Alkynes.

CnH2n-2

C2H2 H:C:::C:H H—C  C—H sp => linear, 180o

acetylene
ethyne

C3H4 CH3CCH methylacetylene

propyne
nomenclature:
common names: “alkylacetylene”
IUPAC: parent chain = longest continuous carbon
chain that contains the triple bond.
alkane drop –ane add -yne
prefix locant for the triple bond, etc.

CH3CH2CCCH3 2-pentyne
ethylmethylacetylene
“terminal” alkynes have the triple bond at the end of the
chain:

CH3
CH3CH2CCH HCCCHCH2CH3
1-butyne 3-methyl-1-pentyne
ethylacetylene sec-butylacetylene
physical properties:
weakly or non-polar, no H-bonding
relatively low mp/bp
water insoluble
Synthesis, alkynes:
1. dehydrohalogenation of vicinal dihalides

H H H
| | |
—C—C— + KOH  — C = C — + KX + H2O
| | |
X X X

H
|
—C=C— + NaNH2  — C  C — + NaX + NH3
|
X
 H H
| |
—C—C— + 2 KOH  — C  C — + KX + H2O
| | heat
X X

CH3CH2CHCH2 + KOH; then NaNH2  CH3CH2CCH

Br Br

“ + 2 KOH, heat
 X2 1. KOH
alkene vicinal dihalide alkyne
2. NaNH2

Br2 1. KOH
CH3CH=CH2 CH3CHCH2 CH3CCH
2. NaNH2
Br Br
Synthesis of propyne from propane

Br2, heat
CH3CH2CH3 CH3CH2CH2-Br + CH3CHCH3
Br
KOH(alc)

CH3CHCH2 CH3CH=CH2
Br2
Br Br

KOH
NaNH2
CH3CH CH CH3C CH
Br
2. coupling of metal acetylides with 1o/CH3 alkyl halides

R-CC-Na+ + R´X  R-CC-R´ + NaX

a) SN2
b) R´X must be 1o or CH3X

CH3CC-Li+ + CH3CH2-Br  CH3CCCH2CH3

note: R-X must be 1o or CH3 to get SN2!

CH3 CH3
CH3C C Na + CH3CCH3 CH3C CH2
Br
+
3o alkyl halide
CH3C CH
E2 elimination!
 alkynes

acids 

bases  some terminal only

metals  terminal only

oxid. 

reduct. 

halogens 
Reactions, alkynes:

1. addition of H2 (reduction)
2. addition of X2
3. addition of HX
4. addition of H2O, H+
5. as acids
6. Ag+
7. oxidation
1. Addition of H2

H H
| |
—CC— + 2 H2, Ni  —C—C—
| |
H H

alkane

requires catalyst (Ni, Pt or Pd)

HCCH + 2 H2, Pt  CH3CH3

[ HCCH + one mole H2, Pt  CH3CH3 + CH2=CH2 + HCCH

]

H
\ /
Na or Li C=C anti-
NH3(liq) / \
H
—CC—
\ /
H2, Pd-C C=C syn-
Lindlar catalyst / \
H H
 CH3 H
\ /
Na or Li C=C anti-
NH3(liq) / \
H CH3

trans-2-butene
CH3CCCH3

H H
\ /
H2, Pd-C C=C syn-
Lindlar catalyst / \
CH3 CH3

cis-2-butene
2. Addition of X2

X X X
| | |
— C C— + X2  — C = C — + X2  — C — C —
| | |
X X X

Br Br Br
CH3CCH + Br2  CH3C=CH + Br2  CH3-C-CH
Br Br Br
3. Addition of hydrogen halides:
H H X
| | |
— C C— + HX  — C = C — + HX  — C — C —
| | |
X H X

a) HX = HI, HBr, HCl

b) Markovnikov orientation

Cl
CH3CCH + HCl  CH3C=CH2 + HCl  CH3CCH3
Cl Cl
4. Addition of water. Hydration.
O
— C  C — + H2O, H+, HgO  — CH2 — C—

H OH
—C=C—
“enol” keto-enol tautomerism

Markovnikov orientation.
CH3CH2CCH + H2O, H2SO4, HgO 
1-butyne
O
CH3CH2CCH3
2-butanone
5. As acids. terminal alkynes only!

a) with active metals

CH3CCH + Na  CH3CC-Na+ + ½ H2 

b) with bases

CH3CCH + CH3MgBr  CH4 + CH3C CMgBr

SA SB WA WB
acid strength:

CH4 < NH3 < HCCH < ROH < H2O < HF

HC CH + NaOH  NR ( H2O = stronger acid! )

CH3CH2CCH + LiNH2  NH3 + CH3CH2CC-Li+

SA WA
6. Ag+ terminal alkynes only!

CH3CH2CCH + AgNO3  CH3CH2CC-Ag+ 

CH3CCCH3 + AgNO3  NR (not terminal)

formation of a precipitate is a test for terminal alkynes.

7. Oxidation

KMnO4

R-CC-R´ hot KMnO4 RCOOH + HOOCR´

carboxylic acids

O3; then Zn, H2O

CH3CH2CCCH3 + KMnO4  CH3CH2COOH +
HOOCCH3

CH3CCH + hot KMnO4  CH3COOH + CO2

CH3CCCH3 + O3; then Zn, H2O  2 CH3COOH

Alkynes

Nomenclature

Syntheses
1. dehydrohalogenation of vicinal dihalide
2. coupling of metal acetylides with 1o/CH3X
Reactions, alkynes:

1. addition of H2 (reduction)
2. addition of X2
3. addition of HX
4. addition of H2O, H+
5. as acids
6. Ag+
7. oxidation