A Publication
of Reliable Methods
for the Preparation
of Organic Compounds
Annual Volume
Org. Synth. 1956, 36, 6
DOI: 10.15227/orgsyn.036.0006
[Propionitrile, 3-anilino-]
Submitted by J. Cymerman-Craig and M. Moyle1.
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
1. An equimolar quantity of aniline benzenesulfonate may be used in place of the hydrochloride.
2. No reaction occurs if the diethylamine is omitted.
3. In a typical run this fraction weighed 4.4 g. and contained 1.6 g. of aniline (estimated as acetanilide) and 2.8 g. of 3-diethylaminopropionitrile.
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
Heininger10 has shown that cupric acetate is a superior catalyst for the cyanoethylation of aniline; N-2-cyanoethylaniline has been obtained in 73% yield by this method. The use of cupric acetate as a catalyst in cyanoethylation is demonstrated in the procedure for the preparation of 3-(o-chloroanilino) propionitrile (p. 146).
This preparation is referenced from:

References and Notes
  1. The University of Sydney, Sydney, Australia.
  2. Cookson and Mann, J. Chem. Soc., 1949, 67.
  3. Braunholtz and Mann, J. Chem. Soc., 1952, 3046; Strepikheev and Bogdanov, Sbornik Statei Obshchei Khim., 2, 1462 (1953) [C. A., 49, 4551 (1955)].
  4. Braunholtz and Mann, J. Chem. Soc., 1953, 1817; Gurvich and Terent'ev, Sbornik Statei Obshchei Khim., Akad. Nauk S.S.S.R., 1, 409 (1953) [C. A., 49, 1048 (1955)].
  5. Bauer and Cymerman, Chem. & Ind. (London), 1951, 615.
  6. Bauer, Cymerman, and Sheldon, J. Chem. Soc., 1951, 3311.
  7. Bekhli, Zhur. Obshchei Khim., 21, 86 (1951) [C. A., 45, 7540 (1951)].
  8. Butskus and Denis, Nauch. Doklady Vysshei Shkoly, Khim. i Khim. Tekhnol., 1958, No. 1, 130, 743 [C. A., 53, 3082, 8028 (1959)].
  9. Bekhli, Doklady Akad. Nauk S.S.S.R., 113, 558 (1957) [C. A., 51, 14577 (1957)].
  10. Heininger, J. Org. Chem., 22, 1213 (1957).

Chemical Abstracts Nomenclature (Collective Index Number);
(Registry Number)

acetic acid (64-19-7)

aniline (62-53-3)

Acetanilide (103-84-4)

sodium hydroxide (1310-73-2)

chloroform (67-66-3)

sodium sulfate (7757-82-6)

aniline hydrochloride (142-04-1)

cupric acetate (142-71-2)

diethylamine (109-89-7)

acrylonitrile (107-13-1)

β-diethylaminopropionitrile (5351-04-2)

Propionitrile, 3-anilino-,
cyanoethylaniline (1075-76-9)

aniline benzenesulfonate

3-(o-chloroanilino) propionitrile (94-89-3)