JPH02134337A - Fluorine-containing aromatic compound - Google Patents

Abstract

NEW MATERIAL:Fluorine-containing aromatic compounds represented by formula I (R is H or CH3; Y is CO or CH2). EXAMPLE:1,1,1,3,3,3-Hexafluoro-2-methacryloyloxy-2-phenyl-propane. USE:A raw material of a novel substance having excellent functions such as higher heat resistance, chemical resistance, weather resistance, low frictional properties, water and oil repellency, low refractive index, transparency and oxygen permeability, or a fluorinating agent capable of conversion to another fluorine-containing compound in itself. PREPARATION:A compound of formula II is reacted with a compound of formula III (X is halogen) to readily obtain a compound of formula I. In addition various useful polymers of a fluorine-containing bisphenol derivative is readily prepared by homopolymerization of the resultant compound or by copolymerization thereof with various monomers having a polymerizable olefinic double bond, e.g., using the radical polymerization method.

Description

[Detailed Description of the Invention] [Industrial Application Field] This invention relates to a novel fluorine-containing aromatic compound that has a radically polymerizable unsaturated bond and is useful as a chemical raw material in various industrial fields. be.

[Conventional technology and its issues]

Aromatic compounds do not have fluorine atoms in their molecules.

It has long been used as a diluent in dental resins, optical materials, and various polymers, or as a precursor compound for these.

Alternatively, it is used in a wide range of application fields as a biofunctional polymer material, typified by contact lens materials.

However, the aromatic compounds that do not have a fluorine atom in their molecules and are used for the above purposes are heat resistant, chemical resistant, weather resistant, low friction, water repellent/10 oil resistant, low refractive index, and transparent. However, in terms of performance such as oxygen permeability, these have not always been fully satisfied.

Therefore, the three inventors developed a novel product with high functionality such as higher heat resistance, chemical resistance, weather resistance, low friction, 18 water/18 oil resistance, low refractive index, transparency, and oxygen permeability. The result of intensive research aimed at providing a fluorine-containing aromatic compound (hereinafter simply referred to as "the present compound") that functions as a raw material for compound synthesis and as a fluorinating reagent that itself can be converted into other fluorine-containing compounds. , which completed this invention.

[Means to solve the problem]

In order to achieve the above object, the two inventors have developed the following general formula (1)
We succeeded in synthesizing a fluorine-containing aromatic compound represented by

In the above formula, R is a hydrogen atom or a methyl group.

Y is a carbonyl group or a methylene group.

[Method of synthesizing this compound]

The present compound is a commercially available 1,1°1.
Using 3,3.3-hexafluoro-2-phenyl-2-propatol (hereinafter referred to as "compound (L)") as a starting material, a compound represented by general formula (3) (hereinafter referred to as "compound (S)") is prepared.
) can be easily synthesized by reacting with

Compound (L) X -Y -C=CHt ・ ・ ・ ・ (3
) Compound (S) In the above formula (3), X is a halogen atom.

Y is a carbonyl group or a methylene group, and R is a hydrogen atom or a methyl group.

By appropriately selecting the compound (S) to be reacted with the compound (L), it is possible to obtain various fluorine-containing aromatic compounds, such as those described in (1) to (2) below.

■ In general formula (1), Y is a carbonyl group.

Compounds in which R is a methyl group, 1.1, 1.3, 3.3
-hexafluoro-2-methacryloyloxy-2-phenyl-propane (hereinafter referred to as "r compound (1a)")
As shown in the following formula [1], compound (L) was converted into methacrylic acid chloride (hereinafter [compound (St)] under basic conditions.
) can be easily synthesized by reacting with J).

[Margin below]

Formula [1] 2 (n) Compound (L) Compound (sl) Compound (L)
Compound (S2) Compound (1a) ■ In general formula (1), Y is a methylene group.

Compounds in which R is a hydrogen atom, 1, 1.1.3, 3.3
-hexafluoro-2-phenyl-2-(2-propenyloxy)propane (hereinafter referred to as [compound (lb) J)]
can be easily obtained by reacting the compound (L) with 3-chloropropene (also known as allyl chloride, hereinafter referred to as [compound (St) J) under basic conditions, as shown in the following formula (II). Can be synthesized.

(Left below) Compound (1b) ■ A compound in which Y is a methylene group and R is a methyl group in the general formula (1), 1,1,1,3,3.3-hexafluoro-2-(2-methyl -2-propenyloxyphenyl)propane (hereinafter referred to as "compound (lc) (also known as methallyl chloride, hereinafter referred to as "compound (S:l)J)" can be easily synthesized.

formula (III) Compound (L) Compound (S,) CF.

Compound (1c) Hereinafter, the compound (1a) will be described as a representative of the present compound of the present invention.
) will be explained in more detail.

Compound (L), which is a starting material, is dichloromethane, chloroform, tetrahydrofuran, dimethyl sulfoxide, N,N-dimethylformamide.

Triethylamine in an equal or excess amount relative to the compound (L) in an organic solvent such as benzene, toluene, pyridine, or ethanol, or in water.

Tributylamine, picoline, N,N-dimethyl-
In the presence of a tertiary amine such as p-toluidine or a base such as sodium hydroxide or potassium hydroxide, the compound (S, react with.

Water or dimethyl sulfoxide are suitable as reaction medium.

The unreacted compound (L) disappears within 20 hours, but the remaining amount of compound (L) can be determined by WI layer chromatography, IH-nuclear magnetic resonance spectrum, '3C-nuclear magnetic resonance spectrum, etc. Preferably tracked.

After a predetermined period of time has elapsed, the two reactions are stopped, and the reaction solution is diluted with an organic solvent such as diethyl ether, ethyl acetate, dichloromethane, chloroform, benzene, toluene, etc., and washed with water repeatedly. Dry in the presence of a desiccant such as

Then, after the desiccant is filtered off, the filtrate is concentrated under normal pressure and further distilled under reduced pressure, whereby the target compound (1a) can be isolated.

This distillation removes impurities, so the compound (1a
) does not need to be further purified and can be used as it is as an intermediate or as a monomer in various reactions, but if necessary, it may be purified using means such as column chromatography. .

[Uses of this compound]

The present compound can be produced by homopolymerizing itself, for example, by radical polymerization, or by copolymerizing it with various polymerizable monomers having olefinic double bonds.2. A polymer can be easily obtained.

Examples of monomers that can be radically copolymerized with this compound include acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, 2-methylpropyl acrylate, 2-methylpropyl methacrylate, Butyl acrylate, butyl methacrylate, 1,1-dimethylethyl acrylate.

1.1-dimethylethyl methacrylate, N-vinyl-
Examples include 2-pyrrolidone, 2-vinylpyridine, 4-vinylpyridine, N-vinylpiperidone, N-vinylcaprolactam, 2-hydroxyethyl acrylate, and 2-hydroxyethyl methacrylate.

〔Example〕

This invention will be described in more detail with reference to Examples below.

Opening↓ 30 with dropping funnel, ball-filled cooling pipe, and thermometer installed
Add 48.9 liters of compound (L) to a 0 ml three-necked flask.
g (0.2mo 1) and 100m of water! ! and 10 g (0.24 mol) of 95% sodium hydroxide.
was slowly added under stirring at room temperature.

After a while, a white precipitate formed.

Further, 100 ml of dichloromethane was added to this, and a small amount of hydroquinone was added as a polymerization inhibitor.

Thereafter, 26 g of methacryloyl chloride (0
, 24 mo were added dropwise.

After dropping, the reaction was continued for 15 hours at a temperature of 25°C.
The reaction solution was transferred to a separatory funnel and washed three times with 100 mJ of water each time.The dichloromethane solution was then dried in the presence of anhydrous sodium sulfate, and the desiccant was filtered off. Concentrated under pressure.

This concentrate was distilled under reduced pressure to obtain 54 g of a colorless and transparent liquid product (yield: 86%).

In addition, confirmation that this product was the present compound (1a) was performed by IH-nuclear magnetic resonance spectrum and 13C-nuclear magnetic resonance spectrum.

The results of these measurements are shown in Tables 1 and 2.

Table 1: Chemical shift values of the IH-nuclear magnetic resonance spectrum of the product and their assignments (CD CI 3.100 MHz, tetramethylsilane) Table 2: Chemical shift values of the IC-nuclear magnetic resonance spectrum of the product and their assignments (CDCIs, 25MHz, Tetramethylsilane) Phenyl groups: c, e, g Tip opening 1 30 with dropping funnel, ball condenser and thermometer attached
In a three-necked flask with a volume of 0ml, 48% of compound (L) was added.
8 g (0.20 mo I), 9.32 g (0.22 mo 1) of 95% sodium hydroxide, and 150 ml of dimethyl sulfoxide were added, and the three-necked flask was heated to a temperature of 110 °C to sufficiently dissolve the sodium hydroxide. After that, one reaction solution was cooled to a temperature of 45°C.

After that, a small amount of hydroquinone was added, and the compound (S
18.3 g (0.24 mol) of 2) was added dropwise.

The reaction solution was gradually heated to a temperature of 65°C for 4.5 hours.

Continue to heat slowly until the temperature reaches 125°C.
．． The reaction continued for 5 hours.

Thereafter, the 9 reaction liquids were cooled to room temperature, and then poured into 300 ml of water.

This product was extracted three times with 200 ml of chloroform, washed five times with 300 ml of water, and dried in the presence of anhydrous sodium sulfate.

The drying agent was filtered off, and the chloroform solution was concentrated under normal pressure and then distilled under reduced pressure to obtain 52.4 g of product (yield, 92%; boiling point, 68-bmmHg).

In addition, confirmation that this product was compound (1b) was performed by IH-nuclear magnetic resonance spectrum and 13C-nuclear magnetic resonance spectrum.

The results of these measurements are shown in Tables 3 and 4.

Table 3 Chemical shift values of the 1H-nuclear magnetic resonance spectrum of the product and its assignment (CDCI: 1.100 MH2, tetramethylsilane) d Table 4 Chemical shift values of the 13c-nuclear magnetic resonance spectrum of the product and its assignment Attribution (CD CI 3 = 25 MHz, tetramethylsilane) Phenyl group: b, c, d Example 3 300 with dropping funnel, ball condenser and thermometer installed
48 mj of the compound (L) was added to a 7-volume three-neck flask.
．． 8 g (0.20 m-o 1), 9.3 g (0.22 mol) of 95% sodium hydroxide and 150 ml of dimethyl sulfoxide were added.

This three-necked flask was heated to a temperature of 110°C.

After sufficiently dissolving the sodium hydroxide, one reaction solution was cooled to a temperature of 45°C.

After that, a small amount of hydroquinone was added to form compound (S3).
20.4 g (0.23 mol) was added dropwise.

The reaction solution was gradually heated to a temperature of 65 to 110°C.
．． After reacting for 5 hours, one reaction solution was cooled to room temperature and poured into 300 ml of water.

This was extracted four times with 100 ml of chloroform, and the extracted chloroform solution was washed three times with 300 ml of water, and then dried in the presence of anhydrous sodium sulfate.

The desiccant was filtered off, the chloroform solution was condensed under normal pressure, and then distilled under reduced pressure to obtain 57.2 g of a colorless and transparent liquid product (yield, 97%; boiling point, 80°C/10 m
, mHg) were obtained.

In addition, confirmation that this product was a compound (IC>) was performed by IH-nuclear magnetic resonance spectrum and 13c nuclear +11 gas resonance spectrum.

The results of these measurements are shown in Tables 5 and 6.

[Margin below]

Table 5 Chemical shift values of the IH-nuclear magnetic resonance spectrum of the product and its attribution (CD CI 3,100 M H2, tetramethylsilane) Table 6 Chemical shift values of the 13c-nuclear magnetic resonance spectrum of the product and its attribution Attribution (CD Cl 3.25 MHz, tetramethylsilane) [blank below] Phenyl group: b, c, d [Effect of the invention] The fluorine-containing aromatic compound of this invention has a polymerizable double bond within two molecules. Therefore, this compound itself can be easily subjected to homoradical polymerization, and can also be copolymerized with other monomers having radically polymerizable functional groups.

Additionally, polymers formed from this compound.

Heat resistance, chemical resistance, weather resistance, low 1? Abrasion, 1a water/tθ
It is a polymeric material with excellent physical properties such as oiliness, low refractive index, transparency, and oxygen permeability, and can be used in a wide range of fields including dental materials, optical materials, contact lens materials, and others.

Patent applicant: Toagosei Chemical Industry Co., Ltd. Reason Man

Claims (1)

[Scope of Claims] A fluorine-containing aromatic compound represented by the following general formula (1). ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(1) In the above formula, R is a hydrogen atom or a methyl group, and Y is a carbonyl group or a methylene group.