Thiazyl chloride

A 2 g quantity of the product of interaction of hexacarbonylmolybdenum and thiazyl chloride, possibly constituted as shown, reacted explosively with water. See other amiaeogen compounds, n-s compounds... 

Thiazyl chloride, treated with aqueous ammonia and then silver nitrate, gives a compound AgN5S3(of unknown structure) which is shock-sensitive and explodes violently. 

Various 2,5-disubstituted furans 1 have been converted into 5-acyl-3-substituted isothiazoles 2 by treatment with ethyl carbamate, thionyl chloride and pyridine. The reactive species produced by this combination of reagents may be the highly reactive thiazyl chloride, NSCl, or a related species such as its trimer (NSCPa. This mixture of reagents was reported to be much more convenient to use than (NSC1)3 and in many cases produced higher yields of isothiazole <99S757>. 

The attempted trifluoromethylation of pentamethylcyclopentadienyllithium by reaction with F3 Cl in the presence of A-phenylmaleimide gave rise to the unexpected Diels-Alder adduct (25).37 The authors proposed that the cyclopentadienyl anion captures the iodine of CF3I to give (26) and trifhjoromethyllithium which then produces difluorocarbene (F2C ) which inserts into the C—I bond of (26) to form the difluoroiodomethylated product. The observed regioselectivity of addition of thiazyl chloride (N=S—Cl) to 2,5-diarylftirans provided support for a mechanism involving carbene and nitrene intermediates (27).38... 

Evidence has been presented for initial electrophilic substitution by thiazyl chloride (NSC1) in die reaction of trithiazyl trichloride with 2,5-diarylfurans (38) which eventually yields 5-aroyl-3-arylisothiazoles.86... 

Thiazyl chloride, see l,3,5-Trichlorotrithiahexahydro-l,3,5-triazine, 4139 Thiazyl fluoride, 4300... 

Considerable interest has been shown in the reaction of 1,3,5-trichlorotrithiatriazine with nucleophiles in order to prepare new heterocyclic S—N systems. Most of the preparative routes to dithiatriazines involve the reactions of nitriles with thiazyl chloride monomer or dimer.18 20,22 However, these methods generally lead to a mixture of products.The silylated imidamide 1 was found to be a mild selective reagent in the reaction with trichlorotrithiatriazine 2.23 Thus, 7-phenyl-l A4, 3/l4-,5/l l-trithia-2,4,6,8,9-pentaazabicyc]o[3.3.1 ]nona-1(9),2,3,5,7-pcn-taene (3) can be prepared in dichloromethane solution from silylated benzimidamide 1 and trichlorotrithiatriazine 2. The molecule8 can be described in terms of a 1,3,2,4.6-dithiatriazine bridged by a N-S-N fragment across the 1,3-sulfur atoms. 

A. Thiazyl Chloride as a Building Block in Sulfur-Nitrogen Chemistry... 146... 

Dithiadiazolylium cations (as the chloride salt) were first prepared in 1977 (77INCL143) from the reaction of thiazyl chloride 11 with organic nitriles. Thiazyl chloride 11 exists as a trimer 11a in the solid state (61AX562), but partial dissociation to the monomer lib occurs in the vapor phase (70IC1079) and in solution (88IC2749). 

Reaction of the sulfur-nitrogen cage, S4N414, with thiazyl chloride 11 in the presence of a chloride acceptor leads to the formation of salts of the 14-ir aromatic cation, S5N5+ (77IS188), 15. 

Thiazyl chloride 11 reacts with norbornadiene 20 and other unsaturated centers to form heterocyclic rings (see Scheme 3). Such reactions are frequently complex e.g., 11 + 20 proceeds via a dechlorination/ cycloaddition process to form 21 (91IC1392), whereas reaction with organic nitriles leads ultimately to formation of 1,2,3,5-dithiadiazolylium salts [2]C1. 

Thiazyl halides, such as thiazyl chloride (XLIV) or thiazyl bromide, the molecular weight of which is unknown, are rapidly solvolyzed by ammonia, in which they dissolve to give a red color. Analysis shows the prod-... 

A second method is to decompose a mixture of sulfuryl chloride and thionyl chloride with ammonia (44)- It is also possible to obtain sulfanuryl chloride by oxidizing thiazyl chloride (LXXVII) with sulfur trioxide (50). 

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