Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
2000-08-28
2002-11-26
Solola, T. A. (Department: 1626)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
active
06486330
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to 4-oxatricyclo[4.3.1.1
3,8
]undecan-5-one derivatives which are useful as materials for photosensitive resins and other functional polymers and as materials for pharmaceuticals, agricultural chemicals, and other fine chemicals, and to a process for producing the derivative.
2. Description of the Related Art
A compound 4-oxatricyclo[4.3.1.1
3,8
]undecan-5-one is known as an intermediate for organic synthesis (e.g., Synthesis, 1986, 741-743). This compound is obtained by introducing an oxygen atom to the adjacent position of a carbonyl group of 2-adamantanone. However, 4-oxatricyclo[4.3.1.1
3,8
]undecan-5-one derivatives having a hydroxyl group or a (meth)acryloyloxy group bonded to a carbon atom at the 1-position are not known.
On the other hand, a lithography technique is used for the formation of fine patterns of semiconductor integrated circuits. The lithography technique includes the steps of covering a substrate having a thin film formed thereon (work) with a resist, subjecting the work to selective exposure to yield a latent image of a target pattern, subjecting the work to developing to form a patterned resist, dry-etching the work using the pattern as a mask, and then removing the resist to yield the target pattern. In the lithography technique, g-ray, i-ray, and other ultraviolet rays are used as light sources. However, with an increasing fineness of patterns, far ultraviolet rays, vacuum ultraviolet rays, excimer laser beams, electron beams, x-rays and other rays having a shorter wavelength are employed as the light sources. To form fine patterns using such a short-wavelength light source (e.g., ArF excimer laser), the resist used must have a satisfactory transparency at the wavelength of the light source, have a good adhesion to the substrate, be resistance to dry etching, and be satisfactorily soluble in a developer in development. As such resist materials, polymers of polymerizable monomers each having a bridged ring or a lactone ring have received attention in recent years (e.g., Japanese Unexamined Patent Application Publication No. 9-73173), but none of them sufficiently satisfies the above requirements.
SUMMARY OF THE INVENTION
Accordingly, an object of the invention is to provide a novel 4-oxatricyclo[4.3.1.1
3,8
]undecan-5-one derivative having a hydroxyl group or a (meth)acryloyloxy group at the 1-position.
Another object of the invention is to provide a 4-oxatricyclo[4.3.1.1
3,8
]undecan-5-one derivative which is useful as a monomeric material for photoresist resins.
A further object of the invention is to provide a process for efficiently producing the 4-oxatricyclo[4.3.1.1
3,8
]undecan-5-one derivative.
After intensive investigations to achieve the above objects, the present inventors found that when a 4-adamantanone derivative having a hydroxyl group or a (meth)acryloyloxy group at the 1-position is oxidized with molecular oxygen by catalysis of an imide compound having a specific structure in the coexistence of a specific compound, a Baeyer-Villiger type reaction proceeds to efficiently yield a corresponding 4-oxatricyclo[4.3.1.1
3,8
]undecan-5-one derivative. The present invention has been accomplished based on these findings.
Specifically, the invention provides, in an aspect, a 4-oxatricyclo[4.3.1.1
3,8
]undecan-5-one derivative shown by the following formula (1):
wherein R is a hydrogen atom or a (meth)acryloyl group, and carbon atoms constituting a ring may have a substituent in addition to the substituents indicated in the formula. Preferred R includes a (meth)acryloyl group.
In another aspect, the invention provides a process for producing a 4-oxatricyclo[4.3.1.1
3,8
]undecan-5-one derivative. This process includes the step of oxidizing an adamantanone derivative shown by the following formula (2):
wherein R is a hydrogen atom or a (meth)acryloyl group, and carbon atoms constituting a ring may have a substituent in addition to the substituents indicated in the formula, with molecular oxygen in the presence of an imide compound shown by the following formula (3):
wherein each of R
1
and R
2
is, identical to or different from each other, a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cycloalkyl group, a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or an acyl group, where R
1
and R
2
may be combined to form a double bond, or an aromatic or non-aromatic ring; X is an oxygen atom or a hydroxyl group; and one or two N-substituted cyclic imido groups indicated in the formula (3) may be further formed on the R
1
, R
2
, or on the double bond or aromatic or non-aromatic ring formed together by R
1
and R
2
, and in the coexistence of an co-oxidizing agent to yield a 4-oxatricyclo[4.3.1.1
3,8
]undecan-5-one derivative shown by the following formula (1):
wherein R is a hydrogen atom or a (meth)acryloyl group, and carbon atoms constituting a ring may have a substituent in addition to the substituents indicated in the formula. The co-oxidizing agent includes, for example, a primary or secondary alcohol.
The invention provides, in a further aspect, a process for producing a 4-oxatricyclo[4.3.1.1
3,8
]undecan-5-one derivative. This process includes the step of allowing a compound of the following formula (1a):
wherein carbon atoms constituting a ring may have a substituent in addition to the substituents indicated in the formula, to react with (meth)acrylic acid or a reactive derivative thereof to yield a compound shown by the following formula (1b):
wherein R
d
is a (meth)acryloyl group, and carbon atoms constituting a ring may have a substituent in addition to the substituents indicated in the formula.
In this specification, both acryloyl group and methacryloyl group are simply referred to as “(meth)acryloyl group”.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In the 4-oxatricyclo[4.3.1.1
3,8
]undecan-5-one derivative of the formula (1), R is a hydrogen atom or a (meth)acryloyl group. Carbon atoms constituting a ring may have a substituent in addition to the substituents (—OR group and oxo group) indicated in the formula. Such substituents include, but are not limited to, methyl group, ethyl group, isopropyl group, and other C
1
-C
4
alkyl groups, hydroxyl group which may have a protective group, and carboxyl group which may have a protective group. As the protective groups, those conventionally used in the field of organic synthesis can be employed.
Typical 4-oxatricyclo[4.3.1.1
3,8
]undecan-5-one derivatives of the formula (1) include, but are not limited to, 1-hydroxy-4-oxatricyclo[4.3.1.1
3,8
]undecan-5-one, 1-(meth)acryloyloxy-4-oxatricyclo[4.3.1.1
3,8
]undecan-5-one, 1-hydroxy-3,8-dimethyl-4-oxatricyclo[4.3.1.1
3,8
]undecan-5-one, 1-(meth)acryloyloxy-3,8-dimethyl-4-oxatricyclo[4.3.1.1
3,8
]undecan-5-one, 1-hydroxy-3,6-dimethyl-4-oxatricyclo[4.3.1.1
3,8
]undecan-5-one, 1-(meth)acryloyloxy-3,6-dimethyl-4-oxatricyclo[4.3.1.1
3,8
]undecan-5-one, 1,8-dihydroxy-4-oxatricyclo[4.3.1.1
3,8
]undecan-5-one, 8-hydroxy-1-(meth)acryloyloxy-4-oxatricyclo[4.3.1.1
3,8
]undecan-5-one, 1,6-dihydroxy-4-oxatricyclo[4.3.1.1
3,8
]undecan-5-one, 6-hydroxy-1-(meth)acryloyloxy-4-oxatricyclo[4.3.1.1
3,8
]undecan-5-one, 1,3-dihydroxy-4-oxatricyclo[4.3.1.1
3,8
]undecan-5-one, 3-hydroxy-1-(meth)acryloyloxy-4-oxatricyclo[4.3.1.1
3,8
]undecan-5-one, 8-carboxy-1-hydroxy-4-oxatricyclo[4.3.1.1
3,8
]undecan-5-one, 8-carboxy-1-(meth)acryloyloxy-4-oxatricyclo[4.3.1.1
3,8
]undecan-5-one, 6-carboxy-1-hydroxy-4-oxatricyclo[4.3.1.1
3,8
]undecan-5-one, 6-carboxy-1-(meth)acryloyloxy-4-oxatricyclo[4.3.1.1
3,8
]undecan-5-one, 3-carboxy-1-hydroxy-4-oxatricyclo[4.3.1.1
3,8
]undecan-5-one, and 3-carboxy-1-(meth)acryloyloxy-4-oxatricyclo[4.3.1.1
3,8
]undec
Daicel Chemical Industries Ltd.
Solola T. A.
LandOfFree
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