Sulfide, chloromethyl methyl

Several chlorophyll derivatives have been prepared by electrophilic substitution, inter alia by formylation reactions. Adopting methods from corrin chemistry.50 alkylation with chloro-methyl methyl ether (caution toxic),32k chloromethyl methyl sulfide,51 and dichloromethyl methyl ether (caution toxic)52 in the presence of Lewis acids are the methods of choice to introduce carbon residues into the chlorin frame work. The compounds listed below have been prepared by these methods. 

Alkynylation of halo acetals. In the presence of ZnCl2 (2 equiv.) the organotin acetylide 1 couples with chloromethyl methyl ether or chloromethyl methyl sulfide to form alkynyl ethers or sulfides, respectively (equation I). 

Intramolecular cyclizationlenolate trapping of allylsilanes (cf., 12,496-497).3 The intermediate enolate formed in the TiCl4-catalyzed cyclization of 1 can be trapped by chloromethyl methyl sulfide to give a decalone derivative with a potential methyl group on the angular position. Actually the reaction results in... 

Reaction of l,3-bis(methylthio)-2-methoxypropane with 2 moles of lithium diisopropylamide5 (or w-butyllithium) effects (a) the elimination of methanol to form l,3-bis(methylthio)propene and (b) the lithiation of this propene to generate l,3-bis(methylthio)allyllithium in solution. Its conjugate acid, l,3-bis(methylthio)propene, can be regenerated by protonation with methanol, and has also been prepared (a) in 31% yield by reaction of methylthioacetaldehyde with the lithio derivative of diethyl methylthiomethylphosphonate,5 (b) in low yield by acid-catalyzed pyrolysis of l,l-bis(methylthio)-3-methoxypropane,6 and (c) in low yield by acid-catalyzed coupling of vinyl chloride with chloromethyl methyl sulfide.7... 

The primary product (29) of the reaction of DMSO and oxalyl chloride decomposes very quickly to 30 even at — 140°C.163 However, the activated DMSO molecule 30 remains stable bellow —20°C, but decomposes above this temperature to chloromethyl methyl sulfide (31), via the reactive species H2C=S(+)-Me. 

Methylthiomethyl esters have been prepared by reaction of trie thy lammonium salts of carboxylic acids with chlorodimethylsulfonium chloride191 or by reaction of the potassium salts of carboxylic acids with chloromethyl methyl sulfide in the presence of sodium iodide and 18-crown-6.192... 

CARBOXYL GROUPS Chloromethyl methyl sulfide. Cobalt(ll) phthalo-cyanine. Dimethyl sulfoxide-/-Butyl bromide. 

HYDROXYL GROUPS t-Butylchlorodi-methylsilane. f-Butyldimethylsilyl perchlorate. f-Butyl chloromethyl ether. Chloromethyl methyl sulfide. 9-Chloro-9-phenylxanthene. 2-Chlorotetrahydro-furane. d-Methoxyethoxymethyl chloride. 2-Tetrahydrothicnyl diphenyl-acetate. Tris(p-bromophenyl)ammonium-yl hexachloroantimonate. 

Methylthiomethyl ethers. MTM ethers of a wide range of alcohols can be prepared in 60-80% yield by reaction of primary or secondary alcohols with chloromethyl methyl sulfide and silver nitrate in the presence of triethylamine (benzene, 20-80°). ... 

AMINO GROUP Boron trifluoride ether-ale. l-r-Bulyloxycarbonyltriazole-1,2,4, Di-t-butyl dicarbonate. 4-Dimethylamino-1-t-butyloxycarbonyl pyridinium chloride. CARBONYL GROUP Ceric ammonium nitrate. 1,2-Dihydroxy-3-bromopropane. Sodium N-chloro-p-toluenesulfonamide. Thallium(lll) nitrate. Trichloroethanol. Trimcthylsilyl cyanide. Chloromethyl methyl sulfide. N,N -Diisopropylhydra-zinc. Trichloroethanol. 

The flask is cooled to 0°C in an ice bath, and chloromethyl methyl sulfide (1.00 mol equiv, 0.42 mol, 35.2 ml) is added dropwise with a syringe over 25 min (Notes 9 and 10). After residues of the sulfide are rinsed into the flask with additional THF (ca. 

Chloromethyl methyl sulfide was obtained from Aldrich Chemical Company, Inc. and distilled under nitrogen prior to use, although direct use of the commercial material without distillation had little effect on the overall efficiency of this procedure. 

WARNING Chloromethyl methyl sulfide has a very unpleasant, penetrating odor and should be handled in a properly ventilated fume hood. Also, because of its structural similarity to chloromethyl methyl ether which is highly toxic and an OSHA-regulated carcinogen, this sulfide should be handled as a substance having potentially similar toxic properties. 

Chloromethyl methyl sulfide Sulfide, chloromethyl methyl (8) methane, chloro(methylthio)- (9) (2373-51-5) lodomethane Methane, iodo- (8,9) (74-88-4)... 

Trapping of the unreacted chloromethyl methyl sulfide in the cold trap is recommended because of the problems summarized in Note 10. 

Chloromethyl methyl sulfide forms a complex with 2 moles of AlCli, which is very electrophilic towards aromatic compounds. High p o ratios of products are observed in reactions with toluene and related substrates. 

Chloromethyl methyl sulfide, CICH2SCH3. Mol. wt. 96.58, b.p. 105. Stench. Suppliers Aldrich, Fluka. 

Methylation of amides. Treatment of an amide, for example, benzamide, with chloromethyl methyl sulfide in TFA or methanesulfonic acid gives the substituted amide in good yield. This product is converted into the N-methyl-amide when refluxed in 90% ethanol in the presence of a large excess of Raney nickel. 

Protection of hydroxyl groups. Hydroxyl groups can be protected as the methylthiomethyl ether, prepared by reaction of a sodium alkoxide with chloromethyl methyl sulfide and sodium iodide (1 eq. of each) at 0° for 1 hr. and... 

This reagent can be prepared in situ by the reaction of chloromethyl methyl sulfide (Aldrich) and sodium iodide in DMF. 

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