Thiocarbonyl chlorides

Physical Properties. Thiophosgene [463-71-8] (thiocarbonyl chloride), CSCI2, is a malodorous, red-yeUow Hquid (bp 73.5°C, ( 20 1.5442). It is only slightly soluble with decomposition in water, but it is soluble in ether and various organic solvents. 

If bromine is used in equation 8, carbon tetrabromide [558-13-4] is formed. With a minor amount of iodine present, and in the absence of iron catalyst, carbon disulfide and chlorine react to form trichioromethanesulfenyl chloride (perchloromethyl mercaptan [594-42-3]), CCI3SCI, which can be reduced with staimous chloride or tin, and hydrochloric acid to form thiophosgene (thiocarbonyl chloride [463-71-8], CSCI2, an intermediate in the synthesis of many organic compounds (see Sulfurcompounds). 

Ethoxycarbonyl chloride is, by virtue of resonance involving the ester function, less reactive than acetyl chloride, and the reagent has found application for selective O-acylation in the steroid field.34 With this reagent, methyl 4,6-O-benzylidene-a-D-glucopyranoside yielded35 2- and 3-esters in the ratio 24 1, and the related benzyl-thiocarbonyl chloride gave the 2-ester in 58% yield.36... 

While acid chlorides react as shown in (123) thiocarbonyl chlorides, presumably because the C=S carbon is less electropositive, give S-acylation with sulfinates (125) (Senning et al., 1968 Nilsson et al., 1971). 

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. 

Cyclic ureas, —NHC(0)NH—, have been similarly produced using carbonyl chloride, N,N -carbonyldiimidazole, carbon monoxide, thiocarbonyl chloride or carbon disulfide... 

Various fused systems, e.g. (494), have been prepared via reactions of compounds of type (492) or (493) with Ci reagents such as phosgene, thiocarbonyl chloride or cyanogen bromide (76T57, 839). 

If the 2-pyridylhydrazine carries a substituent on N-l, reaction with carbonyl chloride, thiocarbonyl chloride, or cyanogen bromide gives a mesoionic compound (74).56,114,119... 

Thiocarbonyl chloride reacts rapidly with nickel carbonyl at the... 

Thiocarbonyl Chloride, Carbon Dichlorosulphlde, or Thiophosgene, CSC12.—Thiocarbonyl chloride is produced by the prolonged action of dry chlorine on carbon disulphide ... 

With certain catalysts a yield of 80 per cent, of thiocarbonyl chloride may be obtained. 

The condensation of 1,4-diamines with a variety of carboxylic acid derivatives, e.g. imidate esters, orthoformic esters, /V-ethoxycarbonylthioamides (77JOC2530), nitriles and ethoxyacetylene, produces the cyclic amidine linkage —N = C(R)NH— (67AHC(8)2l, p. 40). Cyclic ureas, —NHC(0)NH—, have been similarly produced using carbonyl chloride, A, A -carbonyldi imidazole, carbon monoxide, thiocarbonyl chloride or carbon disulfide (67AHC(8)21, p. 38). 

To a solution of cholesterol (0.77 g, 2 mmol) in dichloromethane (10 ml) were added pyridine (0.6 ml, 8 mmol) and phenoxy thiocarbonyl chloride (0.4 ml, 2.2 mmol). After 2 h, methanol (1 ml) was added, and the mixture obtained was washed with 1 M hydrochloric acid solution twice, and dried over Na2S04. After removal of the solvent, the residue was recrystallized from acetone to give phenyl thiocarbonate in 95% yield. Then, (Me3Si)3SiH (0.7 ml, 2.2 mmol) and AIBN (50 mg, 0.5 mmol) were added to the solution of the phenyl thiocarbonate (0.75 g, 1.5 mmol) in toluene (20 ml) and the obtained mixture was heated at 80 °C for 2 h under nitrogen atmosphere. After the reaction, the solvent was removed and the residue was recrystallized from acetone to give cholest-5-ene in 94% yield [14]. 

O.O-divinylester-O-ethylester XII/2, 646 -0,0-divinylester-O-phenylester XII/2, 646 -O-dodecylester-O-methylester XII/2, 603 -O-cstcr-halogcnid-isothiocyanat E2, 680 O-Elhoxycarbonyl- -0,0-diethylester XII/2, 821 -S-(ethoxycaibonyl-methylestei)-0-metliylestei-0-(1,2,2,2-tetrachlor-cthylcstcr) E2, 588 -0-(2-ethoxycarbonyl-l-methyl-elhylester) E2, 678 -(ethoxymethylen-amid)-0,S-diethylester E2, 635 -(ethoxymethylen-amid)-O.S-dimethylester E2, 635 -(ethoxymethylen-amid)-0-(2-isopropyloxycarbonyl-phenylester)-0-methylester E2, 745 S-(Ethoxy-thiocarbonyl)- -chlorid-diethylamid XII/2, 822... 

The condensation of phenoxazine in refluxing benzene with thio-phosgene, in order to obtain the 10-thiocarbonyl chloride, gave only a black unidentified precipitate, while the filtrate yielded a yellow compound to which structure 41 was assigned.77 Phenoxazine treated... 

Heating of diarylthioureas with thiocarbonyl chloride also affords carbodiimides. Alkylchloroformates, upon reaction with thioureas at 5 to 10 °C in the presence of tri-ethylamine give low yields of carbodiimides. 

Bacchetti et aZ. - have studied the reaction between aromatic diazoketones and thiocarbonyl chloride. In this reaction the diazomethyl part is added to the thiocarbonyl group carbon to sulfur and... 

The reaction between 1,1 -dimethyl-2- -chlorothiobenzoylhydrazine (92) and thiocarbonyl chloride gave 2-p-chlorophenyl-4-methyl-... 

The only known compound of this type is a thiocarbamyl derivative. Bromomagnesium ethenetellurolate combined with A/. A -dimethylamino-thiocarbonyl chloride to give orange-red, solid N,N-dimethylaminothiocarbonyl ethenyl tellurium, which is stable at 20° under an atmosphere of argon, but is decomposed by acids. ... 

A,A-Dimethylaminothiocarbonyl Ethenyl Tellurium Under an argon atmosphere 6.38 g (50 mmol) of tellurium are added in one portion to 45.5 ml (23 mmol) of a 0.5 molar solution of vinylmagncsium bromide in tetrahydrofuran at — 78°. The mixture is stirred at — 78° for 1 h, warmed to 0°, and stirred at 0° for I h. The resultant yellowish-brown suspension is cooled to —78°, a solution of 6.18 g (50 mmol) of N,N-dimethylamino-(thiocarbonyl) chloride in 25 ml of tetrahydrofuran (freshly distilled from sodium) is added dropwise to the stirred suspension, and the mixture is stirred at — 78° for 0.5 h, at 0° for 1 h, and at 20" for 0.5 b. The mixture is then poured into ice/water and glacial acetic acid is added dropwise until the magnesium hydroxide has dissolved. The mixture is extracted three times with 150 ml portions of diethyl ether, the combined extracts arc washed three times with water, the ether solution is dried, and evaporated. The dcep-orange-red solid residue is the pure product yield 8.7 g (72%) m.p. < 25°... 

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