1992 Fiscal Year Final Research Report Summary
Reductive carbonylation of nitroaromatic compounds
| Project/Area Number |
03555176
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| Research Category |
Grant-in-Aid for Developmental Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Research Field |
有機工業化学
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| Research Institution | Nagoya University |
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Principal Investigator |
IZUMI Yusuke Nagoya University, Department of Applied Chemistry, Professor, Dr., 工学部, 教授 (00115528)
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| Co-Investigator(Kenkyū-buntansha) |
加藤 祥三 徳山曹達株式会社, つくば研究所, 主幹研究員
URABE Kazuo Nagoya University, Department of Applied Chemistry, Assistant Professor, Dr., 工学部, 助手 (60092540)
KATOH Shozo Tokuyama Soda Co.Ltd., Tsukuba Research Center, Senior Chief Researcher, Dr.
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| Project Period (FY) |
1991 – 1992
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| Keywords | Nitrobenzene / Carbonylation / Palladium / Heteropolyacids / Urethane synthesis / Isocyanate synthesis |
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| Research Abstract |
The Keggin-type heteropolyanion containing Mo or V as addenda atoms, such as H_3PMo_<12>O_<40> and H_4PVMo_<11>O_<40>, showed an appreciable promoting effect on the catalysis of PdCl_2 in the reductive carbonylation of nitrobenzene to form methyl N-phenylcarbamate in the presence of methanol in a moderately polar solvent such as 1,2- dimethoxyethane at 130 - 170ﾟC under an initial CO pressure of 11 - 41 atm. The catalyst was recovered and reused to give the total Pd turnover of 168. Heteropolyanion partially reduced was effective for modifying Pd(II)presumably as a basic macroligand.
As for the synthesis of phenylisocyanate in the absence of alcohol, a catalyst system of PdCl_2-H_3PMo_<12>O_<40> gave the best yield when used in acetonitrile solvent at 170ﾟC under an initial CO pressure of 41 atm.
The palladium-heteropolyanion systems may thus be expected as completely inorganic, practical catalysts for the reductive carbonylation of nitroaromatic compounds.
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