Functionalization of Methylaromatic Hydrocarbons
| Project/Area Number |
03650668
|
|---|
| Research Category |
Grant-in-Aid for General Scientific Research (C)
|
| Allocation Type | Single-year Grants |
|---|
| Research Field |
有機工業化学
|
|---|
| Research Institution | The University of Tokyo |
|---|
Principal Investigator |
FUTAMURA Shigeru The Univ. of Tokyo, RCAST, Lecturer, 先端科学技術研究センター, 講師 (60165446)
|
|---|
| Project Period (FY) |
1991 – 1992
|
| Project Status |
Completed (Fiscal Year 1992)
|
| Budget Amount *help |
¥1,600,000 (Direct Cost: ¥1,600,000)
Fiscal Year 1992: ¥400,000 (Direct Cost: ¥400,000)
Fiscal Year 1991: ¥1,200,000 (Direct Cost: ¥1,200,000)
|
|---|
| Keywords | Dimethylaromatic hydrocarbons / Photobromination / Bis(bromomethyl)aromatics / Hydrolysis / Bis(hydroxymethyl)aromatics / Tetrabutylammonium periodate / Oxidation / Aromatic dialdehydes / メチル芳香族炭化水素 / 照射光の波長の影響 / 溶媒効果 / (ブロモメチル)メチル芳香族化合物 |
|---|
| Research Abstract |
Functionalization of dimethylaromatic hydrocarbons such as 1,4-, 1,8-, 2,3- and 2,6-dimethylnaphtalenes, 4,4' -dimethylbiphenyl and p-xylene was investigated in order to aim at highly selective and convenient syntheses of
1) bis(bromomethyl)aromatics, 2) bis(hydroxymethyl)aromatics and 3) aromatic dialdehydes.
In the synthesis of bis(bromomethyl)aromatics from dimethylaromatic hydrocarbons, visible light irradiation in benzene with N-bromosuccinimide as brominating agent was greatly effective in increasing selectivities of the bis(bromomethyl)aromatics and efficiency of product purification.
Bis(hydroxymethyl)aromatics were produced in good yields by refluxing the bis(bromomethyl)aromatics in strongly basic water in the presence of a phase transfer catalyst like triethylbenzylammonium bromide, whose chemical affinity with the bis(bromomethyl)aromatics could be expected to be high.
Aromatic dialdehydes were produced in good yields in the tetrabutylammonium periodate oxidation of the bis(bromomethyl)aromatics in dioxane. In order to achieve high selectivities of the dialdehydes, it was necessary to add 2.2 mol equivalents of tetrabutylammonium periodate and a bromine trap like anthracene.
The synthetic methods described above are of significance since bis(hydroxymethyl)aromatics and aromatic dialdehydes cannot be synthesized by direct oxidation of dimethylaromatic hydrocarbons.
|
Report
(3 results)
Research Products
(5 results)
