Properties of the Thiomethylene Radical. Ii. The Behavior With Chlorine and Water

Abstract

1. The reactions of several types of organic sulfur compounds with chlorine and water, in acetic acid as a medium, have been studied.

The Preparation of Alkanesulfonyl Halides

“…The preparation of alkanesulfonyl halides may be accomplished conveniently by the chlorination in aqueous media of alkanethiols or certain of their derivatives, such as I, wherein the Y represents a residue that is readily cleaved during the chlorination process. A number of investigations have shown that alkanesulfonyl chlorides result from the chlorination of thiols (I, Y = H) (4), disulfides (Y = SR) (4, 9), thiocyanates (Y = CN) (3,4,10), thiol esters RSY RS02C1 I II (Y = R'CO or R'S02) (4), thiosulfates (Y = S03Na) (4, 7), and isothiouronium salts (Y = C(=NH)NH2-HX) (5, 6). Of these thiol derivatives, the last two, the sodium alkylthiosulfates (III) and the alkylisothiouronium salts (IV), are the most suitable.…”

2-Amino-2-thiazoline. VII. Unequivocal structure assignment of the products of the reaction of 2-amino-2-thiazoline and its analogs with carbethoxy isothiocyanate

“…The steric effect of substitution in the 4 position of the thiazoline ring was investigated by beginning with 2amino-4,4-dimethyl-2-thiazoline (17), prepared from 2amino-2-methylpropanethiosulfuric acid (18) by treatment with alkaline sodium cyanide. Reaction of 17 with 3 gave the cyclized product 2,3,6,7-tetrahydro-6,6-dimethyl-4Hthiazolo[3,2-a]-s-triazin-2-one-4-thione (19) in 67% yield (method A) (eq 4), similar to the yield obtained from 1.…”

“…Caled for C6H7N3OS2; C, 35.81; , 3.51; N, 20.88; S, 31.86. Found: C, 35.70; , 3.60; N, 20.89; S, 31.66. 4,4-Dimethyl-2-amino-2-thiazoline (17). Using the procedure developed by Klayman and Milne,28 a solution of 25.0 g (0.135 mol) of 2-amino-2-methylpropanethiosuifuric acid (18),30 5.6 g (0.14 mol) of NaOH, and 8.33 g (0.17 mol) of NaCN in 200 ml of water was stirred at room temperature for 16 hr.…”

“…2,3,6,7-Tetrahydro-6,6-dimethyI-4H-thiazolo[3,2-a]-s-triazin-2rone-4-thione (19). Compound 19 was prepared by method A from 4,4-dimethyl-2-amino-2-thiazoline (17) in 67% yield as tiny yellow needles: mp 192-193°; ir (KBr) 3100 (NH), 2920 (CH), 1695 (C=0), and 1545 cm™1 (NH); nmr (DMSO-de) 1.67 (s, 3, CH3),…”

“…21 The reaction of 1 with carbethoxy isothiocyanate (3), studied by Capuano and In fact, a single isomer is produced in the reaction, one to which Capuano and Schrepfer13 assigned structure 4; however, these workers presented no evidence for their structure assignment. The later work of Nagano,et al,[16][17][18] indicated that 2-aminothiazole reacts with 3 to give, among other products, a heterobicycle resulting from attack of 3 on the endocyclic aromatic nitrogen atom. Extending the analogy to the case of 1, the endocyclic attack could be favored, and structure 4, proposed by the previous workers, 13 would thus be incorrect.…”