactive than alkynes
addition reaction (e.g. HX, X2)
7. Reactivity towards cataytic Alkynes are more reactive than alkenes
8. Reactivity towards nuclephilic Alkynes are more reactive than alkenes
addition reaction (e.g. CN+)
POINTS TO REMEMBER
H
HX
C-C
X
H
HBr
C-C
(Peroxides)
Halogenation Br
Reaction H
X2
C-C
X
H
X2/H2O(”HOX”)
C-C
(NBS, H2O/DMSO)
X
H OH Anti-Markovikov
1. BH3, THF
+ C-C regiochemistry
2. H2O2, HO Syn addition
H OH
Syn 1. OsO4
C-C Syn addition
addition 2. NaHSO2, H2O
+
HO OH
KMnO4, HO /H2O
C-C Syn addition
Hydroxylation
C=C
+
H Markovnikov
H /H2O regiochemistry
C-C
OH Carbocation
Anti intermolecular
addition H
1. Hg(OAC)2, H2O Markovnikov
C-C regiochemistry
2. NaBH4
OH
H H
H2, Pt
Reduction C-C Syn addition
Cl Cl
Dichloro methylene insertion C
CHCl3, KOH
C C
Ring forming
Reaction
H H
Methylene insertion C
CH2I2, ZN(Cu), ether
C C
X H
2 HX
R C-C H Markovnikov
regiochemistry
Halogenation X H
Reaction X H
2 HX2 X
R C-C
X X
H H
Complete reduction
R C-C H
H2, Pt
H H
Reduction
H H
H2, Lindlar catalyst
C=C Syn addition
R H
Partial
reduction
H H
Li, NH3 (liq.)
C=C Anti addition
R H
R C C H
O H
+ Markovnikov
H /H2O
C-C H regiochemistry
HgSO4
Carbonyl R H Enol intermediate
compound
forming reaction H O Anti-Markovnikov
1. BH3, THF C-C regiochemistry
+ R
2. H2O2, HO Enol intermediate
H H
Chain
NaNH2
lengthening R - C C - CH2 - R Alkyne anion intermediate
RCH2Br
reaction
[O]
RCOOH + CO2
Alkaline or
Acidic condition
Oxidation
1. O3
+ R - CH - CH2 + CO2
2. Zn, H3O
OH OH
Solved Examples
JEE Main/Boards
Example 1: Identify A to C.
2Na Na+NH3+EtOH
HC CH (A) (B)
2CO2/H3O H2/Pd/CaCO3
(C)
Sol: It is an example of ethinylation (addition of ethyne to unsaturated link like C group).

First step is the reaction with the sodium metal to form disodium acetylide with evolution of hydrogen gas.
This reaction shows the acidic character of alkynes.
During this step acetylenic hydrogens are removed as a proton to form stable carbanion.
Now the carbanion reacts with two moles of carbon dioxide and forms an adduct which on treatment with acid
yields acid.
Next step is reduction using Lindlar Catalyst (H2/Pd-CaCO3) the addition is syn.
On treatment with (NH3+EtOH) trans product is formed thus the addition is anti.
O O
2Na
H C CH Na C C Na OO C C C C O
O C
O
O C
H3O
1 4
COOH
HOOC 2 3 HOOC H
H2/Pd/CaCO3 1 2 3 4 Na + NH3 + EtOH 23
Syn-additon
HOOC COOH Anti- addition
H H (A) H COOH
(C) But-2-yn-1,4-dioic acid
Maleic acid or Fumaric acid (B) or
cis-But-2-en-1,4-dioic acid trans-But-2-en-1,4-dioic acid
Example 2: Identify B to G.
2
1 3 Br2 1. NaNH2
Me (B) (C)
2. H2O
Propene
NBS + CCl4 + h
(A)
Cl2+ 500oC (D)
1. Li (D)
(E) 2. Cul (F) (G)
Sol:
•• Addition of Br2 across double bond forms 1,2-dibromo propane.
•• This on treatment with soda lime undergoes double dehalogenation to form an alkyne
•• Now alkyne on the treatment with a brominating agent (NBS- N-Bromosuccinimide) and CCl4 as a solvent in
presence of light.
•• On the other side, the first step is Allylic chlorination using Cl2 at 500 ◦C.
•• The reaction proceeds through radical formation.

•• Now Allyl chloride undergoes chain lengthening reaction to form Hex-1-en-5-yne.
•• The reaction is known as Corey house synthesis
Br
2 3 Br2 3 2
1 Me 1 1. NaNH2
Me Me C CH
2. H2O
(A) Br
(B) (C)
1,2-Dibromopropane Prop-1-yne
o
Cl2 at 500 C Propar-
Allylic gylic NBS + CCl4 + h
radical radical
chlorination brominating
2 3 3 2 1
Cl H
1 Br

(E) (D)

Allyl chloride 3-Bromoprop-1-yne
or or
3-Chloro prop-1-ene propargylic
bromide
Coerey 1. Li
-House 2. Cul
R’
1
2 3

2
CuLi
Br
3 2 1
H
2 4 5 6
1 3
(F) (D)
Diallyl lithium R R’
cuperate
(G)
Hex-1-en-5-yne
Example 3: Alkenes are more reactive than alkynes towards electrophilic addition reaction, yet vinyl acetylene
reacts with 1 mole of HBr at triple bond. Explain why.
Sol:
•• Alkynes are less stable than isomeric diene.
•• Compound (A) is a conjugate diene whereas compound (B) is an alkyne.
•• As heat of formation of diene is less than the heat of formation of alkyne, Vinyl acetate reacts with 1 mole of
HBr to form a conjugate diene and formation of compound (B) is not favoured.
Br
4 3 2 1 HBr
CH3 CH C CH H2 C CH C CH H2C CH C CH2
4 3 2 1
Br Vinyl acetylene
3-Bromobut-1-yne 2-Bromobut-1,3-diene
(B) (A)
The product A (Conjugated diene) is more stable than B (an alkyne)

Example 4: There are two path (a) and (b) For the preparation of a compound (a)
1 2 3
Me
=
4 5
Me

(2-methylpent-1-en-3-yne), which path is correct and why? Also name the paths (a) and (b). Path (a)
Sol: Path (b) is correct because in path (a) compound
does not occur.

Me
Br
vinyl halide which is not reactive, so the reaction
Path (a) is the alkylation of alkyne, whereas path (b) is propinylation (type of ethinylation), i.e., addition of propyne
to unsaturated link like (> C = O) group.
Me
Br Path (a)
H Me NaC Me Me
Me Me
Path (b) O + H2 O (A)
Me
Me
Conc. H2SO4+
Me
Me -H2O
OH
JEE Advanced/Boards
Example 1: Complete the following missing reagents
C CH
(A)
?
(a)
(B)
Br
?
(b) (C)
2 CuLi
?
(c)
(D)
Br
?
?
(e) (d)
Br
(F) (E)
Sol: (i)
(a) HBr + Peroxide
First step is addition of HBr, it takes place according to Markovnikov’s rule.
(b) (1) Li (2) CuI (Corey – House): Second step is Corey House synthesis.
(c) Br Third step is the reaction with alkyl halide.
(d) Br2/CCl4
Bromination using Br2 and CCl4 as a solvent
(e) KOH(s), at 473 K
Last step is double dehalogenation using base like KOH at 473 K
(ii) Cis compound on addition with Br2 (Anti addition) forms a racemic mixture or enantiomer.
Trans compound on addition with Br2 (Anti addition) produces Meso compound (it contains plane of
symmetry)

H H
H
and
H
cis trans

Br2(Anti-addition) Br2(Anti-addition)
racemic or (+) (E) meso and (E)
H Br
H Br H Br
+ Enantiomer
Br H
Due to the plane of

symmetry
Example 2: Convert the following

? ? ?
(B) C Cl
(a) (b) (c)
(D)

? (G)
Cl (d) CuLi H
2
(E) (F)
(H)
Sol:
Cl Allylic
Cl2 alc. KOH chlorination
(a) Cl
+ h
(b) (SO2Cl2 + )
(a) (B) (c )
(A) or (D)
( O Cl + (
Cl

1 2 2
1. Li 3 Me
(D) 3 H
2. Cul
Cl (d) CuLi
2
(b) (E) (F) Less stable More stable
Vinyl Divinyl
isolable diene conjugated diene
chloride lithium
(G) (H)
cuperate
3-Ethenyl cyclo 3-Ethylidene cyclo
pent-1-ene pent-1-ene
Example 3: Convert the following.

2 Br ?
3 (B) ? (C) ? (D) ? Hept-2-yne
Me 1
(E)
Write the structure of (E).
Sol: The structure of E is

7
Me 5
3 2 1
Me
6 4
First prepare 3C – atom alkyne (Me − C ≡ C − H) from (A) and then react 4C – atom RX with alkynide ion to get (E).
Reaction:
Br
2 Br alc.KOH Br2 2
3 3 1
Me 1 (B) Me
Propyne (C) Br
(A)
1,2-Dibromopropane
2NaNH2
Double dehalogenation
Me H
Propene
2NaNH2
3 1
4
Me 2 Br 7
1 2 3 5 Me
Butyl bromide 4
Me C C Me C C
6
Propynide ion Hept-2-yne
(D) (E)
Example 4: Complete the following:

1 mol C2H5Br NaNH2 CH3I
HC CH B C D (E)
NaNH2
Ethyne
(A)
Sol:
C2H5Br 1 2 4
1 mol
HC CH HC CNa HC C C C2H5
NaNH2
(A) Sodium ethynide But-1-yne
(B) (C)
NaNH2
CH3I
CH3 C C C2H5 NaC C C2H5
(E) (D)
Pent-2-yne Sodium butynide
JEE Main/Boards
Exercise 1 (B) Starting with cyclohexyl ethyne, prepare acetyl

cyclohexane.
Q.1 What are alkenes? Discuss briefly the various
methods used for the preparation of alkenes. Describe Q.9 (A) Complete the following reactions:
with a labelled diagram the laboratory preparation of NaNH C H
2 → A →
CH3COCH 3  2 2 B
ethane from ethanol.
H + H (1 equiv ) Al O , ∆
Q.2 Write the major products of the hydrocarbon and → C 
2
Pd
→ D →
2 3
400ºC
E
oxidation of:
(A) 1-Ethyl cyclopentene (B) Complete the following reactions:
2 →A NaNH
(B) Methylene cyclopentene CH3–C≡CH 
CH CH Br 2 2
H CH I
Q.3 Give the missing compounds in the following:  2 2 2→C
→ B 
Lindlar' s catalyst Zn(Cu)
BH .THF CH COOH
(A)
(a) BH333.THF ? CH333COOH ?
(a) ? ? Q.10 Predict the product of the following:
BH3.THF CH3COOH
(a) ? ? Conc. H2SO4/
BH3.THF CH3COOH A
(b) BH33.THF ? CH33COOH ? (A)
(B)
(b) ? ? HCl
B
BH3.THF CH3COOH OH
(b) ? ?
BH .THF CH COOH H2O/H
+
(c) BH333.THF ? CH333COOH ? CH3 A

(C)
(c) ? ?
BH3.THF CH3COOH CH2 (I) B2H6
B
(c) (i) BH3.THF ? ? (ii) H2O2(OH- )
(d) (i) BH33.THF ? (B) H3C
(d) (ii) CH3COOH ? CH3 (i) Hg(OAc)2
(i) BH
(ii) CH33.THF
COOH C
(D)
(d) 3
? (ii) NaBH4
(ii) CH3COOH OH
+
H RCO3H H2O
(C) J
Q.4 Complete the following equation:
(A) CH3C ≡ CCH3 
H2
→ (A) Q.11 (A) Give reasons for the following:
Pt
H When 1-penten-4-yne is treated with HBr in

2 → CH CH CH CH

Pt 3 2 2 3 equimolecular proportion, the addition takes place on
double bond and not on triple bond yielding thereby
(B) CH3 –C ≡ CCH3 
Na + C2H5OH the product
→
(B) + NaOC2H5 CH3CH(Br)CH2C≡CH.
(B) Provide a suitable mechanism for the following
Q.5 Give an account of physical and chemical reactions reaction.
of alkenes.
OH CH3
CH3
Q.6 What are alkynes? How are they prepared in the
laboratory?
Q.12 Three isomeric alkenes A, B and C, (C5H10) are
Q.7 Give an account of physical properties and chemical
hydrogenated to yield 2-methylbutane A and B gave
reactions of alkynes.
the same 3º ROH on oxymercuration-demercuration
B and C give different 1º ROH’s on hydroboration-
Q.8 (A) Starting with any alkyne, prepare ethyl oxidation supply the structures of A, B and C.
cyclohexyl ethyne.
Q.13 3,3-dimethyl-1-butene and HI react to give two Q.6 End product of the following sequence is:
products, C6H13I. On reaction with alc. KOH one isomer, Heat H O
CaO + C  → (A) 
2 → (C)
(1) gives back 3,3-dimethyl-1-butene the other (J)
Hg 2 +
gives an alkene that is reductively ozonized to give 
H SO
→ (C)
2 4
Me2C=O. Give the structures of (I) and (J) and explain
the formation of the latter. (A) Ethanol (B) Ethyl hydrogen sulphate
(C) Ethanal (D) Ethylene glycol
Q.14 Identify X, Y and Z in the following sequence of
reaction giving stereo chemical structure wherever Q.7 The treatment of C2H5MgI with water produces
possible.
(A) Methane (B) Ethane
CCH
(i) Na (i) H2 (I) CH3CO3H
(X)
Pd BaSO4
(Y) +
(ii) H /H2O
(C)(Z)
Ethanal (D) Ethanol
(ii) Br
(i) H2 (I) CH3CO3H

(X)
Pd BaSO4
(Y) +
(Z) Q.8 When isobutene is brominated, the percentage of
(ii) H /H2O
Br
H3C CH3 would be

Exercise 2 CH3
Single Correct Choice Type (A) 0% (B) 83% (C) 10% (D) 100%
Q.1 On heating CH3COONa with soda lime the gas

evolved will be Q.9 Propene can be converted into 1-propanol by
oxidation. Which set of the reagents is used to effect
(A) C2H2 (B) CH4 (C) C2H6 (D) C2H4 the conversion?
(A) OsO4 — CHCl3 (B) O3/Zn — H2O
Q.2 The addition of Br2 to trans-2-butene produces
(C) Alkaline and cold KMnO4 (D) B2H6 and alk. H2O2
(A) (+) 2, 3-dibromobutane
(B) (–) 2, 3-dibromobutane
Q.10 In the following sequence of reactions, identify
(C) rac -2, 3-dibromobutane the product (d)
(D) meso -2,3-dibromobutane HBr HBr alk.KOH
C H ≡ C H  → ( A )  → ( B ) → ( C )
NaNH
Q.3 Isomers which can be interconverted through 2 → (D)

rotation around a single bond are
(A) Ethanol (B) Ethyne
(A) Conformers (B) Diastereomers
(C) Ethanal (D) Ethene
(C) Enantiomers (D) Positional isomers
Q.11 Which one is highly unstable?
Q.4 The olefin, which on ozonolysis gives CH3CH2CHO
(A) CH2=CH–OH (B) CH2=CH–Cl
and CH3CHO
(C) CH2=CH–CH2–Cl (D) CH3–C≡CH
(A) But-1-ene (B) But-2-ene
(C) Pent-1-ene (D) Pent-2-ene
Previous Years’ Questions
Q.5 Which of the C — C bond is strongest?
Q.1 Marsh gas mainly contains (1980)
(A) Formed by sp3–sp3 hybridised carbon atoms (as in
alkanes) (A) C2H2 (B) CH4 (C) H2S (D) CO
(B) Formed by sp2–sp2 hybridised carbon (as in alkenes)
(C) Formed by sp–sp hybridised carbon atoms (as in Q.2 Which of the following will decolourise alkaline
alkynes) KMnO4 solution? (1980)
(D) None of these (A) C3H8 (B) CH4 (C) CCl4 (D) C2H4
Q.3 The compound 1,2-butadiene has (1983) (A) Both are highly ionic
(A) Only sp-hybridised carbon atoms (B) One is oxidising and the other is reducing
(B) Only sp2-hybridised carbon atoms (C) One of the steps is endothermic in both the cases
(C) Both sp and sp2-hybridised carbon atoms (D) All the steps are exothermic in both the cases
(D) sp, sp and sp -hybridised carbon atoms
2 3
Q.10 Which of the following compound will exhibit

geometrical isomerism? (2015)
Q.4 When propyne in treated with aqueous H2SO4 in
presence of HgSO4, the major product is (1983) (A) 1-Phenyl-2-butene
(A) Propanal (B) Propyl hydrogen sulphate (B) 3-Phenyl-1-butene
(C) Acetone (D) Propanol (C) 2-Phenyl-1-butene
(D) 1,1-Diphenyl-1-propane
Q.5 Bayer’s reagent is (1984)
(A) Alkaline permanganate solution Q.11 The reaction of propene with HOCl (Cl2 + H2O)
proceeds through the intermediate : (2016)
(B) Acidified permanganate solution
(A) CH3 – CH+ – CH2 –Cl (B) CH3 - CH(OH) - CH2+
(C) Neutral permanganate solution
(C) CH3 – CHCl - CH2 (D) CH3 – CH+ – CH2 – OH
(D) Aqueous bromine solution
Q.12 The major organic compound formed by the

Q.6 Acidic hydrogen is present in (1985)
reaction of 1, 1, 1-trichloroethane with silver powder is
(A) Ethyne (B) Ethene (2014)
(C) Benzene (D) Ethane (A) Acetylene (B) Ethene
(C) 2-Butyne (D) 2-Butene
Q.7 Hydrogenation of the adjoining compound in the
presence of poisoned palladium catalyst gives (2001)
Q.13 In the reaction,
H LiAlH PCl
Alk.KOH
5 → B 
4 → A 
H3C CH3COOH  →C
CH3
the product C is (2014)
H3C
H H (A) Acetaldehyde (B) Acetylene
(C) Ethylene (D) Acetyl chloride
(A) An optically active compound
(B) An optically inactive compound Q.14 In the following sequence of reactions, the alkene
(C) A racemic mixture affords the compound ‘B’
3 → A  O
2 → B. H O
(D) A diastereomeric mixture CH
= 3CH CHCH3  Zn
The compound B is (2008)

Q.8 The reaction of propene with HOCl proceeds via
(A) CH3CH2CHO (B) CH3COCH3
the addition of (2001)
(C) CH3CH2COCH3 (D) CH3CHO
(A) H+ in the first step
(B) Cl+ in the first step Q.15 The hydrocarbon which can react with sodium in
–
(C) OH in the first step liquid ammonia is (2008)
–
(D) Cl+ and OH single step (A) CH3CH2CH2C ≡ CCH2CH2CH3
(B) CH3CH2C ≡ CH
Q.9 In the presence of peroxide, hydrogen chloride
(C) CH3CH ≡ CHCH3
and hydrogen iodide do not give anti Markownikoff’s
addition to alkenes because (2001) (D) CH3CH2C ≡ CCH2CH3
Q.16 The treatment of CH3MgX with CH3C ≡ C − H (B) Statement-I is true; statement-II is true; statement-II
produces (2008) is not the correct explanation of statement-I.
(A) CH3 − CH ≡ CH2 (B) CH3C ≡ C − CH3 (C) Statement-I is true; statement-II is false.
H H (D) Statement-I is false; statement-II is true.

| |
(C) CH − C = C− CH (D) CH Q.19 Statement-I: Addition of Br2 to 1-butene gives
3 4
3 two optical isomers.
Q.17 The alkene that exhibits geometrical isomerism is: Statement-II: The product contains one asymmetric
(2009) carbon. (1998)
(A) Propene (B) 2-methyl propene
Q.20 Statement-I: 1-butene on reaction with HBr in
(C) 2-butene (D) 2- methyl -2- butane
the presence of a peroxide produces 1 bromobutane.
Q.18 One mole of a symmetrical alkene on ozonolysis Statement-II: It involves the formation of a primary
gives two moles of an aldehyde having a molecular radical. (2000)
mass of 44 u. The alkene is (2010)
Q.21 Statement-I: Dimethyl sulphide is commonly
(A) Propene (B) 1–butene
used for the reduction of an ozonide of an alkene to
(C) 2–butene (D) Ethene get the carbonyl compound.
Statement-II: It reduces the ozonide giving water
Assertion and Reason Type soluble dimethyl sulphoxide and excess of it evaporates.
(2000)
Read the following questions and answer as per the
direction given below: Q.22 Statement-I: Addition of bromine to trans-2-
(A) Statement-I is true; statement-II is true; butene yields meso-2, 3-dibromo butane.
statement-II is a correct explanation of statement-I. Statement-II: Bromine addition to an alkene is an

electrophilic addition.
JEE Advanced/Boards
Exercise 1 (B) on treatment with alcoholic KOH followed by

NaNH2 resulting in the formation of compound (C)
Q.1 Compound (X) (C5H8O) does not appreciably react C6H10. Compound (C) on treatment with H2 (gas) over
with Lucas reagent at room temperature but gives a platinum forms 2-methyl pentane. Compound (C) gives
precipitate with silver nitrate (ammoniacal). With Me ammoniacal AgNO3 test. Ozonolysis of (A) gives two
Mg Br, 0.42gms of (X) gives 22400 mL of CH4 at STP. aldehydes (D) and (E) where E is acetaldehyde. Identify
Treatment of H2 in the presence of Pt catalyst followed A, B, C, D and E.
by boiling with excess HI, gives n-pentane. Suggest the
structure for (X) and write equations involved. Q.4 A hydrocarbon (A) is treated with excess of HCl. A
dihalogen derivative (B) is formed. Compound (B) on
Q.2 Compound (A) C5H10 decolourizes Br2. When (A) treatment with aqueous KOH gives C. Compound (C)
is treated with hot KMnO4, two acids (B) and (C) are can be obtained by heating calcium salt of 2-methyl
formed. When (B) is treated with soda lime, methane propanoic acid with calcium acetate what are A, B and C?
is formed. When (C) is heated with soda lime ethane is
AlBr
formed. What are the structure of (A), (B) and (C). Q.5 CF3CH = CH2 + HBr →
3 X
Q.3 An organic compound (A) C6H12 is treated with Cl2 Q.6 An organic compound (A) C9H12 gave (B) C8H6O4 on
in the presence of CCl4 gives (B) C6H12Cl2. Compound oxidation by alkaline KMnO4. (B) on heating does not
form anhydride. Also (B) reacts with Br2 in the presence Q.15 A hydrocarbon (P) of the formula C8H10, on
of iron to give only one monobromo derivative (C). ozonolysis, gives compound Q (C4H6O2) only. The
C8H5BrO4. What are A, B and C. compound (Q) can also be obtained from an alkyl
bromide, R (C3H5Br) upon treatment with Mg in dry
Q.7 A hydrocarbon (A) C9H10 adds Cl2 to give (B) ether, followed by CO2 and acidification. Identify (P), (Q)
C9H10Cl2. Hydrolysis of (B) gives (C) C9H12O2. Oxidation and (R) and give equations for the reactions.
of (A) gave two acids identified as benzoic acid and
acetic acids. What are A, B and C? Q.16 Two isomeric alkyl bromides (A) and (B) have
molecular formula C5H11Br. (A) on treatment with
Q.8 An organic compound (A) C9H10Br2 forms C9H11OBr alcoholic KOH gives two isomers (C) and (D) of formula
with caustic soda solution the later is resistant to further C5H10. (C) on ozonolysis gives formaldehyde and
action of alkali. (B) on treating with H2SO4 converts 2-methylpropanal. (B) with alcoholic KOH gives (D) and
into (C) with on ozonolysis gives ethanal and another (E). Catalytic hydrogenation of (C), (D) and (E) gives (F)
compound (D). Identify (A) to (D) and give reactions. C5H12. Identify (A) to (F).
Q.9 An organic compound (A) C6H10, on reduction first Q.17 How would you bring about the following
gives (B) C6H12 and finally (C) C6H14. (A) on ozonolysis conversion.
followed by hydrolysis gives two aldehydes (D) C2H4O
and (E), C2H2O2. Oxidation of (B) with KMnO4 gives the (i) 1, 3-Butadiene to racemic - 1, 4-dibromo -2,
acid (F) C4C8O2. Determine the structures of (A) to (F) 3-dideutrobutene
with proper reasoning.
(ii) →
Q.10 An organic compound (A) of molecular formula
C5H8 when treated with Na in liquid ammonia followed Me H NBS (i) Li
by reaction with n-propyl iodide yields (B) C8H14. (A) (iii) C C A 
(ii) Cu P
→B
gives a ketone C5H10O when treated with dil. H2SO4 and H Me (iii) A
HgSO4. (B) on oxidation with alkaline. KMnO4 gives two
(iv) Z-2, 3-Dideutero-2-butene to racemic-erythro-2-
isomeric acids (D) and (E) C4H8O2. Give structures of
Bromo-2,3-Didenterobutane
compounds (A) to (D) with proper reasoning.
(v)
1-Methyl cyclopentene to trans-2-Methyl
Q.11 An organic compound (A) C8H6, on treatment cyclopentane
with dil. H2SO4 containing mercuric sulphate gives (vi) H
a compound (B), which can also be obtained from a
reaction of benzene with acid chloride in the presence O
C
of anhydrous AlCl3. The compound (B) when treated C
with iodine in aq. KOH, yields C and a yellow compound Me
H
(D). Identify A, B, C and D with justification. Me
to (S, S) – Glycol + R, S Glycol
Q.12 An organic compound A (C5H8) on hydrogenation
gives compound B(C5H12). Compound A on ozonolysis
gives formaldehyde and 2-ketopropanal. Deduce Q.18 A compound (A) has C = 85.7%, H = 14.3%. Its
structure of compound A. molecular weight is 70. It does not react with Cl2 in dark
but gave a substitution product C5H9Cl in presence of
Q.13 What are the possible products from 1,4-addition light. What is (A)?
of HBr on CH2 Draw all possible carbocations and
Q.19 An organic compound (A) C6H10 does not react
state which carbocation is more stable with ammoniacal AgNO3 but on reduction first gives (B)
C6H12 and then (C) C6H14. (A) on ozonolysis gives two
aldehydes C2H4O (D) and C2H2O2 (E). Oxidation of (B)
Q.14 +CH with alkaline KMnO4 gives acid (F) C3H6O2. What are (A)
+ CH22=CH–CH=CH
= CH-CH=CH22
of (F)?
H H
Q.20 Two isomeric organic compounds (A) and (B) on
A Predict the structure of A and explain.
reduction with Zn-Cu couple give n-butane. On treating
(A) and (B) with Na and ether separately, n-octane Q.6 Addition of halogen acid (HX) is least in
(C) and 3, 4-diemthylhexane (D) are formed but if a (A) CH2=CHCl (B) CH2=CH2
mixture of (A) and (B) reacts with Na and ether, one
more product (E) in addition to (C) and (D) is (C) CH3–CH=CH2 (D) (CH3)2C=CH2
Q.7 Which of the following alkene will react fastest with

Exercise 2 H2 under catalytic hydrogenation condition?
R R R H
Single Correct Choice Type
(A) (B)
Q.1 A sample of 1.79 mg of a compound of molar mass H H H R
90g mol–1 when treated with CH3MgI releases 1.34 mL
R R R R
of a gas at STP. The number of active hydrogen in the
molecule is (C) (D)
(A) 1 (B) 2 (C) 3 (D) 4 R H R R
CH33 CH3
Q.2 Reaction of Br2 on ethylene in presence of NaCl +
Q.8 Products of the reaction.
+ D2O/D
gives
+
HH33C
C CH2 D2O/DH3C CH2
(A) BrCH2-CH2Br (B) ClCH2-CH2Br CH3

CH33
CH3 CH3 CH3
(C) Both of these (D) None of these CH33 CH3 CH33
(A) H3C CH2D (B) H3C CH
(A) H33C
(A) H
(A) CH2D (B)
(B) H3C CH22D
Q.3 The reaction conditions leading to the best yield of CH3 OD OD
C2H5Cl are CH33 OD OD CH3
CH3 H
UV
(A) C2H6(excess) + Cl2 
light
→ CH33 H CH3
(C) H3C CH3 (D) H3C C
dark (C)
((C H33C
C)) H CH3 (D)
(D) H3C OD D Ch22 CH3 D O
(B) C2H6 + Cl2 
room temp.
→
OD D CH3 D OD
UV
(C) C2H6 + Cl2(excess) 
light
→
Q.9 The C–H bond length is longest in
UV
(D) C2H6 + Cl2  → (A) C2H2 (B) C2H4
(C) C2H6 (D) C2H2Br2
light
Q.4 The treatment of CH3C(CH3)=CHCH3 with NaIO4 or Q.10 Point out (A) in the given reaction sequence:
boiling KMnO4, produces
O /H O ∆
(A) CH3COCH3 + CH2O (B) CH3CH2CHO + CH3CHO
3 2 → (B) 
(A)  → 2CH3COOH+CO2
(C) CH3COCH3 + CO2 (D) CH3COCH3 + HCOOH

Q.11 Hydrogenation of the compound
H3 C
Q.5 What is the chief product obtained when n-butane Me
Me
is treated with bromine in the presence of light at
130ºC? H
CH3 H
H
(A) H3C Br (B) H3C
Br
In the presence of poisoned palladium catalyst gives:
CH3
(A) An optically active compound
H3 C
(C) Br (D) H3C C CH2Br (B) An optically inactive compound
CH3
CH3 (C) A racemic mixture
(D) A diastereomeric mixture
Q.12 H3C Q.17 Which one of the following heptanols can be

CH2 + HBr A dehydrated to hept-3-ene only?
CH3
(A) Heptan-3-ol (B) Heptan-4-ol
(Predominant).
Br A is
Br (C) Heptan-2-ol (D) Heptan-1-ol
H3 C H3 C
(A) Br CH3 (B)
Br
HH
3C
3C
HC
(A) 3 CH3 CH 3 (B) Q.18 Aqueous solution of potassium propanoate is
CH3
H3 C electrolysed. Possible organic products are:
Br (A) n-Butane (B) C2H5COOC2H5
(C) H3C Br (C) CH3–CH3 (D) CH2=CH2

C CH2 CH3 (D) Non of these
(C) H3C C 3 CH2 CH3
CH (D) Non of these
-
CH3 Q.19 + OH
N
Q.13 Identify (B) in the following sequence of reactions
:
CH CH
Cu2Cl2+NH4Cl
(A)
HCl
(B) The above compound undergoes elimination on
heating to yield which of the following products?
(A) CH3CH2Cl (B) CH2=CH-CH2CH2Cl
OH:
Cl +
(A) CH2 (B)
(C) CH (D) H2C N N CH2
CH3 C CH2
Me Me Me Me
Cl
Cl –H O
Q.14 CH3–CH=CH2 →
2 2 Z . Z may be Me (D)
(C)
N N Me
Cl
Me Me Me Me
(A) CH3 CH CH2 (B) CH3 CH CH2
Cl Cl Cl Multiple Correct Choice Type
(C) CH3 CH CH2 (D) CH3 CH CH2

Q.20 CH2=CHCH2CH=CH2 
NBS
→ A, A can be
Cl OH OH Cl (A) CH2 CHCHCH CH2
Br
HCOOH HCOOH
Q.15 (Peroxyformic
(Peroxyformic acid ) acidZ.
) Z may (B) CH2=CHCH=CH–CH2Br
Z. Zbe
may be
(C) CH2=CHCH2CH=CHBr
OH OHOH OH H H H (D) CH2 CHCH2C CH2
(A) (A) (B) (B)
Br
H H
H H OH OH
OH OH
Q.21 Which of the following elimination reactions will
H H H occur to give but-1-ene as the major product?
EtOH
(C) (C) (D) Non Non
(D) of of these
these (A) CH3.CHCl.CH2.CH3 +KOH  →
EtOH
(B) CH3.CH.CH2.CH3+ NaOEt  →
O O ∆
HIO 4
NMe3
+
Q.16 CH3 CH C CH3 +[O] → Z.Z may be
∆
(C) CH3.CH2.CHCl.CH3+Me3CO–K+ →
OH O
(D) CH3.CH2.CHOH.CH3+conc.H2SO4
(A) CH3–CHO (B) CH3–COOH
(C) CH3 C C CH3 (D) None of these
O O
Q.22 Select true statement(s): 3 BH /THF HgSO

Q.28 C 
–
→ A 
H SO
4→B
H2O2 /OH 2 4
(A) I2 does not react with ethane at room temperature
even though I2 is more easily cleaved homolytically
B and C are identical when A is –
than the other halogens.
(A) H H (B) H
(B) Regiochemical outcome of a free radical addition
and an electrophilic addition reaction on propene is (C) (D) H
identical.
(C) The rate of bromination of methane is decreased if Assertion Reasoning Type
HBr is added to the reaction mixture.
Each of the questions given below consists of two
(D) Allylic chloride adds halogens faster than the statements, an assertion (A) and reason (R). Select the
corresponding vinylic chloride. number corresponding to the appropriate alternative
as follows:
Q.23 An alkene on ozonolysis yields only ethanal. There (A) If both Assertion and Reason are true and Reason is
is an isomer of this which on ozonolysis yields: the correct explanation of Assertion .
(A) Propanone (B) Ethanal (B) If both Assertion and Reason are true but Reason is
(C) Methanal (D) Only propanal not the correct explanation of Assertion .
(C) If Assertion is true but Reason is false.
Q.24 CH3–CH=CH–CH3 + CH2N2 
∆
→A
(D) If Assertion is false but Reason is true.
A can be
(A) (B) Q.29 Assertion: In α , β -unsaturated compounds with
N C=C and C=O conjugated, attack of nucleophile takes
N place on C=C.
(C) (D) Reason: The C=O bond is stronger than C=C.
N
N Q.30 Assertion: Alkyl iodides are more reactive than
Q.25 Which of the following will give same product alkyl chlorides for elimination reactions.
with HBr in presence or absence of peroxide. Reason: I– is a better leaving group than Cl–
(A) Cyclohexene
Q.31 Assertion: CH3CH2– is a stronger base than F–.
(B) 1-methylcyclohexene
Reason: The negative charge density on carbon is
(C) 1, 2-dimethylcyclohexene greater than the negative charge density of F–.
(D) 1-butene
Q.32 Assertion: CH3–C≡C–CH3 is more reactive than
CH≡CH towards HCl.
Q.26 The ionic addition of HCl to which of the following
compounds will produces a compound having Cl on Reason: The carbocation formed is more stable in the
carbon next to terminal. case of CH3–C≡C–CH3 than CH≡CH.
(A) CH3.(CH2)3.CH=CH2 (B) CH3.CH=CH2
Q.33 Assertion: CH≡CH reacts with HCl in the presence
(C) CF3.CH=CH2 (D) CF3.CH=CH2 of HgCl2 while CH2=CH2 does not.
Reason: There is more unsaturation in CH≡CH than in
Q.27 Which is/are true statements/reactions? CH2=CH2.
(A) Al4C3 + H2O → CH4
(B) CaC2 + H2O → C2H2 Comprehension Type (34-36)
(C) Mg2C3 + H2O → CH3C≡CH n-Butane is produced by mono bromination of ethane
(D) Me3C–H + KMnO4 → Me3C–OH followed by Wurtz reaction, as follows
Br
(i) CH3CH3 
2 → CH CH –Br
hν 3 2
Na
(ii) CH3CH2Br  → CH3CH2CH2CH3 + CH2=CH2 + Br2 /low conc.
Q.38 14CH3–CH=CH2  →
high temperature
CH3–CH3 + NaBr
Product of the above reaction is
Mechanism: Na → Na++ e- ; (A) Br–14CH2–CH =CH2 (B) 14CH2=CH–CH2–Br
CH3CH2Na+CH3CH2Br → (C) Both (a) and (b) (D) None of these
CH3CH2CH2CH3+CH2=CH2+CH3–CH3
• • Q.39 Trans-2-butene when reacts with Br2, the
CH3CH2Br → CH3CH2 + Br
• product formed is
CH3CH2 + e– → CH3CH2᛫
(A) Racemic mixture (B) Meso form
(C) Optically pure (D) No specific stereochemistry
Q.34 The amount of ethyl bromide required to prepare
55g of butane would be Match the Columns
(A) 106.72 (B) 206.72 (C) 20.67 (D) 2.067
Q.40 Match the entries in column I with entries in
column II
Q.35 If the yield of n-butane was 85%, then the actual
amount of ethyl required to produce 55g of n-butane Column I Column II
would be
(A) CH3–C≡C–CH3cis-2-butene (p) Na/NH3(l)
(A) 2.432g (B) 24.32g (C) 243.2g (D) 0.2432g
(B) CH3–C≡C–CH3 → trans-2-butene (q) H2/Pd/BaSO4
Q.36 The other products which could be formed
(C) CH3C≡C–CH3 → 1-Butyne (r) Alc. KOH, ∆
(A) CH2=CH2 (B) CH3CH2CH3
(C) CH4 (D) CH3CH2CH2–CH2–CH3 (D) CH3–CH3–C≡CH → 2-Butyne (s) NaNH2 , ∆
Comprehension Type (36-38) Q.41 Match List-I with List-II and select the correct
answer
The functional group in alkenes is C–C double bond
which is made of one 𝜎-bond and one 𝜋-bond. The List I (Reaction) List II (Reagents)
weaker 𝜋-bond would tend to attract the electrophile and
(A) CH3–CH=CH2 → CH3–CHBr–CH3 (p) HBr
convert itself to a stable carbonium ion which reacts with
nucleophile remainder to form the addition product. The (B) CH3–CH=CH2 → CH3–CH2–CH2Br (q) Br2
addition reaction of alkenes is stereo specific as well as
stereoselective. i.e., the isomeric alkenes react differently (C) CH3–CH=CH2 → BrCH2–CH=CH2 (r) HBr/Peroxide
with same addendum to give stereochemically different (s) NBS
(D) CH3–CH=CH2 → CH3–CHBr–
products. Where addition of HBr proceeds through
CH2Br
carbocation formation and hence racemisation is
expected. With low concentration of Br2 in vapour phase
substitution predominates over addition. Q.42 Match the column
Column I Column II
Q.37 Reaction of 1,2-dimethylcyclohexene with
Electrolysis (p) Corey-House
bromine water gives the product (A) RCOONa 
→ R–R
reaction
(A) (B) Soda Lime (q) Kolbe electrolysis

(A) Br CH (B) Br Br (B) R–CH2–COOH 
→
Br CH33 Br Br ∆
R–CH3
CH3 Br CH CH (r) Oakwood
CH3 Br CH33 CH33 (i) AgNO
3 → R–Cl
(C) RCOOH 
(ii) Cl2 / ∆ degradation
(C) (D) Br CH
(C) Br OH (D) Br CH33
Br OH
CH3 CH3 CH3 OH

CH3 CH3 CH3 OH
Previous Years’ Questions through the following sequence of reactions, in which

Q is an intermediate organic compound.
Q.1 (CH3)3CMgCl on reaction with D2O produces (1997)
Q.7 The structure of compound P is
(A) (CH3)3CD (B) (CH3)3OD
(C) (CD3)3CD (D) (CD3)3OD (A) CH3CH2CH2CH2—C≡C—H
(B) H3CH2C—C≡C—CH2CH3
Q.2 In the compound, H the C2–C3 bond is
of the type (1999) H3C
(C) H C C C CH3
(A) sp–sp2 (B) sp3–sp3 (C) sp–sp3 (D) sp2–sp3
H3C
Q.3 The product(s) obtained via oxymercuration (HgSO4 H3C

+ H2SO4) of 1-butyne would be (D) H3C C C C H
O H3C
(A) CH3–CH2–C–CH3 (B) CH3 – CH2 – CH2 – CHO
Q.8 The structure of the compound Q is
(C) CH3 – CH2 – CHO + HCHO
(i) dil. H2SO 4 (catalytic
P (i) dil. H2SO 4 /HgSO 4 amount) (–H O)
Q  2 →2
Q.4 Identify a reagent from the following list which  → (ii) O /ethanol
(C6H10 ) (ii) NaBH4 /ethanol 3
can easily distinguish between 1-butyne and 2-butyne. (iii)dil. acid (iii) Zn/H2O
(2002)
O
(A) Bromine, CCl4 (B) H2 , Lindlar catalyst
C (2011)
(C) Dilute H2SO4 , HgSO4 (D) Ammoniacal CuCl2 solution H3C CH3
OH
Q.5 Consider the following reaction H3 C
•
(A) H C C CH2CH3
H3C–CH–CH–CH3 + Br → ’X’ + HBr (A)
H3 C H
D CH3
OH
H3 C
Identify the structure of the major product X (2002)
(B)
(B) H3 C C C CH3
(A) H3C–CH–CH–CH2 (B) H3C–CH–C–CH3 H3 C
H
D CH3 D CH3 OH
H3 C
(C) H3C–C–CH–CH3 (D) H3C–CH–CH–CH3 (C)
(C)
H C CH2 CH CH3
H3 C
D CH3 CH3
(D) CH3CH2CH2CH(OH)CH2CH3
Hg 2 +
Q.6 Ph–C≡C–CH3 
+
→ A ; A is (2003)
H
Q.9 Give reasons for the following in one or two
O sentences: (1983)
(A) Ph (B) Ph
O (i) Methane does not react with chlorine in dark.

H3 C H3 C (ii) Propene reacts with HBr to give isopropyl bromide
OH but does not give n-propyl bromide.
(C) Ph (D) Ph
OH
Q.10 Following statements are true, only under some
specific conditions. Write the condition for each sub
Comprehension Based Questions (Q.7 & 8) question in not more than two sentences:
An acyclic hydrocarbon P, having molecular formula (i) 2-methyl propene can be converted into isobutyl
C6H10, gave acetone as the only organic product bromide by hydrogen bromide
(ii) Ethyne and its derivatives will give white precipitate Q.11 The product X is (2014)
with ammoniacal silver nitrate solution. (1984)
(A) H3CO (A) H3CO (B) (B) H H
Paragraph for Questions 11 and 12
Schemes 1 and 2 describe sequential transformation H H
of alkynes M and N. Consider only the major products H HH H H3CO H3CO
H H
formed in each step for both schemes. (C) CH 3 CH
(C)
2 O CH 3 CH 2 O (D) (D)
1. NaNH2(excess)
1. CH
2. NaNH (excess)
3CH22(1 equivalent)
H H
H 2. CH 3CH2(1 equivalent)
X Scheme-1 H HH H
H 3. CH l(1 equivalent)
3 X Scheme-1 CH3CH2O CH3CH2O
HO M 3. H
4. CH 3l(1 equivalent)
2, Lindlar’s catalyst
HO M 4. H2, Lindlar’s catalyst
1. NaNH2(2 equivalent)
Q.12 The correct statement with respect to product Y is
H 2.
1. NaNH2(2OH
equivalent) (2014)
H 2. Br OH
Br
N +
Y Scheme-2 (A) It gives a positive Tollens test and is a functional
3. H3O (mild) Y Scheme-2
N 3. H
4.
+
H23,OPd/C
(mild) isomer of X.
4. H , Pd/C
5. CrO
2 3
5. CrO3
(B) It gives a positive Tollens test and is a geometrical
isomer of X.
(C) It gives a positive iodoform test and is a functional
isomer of X.
(D) It gives a positive iodoform test and is a geometrical
isomer of X.
PlancEssential Questions
JEE Main/Boards JEE Advanced/Boards
Exercise 1 Exercise 1
Q.3 Q.8 Q.13 Q.15 (b) Q.1 Q.8 Q.13 Q.18 Q.21
Q.20 (a)
Exercise 2
Exercise 2 Q.5 Q.9 Q.14 Q.22 Q.26
Q.1 Q.7 Q.9 Q.14
Q.28 Previous Years’ Questions
Q.6 Q.8
Q.10 Q.13
Answer Key
JEE Main/Boards
Exercise 2
Q.1 B Q.2 C Q.3 A Q.4 D Q.5 C Q. 6 C
Q.7 B Q.8 D Q. 9 D Q.10 B Q.11 A

Q.1 B Q.2.D Q.3 D Q.4 C Q.5 A Q.6 A Q7B
Q.8 B Q.9 C Q.10 A Q.11 A Q.12 D Q.13 C Q.14 D
Q.15 B Q.16 D Q.17 C Q.18 C Q.19 A Q. 20 B Q.21 A
Q.22 B
JEE Advanced/Boards
Exercise 2
Q.1 C Q.2 C Q.3 A Q.4 B Q.5 B,C Q.6 B Q.7 D

Q.8 B Q.9 C Q.10 C Q.11 B Q.12 C Q.13 D Q.14 D
Q.15 C Q.16 A Q.17 B Q.18 A Q.19 B
Multiple Correct Choice Type
Q.20 A,B Q.21 B,C Q.22 A,C,D Q.23 A,C Q.24 A,B,C,D Q.25 A,C Q.26 A,B,D
Q.27 A,B,C,D Q.28 A,C
Assertion Reasoning Type
Q.29 B Q.30 A Q.31 A Q.32 A Q.33 B
Comprehension Type
Q.34 A Q.35 A Q.36 A Q.37 D Q.38 C Q.39 B
Match the Columns

Q.40 A → q; B → p; C → s; D → r Q.41 A → p; B → r; C → s; D → q Q.42 A → q; B → r; C → s; D → p
Previous Years Questions

Q.1 A Q.2 D Q.3 A Q.4 D Q.5 B Q.6 A Q.7 D
Q.8 B Q.11 A Q.12 C
B
CH3.COOH
CH3.COOH Chem i str y | 11.97
B H
H H
Solutions
(b)
BH3.THF B CH3.COOH
H
(b)
BH3.THF 3CH3.COOH
3
JEE Main/Boards (C) BH3.THF CH3.COOH

(c) CH3.COOH
BH3.THF H H
Exercise 1 (c) 3
3 H H
Sol 1: Alkenes are substances which contain less

(D)
(d) Same as (a)
hydrogen than the maximum quantity of hydrogen
which a carbon atom can have (d) H H Same as (a)
H H
Structure:-
Sol 4
H H H
H H H2 H2
H C (A)
(A)
Pt Pt
C H C C
H H H
H
(B)
(B)
Preparation of Alkenes:- Na
+ NaOC2H5
SH5OH
(1) Dehydrohalogenation of Alkyl halide H
(2) Dehyration of Alcohols Sol

5: Physical properties: Refer theory pg.26
(3) Dehalogenation of vicinal dihalides
Chemical properties: Refer theory pg.29
(4) Dehalogenation of geminal dihalide
Sol 6: Alkynes:-
Sol 2: (A)
In the family of hydrocarbon alkynes are the most
unsaturated one with C≡C bond and are highly reactive.
1. BH3, THF
1. BH3, THF + mirror image Preparation:-
2. H2O2, OH–– + mirror image
2. H2O2, OH H
H (1) Dehydrohalogenation
OH
OH (2) From tetradehalogenation
trans additon
trans additon (3) From haloform
Recemic mixture
Recemic mixture
(4) Kolbe’s electrolytic decarboxylation
(B)
OH (5) Berthlot’s reaction
OH
H
H
Sol 7: Physical properties: Refer theory pg.42
Antimarkov's addition
Antimarkov's addition Chemical properties: Refer theory pg.44
BH3.THF
BH3.THF(a)
(a) Sol 8:
3
Sol 3: (A) 3
B
B (A)
(a)
NaNH2
BH3.THF CH3.COOH CH3 C CH
(a) CH3.COOH
3
B H
B Br
H H
B CH3 C C + NH3
(B) (b)
H
BH3.THF CH3.COOH
CH3.COOH
(b)
BH3.THF CH3.COOH 3 CH3 C C
3
B H
H BH3.THF CH3.COOH O
BH3.THF c)
CH(3.COOH (b) H
(b) BH3.THF CH .COOH H
(c)
3
3
3 H
3 H
Br
CH3 C C + NH3
1 1 . 9 8 | Alkenes
CH3 C and
C Alkynes
O (B) OH
(b)
(B) H2O/H
(b)
OH B2H2
Hg2+
H2O2OH-
OH
H2O
Anti-maekonikov’s
addition
Sol 9:
Hg(OAc)2
(A)
+
NaBH4
+
O- Na+ NH O- Na+ OH
O O- Na Markonikov’s
(a) O NaNH2
O- Na NH2
2H (A) addition
(a) NaNH2 H (A)
C2H2 (C) OH OH
(c) H
+
RCO3H
C2H2
+
O- Na+ CHOH
OH + O- Na
H
OH + (B)
H -H2O
(B)
H2(1 equivalent)
H2(1 equivalent)
Br
Al2O3 Sol 11:(a)

(A) HBr
OH Al2O3
OH
Doubled bonds are more electron donating than
triple bond because of difference in electronegativity
(B)
(b)
(i) NaNIH2 H2
and because of which first addition will takes place on
H (i) NaNIH H2
(b) H (ii)
2
Prv
Cindlars double bond rather than triple bond.
(ii) Cindlars
catalyst
Prv
catalyst CH2I2 (B) OH
CH2I2
(b) H2SO4

+
H
Sol 10: (A) OH2
(a) Con. H2SO4/
OH
Sol 12: A
A hydrogenation
B hydrogenation
B
C
C
OH2 C5H10
C5H10
A o HBO
A 3o ROH BHBO different
3 ROH B different
HCl Cl OMDM HBO
1 ROH
o
B OMDM CHBO 1oROH
B C
OH
Sol 13:
-H2O
(B)
(B) (A)(A) (C)(C)
o o
3 3ROH
ROH
I Sol 5: (C) C ≡ C is strongest because it is shortest and

+ HI (2) more orbitals are overlapping.
I
(I) (J)
Sol 6: (C)
H2O
CaO + C CaO2 H-CC-H
Alc. KOH -
2+ -
Ca ( CC )
H2SO4 Hg2+
O
Ozonized CH3-C-H
ethanal
2 O H2O
Sol 7: (B) C2H3MgI  → C2H6
Sol 14
Abstracts acidic hydrogen.
(i) Na
C CH CC
(ii) Br Sol 8: (D) HBr
Br
(X) only product
Na
C C Na
H
Br
H2 (Y)
(X) H
Pd-BaSO4
H H OH
O Sol 9: (D)
(1) CH3COOH Anti-additon
Anti Markonikov’s
Anti Markonikov’s addition addition
+
(2) H /H2O
HBr
Sol 10: (B) HC CH H2C CH Br
H OH Alc. KOH
HO H
HC CH
Exercise 2 Sol 11: (A) Enol form is not net stable as keto is much
more stable.
Sol 1: (B) Dicarboxylation of acid ion Previous Years’ Questions
CH3 C O–Na
NaOH
CH3 H + CO2↑ Sol 1: (B) Methane is produced due to the decay of
vegetables or animal organisms present in swamps and
O marsh, by the action of bacteria. Due to this method of
CH3
formation, methane is also known as marsh gas.
Sol 2: (C) Br2 H Br
+ Mirror
Br H
image Sol 2: (D) Unsaturated compounds which contain
CH3
C=C or C≡C, decolourises the purple colour of alkaline
Recemic mixture
KMnO4 solution.
Sol 3: (A) Definition of conformers. CH2 OH
CH2= CH2 + KMnO4 HO-
+ MnO2
O purple coloured
O3 H CH2 OH
Sol 4: (D) Olefin + H
Zn+H2O
O
Sol 3: (D) Structural formula of 1, 2-butadiene is:
pent-2-ene
1 1 . 1 0 0 | Alkenes and Alkynes
Sol 4: (C) Alkynes undergo Markownikoff’s addition of  •

•
water in presence of H2SO4/HgSO4: CH3 − CH= CH2 + Br → CH3 − CH − CH2Br ∆H < 0


OH  •
CH − CH − CH Br + HBr → CH − CH − CH Br + Br • ∆H < 0
CH3 CC H + H2SO4
HgSO4
CH3 C=CH2  3 2 3 2 2
In case of addition of HCl and HI, one of the propagation

unstable enol
step is endothermic, reaction fail to occur.
O
CH3 C CH3 Sol 10: (A)
acetone
C6H5CH2=CHCH3 has two geometrical isomers
Sol 5: (A) Bayer’s reagent is cold, dilute, alkaline C6H5CH2 H C6H5CH2 CH3
perman-ganate solution, used to detect presence of C=C and C=C
olefinic bonds. H CH3 H H
Trans Cis
Sol 6: (A) Terminal alkynes are slightly acidic, forms salt
with very strong base like Na, NaNH2 etc. So it is 1-Phenyl-2-butene
1
H − C ≡ C −H + Na 
�
→ H − C ≡ C−Na+ + H2 ↑ Sol.11: (D) CH3 – CH+ – CH2 –Cl
2
ethyne
Sol 12: (A)
Sol 7: (B) Hydrogenation with poisoned palladium LiAlH4
CH3COOH CH3CH2OH ‘A’
brings about cis hydrogenation of alkyne and does not
affect double bonds: PCl3
CH3CH2Cl ‘B’
Sol 8: (B)
Alc. KOH
HO- + Cl
+
HOCl
+
Cl CH2=CH2 ‘C’
+
CH3 CH CH2 + Cl CH3 CH CH2 Cl
Ag
2Cl C CH3 CH3C CCH3 +6AgCl
Cl
Cl
HO- CH
3 CH CH2 1, 1, 1- Trichloroethane
CH3 OH
Sol 13: (C)
CH3
H2/Pd
Sol 14: (D)
H3C H H
CH3 H O
H3C CH3 O3
CH3CH=CH - CH3 CH3 - CH CH - CH3
HH O-O
meso-compound H2 O
(optically inactive) 2CH3CHO
Zn
i.e. Reaction is initiated by Cl+( Chloronium ion Sol 15: (B)
electrophile). Θ
Na/Liq.NH
3 → CH CH C ≡ CNa⊕
CH3CH2CH2 ≡ CH 
∆ 3 2
Sol 9: (C) In addition of HBr to an alkene, in presence of It is a terminal alkyne, having acidic hydrogen.
peroxide, both the propagation steps are exothermic:
HBr + HO• → H2O + Br • Note: Solve it as a case of terminal alkynes, otherwise
all alkynes react with Na in liq. NH3
Propagation
Sol 16: (D) CH3 − MgX + CH3 − C ≡ C − H → CH4 JEE Advanced/Boards

Sol 17: (C) H H H CH3 Exercise 1
C=C C=C
CH3 CH3 H3C H Sol 1: (X) Lucas reagent
Cis Trans C5H8O
AgNO3 Ag
Sol 18: (C) 2–butene is symmetrical alkene
H2 Pt (X5)
3 O
CH3 − CH
= CH − CH3 
Zn/H O
→ 2.CH3CHO HI
2
Degree of unsaturation : 2
Molar mass of CH₃CHO is 44 u.
no lucas test
Sol 19: (A) •
•
CH3 − CH2 − CH = CH2 + B r → CH3 −CH2 − CH − CH2Br OH Ag
a sec ondary radical
Therefore, Statement I is correct but Statement II is OH OH

H2
incorrect. Pt
X5
Sol 20: (B) Both Statement I and Statement II are correct HI
and Statement II is correct explanation of Statement I.
Sol 2: (A) Br Br2
dicolourizes
(A) 2
dicolourizes
Sol 21: (A) C5H10 implies unsaturation
C5H10 implies unsaturation
O
CH3 S CH3 hot KMnO4
C=C + O3 C C hot KMnO4
O O (B) + (C)
(B) + (C)
ozonide
Acids
C=O +O=C + (CH3)2SO Acids
CaO
CaO
CaO
CaO
Both Statement I and Statement II are correct and
Statement II is correct explanation of Statement I. CH C2H6
CH4 C2H6 4
O
O
Sol 22: (B) Statement I is correct. Statement II is also
(B) CH3 C OH
correct. Meso form of the product is due to anti addition (B) CH3 C OH
of Br-on cyclic bromonium ion intermediate, hence O O
Statement II is not correct explanation of Statement II.
H5 CC2 HOH
(C) C2 (C) 5 C OH
+ (A) (A)
Br
H3C H C
C= C + Br2 CH3 Sol 3:
CH3 C
H H Cl2 Alc.KOH NaNH2 Ammo
H (A) (B) (C)
CCl4 AgNO3
CH3 C6H12 C6H12Cl2 C6H10
Br
CH3 Ozonolysis H2, Pt
C
CH3
Br- (D) + (E)
H C
H
O
Br
CH3 C H
Cl Cl
(B)
Alc.
Cl
KOH
(D) + (E)
O
CH3 C H
Cl Sol 7: (A) Cl2 H2O
(B)
Cl (B) C9H12O2
C9H10 C9H10Cl2
Alc.
Cl
KOH
oxidation
COOH
(C) terminal alkyne O
(D) + (E) + CH3 C OH
O
H Cl Cl
+ CH3 C H
O (A) (B)
C C CH3 CH CH CH3
Sol 4: H H
X5 Aq. H
(A) (B) (C) H
HCl KOH
dihalogen O (C) OH OH

CH CH CH3
Cl O–
Cl Ca2+
2
NaOH
O Sol 8: (A) NaOH
(B) X
2+
+ CH3 C O
– Ca C9H10Br2 C9H10OBr
2
H2SO4
AlBr3
Sol 5: CF3CH CH2 + HBr (C)
H+[AlBr4 ]– Ozonolysis
O
CH3 CH2 C H + (D)
CF3 CH2 CH2
Since only one –Br is hydrolysed
CF3 CH2 CH2 Br ∴ One is attached to alkyl group and other one to aryl
group.
Sol 6: (A) alk. does not Br OH
(B)
KMnO4 form anhydride (A)
C9H12 C8H6O4
NaOH
Fe Br2
only one monobromo Br Br

derivative
H2SO4
Degree of unsaturation of (A) = 4
So it should contain benzene ring
O3
In the compound (B) both –COOH should be at para CH3 CH2 CHO
Zn/H2
position to give only one bromination product +
O H Br
(A) (B) COOH (C) COOH
Br
Br
COOH COOH
Sol 9: Reduction Sol 11: O

(A) (B) (C)
R C Cl
C6H10 C6H12 C6H14 (A) Dil. H22+
SO4
(B)
Hg
KMnO4
C8H6
Ozonolysis Friedel craft's
I2+KOH alkylation
(F) acid Iodoform
Hydrolysis reaction
C4H8O2
(C) + (D)
(D) + (E) Aldehydes yellow
2CH2O C2H2O2
For reaction (B) → (C) it is iodoform so (D) → CHI3
O O
O
H yellow precipitate and (B) should have acetyl ketone.
O O–
O C
So (A) is (B) (C)
(B) is 1-4 addition
oxidation
(C)
KMnO4
(A)
(F) OH
2
OMDM for alkyne
O
give ketone
Sol 10: (A) Na

liq.NH3 I
(B) Sol 12: (A) Hydrogenation (B)
C5H8 C8H14
C5H8 C5H12
H2SO4 Alk.
Hg2+
KMnO4 O3+Zn/H2O
dil.
H2SO4
(D) + (E) C4H8 O O (A)

C5H10O (C)
isomeric acids O
Ketone C H +
(B)
Degree of unsaturation of (A) = 2
∴ Alkyne. Terminal alkyne because formation of (B) and Sol 13: (A) (B)
branched because formation of ketone (C) H Br
HBr
+
1-4 additon
(A)
1. NaNH 2 Br H
2. +
(C) O
(D),(E) O COOH
OH , H
Compound (A) carbocation is more stable resonance is
in both the compounds but
(A) have 3 α – H
(B) have 0 α – H
Sol 14: Sol 16: (A), (B) C5H11Br

alc.
+ isomeric alkyl bromides (A) 
KOH
→ (C) + (D) isomers
C5H10
Sol 17: D
Br Br
1-4 addtion (i)
H H
D
O
(C) O3 O Br – Br
H C H +
Zn+H2O
H Hydrogenation H2/Ni
Br Br
(C)
(B) Alc.
(D) + (E)
KOH
(C), (D), (E) (ii)
Catalytic
hydrogenation alkyl carbon
NBS
C5H12 gets brominated
(D) is isomer of (C) H Br
Alc. KOH
(D)(D) notnot because
because
willwill
notnot
getget
by by
isomeric
isomeric
alkyl bromide of (B) (iii)
alkyl bromide of (B)
NBS (i) Li
(A)
(B)(B) (D)(D) (E)(E) (ii) CuP
Br
Hydrogenation Li
Hydrogenation
HH LiBr
H (iv)
H
Sol 15: D H
Br D
O3 1. Mg/Et2
(P) (Q) C3H5Br H D MBr D H
+
Zn/H2O 2. CO 2,H
C8H10 C4H6O2 only
Anti-addition
symmetric compound
(v)
Q is an acid because after reaction with CO2, H+ of
RMgBr we get a carboxylic acid. If
O
Br C OH
(R) (Q) O
(vi) H H H OH H OH
MgBr O=C=O H3O HO H + H OH
+
H CH3 CH3
(P) Hydrolysis
H
to satisfy the degree of unsaturation of (P) alkyl group OH OH –H+
H2O 2
must be cyclic.
Sol 18: (A) →

Cl2
C5H9 Cl
Exercise 2
hν

C = 85.7%; h = 14.3%
total molecular weight = 70 Sol 1: (C) Releases 1.34 mL of a gas at STP
C5H10 ∴ 3 moles of CH4
∴ 3 active α - H hydrogen.
Sol
(A)19: Amm.
(A) Amm. Br2
(X) Not(X)
AgNO3
Not a terminal
a terminal Sol 2: (C) CH2 CH2 Br CH2 CH2 Br
AgNO3 NaCl
C6H10 C6H10 Alkyne Alkyne
Br CH2 CH2 Cl
Reduction
Reduction CH2 CH2
Alk. Br
Alk. Br
(B) C6H(B)
12
C6H12 (F) C4 3H(F)
KMnO 6O2
C3H6O2 Cl
KMnO4
(C) C6H(C)
14
C6H14 hν
Sol 3: (A) C2H6 + Cl2 → C2H5Cl
(X5)
(A) O3
(A) O 3 (D) + (E) O
Zn+H(D)
2O + (E)
Zn+H2O C2H4O C2H2O2 boiling
C2H4O CHO
O2 2 2 O Sol 4: (B) KMnO4
O + CH3 C OH
O O
O H O
H H
Oxidative cleavage
H
H H
(A)
(A)
(B) 1-4 addition Sol 5: (B,C) Br2
(B) 1-4 addition h
Br
(C)
(C) +
O
(F) O more stable
(F) OH
OH
⊕
Sol 20: (A) + (B) CH3 − CH2
Sol 6: (B) Carbon is least stable in ↑
isomers
CH2 = CH2
Zn-Cu
Zn-Cu
∴ Addition will be least CH2=CH2
Sol 7: (D) Stability of complex that forms during

Na/Ether (C)
(A) reaction with H2
Na/Ether R R
(B) (D)
But mixture gives (E) R R

Na/Ether is Wurtz reaction and dimerise the alkyl H H
bromide so they are symmetric.
Sol 8: (B) D2O D
(A) D
Br OH–
(E)
Br OH
(B)
D
Sol 9: (C) C-C-H is sp3 hybridised, hence ‘s’ character is
less, So bond length in C-H is longest
Sol 10: (C) Sol 17: (B)

O O O Dehydration
CH3CH2CH2CH(OH)CH2CH2 CH3 →
−H O
O3 (Heptan− 4 −ol) 2
C CH2 C C C OH
H2O CH3CH2CH = CHCH2CH2 CH3
OH OH + CO2 (Hept −3−ene)
Sol 11: (B) Hydrogenate product Sol 18: (A) O–K+
Me O
Sol 19: (B)
H H
OH
same group +
N N
optically inactive compound.
Br
Sol 12: (C) HBr
Multiple Correct Choice Type
Br
Sol 20: (A,B) NBS
Br
Br
Sol 13: (D) CH CH CH2Cl2
NH4Cl
CH2 CH C CH Sol 21: (B,C)
CH CH KOH
HCl (A)
Cl Cl
CH2 CH C CH2
NMe3
H EtOH HC CH
(B)
Cl2
Sol 14: (D) Cl
H2O
Cl
OK
(C)
OH
Cl Cl less hindered –H will get abstracted
Sol 15: (C) conc.H 2SO4

O (D)
O
H–C–O–O–H OH
+ HC – OH
O Sol 22: (A,C,D) but the reaction will be reversible since
O C–I is very week.
O H
C (B) × (C)  (D) more stable system
H O
Sol 23: (A,C)
Sol 16: (A)
O O ozonolysis
Alkane CH3-CHO
HIO4
+ [O] CH3 C H + CH3 C OH
HO Alkene :
O Isomers :
O
+ HCHO HCHO +
O
Sol 24: (A,B,C,D) Sol 27: (A,B,C,D)

H2O
(A) Al4C3  → Al(OH)3 + 3CH4 4Al3+ + 3C4–
+ CH2N2
-N2 (B) Ca2+ –C≡C– + H2O → Ca(OH)2 + HC ≡ CH
+ N2
(C) 2Mg2+ + C34– + H2O → Mg(OH)2 + H3C–C≡CH
CH2-N=N
N=N (D) Me3C–H+KMnO4 → Me3C–OH
Same for trans form.
Sol 28: (A,C)
Sol 25: (A,C) H2 SO4
(A) H C C H CH4 CHO
Br
BH3 /THF
(A)
H2O2 /OH–
CH3 CHO
Br
Br
(B) O
Hg2+
absence presence (B) CH3 C C H
H+
CH3 C CH3
BH3/THF
Br H2O2
(C)
CH3 CH2 CHO
(C) CH3 C O
(D)
C CH3
Br + CH3 C CH2 CH3
presence absence
Hg2+
Sol 26: (A,B,D) +
O
(D) H
(A)
(a) CF
(A) CF33 CH22
CH CH CH
CH2 2 CH CH CHCH
2 2 CH 2 2 O
BH3.THF
HCl
HCl H2O2
CF33 (CH
CF CH
(CH22)3)3 CH CH
2 2 CH3 3
Assertion Reasoning Type

(CH22)3)3 CH
CF33 (CH
CF CH
22 CH
CH
3 3
ClCl Sol 29: (B) When the C=C bond is conjugated with a
C=O group, the electron withdrawing nature of carbonyl
ClCl group polarizes the C=C bond so the nucleophilic
(b)(B) HCl
HCl attack can take place at the C=C carbon.
Sol 30: (A) Alkyl iodides are more reactive than alkyl
chlorides for elimination reactions as I– is a better
(c)(CCF
) CF CH
CH CH
HCl
HCl
CH22
CF33 CH CH22 Cl
Cl leaving group than Cl–
3 3 CH 22 CF
Sol 31: (A) is a stronger base than F–because the

CFCF
3
3 CH
2
CH2
CH2 CH
2
negative charge density on carbon is greater than the
negative charge density of F–.
(D) CH3 CH2 CH CH CH
(d) CH 3 CH2 CH CH CH22
Sol 32: (A) CH3–C≡C–CH3 is more reactive than
HCl CH≡CH towards HCl because the carbocation
HCl
formed is more stable in thecase of
CH3C≡C–CH3 than CH≡CH.
Cl
Cl
Sol 33: (B) Alkynes are electron-rich nucleophiles with Match the Columns
a cylindrical electron cloud formed of two bonds
around a carbon-carbon bond. An electrophilic Sol 40:
reagent can therefore easily react with the relatively (A)
weak alkyne bond.
cis addition
H2/Pd/BaSO4
Comprehension Type (B)
Birch
reduction
(C)
NaNH2,
Sol 34: (A) CH3 CH2 Br
Isomerism
55 gm
(D) Alc. KOH,
m 55 Isomerism
=
208 58
A → q; B → p; C → s; D → r
Sol 35: (A) 2.432g Sol 41: (A) → (p) Markonikov

(B) → (r) Anti-markonikov
Sol 36: (A) Alkenes generally forms by elimination. (C) → (s) Alkylic carbon get brominated
(D) → (q) Br2 addition
Sol 37: (D) Br2 Br CH3
H2O Sol 42: (A) → (q) Free radical mechanism
CH3 OH (B) → (r) Decarboxylation
Anti addition (C) → (s) Free radical mechanism
H2O
(D) → (p) Same as grignard
Br
Br OH
CH3
H Br
14 Sol 1: (A) (CH3)3CMgCl + D2O CH3 C D + Mg (OD)Cl
Sol 38: (C) CH3 CH CH2 Br–Br CH3 CH CH3
CH3
Br
+ Sol 2: (D) According to the IUPAC conventions,
14
Br compound can be numbered as:
Br 1 2 3 4 5 6
CH3 CH CH2 CH2 CH CH3
14 H2 C =CH − CH2 − CH2 − C ≡ C− H
Br Br
Here, C-2 is sp2 and C-3 is sp3 hybridised.
Sol 39: (B)
CH3 Sol 3: (A) Oxymercuration - demercuration brings
H Br about Markownikoff’s addition of water as
Br2
(B) Anti Addition
H Br
HgSO4
CH3 CH3 CH2 C C H +H2SO4
OH O
CH3 CH2 C CH2 CH3 CH2 C CH3
butanone
unstable enol
Sol 4: (B) Ammonical CuCl2 forms red precipitate with terminal alkynes, can be used to distinguish terminal alkynes
from internal alkynes:
3 NH (aq)
CH3 − CH2 − C ≡ C − H + CuCl2 →
CH3 − CH2 − C ≡ C− Cu+ ↓

red−ppt
Sol 5: (B) Bromination is highly selective, occur at the carbon where the most stable free radical is formed:
Sol 6: (A) Reaction proceeds through carbocation intermediate:

Ph − C ≡ C − CH3 + H+ → Ph − =
C+ CH − CH3
OH O
| ||
H2O
 → Ph − C = CH − CH3 ←→ Ph − C − CH2 − CH3
Sol 7, 8: (D, B) The final ozonolysis product indicates that the alkene before ozonolysis is
H3C CH3 O
O3
C C 2 C
Zn-H2O
H3C CH3 H3C CH3
Also P(C6 H10) has two degree of unsaturation and oxymercuration demercuration hydration indicates that it is an
alkyne. As alkyne, on hydration, gives a carbonyl compound which on reduction with NaBH4 gives a 2° alcohol.
O OH
(i) NaBH4
C C +H2O C CH2 + C CH2
(ii) H
o
H
2 alcohol
The secondary alcohol that can give above shown alkene on acid catalyzed dehydration is
CH3 OH CH3 CH3 CH3
H
+ + Me-shift + +
-H
CH3 C CH CH3 CH3 C CH CH3 CH3 C CH CH3 CH3 C C CH3
-H2O
CH3 CH3 CH3 CH3

2o carbocation
CH3 CH3 O
HgSO4 (i) NaBH4
CH3 C C C H CH3 C C CH3 + Q
H2SO4 (ii) H
CH3 CH3
Sol 9: (i) Free radical chorination of alkane require energy which is supplied either in the form of heat or radiation.
+
CH
+
CH2 + H CH3 CH CH3 Br -
CH3 CH3 CH CH3
o
2 Carbocation
Br
Isopropyl bromide
(ii) Addition of HBr proceeds through carbocation intermediates.
Sol 10: (i)

Peroxide
CH3 C = CH2+HBr CH3 CH CH2Br
CH3 CH3
2-methyl propene Isopropyl bromide
In the absence of peroxide, HBr would be added giving tertiary butyl bromide.
(ii) Tertiary alkynes are slightly acidic, forms silver salt with ammoniacal solution of silver nitrate:
3 NH (aq)
R − C ≡ C − H + AgNO3 → R − C ≡ C Ag ↓
white ppt.
Solution for the Q. No. 11 and 12: (A, C)
C CH3CH2l
NaNH2
H O
HO
H3CO
H2, Lindlar’s catalyst

CH3l
O
H H
X
OH
Br
NaNH2 C
H
1 equivalent NaNH2
O
OH O
+
H2O H2,Pd/C CrO3
mild
OH Y

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Chem i str y | 11.

Example 1: Complete the following reactions:

Example 2: Give the major products (not stereoisomers) of the following:

3,5-Dibromo- 5-Bromo-3-ethyl- 3-Bromo- 5-Ethyl cyclo-

Example 5: Give the major and minor products. CH2 CH2 H

Example 6: Dehydration of (A) with conc. CH2 H Br

Write all the possible structures of (A), (B) and (C).

R = ( CH2 ( , the possible structures of (A) can be :

(D1) is obtained when (C2 – C3) bond

Example 9: Give the number of stereoisomers of (A) in the following reactions.

O HOOC - COOH HOOC - Me

Remove O and join

(A) (B) (B)

Other products can be obtained due to carbocation (I) rearrangement.

Example 11: Complete the following reaction:

O3/Red [H] (Conc.H2SO4)

(b) Proceeding reverse: (Retrosynthetic approach)

Example 2: Complete the following reactions:

(c) It is an example of -elimination.

[Two chiral centres; four stereoisomers as in (a)]

(B) PhCO3H +H2O

Example 4: Identify (A), (B) and (C) in the following reaction.

[O] Acidic KMnO4

Sol: First of all we have to calculate degree of unsaturation:

Total number of C atoms in (A)=7 

Possible structure of (A) are as follows:

ii. Other two possibilities of the combination are as follows:

Example 5: Complete the following reactions:

Example 6: Identify (A) to (H)

Reagent I Reagent II Reagent III Reagent IV Reagent V

Example 7: Write the product with its mechanism.

2,2,3-Trimethyl bicyclo [4.4.0] dec-1-ene

Example 8: Which of the following show G.I.?

(g) Ph N=N Ph (h)

CH3 CH3 CH3 CH3

Two same groups

Priority of C2H5 > CH3 and OH > LP of e s

(e) It does not show G.I

Two different groups

(f) It does not show G.I

Two different groups

(g) It shows G.I.

H3C CH3 H3C H H CH3

Example 9: Give IUPAC name to each of the following using E or Z designations.

Priority of HC  C- > (CH3)3C- > CH2=CH-B> (CH3)2CH-

Condensed Stick Bond line IUPAC name Common or trivial name

C3H4 H3C—C≡C—H 3 2 1 Propyne Methylacetylene

C4H6 CH3—CH2—C≡CH 4 But-1-yne Ethylacetylene

C5H8 CH3—CH2—CH2—C≡C—H 4 3-Methyl-but-1-yne Propylacety lene

or 5 Pent-2-yne Ethyl methylacetylene

Above the plane In the plane of

1.3 Isomerism in Alkynes

(iii) Functional isomerism: Alkynes are functional isomers of dienes

CH3—C≡CH and are ring chain isomers.

2.1 From Calcium Carbide

2.2 Double Dehydrohalogenation of Dihalides

Double dehydrohalogenation of a geminal dihalide

Geminal dihalide Sodium amide Alkyne Ammonia Sodium halide

Double dehydrohalogenation of a vicinal dihalide

Vicinal dihalide Sodium amide Alkyne Ammonia Sodium halide

1,1-Dichloro-3,3- Sodium salt of alkyne 3,3-Dimethyl-

1,2-Dibromodecane Sodium salt of alkyne 1-Decyne (54%)

Priority of HC C- > (CH3)3C- > CH2=CH-B> (CH3)2CH-

HC C-Na+ + CH3 Br HC C CH3 + NaBr

HC C-Na+ + CH3 CH2 I HC C CH2CH3 + NaI

HC C-Na+ + CH3 CH2 CH2 Br HC C CH2CH2CH3 + NaBr

3Me CC Me 3BH3+THF Me C=C B

The compound B is (2008)