2-methyl-5-methylthio- chloride

Methyl-propyl)- 69 4-Methyl- -sulfinsaure 461 4-Methyl- -sulfonsaurc-chlorid 461 Methylthio- 500, 525... 

The seemingly straightforward protonolysis of ZnMe2 with 2-(methylthio)ethanol in CH2C12 (Scheme 95) afforded [MeZn(/i3-OCH2CH2SMe)Zn(/i-Cl)Me]2 149.215 The presence of both methyl and chloride substituents on zinc suggests that the solvent (CH2C12) is involved in the reaction, which should call into question the use of dichloro-methane as solvent in the Simmons-Smith reaction. 

This synthesis of sulfenyl chlorides can also be used in the aliphatic series although here the limitation applies that most alkylsulfur halides are too unstable to be isolated from solution. In general, and also in the aromatic series, sulfenyl chlorides are easier to prepare than the bromides, whilst the iodides are known only in a few cases and the fluorides not at all. As an example, Schneider,665 chlorinating methanethiol in anhydrous carbon tetrachloride at —15°, obtained dimethyl disulfide dichloride [chloro(methyl)(methylthio)-sulfonium chloride] which passed into methanesulfenyl chloride when allowed to warm slowly to room temperature ... 

Methylation of the 6,7-dimethyl derivative of 133 with methyl iodide in sodium hydroxide or sodium ethoxide gave two S,N-dimethyl derivatives, whereas in sodamide or ammonia, only the 5-methyl derivative was obtained. Methylation with diazomethane gave four methyl derivatives and with methyl chloride two di-jV-methyl and one 5,/V-dimethy] derivative were obtained (80H1139). Methylation of 153, obtained from 152, gave 4-methyl-3-methylthio-triazinoindole 155, whose hydrolysis or oxidation gave 154 (76T1735). On the other hand, methylation of 156 gave methiodide... 

Alkylation or acylation takes place at the nitrogen in position 1 when l/7-[l,2,4]triazolo[4,3-A][l,2,4]triazole 9 is treated with methyl iodide or acetyl chloride, furnishing compound 10 or 11, respectively <1983S415>. The 7-methyl isomers 13 are obtained after conversion of compounds 9 into the 1-acetyl derivatives 11 followed by methylation with methyl trifluoromethanesulfonate to give the l-acetyl-6-aryl-7-methyl-3-methylthio-17/-[l,2,4]triazolo[4,3-A]-[l,2,4]triazol-7-ium-trifluoromethanesulfonates 12, which upon treatment with aqueous sodium carbonate afford the 7-methyl derivatives 13 <1985BCJ735>. 

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... 

Addition of l,3-bis(methylthio)allyllithium to aldehydes, ketones, and epoxides followed by mercuric ion-promoted hydrolysis furnishes hydroxyalkyl derivatives of acrolein5 that are otherwise available in lower yield by multistep procedures. For example, addition of 1,3-bis-(methylthio)allyllithium to acetone proceeds in 97% yield to give a tertiary alcohol that is hydrolyzed with mercuric chloride and calcium carbonate to saturated aldehyde.8 Similarly, addition of l,3-bis(methylthio)allyl-lithium to an epoxide, acetylation of the hydroxyl group, and hydrolysis with mercuric chloride and calcium carbonate provides a 5-acetoxy-a,/ -unsaturatcd aldehyde,6 as indicated in Table I. Cyclic cis-epoxides give aldehydes in which the acetoxy group is trans to the 3-oxopropenyl group. 

R4 = Et) in methylene chloride in the presence of triethylamine, afforded 5-methylthio- and 5-methyl-3-oxo-3//-lX6, 2,6-thiadiazine-4-carboxylates (1367, R2 = MeS and Me), respectively, in 13-35% yields (86CB1745). 

RING EXPANSION Ferric chloride. Potassium hydride. Rhodium(ll) car-boxylates. Tris(Methylthio)methyl-lithium. 

Synthesis (Tull et al. (Merck Co.), 1975 1976) Friedel-Crafts reaction of fluorobenzene and a-bromoisobutyryl bromide gives 5-fluoro-2-methylindan-1-one, which is treated with 4-methylthiobenzylmagnesium chloride to yield 5-fluoro-2-methyl-1-(4-methylthiobenzyl)indene. Condensation with glyoxylic acid in the presence of N-benzyltrimethyl ammonium hydroxide (Triton B) gives 3-carboxy methylene-5-fluoro-2-methyl-1 -(4-methylthio-ben-zyl) indene, which is isomerized in acid to 5-fluoro-2-methyl-1-(4-methylthiobenzylidene)indene-3-acetic acid. Oxidation with hydrogen peroxide affords sulindac. 

Treating dimethylsulfonium acetylcarbamoylmethylide (297) with isoquinoline IV-oxide in the presence of acetyl chloride in dimethylformamide gave a complex reaction mixture from which 4-methyl-3-methylthio-2//-pyrimido[2,l-a]isoquinolin-2-one (156) and sulfur ylide (236) were isolated in 5.9% and 19.2% yields, respectively (80YZ1261). 

A solution of 22.1 g 2-methyl-4-(methylthio)anisole and 17.5 g dichloro-methyl methyl ether in 600 mL CH2C12 was vigorously stirred, and treated with 24.5 g anhydrous aluminum chloride added portion-wise over the course of 1 min. Stirring was continued for 20 min while the color developed to a dark red. There was added 500 mL H,0 with caution, and stirring was continued until the initial yellow solids redissolved and there were two distinct phases formed. These were separated, and the aqueous phase was extracted with 3x100 mL CH,C12. The... 

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