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Carbon-Metal Bonds
+ – – +
R X R M
Nucleophilic carbon
Organometallic Reagents
Organolithium Reagents
R X + 2Li R Li + LiX
diethyl
ether
Br + 2Li Li + LiBr
35°C
(95-99%)
Preparation of Organomagnesium
Reagents
“Grignard” Reagents
R X + Mg RMgX
diethyl
ether
Br + Mg MgBr
35°C
(95%)
Alkyl halides, vinyl halides, and aryl
halides can all be used to form
organolithium and organomagnesium
compounds
However, these organometallic
compounds cannot be prepared from
compounds containing acidic groups
(OH, NH2, NHR, SH, C=CH, CO2H)
Cannot use H2O, CH3OH, CH3CH2OH,
etc. as solvents
Cannot prepare from substances such
as HOCH2CH2Br, etc.
Synthesis of Alcohols
Grignard or Organolithium Reagents
CH3CH3 + HC CMgBr
weaker acid
Question
• Select the best method to prepare
CH3CH2CCMgI.
• A) CH3CH2CC-I + Mg (in diethyl
ether)
• B) I-CH2CH2CCH + Mg(OH)2 (in
diethyl ether)
• C) CH3CH2CCH + CH3MgI (in
diethyl ether)
• D) CH3CH2CCH + Mg (in diethyl
ether)
Grignard Reactions
• A Grignard reagent, RMgX, is a very strong base
and a good nucleophile; water/moisture MUST be
avoided in its reaction.
Question
If water can’t be used as a solvent, can other
protic solvents be used instead?
MgBr + CH3OH
+ CH3OMgBr
(100%)
Grignard reagents act as nucleophiles
toward the carbonyl group
+ diethyl
– R R C
C ether
MgX O •• • O • + MgX
• •• •–
••
H3O+
two-step sequence
R C
gives an alcohol as
the isolated product •• OH
••
Grignard reagents react with:
H
H + H diethyl
– R R C H
C ether
•O•
+
MgX O •• • •• •– MgX
••
H3O+ H
product is a R C H
primary alcohol
•• OH
••
Example
Mg
Cl MgCl
diethyl
ether
H
C O
H
H3O+
CH2OH CH2OMgCl
(64-69%)
Grignard reagents react with:
• A) B)
• C) D)
Grignard reagents react with aldehydes
H
H + R' diethyl
– R R C R'
C ether
MgX O •• • O • + MgX
• •• •–
••
H3O+ H
product is a R C R'
secondary alcohol
•• OH
••
Example
Mg
CH3(CH2)4CH2Br CH3(CH2)4CH2MgBr
diethyl
ether H3C
C O
H
H3O+
CH3(CH2)4CH2CHCH3 CH3(CH2)4CH2CHCH3
OH OMgBr
(84%)
Question
• What is the product of the reaction of
ethylmagnesium bromide (CH3CH2MgBr) with
butanal (CH3CH2CH2CH=O) followed by dilute
acid?
• A) 2-hexanol
• B) 1-butanol
• C) 3-hexanol
• D) 3-pentanol
Example
O
H2 C CHLi + CH
1. diethyl ether
2. H3O+
CHCH CH2
OH
(76%)
Grignard reagents react with:
R"
R" + R' diethyl
– R R C R'
C ether
•O• +
MgX O •• • •• •– MgX
••
H3O+ R"
product is a R C R'
tertiary alcohol
•• OH
••
Question
• What is the product of the reaction shown at
the right?
• A) B)
• C) D)
Example
Mg
CH3Cl CH3MgCl
diethyl
ether O
(62%)
Question
• Two alcohols, each having the molecular
formula C11H22O, are formed in the reaction of
methyl lithium with 3-(R)-tert-
butylcyclohexanone. These two alcohols are
• A) constitutional isomers.
• B) enantiomers in equal amounts.
• C) enantiomers in unequal amounts.
• D) diastereomers.
Preparation of Tertiary Alcohols
From Esters and Grignard Reagents
Grignard reagents react with esters
•• R'
R' + OCH diethyl
– R ••
3 ••
C ether R C OCH3
••
MgX O •• • O • + MgX
• •• •–
••
•• R'
R' + OCH diethyl
– R ••
3 ••
C ether R C OCH3
••
MgX O •• • O • + MgX
• •• •–
••
–CH3OMgX
this ketone then
goes on to react with R R'
a second mole of the C
Grignard reagent to
give a tertiary alcohol O ••
••
Example
O
2 CH3MgBr + (CH3)2CHCOCH3
1. diethyl ether
2. H3O+
O 2) H3O+
A. O
C.
OH O
B. D.
OH OH
Grignard Reactions
Question
• Which one of the compounds below will
be produced when methylmagnesium
bromide is added to propanoic acid
(CH3CH2CO2H)?
• A) CH3CH2COCH3
• B) CH3CH2CO2-MgBr
• C) CH3CH2CH(OH)CH3
• D) CH3CH2CH2CH3