Organic compounds -- part of the class 532-570 series – Organic compounds – Oxygen containing
Patent
1997-07-23
1999-04-06
Geist, Gary
Organic compounds -- part of the class 532-570 series
Organic compounds
Oxygen containing
568450, 568904, C07C 4702
Patent
active
058921257
DESCRIPTION:
BRIEF SUMMARY
This is the U.S. National stage application of PCT/EP95/03358 filed Aug. 24, 1995 now WO96/07630 published Mar. 14, 1996.
The present invention relates to a novel process for the preparation of n-butyraldehyde and/or n-butanol and to the use of the n-butyraidehyde synthesized by the process of the invention for the preparation of 2-ethylhexanol. The invention also relates to a process for the preparation of 2-ethylhexanol from n-butyraldehyde.
n-Butyraldehyde and n-butanol are products which are produced on a large scale in the chemical industry and have varied uses. n-Butyraldehyde is produced world-wide in amounts of more than 4 million t/yr and serves inter alia as starting material for the preparation of plasticizer alcohols. n-Butanol is employed on a large scale as solvent, for example for coating compositions.
n-Butyraldehyde is prepared nowadays on an industrial scale virtually exclusively by the hydroformylation of propene, for which purpose various processes are used, which essentially make use of cobalt or rhodium hydroformylation catalysts, (Kirk-Othmer: Encyclopedia of Chemical Technology, 4th Edition, Vol. 4, pp. 741-746, John Wiley & Sons, New York 1992).
n-Butanol is one of the quantitatively most important derivatives of n-butyraldehyde and is obtained therefrom by hydrogenation. Other processes for the preparation of n-butanol, such as the hydrogenation of crotonaldehyde, which is in turn produced by aldol condensation of acetaldehyde, are nowadays merely of historical interest or have only regional significance, such as in the case of the microbiological production of n-butanol by fermention of molasses, (Kirk-Othmer: Encyclopedia of Chemical Technology, 4th Edition, Vol. 4, pp. 694-696: John Wiley Sons, New York 1992). These processes, particularly the hydroformylation of propene, demand high investments, for example, for the construction of high-pressure plant for the cobalt-catalyzed hydroformylation or for the purchase of the expensive rhodium catalyst, the plant required for handling during hydroformylation and for working up the spent rhodium-containing catalyst solution. Furthermore the preparation of n-butyraldehyde by the hydroformylation process requires the presence of a synthesis gas plant for the preparation of the synthesis gas required for the hydroformylation. A further drawback of the process is the unavoidable formation of large quantities of the by-product isobutyraldehyde, which, on account of its restricted possibility of further usage in quantity, has a low economical rating.
1,3-Butadiene is a basic chemical which is produced in large amounts in steam crackers and is isolated, by extraction, from the C.sub.4 cut obtained in the cracker, for example, by means of N-methyl pyrrolidone. Although 1,3-butadiene is available in large amounts and is a very cheap raw material, no industrially usable process has been developed hitherto for the preparation of n-butyraldehyde or n-butanol on the basis of 1,3-butadiene. One reason for this is the tendency of 1,3-butadiene to undergo dimerization and polymerization reactions and the formation of mixtures of 1,2- and 1,4-adducts in addition reactions. The reason for this chemical behavior is the presence of two conjugated double bonds in the 1,3-butadiene molecule (Kirk-Othmer: Encyclopedia of Chemical Technology, 4th Edition, Vol. 4, pp. 676-683, John Wiley & Sons, New York 1992).
U.S. Pat. No. 3,391,192 discloses that amines react with 1,3-butadiene in the presence of alkali metal amides to form the corresponding allyl amines. Falk at al (J. Org. Chem. 37, 4243 (1972)) investigated the lithium amide-catalyzed additon of amines to butadiene in relation to the solvent and the amine. Kanuno and Hattori (J. Catal. 85 (1984) 509) describe the catalyzed reaction of butadiene with amines using solid base catalysts such as MgO or CaO. In their experiments, the reaction mixture is passed through a circulated gas reactor over a fixed bed under a total pressure of 100 torr. According to U.S. Pat. No. 4,675,307, strongly basic hydrotalcite
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Kanand Jurgen
Paciello Rocco
Roper Michael
Thome Alfred
BASF - Aktiengesellschaft
Geist Gary
Padmanabhan Sreeni
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