Process for the selective hydration of vinyloxirane to 1,2-butyl

Details Process for the selective hydration of vinyloxirane to 1,2-butyl Process for the selective hydration of vinyloxirane to 1,2-butyl

1998-07-15

1999-07-27

Trinh, Ba K.

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

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

C07D30102

Patent

active

059292610

DESCRIPTION:

BRIEF SUMMARY
The present invention relates to an improved process for preparing 1,2-butylene oxide by catalytic hydrogenation of vinyloxirane over heterogeneous catalysts.
The hydrogenation of vinyloxirane by heterogeneous catalysis is known.
According to U.S. Pat. No. 2,561,984, the hydrogenation of vinyloxirane in ethanol over a palladium on activated carbon catalyst at 25.degree. C./2 bar gives n-butyraldehyde as main product after a reaction time of 3 h. By contrast, Raney nickel catalyst at 25.degree. C. and 2 bar chiefly produces n-butanol after a reaction time of 1.5 h. Nothing is reported about the formation of 1,2-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) at 15.degree. C./1 bar results mainly in the formation of n-butanol. Crotyl alcohol is reported as the most important intermediate compound of the hydrogenation, although the formation of n-butyraldehyde is observed as well. Again there is no mention of the formation of 1,2-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. For instance, hydrogenation of vinyloxirane together with tetrahydrofuran as solvent over a supported palladium catalyst (5% by weight of palladium on activated carbon) at a temperature of from 50 to 55.degree. C. and a pressure of 3.5 bar gives after a reaction time of 3 h a hydrogenation effluent comprising 55% of n-butyraldehyde, only 27% of 1,2-butylene oxide and 9% of n-butanol. If the hydrogenation is carried out over alumina-supported palladium catalysts (5% of Pd/Al.sub.2 O.sub.3), only traces of 1,2-butylene oxide are formed after 6 hours at from 25 to 55.degree. C. and a pressure of 3.5 bar or after 4 hours at 100.degree. C. and 20.7 bar. n-Butyraldehyde is formed as the main product with a selectivity of, respectively, 87% or 78% and quantitative conversion. The two U.S. applications also describe the hydrogenation of vinyloxirane over Raney nickel, when n-butanol is formed as the main product. The 1,2-butylene oxide yield is relatively low at 41%. 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 20.7 bar hydrogen pressure produces after 4.6 h and complete conversion only 40% of 1,2-butylene oxide and also 23% of n-butanol, 24% of butanols, 5% of crotonaldehyde and 3% of n-butyraldehyde. Other platinum catalysts give even lower 1,2-butylene oxide yields.
U.S. Pat. No. 5,077,418 and U.S. Pat. No. 5,117,013 further teach that high 1,2-butylene oxide yields are obtained only with rhodium catalysts. The hydrogenation of vinyloxirane solutions with various supported rhodium catalysts (5% by weight of rhodium on activated carbon, 5% by weight of rhodium on alumina) which, however, have a high content of the costly noble metal rhodium, or hydrated rhodium oxide (Rh.sub.2 O.sub.3 *.times.H.sub.2 O) gives 1,2-butylene oxide contents of 60 to 93%. The disadvantage of this process is the low space-time yield based on the rhodium used. For instance, the space-time yield in Example 2 of U.S. Pat. No. 5,117,013 is only 110 kg of 1,2-butylene oxide/kg of Rh * h.
Neftekhimiya 33 (1993) 131 describes the hydrogenation of vinyloxirane over nickel, palladium and copper catalysts. Using Raney nickel or nickel on kieselguhr as catalyst, the hydrogenation proceeds mainly with cleavage of the epoxide ring, which leads to predominant formation of 1-butenols and n-butanol. The yields of butylene oxide are low. For instance, a hydrogenation trial in methanol at 20.degree. C./60 bar hydrogen pressure over a Raney nickel catalyst pretreated with isopropanol, nicotinic acid, pyridine and morpholine gave a butylene oxide selectivity of only 37% at 89% conversion. Palladium cat

REFERENCES:
patent: 2561984 (1951-07-01), Hillyer et al.
patent: 4897489 (1990-01-01), Monnier et al.
patent: 5077418 (1991-12-01), Falling
patent: 5117013 (1992-05-01), Falling
patent: 5516851 (1996-05-01), Flick et al.
Petroleum Chem. Neftekhimiya, vol. 33, 1993, 120-127.
Angew. Chem. Int. Ed. Engl. 30 (1991), No. 10, Boennemann et al., 1312-1314.
Jrl. Gen. Chem. USSR, vol. 28, No. 9, Sep. 1958, Aizikovich et al., 3076-3080.

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