Enolate anions

1
 Enolate anions
O O OEt OEt

C  C C  C
H3C C OEt O C O
H H H H

Ethyl acetoacetate Diethyl malonate

• Hydrogen  to a carbonyl group is acidic and can be removed

by a strong base to give an enolate anion that contains partially
negative carbon atom
• This anion is stabilized by resonance on both carbonyl groups.
 
O O O O O O

EtO OEt EtO OEt EtO OEt
H H H
2
 Diethyl malonate synthesis
Synthesis of alkylated acetic acid derivatives
Reaction of an enolate anion with primary alkyl halide resulting in alkyl group
becomes attached to the enolate
O ِ O
O O
C OEt C OEt
C2H5ONa RX H C OEt
 H C OH
CH2 HC
C C
C OEt C OEt R R
C OEt H
O O O
alkylated acetic
Diethyl malonate -substituted diethyl malonate acid derivative

C2H5ONa 1) NaOH, H2O 

+
2) H
O
O O
R1 C OEt
+ R1 C OEt H C OH
H R1X R C
R CH C C
C OH  R C OEt R
C OEt C OH
O hydrolysis O
& -CO2 O O
alkylated acetic -disubstituted
acid derivative diethyl malonate diacid
 Acetoacetic ester synthesis
Synthesis of substituted acetone.
O O O O
H2
C C CH2 1) NaOC2H5 C C C
CH3 CH2 O CH3 H3C CH O CH3
2) CH3I
Ethyl acetoacetate CH3
1) NaOC2H5
2) CH3I
NaOH, H2O
O O
H2
C C C O O
H3C C O CH3
C C
H3C CH3 H3C CH ONa

1) NaOH, H2O CH3


H+ / 
O
O
C H C CH3
H3C C H3 C C
H2
H3C CH3 4
3-Methyl-2-butanone 2-butanone
• Give the structure of the product formed on reaction of
ethyl acetoacetate with each of the following:
(a) 1-Bromopentane and sodium ethoxide

(b) Saponification and decarboxylation of the product in part (a)

(c) Methyl iodide and the product in part (a) treated with sodium
ethoxide

(d) Saponification and decarboxylation of the product in part (c)

By chemical equations show how to convert
Ethyl acetoacetate to 4-Phenyl-2-butanone

By chemical equations show how to convert

Methyl propanoate to 2-Methyl-2-butanol
O
CH3
(1) 2 CH3MgX
C H3CH2C OH + CH3OH
H3CH2C OCH3 (2) H2O
CH3

Methyl propanoate 2-Methyl-2-butanol

 By chemical equations show how to convert
Ethanol to 2-methylmalonic acid
Hell -Volhard - Zelinsky
K2Cr2O7 O O
Br2 / P
CH3CH2OH CH3 - C - OH Br CH2C OH
H2SO4
KCN

H3 C O
1) NaOC2H5 H2O/H+
HOOC-CH-COOH HOOC-CH2-COOH CN-CH2 C OH
2) CH3I
Malonic acid

By chemical equations show how to convert

Benzoic acid to N-ethyl benzamide
O O CH2
C
SOCl 2
C
2 CH3 NH2
NH CH3
OH Cl N-ethylamine CH2
benzoic acid benzoyl chloride O
 Summary for
methods of preparation
&
reactions of
carboxylic acid derivatives

9
 Preparation of anhydrides

O O O
-+
R C Cl + R1COONa R C O C R1 + NaCl
anhydride

O
O
C
CH2C - OH  H2C
O
- H2O H2C
CH2C - OH C
O
O

Succinic acid Succinic anhydride

10
 Preparation of esters
O
+
RCOH R`OH / H

O '
O
R OH
R C Cl base R - C - OR`

O O
R`OH
R C O C R1

11
 Preparation of acid amides
O
RCOH R1NH2 / DCC

O
2 R1NH2 O
R C Cl
R - C - NHR1
O O R1NH2
R C O C R1
R1NH2
O
R - C - OR` 12
Carboxylic acid
SOCl2 O
O Acid chloride
R C OH R C Cl

-+
R1COONa

R1OH 2 R1NH2
O O base
Acid anhydride
R C O C R1

R1OH

R1NH2

O
ester
R C OR1

R1NH2

amide 13
R C NHR1
Reactions of acid chlorides

base

14
Reactions of acid anhydrides

15
 Reactions of esters

H+ or OH-

16
Reactions of nitriles