Chloromethyl sulfide

Reaction of bis(chloromethyl)sulfide with sodium sulfide (19) gives poly(thio-formaldehyde) of melting point 220-245° C. If the reaction is carried out in water-alcohol solution, the cyclic compounds, 1,3,5,7,9-oxatetrathiacyclodecane (I) and 1,3,5,7,9,11-oxapentathiacyclododecane (II) (20), are formed. 

Dimethylthiophene was prepared in low yield by first coupling tetraethoxycarbonyl-ethane with bis(chloromethyl) sulfide. Hydrolysis and decarboxylation of the product gave 3,4-tetrahydrothiophenedicarboxylic acid (262). Reduction of the ester of (262) with LAH gave the dialcohol (263), and pyrolysis of the diacetate gave (264) directly (55JA66). 

From Ethyl Chloromethyl Sulfide and Hydrogen Fluoride. . . Jl... 

IS. From Etbyl Chloromothyl Sulfide and Hydrogen Fluoride Propylene sulfide is formed by the reaction of hydrogen fluoride yrith ethyl chloromethyl sulfide. ... 

A few representatives of this heterocyclic system 35 were synthesized in very high yield (85-90%) by the intramolecular nucleophilic cyclization of the acetylene derivatives 36 (81RTC10), which in turn were obtained by treatment of alkynyl(chloromethyl) sulfides with one equivalent of Na2Te, the latter being prepared from elemental sodium and tellurium in liquid ammonia. 

Among other electrophilic reagents ctq>able of twinging about the Pummerer rearrangement are halides of organic and inorganic acids. As these halides transform sulfoxides into a-chlorosulfides they complement the sulfide chlorination route to these compounds. Thionyl chloride reacts readily with sulfoxides and 3-keto sulfoxides methyl phenyl sulfoxide furnishes chloromethyl phenyl sulfide (equation 37). Benzoyl chloride and acetyl chloride behave similarly. d yanuric chloii is transformed into cyanuric acid by dimethyl sulfoxide, which in turn is transformed into methyl chloromethyl sulfide (equation 3g).54,S5... 

Thio-substituted carbenes which are generated from a chloromethyl sulfide and t-BuOK reacted with enamines 147 to give aminocyclopropanes 148 and 149254-256 (equation 36). In some cases, both isomers could be separated by chromatography (examples are given in equation 36)2 . ... 

Alkyl(or aryl)sulfanylcyclopropanes are prepared by the addition of organosulfanylcarbene (carbenoid) to an alkene. This carbene is, in turn, generated via a-elimination of hydrogen chloride from the corresponding alkyl(aryl)chloromethyl sulfides using a base (Houben-Weyl, Vol.4/3, pp248-252 and Vol.E19b, pp 1690-1691 and 1693-1695). 

The simplest and most efficient method yet for the preparation of arylsulfanylcyclopro-panes consists of treating the alkene and aryl chloromethyl sulfide with concentrated aqueous sodium hydroxide and a phase-transfer catalyst. The chlorophenylsulfanyl anion, the formation of which precedes phenylsulfanylcarbene undergoes addition to 1,2-dibenzoylethene and the anion thus formed cyclizes. " ... 

A series of l-(arylsulfanyl)-2-(4-tolyl)cyclopropanes 1 has been prepared by phase-transfer-catalyzed cyclopropanation of 4-methylstyrene with aryl chloromethyl sulfides. ... 

The titanium(IV) chloride-promoted reactions of enol silyl ethers with aldehydes, ketones, and acetals, known as Mukaiyama reaction, are useful as aldol type reactions which proceed under acidic conditions (eq (23)) [20], Enol silyl ethers also undergo the Michael type reactions with enones or p.y-unsaturated acetals (eq (24)) [21]. Under similar reaction conditions, enol silyl ethers are alkylated with reactive alkyl halides such as tertiary halides or chloromethyl sulfides (eq (25)) [22], and acylated with acid halides to give 1,3-diketones (eq (26)) [23]. 

Preparation. The reagent is prepared1 in 67% yield by the Arbusov reaction of triethyl phosphite and ally chloromethyl sulfide.2... 

AUylbenzene, 86 Allyl benzoate, 26 Allyl chloride, 104 Allyl chloromethyl sulfide, 94 Allyl ethers, 246-247 Allylic alcohols, 150, 151-152, 328 Allylic chlorides, 151-152, 293 Allylic coupling, 211 Allylic hydroxylation, 246 Allylic oxidation, 35, 55-56, 171 2-Allylisopropyl bromide, 224 JT-Allylnickel bromide, 210 Allylphosphoric dichloride, 104 Alumina, 6... 

Formaldehyde dibenzyl dithioacetal, m.p. 55° (from 2-propanol), is formed analogously in 90% yield (4.8 g) from benzyl chloromethyl sulfide (3.5 g) and a-toluenethiol (3 g). 

Dithietanef Bis(chloromethyl) sulfoxide (1) reacts with aqueous sodium sulfide in the presence of 1 equiv. of this phase-transfer catalyst to form 1,3-thietane 1-oxide (2) in 36% yield. Bis(chloromethyl) sulfide does not undergo this reaction. However, the product (3) that would have been formed can be obtained by reduction of (2) with borane-tetrahydrofurane (5, 48). The microwave spectra... 

Sulfur substituted carbenes have been generated by the phase transfer method with reasonable success. Treatment of either phenyl(chloromethyl) sulfide or phenyl-(dichloromethyl) sulfide with 50% aqueous sodium hydroxide solution in the presence of both an olefin and a phase transfer catalyst (usually BTEAC) results in the... 

Methods for the preparation of tritiated methyl iodide in the laboratory use variations of the sp tritiodehalogenation approach. Palladium-catalyzed tritiodechlorinations of chloro-methyl ester 113 and of chloromethyl sulfide 115 ° have been developed as less hazardous alternatives to the older laboratory procedure for C HH2l at 15-22 Ci/mmol starting from bis(chloromethyl)ether °. The initially formed nonvolatile monotritiated 114 and 116 can be conveniently isolated, purified and finally subjected to ester cleavage with either lithium iodide or hydriodic acid, or, in the second case, by thermolysis of the intermediately generated sulfonium salt 117. 

Related Reagents. Benzyl Chloromethyl Sulfide r-Butyl Chloromethyl Ether 2-Chloroethyl Chloromethyl Ether Chloromethyl Methyl Ether Chloromethyl Methyl Sulfide (p-Methoxy-benzyloxy)methyl Chloride 2-Methoxyethoxymethyl Chloride 2-(Trimethylsilyl)ethoxymethyl Chloride. 

Chlorothioethers s. a,o-Di-chloromethyl sulfide (2-Chloro-l,l,2-trifluoroethyl)-diethylamine s. 2-Chloro-1,1,2-trifluoro-triethylamine 2-Chloro-l,l,2-trifluorotriethyl-amine as reagent 17, 549 suppl. 23 22, 571 Chlorotris(triphenylphosphine)-rhodium... 

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