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Elimination of HBr from meso-1,2-dibromo-1,2-diphenylethane gave cis-2-

bromostilbene, while the (+) or (-) isomer gave the trans alkene.

Anti-elimination has also been demonstrated in cases where


the electrofuge is not hydrogen. In the reaction of 2,3-dibromobutane with
iodide ion, the two bromines are removed In this case, the meso compound gave
the trans alkene and the dl pair the cis

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

2. No matter what the mechanism, if there is a double bond (C=C or C=O) or an


aromatic ring already in the molecule that can be in conjugation with the new
double bond, the conjugated product usually predominates, sometimes even when
the stereochemistry is unfavorable

Predict the product when each of the following undergoes HOFFMEN ELIMINATION.
O
Ph

Me OH
H3C NMe3
OH

O
Ph

Me OH

Give the structure of 3 alkene in decreasing ration

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

Catalytic hydrogenation at triple bond is faster than double bond.


Halogen addition at triple bond is slower than double bond.
H-X addition is slower in triple bond than double bond.
The addition of HCl, HBr, and HI to allene has been studied in some detail. In
each case a 2-halopropene is formed, corresponding to protonation at a terminal carbon.
The initial product can undergo a second addition, giving rise to 2,2-dihalopropanes.
The regiochemistry reflects the donor effect of the halogen. Dimers are also formed, but
we have not considered them.
X X

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 CH3CCCH3
CH3-CH2CCH
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 + CH3CH2CCNa CH3CH2CCH
CH3CCCH3 +

Conditions:

• Metals: Li, K, Na, occasionally Ca or Mg.


• Co-solvents: diethyl ether, THF, glymes.
• Proton sources (where appropriate): t-BuOH and EtOH are most common, also
MeOH, NH4Cl, and water.