Organic compounds -- part of the class 532-570 series – Organic compounds – Oxygen containing
Reexamination Certificate
2000-10-03
2003-02-04
Richter, Johann (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Oxygen containing
C568S361000, C568S821000, C568S823000, C568S832000
Reexamination Certificate
active
06515185
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a method of producing cyclododecanone and cyclododecanol. More particularly, the present invention relates to a method of producing cyclododecanone and cyclododecanol by a catalytic reaction of an epoxycyclododecane compound with hydrogen. Cyclododecanone and cyclododecanol can be easily converted to a lactum compound, lactone compound or a dicarboxylic acid compound by a conventional method and thus are important intermediate materials for producing synthetic resins or fibers of polyamide 12 and polyesters.
2. Description of the Related Art
As a process for producing cyclododecanone and cyclododecanol by a catalytic reaction of epoxycyclododecane compounds with hydrogen, J. Mol. Catal., Vol 169, pp 95-103 (1991) discloses a catalytic hydrogenating reaction of 2-epoxy-5,9-cyclododecadiene with hydrogen. In this reaction of the reference, 1,2-epoxy-5,9-cyclododecadiene is brought into contact with hydrogen in the presence of a palladium-carrying catalyst at a reaction temperature of 90° C. under a hydrogen gas pressure of 1,275 kPa (13 kg/cm
2
) on gauge, and epoxycyclododecane is produced as a principal reaction product. Cyclododecanol is produced as a by-product in a yield of 4% and no cyclododecanone is produced. Also, the Draft of 24-th Symposium “Development of Reaction and Synthesis, Nov. 5-6, 1998, pp 68, discloses a process of catalytic reaction of 1,2-epoxy-5,9-cyclododecadiene with hydrogen in the presence of a palladium catalyst at room temperature under the ambient atmospheric pressure. In this process, epoxycyclododecane is produced as a principal product, cyclododecanol is produced, as a by-product, in a yield of 5%, and no cyclododecanone is produced.
Further, Neftekhimiya, 16 (1), 114-119 (1976) discloses a catalytic reaction of 1,2-epoxy-5,9-cyclododecadiene with hydrogen in the presence of a palladium-carried catalyst at a reaction temperature of 140° C. under a hydrogen gas pressure of 8,106 kPa (80 atmospheres). In this reaction, epoxycyclododecane was produced in a yield of 49.5%, cyclododecanol in a yield of 33.3%, and cyclododecanone in a yield of 3.4%.
In view of the prior arts, a method enabling both cyclododecanone and cyclododecanol to be produced, each in a satisfactory yield from epoxycyclododecane compounds, has not yet been provided.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a method of producing cyclododecanone and cyclododecanol from epoxycyclododecane compounds with satisfactory yields thereof.
The above-mentioned object can be attained by the method of producing cyclododecanone and cyclododecanol of the present invention, which comprises bringing an epoxycyclododecane compound and hydrogen into contact with each other in the presence of a solid catalyst comprising:
(a) a catalytic component comprising at least one platinum group metal;
(b) a promoter component comprising at least one member selected from the group consisting of VIII group, Ib group, IIb group, IIIb group, IVb group, Vb group, VIb group and VIIb group elements, and lanthanoid elements and compounds of the above-mentioned elements; and
(c) a carrier on which the catalytic component and the promoter component are supported, to thereby hydrogenate the epoxycyclododecane compound and produce cyclododecanone and cyclododecanol.
In the method of producing cyclododecanone and cyclododecanol of the present invention, the epoxycyclododecane compound is preferably selected from the group consisting of monoepoxycyclododecadiene, monoepoxycyclododecene and monoepoxycyclododecane.
In the method of producing cyclododecanone and cyclododecanol of the present invention, the promoter component (b) of the solid catalyst preferably comprises at least one member selected from the group consisting of nickel metal, iron metal, copper metal, iron(III) nitrate, iron(III) chloride, iron(II) chloride, iron(II) sulfate, triiron tetraoxide, iron(III) hydroxide, cobalt nitrate, cobalt bromide, cobalt oxide, cobalt hydroxide, nickel nitrate, nickel oxide, nickel hydroxide, copper nitrate, copper acetate, silver oxide, gold hydroxide, yttrium chloride, titanium chloride, vanadium oxide, tungsten oxide, molybdenum oxide, manganese nitrate, rhenium oxide, zinc nitrate, zinc chloride, zinc hydroxide, cadmium nitrate, cadmium oxide, mercury oxide, cerium oxide, samarium chloride, dysprosium chloride, and ytterbium oxide.
In the method of producing cyclododecanone and cyclododecanol of the present invention, the carrier (c) of the solid catalyst preferably comprises an inert inorganic material selected from the group consisting of activated carbon, &agr;-alumina, &ggr;-alumina, silica, silica-alumina, titania, zeolite and spinel.
In the method of producing cyclododecanone and cyclododecanol of the present invention, the catalytic component (a), for the solid catalyst is preferably present in an amount of 0.01 to 20% by weight, based on the weight of the inert carrier.
In the method of producing cyclododecanone and cyclododecanol of the present invention, the metal atomic ratio (a)/(b) of the catalytic component (a) to the promoter component (b) for the solid catalyst is preferably 10,000:1 to 1:4.
In the method of producing cyclododecanone and cyclododecanol of the present invention, the solid catalyst is preferably present in a molar amount, in terms of the platinum group metal, of 0.00001 to 0.1 times the molar amount of the epoxycyclododecane compound.
In the method of producing cyclododecanone and cyclododecanol of the present invention, the hydrogenation reaction of the epoxycyclododecane compound with hydrogen in the presence of the solid catalyst is preferably carried out at a reaction temperature of 60 to 250° C. under a hydrogenr gas pressure of 98 to 14,710 kPa on gauge.
In the method of producing cyclododecanone and cyclododecanol of the present invention, the hydrogenation reaction of the epoxycyclododecane compound with hydrogen is preferably carried out in an organic liquid medium comprising at least one member selected from the group consisting of n-hexane, n-heptane, n-tetradecane, cyclohexane, tetrahydrofuran, dioxane, methyl alcohol, ethyl alcohol, tertiary butyl alcohol, tertiary amyl alcohol, ethyl acetate and butyl acetate.
In the method of producing cyclododecanone and cyclododecanol of the present invention, the liquid medium is preferably employed in an amount not exceeding 20 times the weight of the epoxycyclododecane compound.
In the method of producing cyclododecanone and cyclododecanol of the present invention, the platinum group metal is preferably palladium.
In the method of producing cyclododecanone and cyclododecanol of the present invention, the promoter for catalyst preferably comprises at least one member selected from the group consisting of VIII group, Ib group and IIb group elements, lanthanoid elements, and compounds of the elements.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In the method of the present invention, an epoxycyclododecane compound and hydrogen are brought into contact with each other in the presence of a specific solid catalyst, to produce cyclododecanone and cyclododecanol.
The epoxycyclododecane compound usable as a starting material for the method of the present invention is defined as an organic compound constituted from a saturated or unsaturated 12-membered cyclic hydrocarbon structure and an epoxy group attached to the cyclic hydrocarbon structure. The epoxycyclododecane compound for the method of the present invention is preferably selected from the group consisting of epoxycyclododecadiene, epoxycyclododecene, and epoxycyclododecane. In the above-mentioned epoxycyclododecane compounds, the epoxy ring structure and double bond structure may be of cis-type of trans type, or of other any type.
The epoxycyclododecane compound subjected to the method of the present invention may be in a trade-available grade or a grade refined by a conventional refining means, for example, distillation.
The solid catalyst usable for the method of the presen
Kuroda Nobuyuki
Nakamura Takato
Shiraishi Hiroshi
Morgan & Lewis & Bockius, LLP
Richter Johann
Ube Industries Ltd.
Witherspoon Sikarl A.
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