Organic Syntheses, CV 4, 283
Submitted by Rip G. Rice and Earl J. Kohn
1.
Checked by Max Tishler, W. H. Jones, and W. F. Benning.
1. Procedure
In a
5-l. three-necked flask, fitted with an
efficient stirrer (Note
1), a
stopper, and a
reflux condenser, are placed, in order,
184.2 g. (1 mole) of benzidine (Note
2),
500 ml. of commercial absolute ethanol, about
125 g. of Raney nickel,
2 and
500 ml. of ethanol. The mixture is heated under reflux with stirring for a total of 15 hours (Note
3). The volume is brought to 3 l. with
95% ethanol, and about 150 g. of filter aid ("Super-Cel") is added with stirring. The mixture is heated to boiling, filtered rapidly through a

-in. layer of filter aid on a
Büchner funnel into a
4-l. filter flask (Note
4) and (Note
5), and the
nickel is washed well with hot
95% ethanol (Note
6). The filtrate is concentrated to a volume of 1.5 l., cooled slowly to room temperature, then chilled in a refrigerator and filtered. The yield is
185–202 g. (
77–84%) of light gray or purplish gray flakes, m.p.
105–115°.
The crude product is dissolved in
1.5 l. of hot 95% ethanol, the solution is treated with
5 g. of activated carbon, and the mixture is filtered rapidly with suction. The filtrate is made up to 1.5 l. with
95% ethanol and heated to dissolve the solid. The solution is allowed to cool slowly to room temperature, then chilled in a refrigerator and filtered. The yield is
143–161 g. (
60–67%) of colorless flakes melting at
115–116° (Note
7).
2. Notes
1. Efficient stirring is necessary to keep the
nickel uniformly distributed throughout the reaction mixture; otherwise, the yield is decreased considerably.
3. The refluxing time does not have to be continuous. The submitters heated the reaction mixture for 7 hours, allowed the mixture to stand overnight, and continued the refluxing the next day.
4. This operation should be carried out in a
well-ventilated hood.
5. To prevent clogging of the Büchner funnel during filtration it is necessary to preheat the funnel and keep it hot during filtration.
6. The
nickel is pyrophoric and must be kept moist to prevent spontaneous ignition.
7. The method has been applied successfully by the submitters
3 to the preparation of
N,N'-dibutylbenzidine (
61% crude yield), N-ethyl-, N-propyl-, N-butyl-, N-amyl-, and N-benzylani- lines (80–84% yields),
N-hexylaniline (
72%), and N-isobutyl- and N-isoamylanilines (41, 49%).
N-Propylbutylamine was obtained from
propyl alcohol and
butylamine in
57% yield. The submitters state that no alkylation of
benzidine took place with
methyl alcohol or of
aniline with
methyl, isopropyl, or sec-butyl alcohol. The method has been applied to the synthesis of other N-alkyl and N-cycloalkyl aromatic amines.
4,5
3. Discussion
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