Ortho-amino thiophenols

I.2 Pyrrolo-benzothiazepines with other fusion modes. Thiazepine with fused pyrrole ring 250b can be prepared by condensing ortho-amino thiophenol with pyrrole carbaldehyde 249 in moderate yield (Equation (31), Section 3.1.1.4... 

Benzo[b][l,5]Thiazepines by a Consecutive SCR of Acid Chlorides, Alkynes, and Ortho-Amino Thiophenols... 

Ortho-a.mino thiophenols react with 7-chlorobutyrophenone and related aromatic ketones to afford separable mixtures of thiazocines and benzothiazoles. The latter apparently arise from initial A -alkylation rather than the desired 5-alkylation, and the product ratio is quite dependent on the nature of the base used to effect the condensation <84JOCli6>. Isolation of the intermediate amino ketone derived from 5-alkylation, followed by acid-catalyzed dehydration with azeotropic removal of water, affords exclusively the thiazocines in good to excellent yield (Slcheme 36). 

The dimer of hexafluorothioacetone (217) reacts, as shown in Scheme 8, with mercuric fluoride-potassium fluoride to give the mercuric mercaptide of perfluoropropane-2-thiol in DMF, potassium flucnide promotes the reaction of (217) with alcohols, thiols, thiophenols, and olefins to give products derived from the thioacetone monomer. Reaction with styrene gave the bis-Diels-Alder adducts (218) and (219) thietan (220) is obtained with cyclohexene. Amino-alcohols, o-aminophenol, o-aminothiophenol, and o-phenylenediamine yield 2,2-bis(trifluoromethyl)-l,3-het ocyclic derivatives, e.g. (221). 1,3-Dithietans did not react with Fe2(CO) and were discarded as possible intermediates in the ortho-metallation reactions of thiobenzophenones. The hydrolysis reactions of a 1,3-cyclodisiladithietan and its reaction with o-hydroxymercuribenzoic acid have been investigated. ... 

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