Organic Syntheses, CV 4, 205
Submitted by J. Cymerman-Craig and M. Moyle
1.
Checked by William S. Johnson and Duff S. Allen, Jr..
1. Procedure
A mixture of
12.95 g. (0.10 mole) of aniline hydrochloride (Note
1),
6.6 g. (0.12 mole) of acrylonitrile, and
9.1 g. (0.12 mole) of diethylamine (Note
2) is placed in a
100-ml. round-bottomed flask fitted with an efficient reflux condenser and heated for 2.5 hours in a bath maintained at 180°.
The melt is cooled to 0°,
50 ml. of 10% aqueous sodium hydroxide solution is added, and the mixture is extracted with four
50-ml. portions of chloroform. The combined
chloroform extracts are washed with two 25-ml. portions of water, and these in turn are extracted with
10 ml. of chloroform. The organic layers are combined and dried partially over
anhydrous sodium sulfate. The solvent is removed by distillation on the
steam bath, and the residue is distilled at reduced pressure from a
50-ml. distilling flask. After a fore-run of about 4 g. (Note
3), b.p.
60–70°/1.5 mm. (bath temperature taken up to 125°), the
cyanoethylaniline is collected at
115–120°/0.01 mm. The product solidifies in the form of colorless plates, m.p.
48–51° (Note
4). The yield is
10.5–11.4 g. (
72–78%) (Note
5).
2. Notes
4. Reported properties are b.p.
178–186°/16 mm. and m.p.
51.5°.2
5. The submitters have found that other arylamines may be employed in a similar manner in place of
aniline. Thus
N-2-cyanoethyl-p-anisidine was obtained in
76% yield as plates, m.p.
62–64°, b.p.
130–140°/0.01 mm.;
N-2-cyanoethyl-m-chloroaniline, in
42% yield as needles, m.p.
44–46°, b.p.
125–130°/0.01 mm.;
N,N'-bis-2-cyanoethyl-o-phenylenediamine, in
70% yield as needles, m.p.
116–118°, b.p.
190–200°/0.01 mm.; and
N,N'-bis-2-cyanoethyl-p-phenylenediamine in
22% yield as plates, m.p.
138–139°.
3. Discussion
N-2-Cyanoethylaniline has been prepared (accompanied by much of the N,N'-bis-2-cyanoethyl compound) by heating
aniline,
acrylonitrile, and
acetic acid in an autoclave,
2,3 or at refluxing temperature for 10 hours in the presence of various inorganic catalysts.
4 The substance also has been obtained, free of the N,N'-bis-2-cyanoethyl compound from aniline salts and
β-diethylaminopropionitrile.
5,6,7 A number of other cyanoethylated compounds have been heated with
aniline and water to form
N-2-cyanoethylaniline,
8 and a study has been made of the conditions for the addition of aromatic amines to
acrylonitrile.
9
This preparation is referenced from:
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