Thio anilides

A few 5-phenylimino-3-pyrazolin-4-carboxanilides and thio-anilides are known (Table XIX). These were prepared by the reaction of phenylisothiocyanates or N,N-diphenylthiourea with the corresponding 5-imino-3-pyrazoline826 or by methylation at N-2 of a 5-imino-2-pyrazolin-4-carboxanilide.826... 

Methyl-IPs are readily oxidized by elemental sulphur by the Wilgerodt-Kindler reaction. Yutilov and Shcherbina found that compounds 295, 619, 620 and 621 were cleanly oxidized with sulphur in the presence of aromatic amines at 170-180 °C to give IP 2-thiocarbanilides 622-625. At a ratio of 2-methyl-IP-sulphur-amine of 1 5 4, the reaction was complete in 15-20 h, and the yields of the resulting thio-anilides were 60 81%. IbP 623 and 624 were obtained in quantitative yield at an equimolar ratio of the substrate and sulphur and double excess of aniline (96ZOR586, 96JOU564). 

The Hantzsch thiazole synthesis from thioamides and a-halogeno-ketones has been applied to iVAr-(dimethyl)dithio-oxamide to give 2-(dimethylthio-carbamoyl)thiazoles, but in some cases it took another course. Thus, 1-alkylthiocarbamoyl-l-cyanoacetophenones (91) react with bromo-ketones with elimination of alkylamine, giving 2-methylidene-l,3-oxathioles (92). The thio-anilide of acetoacetic acid reacts with 2-bromo-l-tetralone to give the spiro-... 

Ethyl 2-bromocyclohexanone-6-carboxylate condenses with aromatic thio-anilides in the presence of base to give compounds (7), which are readily dehydrated to 4,5,6,7-tetrahydrobenzothiazoles. Compounds with Ar = NHAr may be prepared similarly. ... 

Therapeutic Function Antiarthritic Chemical Name [ [(PhenylcarbamoyOmethyl] thio] gold Chemical Name Aurothloglycolllc acid anilide Structural Formula nhcoch,sau... 

This indicates that there is a greater contribution from canonical structures of the form shown in (3) this is in accord with results obtained from i.r. and u.v. studies. Another corresponding trend is observed in the anilides and thioanilides, where introduction of sulphur in place of oxygen in the anilides should cause a smaller downfield shift than observed between the amides and the corresponding thioamides, since there will already be some delocalization of charge present through structures shown in (3). The value for selenobenzamide, only 3 8p.p.m. downfield from thiobenzamide, perhaps reflects the similarity of bond order 5 and n electron densities between the thio- and seleno-amides. A summary of the chemical shifts in these systems is shown in Table VII. 

No Name "d Df thiuronium picrate Ihyl amide Anilide cunc halide 2 naph ihyl phenyl thio phenyl sulfone Miscellaneous... 

No Name Melting point, C Boiling point, c S-Alkyl thiuronium picrate 1 Naphthyl amide Anilide Alkyl mer- curic halide Picrate of 2-naph- thyl ether 2,4-Di nitro- phenyl thio- ether 2,4-Di- nitro- phenyl sulfone Miscellaneous... 

CgsHaaXgOsSs S.S -J nzyiiden-bis- [thio lykoU sAure anilid] 12, 4, II 251. 

C HjoNsOgS S- [2-Nitro-phenyl] N-ben liden thiohydroxylamin 111z2. S [4-Nitro-phenyl]-N-benzyliden-thio h3rdr( 7]aiDm 7 1122. o-Cyan-benzolsulfons uie-anilid 12, 571. p-Cyan-benzolsuUons ure-anilid 12, 572. teenzoleulfonyl-phenyl-eyanamid 1 577. Thiobenzoe8 ure-[4-nitio-aiiilid] 12II391. 

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