CARBONYL – CONTAINING COMPOUNDS

O
C

A Carbonyl group

Compounds that contain a carbonyl group include the following:

O O O O O
C C C C C
R R R H R OH R NH2 R OR'

Ketone Carboxylic An Amide An Ester

An Aldehyde
acid

The chemistry of the carbonyl group

- The carbonyl group is highly polarized

partial partial
positive negative
C O

- Carbonyl compounds undergo nucleophilic addition reactions.

C O + Nu Nu C O

- Carbonyl compounds also undergo nucleophilic substitution reactions.

O O
C + Nu C + L
L Nu

ORGANOMETALLIC COMPOUNDS

A. Organomagnesium halides – Grinard reagents

Et2O
+ Mg RMgX Grinard reagents
RX
Et2O
ArX + Mg ArMgX

1
The order of reactivity of halides with magnesium is RI > RBr > RCl. RMgBr is the most
commonly used Grinard reagent.

Et2O
E. g, C6H5Br + Mg C6H5MgBr
0
35 C

1. Reaction of Grinard reagents with oxiranes (Epoxides).

H2C CHCH3 Et2O C6H5CH2CHOMgBr

E. g, C6H5MgBr +
O
CH3

H3O

C6H5CH2CHOH

CH3
2. Reaction of Grinard reagent with the carbonyl compounds.

In general
(1) Ether
RMgX + C O R C OH + MgX2
(2) H3O

Mechanism
Step 1. R Mg2+X + C O R C OMg2+ + X

Step 2.
R C OMg2+
H OH2 R C OH H2O + MgX2

Grinard additions to carbonyl compounds can be used to prepare primary, secondary and tertiary
alcohols.

(a) Grinard reagents react with formaldehyde to give primary alcohols.

2
 Et2O H H
H3O
RMgX + HCHO R C OMgX R C OH
H H

(b) Grinard reagents react with higher aldehyde to give secondary alcohols

Et2O R' R'

H3O
RMgX + R'CHO R C OMgX R C OH
H H

20 alcohol
(c) Grinard reagents react with ketones to give tertiary alcohols

Et2O R' R'

H3O
RMgX + R'COR'' R C OMgX R C OH
R'' R''

30 alcohol
(d) A Grianard reagent also adds to the carbonyl group of an ester. The initial product is
unstable and it looses a Magnesium alkoxide to form a ketone. Ketones are, however,
more reactive towards Grinard reagents than esters. Therefore, as soon as a molecule of a
ketone is formed in the mixture, it reacts with a second molecule of the Grinard reagent.
After hydrolysis, the product is a tertiary alcohol with two identical alkyl groups that
corresponds to the alkyl portions of the Grinard reagent.

R' R' R'

R MgX + C O R C OMgX C O
R''O - R''OMgX
OR'' R

RMgX R' R'

H3O
R C OMgX R C OH
R R

30 alcohol

3
 Specific example

H3C CH3 H3C

CH3CH2MgBr + C O H3CH2C C OC2H5 C O
C2H5O - C2H5OMgBr
OMgBr H3CH2C

CH3CH2MgBr CH3 CH3

H3O
H3CH2C C OMgBr H3CH2C C OH
CH2CH3 CH2CH3

30 alcohol

Planning a Grinard Synthesis - How to prepare a compound shown below:

C6H5
H3CH2C C CH2CH3
OH
1. We can use a ketone with two ethyl groups and allow it to react with
phenylmagnesium bromide.

Analysis

C6H5 O
H3CH2C C CH2CH3 H3CH2C C CH2CH3 + C6H5MgBr
OH

Synthesis

C6H5
O (1) Ether
+ C6H5MgBr H3CH2C C CH2CH3
H3CH2C C CH2CH3
(2) H3O OH

3-Phenyl-3-pentanol

4
 2. We can use a ketone with ethyl and phenyl groups and allow it to react with
ethylmagnesium bromide.

3. Or we can use an ester of benzoic acid and allow it to react with two molar
equivalents of ethylmagnesium bromide.

Analysis

C6H5 O
H3CH2C C CH2CH3 C6H5 C OCH
3
+ 2 CH3CH2MgBr
OH

Synthesis

O C6H5
(1) Ether
C6H5 C OCH
3
+ 2 CH3CH2MgBr H3CH2C C CH2CH3

(2) H3O OH

3-Phenyl-3-pentanol

B. OrganoLithium (RLi) reagents react with carbonyl compounds in the same way as
the Grinard reagents.

H3O
R Li + C O R C OLi R C OH

5
 C. Organo copper reagents, either as RCu or R2CuLi, add to α, β- unsaturated
carbonyl compounds and they add almost exclusively in the conjugate manner.

Examples
O
O (1) CH3Li
(a) H3CHC C C CH3 CH3CHCH2CCH3
H
(2) H2O
CH3

O O O

(b) (1) (CH3)2CuLi

+
(2) H2O CH3 CH3
CH3 CH3 CH3

2 % yield
98 % yield

As observed in example (b) above, with alkyl substituted cyclic α, β- unsaturated ketone,
Lithium dialkycuprates (R2CuLi) add predominantly in the less hindered way to give the product
with the alkyl groups trans to each other.