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bromostilbene, while the (+) or (-) isomer gave the trans alkene.
1. No matter what the mechanism, a double bond does not go to a bridge head
carbon unless the ring sizes are large enough (Bredt’s rule,). This means, for
example, not only that A gives only B and not C.
Br
. C A B
Predict the product when each of the following undergoes HOFFMEN ELIMINATION.
O
Ph
Me OH
H3C NMe3
OH
O
Ph
Me OH
C2H5
H 3C NMe3 OH
C 2H 5
C2H5 C2H5
Predict the product when each of the following undergoes HOFFMEN ELIMINATION
Cl
O
Me
Me2NH MeI EXCESS
A
B
LAH/H2O Ag2O/
N Cl Cl
Me OH
O O
NMe2
Me2N NMe2
N B
A
Me
If the addition is syn, the product will be the erythro dl pair, because each carbon has a 50%
chance of being attacked by Y:
Y W A W E
Y R
A Y
T
B A B H
A B R
B O
d,l
P
OR Y A
W Y W I
A
R
A
A B
B A B
B
On the other hand if the additions is ANTI threo d,l pair will be formed.
Y
A Y A B
A T
H
R
E
B A B W
W B O
d,l
P
A
I
W A
A W A B R
B A B Y
Y B
Of course, the trans isomer will give the opposite results: the threo pair if the addition
is syn and the erythro pair if it is anti. The threo and erythro isomers have different
physical properties. In the special case where Y=W (as in the addition ofBr2), the
"erythro pair"is a meso compound. In addition to triple-bond compounds of the type
AC≡CA, syn addition results in a cis alkene and anti addition in a trans alkene.
Addition to triple bonds cannot be stereospecific, though it can be, and often is,
stereoselective
CH3C=CH2 + CH3CCH3
H2C C CH2 + HX
X
The presence of a phenyl group results in the formation of products from
protonation
at the center carbon
HX PhCH=CHCH2Cl
PhHC C CH2 +
Two alkyl substituents, as in 1,1-dimethylallene, also lead to protonation at the
center
carbon
HX (CH3)2C=CHCH2Cl
(H3C)2C C CH2 +
Isomerisation
Acetylene homologues isomerizes when heated with ethanolic potassium hydroxide
,the triple bond moving towards the centre of the chain.
KOH CH3CH=C=CH2 CH3CCCH3
CH3-CH2CCH
On the other hand when alkynes are heated with sodamide in an inert solvent the
triple bond moves towards the end of the chain
H
NaNH2 NH3 + CH3CH2CCNa CH3CH2CCH
CH3CCCH3 +
Conditions: