ALKYNES

Alkynes.
C2H2

CnH2n-2
HC CH
acetylene ethyne

H:C:::C:H

sp => linear, 180o

C3H4

CH3CCH

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.

CH3CH2CCCH3

2-pentyne

ethylmethylacetylene

terminal alkynes have the triple bond at the end of the chain: CH3 HCCCHCH2CH3

CH3CH2CCH

1-butyne
ethylacetylene

3-methyl-1-pentyne
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 | | CC | | X X
H | C=C | X

H | + KOH C = C | X

+ KX + H2O

+ NaNH2 C C + NaX + NH3

H H | | CC | | X X

+ 2 KOH C C heat

+ KX + H2O

CH3CH2CHCH2 + KOH; then NaNH2 CH3CH2CCH Br Br + 2 KOH, heat

X2 alkene vicinal dihalide

1. KOH alkyne

2. NaNH2

Br2
CH3CH=CH2

1. KOH
CH3CHCH2 CH3CCH 2. NaNH2 Br Br

Synthesis of propyne from propane Br2, heat CH3CH2CH3 CH3CH2CH2-Br + CH3CHCH3 Br KOH(alc) CH3CHCH2 Br Br KOH NaNH2 CH3CH CH Br CH3C CH CH3CH=CH2

Br2

2. coupling of metal acetylides with 1o/CH3 alkyl halides

R-CC-Na+ + RX R-CC-R + NaX

a) SN2

b) RX must be 1o or CH3X
CH3CC-Li+ + CH3CH2-Br CH3CCCH2CH3

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

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

CH3C C Na +

alkynes acids

bases
metals

some terminal only

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

CC

+ 2 H2, Ni

H H | | CC | | H H
alkane

requires catalyst (Ni, Pt or Pd)

HCCH + 2 H2, Pt CH3CH3 [ HCCH + one mole H2, Pt CH3CH3 + CH2=CH2 + HCCH ]

Na or Li NH3(liq) CC H2, Pd-C Lindlar catalyst

H \ / C=C / \ H

anti-

\ / C=C / \ H H

syn-

Na or Li NH3(liq)

CH3 H \ / C=C / \ H CH3 trans-2-butene

anti-

CH3CCCH3 H H \ / C=C / \ CH3 CH3 cis-2-butene

H2, Pd-C Lindlar catalyst

syn-

2. Addition of X2 X X X | | | C C + X2 C = C + X2 C C | | | X X X

CH3CCH + Br2

Br Br Br 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 CH3CCH + HCl CH3C=CH2 Cl

Cl + HCl CH3CCH3 Cl

4. Addition of water. Hydration. O

C C + H2O, H+, HgO CH2 C

OH

C=C
enol keto-enol tautomerism

Markovnikov orientation.

CH3CH2CCH + H2O, H2SO4, HgO

1-butyne O

CH3CH2CCH3
2-butanone

5. As acids.

terminal alkynes only!

a) with active metals CH3CCH + Na CH3CC-Na+ + H2

b) with bases

CH3CCH + CH3MgBr CH4 + CH3C CMgBr

SA SB WA WB

acid strength:

CH4 < NH3 < HCCH < ROH < H2O < HF
HC CH + NaOH NR CH3CH2CCH + LiNH2
SA

( H2O = stronger acid! ) NH3 + CH3CH2CC-Li+

WA

6. Ag+

terminal alkynes only!

CH3CH2CCH + AgNO3 CH3CH2CC-Ag+

CH3CCCH3 + AgNO3 NR (not terminal)

formation of a precipitate is a test for terminal alkynes.

7. Oxidation

KMnO4

R-CC-R

hot KMnO4

RCOOH + HOOCR
carboxylic acids

O3; then Zn, H2O

CH3CH2CCCH3

KMnO4 CH3CH2COOH + HOOCCH3

CH3CCH + hot KMnO4 CH3COOH + CO2

CH3CCCH3 + 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