Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
2001-06-19
2002-07-02
Rotman, Alan L. (Department: 1625)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
C568S326000, C568S445000, C568S665000, C568S817000
Reexamination Certificate
active
06414167
ABSTRACT:
BACKGROUND OF THE INVENTION
The present invention relates to novel fluorine-containing cycloalkane derivatives, which are useful as monomers for producing various functional polymers (having functions of water-repellency, oil-repellency, low water absorption, heat resistance, weatherability, corrosion resistance, transparency, photosensitivity and the like) and useful as raw materials of the same, and processes for producing such derivatives.
Aliphatic cyclic compounds, obtained by bonding a hydroxyl group to a ring (e.g., adamantane and bicycloalkane), have been used as monomers for producing functional polymers or as raw materials of the same. There is, however, a recent demand for novel monomers or their raw materials for providing superior functional polymers.
SUMMARY OF THE INVENTION
It is therefore an object of the present invention to provide a novel fluorine-containing cycloalkane derivative (e.g., an octafluorotricyclodecane derivative), which may be useful as a monomer for producing various functional polymers (having functions of water-repellency, oil-repellency, low water absorption, heat resistance, weatherability, corrosion resistance, transparency, photosensitivity and the like) or as a raw material of the same.
It is another object of the present invention to provide a process for producing such novel fluorine-containing cycloalkane derivative.
According to the present invention, there is provided an octafluorotricyclodecane derivative represented by the general formula (1),
where R
1
is a hydrogen atom, a halogen atom, a hydrocarbon group or a halogenated hydrocarbon group, m is 0 or 1, and R
2
is represented by the general formula (2),
where R
3
is a hydrogen atom or a hydrocarbon group optionally having a substituent.
According to the present invention, there is provided a first process for producing a first octafluorotricyclodecane derivative represented by the general formula (6),
where R
3
is defined as above. The first process comprises reacting a second octafluorotricyclodecane derivative, which is represented by the general formula (4), with a carboxylic acid represented by the general formula (5),
where R
1
is defined as above,
R
3
COOH (5)
where R
3
is defined as above.
According to the present invention, there is provided a second process for producing an octafluorotricyclodecane derivative represented by the formula (8).
The-second process comprises (a) conducting an epoxidation of 2,3,3,4,4,5,5,6-octafluorotricyclo[5.2.1.0
2,6
]-8-decene, thereby obtaining an epoxy compound represented by the formula (7); and (b) reducing said epoxy compound into said octafluorotricyclodecane derivative.
According to the present invention, there is provided a third process for producing an octafluorotricyclodecane derivative represented by the general formula (4). The third process comprises (a) conducting a rearragement reaction of an epoxy compound represented by the formula (7), thereby obtaining a ketone represented by the formula (9); (b) reacting said ketone with an organic metal compound represented by the general formula R
1
MX where R
1
is a hydrogen atom, a hydrocarbon group or a halogenated hydrocarbon group, M is a metal, and X is a halogen atom, thereby obtaining a product; and (c) hydrolyzing said product into said octafluorotricyclodecane.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
It is possible to efficiently produce the respective target octafluorotricyclodecane derivatives by the first to third processes.
As stated above, R
1
in the general formula (1) is a hydrogen atom, a halogen atom, a hydrocarbon group or a halogenated hydrocarbon group. This halogen atom may be fluorine, chlorine or bromine. Examples of the hydrocarbon group are C
1
-C
20
hydrocarbon groups, such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclopentyl group, cyclohexyl group, phenyl group, benzyl group, and phenethyl group. Of these, C
1
-C
10
hydrocarbon groups are preferable, more preferably C
1
-C
4
hydrocarbon groups. Examples of the halogenated hydrocarbon group are those obtained by partially or fully replacing hydrogen atoms of the above alkyl groups with halogen atoms, such as trifluoromethyl group, 2,2,2-trifluoroethyl group, 1,1,1,3,3,3-hexafluoroisopropyl group.
As stated above, R
3
in the general formula (2) is a hydrogen atom or a hydrocarbon group optionally having a substituent. This hydrocarbon group is preferably selected from C
1
-C
20
hydrocarbon groups. Examples of the hydrocarbon group, which is free of a polymerizable double bond, are methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclopentyl group, cyclohexyl group, phenyl group, benzyl group, and phenethyl group. Examples of the optional substituent are acyl group, allyl group, alkoxyl group, alkoxycarbonyl group, carboxyl group, carbonyl group, hydroxyl group, and nitrile group. Furthermore, R
3
may be a monovalent group represented by the general formula (3) having a polymerizable double bond,
where each of R
4
, R
5
, and R
6
is independently a hydrogen atom, a halogen atom, or a hydrocarbon group optionally having a substituent, and n is an integer of 0-8. This halogen atom may be fluorine, chlorine or bromine. This hydrocarbon group is preferably selected from C
1
-C
20
hydrocarbon groups, such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclopentyl group, cyclohexyl group, phenyl group, benzyl group, and phenethyl group. Of these, C
1
-C
10
hydrocarbon groups are preferable, more preferably C
1
-C
4
hydrocarbon groups. Examples of the optional substituent are acyl group, allyl group, alkoxyl group, alkoxycarbonyl group, carboxyl group, carbonyl group, hydroxyl group, vinyl group, and nitrile group.
Concrete examples of R
2
are vinyl group, allyl group, acryloyl group and methacryloyl group.
The process for producing the octafluorotricyclodecane derivative represented by the general formula (1) will be described in detail in the following.
It is possible to produce the target octafluorotricyclodecane derivative represented by the general formula (1) from a starting material of 2,3,3,4,4,5,5,6-octafluorotricyclo[5.2.1.0
2,6
]-8-decene by using the first, second or third process via an intermediate such as an epoxy derivative represented by the formula (7), a ketone derivative represented by the formula (9), and an alcohol derivative represented by the formula (4) or (8). In other words, each starting material, represented by the formula (4) or (7), of the first and third processes can be produced from 2,3,3,4,4,5,5,6-octafluorotricyclo[5.2.1.0
2,6
]-8-decene
In the invention, the process for synthesizing the octafluorotricyclodecane derivative (an epoxy compound) represented by the formula (7) is not particularly limited. For example, it can be synthesized by treating 2,3,3,4,4,5,5,6-octafluorotricyclo[5.2.1.0
2,6
]-8-decene with a peracid in a solvent to proceed an epoxidation, as in the second process. This solvent is not particularly limited, so long as it can dissolve 2,3,3,4,4,5,5,6-octafluorotricyclo[5.2.1.0
2,6
]-8-decene and the peracid. Exemplary solvents are methylene chloride, diethyl ether, and tetrahydrofuran. Examples of the peracid are peracetic acid, metachloroperbenzoic acid and monoperoxyphthalic acid. The temperature and the period of time for conducting the epoxidation may be suitably selected depending on the reagent types and the like. It is preferably conducted at a temperature of 0-100° C. for 1-48 hr.
In the invention, the process for synthesizing the octafluorotricyclodecane derivative (a ketone compound) represented by the formula (9) is not particularly limited. For example, it can be synthesized by a rearrangement reaction of the epoxy compound represented by the formula (7) using an acid catalyst, as in the third process. Examples of this acid cat
Miyazawa Satoru
Ootani Michitaka
Tsutsumi Kentaro
Central Glass Company Limited
Covington Raymond
Crowell & Moring LLP
Rotman Alan L.
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