Iminodithiocarbonic acid

Amide mercaptals Dithiocarbamic acid esters Dithiourethans Iminodisulfides Iminodithiocarbonic acid esters... 

Iminodithiocarbonic acid esters Dithiocarbimidates 15 Immoniodithiocarbonate esters Mercaptal S-arylimines Sulfenylthiocyanates... 

Iminodithiocarbonic acid esters. Phenyl isocyanide dichloride heated 7 hrs. at 110° with dimethylthallium thiophenoxide in toluene diphenyl N-phenyldithio-carbonimidate. Y 88.6%. F. e., also replacement of one Cl-atom and stepwise replacement by 2 different functions, s. B. Walther and W. Kolbe, Z. Chem. 13, 192 (1973). 

Solid-phase syntheses of triazines (Table 15.32) include the cyclocondensation of polystyrene-bound isothiuronium salts with /V-(cyano)iminodithiocarbonates and the cyclization with simultaneous cleavage from the support of derivatives of a-amino acid hydrazides (Table 15.32). (Benzylthio)triazines, such as those listed in Table 15.32 (Entries 1 and 2), have been cleaved from a support by oxidation to sulfoxides or sul-fones with N-benzenesulfonyl-3-phenyloxaziridine, followed by nucleophilic cleavage with primary or secondary aliphatic amines or with electron-rich anilines (see Section 3.8). 

N-Bis(methylthio)methylene derivatives of amines (iminodithiocarbonates) were first introduced by Hoppe and Beckmann468 for the synthesis of a-amino acids from glycine. The A bis(methylthio)methyleneamines are prepared by reaction of a primary amine with carbon disulfide (HAZARD) in the presence of triethylamine and iodomethane to form a methyl dithiocarbamate derivative, which is then S-alkylated with a second equivalent of iodomethane in the presence of potassium carbonate as the base. Scheme 8,233 illustrates an alternative one pot procedure applied to the synthesis of /erf-butyl N-[bis(methylthio)-methylene]glycinate and its use in diastereoselective conjugate addition under... 

Synthesis of 1,3-selcnazole derivatives has been achieved by reactions of dimethyl A -(ethoxycarbonylmethyl)iminodithio-carbonate with selenothioethanoic acid 3 -ester < 1997JA8592>. Nucleophilic attack of the carbanion derived from dimethyl A -(ethoxycarbonylmethyl)iminodithiocarbonate at the C=Se group, followed by the elimination of -butyl thiolate, affords an intermediate which forms the selenazole by intermolecular nucleophilic attack (Scheme 11) <2003NJC1622>. 

Olefin synthesis. This reagent has an advantage over trialkyl phosphites (see Trimethyl phosphite, 1, 1233, and this volume) for stereospecific generation of olefins from trithio- and thionocarbonates in that the conditions are mild (30°)-s Thus optically active /rans-cyclooctene (6) has been prepared from cis-cyclooctene in the following way.3 Addition of thiocyanogen to cis-cyclooctene (3) affords trans-, 2-dithiocyanocyclooctane (4), which when refluxed with 47% hydrobromic acid affords the iminodithiocarbonate (5). This was resolved via the salt with (—)-l-phenyl-ethanesulfonic acid by thirteen recrystallizations from 2-butanone. The (+)-(5) was... 

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