Thiobenzanilides

Fleischer1 prepared benzylaniline by heating aniline with benzyl chloride at i6o°. This reaction may be very violent and always leads to mixtures. Bernthsen and Trompetter 2 reduced thiobenzanilide with zinc and hydrochloric acid or sodium amalgam, while O. Fischer 3 reduced bcnzalaniline with sodium and alcohol, to benzylaniline. Knoevenagel4 obtained a 32 per cent yield of benzylaniline from benzyl alcohol and aniline in the presence of iodine. Ullmann5 describes the preparation of benzylaniline from benzyl chloride and excess of aniline at low temperatures. 

Zur Reduktion von Thiobenzanilid zu Benzaldehyd, Anilin und Benzaldehyd-phenyli-min s. Lit.2. 

Many of the reagents developed initially for the recovery of base or radioactive metals have also been investigated as potential PGM extractants, e.g., phosphine oxides,310-313 dialkylsulfoxides,314 dialkyl-and diphemd-thioureas,296,315-317 thiopicolinamides, thiobenzanilide,319 phosphate diesters,320 tetra-... 

Shkil, A. N. Zolotov, Y. A. Solvent-extraction of platinum with thiobenzanilide-separation of platinum from copper. J. Anal. Chem. USSR 1988, 43, 1188-1193. 

They proposed a mechanism as shown in Scheme 10, because they found close contact between the oxygen atom of the C=0 group and the carbon atom of the C=S group in a range of 2.77-2.86 A. These contacts are well below the sum of the van der Waals radii for oxygen and carbon (3.22 A). Thus, in the crystalline state, the oxygen atom is ideally positioned for excited-state nucleophilic attack on the C=S double bond, and this process may be the first step of the mechanism by which thiobenzanilides are formed in this medium. This would lead reversibly to the 1,3-oxazetidinium ion 18, which could react with water present in the medium and then break down, via species 19, to the enol of thiobenzanilide 16 and 3-phenylpropanoic acid 17. 

No aminothiophenones can be obtained by photorearrangement of JV-aryl amides of thiocarboxylic acids. The formation of 2-ethoxybenzthiazole (143) by oxidative photodehydrogenation of 142 is of some interest.11 Similarly, 2-phenylbenzthiazole originates by photocyclization of thiobenzanilide in the presence of oxygen."... 

Dithiobenzoic acid is reported to react with sulfur dichloride to give a compound C7H5S3CI which was suggested to be 4-phenyltrithietanylium chloride (Scheme 139). The reaction of the latter with aniline gives sulfur and thiobenzanilide (68JHC141). 

The first published example of the anodic cyclization with carbon-sulfur bond formation was the oxidation of thiobenzanilide to 2-phenyl-l,3-benzothiazole.120 The oxidation of the thioacetanilides (106) and /V-(3-coumaryl)thioacetamide (108) at a platinum electrode in CH3CN-Et4NC104 gave the expected 1,3-thiazole derivatives 107 and 109 in 60-75% yield169 [Eqs. (81) and (82)]. 

Synthesis of thietane-fused (1-lactam was reported by Sakamoto et al. [212] involving solid-state photoreaction of /V-(a,(5-unsatu rated carbonyl) thiobenzanilide demonstrating a single-step photochemical route to (5-lactam, as outlined in Scheme 52. 

The reaction of thiobenzanilide (47) with bromoacetic acid (48) in the presence of triethylamine affords S-carboxymethylisothiobenzanilide (49) [Eq. (14)], which, when treated with acetic anhydride and triethylamine, gives the tentatively assigned pseudobase 50 [Eq. (15)].81 When 50 is subjected to either ethanol, benzene, or chloroform, benzoylthioglycolic acid anilide (51) is isolated a mechanism has been proposed.81... 

Recent analyses of a Free-Wilsontype have included the in vitro inhibitory activity of a series of heterocyclic compounds against K. pneumonia (197). Other applications of the Free-Wilson approach have included studies on the antimycobacterial activity of 4-alkyl-thiobenzanilides, the antibacterial activity of fluoronapthyridines, and the benzodiazepine receptor-binding ability of some non-benzodi-apzepine compounds such as 3-X-imidazo-[l,2-6]pyridazines, 2-phenylimidazo[l,2-o ]pyri-dines,2-(alkoxycarbony)imidazo[2,l-p]benzo-thiazoles, and 2-arylquinolones(198-200). 

Thiobenzanilide, on anodic oxidation in CH3CN-TEAP at a platinum electrode, yields 2-phenylbenzothiazole other aromatic thiobenzamides react similarly [41]. Analogously, oxidation of A-(2-pyridyl)-thiobenzamide at controlled potential gives 2-phenyl-1,2,4-thiadiazolo[2,3- -] pyridinium perchlorate (XXXI) in 80% yield [41] ... 

Rh (also Ir, Pd, and Pt) can be extracted with bis-(2-ethylhexyl)dithiophosphoric acid [8]. Ir can be extracted with mercaptobenzothiazole [9] or thiobenzanilide [ 10]. Rhodium has been separated from Ir by the extraction (CHCI3) of its complex with 2-mercaptobenzimidazole [11]. HDEHP has been used for extraction separation of Rh from Ru and Ir [12]. Extraction of Rh (and other noble metals) by thiourea and its derivatives was studied [13]. 

The reaction of (62) with aniline affords, primarily by attack at the 4-position, a ring-opened intermediate which either recloses with liberation of H2S to yield (63), or reacts with a second molecule of aniline to produce the thiobenzanilide (64) and the disulfide (65) (Scheme 13) <78CB3178>. 

Thiobenzanilide is best prepared with pyridine as solvent.438... 

Der Einsatz von Thiocarbonsaure-amiden ist moglich, wurde aber nicht systematisch un-tersucht. So entsteht bei der Umsetzung von Thiobenzanilid mit Nitrosylchlorid 44% Ben-zoesaure-chlorid-phenylimid13 ... 

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