Synthesis and Reactions of 2, 6-Dimethoxyphenylthio Derivatives

2, 6-二甲氧基苯硫基衍生物的合成与反应

• 批准号: 02650629
• 负责人: WADA Masanori
• 金额: $ 1.09万
• 依托单位: Tottori University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1990
• 资助国家: 日本
• 起止时间: 1990 至 1991
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-02650629/
• 关键词: 2, 6-Dimethoxybenzenethiol; 2, 6-Dimethoxyphenylthio derivatives; Silver (I) complex; Trigonal prismatic structure; 2, 6-Dimethoxybenzeneselenol; 2, 6-Dimethoxybenzenetellurol; Bis (2.6-dimethoxyphenyl) dimethyltin; 1-Halo-2, 6-dimethoxybenzene; 1

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.

本文报道了一种简便的方法，合成了无色无臭结晶的2.6-二甲氧基苯乙胺PHISH[PHI=2.6-（MeO）_2C_6H_3]。还合成了2，6-二甲氧基苯硫基衍生物，如二硫化物PHISSPHI、不对称二芳基硫化物PHISR、二硫醚PHIS（CH_2）_nSPHI。锍盐[PHIRR'S] ClO_4。亚砜PHI_2SO和砜PHI_2SO_2。二硫醚PHISCH_2CH_2SPHI与高氯酸银形成2：3的配合物。晶体结构表明，两个Ag^+离子通过一个螯合（OSSO）配体和一个桥联（OS）配体形成六配位的三角棱柱结构。在氯化锂存在下，由2.6-二甲氧基苯基锂和单质硒合成了2.6-二甲氧基苯硒烯醇PHISeH，该化合物也是一种无气味的晶体。还得到了一些2.6-二乙氧基苯硒基衍生物，如PHISePHI，PHISeSePHI，PHISeMe，PHISeCH_2CH_2CN和PHISe（CH_2）_nSePHI（n= 1-4）。2.6-还将二甲氧基苯碲酚PHITeH制备为晶体（mp ca.以2，6-二甲氧基苯基锂和二甲基二氯化锡或二甲基硫化锡为原料，合成了双（2，6-二甲氧基苯基）二甲基锡Me_2PHI_2Sn。该化合物与N-氯代琥珀酰亚胺和N-溴代琥珀酰亚胺在甲醇中反应，分别得到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。

项目成果

M.Wada,K.Kajihara,K.Nishimura,K.Tenma,T.Morikawa,and T.Erabi: "2,6-Dimethoxybenzenethiol,an Odorless Crystalline Thiol,and its Derivatives" Bulletin of the Chemical Society of Japan.

M.Wada、K.Kajihara、K.Nishimura、K.Tenma、T.Morikawa 和 T.Erabi：“2,6-二甲氧基苯硫醇，一种无味结晶硫醇及其衍生物”日本化学会通报。

M. Wada, K. Tenma, K. Kajihara, T. Erabi, S. Ikemizu, Y. Takemoto, and T. Tsukihara: "Synthesis and Crystal Structure of 2 : 3 Complex of AgCIO_4 and Bis (2, 6-dimethoxyphenylthio) ethane" Chemistry Express. 6. 301-304 (1991)

M. Wada、K. Tenma、K. Kajihara、T. Erabi、S. Ikemizu、Y. Takemoto 和 T. Tsukihara：“AgCIO_4 和双（2, 6-二甲氧基苯硫基）2:3 复合物的合成和晶体结构

M.Wada,K.Tenma,K.Kajihara,T.Erabi,S.Ikemizu,Y.Takemoto,and T.Tsukihara: "Synthesis and Crystal Structure of 2:3 Complex of AgClO_4 and Bis(2,6-dimethoxyphenylthio)ethane" Chemistry Express. 6. 301-304 (1991)

M.Wada,K.Tenma,K.Kajihara,T.Erabi,S.Ikemizu,Y.Takemoto,and T.Tsukihara:“AgClO_4和双(2,6-二甲氧基苯硫基)2:3配合物的合成和晶体结构

M.Wada,K.Kajihara,T.Morikawa,and T.Erabi: "2,6-Dimethoxybenzeneselenol,a Crystalline Selenol with Littele Odor" Chemistry Express. 6. 875-878 (1991)

M.Wada、K.Kajihara、T.Morikawa 和 T.Erabi：“2,6-二甲氧基苯硒醇，一种具有轻微气味的结晶硒醇”化学快报。

M.Wada,H.Wakamori,A.Hiraiwa,and T.Erabi: "Selective Preparation of 1-Halo-2,6-dimethoxybenzenes from Bis(2,6-dimethoxyphenyl)dimethyltin" Bulletin of the Chemical Society of Japan. 65. (1992)

M.Wada、H.Wakamori、A.Hiraiwa 和​​ T.Erabi：“从双（2,6-二甲氧基苯基）二甲基锡中选择性制备 1-卤代-2,6-二甲氧基苯”日本化学会通报。