Chemistry of inorganic compounds – Modifying or removing component of normally gaseous mixture – Nitrogen or nitrogenous component
Reexamination Certificate
1999-02-19
2002-10-22
Griffin, Steven P. (Department: 1754)
Chemistry of inorganic compounds
Modifying or removing component of normally gaseous mixture
Nitrogen or nitrogenous component
C423S235000, C423S246000, C423S247000, C564S188000, C560S141000, C560S220000, C568S344000, C568S351000
Reexamination Certificate
active
06468487
ABSTRACT:
TECHNICAL FIELD
The present invention relates to a catalyst useful for directly and efficiently nitrating and/or carboxylating a substrate by using at least one reactant selected from (i) a nitrogen oxide and (ii) a mixture of carbon monoxide and oxygen, and a compound obtained by using the catalyst and a process for producing the compound (a nitration/carboxylation process, a process for producing a compound having a nitro group and/or carboxyl group, a novel adamantane derivative, and a process for producing an adamantane derivative) using the catalyst.
BACKGROUND ART
Nitro compounds are commonly utilized as a raw material for medicine, agricultural chemicals, dyes, solvents and explosives, a raw material for amino compounds, and the like. Moreover, carboxylic acids (carboxy compounds) are useful as a raw material of a variety of compounds such as esters. Among them, dicarboxylic acids are useful as a raw material of polyesters.
Nitration of hydrocarbons is generally conducted by a nitric acid process which employs a mixed acid (a mixture of nitric acid and sulfuric acid). However, the nitric acid process requires a strong acid with high concentration in a large amount. Besides, since the nitration reaction is exothermic, it is difficult to improve its reaction operability. Furthermore, in the nitric acid process, large amounts of nitrogen oxides produce, which cause environmental pollution and thus have to be treated in a proper manner.
As a nitration process, use of N
2
O
5
and ozone in the presence of an iron catalyst has been suggested for nitration of aromatic compounds (e.g., toluene) or alicyclic compounds (e.g., adamantane). Due to the use of NO
3
as a reactant, this nitration process can proceed smoothly at a lower temperature. However, a catalyst should be incorporated in order to increase the reaction rate, and additional equipment such as an ozone-generating apparatus should be installed for the generation of ozone.
Carboxyl compounds (e.g., phthalic acid) can be obtained by, for example, an oxidation of a substrate (e.g., naphthalene). In Such oxidation reaction, a carboxyl compound having carbon atoms fewer than a substrate can be usually obtained. Moreover, in order to obtain a carboxyl compound of a bridged cyclic hydrocarbon (e.g., 1-carboxyladamantane) by an oxidation reaction, it is required that a group which can be converted to a carboxyl group by oxidation (e.g., methylol group) is introduced to a methine carbon atom, and then the methine carbon atom is oxidized. It is considerably difficult.
As a carboxylation process of a hydrocarbon compound, for example, a process for providing a carboxylic acid by using Grignard reaction is broadly known. In this process, many reaction steps are required since a substrate can not be directly carboxylated and include that a special compound such as an organic metal compound (e.g., a Grignard compound) is previously prepared from a substrate, carbon dioxide is allowed to act on the organic metal compound, and the organic metal compound is hydrolyzed to be carboxylated. Further, it is difficult to prepare the organic metal compound, additionally the compound is not convenient to handle.
Japanese Patent Application Laid-open No.38909/1996 (JP-A-8-38909) discloses a process which comprises contacting a substrate with oxygen to oxidize in the presence of an imide compound such as N-hydroxyphthalimide to provide a corresponding oxide (e.g., a carboxylic acid). In this process, a process for producing adipic acid from cyclohexane is described. In this process, a carboxyl compound having the same number of carbon atoms as a substrate can be obtained usually.
On the other hand, adamantane has a three-dimensionally symmetric structure and skeletons which insure mutual stabilization of each ring, and as a result, endowed with distinctive functions. Various highly functionalized copolymers can be obtained, for example, by introducing a functional group such as a carboxyl group or an amino group to adamantane and optionally deriving to other derivatives thereof. There have been proposed various production processes for obtaining such copolymers from a functional group-introduced adamantane derivative. The processes include, for example, a process of producing a polyester [e.g., Japanese Patent Application Laid-open No. 21090/1975 (JP-A-50-21090)], a process of producing a polycarbonate [e.g., U.S. Pat. No. 3,594,427], a process for producing a polyamide or a polyimide [e.g., U.S. Pat. No. 3,832,332], a process for producing a polyurethane [e.g., Japanese Patent Publication No. 12891/1969 (JP-B-44-12891)], a process for producing a polysulfone and a polysulfonate [e.g., U.S. Pat. No. 3,753,950], and a process for producing a vinyl polymer [e.g., Japanese Patent Publication No. 28419/1971 (JP-B-46-28419)].
These polymers provided from an adamantane derivative have generally excellent functions or characteristics (high functionality). They have, for example, optical characteristics such as small light-inducing loss, high refractive index, double refraction index, excellent characteristics such as moisture resistance, excellent heat resistance (heat resisting property) and thermal expansivity. Such excellent characteristics cannot be achieved with the use of conventional polymers. Accordingly, applications of said polymer have been investigated for optical materials such as optical fibers, optical elements, optical lenses, hologram, optical discs, and contact lenses, transparent resin coating compositions for organic glasses, electric conductive polymers, photosensitive materials, fluorescent materials and so forth.
On the other hand, an amino derivative derived from an alcohol of an adamantane is useful for introducing various pharmaceuticals and/or agricultural chemicals each having excellent pharmacological activity, and is used as a therapeutic agent for Parkinson's disease such as “SYMMETREL” (a trade name). A diamino body of adamantane is useful as an intermediate material for antibacterial drugs (agents) or antiviral drugs (agents).
The above mentioned diamino body (diamino form) of the adamantane is produced by aminating a dihalo body obtained by halogenating a diol body of an adamantane. However, in a process for the formation of a salt of the diamino body obtained by aminating the dihalo body of adamantane, a side reaction tends to occur, additionally it is difficult to separate and collect a free diamino body in a high yield.
It is, therefore, an object of the present invention to provide a catalyst which can efficiently nitrate and/or carboxylate a substrate, and a nitration and/or carboxylation process using the catalyst.
It is another object of the present invention to provide a catalyst which can nitrate or carboxylate a substrate by using at least one reactant selected from (i) a nitrogen oxide and (ii) a mixture of carbon monoxide and oxygen even in a mild or moderate condition, and a nitration and/or carboxylation process of a substrate using the catalyst.
A further object of the present invention is to provide a catalyst which can provide a compound having at least one functional group selected from nitro group and carboxyl group with high conversion and selectivity, and a process for producing the compound having a functional group by using the catalyst.
Another object of the present invention is to provide a process for nitration which can utilize effectively nitrogen oxides, which cause environmental pollution, for providing nitro compounds with high conversion and selectivity.
Further object of the present invention is to provide a process for producing a carboxyl compound which has more carbon atoms than the number of carbon atoms of a substrate, efficiently with simple operation at fewer steps.
Still further object of the present invention is to provide a novel adamantane derivative.
Still another object of the present invention is to provide a process which can produce a diamino body of adamantane in high yield.
DISCLOSURE OF INVENTION
The
Ishii Yasutaka
Nakano Tatsuya
Sakaguchi Satoshi
Birch & Stewart Kolasch & Birch, LLP
Daicel Chemical Industries Ltd.
Griffin Steven P.
Ildebrando Christina
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