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Pinacol Rearrangement
Wagner-Meerwin Rearrangement
Beckman Rearrangement
PINACOL
REARRANGEMENT
Wilhelm Rudolph Fittig
(6 December 1835 19 November 1910) was a
German chemist. Fittig discovered the
pinacol coupling reaction.
OH
OH
CH3
CH3
CH3
OH
OH
Pinacol
CH3
CH3
CH3
CH3
CH3
Pinacolone
Mechanisms:
Step1: reversible protonation to a hydroxyl group and elimination of
water molecule
R
OH2
OH
H
C
OH
OH
R
R
OH
R
R
R
OH
C
R
OH
Bridged intermediate
C
R
R
R
C
R
R
OH
C
OH
R3C
OH
Bridged intermediate
R3C
R3C
O
O
5
STEREOCHEMISTRY:
Ph
Ph
Me
HO
1.
2.
Me
OH
2-methyl-1,1-diphenylpropane
Answer of
Q1
Stability order of
carbenium ion is
Ph2CH
> Ph
>(CH3)2C
.CH3CH
Usually that OH receives the proton which produces the more stable
carbenium ion by elimination of water molecule.
thus in this example OH gr. On the C atom holding the phenyl gr Will
receive the proton since the stability of diphenyl carbenium ion is greater
than that OH dimethyl carbenium ion.
Stability of carbenium ion depend on the delocalization of positive charge
on the C atom either through resonance or through hyper conjugation.
7
Answer of
Q2
Me
Me
H2SO4
Ph
C
HO
Me
OH
Ph
Ph
Me
2-methyl-1,1-diphenylpropane-1,2-diol
8
10
11
12
13
Wagner-Meerwein rearrangement
OH conc. H SO
2
4
OH2
H
+
_H O
2
The Wagner-Meerwein
rearrangement is an organic
reaction used to convert an
alcohol to an olefin using an
acid catalyst.
Methyl shift
H H
_
H+
Mechanism
15
BEKMANN REARRANGEMENT
The Beckmann rearrangement, named after
the
German
chemist
ERNST
OTTO
BECKMAN (18531923),
It is an acid catalyzed conversion of keto
oximes to N substituted amides usually called
the Bechmann rearrangement.
It is
reaction
R'
C
R
1.PCL5/ether
N
or H2SO4
OH
2.H2O
NHR'
16
OXIMES
oIn organic chemistry, compounds containing the grouping C = N-OH,
derived from aldehyde and Ketones by condensing them with hydroxylamine.
oTwo types of oximes are known:
Aldoxime: combination of aldehyde with hydroxylamine.
Ketoxime: Combination of Ketones with hydroxylamine.
RCHO
+
R2CO
NH2OH
RHC=NOH
R2C=NOH
17
MECHANISM
Step1) Formation of a better leaving group
R
C
OH
H2SO4
OH2
C
R'
R'
C
R'
OH2
OH2
N
R.D.step
R'
R'
R'
18
R'
H2 O
OH2
C
R
R'
-H
R'
NHR
19
20
GRIGNARD REACTION
Franois Auguste Victor Grignard (May 6,
1871 in Cherbourg - December 13, 1935 in Lyon)
was a Nobel Prize-winning French chemist.
RX + Mg
Introduction
Anhydrous ether
RMgX
Grignard
reagent
21
Organolithium compound:
Less prone to unwanted side reaction. Lithium is more
electropositive than magnesium. Carbon lithium bond are more
polar than carbon magnesium bond. This are more reactive than
Grignard reagent.
halide.(R=ALKYL/ARYL/ALKENYL) halide in order of reactivity
(I> Br> Cl>> F).
RX + 2Li
Anhydrous ether
RLi +LiX
Grignard reagent
Reaction:
C
O + RMgX
OH
Mg(OH)X
Mechanism:
Alcohol
23
STEREOCHEMISTRY
the reaction of carbonyl group can establish a steriocenter.if the
reactant are symmetric ,equal amount of the two enantiomers are
formed,
Me
1)MeMgI
Ph
Et
2)H
HO
OH
Me
+
Ph
Ph
Et
1Parts
Et
1 part
Me
Mr
1)MeMgI
Ph
Me
CHO
2)H
Ph
HO
2 PART
Me
Mr
Ph
H
1 PART
OH
24
REACTIONS:
reactions are classified with reference to the type of
compound which is obtained.
Hydrocarbons:
XMg
R +
CH3
CH3
+ MgX2
Grignard reagent react with alkyl halides and related compounds in the
SN2manner.the reaction with saturated halide are slow and the yields poor ,but
allyl and benzyl halide(more reactive than alkyl halide)react Efficiently.
oAlcohol:
R'
XMg
+
"R
R'
O
R
"R
H
O
MgX
R'
R
OH
"R
Grignard reagent react at the carbonyl carbon of aldehyde and ketone to give
alcohols.
25
Aldehyde:
EtO
OEt + RMgX
OEt + RMgOEt + X
EtO
EtO
oKetones:
Three methods are available
1)from nitriles.
RMgX +
R
O
R
26
R
RMgX +
R'
MgX
R"2NH
N2"R
O+
1)PhCOCl
C6H11
Ph
C6H11MgBr
2)H
O
27
1) hydro peroxide
Me3C
O2
MgX
Me3C
MgX
Mg3C
CO2H
2) Thiols
RMgX
+ S
MgX
28
3) sulfinic
acids
O
RMgX
+ SO2
H
MgX
OH
R
S
O
4)iodide.
RMgX + I
I +
MgXI
5)amines
RMgX + NH2
OCH3
NH2 + MgX(OCH3)
29
Limitation:
30