1.3- Dimethyl-4 -methylthio- -chlorid

Addition of a sulfenyl chloride to an alkene in the presence of silver fluoride affords (3-fluoro sulfides, as shown in equation (2).18 The same trans adducts can also be prepared from the sulfenyl chloride adducts and silver fluoride. An alternative procedure for the formal addition of methanesulfenyl fluoride to alkenes involves the use of dimethyl(methylthio)sulfonium tetrafluoroborate and triethylamine tris(hy-drofluoride) as in equation (3).19... 

Examples of 5-exo cyclizations in which the hydroxy group is constrained by a five-membered ring are shown by equation (53). The stereoselectivity in these cyclizations ranges from quite high in iodocy-clization (9 1 in H2O and >20 1 in CH2CI2) to only moderate (2—3 1) with mercury and phenylselenenyl chloride. P This type of cyclization has been widely applied to synthesis of prostacyclins.146 Similar cyclizations with dimethyl(methylthio)sulfonium fluoroborate have been reported recently.35... 

Aldehydes Alkyldimesitylborane. Chloro-methyltrimethylsilane. Diethyl[(2-tetrahy-dropyranyloxy)methylphosphonate. N, N-Dimethylchloromethyleniminum chloride. Dimethyl(methylthio)sulfonium tetrafluoro-borate. Methoxy(phenylthio)methyllithium. Methylthiomethyl p-tolyl sulfone. 1-Phenyl thio- 1 -trimethylsilylethylene. Tetrakis-(triphenylphosphine)palladium. Thexyl-chloroborane-Dimethyl sulfide. 

Chlor-methylthio-methylen)-dimethyl-iminium-chlorid ergibt in elektrophiler Substitution mit elektronen-reichen Heterocyden Aryl-(methylthio-methylen)-iminium-chloride (36- 90%)765 ... 

Related Reagents. Benzenesulfenyl Chloride 2-(Methyl-thio)- li/-isoindole-1,3(2/ -dione N- ferf-Butylthiophthalimide 7V-Phenylthiophthaliinide Dimethyl(methylthio)sulfoniumTetra-fluoroborate Ethyl Thiosulfinate Disulfur Dichloride. 

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... 

There is the raw stuff potentially available to answer this question. There are a couple of compounds known with the sulfur in the 4-position, which is the location of the oxygen atom in psilocybin. The 4-thio analogues have been synthesized from 4-methylthio-indole, via the oxalyl chloride method and reaction with the appropriate amine. With dimethylamine, the indoleglyoxylamide was made in a 43% yield and had a mp 163-164 °C. With diisopropylamine, the amide was made in a 27% yield and had a mp 190-192 °C. The final amines were prepared by the reduction of these amides with LAH in THF. N,N-Dimethyl-4-thiotryptamine (4-MeS-DMT) was obtained in a 68% yield and melted at 108-110 °C N,N-diisopropyl-4-methylthiotryptamine (4-MeS-DIPT) was obtained in a 61% yield and melted at 92-94 °C. In animal studies of behavioral disruption with these three compounds, there was systematic drop of potency in going from the 5-MeS-DMT to 4-MeS-DMT to 4-MeS-DIPT. 

Methylthio)thioindoxyl has been prepared by treatment of thioresorcinol dimethyl ether with chloroacetyl chloride and aluminum chloride.352... 

Methyl-l-penten-3-one-l-ol 1 and glacial acetic acid in benzene was added to pyrrolidine to give 2-methyl-l-pen ten-1-[N-pyrrolidinyl]-3-one 2. Compound 2 when treated with oxalyl chloride and methanol was added, 3,5-dimethyl-2-methoxycarbonyl-4-pyrone 3 was produced. Treatment of compound 3 with sodium borohydride in methanol gives 3,5-dimethyl-2-hydroxymethyl-4-pyrone 4. Compound 4 was converted to 3,5-dimethyl-2-hydroxymethyl-4-pyridone 5 by heating compound 4 with aqueous ammonia in a sealed flask. Compound 5 was converted to 4-chloro-2-chloromethyl-3,5-dimethyl pyridine 6 by treatment with phosphorous oxychloride. Treatment of compound 6 with 5-methoxy-2-mer-captobenzimidazole in tetrahydrofuran gave 2-[2-(4-chloro-3,5-dimethyl pyridinyl)methylthio]-5-methoxy benzimidazole 7. When compound 7 was treated with potassium hydroxide in dimethyl sulfoxide containing methanol, 2-[2-(3,5-dimethyl-4-methoxypyridinyl)methylthio]-5-methoxy... 

Dimethyl- -(1-ethylthio-ethylester) E2, 271 Dimethyl- -[(4-fluor-phenyl)-methylester] E2, 272 Dimethyl- [2-(4-methylthio-phenylthio)-ethylester] aus Dimethyl-dithiophosphinsaure und 2-Brom-l-(4-methylthio-phenylthio)-ethan XII/1, 283 Dimethyl- -[(4-methylthio-phenylthio)-methyl-ester] XII/1, 283 Dimethyl- -phenylester E2, 269 Dimethyl- -trimethylsilylester E2, 266 Dimethyl- -(2-vinylthio-ethylester) E2, 271 Diphenyl- XII/1, 59, 227, 279, 284. 289 El, 172-El, 262, 265, 269, 271ff., 274 aus Benzol, Phosphor(V)-sulfid und Aluminium-chlorid XII/1, 272... 

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