LMZ/CHEM109A/ Winter 2010

Chapters 6: Reactions of alkynes

I. . Nomenclature of Alkyne: (CnH2n-2) (Sec. 6.1-6.2)
1. Find the longest chain containing the triple bond or multiple bonds
2. Number the carbon atoms in the chain, beginning at the end nearer the triple bond
3. If the triple bond is equidistance from the two ends, begin at the end nearer the first
branch point
CH
3
CH
2
CH
3
C CH CH
3
C e.g. 5


4. Write the full name, numbering the substituents according to their position in the
chain end listing them alphabetically
5. If more than one triple bond is present, indicate the position of each and use the
suffixes: diyne, triyne, tetrayne and so on.
6. When both double and triple bonds are present, i.e. enyne, number the chain from
the end nearer the first multiple bond, whether double or triple
C C
H
C CH H
3
C
H
3
C e.g. 6


7. When there is a choice in numbering, double bond receives a low number.
CH
2
C CH CH H
2
C e.g. 7


8. For alkenes with other functional groups, numbering priority:






- the group with higher priority should be assigned with a lower number.
e.g.


II. Physical property and structure (sec. 6.3-6.4)
- physical property similar to alkanes, low b.p., generally soluble in non-polar solvent
- C-C triple bond linear, one , 2 bonds.

III. Mechanism of an electrophilic addition (sec. 6.5)

- two additions








- alkyne less reactive than alkene in electrophilic addition reaction

















IV. Electrophilic addition of HX to alkynes (Sec. 6.6)
(sometimes ZnCl
2
and HgCl
2
are used as catalyst, lewis acid)
CH
3
C C H
1 equiv. HX
CH
3
C C H
excess HX
CH
3
C C
H
X
H
CH
3
C C H
X H
H X
OR

Mechanism:












V. Electrophilic addition of halogens (X
2
=Cl
2
or Br
2
) to alkynes (sec. 9.9D)


D. Addition of water (Hydration of alkenes and alkynes) and addition of alcohol



LMZ/CHEM109A/ Winter 2010

VI. Hydration of Alkynes (catalyzed by mercuric ion) (Sec. 6.7)

- internal alkynes





- terminal alkynes
CH
3
C C H
H
2
O, H
2
SO
4
HgSO
4
CH
3
C C H
OH H
H
3
C C
O
CH
3
enol
ketone
tautomerization

mechanism:








VII. Hydroboration of alkyne (Sec. 6.8)
- Internal alkynes







- terminal alkynes
CH
3
C C H
1. R"
2
BH
B H R"
2
BH
diamylborane
-bulky, add only once to
triple bond
2. H
2
O
2
, OH
-
CH
3
C CH
BR
2
H
CH
3
C CH
O H
CH
3
C
H
CH
O H
H
aldehyde

- divergent reactivity






VIII. Reduction of alkynes (sec. 6.9)
1. Hydrogenation
cis addition
of hydrogens
C C
C C
Pd/C
2H
2
(or excess)
Lindlar Catalyst
Lindlar Catalyst: Pd on CaCO
3
or Pd on BaSO
4
, partially deactivated by
treatrment with lead acetate (Pb(OAc)
2
) and quinoline
H
H
H H
H H
i)
ii)
H
2
H
D
H
R
or H
2,
Pd/C
H
2
, PtO
2
, H
+
D
R
only reduce C C C C
C O , C N or
and
not
iii)

e.g.,

or excess H
2,
Pd/C
excess H
2
, PtO
2
, H
+
??
??
Lindlar Catalyst
excess H
2



c) Stereochemistry: mainly form cis-double bonds

2. Dissolved Metal Reductions
1. Li /NH
3
or Na/NH
3
2. H
2
O
C C
H
H
trans addition
of hydrogens


e.g.,
??
1. Li/NH
3
or Na/NH
3
2. H
2
O

Mechanism:






LMZ/CHEM109A/ Winter 2010

IX. Deprotonation of terminal alkyne and its reaction
- C(sp)-H bond acidic






- deprotonation with base [pK
a
(NH
3
) = 38, pK
a
(H
2
O) = 15.7]







- Reaction using depronated terminal alkynes -alkylation reaction




IX. Designing a synthesis I: an introduction to multistep synthesis
- multistep synthesis:












- retrosynthetic analysis