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Chem 51B
S. King
Chapter 11 Alkynes
I. Introduction: Alkynes are hydrocarbons with carbon-carbon triple bonds.
H
terminal alkyne:
internal alkyne:
II. Nomenclature:
Simple alkynes are named much like alkenes, except the ending is changed from -ane
to -yne.
Number the chain from the end closest to the triple bond.
Substituents are named as they are in alkenes.
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Br
CH3
OH
Example:
HC
HC
CCH2
CCH2OH
H
C
C
H
H
C
H
H
CH3 C
H
C
C
H
When carbon has more s character, the electrons are closer to the nucleus - in
effect, carbon w/ more s-character is more electronegative - electrons are pulled
in toward the nucleus they are lower in energy and less available for reaction.
Compare an sp3, sp2 and sp orbital:
CH3CH2C
+ NaNH2
NH3(liq)
-33C
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Dont try to use NaOH for this! It is not a strong enough base (it is a weaker base
than acetylide ion)!!
CH3CH2C
H +
OH
Relative Acidities:
Approximate pKa values (rounded to nearest 5)
<0
H
H
10
15
25
35
RCOH
H
NH4
RC
ROH
NH3
CH
O
R
R2C
C
H
RNH3
RNH2
H2O
H
R2NH2
H
R
50
H
O
45
CH4
RCH3
R2NH
R3NH
H
OH
The anion derived from deprotonation is a good nucleophile. It reacts with primary
halides and methyl halides to give internal alkynes, and epoxides to give alcohols:
CH3 C
NaNH2
NH3(liq)
CH3 C
C Na
CH3CH2
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Br
1. CH3 C
2. H3O+
Careful! Acetylide ion is a great nucleophile but also a strong base! Use primary
or methyl alkyl halides or tosylates only. Reaction with secondary alkyl
halides will give E2 rather than SN2 reaction.
Br
CH3 C
Cl H
R
or
Br Br
vicinal dihalide
2 NaNH2
Cl H
geminal dihalide
Br Br
Careful! If you are making a terminal alkyne, you need 3 equivalents of NH2 . Why?
As soon as the terminal alkyne is formed, it will be deprotonated by the
strongly basic NH2 (acid/base reactions are faster than E2 reactions). If
you dont use 3 equivalents, you will run out of base and will get
incomplete conversion.
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Br Br
If you are making a terminal alkyne, you must add a final protonation step!
Vicinal dihalides are made from alkenes and bromine! The conversion of an alkene to
an alkyne, therefore, involves two steps:
RCH
CHR
RCH
RC
CR
CH2
RC
CH
CH
1 eq HBr
1 eq HBr
CCl4
CCl4
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Mechanism:
Important point about this mechanism: There is some doubt about whether a vinylic
cation is actually formed in this reaction. Why?
1) vinyl cations are very unstable 2) trans products predominate 3) more than one
halogen appears in the rate law!
R
R > R
H
H > RCH
R ! R
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H
H > RCH
H ! H
CH3
H2O
H2SO4
(cat.)
Mechanism:
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H2O
OH
H3O+ or HO!
Terminal alkynes are less reactive and require the use of an additional catalyst,
HgSO4:
CH3
C H
H2O
H2SO4
HgSO4
C H
H2O
H2SO4
HgSO4
C CH2CH3
H2O
H2SO4
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1 eq Br2
CCl4
CCl4
D. Hydroboration/Oxidation of Alkynes
Like alkenes, alkynes undergo hydroboration when treated with borane reagents.
CH3C
CCH3
BH3!THF
CCH(CH3)2
BH3!THF
H3C
CH(CH3)2
C
CH
BH3!THF
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H3C
CH(CH3)2
C
H
C
BR2
H3C
CH3
C
H2O2/HO
H2O2/HO
BR2
Dont do this:
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Compare the result obtained when a terminal alkyne undergoes acid catalyzed
hydration vs. hydroboration/oxidation.
H2O, H2SO4
CH3C
HgSO4
CH
1. BH3/THF
2. H2O2, HO
CH
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