A Publication
of Reliable Methods
for the Preparation
of Organic Compounds
Annual Volume
Org. Synth. 1935, 15, 45
DOI: 10.15227/orgsyn.015.0045
[Benzenesulfenyl chloride, o-nitro-]
Submitted by Max H. Hubacher
Checked by Louis F. Fieser and D. J. Potter.
1. Procedure
In a 1-l. three-necked flask, fitted with a thermometer, a reflux condenser, and an inlet tube extending to the bottom of the flask and drawn out to a small opening, are placed 600 cc. of dry carbon tetrachloride, 154 g. (0.5 mole) of di-o-nitrophenyl disulfide, m.p. 193–195° (Org. Syn. Coll. Vol. I, 1941, 220), and 0.25 g. of iodine. To the upper end of the condenser is attached a glass tube which dips below the surface of a little carbon tetrachloride contained in a test tube. A current of chlorine, dried with sulfuric acid, is passed into the reaction mixture, the temperature of which is maintained at 50–60°. The rate of flow of the chlorine (about 16–17 g. per hour) is regulated so that little or no gas escapes through the carbon tetrachloride trap. The yellow di-o-nitrophenyl disulfide gradually disappears, and after two to two and one-half hours a homogeneous, dark yellow solution is obtained (Note 1). The warm solution is filtered from a small amount of dark residue through a warm Büchner funnel, the flask and filter being rinsed with 30 cc. of warm carbon tetrachloride. The yellow filtrate (Note 2) is cooled to 5° and the product allowed to crystallize. The cake of crystals is broken with a rod, collected on a Büchner funnel, and drained well. The product is dried rapidly (two hours) at 50° and bottled (Note 3). This material melts at 73–74.5° and weighs 126–135 g. (66–71 per cent of the theoretical amount). A further crop is obtained by removing the solvent from the mother liquor by distillation from a water bath (Note 4), the dark, residual oil being poured into an evaporating dish. The last traces of carbon tetrachloride are removed by drying at 50°, during which process the oil crystallizes. This material melts at 67–72° and weighs 48–58 g. It is pure enough for most purposes (Note 5). The total yield is 183–184 g. (96–97 per cent of the theoretical amount) (Note 6) and (Note 7).
2. Notes
1. An excess of chlorine will do no harm.
2. For many purposes this filtered solution can be used without purification after distilling about 100 cc. of the solvent to remove the excess chlorine. The yield of material in solution is considered as 98 per cent of the theoretical amount.
3. The pure material melts at 74.5–75°. When in contact with moist air, o-nitrophenylsulfur chloride decomposes within a few days, giving off hydrogen chloride. Stored in a brown, glass-stoppered bottle and sealed well, the material can be kept for many months.
4. Since o-nitrophenylsulfur chloride decomposes spontaneously when heated to about 170°, it is advisable to use a water bath when removing the solvent.
5. This material may be crystallized from hot carbon tetrachloride (2 cc. per gram), the filtered solution being cooled to 5°. The recovery of a product melting at 70–73° is 75 per cent.
6. Practically the same method can be used for the preparation of o-nitro-p-chlorophenylsulfur chloride (m.p. 95–97°); the chlorination of the disulfide (m.p. 212–213°) in this case proceeds much more slowly. 2,4-Dinitrophenylsulfur chloride can be prepared by the chlorination of the corresponding disulfide in nitrobenzene suspension at 120–130°. As the chloride is explosive the solvent must be removed by distillation in vacuum at 130°. The crude material melts at 89–92°. After crystallization from carbon tetrachloride it melts at 94–95°.
7. The arylsulfur chlorides are used for the introduction of the ArS- group, their reactions being analogous to those of acid chlorides.
3. Discussion
o-Nitrophenylsulfur chloride has always been prepared by the chlorination of the disulfide.1
This preparation is referenced from:

References and Notes
  1. Zincke, Ber. 44, 770 (1911); Zincke and Farr, Ann. 391, 63 (1912).

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

sulfuric acid (7664-93-9)

hydrogen chloride (7647-01-0)

carbon tetrachloride (56-23-5)

iodine (7553-56-2)

chlorine (7782-50-5)

Nitrobenzene (98-95-3)

2,4-Dinitrophenylsulfur chloride (528-76-7)

Di-o-nitrophenyl disulfide (1155-00-6)

o-Nitrophenylsulfur chloride,
Benzenesulfenyl chloride, o-nitro- (7669-54-7)

o-Nitro-p-chlorophenylsulfur chloride (4153-06-4)