Organic compounds -- part of the class 532-570 series – Organic compounds – Carboxylic acids and salts thereof
Patent
1997-01-13
1998-01-06
Dees, Jose G.
Organic compounds -- part of the class 532-570 series
Organic compounds
Carboxylic acids and salts thereof
562890, 562895, 560233, C07C 5114, C07C 5156, C07C 6738
Patent
active
057056838
DESCRIPTION:
BRIEF SUMMARY
This Application is a 371 of PCT/EP95/02560 filed Jul. 3, 1995.
The present invention relates to an improved process for carbonylating olefins with carbon monoxide in the presence of water, an alcohol or a carboxylic acid and a halogen-free catalyst.
Weissermel et al. describe in Industrielle Organische Chemie, 1978, 2nd edition, Verlag Chemie, p. 132 the carbonylation of olefins by the Reppe process, for example the synthesis of propionic acid from ethylene, carbon monoxide and water in the presence of catalysts. The catalyst used is nickel propionate, which is converted under the reaction conditions into nickel tetracarbonyl. A high conversion of the carbon monoxide is achieved only at high pressures (200-240 bar) and temperatures (270.degree.-320.degree. C.). These reaction conditions require a high technical outlay in the construction of suitable reactors and, owing to the corrosivity of the product under the reaction conditions, special and costly materials of construction.
GB-A 1 063 617 teaches the carbonylation of olefins with nickel and cobalt catalysts in the presence of boric acid. Again high pressures and temperatures are required.
Carbonylations of olefins can be carried out with noble metal catalysts at pressures of about 100 bar. For instance, EP-A 495 547 discloses catalysts consisting of a palladium source and bidentate phosphine ligands. However, catalysts of this type are frequently inactivated after a short reaction time by deposition of metallic palladium; more particularly, the phosphine ligands used are not thermally stable under the desired reaction conditions.
EP-A 329 252 relates to a catalyst system for the carbonylation of olefins, which comprises a ruthenium component and also an oxygen compound of phosphorus, antimony, arsenic, molybdenum or tungsten. However, the activity of such catalysts is low, so that they are little suited for use on an industrial scale.
It is an object of the present invention to provide a process for carbonylating olefins which avoids the abovementioned disadvantages.
We have found that this object is achieved by the above-indicated process, which comprises using a catalyst comprising nickel or a nickel compound and at least one of the metals of the group consisting of chromium, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver and gold, or a compound of these metals.
The following reaction equation illustrates the process of the present invention taking the example of the conversion of ethylene into propionic acid: ##STR1##
Suitable starting materials for the process of the present invention are aliphatic and cycloaliphatic alkenes with, preferably, 2-50, particularly preferably 2-7, carbon atoms. Examples which may be mentioned are ethylene, propylene, isobutene, 1-butene, 2-butene and the isomers of pentene and hexene and also cyclohexene, of which ethylene is preferred.
These olefins are reacted with water to prepare carboxylic acids, with alcohols to prepare carboxylic esters, and with carboxylic acids to prepare carboxylic anhydrides.
The alcohols comprise aliphatic and cycloaliphatic compounds with, preferably, 1-20 carbon atoms, particularly preferably with 1-6 carbon atoms, such as methanol, ethanol, n-propanol, isopropanol, isobutanol, tert-butanol, stearyl alcohol, diols such as ethylene glycol, 1,2-propanediol and 1,6-hexanediol, and also cyclohexanol. If diols are reacted, mono- and diesters may be obtained depending on the chosen stoichiometric ratios, diesters being prepared by employing the diol and the olefin in a molar ratio of about 1:2 and the monoesters being prepared by employing the diol in excess.
Carbonylation of the olefin in the presence of anhydrous carboxylic acids gives carboxylic anhydrides. The carboxylic anhydrides which can be formed are preferably symmetrical, but can also be asymmetrical, depending on the choice of carboxylic acid.
The starting compounds mentioned are reacted with carbon monoxide which can be employed in pure form or diluted with inert gases such as nitro
REFERENCES:
patent: 2658075 (1953-11-01), Reppe et al.
patent: 2768968 (1956-10-01), Reppe et al.
patent: 3717670 (1973-02-01), Schultz
patent: 4431593 (1984-02-01), Jenck
patent: 4625055 (1986-11-01), Rizkalla
Hohn Arthur
Hupfer Leopold
Lippert Ferdinand
Schafer Martin
BASF - Aktiengesellschaft
Dees Jos,e G.
Keys Rosalynd A.
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