A Publication
of Reliable Methods
for the Preparation
of Organic Compounds
Annual Volume
Org. Synth. 1959, 39, 8
DOI: 10.15227/orgsyn.039.0008
[3,4-Thiophenedicarbonitrile, 2,5-diamino-]
Submitted by W. J. Middleton1
Checked by James Cason and Ralph J. Fessenden.
1. Procedure
Since carbon disulfide is highly flammable and hydrogen sulfide highly toxic, this reaction should be carried out in a hood, with due precaution against fire. It is also recommended that tetracyanoethylene not be allowed to come into contact with the skin.
A 1-l. three-necked flask is fitted with a sealed mechanical stirrer, a condenser protected by a drying tube, a thermometer, and an inlet tube extending to the bottom of the flask. A solution of 25.6 g. (0.2 mole) of recrystallized tetracyanoethylene (p. 877) in 300 ml. of acetone is placed in the flask, and 300 ml. of carbon disulfide is added. The flask and its contents are cooled to 0° by means of a salt-ice bath. With good stirring, hydrogen sulfide is passed into the reaction mixture at a moderate rate while the temperature is maintained at 0–5°. The solution becomes milky after a few minutes owing to the formation of colloidal sulfur. The hydrogen sulfide addition is continued for about 30 minutes, or until the solution is thoroughly saturated.
The hydrogen sulfide addition is temporarily suspended, and 100 ml. of pyridine is added rapidly in one portion through the condenser as the solution is stirred vigorously (Note 1). The solution becomes clear, and then 2,5-diamino-3,4-dicyanothiophene begins to precipitate immediately. The hydrogen sulfide addition is resumed and is continued for about 30 minutes while the temperature of the reaction mixture is maintained at 0–5°. Finally, the reaction mixture is stirred for an additional 30 minutes at 0–5°, then the yellow precipitate of the thiophene is collected on a Büchner funnel, thoroughly washed with about 500 ml. of acetone, and dried in the air or in a vacuum desiccator. The yield of crude product of yellow or buff color amounts to 30–31 g. (92–95%).
This material is sufficiently pure for most purposes. If a purer product is desired, the crude material is dissolved in 300 ml. of dimethylformamide, 10 g. of activated alumina (48–100 mesh) is added, and the mixture is filtered. The filtrate is heated to 80–90° on a steam bath, then 1 l. of boiling water is added immediately (Note 2). The resultant mixture is cooled in an ice bath, and the light buff crystals of 2,5-diamino-3,4-dicyanothiophene that separate are collected on a Büchner funnel and thoroughly washed with 500 ml. of acetone; weight 26–28 g. (79–85%). The product has no definite melting point but sublimes with some decomposition when heated above 250°.
2. Notes
1. Unless the pyridine is added quite rapidly, some of the product will begin to precipitate before all of the sulfur has dissolved, and the final product will be contaminated with sulfur.
2. This operation should be carried out as rapidly as possible, since prolonged heating in dimethylformamide results in loss of product.
3. Discussion
2,5-Diamino-3,4-dicyanothiophene has been prepared only by the action of hydrogen sulfide or sodium sulfide on tetracyanoethylene or tetracyanoethane.2 Unlike most aminothiophenes, 2,5-diamino-3,4-dicyanothiophene is very stable and can be stored indefinitely. Its amino groups show the normal reactivity of aromatic amines. For example, they readily condense with aromatic aldehydes to form highly colored bis-anils.2 Hot 10% sodium hydroxide rearranges 2,5-diamino-3,4-dicyanothiophene to 2-amino-3,4-dicyano-5-mercaptopyrrole.2

References and Notes
  1. Contribution No. 483 from Central Research Department, Experimental Station, E. I. du Pont de Nemours & Co., Wilmington, Delaware.
  2. Middleton, Englehardt, and Fisher, J. Am. Chem. Soc., 80, 2822 (1958).

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


sodium hydroxide (1310-73-2)

hydrogen sulfide (7783-06-4)

sulfur (7704-34-9)

acetone (67-64-1)

pyridine (110-86-1)

carbon disulfide (75-15-0)

sodium sulfide (1313-82-2)

dimethylformamide (68-12-2)

3,4-Thiophenedicarbonitrile, 2,5-diamino- (17989-89-8)

Tetracyanoethylene (670-54-2)