Butyrolactone-preparation process

Details Butyrolactone-preparation process Butyrolactone-preparation process

1998-02-12

1999-10-05

Trinh, Ba K.

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

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

549323, C07D30733

Patent

active

059627000

DESCRIPTION:

BRIEF SUMMARY
The invention relates to a process for the preparation of butyrolactones by reaction of acetylenes with carbon monoxide and hydrogen gas or hydrogen formed in situ in the presence of transition metal catalysts via the stage of the corresponding 2-(5H)-furanones, and to an improved process for the preparation of these furanones, which can also be converted into the butyrolactones in a separate hydrogenation step.
.gamma.-Butyrolactone is an important product of the chemical industry. It is used as an intermediate for the preparation of pyrrolidone and its derivatives and also as a solvent.
Butyrolactone is prepared industrially by various multistage processes. The dehydrocyclization of 1,4-butanediol thus leads in high yields to butyrolactone. Alternatively, maleic anhydride can be partially hydrogenated to give butyrolactone. Both starting compounds for the preparation of .gamma.-butyrolactone are only accessible from basic chemicals in multistage processes (Weissermel, Arpe, Industrielle Chemie, p. 97).
The reaction of alkynes and CO in the presence of rhodium catalysts has been described for the preparation of unsaturated 2(5H)-furanones, which are used as intermediates for the preparation of drugs (Joh et al., Inorg. Chim. Acta, 220 (1994) 45; Organometallics 10 (1991) 2493; JP-A 88/68580).
It is an object of the present invention to provide a process which, starting from simple basic chemicals such as alkynes and CO, leads in one step or at most 2 steps to butyrolactones. It is furthermore an object of the present invention to provide butyrolactones substituted in the 3- or 4-position, which are of interest as intermediates in fine product chemistry.
It is finally an object to improve the process for the preparation of 2-(5H)-furanones, from which in a second step butyrolactones can be prepared by hydrogenation, such that industrial preparation is possible.
We have found that this object is achieved by a process for the preparation of butyrolactones of the formula I ##STR2## where the substituents R.sup.1 and R.sup.2 are hydrogen, alkyl or hydroxyalkyl groups preferably having 1 to 8 C atoms or aryl and trialkylsilyl groups, if appropriate carrying inert substituents, by reacting an alkyne of the formula II monoxide and hydrogen gas or with hydrogen formed in situ in the presence of a transition metal catalyst at elevated pressure and elevated temperature. Hydrogen formed in situ is in this case advantageously generated using CO and water by means of the water-gas equilibrium CO+H.sub.2 O.apprxeq.H.sub.2 +CO.sub.2.
It was surprising here that it is possible to prepare butyrolactones in one step, ie. that the 2-(5H)-furanones formed as intermediates react further under the reaction conditions to give the butyrolactones.
Alternatively, the preparation, which is known per se, of 2-(5H)-furanones of the formula I ##STR3## where the substituents R.sup.1 and R.sup.2 are hydrogen, alkyl or hydroxyalkyl groups, or aryl or trialkylsilyl groups, if appropriate carrying inert substituents, can also be improved by reacting alkynes of the formula II monoxide and hydrogen formed in situ from carbon monoxide and water or with hydrogen gas in the presence of transition metal catalysts, amine bases and halides at 60-140.degree. C. and total pressures of 20-350 bar.
Although Takashi Joh et al. in Organometallics 1991, 10, p. 2494 left column, first paragraph states: "The use of hydrogen gas as a hydrogen source in place of water gave hydroxymethylated product 4 and stilbene 5, and no furanone was obtained", it was surprisingly further found that furanones of the abovementioned formula I are obtained even without the necessity of halide addition if the reaction is carried out at a hydrogen partial pressure of more than 50 bar.
It is then also possible to separately hydrogenate the 2-(5H)-furanones thus obtained in markedly higher space-time yields in a second step. The hydrogenation can in this case be carried out continuously in a manner known per se or in a batch procedure using hydrogenation catalysts known per se, eg

REFERENCES:
Chemical Abstracts, vol. 121, Aug. 29, 1994, No. 9.
Derwent JP 63068580, 1988.
Organometallics, 1991, 10, 2493-2498.
Inorganica Chimica Acta, 220 (1994), 45-53.
Industrielle Organische Chemie, Verlag Chemie, 1978.

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