226 Dienes Alkynes Lec

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DIENES
Dienes are alkenes with 2 double bonds.
IUPAC: Same as alkene, but change -ene to -adiene and
use two numbers to locate the two double bonds (number
from the end of the chain which makes the smaller of
these numbers smaller).
Double bonds separated by more than one single bond
are isolated. Compounds with isolated double bonds
have the same chemical properties as alkenes.
Double bonds that alternate with single bonds,
eg C=C-C=C, are conjugated.
Double bond arrangements like C=C=C are cumulated.
Compounds containing two carbon-carbon cumulated
double bonds are called allenes.
Conjugated dienes differ from simple alkenes in that they
+ are more stable,
+ undergo 1,4-addition, and
+ are more reactive.
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Stability
In conjugated systems, not only is there bonding
between the first and second and again between the third
and fourth carbon atoms, as indicated in the structural
formulas, but there is also some bonding between the
second and third carbons. [Remember: The more
bonding the more stable the molecule.]
We can see this using the resonance model
Clearly, none of the three structures on the right
contributes very much to the hybrid (the actual structure
of the molecule); but there are three of them, so taken
together they would produce some double bond
character between the second and third carbons.
Although it is beyond the scope of this course, molecular
orbital theory the theory that deals with molecular
orbitals and how they form from atomic orbitals also
predicts bonding between the second and third
carbons. This bonding arises from the first orbital (see
below) which unites all four p atomic orbitals (one from
each of the sp
2
hybridized carbons in the conjugated
system).
3
p
p*
0.68
-0.68
-1.68
1.68
_
_
_
_
_
_
1.0
-1.0
Energy
0
Two isolated p-bonds. Conjugated p-system.
E
p
= -4.0
E
p
= -4.72
Energy (Huckel) of Two Isolated vs Conjugated Double Bonds
p
1
p
2
p
3
p
4
We see that the calculated bonding energy is lower in
the conjugated system by 0.72 units, meaning that the
conjugated molecule is more stable than the non-
conjugated one.
4
Y
Z
Y Z
YZ
1,2-addition 1,4-addition
Note the "shift"
of the -bond.
1
2
3
4
1
2
3
4
1
2
3
4
Electrophilic Addition to Conjugated Dienes:
1,2- vs. 1,4- Addition
eg CH
3
CH=CH-CH=CHCH
3
+ HCl ) ) ) ) ) ) ) >
CH
3
-CH
2
-CHCl-CH=CHCH
3
via 1,2-addition
+
CH
3
-CH
2
CH=CH-CHCl-CH
3
via 1,4-addition
This reaction occurs in the usual way that is to say, via
a carbocation. However, in this case the carbocation that
forms preferentially is a resonance stabilized one. It has
the positive charge on a carbon that is attached to a
carbon with a double bond; these carbocations are called
allylic and they are particularly stable.
5
Since the positive charge is shared between
ordinary 2
o
carbocation
4
3
2
1
CH
3
H
H
H
CH
3
H
H
2
o
allylic type of carbocation; ~ stability of 3
o
carbocation.
H
CH
3
H
H
H
H
CH
3
HCl
4
3
2
1
4
3
2
1
4
3
2
1
CH
3
H
H
H
H
CH
3
H
CH
3
H
H
H
CH
3
H
Cl +
Not formed:
the carbons labeled 2 & 4, Cl can attack either.
Reactivity of Conjugated Dienes
Owing to the formation of resonance stabilized allylic
carbocations when undergoing electrophilic addition,
conjugated dienes are especially reactive.
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C C H
H
H H
H
H
1.09 A
1.54 A
C C
H
H
H
H
1.08 A
1.33 A
H C C H
1.06 A
1.20 A
H C C H
-bond
top/bottom
-bond -bond
front/back
Alkynes, -CC-
The triple bond consists of an sp-sp -bond and two -
bonds. The remaining sp orbital on each carbon is
oriented 180
o
from the former sp orbital and forms a -
bond with another atom.
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C C
R
2
H
H
R
1
R
1
C C R
2
C C
R
2
H
R
1
H
Li
o
or Na
o
NH
3
liquid
H
2
Lindlar catalyst
Reactions of Alkynes
Reduction to an alkene
Geometrical isomerism possible for product, except when
alkyne is terminal (has triple bond at end).
Each of these reactions is stereoselective in that each
yields predominantly one stereoisomer of two or more
possible ones.
Reduction to an alkane
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R
1
C C R
2
H
2
Pt catalyst
R
1
C C R
2
H
H
H
H
R
1
C C R
2
R
1
C C R
2
X
X
X
X
X
2
R
1
C C R
2
X
X
X
2
X
2
= Cl
2
, Br
2
R
1
C C R
2
R
1
C C R
2
H
H
X
X
R
1
C C R
2
H
X
HX HX
HX = HCl, HBr, HI
typically anti addition
Addition of halogens
Both steps generally show anti addition.
Although triple bonds are usually less reactive than
double bonds toward electrophilic addition, this reaction
can often be stopped at the first step.
Addition of hydrogen halides
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R
1
C C R
2
H
H
X
X
HX
R
1
C C
R
2
H
X
R
1
C C R
2
H
H
X
R
1
C C R
2
H
H
X
X
Terminal alkynes show Markovnikov addition in first step.
Reaction can often be stopped after the first step even
though alkynes are less reactive toward electrophilic
addition than alkenes. This lower reactivity of alkynes is
at least partly due to vinylic cations being less stable than
comparable alkyl cations --- 2
o
vinylic ~ 1
o
alkyl;
1
o
vinylic ~ methyl.
Note formation of geminal dihalide in the second step.
This is the result of resonance stabilization of the
intermediate carbocation (and the transition state leading
to it), as shown below. Evidently, this has more
importance than the destabilizing inductive effect of the
electronegative element.
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H C C CH
3
H
2
O, H
2
SO
4
HgSO
4
H
2
C C
CH
3
OH
H
2
C C
CH
3
O
H
an enol a ketone
Hydration of Alkynes - Tautomerism
Usually the equilibrium favors the ketone
(or CH
3
- CHO, when the alkyne is acetylene).
This is an acid - base equilibrium and -OH is a stronger
acid than -CH
3
.
Structural isomers which exist in equilibrium with
each other are called tautomers. The particular type of
tautomerism shown above is keto - enol tautomerism.
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Acidity of Alkynes Alkynes in Synthesis
In general, it is possible to convert a terminal alkyne to an
anion by removing the terminal hydrogen. This is usually
accomplished by using a base which is stronger than an
acetylide anion:
R-C/ C-H + Na
+
NH
2
-
> R-C/ C
-
Na
+
+ NH
3
The acetylide anion can be used in synthesis, to make
larger molecules, by reacting it with alkyl halides in a
substitution reaction:
R-C/ C
-
Na
+
+ ClCH
2
-R' > R-C/ C-CH
2
-R' + Na
+
Cl
-
Example problem 1
Synthesize 2-hexyne from starting materials which do not
contain more than 3 carbons.
Solution 1
CH
3
-C/ C-H + NaNH
2
> CH
3
-C/ C
-
Na
+
+
NH
3
CH
3
-C/ C
-
Na
+
+ C
2
H
5
-CH
2
Cl > CH
3
-C/ C-CH
2
-
C
2
H
5
+ NaCl
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Example problem 2
Synthesize 4-octyne from starting materials which do not
contain more than 3 carbons.
Solution 2
H-C/ C-H + NaNH
2
> H-C/ C
-
Na
+
+ NH
3
H-C/ C
-
Na
+
+ C
2
H
5
-CH
2
Cl >
H-C/ C-CH
2
-C
2
H
5
+ NaCl
H-C/ C-CH
2
-C
2
H
5
+ NaNH
2
>
Na
+ -
C/ C-CH
2
-C
2
H
5
+ NH
3
Na
+ -
C/ C-CH
2
-C
2
H
5
+ C
2
H
5
-CH
2
Cl >
C
2
H
5
-CH
2
-C/ C-CH
2
-C
2
H
5
+ NaCl

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