Method of hydrogenating epoxidized C6—C12...

Details Method of hydrogenating epoxidized C6—C12... Method of hydrogenating epoxidized C6—C12...

1999-12-22

2002-01-01

Vollano, Jean F. (Department: 1621)

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

Organic compounds

Oxygen containing

C568S361000, C568S821000, C568S822000

Reexamination Certificate

active

06335472

ABSTRACT:

BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a method of hydrogenating epoxidized C
6
-C
12
cyclohydrocarbon compounds. More particularly, the present invention relates to a method of hydrogenating epoxidized C
6
-C
12
cyclohydrocarbon compounds, to produce, for example, C
6
-C
12
cycloalkanols and/or C
6
-C
12
cycloalkanones. The C
6
-C
12
cycloalkanols, for example, cyclododecanol and the C
6
-C
12
cycloalkanones, for example, cyclododecanone, are useful as intermediate compounds for producing lactams, lactones and polycarboxylic acids, which are useful for polyamides and polyesters for synthetic resins and synthetic fibers.
2. Description of the Related Art
It is known that a mixture of a cycloalkanone with a cycloalkanol can be produced by oxidizing a cycloalkane with air in the presence of a catalyst comprising boric acid. In this method, the air oxidation is effected in successive reactions and thus a plurality of by-products are produced during the reactions. Thus, the conversion of the cycloalkane must be low and the yield of the target mixture of cycloalkanol with cycloalkanone is usually low. For example, in the air oxidation of cyclododecane in the presence of a boric acid catalyst, it is known that the mixture of cyclododecanone with cyclododecanol is obtained in a yield of 20 to 25%. Also, it is known that when cyclohexane is oxidized with air, the yield of the mixture of cyclohexanone with cyclohexanol is several %.
Also, it is known that epoxidized cycloalkanes and/or epoxidized cycloalkenes can be produced by epoxidizing corresponding cycloalkenes with a high yield. If the epoxidized compounds can be converted to corresponding cycloalkanones and cycloalkanols with a high efficiency, the cycloalkanones and the cycloalkanols can be expected to be obtained at a high yield. However, only a small number of reports can be found on methods of converting an epoxidized cycloalkane and/or an epoxidized cycloalkene to a mixture of cycloalkanone with cycloalkanol. For example, J. Mol. Catal., Vol. 69, pages 69 to 103 (1991) discloses a method of hydrogenating a monoepoxycyclododecadiene with hydrogen in the presence of a catalyst comprising palladium carried on a carrier consisting of &ggr;-alumina, under a hydrogen gas pressure of 1.3 MPa at a temperature of 90° C. In this method, cyclododecanol was produced with a yield of 20% or less and no cyclododecanone was produced. When a catalyst comprising palladium carried on a carrier consisting of titania or silica was used in place of the above-mentioned palladium catalyst carried on &ggr;-alumina, the yield of cyclododecanol was low and unsatisfactory.
Also, the Drafted Report of 24th Symposium of Development in Reaction and Synthesis, Nov. 5 to 6, 1998, page 68, discloses a method of hydrogenating 1,2-epoxy-5,9-cyclododecadiene with hydrogen at ambient atmospheric pressure and room temperature in the presence of a catalyst comprising palladium carried on a carrier consisting of a carbon material. In this method, cyclododecanol was produced with a yield of 5% and no cyclododecanone was obtained.
Further, Neftekhimiya, 16(1), 119—119, (1976) discloses a method in which 1,2-epoxy-5,9-cyclododecadiene is brought into contact with hydrogen in the presence of a palladium-carrying catalyst under a hydrogen pressure of 9.06 MPa (80 atmospheres) at a temperature of 140° C. By this method, 49.5% of epoxycyclododecane, 33.3% of cyclododecanol and 3.4% of cyclododecanone were obtained. In this method, the yields of cyclododecanol and cyclododecanone were unsatisfactory.
As mentioned above, when the 1,2-epoxy-5,9-cyclododecadiene is hydrogenated with a hydrogen gas by the known methods, the yields of cyclododecanol and cyclododecanone are very low and unsatisfactory.
As an analogous method, Synthetic Communication, 25(15), pages 2267 to 2273 (1995) discloses a method of synthesizing cyclohexanol by hydrogenating 1,2-epoxy-5,9-cyclohexane. In this method, 1,2-epoxy-5,9-cyclohexane was reduced with ammonium formate (HCOONH
4
) in the presence of a catalyst comprising palladium carried on a carrier consisting of activated carbon, and as a result, cyclohexanol was produced with a yield of 50% and no cyclohexanone was obtained. This method is, however, disadvantageous in that the ammonium formate (HCOONH
4
) which is used as a hydrogen-supply source, is expensive, and the yields of cyclohexanol and cyclohexanone are low although the expensive hydrogen-supply source is employed. Therefore, this method is practically unusable as a production method of cycloalkanone and cycloalkanol which are useful for producing lactam materials.
Accordingly, no method of producing C
6
-C
12
cycloalkanols and C
4
-C
12
cycloalkanones with a satisfactory yield, from epoxidized C
6
-C
12
cyclohydrocarbon compounds, for example, C
6
-C
12
cycloalkanes cycloalkadienes and/or cycloalkenes, has been known.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a method of hydrogenating epoxidized C
6
-C
12
cyclohydrocarbon compounds in the presence of a platinum group metal-containing catalyst with a high efficiency.
Another object of the present invention is to provide a method of hydrogenating epoxidized C
6
-C
12
cyclohydrocarbon compounds in the presence of a platinum group metal-containing catalyst in one single-step reaction with a high yield of hydrogenated cyclohydrocarbon compounds.
The above-mentioned objects can be attained by the method of the present invention.
The method of the present invention for hydrogenating epoxidized C
6
-C
12
cyclohydrocarbon compounds, comprising bringing a starting material comprising at least one epoxidized cyclohydrocarbon compound having 6 to 12 carbon atoms into contact with hydrogen under a hydrogen pressure of 0.1 to 5.4 MPa on gauge at a temperature of 100 to 280° C. in the presence of a catalyst comprising a catalytic metal component comprising at least one platinum group metal.
In the hydrogenating method of the present invention, the starting material may comprise at least one member selected from the group consisting of monoepoxy C
6
-C
12
cycloalkenes, monoepoxy C
6
-C
12
cycloalkanes and monoepoxy C
6
-C
12
cycloalkadiens and the resultant hydrogenation reaction product may comprise at least one member of C
6
-C
12
cycloalkanones and C
6
-C
12
cycloalkanols.
In the hydrogenating method of the present invention, the catalytic metal component of the catalyst is optionally carried on an inert carrier comprising at least one member selected from the group consisting of activated carbon, alumina, silica, silica-alumina, titania, zeolites and spinel, especially &agr;-alumina.
In an embodiment of the hydrogenating method of the present invention, the starting material comprises at least one member selected from the group consisting of monoepoxy cyclododecanes, monoepoxy cyclododecenes and monoepoxy cyclododecadienes, and is brought into contact with hydrogen under a hydrogen pressure of 0.1 to 5.4 MPa on gauge at a temperature of 100 to 280° C., in the presence of a catalyst comprising, as a catalytic metal component, at least one metal selected from the group consisting of palladium and ruthenim, to produce cyclododecanol and cyclododecanone.
In another embodiment of the hydrogenating method of the present invention, the starting material comprises 1,2-epoxy-5,9-cyclododecadiene and is brought into contact with hydrogen under a hydrogen pressure of 0.1 to 3.9 MPa on gauge at a temperature of 100 to 280° C., in the presence of a catalyst comprising, as a catalytic metal component, at least one platinum group metal, to produce cyclododecanone.
In still another embodiment of the hydrogenating method of the present invention, the catalytic metal component of the catalyst is carried on an inert carrier comprising a-alumina, and the starting material is hydrogenated into a mixture of C
6
-C
12
cycloalkanone with C
6
-C
12
cycloalkanol.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In the method of the present invention, hydrogenating epoxidized C
6

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