188 Reaction Mechanism

H
Et Cl H
C C CH3
H Cl Cl
2-hexyne Et CH3 Et CH3
(X) (A)
E+Z
E+Z

H
H Cl
Cl
Et CH3 Et CH3
(Y) (B)
E+Z
E+Z
1-Hexyne reacts with a catalytic amount of sulfuric acid is an aqueous solvent to give vinylic carbocation,
followed by reaction with water on tautomerism generate ketones.

H
H •• H O H
••
H O H O CH3
H+
H2O •• tautomerism
Bu C C H C C ••
–H+
Bu H Bu H Bu H Bu

Hydration of alkynes and Tautomerism:

Addition of water to alkynes requires a strong acid. The initial product from the addition of water to an alkyne
is an enol and this immediately rearranges to more stable keto tautomer.
R O H O
H3O+ Tautomerisation
R C C R C C R CH2 C R
HgSO4
Addition Keto tautomer
H H
(Enol tautomer)
HgSO4
H C C H + H2O H2SO4
H3C CHO

HgSO4 C
R C C H + H2O H2SO4 R CH3
Hydroboration Reaction:
Diborane react readily with alkynes.
Addition of disiamylborane to alkyne, as with alkenes, the B–H reagent group adds in an apparently anti-
Markovnikov manner, due to the fact that the boron is the electrophilic not the hydrogen.
H2O2
R C C H + (C5H11)2B H R C C B(C5H11)2
NaOH
H H
O

R CH2 C H R C C OH
H H
Oxidation: Reaction of alkynes with oxidising agents such as potassium permaganate and ozone usually result
in cleavage of triple bond to give carboxylic acid products.
R C C R' + [O] RCO2H + R'COOH
Reaction Mechanism 189
Nucleophilic addition reactions:
The sp-hybrid carbon atoms of the triple-bond rendr alkynes more electrophilic than similarly substituted
alkenes.
As a result, alkynes sometimes undergo addition reaction iniaited by bonding to nucleophile.
C2H5OH
H C C H + KOC2H5 H2C C O C2H5
150ºC H
Ba(CN)2
H C C H + HCN H2C C CN
H
Acidity of terminal alkyne:
pKa value of ethene is estimated at 44, and pKa of ethyne (acetylene) is found to be 25. This increase in acidity
permits the isolation of insoluble silver and copper salts of such compounds.
NH4OH
R C C H + Ag(NH3)2 R C C Ag + NH3 + NH4
ether
R C C H + NaNH2 R C C Na + NH3
R C C H + H3C I R C C CH3 + NaI
ether
H3C C C H + NaNH2 H3C C C Na + NH3
H3C C C Na + C2H5 Br H3C C C C2H5 + NaBr
The enhanced acidity of terminal alkynes relative to alkanes also leads to metal exchange reaction when there
compounds are treated with organolithium or Grignard reagents.
ether
R C C H + C2H5MgBr R C C MgBr + C2H6

H C C CH2 CH2 Br + Mg
ether H C C CH2 CH2 MgBr

C2H5MgBr
BrMg C C CH2 CH2 MgBr
C3H7 NaNH2
Br C3H7 C C Na
–HBr

5.1. (I) Addition to Allene

H H
H2C C CH2 C C C
H
H
Orbital description
(Terminal atoms are perpendicular to each other)
The attack by a proton on allene might conceivably lead to the allyl cation or the 2-propyl cation.

H H
H2C C CH2 H2C C CH2 H3C C CH2
H
Protonation at the centre carbon without rotation of one of the terminal methylene group leads to a primary
carbocation that is not stabilised by resonance, because the adjacent -bond is orthogonal to empty p-orbital.
As a result, protonation both in solution and gas phase occurs at a terminal carbon to give the 2-propenyl
cation, not the allylic cation. The addition of HCl, HBr, HI to allene has been studied in some detail. In each
case a 2-halopropene is formed, corresponding to a protonation at terminal carbon.
X X

H2C C CH2 + HX H3C C CH2 + H3C C CH3

X
190 Reaction Mechanism
The presence of phenyl group results in the formation of products from protonation at the centre carbon.
HCl
Ph C C CH2 Ph C C CH2 Cl
H HOAc H H
Two alkyl substituents, as in 1, 1-dimethlyallene, also lead to protonation at the centre carbon.
HCl
(H3C)2C C CH2 (H3C)2C CHCH2Cl

5.1. (J) SUMMARY

NR2

OR
HO
R2NH RO
HO
OR OH
O
Br m-CPBA OsO4 HO
ROH
Br (i) O3 O
Br Br2 O +
(ii) Me2S
Br Br Hg(OAc)2
HBr
HBR2
BR2

OAc
Hg
H2O2, NaOH
Br
H2O OH
NaBH4
Br

OH
Reaction Mechanism 191
5.1. (K) PRACTICE SET

H Br

1. H Br Br
–Br

OH
D BH2
BH3.THF H2O2, OH
2. H D H D

D D D

CH3
HBr
Br
3.
CH3

H3O
4.
OH

HO Br2
5. + HBr
O Br

H3O+
6.

O HO
Br CH3
Br
CH3
7. Br2
+ Enantiomer
CH2Cl2 (solvent)
Cl
Cl

8. HCl
(Excess)

HCl Cl
9. +

Cl
 192 Reaction Mechanism

Cl
HCl
+
10.

Cl
OH

Br
Br2
11.
H2O

O
OH
OH
HgO
H2SO4
12.

OH

(i) Hg(OAc)2, H2O +

13. (ii) NaBH4 OH

Minor Major
O
+
14. Bu C C H
H
H2O
Bu CH3

H
H Cl Cl
15. Cl
3º carbocation

OH O
H2SO4(cat.) ••
OH2 Tautomerism
16. ••

Cl

Cl
Cl
17. Cl2
Cl +
MeO MeO MeO
Reaction Mechanism 193

OH
CH3
CH3
••
Hg(OAc)2 OH2
•• CH3
18.
HgOAc
Hg
OH
OAc NaBH4

CH3

Me Me

Cl OH OH
19.
Cl

20. H3B NEt3 B