Adamantane derivatives and processes for the preparation...

Details Adamantane derivatives and processes for the preparation... Adamantane derivatives and processes for the preparation...

2001-07-06

2003-12-30

Killos, Paul J. (Department: 1623)

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

Organic compounds

Carboxylic acid esters

C560S128000, C560S129000, C560S157000, C560S205000

Reexamination Certificate

active

06670499

ABSTRACT:

This application is the national phase under 35 U.S.C. §371 of PCT International Application No. PCT/JP00/07810 which has an International filing date of Nov. 7, 2000, which designated the United States of America and was not published in English.
TECHNICAL FIELD
The present invention relates to novel adamantane derivatives which are useful, for example, as dental materials or raw materials therefor, and as raw materials for optical materials such as lenses.
BACKGROUND ART
Adamantane compounds have a variety of functions due to their special non-aromatic and rigid ring structures and receive attention in various areas.
For example, proposes have been made to use polymerizable monomers each having an adamantane skeleton or polymers thereof as dental materials. Such dental materials include, for example, cementing materials for setting inlays, crowns and other teeth crown materials to cavities or abutments, bonding materials for bonding with tooth or restorative dental materials to thereby hold the restorative dental materials, filling materials for packing or filling the socket of a tooth, and surface lubricants.
Japanese Unexamined Patent Application Publication No. 63-233906 discloses a dental material containing an acrylic polymer comprising, as a monomer, a (meth)acrylic ester of an alcohol having an adamantane skeleton. Japanese Unexamined Patent Application Publication No. 63-233907 discloses a dental material containing a urethane derivative of adamantane. Japanese Unexamined Patent Application Publication No. 4-80223 and Japanese Unexamined Patent Application Publication No. 4-360809 each disclose a dental surface lubricant containing a polymerizable urethane compound having an adamantane skeleton, a volatile compound, and a polymerization initiator.
However, these dental materials are not always satisfactory in, for example, water resistance, stability and luster.
DISCLOSURE OF INVENTION
Accordingly, an object of the present invention is to provide novel adamantane derivatives which are useful as, for example, raw materials for dental materials.
After intensive investigations to achieve the above objects, the present inventors have found novel adamantane derivatives in which two (meth)acryloyloxyalkyl groups are bonded with an adamantane ring through ester groups, novel adamantane derivatives in which two adamantane rings are bonded through an alkylene group and two urethane bonds, which two adamantane rings each have a (meth)acryloyloxy group bonded thereto directly or through a coupling group, and novel adamantane derivatives each having a structure in which a group containing an adamantane ring hangs on the alkylene group of an alkylene glycol di(meth)acrylate. The present invention has been accomplished based on these findings.
Specifically, the present invention provides, in an aspect, an adamantane derivative represented by the following Formula (1), (6) or (9):
[wherein, in Formula (1), R
1
is a hydrogen atom or a methyl group; each of R
2
and R
3
is, identical to or different from each other, a hydrogen atom or a methyl group; each of A
1
and A
2
is, identical to or different from each other, a —C(═O)—O— group or —O—C(═O)— group, where the right-hand sides of these two groups are on the adamantane ring side; each of X
1
and X
2
is, identical to or different from each other, a straight- or branched-chain alkylene group having from 1 to 12 carbon atoms, in Formula (6), each of R
4
and R
5
is, identical to or different from each other, a hydrogen atom or a methyl group; each of R
6
and R
7
is, identical to or different from each other, a hydrogen atom or a methyl group; each of A
3
and A
4
is, identical to or different from each other, a group represented by the following formula:
—A
5
—O—C (═O)—
(wherein A
5
is a straight- or branched-chain alkylene group having from 1 to 6 carbon atoms, where the right-hand side of the above formula is on the adamantane ring side); X is a straight- or branched-chain alkylene group having from 1 to 12 carbon atoms; and each of m and n denotes 0 or 1, in Formula (9), R
8
is a hydrogen atom or a methyl group; each of R
9
and R
10
is, identical to or different from each other, a hydrogen atom or a methyl group; R
11
is a hydrogen atom, a straight- or branched-chain alkyl group having from 1 to 4 carbon atoms, or a group represented by the following Formula (10):
 —(CH
2
)
s
—O—R
12
  (10)
(wherein R
12
is an acryloyl group, a methacryloyl group, an 1-adamantylcarbonyl group or a 3,5-dimethyladamant-1-ylcarbonyl group; and s denotes an integer from 1 to 6); and
each of p, q and r denotes an integer from 1 to 6].
In another aspect, the present invention provides a process for producing an adamantane derivative (hereinafter briefly referred to as “Production Process 1”), which process includes the step of allowing an adamantanedicarboxylic acid represented by the following Formula (2) or a reactive derivative thereof:
(wherein R
1
is a hydrogen atom or a methyl group) to react with (meth)acrylic hydroxyalkyl esters represented by the following Formulae (3a) and (3b):
(wherein each of R
2
and R
3
is, identical to or different from each other, a hydrogen atom or a methyl group; and each of X
1
and X
2
is, identical to or different from each other, a straight- or branched-chain alkylene group having from 1 to 12 carbon atoms)
to thereby yield an adamantane derivative represented by the following Formula (1a):
(wherein R
1
, R
2
, R
3
, X
1
and X
2
have the same meanings as defined above).
In a further aspect, the present invention provides a process for producing an adamantane derivative (hereinafter briefly referred to as “Production Process 2”), which process includes the step of allowing an adamantanediol represented by the following Formula (4):
(wherein R
1
is a hydrogen atom or a methyl group) to react with (meth)acryloyloxy-group-containing carboxylic acids represented by the following Formulae (5a) and (5b) or reactive derivatives thereof:
(wherein each of R
2
and R
3
is, identical to or different from each other, a hydrogen atom or a methyl group; and each of X
1
and X
2
is, identical to or different from each other, a straight- or branched-chain alkylene group having from 1 to 12 carbon atoms)
to thereby yield an adamantane derivative represented by the following Formula (1b):
(wherein R
1
, R
2
, R
3
, X
1
and X
2
have the same meanings as defined above).
The present invention provides, in still another aspect, a process for producing an adamantane derivative, which process includes the step of allowing adamantanol derivatives represented by the following Formulae (7a) and (7b):
[wherein each of R
4
and R
5
is, identical to or different from each other, a hydrogen atom or a methyl group; each of R
6
and R
7
is, identical to or different from each other, a hydrogen atom or a methyl group; each of A
3
and A
4
is, identical to or different from each other, a group represented by the following formula:
—A
5
—O—C(═O)—
(wherein A
5
is a straight- or branched-chain alkylene group having from 1 to 6 carbon atoms, where the right-hand side of the above formula is on the adamantane ring side); and each of m and n independently denotes 0 or 1]
to react with a diisocyanate compound represented by the following Formula (8):
OCN—X—NCO  (8)
(wherein X is a straight- or branched-chain alkylene group having from 1 to 12 carbon atoms)
to thereby yield the adamantane derivative represented by Formula (6).
In addition and advantageously, the present invention provides a process for producing an adamantane derivative, which process includes the step of allowing an adamantanecarboxylic acid represented by the following Formula (11) or a reactive derivative thereof:
(wherein R
8
is a hydrogen atom or a methyl group) to react with a compound represented by the following Formula (12):
[wherein each of R
9
and R
10
is, identical to or different from each other, a hydrogen atom or a methyl group; R
11
is a hydrogen atom, a straight-

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