Org. Synth. 1952, 32, 50
DOI: 10.15227/orgsyn.032.0050
1,2-DI-1-(1-CYANO)CYCLOHEXYLHYDRAZINE
[Cyclohexanecarbonitrile, 1,1'-hydrazodi-]
Submitted by C. G. Overberger, Pao-tung Huang, and M. B. Berenbaum
1.
Checked by N. J. Leonard and E. H. Mottus.
1. Procedure
Caution! These operations should be conducted in an efficient hood.
In a 600-ml. screw-capped bottle are placed 15.4 g. (0.32 mole) of sodium cyanide, 20.5 g. (0.16 mole) of hydrazine sulfate (Note 1), and 400 ml. of ice water. The bottle is capped to prevent loss of hydrogen cyanide (Note 2) and held in an ice bath for 15 minutes. To the cooled mixture is added 29.4 g. (0.3 mole) of cyclohexanone. The bottle is recapped and cooled for an additional 15 minutes. The bottle is then shaken intermittently over a period of 6 hours and allowed to stand an additional 14 hours. The bottle is cooled again before opening. The suspension is filtered by means of suction, and the cake is washed thoroughly with 250 ml. of ice water. After the crude product has been pressed dry on the filter (Note 3), it is transferred to a 500-ml. Erlenmeyer flask and 150 ml. of boiling 95% ethanol is added. The suspension is brought into solution as rapidly as possible by warming on a hot plate (Note 4) and is filtered quickly through a prewarmed 7.5-cm. Büchner funnel. An additional 10 ml. of hot 95% ethanol is used to dissolve any organic residue on the filter, and the combined filtrates are warmed to redissolve any precipitate. The solution is allowed to stand undisturbed for 6 hours in an icebox. The product is collected on a Büchner funnel, washed with 15 ml. of cold 95% ethanol, and then dried over solid calcium chloride in a vacuum desiccator. The yield of product is 24.5–26 g. (66–70%); m.p. 147–149° (Note 5).
2. Notes
1.
Technical
hydrazine sulfate of known purity is suitable.
2.
Both
hydrazine and
hydrogen cyanide are toxic, and appropriate precautions should be taken.
3.
The checkers have used the dry, crude product directly in the conversion to
1,1'-azo-bis-1-cyclohexanenitrile (see
p. 66) with an over-all yield of
72% based upon
cyclohexanone.
4.
Excessive or prolonged heating will result in a decreased yield owing to decomposition of the product.
5.
1,2-Di-2-(2-cyano)propylhydrazine (2,2'-hydrazo-bis-isobutyronitrile) may be prepared in a similar manner from
acetone. The crude product (m.p.
89–91°; yield
88–93%) can be oxidized directly to
2,2'-azo-bis-isobutyronitrile. The dried impure material can be recrystallized from
ether; m.p.
91.5–92.5°; (
72–77%).
3. Discussion
1,2-Di-1-(1-cyano)cyclohexylhydrazine has been prepared by a procedure similar to that used by Hartman.
2 The procedure has been substantiated by Overberger, O'Shaughnessy, and Shalit.
3
Appendix
Chemical Abstracts Nomenclature (Collective Index Number);
(Registry Number)
1,2-Di-1-(1-cyano)cyclohexylhydrazine
1,2-Di-2-(2-cyano)propylhydrazine (2,2'-hydrazo-bis-isobutyronitrile)
ethanol (64-17-5)
calcium chloride (10043-52-4)
ether (60-29-7)
Cyclohexanone (108-94-1)
sodium cyanide (143-33-9)
hydrogen cyanide (74-90-8)
acetone (67-64-1)
Hydrazine sulfate (10034-93-2)
hydrazine (302-01-2)
2,2'-Azo-bis-isobutyronitrile
1,1'-AZO-bis-1-CYCLOHEXANENITRILE (2094-98-6)
Cyclohexanecarbonitrile, 1,1'-hydrazodi- (17643-01-5)
Copyright © 1921-, Organic Syntheses, Inc. All Rights Reserved