Supplementary

Topic

Imine Derivatives

Just as the reaction of an aldehyde or ketone with a 1 amine forms an imine (Section 21.11) in
the presence of mild acid, so, too, reaction of an aldehyde or ketone with a reagent having the
general structure NH2Z (where Z contains an O or N atom bonded to the NH2 group) forms an
imine derivative. The overall reaction results in replacement of C O by C NZ.
R
General reaction

+
C O
R'
R' = H or alkyl

H2N Z

mild acid

+
C N
Z
R'
imine derivative

H2O

Thus, treatment of an aldehyde or ketone with hydroxylamine (NH2OH), 2,4-dinitrophenylhydrazine [(O2N)2C6H3NHNH2], or semicarbazide (NH2NHCONH2) forms oximes, 2,4-dinitrophenylhydrazones, and semicarbazones, respectively.
Examples

CH3CH2CH2

CH3CH2CH2

C O

H2N OH

C N

mild acid

H
hydroxylamine

oxime

CH3

O2N

CH3
C O

OH

O2N
C N

+
H2NNH

CH3

NO2

mild acid

CH3

NO2

H
2,4-dinitrophenylhydrazine

2,4-dinitrophenylhydrazone

O
O

H2NNH C
NH2
semicarbazide

N
mild acid

N
H

NH2

semicarbazone

The mechanism for these reactions is exactly the same as the mechanism for imine formation
with a 1 amine. There are two key steps: nucleophilic addition of the NH2Z reagent, and loss
of water to form the C N of the imine derivative.

B-1

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B-2

Topic B

Imine Derivatives

Mechanism B.1 Conversion of an Aldehyde or Ketone to an Imine Derivative

Part [1] Nucleophilic addition to the carbonyl group

[1]

C O
R'

OH

[2]

R C NH2Z

proton
transfer

R'

NH2Z nucleophilic
attack

Nucleophilic attack of the reagent NH2Z,

R C NHZ

followed by proton transfer, forms an

unstable intermediate (Steps [1][2]). These
steps result in the addition of H and NHZ to
the carbonyl group.

R'

Part [2] Elimination of H2O to form the imine derivative

+

OH

H OH2

R C NHZ

OH2

[3]

[4]

R C NHZ
R'

R'

[5]

C N
R'
Z
imine
derivative

C NZ
R'
H
H2O

H2O
elimination
of H2O

Elimination of H2O forms the imine derivative

in three steps. Protonation of the OH group

in Step [3] forms a good leaving group,
leading to loss of water in Step [4], giving a
resonance-stabilized cation. Loss of a proton
forms the imine derivative in Step [5].

H3O+

C NZ
R'

resonance-stabilized cation

Imine derivatives were once widely used to characterize carbonyl compounds. Reaction of a
liquid aldehyde or ketone with NH2Z generally forms a solid imine derivative as product. Since
the melting points of thousands of these derivatives are known, this experimental value can be
compared to known melting points to help identify the carbonyl compound from which it was
derived. Today, carbonyl compounds are more commonly identified using the spectroscopic
techniques discussed in Chapters 13 and 14.

Problem B.1

What imine derivative is formed when cyclopentanone is treated with each reagent in the presence
of mild acid?
O2N

b. H2NNH C

a. H2N OH

c. H2N NH2

d. H2NNH

NO2

NH2

Problem B.2

Draw the product formed when each carbonyl compound is treated with 2,4-dinitrophenylhydrazine.
O

a.

Problem B.3

b.

CHO

c. CH3CH2CHO

d.

What carbonyl compound and NH2Z reagent are used to prepare each imine derivative?
NH2

NOH

a.

Problem B.4

smi75624_topicB.indd B-2

NNH

b.

NNH

c.

Although semicarbazide (H2NNHCONH2) contains two NH2 groups, only one reacts to form a
semicarbazone. Explain why the two NH2 groups have different reactivities.

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Topic B

Problem B.5

B-3

Imine Derivatives

Purpald (A) is the trade name for a reagent that reacts with an aldehyde to form a colorless
compound B, which is air-oxidized to give a magenta or purple product C.
N N

N N
HS

N
NH2
Purpald
A

NHNH2

RCHO
[1]

HS

N N
O2

NH

HN

NH
R
B

[2]

HS

2 H2O

R
C

a. Draw a stepwise mechanism for the conversion of A to B.

b. Explain why ketones react with Purpald, but do not form a colored product; that is, Reaction [1]
occurs, but Reaction [2] does not.

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