Polymerizable alicyclic esters and process producing the same

Details Polymerizable alicyclic esters and process producing the same Polymerizable alicyclic esters and process producing the same

2000-07-20

2001-04-17

Gitomer, Ralph (Department: 1623)

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

Organic compounds

Carboxylic acid esters

Reexamination Certificate

active

06218569

ABSTRACT:

TECHNICAL FIELD
The present invention relates to polymerizable alicyclic esters which are useful as monomers for photosensitive resins and other functional polymers, and to a process for producing the esters.
BACKGROUND ART
Alicyclic compounds each having a polymerizable unsaturated group are used as monomers for resist resins and other functional polymers, and have received attention in recent years.
However, no knowledge has been obtained about alicyclic ester compounds each having a polycyclic carbon ring composed of two or three non-aromatic carbon rings each having two carbon atoms in common and having a polymerizable unsaturated carboxylic acyloxy group bonded to a carbon atom at the junction position between two rings, and about processes for producing the ester compounds.
DISCLOSURE OF INVENTION
Accordingly, an object of the invention is to provide a novel alicyclic ester compound having a polycyclic carbon ring composed of two or three non-aromatic carbon rings each having two carbon atoms in common and having a polymerizable unsaturated carboxylic acyloxy group bonded to a carbon atom at the junction position between two rings, and a process for producing the ester compound.
The present inventors made intensive investigations to achieve the above object, and found that when an alicyclic alcohol having a polycyclic carbon ring composed of two or three non-aromatic carbon rings each possessing two carbon atoms in common and having a hydroxyl group on a carbon atom at the junction position between two rings is allowed to react with a polymerizable unsaturated carboxylic acid in the presence of a specific catalyst, an esterification reaction smoothly proceeds to yield a corresponding novel alicyclic ester, even though the hydroxyl group is bonded to a sterically crowded position. The invention, has been accomplished based on these findings.
Specifically, the invention provides a polymerizable alicyclic ester shown by the following formula (1) or (2):
wherein each of ring A, ring B, ring C, ring D, and ring E is a non-aromatic carbon ring, R is a polymerizable unsaturated group, and each of R
a1
, R
b1
and R
c1
is, identical to or different from one another, a hydrogen atom, a hydroxyl group which may be protected by a protective group, or an RCO
2
group, where R has the same meaning as defined above.
The invention provides, in another aspect, a process for producing a polymerizable alicyclic ester. The process includes the step of allowing an alicyclic alcohol shown by the following formula (3) or (4):
wherein each of ring A, ring B, ring C, ring D, and ring E is a non-aromatic carbon ring, and each of R
a2
, R
b2
, and R
c2
is, identical to or different from one another, a hydrogen atom or a hydroxyl group which may be protected by a protective group, to react with an unsaturated carboxylic acid shown by the following formula (5):
RCO
2
H  (5)
wherein R is a polymerizable unsaturated group, or a reactive derivative thereof in the presence of a catalyst composed of a compound of Group 3 element of the Periodic Table of Elements to yield the ester of the formula (1) or (2).
In the present description, “acryl” and “methacryl” may be abbreviated to “(meth)acryl”, and “acryloyl” and “methacryloyl” may be abbreviated to “(meth)acryloyl”.
BEST MODE FOR CARRYING OUT THE INVENTION
In the invented polymerizable alicyclic esters, each of the ring A, ring B, ring C, ring D, and ring E is a non-aromatic carbon ring. Such non-aromatic carbon rings include monocyclic or polycyclic rings (e.g., bridged rings) each having about 3 to 20 carbon atoms. The carbon rings may have a double bond as far as the rings are non-aromatic. If the carbon rings are polycyclic rings, the carbon rings may each have an additional aromatic ring, as far as a ring joined to the adjacent ring (the ring A, ring B, ring C, ring D or ring E) is a non-aromatic carbon ring.
Typical examples of the non-aromatic carbon rings include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclopentene ring, cyclohexane ring, cyclohexene ring, cycloheptane ring, cyclooctane ring, cyclodecane ring, cyclododecane ring, cyclopentadecane ring, and other monocyclic rings; perhydroindene ring, decalin ring, norbornane ring, norbornene ring, bicyclo[2.2.2]octane ring, and other bridged rings. Among these rings, cyclopentane ring, cyclohexane ring, and bridged rings are preferred.
The non-aromatic carbon rings may have a substituent. Such substituents include halogen atoms such as fluorine, chlorine, bromine, or iodine atom; alkyl groups such as methyl, ethyl, isopropyl, and other C
1
-C
6
alkyl groups, especially C
1
-C
4
alkyl groups; cycloalkyl groups; aryl groups such as phenyl group and naphthyl group; hydroxyl group; alkoxy groups such as methoxy, ethoxy, isopropoxy, and other C
1
-C
6
alkoxy groups, especially C
1
-C
4
alkoxy groups; acyloxy groups such as acetyloxy, propionyloxy, (meth)acryloyloxy, and other C
2
-C
6
aliphatic acyloxy groups, especially C
2
-C
4
aliphatic acyloxy groups; carboxyl group; alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, and other C
1
-C
6
alkoxycarbonyl groups, especially C
1
-C
4
alkoxycarbonyl groups; substituted or unsubstituted carbamoyl groups such as carbamoyl group; methylcarbamoyl, dimethylcarbamoyl, diethylcarbamoyl, and other mono- or di-C
1
-C
4
alkyl-substituted carbamoyl groups; acyl groups such as acetyl, propionyl, and other C
2
-C
6
aliphatic acyl groups, especially C
2
-C
4
aliphatic acyl groups; oxo group; substituted or unsubstituted amino groups such as amino group, methylamino, ethylamino, propyl amino, dimethylamino, diethylamino, and other mono- or di-C
1
-C
6
alkyl-substituted amino groups, especially mono- or di-C
1
-C
4
alkyl-substituted amino groups; cyano group; and nitro group. The hydroxyl group, carboxyl group, and amino group may be protected by a conventional protective group.
In the formula (1), polycyclic carbon rings formed by the ring A and the ring B include, but are not limited to, perhydroindene ring, decalin ring, perhydrofluorene ring, perhydroanthracene ring, perhydrophenanthrene ring, and tricyclo[5.2.1.0
2,6
]decane ring. In the formula (2), polycyclic carbon rings formed by the ring C, the ring D, and the ring E include, but are not limited to, perhydroacenaphthene ring and perhydrophenalene ring.
The polymerizable unsaturated groups in the substituent R include hydrocarbon groups each having a polymerizable double bond such as vinyl group, isopropenyl group, allyl group, allylmethyl group, and other allyl-C
1
-C
4
alkyl groups, 2-methyl-2-propenyl group and other &agr;-alkyl-substituted vinyl-C
1
-C
4
alkyl groups; and hydrocarbon groups each having a polymerizable triple bond such as ethynyl group, 2-propynyl group and other ethynyl-C
1
-C
4
alkyl groups. Preferred polymerizable unsaturated groups each have an &agr;,&bgr;-ethylenically unsaturatedbond. Such preferred polymerizable unsaturated groups include vinyl group, isopropenyl group, and allyl group, of which vinyl group or Isopropenyl group is typically preferred.
Each of the substituents R
a1
, R
b1
and R
c1
is, identical to or different from one another, a hydrogen atom, a hydroxyl group which may be protected by a protective group, or an RCO
2
group, where R has the same meaning as defined above. The protective groups for hydroxyl group may be conventional protective groups Such protective groups include, but are not limited to, alkyl groups such as methyl and t-butyl groups; alkenyl groups such as allyl group; cycloalkyl groups such as cyclohexyl group; aryl groups such as 2,4-dinitrophenyl group; aralkyl groups such as benzyl, 2,6-dichlorobenzyl, 3-bromobenzyl, 2-nitrobenzyl, and triphenylmethyl groups; substituted methyl groups such as methoxymethyl, methylthiomethyl, benzyloxymethyl, t-butoxymethyl, 2-methoxyethoxymethyl, 2,2,2-trichloroethoxymethyl, bis(2-chloroethoxy)methyl, and 2-(trimethylsilyl)ethoxymethyl groups; substituted ethyl groups such as 1-ethoxyethyl, 1-methyl-1-methoxyethyl,

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