3: Alkyne / - 2102/1102 2nd semester

Stability :
extra" bond in an alkyne is weaker than the alkene bond: As with hydrocarbons in general, alkynes are non-polar and are insoluble in water but soluble in non-polar organic solvents The bonds are a region of high electron density so alkynes are typically nucleophiles. Alkynes typically undergo addition reactions in which one or both of the -bonds are converted to new s bonds. Terminal alkynes, R-CC-H, are quite acidic for hydrocarbons, pKa = 26 Deprotonation of a terminal acetylene gives an acetylide ion.

1 - Acidity of Terminal Alkynes

This carbanion can be used as a C centered nucleophile. These are important systems because the reaction of a carbanion with a C centered electrophile (such as alkyl halides) allows for the formation of new C-C bonds and hence larger more complex molecules.

2- Reaction with Grignard reagents:

CH3MgBr HC Acytelene CH HC CMgBr + CH4

CH3-Br

HC Propyne

C- CH3

MgBr2

3 - Alkylation of Alkynes

NaNH2 , NH3 HC Acetylene NaNH2 , NH3 CH3-C CH3- CH2Br 2-Pentyne CH HC C Na

CH3-Br CH3-C Propyne CH

C-CH2-CH3

CH3-CH2-CH2 CH3-CH2-CH2-C 1-Pentyne CH + RX C H C

CH3

H Cis-2-Hexene

Solution NaNH2 , NH3 CH3-CH2-CH2-C CH + CH3-CH2-CH2-C C Na

CH3I CH3-CH2-CH2 C H Cis-2-hexene C H CH3 H2 , Lindler Catalyst CH3-CH2-CH2-C C - CH3

4 - Preparation of Alkynes via Elimination reactions

5-Addition Reactions of Alkynes 1 - Hydrogenation of Alkynes

CH3-CH2-CH2 - CH2 Octane H H2 / Pd C CH3-CH2-CH2 - C 4-Octyne Na / NH3 C - CH2 - CH2- CH3 Lindler catalyst CH3-CH2-CH2

CH2 - CH2 - CH2- CH3

H C CH2-CH2 - CH3

Cis - 4 - Octene H C CH3-CH2-CH2 Trans - 4 - Octene CH2-CH2 - CH3 C H

6 - Hydration of Alkynes

7 - Ozonolysis of Alkynes