Preparation of 1,2-butylene oxide

Details Preparation of 1,2-butylene oxide Preparation of 1,2-butylene oxide

1996-09-09

1999-02-09

Trinh, Ba K.

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

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

549513, C07D30102

Patent

active

058697071

DESCRIPTION:

BRIEF SUMMARY
DESCRIPTION

This application is a 0371 of PCT/EP95/00656, dated Feb. 23, 1995.
The present invention relates to a process for preparing 1,2-butylene oxide by catalytic hydrogenation of vinyloxirane over a heterogeneous catalyst.
The catalytic hydrogenation of vinyloxirane is known.
According to U.S. Pat. No. 2,561,984, the hydrogenation of vinyloxirane in ethanol over a palladium/activated carbon catalyst at 25.degree. C./2 bar gives n-butyraldehyde as main product after a reaction time of 3 hours. In contrast, Raney nickel as catalyst results in formation of mainly n-butanol at 25.degree. C. and 2 bar after a reaction time of 1.5 hours. Nothing is recorded about the formation of butylene oxide.
A paper by Aizikovich et al. (J. Gen. Chem. USSR, 28 (1958) 3076) describes the catalytic hydrogenation of vinyloxirane in methanol or ethanol over platinum, palladium and Raney nickel catalysts. A supported palladium catalyst (1.8% by weight of palladium on calcium carbonate) results in formation of mainly n-butanol at 15.degree. C./1 bar. In this document, the most important intermediate in the hydrogenation is regarded as crotyl alcohol, although the formation of n-butyraldehyde is also observed. In this paper too, there is no reference to the formation of butylene oxide.
In U.S. Pat. No. 5,077,418 and U.S. Pat. No. 5,117,013 it is reported that the hydrogenation of vinyloxirane solutions over palladium-containing catalysts gives n-butyraldehyde as main product. Thus, hydrogenation of vinyloxirane together with tetrahydrofuran as solvent over a palladium/activated carbon catalyst (5% by weight of palladium on activated carbon) at from 50.degree. to 55.degree. C. and a pressure of 3.5 bar gives, after a reaction time of 3 hours, a hydrogenation product containing 55% of n-butyraldehyde, only 27% of butylene oxide and 9% of n-butanol.
If the hydrogenation is carried out over supported catalysts containing palladium on aluminum oxide (5% Pd/Al.sub.2 O.sub.3), only traces of butylene oxide are formed after a reaction time of 6 hours at from 25.degree. to 55.degree. C. and a pressure of 3.5 bar or after a reaction time of 4 hours at 100.degree. C. and a pressure of 20.7 bar. Quantitative conversion gives n-butyraldehyde as main product at a selectivity of 87% or 78%.
In addition, the hydrogenation of vinyloxirane over Raney nickel as hydrogenation catalyst at 50.degree. C. and 3.5 bar is described, with 58% of n-butanol being formed as main product. The yield of butylene oxide is, at 41%, low. In the hydrogenation of vinyloxirane over a supported platinum catalyst (1% by weight of Pt/Al.sub.2 O.sub.3) at 100.degree. C. and a hydrogen pressure of 20.7 bar, only 40% of butylene oxide together with 23% of n-butanol, 24% of various butenols, 5% of crotonaldehyde and 3% of n-butyraldehyde are found for complete conversion after a reaction time of 4.6 hours. Other platinum-containing catalysts give even lower butylene oxide yields.
Furthermore, U.S. Pat. No. 5,077,418 and U.S. Pat. No. 5,117,013 teach that high butylene oxide yields are only obtained using rhodium-containing catalysts. Various supported rhodium catalysts (5% by weight of rhodium on activated carbon; 5% by weight of rhodium on aluminum oxide), which have a high content of the expensive noble metal rhodium, or hydrated rhodium oxide (Rh.sub.2 O.sub.3.xH.sub.2 O) give butylene oxide contents of 60-93% in the hydrogenation of vinyloxirane solutions. A disadvantage of this process is the low space-time yield based on the amount of rhodium used. Thus, the space-time yield in Example 2 of U.S. Pat. No. 5,117,013 is only 119 kg of 1,2-butylene oxide/kg Rh*h.
Neftekhimiya 33 (1993) 131 describes the hydrogenation of vinyloxirane over catalysts containing nickel, palladium and copper. Using Raney nickel or nickel on kieselguhr as catalyst, the hydrogenation proceeds primarily with opening of the epoxide ring which leads to the predominant formation of 1-butenols and n-butanol. The yields of butylene oxide are low. For example, Raney nickel with methanol as solvent

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Neftekhimiya, 33(2), (1993), p. 313.
Catalytic Hydrogenation of Vinylethylene Oxides, Aizikovich et al., J. Gen Chem USSR 28 3076 (1958).
Balbolov, E. et al, J. Mol. Catal., 1991, 69, pp. 95-103.

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