Synthesis and Reactions of 2, 6-Dimethoxyphenylthio Derivatives

建立了一种制备2.6-二甲氧基苯硫醇PHISH[PHI=2.6-(MeO)_2C_6H_3]的简便方法，该方法具有绝对的气味和结晶性。还制备了2,6 -二甲氧基苯基硫衍生物，如二硫化物phisphi、不对称二芳基硫化物phispr、二硫醚phisphi (CH_2)_nSPHI。锍盐(PHIRR) CIO_4。亚砜PHI_2SO_2和砜PHI_2SO_2。这些衍生物也是结晶性和无味的。双硫醚PHISCH_2CH_2SPHI与高氯酸银形成2∶3络合物。晶体结构表明，在螯合（OSSO）配体和桥接（OS）配体的作用下，两个Ag +离子呈六配位结构，具有不同寻常的三角棱柱状结构。在氯化锂存在下，以2.6-二甲氧基苯基锂和单质硒为原料，制备了具有较低气味的2.6-二甲氧基苯烯醇PHISeH。另外还得到了一些2.6-二乙氧基苯基硒基衍生物PHISePHI、PHISeSePHI、PHISeMe、PHISeCH_2CH_2CN和PHISe(CH_2)_nSePHI （n= 1-4）。以2.6-二甲氧基苯基锂和二氯化二甲基锡或硫化二甲基锡为原料，制备了双（2.6-二甲氧基苯基）二甲基锡Me_2PHI_2Sn。该化合物与n -氯丁二酰亚胺和n -溴丁二酰亚胺在甲醇中反应，分别生成1-氯-2.6-二甲氧基苯和1-溴-2.6-二甲氧基苯。在硫化钾存在下与碘反应得到1-碘-2.6-二甲氧基苯和二甲基硫化锡。

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.