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Org. Synth. 1948, 28, 82
DOI: 10.15227/orgsyn.028.0082
p-NITROPHENYL SULFIDE
[Sulfide, bis-(p-nitrophenyl)]
Submitted by Charles C. Price and Gardner W. Stacy.
Checked by Cliff S. Hamilton and Paul D. Berry.
1. Procedure
In a 1-l. round-bottomed flask equipped with a reflux condenser are placed 157.5 g. (1 mole) of p-chloronitrobenzene, 160 g. (1 mole) of potassium xanthate (Note 1), and 450 ml. of 95% ethanol. This reaction mixture is heated under reflux on a steam bath for 48 hours. The crystalline product, which deposits from solution during the course of the reaction, is collected by filtration, crushed into small particles in a mortar, and washed twice with hot ethanol and once with hot water. The yield of p-nitrophenyl sulfide melting at 158–160° is 105–113 g. (76–82%). This product is pure enough for most purposes. Recrystallization from glacial acetic acid (15 ml. per gram) raises the melting point to 160–161°.
2. Notes
1. Potassium xanthate may be prepared in the following manner: With heating, 300 g. (5.36 moles) of potassium hydroxide is dissolved in 3 l. of absolute ethanol. The solution is then cooled in an ice bath, and the temperature is kept below 10° while carbon disulfide is added in portions with stirring until the solution is no longer alkaline; about 456 g. (360 ml., 5.95 moles) of carbon disulfide is required. The potassium xanthate is collected by suction filtration and air-dried on large sheets of filter paper; yield, 429–472 g. (50–55%).
3. Discussion
p-Nitrophenyl sulfide has been prepared by the reaction between p-chloronitrobenzene and sodium sulfide.1 This is not a practical means of preparation, however, because of the variety of substances formed.2 The method described has been published.3 A preparation of pure p-nitrophenyl sulfide has been reported from p-chloronitrobenzene and sodium thiosulfate.4

References and Notes
  1. Nietski and Bothof, Ber., 27, 3261 (1894).
  2. Kehrmann and Bauer, Ber., 29, 2362 (1896).
  3. Price and Stacy, J. Am. Chem. Soc., 68, 498 (1946).
  4. Dall'Olio, Chimica e industria, 28, 73 (1946) [C. A., 41, 380 (1947)].

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

ethanol (64-17-5)

acetic acid (64-19-7)

sodium thiosulfate (7772-98-7)

potassium hydroxide (1310-58-3)

carbon disulfide (75-15-0)

sodium sulfide (1313-82-2)

p-chloronitrobenzene (100-00-5)

potassium xanthate

p-Nitrophenyl sulfide,
Sulfide, bis-(p-nitrophenyl) (1223-31-0)