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Two new DOM analogs made and evaluated

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azole:
Ring alkylthioalkylation with RSCHClR' - Lewis acid.

Post 423031 (GC_MS: "New, convenient route to erbstatin", Novel Discourse)

Post 439768 (missing) (Lego: "P2Ps from benzenes by Friedel-Crafts reaction", Methods Discourse)

Ethoxycarbonylmethylthiomethylation of Aromatic Compounds by Friedel-Crafts Reaction with Ethyl alpha-(Chloromethylthio)-acetate
Y. Tamura, T. Tsugoshi, H. Annoura, H. Ishibashi
Synthesis, 1984, 326-327.


Methylation of Polysubstituted Electron-Rich Aromatics and Their Birch Reduction
James B. Hendrickson and P. Myshkin DeCapite
J. Org. Chem., 50, 2112-2115 (1985).


Methylthiomethylation with DMSO-(CF3CO)2O-SnCl4

Alkylation of Aromatic Compounds with Pummerer Rearrangement Intermediates. Application to the Preparation of Methyl-Aryl Compounds
I. K. Stamos
Tetrahedron Lett., 26(23), 2787-2788 (1985).


Methylthioalkylation with MeS(O)CHR-SMe or TolSO2CHR-SMe - AlCl3.

Novel and Effective Methods for alpha-Thioalkylation of Aromatic Compounds
Y. Torisawa, A. Satoh, S. Ikegami
Tetrahedron Lett., 29(14), 1729-1732 (1988).


Amides are N-methylated by 1) methylthiomethylation (MTM-Cl/ CF3COOH); 2) desulfurization with Raney Ni.

Simple Methylation of Amides
L. Bernardi, R. de Castiglione, and U. Scarponi
J. Chem. Soc., Chem. Commun., 1975, 320-321.


Intramolecular ring alkylsulfenylation with RSSO2Me - AlCl3 in MeNO2.

Improved Syntheses of Benzo-1,4-dithiin and of Benzo-1,4-oxathiin
J. H. Verheijen, H. Kloosterziel
Synthesis, 1975, 451-452.

Rhodium:
The ortho-Methylthiomethylation of Phenols
P.G. Gassman & D.R. Amick
Tetrahedron Letters, No. 11, pp 889-892 (1974) (https://www.thevespiary.org/rhodium/Rhodium/pdf/ortho-methylthiomethylation.ncs-r2s.pdf)

Summary:
Treatment of phenols with an azasulfonium salt prepared from NCS and (CH3)2S at -25°C, followed by triethylamine gives an ylide, which via a complex cyclic rearrangement yields the corresponding o-methylthiomethyl-phenol in 60-70% overall yield on most substrates.
Methylthiomethyl functions easily undergoes reductive desulfurization with Raney-Ni to give methylbenzenes, so this is a viable route to ortho-methylphenols from phenols in two steps.




Excerpt from the article:
We now wish to report a new method for the synthesis of ortho-alkylated phenols from phenols and dialkyl sulfides. The process involves the reaction of N-chlorosuccinimide (3) with a dialkyl sulfide, to give an azasulfonium salt, 5. When phenol is added to a methylene chloride solution of an intermediate is formed, which has been assigned structure 6 on the basis of mechanistic considerations. Treatment of 6 with a base, such as triethylamine, should give the ylide 7, which would be expected to yield the dienone 8 via a Sommelet-Hauser type rearrangement. Proton transfer and accompanying rearomatization would then produce the o-methylthiomethylphenol, 2.

General procedure:
0.40 mole of N-chlorosuccinimide (3) in 2 liters of dry methylene chloride was combined with 0.50 mole of dialkyl sulfide at 0 to -5°C to give the azasulfonium salt, 5. The temperature was lowered to -25°C and 0.8 mole of a suitable phenol, 1, in 100 ml of methylene chloride was added over a 15-min period. The reaction mixture was stirred for 30 min, 0.41 mole of triethylamine was added at -25°C, and the reaction mixture was allowed to warm slowly to room temperature. Removal of the solvent and salts, and distillation of the residue gave the o-methylthiomethylphenol, 2, and also permitted recovery of any unreacted phenol.   

demorol:
Superelectrophilic Methylthiomethylation of Aromatics with Chloromethyl Methyl Sulfide/Aluminum Chloride (MeSCH2Cl:2 AlCl3) Reagent
George A. Olah, Qi Wang, Gebhard Neyer
Synthesis 1994, 3, 276-278




Abstract - Effective methylthiomethylation of aromatics was achieved by using chloromethyl methyl sulfide /aluminum chloride (MeSCH2Cl:2 AlCl3) as the alkylating agent. Excess aluminum chloride activates the thiocarboxonium ion intermediate by coordinating with sulfur and thus disminishes back donation of "electron density" into the carbocationic center, rendering it a superelectrophilic methylthiomethylating agent.


Methylthiomethylation of Aromatics; Typical Procedure:
To a stirred mixture of AlCl3 (2.7 g, 20 mmol) and the corresponding arene (10.2 mmol) was added chloromethyl methyl sulfide (1.01 g, 95%, 10 mmol) in CH2Cl2 (25 mL) at 0°C. After stirring at 0°C for 30 min, the mixture was quenched with ice, and extracted with CH2Cl2 (3×20 mL), the combined organic layers were washed sequentially with water, aq NaHCO3, brine, and dried (CaCl2). After filtration and evaporation of the solvent, the products were obtained by distillation (Table 1).

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