Dimethyl trithiocarbonate

Cycloadditions of benzonitril-4-nitrobenzylide to a variety of carbon to heteroatom multiple bonds including methyl dithiobenzoate and dimethyl trithiocarbonate (Scheme 148), X = MeS or Ph, have been examined in detail by Huisgen et al. (757). 

The chiral hexahydropyrimido[l,2- ]pyrimidine 186, a potential enantioselective catalyst, was prepared from the triamine 185 and dimethyl trithiocarbonate (Scheme 29) <1995TA2829>. 

It is of note that no significant amounts of dimethyl trithiocarbonate were formed in the process, although similar conditions yielded trithiocarbonates from CS2 and alkyl halides in excellent yields but much... 

Minkwitz and co-workers have recently obtained the X-ray crystal structure of protonated thiocarbonic acid, protonated (9,5-dimethyl dithiocarbonate, and protonated dimethyl trithiocarbonate. Protonated thiocarbonic acid 354 has C—S bond lengths of 1.683-1.708 A.662 The small differences imply a nonequal distribution of the positive charge over the S atoms. All hydrogen atoms have trans positions and they are... 

The cleavage of the sulfur-carbon bond of thioacetals and thioketals,671 thioortho-formates672 [Eq. (3.101)], and tetraalkyl thioorthocarbonates673 [Eq. (3.102)] leads to the corresponding mono-, di-, and trithiocarbenium ions, respectively. Trimethylthio-carbenium ion 361 was also prepared by methylating dimethyl trithiocarbonate [Eq. (3.102)]. 

Methyl chlorodithioformate has also bran used to prepare the methyl cyclopropanecarbodithioate (77 equation 66), whereas dimethyl trithiocarbonate was reacted with the carbanions of ketones and... 

P-Oxo dithioester 53 was prepared from ketone 54 on treatment with dimethyl trithiocarbonate in the presence of t-BuOK in a mixture of benzene and DMF (Scheme 13) [47]. Spectroscopic observations revealed that the dithioester 53 exists mostly in the enolic form 55. The reaction of 53/55 with hydrazine gives the tricyclic compound 56. A Diels-Alder reaction of 9-methylanthracene with 57 forms the adduct 58 in 93% yield (Scheme 14) [48]. The thermolysis of 58 in refluxing chloroform resulted in the elimination of PhSO, yielding anthracenecarbodithioate 59 with a yield of 82% through the carbocation intermediate 60. 

The reaction of diphenyl trithiocarbonate with phenyl-lithium, which takes place at -78 °C to form (446), constitutes a further example of a thiophilic addition to the thiocarbonyl double bond. Compound (446) appeared to be stable in solution below -20 C, and its structure was confirmed by its reactions with deuterium oxide and methyl iodide, affording (447) and (448), respectively. Dimethyl trithiocarbonate reacted with two equivalents of dimethylsulphoxonium methylide to form... 

The cycloaddition of (27) to dimethyl trithiocarbonate occurs readily in the cold in a direction opposite to that of (di)thiobenzoates, yielding (31) the... 

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