Org. Synth. 1960, 40, 103
DOI: 10.15227/orgsyn.040.0103
α,α,α-TRICHLOROACETANILIDE
[Acetanilide, α,α,α-trichloro-]
Submitted by Bernard Sukornick
1
Checked by John D. Roberts and Eugene I. Snyder.
1. Procedure
Into a 1-l. three-necked flask, fitted with a mechanical stirrer, a reflux condenser, a thermometer (Note 1), and a dropping funnel, is placed a solution of 265 g. (1 mole) of hexachloroacetone (Note 2) in 400 ml. of hexane (Note 3). To the stirred solution is added, dropwise, 93 g. (1 mole) of aniline (Note 4) over a period of 35–40 minutes. During this time the temperature rises to about 55°. After the addition is complete, stirring is continued at 65–70° for 45 minutes.
The hot solution is poured into a 1-l. beaker and cooled to 0–5°. The solid is collected on a filter and air-dried; it weighs 208–218 g. (87–91%) and melts at 90–92°. One recrystallization from 400 ml. of 90% ethanol (Note 5) yields 160–165 g. (67–69%) (Note 6) of product melting at 92.5–93.0° (Note 7). A second crop of 9–16 g. (4–7%), m.p. 93.5–95.5°, can be obtained by concentrating the filtrate to 200 ml. and cooling (Note 8).
2. Notes
1.
The thermometer and the reflux condenser are fitted to a
two-necked adapter.
2.
Commercial hexachloroacetone (Allied Chemical Corporation) was distilled and the fraction boiling at
93–97°/24 mm. was used.
3.
Technical grade hexane suffices.
4.
Technical grade aniline was purified by simple distillation and the light-yellow distillate was used directly.
5.
The
90% ethanol was prepared by adding 22 ml. of water to
378 ml. of 95% ethanol.
6.
The submitter reports a
76–81% yield of product melting at
94–96°.
7.
The melting point is raised to
93.5–94.0° by carefully washing the product on a
Büchner funnel with
50 ml. of iced 90% ethanol.
8.
The submitter has applied this procedure successfully to several amines
2 (see Table I).
TABLE I
|
|
Amine
|
Yield of N-Trichloroacetylamine, %
|
M.p., °C*
|
|
|
3-Chloroaniline
|
93
|
101
|
|
4-Chloroaniline
|
97
|
125–127
|
|
2-Toluidine
|
83
|
98
|
|
3-Toluidine
|
79
|
102–103
|
|
4-Toluidine
|
70
|
115
|
|
4-Fluoroaniline
|
83
|
96
|
|
Benzidine
|
65
|
301 (dec.)
|
|
Benzylamine
|
84
|
87–90
|
|
2-Phenylethylamine
|
97
|
117–120
|
|
Ammonia
|
96
|
141
|
|
Dimethylamine
|
89
|
b.p. 110–111°/16 mm.
|
|
2-Aminothiazole
|
80
|
196–198 (dec.)
|
|
*All melting points are uncorrected.
|
3. Discussion
Trichloroacetanilide has been prepared from
hexachloroacetone and
aniline,
3 from
trichloroacetyl chloride and
aniline,
4 by the action of
aniline magnesium iodide on
ethyl trichloroacetate,
5 by heating
N-phenyltrichloroacetimidyl chloride with dilute
methanol,
6 and from
trichloroacetic acid and
aniline in the presence of
phosphorus oxychloride7 or
dicyclohexylcarbodiimide,
8 and from
trichloroacetyl diethyl phosphonate and
aniline.
9
Appendix
Chemical Abstracts Nomenclature (Collective Index Number);
(Registry Number)
N-phenyltrichloroacetimidyl chloride
trichloroacetyl diethyl phosphonate
ethanol (64-17-5)
ammonia (7664-41-7)
methanol (67-56-1)
aniline (62-53-3)
Phosphorus Oxychloride (21295-50-1)
dimethylamine (124-40-3)
benzylamine (100-46-9)
benzidine (92-87-5)
trichloroacetic acid (76-03-9)
2-phenylethylamine (64-04-0)
4-Toluidine (106-49-0)
hexane (110-54-3)
ethyl trichloroacetate (515-84-4)
dicyclohexylcarbodiimide (538-75-0)
trichloroacetyl chloride (76-02-8)
α,α,α-Trichloroacetanilide,
Trichloroacetanilide,
Acetanilide, α,α,α-trichloro- (2563-97-5)
hexachloroacetone (116-16-5)
N-Trichloroacetylamine
3-Chloroaniline (108-42-9)
4-Chloroaniline (106-47-8)
2-Toluidine (95-53-4)
3-Toluidine (108-44-1)
4-Fluoroaniline (371-40-4)
2-Aminothiazole (96-50-4)
aniline magnesium iodide
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