1991 Fiscal Year Final Research Report Summary
Synthesis and Reactions of 2, 6-Dimethoxyphenylthio Derivatives
| Project/Area Number |
02650629
|
|---|
| Research Category |
Grant-in-Aid for General Scientific Research (C)
|
| Allocation Type | Single-year Grants |
|---|
| Research Field |
Synthetic chemistry
|
|---|
| Research Institution | Tottori University |
|---|
Principal Investigator |
WADA Masanori Tottori University, Faculty of Engineering, Professor, 工学部, 教授 (30029053)
|
|---|
| Co-Investigator(Kenkyū-buntansha) |
ERABI Tatsuo Tottori University, Faculty of Engineering, Associate Professor, 工学部, 助教授 (60032025)
|
|---|
| Project Period (FY) |
1990 – 1991
|
| Keywords | 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 |
|---|
| Research Abstract |
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.
|
