Adamantanemethanol derivatives and production processes thereof

Details Adamantanemethanol derivatives and production processes thereof Adamantanemethanol derivatives and production processes thereof

1999-12-21

2002-02-05

Shippen, Michael L. (Department: 1621)

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

Organic compounds

Oxygen containing

C556S449000, C558S429000, C560S117000, C562S449000, C568S373000, C568S665000, C568S818000

Reexamination Certificate

active

06344590

ABSTRACT:

TECHNICAL FIELD
The present invention relates to novel adamantanemethanol derivatives which are useful as, for example, monomers or their materials for photosensitive resins and other functional polymers and to production processes thereof.
BACKGROUND ART
Alicyclic compounds each having a hydroxymethyl group have been used as monomers or their materials for resist resins, and pharmaceutical intermediates, and have received attention in recent years.
However, adamantanemethanol derivatives having a hydrocarbon group, which hydrocarbon group is bonded to a carbon atom adjacent to a hydroxyl group and has a methine carbon atom at a bonding site with the carbon atom, and adamantanemethanol derivatives each having a hydroxyl group protected by a protective group on its adamantane ring, and production processes thereof have not yet been known.
DISCLOSURE OF INVENTION
Accordingly, it is an object of the present invention to provide adamantanemethanol derivatives each having a hydrocarbon group, which hydrocarbon group is bonded to a carbon atom adjacent to a hydroxyl group and has a methine carbon atom at a bonding site with the carbon atom, adamantanemethanol derivatives each having a hydroxyl group protected by a protective group on the adamantane ring, and other novel adamantanemethanol derivatives, and production processes thereof.
After intensive investigations to achieve the above object, the present inventors found that novel adamantanemethanol derivatives each having a specific substituent introduced into a carbon atom adjacent to a hydroxyl group (carbon atom at the &agr;-position) can be obtained by allowing organometallic compounds on 1-acyladamantane derivatives and/or 1-adamantanecarboxylic acid derivatives. The present invention has been accomplished based on the above finding.
To be more specific, the invention provides, in an aspect, an adamantanemethanol derivative represented by the following formula (1):
[wherein R
a
is a hydrogen atom or a hydrocarbon group; R
b
is a hydrocarbon group having a carbon atom, to which carbon atom at least one hydrogen atom is bonded, at a bonding site with the adjacent carbon atom; R
c
, R
d
and R
e
are each, identical to or different from one another, a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group which may be protected by a protective group, a hydroxymethyl group which may be protected by a protective group, an amino group which may be protected by a protective group, a carboxyl group which may be protected by a protective group, a nitro group, an acyl group, or a group represented by the following formula (2):
(wherein R
a
and R
b
have the same meanings as defined above); where the other carbon atoms of carbon atoms constituting the adamantane skeleton than those at the bridgehead positions may have a substituent; provided that (a) when R
a
is a hydrogen atom or a methyl group and R
b
is a methyl group, a hydroxyl group which is protected by a protective group, a hydroxymethyl group which may be protected by a protective group, an amino group which may be protected by a protective group, a carboxyl group which may be protected by a protective group, a nitro group, an acyl group or a group represented by the formula (2) is bonded to at least one carbon atom constituting the adamantane skeleton; and (b) when one of R
a
and R
b
is a methyl group and the other is an ethyl group, at least one substituent, in addition to the HO—C(R
a
)(R
b
)— group indicated in the formula (1), is bonded to the adamantane ring].
In the formula (1), R
b
may be a hydrocarbon group having a methine carbon atom at a bonding site with the adjacent carbon atom. Separately, R
a
and R
b
may be, identical to or different from each other, a C
2
-C
10
alkyl group or a 3- to 8-membered cycloalkyl group, or R
a
and R
b
may be the same hydrocarbon group. Furthermore, a hydroxyl group protected by a protective group may be bonded to at least one carbon atom constituting the adamantane skeleton.
The compounds represented by the formula (1) include adamantanemethanol derivatives represented by the following formula (1c):
[wherein R
a
is a hydrogen atom or a hydrocarbon group; R
b
is a hydrocarbon group having a carbon atom, to which carbon atom at least one hydrogen atom is bonded, at a bonding site with the adjacent carbon atom; R
d
and R
e
are each, identical to or different from each other, a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group which may be protected by a protective group, a hydroxymethyl group which may be protected by a protective group, an amino group which may be protected by a protective group, a carboxyl group which may be protected by a protective group, a nitro group, an acyl group, or a group represented by the following formula (2):
(wherein R
a
and R
b
have the same meanings as defined above); provided that R
d
and R
e
are not concurrently hydrogen atoms]. In these adamantanemethanol derivatives, R
d
may be a hydroxyl group which may be protected by a protective group.
The invention provides, in another aspect, a process for the production of an adamantanemethanol derivative (hereinafter may be referred to as “production process 1”), the process comprising the step of reacting an adamantane derivative represented by the following formula (3):
with an organometallic compound represented by the following formula (4):
R
y
—M   (4)
to give a compound represented by the formula (1).
In the above formulae (3) and (4), R
x
and R
y
each represent the aforementioned R
a
or R
b
, and R
y
is R
b
when R
x
is R
a
, and R
y
is R
a
when R
x
is R
b
; R
c1
, R
d1
and R
e1
are each, identical to or different from one another, a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group which may be protected by a protective group, a hydroxymethyl group which may be protected by a protective group, an amino group which may be protected by a protective group, a carboxyl group which may be protected by a protective group, a nitro group or an acyl group; where the other carbon atoms of carbon atoms constituting the adamantane skeleton than those at the bridgehead positions may have a substituent; provided that (a) when both R
x
and R
y
are methyl groups, or one is a hydrogen atom and the other is a methyl group, a hydroxyl group which is protected by a protective group, a hydroxymethyl group which may be protected by a protective group, an amino group which may be protected by a protective group, a carboxyl group which may be protected by a protective group, a nitro group, an acyl group, or a group represented by the formula (2) is bonded to at least one carbon atom constituting the adamantane skeleton; and (b) when one of R
x
and R
y
is a methyl group and the other is an ethyl group, at least one substituent, in addition to the R
x
C(═O)— group indicated in the formula (3), is bonded to the adamantane ring; M is a metal atom which may have a ligand, or a group represented by the following formula (5):
—MgY   (5)
(wherein Y is a halogen atom).
In a further aspect, the invention provides a process for the production of an adamantanemethanol derivative (hereinafter may be referred to as “production process 2”), the process comprising the steps of: subjecting a hydroxyadamantanecarboxylic acid derivative represented by the following formula (12a):
(wherein R
z1
is a hydrogen atom or a hydrocarbon group which may have a substituent; R
d1
and R
e1
are each, identical to or different from each other, a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group which may be protected by a protective group, a hydroxymethyl group which may be protected by a protective group, an amino group which may be protected by a protective group, a carboxyl group which may be protected by a protective group, a nitro group or an acyl group; where the other carbon atoms of carbon atoms constituting the adamantane skeleton than those at the bridgehead positions may have a substituent) to a reaction for the introduction of a protective group to give a c

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