JP2002255875A - Fluorine-containing cyclic compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new fluorine-containing cyclic compound useful as a raw material for a polymer, a functional material, a medicine, an agrochemical, etc. SOLUTION: This fluorine-containing cyclic compound is represented by general formula (1) (R<1> and R<2> are each independently a hydrogen atom or a monofunctional organic group; n is an integer of 0-5).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel fluorine-containing cyclic compound. The fluorinated cyclic compound is useful as a raw material for polymer compounds, functional materials, medical and agricultural chemicals, and the like.

[0002]

2. Description of the Related Art Aliphatic cyclic compounds obtained by introducing an acidic site into a cyclic compound such as bicycloalkane are used as a monomer or a raw material for producing a functional polymer compound. Recently, attempts have been made to synthesize high molecular weight compounds having both high transparency and positive characteristics by introducing acidic alcohol groups into the norbornene ring as a resin for positive resist (CGWillson et al., Providing Fluorine-Containing Cyclic Compounds) The purpose is to:

[0003]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have obtained a novel fluorine-containing compound, and have completed the present invention.

That is, the present invention provides a compound represented by the general formula (1)

[0005]

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(Wherein R ¹ and R ² each independently represent a hydrogen atom or a monovalent organic group, and n represents an integer of 0 to 5).

[0007]

Embodiments of the present invention will be described below in detail.

In the fluorine-containing cyclic compound of the present invention represented by the general formula (1), R ¹ and R ² each independently represent a hydrogen atom or a monovalent organic group; Represents an integer. Among these, the compound in which p is 0 and R ¹ and R ² are both hydrogen atoms has the formula (2)

[0009]

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Fluorine-containing diol represented by the formula:

The monovalent organic groups represented by R ¹ and R ² have the general formula (3)

[0012]

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(Wherein R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group, a fluoroalkyl group, or a cycloalkyl group, and R ⁵ each independently represent a hydrogen atom, an alkyl group, a fluoroalkyl group, or a cycloalkyl group. Alkyl group, cycloalkylalkyl group, or a group in which any hydrogen atom of these groups is substituted with an alkyl group, fluoroalkyl group, cycloalkyl group, alkoxy group, fluoroalkoxy group, hydroxy group, amino group, alkylamino group And R ³ and R ⁴ may be linked to form an alkylene group or a fluoroalkylene group.
Is an integer of 0 to 6, and q and r each independently represent 0 or 1. ) Is a monovalent organic group.

R ³ , R ⁴ and R ⁵ have about 1 to 20 carbon atoms, preferably about 1 to 10 carbon atoms. p is an integer of 0 to 6, and is preferably an integer of 0 to 3.

Examples of the alkyl group or cycloalkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, 2-hexyl, and the like. Ethylhexyl group, n-octyl group, decyl group, dodecyl group, tert-amyl group, 1,1-diethylpropyl group, 1-ethylcyclopentyl group, 1-butylcyclopentyl group, 1-ethylcyclohexyl group,
1-butylcyclohexyl group, 1-ethyl-2-cyclopentenyl group, 1-ethyl-2-cyclohexenyl group,
Triethylcarbyl group, 1-ethylnorbornyl group, 1-
Examples thereof include a methylcyclohexyl group, a 1-ethylcyclopentyl group, a 2- (2-methyl) adamantyl group, and a 2- (2-ethyl) adamantyl group.
0, especially 1 to 15 are preferred.

As the fluoroalkyl group, a group in which part or all of the hydrogen atoms of the above-mentioned alkyl groups have been substituted with fluorine atoms, for example, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 3,3,3 -Trifluoropropyl group, 1,1,2,2,3,3,3-heptafluoropropyl group and the like.

The trialkylsilyl group is preferably an alkyl group having 1 to 6 carbon atoms. Specifically, a trimethylsilyl group, a triethylsilyl group, a dimethyl-ter
t-butylsilyl and the like.

Specific examples of the monovalent organic groups represented by R ¹ and R ² in the general formula (1) include —CH ₂ —O—C
_{H 3, -CH 2 -O-CH} 2 -CH 3, -CH 2 -O- (C
_{H 2) 2 -CH 3, -CH} 2 -O- (CH 2) 3 -CH 3, -
CH ₂ —O—CH (CH ₃ ) —CH ₃ , —CH ₂ —O—C
_{(CH 3) 2 -CH 3,} -CH (CH 3) -O-CH 3, -
_{CH (CH 3) -O-CH} 2 -CH 3, -CH (C 2 H 5)
_{-O-CH 3, -CH (C} 3 H 7) -O-CH 3, -CH
_{(C 2 H 5) -O-} CH 2 -CH 3, -CH (CH 3) -O
— (CH ₂ ) ₂ —CH ₃ , —CH (CH ₃ ) —O— (C
_{H 2) 3 -CH 3, -CH} (C 2 H 5) -O- (CH 2) 2 -
_{CH 3, -CH (C 2 H} 5) -O- (CH 2) 3 -CH 3, -
_{CH (C 3 H 7) -O-} (CH 2) 2 -CH 3, -CH (C 3
_{H 7) -O- (CH 2)} 3 -CH 3, -CH (CH 3) -O
- cyclohexyl, -CH (CH ₃₎ -O- _{cyclopentyl, -C (CH 3) 2 -O} -CH 3, -C (CH 3) 2 -
Groups such as _{O-CH 3, -CH 2 -OH} , - (CH 2) 2 -O
_{H, - (CH 2) 3} -OH, - (CH 2) 4 -OH, - (C
_{H 2) 5 -OH, - (} CH 2) -OH, -CH 2 -O- (C
_{H 2) 3 -CH 3, -} (CH 2) 2 -O- (CH) -CH,
_{- (CH 2) 2 -O- (} CH 2) 2 -CH 3, - (CH 2) 2
-O-CH ₂ -CH, -CH- (cyclohexylene) -
A tert-butoxycarbonyl group, such as a group such as CH ₂ —OH, a tetrahydrofuran-2-yl group, a 2-methyltetrahydrofuran-2-yl group, a tetrahydropyran-2-yl group, a 2-methyltetrahydropyran-2-yl group; Tert-butoxycarbonylmethyl group, tert
-Amyloxycarbonyl group, tert-amyloxycarbonylmethyl group, 1,1-diethylpropyloxycarbonyl group, 1,1-diethylpropyloxycarbonylmethyl group, 1-ethylcyclopentyloxycarbonyl group, 1-ethylcyclopentyloxycarbonylmethyl Group, 1-ethyl-2-cyclopentenyloxycarbonyl group, 1-ethyl-2-cyclopentenyloxycarbonylmethyl group, 1-ethoxyethoxycarbonylmethyl group, 2-tetrahydropyranyloxycarbonylmethyl group, 2-tetrahydrofuranyloxy Examples include a carbonylmethyl group and the like.

Further, a group represented by the following formula can also be exemplified.

[0020]

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Where R⁹Is a straight chain having 1 to 6 carbon atoms,
Shows a branched or cyclic alkyl group, specifically methyl
Group, ethyl group, propyl group, isopropyl group, n-butyl
Group, sec-butyl group, n-pentyl group, n-hexyl
Group, cyclopropyl group, cyclopropylmethyl group,
Clobutyl, cyclopentyl, cyclohexyl, etc.
Can be exemplified. R^TenIs a straight-chain, branched or branched chain having 2 to 6 carbon atoms.
Represents a cyclic alkyl group, specifically, an ethyl group,
Pill group, isopropyl group, n-butyl group, sec-butyl
Group, n-pentyl group, n-hexyl group, cyclopropyl
Group, cyclopropylmethyl group, cyclobutyl group,
Examples thereof include a lopentyl group and a cyclohexyl group. R¹¹
May include a hydrogen atom and a heteroatom having 1 to 6 carbon atoms.
Monovalent hydrocarbon group, also via a heteroatom having 1 to 6 carbon atoms
Shows good monovalent hydrocarbon groups. As a hetero atom, oxygen
Atom, sulfur atom, and nitrogen atom;
H, -OR (R is an alkyl group, the same applies hereinafter), -O-,-
S-, -S (= O)-, -NH _Two, -NHR, -NR_Two,
It can be contained or intervened as -NH-, -NR-
You.

Examples of R ¹¹ and R ¹² include a hydrogen atom, an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkoxy group, an alkoxyalkyl group and the like. These can be any of linear, branched and cyclic. May be. Specifically, methyl, hydroxymethyl, ethyl, hydroxyethyl, propyl, isopropyl, n-butyl, sec-butyl, n-pentyl, n-hexyl, methoxy, methoxymethoxy Group, ethoxy group, tert-butoxy group and the like.

Of these, methoxymethyl, ethoxyethyl, butoxyethyl, ethoxypropyl and the like are preferred.

The method for producing the fluorine-containing cyclic compound represented by the general formula (1) will be described below. In the present specification, 1,1,1,7,7,7-hexafluoro-2,6- represented by the chemical formula
Bis (trifluoromethyl) -3-heptene-2,6-diol (1,1,1,7,7,7-hexafluoro-2,6-bis (trifluoromethyl)-
3-Heptene-2,6-diol) is sometimes referred to as “HBHD”.

[0025]

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The fluorinated cyclic compound represented by the formula (1) has the general formula (4)

[0027]

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(Wherein R ¹ and R ² are the same as those in the general formula (1)). The compound can be obtained by reacting an HBHD derivative represented by the following formula with dicyclopentadiene. Also, HBH
From D and dicyclopentadiene, a diol represented by the formula (2) can be obtained by a similar reaction. The same reaction can be performed by using cyclopentadiene instead of dicyclopentadiene. The reaction method is HBH
It can be carried out by mixing the D derivative and dicyclopentadienecyclopentadiene in a sealed container in a heated or non-heated state in the presence or absence of a solvent. Any solvent can be used without particular limitation as long as it is inert to the reaction and can dissolve dicyclopentadiene or cyclopentadiene and the HBHD derivative. For example, methylene chloride,
Examples include tetrahydrofuran, toluene, dimethylformamide and the like. However, a solvent is not required. The reaction temperature and time can be appropriately selected, but are 0 to 200 ° C, preferably 100 to 200 ° C. The reaction time varies depending on the type of the HBHD derivative and the reaction temperature, but is about 1 to 200 hours. HB in the reaction
The molar ratio between HD and dicyclopentadiene or cyclopentadiene may be 1/100 to 100/1.

HBHD is described, for example, in the literature (J. Org. Chem. (19)
68), 33 (6), 2302-2310).

The HBHD derivative represented by the general formula (4) can be obtained by forming an oxygen-carbon bond with a hydroxy group of HBHD by a conventional method. For example, it can be produced from HBHD and an alkyl halide or a halide of a corresponding organic group by a nucleophilic substitution reaction. For example, mixing is performed at 100 ° C. or lower, usually 50 ° C. or lower, preferably 10 ° C. or lower in the presence of a metal hydride such as sodium hydride, and in some cases, the mixture is heated by adding a quaternary ammonium salt.
Alkyl halide is usually added to 1 mole of HBHD derivative per mole.
It is used in an amount of at least 1 mol, preferably 1 to 100 mol, more preferably 1 to 30 mol.

Further, the fluorine-containing cyclic compound represented by the general formula (1) can be obtained by forming an oxygen-carbon bond from the fluorine-containing diol represented by the formula (2) by a conventional method. For example, when producing a fluorine-containing cyclic compound represented by the formula (1) which does not contain a functional group active in a hydroxyl group and a halogen of an alkyl halide under reaction conditions,
A fluorine-containing cyclic diol represented by the formula (2) and an alkyl halide or a corresponding general formula (5)

[0032]

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(Wherein R is R ¹ or R ² of the general formula (1))
And X represents chlorine, bromine, fluorine or iodine. ) Can be produced by a nucleophilic substitution reaction. For example, in the presence of a metal hydride such as sodium hydride 100
C., usually 50.degree. C. or less, preferably 10.degree. C. or less, and in some cases, the mixture is added with a quaternary ammonium salt and then heated.

In any of these cases, the product after the reaction can be separated and purified by a conventional method. For example, concentration, distillation, extraction, recrystallization, filtration, column chromatography, etc. can be used. The above methods may be used in combination.

The fluorine-containing cyclic compound represented by the general formula (1) can be homopolymerized to produce a homopolymer.

The polymerization method is not particularly limited.
The fluorine-containing cyclic compound represented by the general formula (1) may be subjected to conventional metallocene polymerization, radical polymerization, or ionic polymerization, and a solvent may be used for the polymerization. For example, acetone, butyl acetate, toluene, methylene chloride ,
Tetrahydrofuran, dimethylformamide and the like can be used as the solvent. Examples of the metallocene catalyst include trimethoxy (pentamethylcyclopentadienyl) titanium (IV, biscyclopentadienyl zirconium dichloride, nickel (II) acetylacetonate, and palladium (II) bisacetylacetonate.
At this time, it is preferable to use a co-catalyst methylaluminoxane. The temperature and time of the reaction can be appropriately selected,
-78 ° C to 200 ° C for 5 minutes to 100 hours, preferably 2
A homopolymer can be obtained by conducting the reaction at 0 ° C to 80 ° C for 1 hour to 24 hours.

The polymer containing the fluorine-containing cyclic compound represented by the general formula (1) as a copolymer component can be produced, for example, by the following method.

[0038] The polymerization method is not particularly limited.
Conventional metallocene polymerization, radical polymerization, or ionic polymerization may be performed on the fluorine-containing cyclic compound represented by the general formula (1) and a hydrocarbon having a polymerizable double bond, and a solvent may be used for the polymerization. For example, acetone, butyl acetate, toluene, methylene chloride, tetrahydrofuran, dimethylformamide and the like can be used as the solvent.
Examples of the catalyst include trimethoxy (pentamethylcyclopentadienyl) titanium (IV), biscyclopentadienyl zirconium dichloride, and nickel acetylacetonate. In this case, it is preferable to use methylaluminoxane as a cocatalyst. The reaction temperature and time can be appropriately selected, but a copolymer can be obtained by conducting the reaction at -78 ° C to 200 ° C for 5 minutes to 100 hours, preferably at 20 ° C to 80 ° C for 1 hour to 24 hours. The hydrocarbon having a polymerizable double bond is not particularly limited as long as it is a compound having a polymerizable double bond, and chain olefins, for example, ethylene, propylene, butene, and the like having a cyclic olefin skeleton, cyclobutene, Cyclopentene, cyclohexene or the like or a substituent bonded thereto, further acrylates, methacrylates, carboxylate vinyl esters, hydrocarbons having a polymerizable double bond having a functional group, and the like. A hydrocarbon in which an arbitrary hydrogen atom is replaced by a fluorine atom can also be preferably used. As a matter of course, the copolymerization reaction may be carried out using two or more of these other monomers in combination.

[0039]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 "Synthesis of diol compound represented by formula (2)"

[0041]

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Under a nitrogen atmosphere, dicyclopentadiene (68.98 g, 0.52 mol) was placed in a 2 L autoclave at room temperature.
l), 1,1,1,7,7,7-hexafluoro-2,
6-Bis (trifluoromethyl) -3-heptene-2,6-diol (HBHD, 1171.25 g, 3.13 mol) was added, the reaction tube was sealed, and the mixture was heated to an internal temperature of 200 ° C., stirred for 72 hours, and heated at a temperature Maintained. Subsequently, the autoclave was allowed to cool to reduce the internal pressure, and then the contents were transferred to a flask, and unreacted HBHD was removed by flash distillation. Subsequently, it was isolated and purified by distillation under reduced pressure. The compound was identified by mass spectrometry. m / z: 440, 389, 207, 15
1, 117, 91, 67, 32.

[0043]

According to the present invention, a monomer of a functional polymer compound having water repellency, oil repellency, low water absorption, heat resistance, weather resistance, corrosion resistance, transparency, photosensitivity, etc., or its raw material, etc. Provided is a novel fluorine-containing cyclic compound useful as a compound.

 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Kentaro Tsutsumi 2805 Imafukunakadai, Kawagoe-shi, Saitama Central Glass Co., Ltd. Chemical Research Laboratory (72) Inventor Kazuhiko Maeda 3-7-1 Kandanishikicho, Chiyoda-ku, Tokyo Central Glass Co., Ltd. F term (reference) 4H006 AA01 AA02 AC21 AC43 FC26 FE11 FE71 FE74

Claims (6)

[Claims] 1. A compound of the general formula (1) (Wherein, R ¹ and R ² each independently represent a hydrogen atom or a monovalent organic group, and n represents an integer of 0 to 5). 2. The monovalent organic groups represented by R ¹ and R ² are each independently represented by the general formula (3): (Wherein, R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group, a fluoroalkyl group, or a cycloalkyl group;
R ⁵ is independently a hydrogen atom, an alkyl group, a fluoroalkyl group, a cycloalkyl group, a cycloalkylalkyl group, or any hydrogen atom of these groups is an alkyl group, a fluoroalkyl group, a cycloalkyl group, an alkoxy group, a fluoro group, It represents a group substituted with an alkoxy group, a hydroxy group, an amino group, an alkylamino group, or a trialkylsilyl group. R ³ and R ⁴ may be linked to form an alkylene group or a fluoroalkylene group. p represents an integer of 0 to 6, and q and r each independently represent 0 or 1. The fluorine-containing cyclic compound according to claim 1, which is a monovalent organic group represented by the formula: 3. A fluorine-containing diol represented by the formula (2). Embedded image 4. Dicyclopentadiene or cyclopentadiene and a compound of the general formula (4) (Wherein R ¹ and R ² are the same as in the general formula (1)). A method for producing a fluorine-containing diol represented by the general formula (1), comprising reacting the same. 5. A reaction of dicyclopentadiene or cyclopentadiene with 1,1,1,7,7,7-hexafluoro-2,6-bis (trifluoromethyl) -3-heptene-2,6-diol. A method for producing a fluorine-containing diol represented by the formula (2): 6. A fluorine-containing diol represented by the formula (2) and a general formula (5): (Wherein, R represents a monovalent organic group represented by R ¹ or R ² in the general formula (1), and X represents chlorine, bromine, fluorine or iodine). A method for producing a fluorine-containing cyclic compound represented by the general formula (1), which comprises reacting in the presence of a metal.