Reactions with Sulfur Dichloride

Methylphenol is converted to 6-/ f2 -butyl-2-methylphenol [2219-82-1] by alkylation with isobutylene under aluminum catalysis. A number of phenoHc anti-oxidants used to stabilize mbber and plastics against thermal oxidative degradation are based on this compound. The condensation of 6-/ f2 -butyl-2-methylphenol with formaldehyde yields 4,4 -methylenebis(2-methyl-6-/ f2 butylphenol) [96-65-17, reaction with sulfur dichloride yields 4,4 -thiobis(2-methyl-6-/ f2 butylphenol) [96-66-2] and reaction with methyl acrylate under base catalysis yields the corresponding hydrocinnamate. Transesterification of the hydrocinnamate with triethylene glycol yields triethylene glycol-bis[3-(3-/ f2 -butyl-5-methyl-4-hydroxyphenyl)propionate] [36443-68-2] (39). 2-Methylphenol is also a component of cresyHc acids, blends of phenol, cresols, and xylenols. CresyHc acids are used as solvents in a number of coating appHcations (see Table 3). 

Zirconium-benzyne complexes have been used rather extensively in organic synthesis.8 45 For this purpose, one particularly important characteristic of zirconium-aryne complexes is that olefin insertion into the Zr—C bond occurs stereospecifically. Thus, when generated in situ, the zirconium-benzyne complex (45) reacts with cyclic alkenes to give exclusively the cis-zirconaindanes (46), which upon treatment with electrophiles provide access to a variety of m-difunctionalized cycloalkanes (47-49) (Scheme 5).46 For example, carbonylation of intermediate 46 affords tricyclic ketone 49, reaction with sulfur dichloride gives thiophene 48, and reaction of 46 with tert-butylisocyanide followed by I2 gives 47 via 50 and, presumably, intermediate 51 [Eq. (12)]. 

Finally in this category, the efficient synthesis of 3,4-dimethoxythiophene from 2,3-dimethoxy-l,3-butadiene on reaction with sulfur dichloride is notable it was easily transformed into EDOT (31.6.6.1). Here the sulfur source is electrophilic in character. 

Heat is required for this reaction. With sulfur dichloride oxide ... 

Reaction with Sulfur Electrophiles. Bisa2iridine compounds can be prepared from sulfur dichloride, thionyl chloride, or sulfuryl chloride... 

The bulk of 4-methylphenol is used in the production of phenoHc antioxidants. The alkylation of 4-methylphenol with isobutylene under acid catalysis yields 2-/ f2 -butyl-4-methylphenol [2409-55-4] and 2,6-di-/ f2 -butyl-4-methylphenol [128-37-0]. The former condenses with formaldehyde under acid catalysis to yield 2,2 -methylene bis(6-/ f2 -butyl-4-methylphenol) [119-47-1], which is widely used in the stabilization of natural and synthetic mbber (43). The reaction of 2-/ l -butyl-4-methylphenol with sulfur dichloride yields 2,2 -thiobis(6-/ l -butyl-4-methylphenol) [90-66-4]. 

Antioxidants used in lubricants are also made by reaction of sulfur dichloride with phenols ... 

The 1,5-isomers 13.3 (E = S) are colourless, air-stable solids. They are prepared by the cyclocondensation reaction of R2PN2(SiMe3)3 with sulfur dichloride or thionyl chloride. A similar cyclocondensation process, using a mixture of SeCU and Sc2Cl2 as a source of selenium, produces a mixture of the isomers 13.2 and 13.3 (E = Se, R = Ph). The structures of 13.3 (E = S, R = alkyl, aryl) are folded eight-membered rings with a cross-ring S S distance of ca. 2.50 This structural... 

An interesting variant of this reaction is the formation of 2-thiaadamantane-4,8-dione by hydrolysis of the reaction product of the bispyrrolidine enamine of bicyclo[3.3.1]nonane-2,6-dione with sulfur dichloride (106). 

An interesting bridged-sulfur compound, which is a natural constituent of Iranian oil, has been synthesized 478) by the reaction of a bicyclic bis-enamine with sulfur dichloride and subsequent Wolff-Kishner reduction of an initial sulfur-bridged diketone. Sulfur dichloride has also been added to a number of vinylogous amides 479). 

Alkenes and alkynes react with sulfur dichloride (SC12), giving 2-chloroethyl(or vinyl)sulfenyl chlorides. The reaction is an electrophilic addition to the multiple bond, and consequently the possible intermediacy of thiiranes, or thiiranium ions analogous to bromonium ions, has been... 

Diiminosuccinonitrile reacts with sulfur dichloride in dichloromethane at room temperature to give 1,2,5-thiadiazole-3,4-dicarbonitrile 226 in 93% yield <1972JOC4136>. The addition of catalytic naked chloride to the reaction mixture gave the bi-l,2,5-thiadiazole 227 <1991CB1517>. No experimental data were given for this transformation, but it was shown that the bi-l,2,5-thiadiazole 227 can be formed directly from dicyanothiadiazole 226 under analogous reaction conditions (Equation 53) <1991CB1517>. 

Hydrazones react65 with sulfur dichloride S2C12 to yield cyclic oligosulfides, thioketones, and ketones in the presence of triethylamine only thioketones are formed via thiosulhnes and dithiiranes as intermediates, Scheme 6, (Okazaki reaction). 

The reaction of the propargyl alcohols 53 with the reagent 54 furnished the S-alle-nylsulfinylamines 55 in good to excellent yields [108, 109]. Furthermore, the propargyl alcohols can be transformed with sulfur dichloride to the S-allenylsulfmates 56, which isomerize on heating in solution to the diallenyl sulfones 57 [79, 110, 111]. 

The reaction of sulfur dichloride with benzonitrile in the presence of a Lewis acid catalyst yields 3,5-diphenyl-l,2,4-thiadiazole (39), along with the 3-o-chlorophenyl (278) and 3-p-chlorophenyl (279) analogues in a total yield of 80%. The proposed mechanism proceeds via a complex between benzonitrile, Lewis acid for example, aluminum trichloride, and sulfur dichloride to give an intermediate (280) which then adds a second molecule of nitrile (Scheme 62) <83BCJ180>. 

Chlorine readily combines with many nonmetals. Reaction with sulfur yields sulfur dichloride, SCI2 and with phosphorus the products are phosphorus trichloride, PCI3 and phosphorus pentachloride, PCI5. 

Osmium tetroxide forms hahde complex ions, hexachloroosmates, such as [OsCle], [OsCle], and [OsCle] . The former ion [OsCle] is obtained by reaction of the tetroxide with sulfur dichloride and chlorine at ambient temperature ... 

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