Adamantane derivatives and process for producing them

Details Adamantane derivatives and process for producing them Adamantane derivatives and process for producing them

1998-11-10

2002-05-21

Killos, Paul J. (Department: 1623)

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

Organic compounds

Oxygen containing

C502S167000, C548S545000, C548S549000, C548S551000, C548S552000, C548S152000, C562S498000, C562S499000, C562S502000, C562S501000, C564S457000, C564S458000

Reexamination Certificate

active

06392104

ABSTRACT:

TECHNICAL FIELD
This invention relates to a novel adamantane derivative, which has a hydroxyl group together with a nitro group, an amino group, an acyloxy group, a carboxyl group, a hydroxymethyl group or the like, and to a process for producing the same.
BACKGROUND ART
The 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 copolymers each having enhanced or improved functions or characteristics can be obtained by introducing a hydroxyl group into an adamantane and, if necessary, inducing them into an acrylic acid derivative or a carbonate. There have been proposed various production processes for obtaining such copolymers from a functional group (e.g., a hydroxyl group, an amino group, a carboxyl group) -introduced adamantane. 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)].
Generally, these polymers provided from an adamantane derivative have excellent functions or characteristics (high functionality) such as, for example, small light-inducing loss, high refractive index, double refraction index and other optical characteristics, and moisture resistance, excellent heat resistance, coefficient of thermal expansion and other characteristics. Such excellent characteristics cannot be achieved by using conventional polymers. Accordingly, they have been investigated applications of said polymer for optical fibers, optical elements, optical lenses, hologram, optical discs, contact lenses and other optical materials, transparent resin coating compositions for organic glasses, electric conductive polymers, photosensitive materials, fluorescent materials and so forth.
Moreover, 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 utilized for producing a therapeutic agent for Parkinson's disease such as “SYMMETREL” (a trade name).
Thus, an adamantane having a functional group such as a hydroxyl group is applied to various uses.
As a process for producing an alcohol of the adamantane, there have been proposed process, such as a process for hydrolyzing a bromide of adamantane [Japanese Patent Application Laid-open No. 196744/1990 (JP-A-2-196744)], a process for oxidizing an adamantane using chromic acid [Japanese Patent Publication No. 16621/1967 (JP-B-42-16621)], a process for oxidizing a fused adamantane with oxygen using a cobalt salt as a catalyst [Japanese Patent Publication No. 26792/1967 (JP-B-42-26792)], a biological process [J. Chem. Soc., Chem. Comm., 1833 (1996)]. However, introduction of a hydroxyl group (specifically, a plurality of hydroxyl groups) to adamantane by using these processes is difficult.
Japanese Patent Application Laid-open No. 38909/1996 (JP-A-8-38909) proposes a process for oxidizing a substrate with oxygen by using an imide compound as a catalyst. By applying the above oxidation process to the oxidation of a substrate such as adamantane, an adamantanol is obtained.
It is, therefore, an object of the present invention to provide a novel adamantane derivative and a process for producing the same.
It is another object of the present invention to provide an adamantane derivative having at least one hydroxyl group and at least one functional group selected from a nitro group, an amino group, an acylamino group, a carboxyl group, hydroxymethyl group and other groups, and a process for producing the same.
A further object of the invention is to provide a process for producing the above mentioned adamantane derivative effectively with high transformation rate or conversion and selectivity even under mild or moderate conditions.
DISCLOSURE OF INVENTION
The present inventors did intensive investigation to accomplish the above objects, and as a result, found that oxidation of a specific adamantane derivative with oxygen by using an oxidation catalyst comprising a specific imide compound or the imide compound and a co-catalyst provides a novel adamantane derivative efficiently.
Thus, a novel adamantane derivative of the present invention is shown by the following formula (1):
wherein X
1
represents a hydroxyl group which may be protected by a protective group, X
2
represents a nitro group, an amino group or N-substituted amino group which may be protected by a protective group, a hydroxyl group which may be protected by a protective group, a carboxyl group which may be protected by a protective group, a hydroxymethyl group which may be protected by a protective group, or an isocyanato group;
(i) when X
2
is a nitro group, X
3
and X
4
may be the same or different from each other and each may represent a hydrogen atom, an alkyl group, a nitro group, a hydroxyl group which may be protected by a protective group, an amino group or N-substituted amino group which may be protected by a protective group, a carboxyl group which may be protected by a protective group, a hydroxymethyl group which may be protected by a protective group, or an isocyanato group, excluding the case where X
3
and X
4
are both hydrogen atoms when X
1
is hydroxyl group;
(ii) when X
2
is an amino group or N-substituted amino group which may be protected by a protective group, X
3
and X
4
may be the same or different from each other and each may represent a hydrogen atom, an alkyl group, an amino group or N-substituted amino group which may be protected by a protective group, a hydroxyl group which may be protected by a protective group, a carboxyl group which may be protected by a protective group, a hydroxymethyl group which may be protected by a protective group, or an isocyanato group, excluding the case where X
3
and X
4
are both hydrogen atoms or alkyl groups when X
1
is hydroxyl group;
(iii) when X
2
is a hydroxyl group which may be protected by a protective group, X
3
and X
4
may be the same or different from each other and each may represent a hydrogen atom, an alkyl group, a hydroxyl group which may be protected by a protective group, a carboxyl group which may be protected by a protective group, a hydroxymethyl group which may be protected by a protective group, or an isocyanato group, excluding the case where X
3
and X
4
are both hydrogen atoms or alkyl groups when X
1
is hydroxyl group or a saturated aliphatic acyloxy group and X
2
is hydroxyl group or a saturated aliphatic acyloxy group and excluding the case where X
3
and X
4
is a combination of hydrogen atom and a carboxyl group which may be protected by a protective group when X
1
and X
2
are both hydroxyl groups;
(iv) when X
2
is a carboxyl group which may be protected by a protective group, X
3
and X
4
may be the same or different from each other and each may represent a hydrogen atom, an alkyl group, a carboxyl group which may be protected by a protective group, a hydroxymethyl group which may be protected by a protective group, or an isocyanato group, excluding the case where X
3
and X
4
are both hydrogen atoms or alkyl groups or a combination of a hydrogen atom and an alkyl group when X
1
is a hydroxyl group or a saturated aliphatic acyloxy group;
(v) when X
2
is a hydroxymethyl group which may be protected by a protective group, X
3
and X
4
may be the same or different from each other and each may represent a hydrogen atom, an alkyl group, a hydroxymethyl group which m

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