Org. Synth. 1930, 10, 28
DOI: 10.15227/orgsyn.010.0028
DIPHENYLMETHANE IMINE HYDROCHLORIDE
[Benzohydrylideneimine, hydrochloride]
Submitted by Arthur Lachman
Checked by C. R. Noller
1. Procedure
A
piece of glass tubing 80 cm. long and 2 cm. in internal diameter is sealed at one end and loosely packed with
49 g. (0.25 mole) of benzophenone oxime (p. 70). The tube is supported in a nearly horizontal position, dipping slightly toward the closed end, and connected to a small
filter flask by means of
rubber stoppers and a piece of glass tubing bent at a right angle. The system is evacuated by means of a
water pump, and dry
carbon dioxide is admitted; the system is re-evacuated and
carbon dioxide is admitted again. The oxime is then heated with a free flame, beginning at the upper end and heating at one spot until decomposition takes place before heating a further portion
(Note 1). When all the oxime has been decomposed, the mixture which has collected at the closed end of the tube
(Note 2) is heated strongly for a short time to complete the decomposition, and allowed to cool. Suction is again applied to the tube, and the condensed water is driven out by gently warming the tube. The liquid is then transferred to a
small distilling flask and distilled at a pressure of about 20 mm. The distillate, consisting of a mixture of
benzophenone and
diphenylmethane imine, is dissolved in
400 cc. of ligroin (60–90°), and the imine hydrochloride is precipitated by bubbling in dry
hydrogen chloride. The salt is filtered with suction
(Note 3), washed with a little
ligroin, dried, and preserved in a dry atmosphere
(Note 4). It sublimes without decomposition at 230–250°
(Note 5). The yield is
16–18 g. (
59–66 per cent of theoretical amount)
(Note 6).
2. Notes
1.
When the heating is carefully done, no material is carried out of the tube with the gases.
2.
Care should be taken to prevent any drops of water that have condensed in the cool portion of the tube from running back and mixing with the liquid that is being heated.
3.
Benzophenone may be recovered from the filtrate.
4.
In moist air the hydrochloride is changed to a mixture of
benzophenone and
ammonium chloride. The free base on standing in air gives off
ammonia and gradually deposits crystals of
benzophenone.
5.
The imine salt can be converted into the free base by the method of Hantzsch and Kraft, which involves treating a solution of the salt in
chloroform with dry
ammonia.
6.
The yield depends greatly on the quality of the
benzophenone oxime. If this contains moisture or has been exposed to moist air, especially in a closed space, for any length of time, the yield is markedly decreased.
3. Discussion
Diphenylmethane imine (or its hydrochloride) has been obtained by heating
diphenyldichloromethane with
urethane at 130°;
1 by the action of
ammonia on
diphenyldibromomethane;
2 by treating
benzophenonechloroimide with
phosphorus pentachloride in
ether solution,
3 or dry
hydrogen chloride in
ligroin solution;
4 by the action of
phenylmagnesium bromide on
N-bromobenzamide,
2 benzonitrile,
5 cyanogen bromide,
6 cyanogen chloride,
7 and alkyl thiocyanates.
8 It has also been obtained by passing a mixture of
ammonia and
benzophenone vapor over
thorium oxide at 380–390°;
9 by the catalytic reduction of
benzophenone oxime using
hydrogen and a nickel catalyst in
absolute alcohol solution at ordinary temperature and pressure;
10 by passing a mixture of
hydrogen and
benzophenone oxime vapor over reduced
copper at 200°;
11 and by the action of
sodium ethoxide on
N-monochlorodiphenylmethylamine in alcoholic solution.
12 The method described here has been previously published by Lachman.
13
This preparation is referenced from:
Appendix
Chemical Abstracts Nomenclature (Collective Index Number);
(Registry Number)
ligroin
Benzohydrylideneimine, hydrochloride
Diphenylmethane imine (or its hydrochloride)
benzophenonechloroimide
alcohol (64-17-5)
hydrogen chloride (7647-01-0)
ammonia (7664-41-7)
ether (60-29-7)
ammonium chloride (12125-02-9)
hydrogen (1333-74-0)
benzonitrile (100-47-0)
phosphorus pentachloride (10026-13-8)
chloroform (67-66-3)
carbon dioxide (124-38-9)
thorium oxide
copper (7440-50-8)
nickel (7440-02-0)
Benzophenone (119-61-9)
diphenyldichloromethane (2051-90-3)
sodium ethoxide (141-52-6)
Phenylmagnesium bromide (100-58-3)
Benzophenone oxime (574-66-3)
diphenylmethane imine hydrochloride (5319-67-5)
Cyanogen bromide (506-68-3)
diphenylmethane imine (1013-88-3)
urethane (51-79-6)
diphenyldibromomethane
N-bromobenzamide
cyanogen chloride (506-77-4)
N-monochlorodiphenylmethylamine
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