Carboxylic acid derivative preparation process

Details Carboxylic acid derivative preparation process Carboxylic acid derivative preparation process

1997-11-10

1999-12-14

Carr, Deborah D

Organic compounds -- part of the class 532-570 series

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

546257, 546262, 546264, 5462794, 554 68, 554157, 564126, 564130, 560179, 560215, C07D21356

Patent

active

060020105

DESCRIPTION:

BRIEF SUMMARY
BACKGROUND OF THE INVENTION

1. Field of the Invention
The invention relates to a process for preparing carboxylic acid derivatives from carbonitriles and alcohols at elevated temperatures on titanium oxide catalysts.
2. Description of the Related Art
DE-A 27 14 767 discloses a process for preparing carboxylic acid derivatives by gas-phase reaction of nitrites with alcohols and water on solid, metal-containing catalysts such as copper, zinc, chromium, bismuth, manganese, iron, nickel, cadmium on carriers such as Al.sub.2 O.sub.3, SiO.sub.2, ZrO.sub.2 or TiO.sub.2. Dehydration and etherification are found as side reactions.
EP-A 412 310, for example, discloses a process for preparing carboxamides by hydration of nitrites with water on manganese-containing catalysts, which can subsequently be reacted with alcohols by acid catalysis, in the presence of metal salts, eg. as disclosed in U.S. Pat. No. 4,613,684, or in the gas phase on solid catalysts, eg. as disclosed in EP-A 561 614, or with formic ester resulting in formamide formation, eg. as disclosed in EP-A 392 361, on metal oxides to give the carboxylic acid derivatives.
The disadvantages for industrial application are the two stages and the formation of byproducts, such as production of salt or formamide formation.
DE-A 43 39 648 discloses a process for preparing caprolactam (a cyclic amide) by reacting aminocapronitrile with water in an ethanolic solution on a titanium oxide catalyst.


BRIEF SUMMARY OF THE INVENTION

We have found that the above mentioned disadvantages of the prior art processes are overcome by a novel and improved process for preparing carboxylic acid derivatives of the formula I ##STR2## where X is OR.sup.2 or NH.sub.2, C.sub.3 -C.sub.12 -cycloalkyl, C.sub.4 -C.sub.12 -alkylcycloalkyl, C.sub.4 -C.sub.12 -cycloalkylalkyl, C.sub.5 -C.sub.20 -alkylcycloalkylalkyl, aryl, C.sub.7 -C.sub.20 -aralkyl, C.sub.7 -C.sub.20 -alkylaryl, a heteroaliphatic or heteroaromatic ring with 5 to 8 carbon atoms and III under from 0.1 to 350 bar in the presence of a heterogeneous catalyst, wherein the reaction is carried out in liquid phase.


DETAILED DESCRIPTION OF THE INVENTION

The process according to the invention can be carried out in the following way:
The carbonitrile II can be brought into contact with an alcohol III, preferably dissolved in the alcohol III, at from 50 to 300.degree. C., preferably 100 to 290.degree. C., particularly preferably 140 to 270.degree. C., under from 0.1 to 350 bar, preferably 1 to 200 bar, particularly preferably 30 to 140 bar, in liquid phase with a titanium oxide catalyst, as a rule in pressure-stable apparatus such as autoclaves and tubular reactors, preferably tubular reactors. The result is, as a rule, an alcoholic solution of the carboxylic ester and of the carboxamide I, from which the carboxylic ester and the carboxamide I can be obtained by conventional methods, for example by distillation, extraction or crystallization.
The carboxamide can be returned to the reactor together with fresh carbonitrile II.
The reaction of solid carbonitriles II or solid alcohols III can be carried out in inert solvents, for example in ethers, preferably ethers with 2 to 20 carbon atoms, particularly preferably ethers with 4 to 12 carbon atoms, such as diethyl ether, methyl tert-butyl ether or tetrahydrofuran, hydrocarbons, preferably hydrocarbons with 5 to 30 carbon atoms, particularly preferably hydrocarbons with 5 to 12 carbon atoms, such as toluene and xylene or, advantageously, in the appropriate carboxylic ester I.
Examples of suitable heterogeneous catalysts are acidic, basic or amphoteric oxides of elements of groups IIA, IIIA, IVA of the Periodic Table of the Elements, such as calcium oxide, magnesium oxide, boron oxide, aluminum oxide, tin oxide or silicon dioxide, pyrogenic silica, as silica gel, kieselguhr, quartz, furthermore oxides of metals of groups IIB, IIIB, IVB, VB, VIB and VIIB of the Periodic Table of the Elements, such as titanium oxide, especially titanium dioxide, eg. amorphous, as anatase or rutile, zircon

REFERENCES:
patent: 3957804 (1976-05-01), Ishioka et al.
patent: 4613684 (1986-09-01), Aayoma et al.
patent: 4987256 (1991-01-01), Ebata et al.
patent: 5103055 (1992-04-01), Cesa
Chem. Abst., vol. 78, No. 5, 1973.

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