ALKYNES AND ALKADIENES JEE ADVANCED-VOL - V

ALKYNES AND ALKADIENES

ADDITION REACTIONS
Summary
 Alkynes undergo addition reactions in an analogous fashion to those of alkenes.
 The high electron density of the π bonds makes them nucleophilic.
 Two factors influence the relative reactivity of alkynes compared to alkenes:
1. increased nucleophilicity of the starting π system (C C  vs  C=C), and
2. stability of any intermediates (for example carbocations)

Reactions
 Hydrogenation
 Dissolving Metal reduction
 Hydrohalogenation
 Hydration
 Halogenation
 Ozonolysis

Hydrogenation of Alkynes

Reaction Type: Syn Addition

Summary
 Alkynes can be partially reduced to cis-alkenes with H2 in the presence of poisoned catalysts.
(eg. Pd / CaCO3 / quinoline which is also known as Lindlar’s catalyst)
 The “poisoned” catalyst prevents over-reduction, to alkane
 Alkynes can be reduced to alkanes with H2 in the presence of catalysts (Pt, Pd, Ni etc.)
 The new C-H s bonds are formed simultaneously from H atoms absorbed onto the metal surface.
 The reaction is stereospecific giving only the syn addition product.

CATALYTIC HYDROGENATION
Step 1: Hydrogen gets adsorbed onto the metal surface.
Step 2: Alkyne approaches the H atoms adsorbed on the metal surface.

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Step 3: C  C  reacts with the H atoms on the surface forming the two new C-H s bonds generating the alkene.

Dissolving Metal Reduction of Alkynes

Reaction Type: Addition

Summary

 Alkynes can be reduced to trans-alkenes using Na in NH3 (liq.)

 This reaction is stereospecific giving only the trans-alkene via an anti addition.

 Note that the stereochemistry of this reaction complements that of catalytic hydrogenation (syn)

 The reaction proceeds via single electron transfer from the Na with H coming from the NH3

 These reaction conditions do not reduce alkenes, hence the product is the alkene.

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MECHANISM FOR THE REDUCTION OF ALKYNES WITH Na / NH3

Step 1: Sodium transfers an electron to the alkyne giving a radical anion.

Step 2: The radical anion removes a proton from the ammonia in an acid / base reaction.

Step 3: A second atom of sodium transfers another electron to the alkyne giving an anion.

Step 4: The anion removes a proton from the ammonia in an acid / base reaction.

Reaction of Alkynes with Hydrogen Halides

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Reaction type: Electrophilic Addition

Summary

 When treated with HX alkynes form vinyl halides.

 Hydrogen halide reactivity order : HI > HBr > HCl > HF (paralleling acidity order).

 Regioselectivity predicted by Markovnikov’s rule with the H adding to the C with the most H already
present.

 Reaction proceeds via protonation to give the more stable carbocation intermediate.

 Not stereoselective since reaction proceeds via planar carbocation.

 In the presence of excess HX, a second addition can occur to the product alkene giving a geminal dihalide

 For HBr, care must be taken to avoid the formation of radicals as the alternate radical addition occurs with
opposite regiochemistry:

MECHANISM FOR REACTION OF ALKYNES WITH HBr

Step 1: An acid/base reaction. Protonation of the alkyne to generate the more stable carbocation. The π electrons
act pairs act as Lewis base.

Step 2: Attack of the nucleophilic bromide ion on the electrophilic carbocation creates the alkenyl bromide.

Step 3: In the presence of excess reagent, a second protonation occurs to generate the more stable carbocation.

Step 4: Attack of the nucleophilic bromide ion on the electrophilic carbocation creates the geminal dibromide.

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Hydration of Alkynes

Reaction type: Electrophilic Addition

Summary
 Alkynes can be hydrated to form enols that immediately tautomerize to ketones
 Reagents:  aq. acid, most commonly H2SO4, with a mercury salt
 Regioselectivity predicted by Markovnikov’s rule
 Reaction proceeds via protonation to give the more stable carbocation intermediate.
 Not stereoselective since reactions proceeds via planar carbocation.

MECHANISM FOR REACTION OF ALKYNES WITH H3O+

Step 1: An acid / base reaction. Protonation of the alkyne to generate the more stable carbocation. The π
electrons act pairs as a Lewis base.
Step 2: Attack of the nucleophilic water molecule on the electrophilic carbocation creates an oxonium ion.

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Step 3: An acid / base reaction,deprotonation by a base generates the alcohol and regenerates the acid catalyst
forming an unstable enol.
Step 4: An acid / base reaction. Reprotonation by the acid catalyst occurs on the carbon. The oxygen atom
electrons help facilitate this process generating an oxonium ion.
Step 5: Another acid / base reaction. Deprotonation of the oxonium ion creates the ketone. Steps 4 and 5 show the
acid catalyzed tautomerization of the enol to the ketone.

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ALKADIENES

* These are functional isomers of alkynes with two double bonds. The following types exist.

 

Conjugated isolated cumulative { stability of dienes}

Conjugated systems are more stable.

* Addition reaction of conjuted diene are of two types 1,2- and 1,4 -addition.
* 1,2- addition, kinetically controlled reaction which depends on the stability of intermediate and rate
of slowest step, the reaction which is also called rate determinig step.
* 1,4-addition reaction depends on stability of the product formed. These reactions takes palce
comparatively at high temperature and their intermediates are comparatively less stable. Product of
1,4-addition are called thermonamically controlled products.

HBr CH 3  CH Br  CH  CH 2  CH 3  CH  CH  CH 2  Br
 800 C 80% 20%

CH 2  CH  CH  CH 2

HBr CH 3  CHBr  CH  CH 2  CH 3  CH  CH  CH 2 Br
20% 80%
400 C

DIELS-ALDER Reaction :-

Concerted step cycloaddition between diene and an dienophile.

COO me

fast

* Transoid forms with restricted rotation to get converted into cis forms due to not give Diels-Alder reaction.
CH2

Eg:

* Electron donating groups on diene will favour Diels-Alder reaction.

* Electron with drawing groups on dienophile enhances the reactivity.

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N
N
Dienes:-
N
N
N N 0

O
N N

O O S

o O
o S N
NO2
N
Dienophile:
N
o R
Signlet 
N O H 3C O
Cl O
N
H2C Cl O O
O
SO 2Ph N Cl N

N OTs O O

O O O
O
O OEt
EtO OEt
H3C
EtO O
CH2
O
H3C CH3 Cl
O O

Few examples of Diels-Alder reaction:-

CH3 COOMe CH3
COOMe
150 °C
+
1) Toluene
CH2 COOMe COOMe
85% adduct
Diene Dienophile

COOEt
N COOEt
10 °C N
2)
+ N
Ether N
EtOOC COOEt
100%
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COOEt O O
MeOOC MeOOC COOEt MeOOC COOEt
O 
3) +
-CO2
O COOEt COOEt
COOEt

O
O
O
4) O
+
O

COOEt O
COOEt
O
5) + 
COOEt COOEt

X X
Z Z

+ CH2
6)
CH2
(ortho relation)
Major

X = alkyl, aryl, OR , Me3 SiO, R3 N etc.,

Z = CHO,  COR,  COOH ,  COOR,  NO2 ,  CN , halogens etc.,

Z Z
CH2

+ CH2
+
7) X CH2 X X Z
(Para relation) (Meta relation)
Major Minor
Halogen Addition to Dienes :-

 Mixture of 1,2 and 1,4- addition products are obtained when 1,3- butadiene reacts with
chlorine (or) bromine.
 Addition of Br2 at low temperature :1,2- addition production(Reversible kinetically controlled)
is major, While at high temperature 1,4 addition product(Irreversible Thermodynamically controlled)
is major.
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Br2 CCl4

Br
Br
 Br
Br
54% 46% at  15 c 0 

LEVEL-IV

SINGLE CORRECT ANSWER TYPE QUESTIONS

1. When propyne is treated with aqueous H2SO4 in presence of HgSO4, the major product is
(A) Propanol (B) Propyl hydrogen sulphate
(C) Acetone (D) Propanal
2 Which of the following reacts with ammonical AgNO3 solution
(A) Ethyne (B) Ethylene (C) But-2-yne (D) Ethane
3. In the reaction
H O
Ph  C  C  CH3 
3
HgSO 4
 A, A is

O
Ph Ph
Ph
O OH
(A) (B) (C) (D)
H3C H3C
H3C
4. 2-Butyne which treated with lithium in presence of liquid ammonia gives
(A) cis-2-butene (B) trans-2-butene (C) n-butane (D) 1-butyne
5. In the following sequence of reactions, the product (D) is

HBr HBr alc KOH NaNH2

CH  CH   A   B   C  D
(A) Ethanol (B) Ethyne (C) Ethanal (D) Ethene
6. Acidic hydrogen is present in
(A) ethyne (B) ethane (C) benzene (D) ethene
7. Which is the most suitable reagent among the following to distinguish compound (III) from the
rest of the compounds
(I)CH3 — C  C —CH3 (II)CH 2 —CH2 —CH2 —CH3
(III)CH3 —CH2 — C  C H (IV)CH3—CH = CH2
(A)Br2 in CCl4 (B)cold aq Alk KMnO4 (C)Ammonical AgNO3 solution (D)All of these
8. The reagent(s) for the following conversion, Br Br 
?
 H H is/are
(A)alcoholic KOH (B)alcoholic KOH followed by NaNH2
(C)aqueous KOH followed by NaNH2 (D)Zn/CH3 OH
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ALKADIENES

9. The compound 1, 2-butadiene has

(A) only sp-hybridized carbon atoms (B) only sp2-hybridized carbon atoms
(C) both sp & sp2-hybridized carbon atoms (D) sp, sp2 and sp3 hybridized carbon atoms
Br2
10. In the reaction : H 2C  CH  CH  CH 2 
1800 C
  X  ; [X] will be :
(A) BrCH 2  CH  CH  CH 2  Br (B) CH 2 Br  CHBr  CH  CH 2
Br H Br Br Br
| | | | |
(C) CH  C  C  CH (D) CH  C  C  CH
2 3 3 3

11. Reductive ozonolysis of allene, CH 3  CH  C  CH 2 will be

(A) only CH 3  CHO (B) only CH 2O
(C) only CO2 (D) mixture of CH 3CHO, HCHO and CO2
12. Which of the following is cummulative diene?
(A) H 2C  C  CH 2 (B) H 2C  CH  CH 2  CH  CH 2
(C) H 2C  CH  CH  CH 2 (D) All of these
13. Arrange the compounds (1), (2) and (3) in their decreasing order of stability :
H2C  C  CH2 H2C  CH  CH2  CH  CH2 H 2C  CH  CH  CH 2
;
1  2  3
(A) 1  2  3 (B) 2  3  1 (C) 3  1  2 (D) 3  2  1

14. Which of the following will yield a mixutre of 2-chlorobutene and 3-chlorobutene on treatment
with HCl?
H 2 C  C  CH  CH 2
(A) H 2C  C  CH  CH 3 (B) CH 3
|

(C) H 2C  CH  CH  CH 2 (D) HC  C  CH  CH 2

MULTIPLE CORRECT ANSWER TYPE QUESTIONS

H2 O ,H O
C4 H6 
Pd /Baso4
 C4 H8 
3 2
 2CH3COOH
15.
(A) (B)
Which of the following does not represent compounds A & B correctly
(A) CH3—C  C—CH3, CH3—CH = CH —CH3
(B) CH2 = CH—CH = CH2, CH3—CH = CH —CH3
(C) CH3—CH2—C  CH, CH3—CH2—CH = CH2

(D) , CH3—CH = CH —CH3

16. Which of the following compounds on reductive ozonolysis give only glyoxal
(A) Ethylene (B) Benzene (C) Toluene (D) Cyclobuta-1, 3-diene

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17. Which of the following reduces 2-Butyne into cis-2-butene.
(A) Na/NH3(l) (B) BH3 followed by CH3COOH
(C) H2/Pd-BaSO4 (D) Li/NH3(l)
HgSO4/H2SO4
18.
BH3/THF
A B
H2O2/OH

Hg(OAC)2, H2O
NaBH4

B is identical when A is
(A) CH  CH (B) CH3 – CH  CH
(C) CH3– CH  CH – CH3 (D) CH3 – CH2 – CH  CH
19. Ammonical silver nitrate reacts with
(A) ethyne (B) ethylene (C) butyne-1 (D) butyne-2
20. Which of the following statements are correct:
(A) Hydrogenation of 2-butyne in presence of Na and liquid ammonia yields trans-2-butene
(B) Hydrogenation of 2-butyne in presence of Lindlar’s catalyst yields cis-2-butene
(C)Hydrogenation of 2-butyne in presence of Pt catalyst gives cis-2-butene
(D) Hydrogenation of 2-butyne in presence of Ni2B catalyst gives cis-2-butene
21. Which is/are true statements/reactions?
(A)Al4C3 + H2O  CH4 (B)CaC2 + H2O  C2H2
(C)Mg2C3 + H2O  CH3C  CH (D)SiC + 4H2O  CH4+ Si(OH)4
22. Which gases are poisonous?
(A)Lewisite (B)Mustard gas (C)Phosgene (D)MIC

COMPREHENSION TYPE QUESTIONS

PASSAGE : 1
In the following sequence of reactions products (A) to (H) are formed.
H Me Aq.solution of A
B(gas) + C (gas) + D(gas) + 2KOH
Electrolysis
KOOC COOK cathode
C2H5MgBr anode
NBS/CCl4

F(gas) + E G
G

23. The gases B, C and D respectively are:

A) B is CH CH, C is CO2, D is H2 B) B is CH CH, C is H2, D is CO2
H3C CH , C is CO , D is H
C) B is 2 2
D) B is H3C H, C is H2, D is CO2
24. Compound G is
Br Br
Br Br
A) Br CH B) C) D)
Br Br Br Br
Br
25. Compound F is
A) C2 H 6 B) CH 3  C  CH C) D)

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PASSAGE : 2
In the following sequence of reactions the products A to G are formed:

  O3/oxidation
A(g) + B(g)
i) 2CH4(g) ii) 4 moles of A C D only
1773K Ni(CN)4 + THF

mole of NaNH2 3 mole of E O3/reductive

A E F G only
iii) Red hot tube
C2H5I
26. Compounds A and B respectively are:
A) Ethane and O2 B) Ethene and H2
C) Ethyne and O2 D) Ethyne and H2
27. Compound C is:
A) benzene B) Mesitylene
C) Cycloocta-1,3,5-triene D) Cycloocta-1,3,5,7-tetraene
28. Compound G is
A) 2 – oxobutanal B) 2 – oxobutanoic acid
C) Methyl glyoxal D) 2-oxopropanoic acid

MATRIX MATCH TYPE QUESTIONS

29. Match the Column

Column – I Column - II
(A)n-Hexane 
 Benzene (p)Wurtz reaction
(B)Acetylene 
 Benzene (q)Frankland reaction
(C)CH3 – CH2 – Br 
 n-Butane (r)Aromatisation
(D)(CH3)3 C – X 
 (CH3)3C – C (CH3)3 (s)Polymerisation
30. Match the Column
Column – I Column - II
HCl
(A)CH3 – CH = CH2  (p)Nucleophilic addition

NBS
(B)CH3—CH = CH2  (q)Free radical addition

HBr
(C)CH3–CH = CH2 
peroxide
 (r)Electrophilic addition

(D)CH  CH 
HgSO4 /H3O (s)Free radical substitution reaction

INTEGER TYPE QUESTIONS

31. One mole of 1,2-Dibromopropane on treatment with x moles of NaNH 2 followed by treatment
with ethyl bromide gave 2- pentyne. The value of ' x ' is

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KEY - LEVEL-IV
SINGLE ANSWER TYPE QUESTIONS
1) C 2) A 3) A 4) B 5) B 6) A 7) C 8) B 9) D 10) A 11) D
12) A 13) D 14) A

MULTIPLE ANSWER TYPE QUESTIONS

15) B,C,D 16) B,D 17) B,C 18) A,C 19) A,C 20) A,B,D 21) A,B,C
22) A,B,C,D

COMPREHENSTION TYPE QUESTIONS

23) C 24) A 25) D 26) D 27) D 28) A

MATRIX MATCHING TYPE QUESTIONS

29) A-R,B-S,C-P,Q,D-Q 30) A-R,B-S,C-Q,D-P

INTEGER ANSWER TYPE QUESTIONS

31) 3

LEVEL-IV

HINTS

aq H2SO4 tautomerise
CH3 – C CH CH3 – CH = CH2 CH3– C – CH3
1. HgSO4

OH O
AgNO3  NH4OH
2. H—C  C —H  Ag  C  C  Ag
3.

OH 2
H 2O
H+
Ph – C C CH3 Ph Ph
CH 3
H3C

- H+

OH O
Ph Ph C CH 2CH3

H3C
keto form
Enol form

H3C H
Li/NH3 (  )
4. CH3  C  C  CH3 
H CH3

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5.
KOH NaNH
Br   CH 2  CHBr 
2
H C  C  H
HBr HBr
|  c d
HC  CH   CH2  CH  Br   CH3  CH  Br
(A ) (B)

6. Hydrogen of ethyne is acidic in nature due to sp Hybrid carbon

7. Terminal alkyne reacts with ammonical AgNO3 solution and give white precipitate

Br Br H
H
alc.KOH

8. H H NaNH2
H HC CH
H Br H
vinylic bromide is more stable: stronger base (–NH2) is required to proceed elimination

SP 2 SP SP 2 SP3
9. CH 2  C  CH  CH 3
1,2 butadiene

10. High temperature favours 1,4 addition

11. CH 3CHO  CO2  CH 2O
12. CH 2  C  CH 2
13. Conjugate diene > Isolate diene > Cumulative diene
14. H 2C  C  CH  CH 3
H2
15. CH 3—C C —CH3 
Pd / BaSO4
 CH3—CH = CH—CH3 
O3 /H2O
 2CH3—COOH
16.

O3
CHO

Zn/HO
2
3
CHO

O3
CHO

Zn/HO
2
2
CHO

17. BH3 / CH3COOH and H 2 / Pd - BaSO 4 reduces 2-butyne to cis-2-butene

18. In case of symmetrical alkynes the product formed in all the abvoe three cases will be same.
19. Terminal alkynes reacts with Ammonical silver nitrate to form silver acetylides
20. Hydrogenation of alkynes gives trans-alkenes
21. Sic cannot undergo hydrolysis
22. All are poisonoues gases
2 2NaNH NaNH
2  NaC  C  CH
C H 2  C H  CH 3  CH  C  CH 3 
31. | | 3
Br Br

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PREVIOUS YEAR IIT JEE QUESTIONS

63. In the compound CH 2  CH  CH 2  CH 2  C  CH , the C2–C3 bond is of the type :

[IIT-JEE 1999]
(A) sp–sp2 (B) sp3–sp3 (C) sp–sp3 (D) sp2–sp3
64. Identify a reagent from the following list which can easily distinguish between 1-butyne and
2-butyne : [IIT-JEE 2002]
(A) bromine, CCl4 (B) H2, Lindlar catalyst
(C) dil. H2SO4, HgSO4 (D) ammonical Cu2Cl2 solution
65. How many chiral compound are possible on mono chlorination of 2-methyl butane?
[IIT-JEE 2004]
(A) 2 (B) 4
(C) 6 (D) 8
66. The synthesis of 3-octyne is achived by adding a bromolkane into a mixture of sodium amide and
an alkyne. The bromoalkane and alkyne respectively are [ IIT-JEE-2010]
(A) BrCH 2 CH 2 CH 2CH 2 CH 3 and CH3CH 2C  CH (B) BrCH 2 CH 2 CH 3 and CH 3CH 2 C  CH
(C) BrCH 2CH2CH 2CH 2CH3 andCH3  C  CH (D) BrCH2CH2 CH2CH3andCH3CH 2C  CH

PREVIOUS IIT JEE KEY

63) D 64) D 65) A 66) D

PREVIOUS IIT JEE SOLUTIONS

C C COOH Br
62.
(A) (B) (C)

C H  C H 2  C  C  C H 2  CH 2  C H 3
66.
3-octyne

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