hydrolysis of carbides.
HC CH + Ca(OH)2
CH3 - C CH + 2Mg(OH)2
The two hydrogen atoms of acetylene are acidic in nature and can be
replaced by a strong base like sodium or sodamide.
HC CH + Na
HC CH + NaNH2
HC C-Na+ + H2
HC C-Na+ + NH3
Sodium acetylide when treated with primary alkyl halide gives 1-alkynes
following nucleophilic substitution reaction by SN2 mechanism.
Secondary alkyl halide gives poor yield of 1-alkyne because substitution
reaction is accompanied by elimination reaction with acetylide ion
(HC C-) functioning as a strong base. Tertiary alkyl halides do not
undergo any substitution reaction because of steric hindrance. Instead
they undergo elimination reaction easily forming alkene as the only
product.
HC C- + CH3CH2CH2 - Cl
HC C - CH2CH2CH3 + Cl-
alc. KOH
CH3C CH
Br Br
NaNH2
CH3CCH
Br
vic. dibromide
Br
CH3C CH2CH3
Br
gem. dibromide
alc. KOH
CH3C CHCH3
Br
NaNH2
CH3CCCH3
CH3 - CH - CH
Br
But the why cant we just use NaNH2? If it can abstract proton from
less acidic vinylic halides it can certainly do so from the more acidic
saturated dihalide.
We dont use NaNH2 because that would cause an increase in the
concentration of NH2- which would then behave as a nucleophile than
as a base and cause substitution to yield amines.
Because the vinylic carbons are electron rich due to electron cloud so
nucleophiles cannot approach them directly. Moreover the C - Br bond
is partially double so it wont be a good leaving group.
CH3CCCH3
CH3 - C CH + HBr
CH3 - C = CH2
HBr
Br
CH3 - C - CH3
Br
HBr
Br
Peroxide
Br
CH3 - CH - CH2
Br
CH3 - C CH + HBr
Peroxide CH3 - CH = CH
HBr
Br
CH3 - CH2 - CH
Br HBr Peroxide
Br
CH3 - C CH + Cl2
CH3 - C = CH
Cl
Cl2
CH3 - C - CH
Cl Cl
CH3 - C CH + H2O
H2SO4
CH3 - C = CH2
HgSO4
CH3 - C - CH3
OH
CC + Hg
Hg+
H2 O
C=C
+
OH2
Hg+
H+
C=C
OH
H3 O+
Hg2+
CH=C
OH
CH2C
O
3CH3 - C CH + BH3
(CH3 - CH = CH)3B
Trialkenyl boranes on hydrolysis yield alkenes.
3CH COOH
3
(CH3 - CH = CH)3B
3CH3 - CH = CH2
If the alkene can show stereochemistry then only cis alkene is formed.
Oxidation of trialkenylborane with alkaline H2O2 results in the
formation of carbonyl compounds. Terminal alkynes give rise to
aldehydes whereas internal alkynes give rise to ketones.
OH
H2O2 in NaOH
(CH3 - CH = CH)3B
3CH3 - CH2 = CH
O
3CH3 - CH2 - CH
2CH3 - C CH
+
Mechanism H3O
CH3 - C CH
CH3 - C CH
NH3
Cu+
CH3 - C CCu+
CH3 - C = CH
Cu+
CH3 - C C-
2CH3 - C C -C = CH2
CH3 - C = CH
CH3 Cu
CH3 - C C - C = CH
H+
CH3
CH3 - C C - C = CH2
CH3 - C CH
CH3 - C C - CH3
CH3 - COOH
H+
KMnO4 in OH-,
H+
O
CH3CCH + O3
CH3C
O
CH
O
CO2
2CH3 - COOH
H2O
CH3COOH + HCOOH
O
CH3CCCH2CH3 + O3
CH3C
O
(i) O3
(ii) H2O
HC CH + HCl
Hg2+
H2C = CHCl
Polymerization
- H2C - CH Cl
n
HC CH + HCN
Cu2Cl2
HCl
H2C = CHCN
Polymerization
- H2C - CH NC
n
Acetic acid adds to ethyne in the presence of Hg2+ ion to give vinyl
acetate, which is used as monomer in the preparation of polyvinyl
O
acetate (PVA).
Hg2+
H2C = CH - O - C - CH3
HC CH + CH3COOH
- H2C - CH H3C-C-O
O
3 CH3 - C C - CH3
1,3,5-Trimethylbenzene
R - C CH + X2
Water
R - C = CHX
R - C - CHX2
-H2O
R - C - CHX2
OH
CH3CH2CH2 - C C - CH3
NaNH2
Alc. KOH
CH3CH2CH2 - CH2 - C CH
Mechanism
CH3CH2CH2 - C C - CH2
NH2-
CH3CH2CH2 - C C - CH2
H
CH3CH2CH2 - C = C = CH2
NH2-
NH3
CH3CH2CH2 - C = C = CH2
CH3CH2CH2 - C = C = CH
H
CH3CH2CH2 - C - C CH
H
Alc. KOH
NH3
CH3CH2CH2 - CH2 - C CH
Terminal alkynes are weakly acidic. pKa values are : Acetylene: 25;
H2O: 15.7; Alcohols: 16-19; NH3: 34; Ethylene: 44; CH4: 50.