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Title: Preparation of dialkyl oxalates by CO-coupling

Abstract

Preparation of dialkyl oxalates by CO-coupling of carbon monoxide and alcohols (as their nitrite esters) was investigated since oxalic esters may become raw materials for ethylene glycol. Liquid-phase reaction of n-butyl nitrite (40.3-332 mmole) with carbon monoxide over 0.2 g of 2Vertical Bar3< palladium/carbon at 50 atm CO pressure in a bubbling column for 0.5 or 1.0 hr at 70/sup 0/ or 90/sup 0/C gave 15.4-32.6 mmole yields of di-n-butyl oxalate. The nearly stoichiometric amount of nitrogen oxide liberated reacted with alcohol (n-butanol) and oxygen (at 4-5 atm) to eliminate the loss of nitrite. The reaction had better selectivity at the lower temperature and higher total pressure. The apparent activation energy was 3-12 kcal/mole at 35/sup 0/-110/sup 0/C, and the reaction rate was nearly proportional to the amount of catalyst. A variety of palladium(II) salts were also effective, but other Group VIII metals were not. Vapor-phase reaction of carbon monoxide, nitric oxide, methyl nitrite, and small amounts of methanol and water over 18.5 g of 0.96Vertical Bar3< palladium on carbon gave 97-98Vertical Bar3< selectivity under optimum conditions.

Authors:
; ; ; ;
Publication Date:
Research Org.:
Ube Ind. Ltd.
OSTI Identifier:
6949749
Alternate Identifier(s):
OSTI ID: 6949749
Report Number(s):
CONF-790415-
Journal ID: CODEN: ACPCA
Resource Type:
Conference
Journal Name:
Am. Chem. Soc., Div. Pet. Chem., Prepr.; (United States)
Additional Journal Information:
Journal Volume: 24:1; Conference: 177. national meeting of the American Chemical Society, Honolulu, HI, USA, 1 Apr 1979
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CARBON; CATALYTIC EFFECTS; CARBON MONOXIDE; CHEMICAL REACTIONS; NITRIC ACID ESTERS; OXALIC ACID ESTERS; CHEMICAL PREPARATION; PALLADIUM; ACTIVATION ENERGY; ALCOHOLS; CATALYSTS; EXPERIMENTAL DATA; METALS; PHASE TRANSFORMATIONS; PRESSURE EFFECTS; REACTION KINETICS; TEMPERATURE EFFECTS; CARBON COMPOUNDS; CARBON OXIDES; CARBOXYLIC ACID ESTERS; CHALCOGENIDES; DATA; ELEMENTS; ENERGY; ESTERS; HYDROXY COMPOUNDS; INFORMATION; KINETICS; NONMETALS; NUMERICAL DATA; ORGANIC COMPOUNDS; OXIDES; OXYGEN COMPOUNDS; PLATINUM METALS; SYNTHESIS; TRANSITION ELEMENTS 400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)

Citation Formats

Nishimura, K., Uchiumi, S., Fujii, K., Nishihira, K., and Itatani, H. Preparation of dialkyl oxalates by CO-coupling. United States: N. p., 1979. Web.
Nishimura, K., Uchiumi, S., Fujii, K., Nishihira, K., & Itatani, H. Preparation of dialkyl oxalates by CO-coupling. United States.
Nishimura, K., Uchiumi, S., Fujii, K., Nishihira, K., and Itatani, H. Thu . "Preparation of dialkyl oxalates by CO-coupling". United States.
@article{osti_6949749,
title = {Preparation of dialkyl oxalates by CO-coupling},
author = {Nishimura, K. and Uchiumi, S. and Fujii, K. and Nishihira, K. and Itatani, H.},
abstractNote = {Preparation of dialkyl oxalates by CO-coupling of carbon monoxide and alcohols (as their nitrite esters) was investigated since oxalic esters may become raw materials for ethylene glycol. Liquid-phase reaction of n-butyl nitrite (40.3-332 mmole) with carbon monoxide over 0.2 g of 2Vertical Bar3< palladium/carbon at 50 atm CO pressure in a bubbling column for 0.5 or 1.0 hr at 70/sup 0/ or 90/sup 0/C gave 15.4-32.6 mmole yields of di-n-butyl oxalate. The nearly stoichiometric amount of nitrogen oxide liberated reacted with alcohol (n-butanol) and oxygen (at 4-5 atm) to eliminate the loss of nitrite. The reaction had better selectivity at the lower temperature and higher total pressure. The apparent activation energy was 3-12 kcal/mole at 35/sup 0/-110/sup 0/C, and the reaction rate was nearly proportional to the amount of catalyst. A variety of palladium(II) salts were also effective, but other Group VIII metals were not. Vapor-phase reaction of carbon monoxide, nitric oxide, methyl nitrite, and small amounts of methanol and water over 18.5 g of 0.96Vertical Bar3< palladium on carbon gave 97-98Vertical Bar3< selectivity under optimum conditions.},
doi = {},
journal = {Am. Chem. Soc., Div. Pet. Chem., Prepr.; (United States)},
number = ,
volume = 24:1,
place = {United States},
year = {1979},
month = {2}
}

Conference:
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