Dimethylthiocarbamyl chloride

Dimethylthiocarbamyl chloride, synthesis of, 51, 140 with 2-naphthol to give 0-2-naphthyl dimethylthiocarba-mate, 51, 139... 

Dimethylthiocarbamyl chloride can be prepared as described in Org. Syn., Coll. Vol. 4, 310 (1963), or by rapidly adding 740 g. (10.5 moles) of chlorine dissolved in 3 1. of carbon tetrachloride to a stirred refluxing suspension of 2400 g. (10 moles) of tetramethylthiram disulfide (Note 9) in 5 1. of carbon tetrachloride. After the addition is complete, approximately one-half of... 

A. O-2-Naphthyldimethylthiocarbamate. A solution prepared by dissolving 21.6 g. (0.15 mole) of 2-naphthol (Note 1) in 100 ml. of water containing 8.4 g. (0.15 mole) of potassium hydroxide is cooled below 10° in a 500-ml. three-necked flask equipped with a stirrer, a thermometer, and a 125-ml. addition funnel. A solution of 24.8 g. (0.20 mole) of dimethylthiocarbamyl chloride (Note 2) in 40 ml. of dry tetrahydrofuran (Note 3) is added during 20-30 minutes to the stirred solution at such a rate that the temperature never exceeds 12°. After the addition is complete, the cooling bath is removed and stirring is continued for 10 minutes. 

The submitters have prepared the following thiocarbamyl chlorides by the chlorination of the corresponding disulfides dimethylthiocarbamyl chloride, b.p. 90-95°/0.5 mm., m.p. 42.5-43.5°, carbon tetrachloride reaction medium diisopropylthio-carbamyl chloride, m.p. 69-71°, benzene reaction medium diiso-butylthiocarbamyl chloride, m.p. 46-48°, no solvent. 

Rearrangements Aluminum bromide. Calcium carbonate. Dimethylthiocarbamyl chloride Dimsylsodium. 1,3-Dithiane. Lithium diethylamide. Manganese dioxide. Methyl vinyl ketone, 4a —> 5a. Michler s ketone. Norbornene. Perchloric acid. Pinacol-type see Potassium /-butoxide. Potassium /-butoxide. Silver perchlorate. Thallium triacetate. Triethyloxonium-fluoroborate. 

Carboxylic acid thioamides. Ca. 2 moles AICI3 added slowly with ice-cooling to anisole and dimethylthiocarbamyl chloride, stirred at room temp., finally warmed 15 min. at 40° p-methoxy-N,N-dimethylthiobenzamide. Y 11%. F. e., also thioketones, thiono- and dithio-carboxylic acid esters, s. H. Viola, S. Scheithauer, and R. Mayer, B. 101, 3517 (1968). 

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