From Dithiocarbonates

In a similar reaction, [MoS 412 reacts with C4S5O, the monothiocarbonyl derivative of TPD, to give the same products as above, showing the preferential reactivity of the thiometalate for the dithio- versus the trithiocarbonate. It was also found that the tetrasulfido complex ZnS4(pmdta) (Section III. A) reacts with TPD to give Zn(S2C2S2CO)(pmdta) (189). 

Relevant to the quest for molybdopterin-related ligands, heterocycle-substituted trithiocarbonates were shown to give modest yields of the CpCo (dithiolene) when treated with CpCo(cod) (cod = 1,5-cyclooctadiene, Eq. 26) (85). 

The CpCo platform has been employed to display and interrogate the dithiolene unit with respect to the ligand-based reactivity. The dithiolene ligand cannot, however, be readily removed from the CpCo site. 

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An analogous preparation of thioxopenams from dithiocarbonates (75, R = t-C4H2(CH2)2Si, R = OC H ) has also been described (115). Additionally, an iatramolecular Michael addition reaction to form the [2,3] bond has been exploited ia penem synthesis to prepare FCE 22101 (69) (116). 

Condensation. Generation of stabilized free radicals from dithiocarbonate esters via C—S bond cleavage is promoted by BusSnSnBus. By providing an alkene and a trapping agent, homologation of a carbon chain while performing functionalization, for example,... 

Various S-nucleophiles are allylated. Allylic acetates or carbonates react with thiols or trimethylsilyl sulfide (353) to give the allylic sulfide 354[222], Allyl sulfides are prepared by Pd-catalyzed allylic rearrangement of the dithio-carbonate 355 with elimination of COS under mild conditions. The benzyl alkyl sulfide 357 can be prepared from the dithiocarbonate 356 at 65 C[223,224], The allyl aryl sufide 359 is prepared by the reaction of an allylic carbonate with the aromatic thiol 358 by use of dppb under neutral condi-tions[225]. The O-allyl phosphoro- or phosphonothionate 360 undergoes the thiono thiolo allylic rearrangement (from 0-allyl to S -allyl rearrangement) to afford 361 and 362 at 130 C[226],... 

A number of catalysts of Pd(II), Pt(II), Rh(I), and Ir(I) induce rearrangements of 0-a11y1ic-.9-methy1 dithiocarbonates at 25°C (45). In a relatively low temperature procedure, olefins readily form from certain classes of xanthate esters (46) ... 

Carbon disulfide [75-15-0] (carbon bisulfide, dithiocarbonic anhydride), CS2, is a toxic, dense liquid of high volatiUty and fiammabiUty. It is an important industrial chemical and its properties are well estabUshed. Low concentrations of carbon disulfide naturally discharge into the atmosphere from certain soils, and carbon disulfide has been detected in mustard oil, volcanic gases, and cmde petroleum. Carbon disulfide is an unintentional by-product of many combustion and high temperature industrial processes where sulfur compounds are present. 

Industrially important dithiocarbonates (xanthates) result from reaction with various alcohoHc alkaHes ... 

When ethanol is replaced by cellulose, sodium cellulose xanthate is obtained this dissolves in aqueous alkali to give a viscous solution (viscose) from which either viscose rayon or cellophane can be obtained by adding acid to regenerate the (reconstituted) cellulose. Trithiocarbonates (CS3 "), dithiocarbonates (COS2 "), xanthates (CS2OR ), difhiocarbamates (CS2NR2 ) and 1,2-dithiolates have an extensive coordination chemistry which has been reviewed. ... 

A different approach leading to thianthrene derivatives starts from 0-ethyl or 0-isopropyl dithiocarbonate 394, when heated with chlorodinitrobenzene derivative 59 provided intermediate 395, the compound having all features necessary for denitrocyclization reaction to the final product 396, which was the only isolated compound (Scheme 61). Its structure was assigned by X-ray crystallography (77JOC2896). 

The anionic species ROCS2 resulted from O-alkyl(aryl) esters of the hypothetical dithiocarbonic acids, ROC(S)SH, better known as xanthates, are versatile ligands and they generate an extensive coordination chemistry. The interest for metal xanthates is stimulated by their potential use as single source precursors for nanoscopic metal sulfides in photochemical or thermal vapor deposition systems under mild conditions,218 221 e.g. for Zn,222 Cd,223 In,224... 

The 0,5-dialkyl dithiocarbonates (Table 4.8) are readily prepared under phase-transfer catalytic conditions by the reaction of an alkylating agent with potassium O-alkyl dithiocarbonate [35, 39], which can be obtained from carbon disulphide and the appropriate potassium alkoxide [cf. 40]. Monosaccharides are converted into 5-glycosyl dithiocarbonates via the in situ formation of the tosylate, followed by reaction with potassium O-alkyl dithiocarbonate (Scheme 4.6) [41], In a similar manner, 5-glycosyl 7V,7V-diethyldithiocarbamates are obtained from the monosaccharide and A.A-diethyldithiocarbamate (see 4.3.2) [42]. 

Symmetrical 5,5-dialkyl dithiocarbonates have been obtained by thermal rearrangement of the corresponding (9,5-dialkyl esters in the presence of Aliquat [43]. This procedure is not suitable for the preparation of unsymmetrical 5,5-dialkyl dithiocarbonates, as it has been reported that disproportionation of the products can lead to a mixture of the symmetrical and unsymmetrical esters. Alternatively, they can be prepared by a base-catalysed disproportionation of 5-alkyl-O-methyl dithiocarbonates [44] (Table 4.9). These methods for the synthesis of the 5,5-dialkyl esters are more convenient than the traditional procedures from the thiol and phosgene. 

Synthesis of symmetrical S,S-dialkyl dithiocarbonates from potassium O-methyl dithiocarbonate... 

The S-alkyl-O-methyl dithiocarbonate, prepared by procedure 4.1.14 from MeOCS2K (48.26 g, 0.33 mol), is extracted from the reaction mixture with Et20 (3 x 25 ml). The ethereal extracts are washed with H20 (3 x 100 ml) and evaporated under reduced pressure at 40°C. Aqueous Na2C03 (2%, 300 ml) is added and the aqueous mixture is stirred at 50°C for ca. 3 h. The mixture is then extracted with EtjO (3 x 50 ml) and the dried (Na2S04) extracts are evaporated under reduced pressure at 70 °C. The temperature of the residue is maintained at 70°C for 30 min and the 5,5-dialkyl ester, which is contaminated with the 0,5-dialkyl ester, the dialkyl sulphide and the disulphide, is isolated by chromatography from silica. 

An unusual reaction of methoxythiocarbonyl chloride with tetra-n-butylammo-nium iodide in the presence of sodium thiosulphate leads to the formation of 0,5-dimethyl dithiocarbonate [49], The reaction appears to involve a reduction step, with the iodide anion being regenerated from the released iodine by the thiosulphate ions (Scheme 4.7). In the absence of the thiosulphate ions, the thiocarbonyl chloride decomposes to yield chloromethane and carbonyl sulphide. 

In a one-pot synthesis of thioethers, starting from potassium 0-alkyl dithiocarbonate [36], the base hydrolyses of the intermediate dialkyl ester, and subsequent nucleophilic substitution reaction by the released thiolate anion upon the unhydrolysed 0,5-dialkyl ester produces the symmetrical thioether. Yields from the O-methyl ester tend to be poor, but are improved if cyclohexane is used as the solvent in the hydrolysis step (Table 4.13). In the alternative route from the 5,5-dialkyl dithiocarbonates, hydrolysis of the ester in the presence of an alkylating agent leads to the unsymmetrical thioether [39] (Table 4.14). The slow release of the thiolate anions in both reactions makes the procedure socially more acceptable and obviates losses by oxidation. 

Selected examples of unsymmetrical thioethers from 5,5-dialkyl dithiocarbonates... 

One-pot synthesis of thioethers from potassium O-alkyl dithiocarbonate... 

Method A The 0,5-dialkyl dithiocarbonate is prepared by procedure 4.1.14 from O-alkyl potassium dithiocarbonate (50 mmol). The mixture is cooled to 50 °C and, without isolation of the ester, KOH pellets (14 g, 0.25 mol) are added portionwise at <80 °C. The mixture is stirred at 80 °C until GLC analysis indicates the complete disappearance of the ester (ca. 30 min). Petroleum ether (b.p. 40-60 °C, 150 ml) is added and the organic phase is separated, dried (Na2S04), filtered through silica, and fractionally distilled to give the thioether. 

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