Organic compounds -- part of the class 532-570 series – Organic compounds – Oxygen containing
Reexamination Certificate
2001-08-06
2003-08-19
Shippen, Michael L. (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Oxygen containing
C568S814000, C568S826000, C568S835000, C568S838000, C568S867000
Reexamination Certificate
active
06608235
ABSTRACT:
TECHNICAL FIELD
The present invention relates to a method of reducing an epoxy group-containing organic compound with hydrogen. More particularly, the present invention relates to a method of reducing an epoxy group-containing compound, particularly an epoxy group-containing cycloaliphatic compound, with hydrogen in the presence of a nickel catalyst, with high efficiency, to thereby produce a target compound, particularly a cycloaliphatic saturated alcohol, at high selectivity. The compound, particularly the cycloaliphatic saturated alcohol, produced by the method of the present invention can be converted to, for example, a lactam compound, a lactone compound or a dibasic organic acid, which are useful as materials for producing polyester or polyamide synthetic fibers or resins.
BACKGROUND ART
A cycloaliphatic alcohol, for example, cycloalkanol can be produced by a method in which a cycloalkane corresponding to the alcohol is oxidized with air in the presence of a boric acid catalyst. The conventional air oxidation method is, however, disadvantageous in that since a plurality of types of by-products are produced in a large amount due to successive reactions, and thus the conversion of the cycloalkane must be controlled to a low level, the target cycloalkanol is obtained only in a low yield and the reaction result is unsatisfactory. For example, when cyclododecane is oxidized with air in the presence of a boric acid catalyst, the target cyclododecanol and cyclododecanone are obtained only in a total yield of about 20%. On the other hand, since an epoxycycloalkane and/or an epoxycycloalkene can be produced with a high yield by an epoxidizing reaction of a cycloalkene, if the epoxy compound can be converted to a cycloalkanol with a high efficiency, the cycloalkanol can be produced from the cycloalkene with a high yield.
However, there are few reports concerning the method of converting the epoxycycloalkane and/or epoxycycloalkene to the cycloalkanol.
For example, Japanese Examined Patent Publication No. 47-38, 437 discloses a hydrogenation method in which hydrogen is brought into contact with epoxycyclododecane, to produce cyclododecanol and isomerized cyclododecanone, and in which method, Raney nickel is used as a catalyst.
The Japanese publication, however, does not indicate the yields of the cyclododecanol and cyclododecanone. Therefore, the method of the Japanese publication was carried out by the inventors of the present invention. As a result, it was found that, in the hydrogen-reduction procedure of the epoxycyclododecane compound, a disoxidation reaction of the epoxy group occurred and various hydrocarbons, for example, cyclododecane were produced as by-products in a large amount, and thus the selectivity to the target compounds, namely cyclododecanol and cyclododecanone was unsatisfactory.
Also, Neftekhimiya, 16(1), 114-119, 1976, discloses a method of reducing 1,2-epoxy-5,9-cyclododecadiene with hydrogen by using a nickel catalyst carried on chromium oxide. This method uses a toxic chromium compound and thus is difficult to utilize in practice.
Generally, it is well known that in a hydrogenation reaction of the epoxy compound in the presence of a nickel catalyst, various types of by-product compounds are produced in a large amounts due to disoxidation reaction of the epoxy compound (Tokyo Kagaku-dojin, LECTURE ON ORGANIC REACTION MECHANISM 13, CATALYTIC REACTIONS ((Second Volume), written by Mikio Mitsui).
Further, in J. Mol. Catal., Vol. 69, pages 95-103 (1991), a report concerning hydrogenation of epoxycyclododecadiene is described.
In a reaction example shown in this report, when epoxycyclododecadiene is subjected to a reduction reaction with a hydrogen gas in the presence of a palladium catalyst carried on &ggr;-alumina under a reduced pressure of 1.3 MPa at a reaction temperature of 90° C., cyclododecanol is obtained at a yield of 20%. In the report, a palladium catalyst carried on titania and a palladium catalyst carried on silica were employed. In each case, the yield of the cyclododecanol was less than 20%.
Further, in a Drafted Report, page 68, of the 24th “Progress in Reaction and Synthesis” Sympodium, Nov. 5 to 6, 1998, a hydrogenation reaction of an epoxycyclododecadiene in the presence of a palladium catalyst carried on a carbon material is reported. In this case, the target cyclododecanol was produced at a yield of 5%.
As mentioned above, it is known that the yield of the cyclododecanol by the catalytic hydrogenation reaction of the epoxycyclododecadiene with a hydrogen gas is extremely low.
Furthermore, as an analogous reaction, a method of synthesizing cyclohexanol by a hydrogenation reaction of an epoxycyclohexane is reported in Synthetic Communication, 25(15), p 2267-2273, (1995).
In the method of the publication, it is reported that when an epoxycyclohexane was reduced with ammonium formate (HCOONH
4
) in the presence of a palladium catalyst carried on activated carbon, the yield of the resultant cyclohexanol was 50%. In this method, however, ammonium formate (HCOONH
4
) used as a hydrogen-supply source is expensive, the yield of the cyclohexanol obtained by using the expensive hydrogen-supply source is low, and therefore, this method cannot be utilized as a practical method of producing cycloalkanol to be used as a material for producing a lactam.
As mentioned above, a method of producing a hydrogen-reduced compound at a high yield by catalytically reacting an epoxy group-containing organic compound with a hydrogen gas, which is cheap, as a hydrogen-supply source has not yet established, and thus the development of this method is in strongly demand.
DISCLOSURE OF THE INVENTION
An object of the present invention is to provide a method of catalytically reacting an epoxy group-containing organic compound with hydrogen to produce a corresponding hydrogen-reduced compound with a high yield.
A further object of the present invention is to provide a method of catalytically reacting an epoxy group-containing organic compound with hydrogen, while a production of a by-product comprising hydrocarbon compounds due to a disoxidation reaction of the epoxy group-containing organic compound is restricted, to produce a target hydrogen-reduced product at a high yield.
The above-mentioned objects can be attained, by the hydrogen-reduction method of the present invention, for an epoxy group-containing organic compound.
The method of the present invention for reducing an epoxy group-containing organic compound with hydrogen comprises bringing an epoxy group-containing organic compound into contact with hydrogen in the presence of a nickel catalyst, to reduce the epoxy group-containing organic compound in a hydrogen reduction reaction system, in which the reduction reaction system further comprises a basic substance.
In the method of the present invention, the basic substance preferably comprises at least one member selected from the group consisting of hydroxides of alkali metals, carbonates of alkali metals, alkoxides of alkali metals, hydroxides of alkaline earth metals, carbonates of alkaline earth metals, amine compounds having 1 to 3 alkyl groups each having 1 to 12 carbon atoms, and basic oxides of alkaline earth metals and rare earth elements.
In the method of the present invention, the basic substance is preferably present in a total molar amount of 0.01 to 10 times the molar amount of nickel atoms contained in the nickel catalyst.
In the method of the present invention, in the hydrogen reduction reaction system, the basic substance may be carried on the nickel catalyst.
In the method of the present invention, the epoxy group-containing organic compound is preferably selected from epoxy group-containing saturated and unsaturated cycloaliphatic organic compounds having 5 to 20 carbon atoms.
In the method of the present invention, the epoxy group-containing organic compound is selected from the group consisting of, for example, epoxycyclododecane, epoxycyclododecene, epoxycyclododecadiene, epoxycyclohexane, epoxycyclohexene, epoxycyclooctane, and epoxycyclooctene.
Kuroda Nobuyuki
Matsuzaki Tokuo
Nakamura Takato
Takemoto Hirofumi
Yamanaka Mitsuo
Morgan & Lewis & Bockius, LLP
Shippen Michael L.
Ube Industries Ltd.
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