Synthesis and Reactions of 2, 6-Dimethoxyphenylthio Derivatives

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A facile method was established for the preparation of 2.6-dimethoxybenzenethiol PHISH[PHI=2.6-(MeO)_2C_6H_3], which is absolutely odoriess and crystalline. Also prepared were 2, 6-dimethoxyphenylthio derivatives, such as disulfide PHISSPHI, unsymmetric diaryl sulfides PHISR, dithio ethers PHIS(CH_2)_nSPHI. sulfonium salts[PHIRR'S]CIO_4. sulfoxide PHI_2SO, and sulfone PHI_2SO_2. These derivatives also were crystalline and odorless.The dithio ether PHISCH_2CH_2SPHI formed a 2 : 3 complex with silver perchlorate. The crystal structure showed that the two Ag^+ ions were six-coordinated with unusual trigonal prismatic structure by a chelating(OSSO)ligand and a bridging(OS) ligand.2.6-Dimethoxybenzeneselenol PHISeH, which also is crystalline with little odor, was prepared from 2.6-dimethoxyphenyllithium and elemental selenium in the presence of lithium chloride. Some other 2.6-dinethoxyphenylseleno derivatives, such as PHISePHI, PHISeSePHI, PHISeMe, PHISeCH_2CH_2CN, and PHISe(CH_2)_nSePHI (n= 1-4), also were obtained as crystalline compounds. 2.6-Dimethoxybenzenetellurol PHITeH also was prepared as crystals (mp ca. 15ﾟC).Bis(2.6-dimethoxyphenyl)dimethyltin Me_2PHI_2Sn was prepared from 2.6-dimethoxyphenyllithium and dimethyltin dichloride or dimethyltin sulfide. The compound reacted with N-chlorosuccinimide and with N-bromosuccinimide in methanol to afford 1-chloro-2.6-dimethoxybenzene and 1-bromo-2.6-dimethoxybenzene, respectively. A reaction with iodine in the presence of potassium sulfide afforded 1-iodo-2.6-dimethoxybenzene and dimethyltin sulfide.