JPS6223729B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a new substance β, β, β', β'-tetrafluorodivinylbenzene and a method for producing the same. Although many reports have been made regarding the synthesis of fluorine-containing compounds having unsaturated bonds, there are few that suggest useful applications. For example, the synthesis of β,β-difluorovinylbenzene is known,
No known useful uses. As a result of many years of research into the synthesis of fluorine-containing compounds, the present inventors have found that a new compound β, β, β', β'-tetrafluorodivinylbenzene, represented by the following formula, has been found to be a common polymer raw material. It was discovered that it is also useful as a crosslinking agent, and the present invention was completed. The new substance β, β, β′, β′-tetrafluorodivinylbenzene of the present invention has the general formula

It is shown by [Formula]. This β, β, β', β'-tetrafluorodivinylbenzene (hereinafter simply referred to collectively as TFDVB) includes (1) ortho-substituted product (hereinafter simply referred to as o-TFDVB) (2) meta-substituted product (Hereinafter, simply abbreviated as m-TFDVB) (3) Para-substituted product (hereinafter, simply abbreviated as p-TFDVB). TFDVB is a colorless and transparent liquid at room temperature and pressure, and is soluble in common organic solvents such as benzene, ether, chloroform, ethyl acetate, and alcohol, but insoluble in water. In addition, their boiling points are 56-59℃/5mmHg for o-TFDVB and 5mmHg for m-TFDVB, respectively.
is 73-75℃/7mmHg, p-TFDVB is 86-87.5
℃/26mmHg. The TFDVB of the present invention can be analyzed and confirmed by the following methods (a) to (d). (a) Elemental analysis (EA) The theoretical weight ratios of H, C, and F elements in TFDVB are H3.0%, C59.4%, and F37.6%. On the other hand, o produced in the production example described below
-Actual measurements of TFDVB are H3.2%, C59.2%, F37.1
%, m-TFDVB is H3.3%, C59.0%,
F37.1%, p-TFDVB is H3.0%, C59.2
%, F37.3%, both of which agree well with the theoretical values. (b) Infrared absorption spectrum (IR) o-TFDVB shows strong absorption based on 〓C=CF ₂ at 1725 cm ^-1 and at 1495 cm ^-1

Weak absorption based on [Formula] is observed. m-TFDVB is 1730cm ^-1〓C =CF ₂
(strong), to 1495cm ^-1

Absorption of [formula] (weak) is observed. p- TFDVB has 1730cm ^-1〓C =CF ₂ (strong),
to 1500cm ^-1

Absorption of [formula] (weak) is observed. (c) Mass spectrum (MS) TFDVB has a molecular ion peak (M ⁺ ) m/
e202 is detected. Generally, in the case of fluorine-containing compounds, many complex transition ion peaks that are not seen in the case of other hydrocarbon compounds are observed, but this is because the stability of the produced ions is completely different between the two. . TFDVB also m/e182
(M ⁺ −HF), 152 (M ⁺ −CF ₂ ), 151 (M ⁺ −
Complex peaks such as CF ₂ H) and 133 (M ⁺ −CF ₃ ) are commonly seen. However, the relative intensities (RI) of those peaks differ depending on the o-, m-, and p-substituted substances. (d) Fluorine 19 nuclear magnetic resonance spectrum ( ¹⁹ F−
NMR): p-TFDVB will be explained as an example, but other
TFDVB can also be measured in the same way. , the signal of F(a) is -82.9ppm on the high magnetic field side (negative value) from the CFCl ₃ standard, and the signal of F(b)
The signal appears at -80.9ppm. Since the two difluorovinyl groups in the molecule are in the same magnetic environment, the chemical shift values δ of the two F(a) or F(b) are the same. F(a), F
(b) appears as four signals split into double doublets (dd). F(a) and F(b)
The coupling constant J with is 32.0Hz, and F(a)
The J between and cis H atom is 3.9Hz. Further F
J between (b) and F(a) is 32.0Hz, and F(b) and trans
J with H atom is 25.6Hz. The TFDVB of the present invention is a completely unknown new substance and can be widely used as a general raw material for polymers. Furthermore, TFDVB is a reactive reagent having two vinyl groups in its molecule, and can also be used as a crosslinking agent. Furthermore, since the polymer produced from TFDVB has strong C--F bonds in its main chain, it is chemically more stable than conventional C--H polymers. Furthermore, by making TFDVB absorb oxygen, it is possible to obtain an oxygen-containing polymer. Next, a typical method for producing the novel compound TFDVB of the present invention will be listed and explained below. (1) Phthaldialdehyde ( ₂ ) A difluoromethane compound represented by the general formula CF ₂ ) by reacting at least one compound selected from the group consisting of a reducing metal, an alkali metal iodide or an alkaline earth metal iodide, and a tertiary phosphine.
A method of manufacturing TFDVB is provided. (1) As the phthaldialdehyde that can be used as a raw material, ortho-, meta-, and para-substituted products, that is, orthophthaldialdehyde, isophthaldialdehyde, and terephthaldialdehyde can be used without particular limitation. By using these phthaldialdehydes, the corresponding o
- TFDVB, m-TFDVB, p-TFDVB are generated. (2) Difluoromethane compound has the general formula CF ₂ X ₂
(However, X is a halogen atom selected from the group consisting of the same or different types of chlorine, bromine, and iodine.) Compounds represented by the formula can be used without particular limitation. Of course, two or more types of difluoromethane compounds can also be used. In particular, difluoromethane compounds having one or more bromine atoms bonded within the molecule tend to be more favorable than other types of difluoromethane compounds in terms of yield. (3) Reducing metals are not particularly limited as long as they have reducing properties, such as Na, Mg, Al,
Cd, Hg, Cu, Fe, Ni, Runny Nickel,
Sn, Zn, Zn-Cu couples, etc. can be used. In particular, from the viewpoint of yield, Cu, Fe,
Ni, Raney nickel, Sn, Zn, Zn--Cu couples are used, and Zn, Zn--Cu couples are particularly preferred. Usually, one type of metal is used, but two or more types of metals can be activated and used in combination. In general, it is better to use metals in powder form, but they can also be used even if they are activated by increasing the surface area, such as in ultrafine powders. In addition, when using an alkali metal iodide or an alkaline earth metal iodide, it may be prepared in advance and added to the reaction system. You can adjust it. In general, alkali metal iodides are preferable to alkaline earth metal iodides in terms of yield, and the most preferably used are NaI and KI. Furthermore, as a tertiary phosphine, the general formula
R ₃ P (However, R is usually the same or different alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, cycloalkynyl group, aralkyl group, aryl group, secondary amino group, etc.) Any compound represented by can be used without particular limitation. Specifically, R in the above general formula is CH ₃ —, C ₂ H ₃ —, C ₃ H ₇ —, C ₄ H ₉
--,

[Formula] C ₄ H ₇ ―,

【formula】

【formula】

【formula】

[Formula] (CH ₃ ) ₂ N―,

【formula】

Compounds such as [Formula] are preferably used. In particular, from the viewpoint of obtaining raw materials and reaction yield, preferably R in the above general formula is

【formula】

[Formula] (CH ₃ ) ₂ N ―,

【formula】

Compounds of the formula are preferred. In addition, in this production method, when the above two types of reducing metal and tertiary phosphine are selected and used together, that is, a system using four component raw material compounds, the reaction system is much more effective than any other combination of reaction systems. It is preferable because it is excellent in terms of yield. In the reaction of this production method, the raw material compounds may be mixed in any order and the reaction may be carried out. Further, the reaction can be carried out by mixing all of these raw material component compounds in one step, or the reaction can be carried out by mixing these raw material component compounds in several stages. The reaction conditions in this production method are not particularly limited, but it is generally carried out in the presence of a solvent. The solvent to be used is an anhydrous polar nonaqueous solvent that does not react with the raw materials without any particular restriction. Typical examples of the polar nonaqueous solvent include ethers such as tetrahydrofuran, dioxane, monoglyme, diglyme, triglyme, and tetraglyme. Solvent; For example, oxosulfur solvents such as dimethyl sulfoxide and sulfolane; Acetonitrile,
Nitrile solvents such as propionitrile and benzontrile; amide solvents such as dimethylformamide, diethylformamide, dimethylacetamide, N-methylpyrrolidone, and hexamethylphosphoramide are preferably used. Among the above-mentioned solvents, nitrile solvents and amide solvents are particularly preferred because the desired reaction proceeds quickly. Note that the method and order of mixing the raw material component compounds and the solvent used are not particularly limited. The reaction temperature in this production method is not particularly limited, but it is usually preferably selected from a temperature range of -30°C or higher and 250°C or lower. At temperatures lower than -30°C, the progress of the reaction is generally extremely slow, and even at temperatures higher than 250°C, the reaction proceeds, but the raw materials or products may be altered or decomposed, or side reactions may occur. There is a tendency to Therefore, from the viewpoint of yield of the target product, the reaction temperature is preferably selected from a temperature range of -30°C to 250°C, more preferably selected from a temperature range of -10°C to 180°C. is preferred. The reaction in this production method is usually conveniently carried out under natural pressure at the reaction temperature with the raw material components and solvent charged, but it may be carried out under increased or reduced pressure if necessary. It's okay. Note that the reaction atmosphere is not particularly limited, and substitution with an inert gas often gives preferable results. The reaction time in this production method varies depending on the raw material components used, the type of solvent, the reaction temperature, etc., and cannot be absolutely limited, but it is generally preferable to select it within the range of several minutes to several days. Depending on the reaction, it is preferable to select other conditions so that the reaction time ranges from several minutes to several hours. However, when using orthophthaldialdehyde as a raw material component compound, the reaction tends to proceed more easily if the reaction conditions are made stricter than when using other types of phthaldialdehyde. The material of the reaction vessel in this manufacturing method is not particularly limited as long as it is not involved in the reaction and is resistant to corrosion, but glass, metals such as stainless steel, Teflon, etc. are generally suitably used. When implementing this production method, in order to uniformly disperse the reaction heat and uniformly disperse the raw material component compounds, etc.
Means of stirring the reaction system can often be employed as a suitable means. When TFDVB is produced by the reaction in this production method, β,β-difluorovinylbenzaldehyde may be produced as a by-product. This is produced by converting only one of the two aldehyde groups in the raw material phthaldialdehyde into difluoromethylene olefin, and it is ortho-, meta-, para- -Produces the substituted β,β-difluorovinylbenzaldehyde. If necessary, this compound can be separated and recovered together with TFDVB, which is the object of the present invention, for use. TFDVB manufactured by this manufacturing method
In order to separate it from the mixture in the reaction vessel, ordinary operations such as distillation can be applied. Further, solvent extraction methods, chromatography methods, etc. can also be applied, and these separation methods can also be applied in combination. (1) Phthaldialdehyde (2) Difluoromethane compound represented by the general formula CF ₂ HX (where X is a halogen atom selected from the group consisting of chlorine, bromine and iodine) (3) Tertiary phosphine and (4 )
By reacting basic compounds, β, β,
A method of producing β', β'-tetrafluorodivinylbenzene is provided. As the phthaldialdehyde used as a raw material, those similar to those described in the above production method can be used. In addition, the difluoromethane compound has the general formula
CF ₂ HX (where X is a halogen atom selected from the group consisting of chlorine, bromine and iodine)
The compound represented by is used without particular limitation,
It is also possible to use two or more difluoromethane compounds. As the tertiary phosphine, those similar to those described in the above production method can be used. Basic compound means a Lewis base, and has the general formula
It is not particularly limited as long as it is a basic compound that reacts with the compound represented by HX (where X is a halogen atom selected from the group consisting of chlorine, bromine, and iodine). Examples of basic compounds that are generally preferably used include organic lithium compounds such as methyllithium, ethyllithium, and phenyllithium; alkali metal alkoxides such as potassium t-butoxide, sodium methoxide, and sodium ethoxide. In the reaction of this production method, each raw material component may be mixed in any order to carry out the reaction, and all raw material component compounds may be mixed and reacted in one step, or several The reaction can also be carried out by mixing the raw material components in stages. Although the reaction conditions in this production method are not particularly limited, it is generally carried out in the presence of a solvent. The solvent to be used can be used without any particular restriction as long as it does not react with the raw materials, and generally includes hydrocarbon solvents such as benzane, n-hexane, cyclohexane, heptane, benzene, etc., and diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, etc. It is preferable to use an ether solvent such as glyme because the desired reaction can proceed easily. The method and order of mixing the raw material component compound and the solvent used in this production method are not particularly limited. The reaction temperature, reaction pressure, reaction atmosphere, reaction time, material of the reaction vessel,
Stirring of the reaction system, separation of by-products and target product, etc. are the same as described for the production method. The β, β, β′, β′-tetrafluorodivinylbenzene of the present invention includes (1) phthaldialdehyde and
(2) It can also be produced by reacting tertiary phosphine difluoromethylene. The phthaldialdehyde used as a raw material can be the same as that described in the production method. Tertiary phosphine difluoromethylene has the general formula R ₃ P-CF ₂ (where R is generally the same or different alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, cycloalkynyl group, aralkyl group, aryl group). This is a phosphorus ylide compound represented by a group of atoms such as a group or a secondary amino group. Specifically, R in the above general formula is CH ₃ --, C ₂ H ₅ --, C ₃ H ₇ --,
C ₄ H ₉ ―、

[Formula] C ₄ H ₇ ―,

【formula】

【formula】

【formula】

[Formula] (CH ₃ ) ₂ N―,

【formula】

Compounds such as [Formula] are preferably used. From the viewpoint of obtaining raw materials and reaction yield, preferably R in the above general formula is

【formula】

[Formula] (CH ₃ ) ₂ N ―,

【formula】

Compounds of the formula are preferred. Tertiary phosphine difluoromethylene is generally synthesized by reacting (trapping) difluoromethylene carbene generated in advance with tertiary phosphine. usually,
There are various known methods for synthesizing tertiary phosphine difluoromethylene, which are preferably used, and these known methods can be used in the present invention. Typical methods are illustrated below. (i) Usually in an anhydrous polar non-aqueous solvent, preferably an amide solvent such as dimethylformamide; a nitrile solvent such as acetonitrile; At a reaction temperature selected from a temperature range,
A method of mixing tertiary phosphine and an alkali metal salt of chlorodifluoroacetic acid. (ii) Generally in an anhydrous polar nonaqueous solvent, preferably an amide solvent such as dimethylformamide or hexamethylphosphoramide; a nitrile solvent such as acetonitrile; or an ether solvent such as diglyme, triglyme, tetraglyme, etc. is a reaction temperature selected from a temperature range of 10°C to 200°C. Method of mixing with difluoroacetic acid ester. (iii) For example, CF ₃ Br, CF ₂ Br ₂ , CF ₂ Cl ₂ ,
A method in which difluoromethylene carbene, which is generated by mixing trifluorohalomethane or difluorohalomethane such as CF ₂ ClBr, and an organolithium compound such as butyllithium or phenyllithium, is reacted with tertiary phosphine. etc. are generally preferably used. In addition to these methods (i) to (iii), it is also possible to obtain tertiary phosphine difluoromethylene by the following method. That is, decomposition of difluoroketene CF ₂ =C=O, or decomposition of difluorodiazomethane CF 2 N 2 , or decomposition of difluorodiazomethane CF ₂ N ₂ , or the general formula CF ₂ X (where X is a halogen selected from the group consisting of chlorine, bromine and iodine CF ₂ X ₂ (where X is a halogen atom selected from the group consisting of the same or different chlorine, bromine and iodine)
Decomposition of difluoromethane compounds represented by , or decomposition of gem-difluorocyclopropane compounds, or decomposition of compounds represented by difluorodiazirine, Me ₃ SnCF ₃ , C ₆ H ₅ HgCF _3, etc. A tertiary phosphine difluoromethylene phosphorane is obtained by reacting difluoromethylene carbene generated by a generally preferably used difluoromethylene carbene generating means with a tertiary phosphine. Note that the production method may involve reacting phthaldialdehyde and tertiary phosphine difluoromethylene, but it is also possible to use raw materials that produce tertiary phosphine difluoromethylene in the reaction system. In the latter method, the object of the present invention can also be obtained as a one-step reaction by allowing the raw material for producing tertiary phosphine difluoromethylene and phthaldialdehyde to be present in the same reaction system. In the reaction of the production method, when synthesizing tertiary phosphine difluoromethylene, it is generally carried out in the presence of a solvent, and the solvent used at this time is directly mixed with tertiary phosphine difluoromethylene and phthaldifluoromethylene. It is suitable for use in reactions with aldehydes. Anhydrous solvents that do not react with the raw materials can be used without any particular restrictions. The method and order of mixing the raw material component compound of tertiary phosphine difluoromethylene used in the production method and phthaldialdehyde with the solvent are not particularly limited. Also, the reaction temperature, reaction pressure,
The reaction atmosphere, reaction time, material of the reaction vessel, stirring of the reaction system, separation method of by-products and target product, etc. are the same as described for the production method. Although the manufacturing method of TFDVB has been described above, the manufacturing method and the mechanism of action of the manufacturing method are not clear. There is a possibility that tertiary phosphine difluoromethylene is used as an intermediate in both the manufacturing method and the reaction of the manufacturing method, but tertiary phosphine difluoromethylene was confirmed in the manufacturing method and the reaction product system in the manufacturing method. I couldn't do it. Therefore, at present, it cannot be recognized that the above-mentioned manufacturing method and the manufacturing method and the manufacturing method react by the same mechanism. Examples are shown below, but these examples are for specifically explaining the present invention, and the present invention is not limited to these examples. The yield is the ratio of isolated TFDVB to the theoretically obtained target product TFDVB based on phthaldialdehyde used as a raw material.
It shows. Example 1 1.5 g of terephthaldialdehyde, 10.5 g of triphenylphosphine and 3.0 g of zinc powder were placed in a 100 ml three-necked flask, and then 30 ml of dimethylformamide was added and stirred. Next, after replacing the air in the reaction vessel with nitrogen, gradually
8.4g of CF ₂ Br ₂ was added dropwise, and after the addition was completed, the mixture was further heated at room temperature.
The reaction was continued with stirring for 90 minutes. Transfer the contents of the three-necked flask to a separatory funnel,
The target product was extracted with 90 ml of diethyl ether, and the ether extracted solution was washed with pure water to remove dimethylformamide in the ether extracted solution, and then dried over Glauber's salt. When the obtained ether solution is distilled, bp86 ~
2.1 g (93% yield) of p-TFDVB was obtained at a temperature of 87.5°C/26 mmHg. Similarly, when isophthaldialdehyde was used, m-TFDVB was obtained with a yield of 89%, and when orthophthaldialdehyde was used, o-TFDVB was obtained with a yield of 85%. Table 1 shows the analysis results and physical property values of TFDVB.

[Table] Example 2 21 g of triphenylphosphine, 5.2 g of zinc powder, 2.7 g of terephthaldialdehyde, and 80 ml of dimethylformamide were placed in a 300 ml glass autoclave and stirred. Next, after cooling the reaction vessel with dry ice-methanol, CF ₂ BrCl gas was blown into it, and 20 ml of it in a liquid state was added. Heat the reaction vessel
By stirring at 80° C. (gauge pressure 6 Kg/cm ² ) for 90 minutes, p-TFDVB was obtained in a yield of 91%.
Similarly, yield 88 from isophthaldialdehyde
m-TFDVB was obtained with a yield of 82%, and o-TFDVB was obtained with a yield of 82% from ortho-phthaldialdehyde. Example 3 Using the same procedure as in Example 2, 21 g of triphenylphosphine, 5.2 g of zinc powder, 2.7 g of phthaldialdehyde, and 20 ml of CF ₂ Cl ₂ gas in liquid form were added to a 300 ml glass autoclave, and dimethylformamide was added.
The mixture was stirred in 80 ml at 80°C for 90 minutes. The yield of o-, m-, and p-substituted products was 80% from p-phthaldialdehyde, 78% from m-phthaldialdehyde, and 52% from o-phthaldialdehyde, respectively. TFDVB was obtained. Example 4 When 1.5 g of terephthaldialdehyde, 3.0 g of zinc powder, and 8.4 g of CF ₂ Br ₂ were stirred in 30 ml of dimethylformamide at 80°C for 90 minutes in a 100 ml three-necked flask, p-TFDVB was obtained with a yield of 10%. Obtained. Example 5 In a 100 ml three-necked flask, 1.5 g of terephthaldialdehyde, 10.5 g of triphenylphosphine,
8.4 g of CF ₂ Br ₂ in 30 ml of tetraglyme at 80℃, 90
After stirring for a minute, p-TFDVB was obtained in a yield of 51%. Example 6 A reaction was carried out in the same manner as in Example 1 except that only the type of solvent was changed. The same volume of solvent as in Example 1 was used. The results obtained when terephthaldialdehyde was used are shown below. Solvent Yield n-Hexane 10% Tetrahydrofuran 70 Dioxane 71 Monoglyme 72 Diglyme 70 Tetraglyme 69 Sulfolane 78 Dimethylsulfoxide 77 Acetonitrile 90 Propionitrile 88 Benzonitrile 91 Diethylformamide 90 Dimethylacetamide 89 N-Methylpyridine Lolidone 89 Hexamethylphosphoramide 90 Example 7 A reaction was carried out in the same manner as in Example 1 by changing only the type of reducing metal or metal iodide. The reducing metal or metal iodide was used in the same gram equivalent amount as the zinc used in Example 1. Below, each result when using terephthaldialdehyde is shown. Reducing metal or metal iodide Yield Na 18% Mg 12 Al 12 Cd 15 Hg 12 Cu 68 Fe 70 Raney-Ni 71 Sn 80 Zn-Cu couple 93 MgI ₂ 10 NaI 15 Example 8 In the method of Example 1, three The reaction was carried out by changing only the type of phosphine. The tertiary phosphine was used in an equimolar amount to the triphenylphosphine used in Example 1. less than,
Each result when using terephthaldialdehyde is shown.

【table】

[Table] Example 9 A reaction was carried out in the method of Example 1, with only the reaction temperature being changed. Below, each result when using terephthaldialdehyde is shown. Reaction temperature Yield -30℃ 3% 50℃ 93% 140℃ 89% 210℃ 69% Example 10 Terephthaldialdehyde 2.7g, triphenylphosphine 21 in a 300ml glass autoclave
g, 7 g of phenyllithium, and 50 ml of n-hexane were added and stirred. The reaction vessel was cooled with dry ice-methanol, and CF ₂ HCl gas was blown into it as a liquid.
Added 20ml. When the reaction vessel was heated and stirred at 80°C for 10 hours, p-TFDVB was obtained in a yield of 85%.
Similarly, when using isophthaldialdehyde, m-
TFDVB was obtained with a yield of 82%, and o-TFDVB was obtained with a yield of 74% from ortho-phthaldialdehyde. Example 11 The reaction of Example 10 was carried out by changing only the type of solvent. The same volume of solvent as in Example 10 was used. Below, each result when using terephthaldialdehyde is shown. Solvent Yield Benzene 81% Diethyl ether 80% Tetrahydrofuran 80% Ethyl acetate 33% Example 12 In the reaction of Example 10, only the type of tertiary phosphine was changed. The tertiary phosphine was used in an equimolar amount to the triphenylphosphine used in Example 10. The results obtained when terephthaldialdehyde was used are shown below.

[Table] Example 13 The reaction of Example 10 was carried out by changing only the reaction temperature. Below, each result when using terephthaldialdehyde is shown. Reaction temperature Yield -20°C 51% 40°C 83% 100°C 80% 230°C 69% Example 14 5.4 g of terephthaldialdehyde, 40 g of triphenylphosphine, 15 g of phenyllithium and 30 ml of bromodifluoromethane CF ₂ HBr were added to 70 ml of tetrahydrofuran. When the mixture was stirred and reacted at 50°C for 6 hours, p-TFDVB was obtained in a yield of 81%. Example 15 1.5 g of terephthaldialdehyde, 10.5 g of triphenylphosphine, and 10 ml of diglyme were placed in a 100 ml three-necked flask and stirred. Next, the reaction flask was heated to 140°C, and a diglyme solution containing 7.0 g of sodium chlorodifluoroacetate was slowly dropped into the flask from the dropping funnel. When the addition was completed, the reaction temperature was raised to 100°C and stirred for 6 hours.
p-TFDVB was obtained with a yield of 71%. Example 16 1.5 g of terephthaldialdehyde, 10.5 g of triphenylphosphine, 2 g of lithium chloride, 8 g of hexamethylphosphoramide, and 30 ml of triglyme were placed in a 100 ml three-necked flask and stirred. Next, heat the reaction vessel to 80°C, and slowly add 6.5 ml of methyl chlorodifluoroacetate into it through the dropping funnel.
g of triglyme solution was added dropwise. After the dripping is finished,
After further stirring at 80°C for 4 hours, p-TFDVB
was obtained with a yield of 70%. Example 17 Put 30ml of tetraglyme as a solvent into a 100ml three-necked flask, and add 1.5g of terephthaldialdehyde, 7.0g of sodium iodide, and 8.4g of CF ₂ Br ₂
and continued stirring at 110℃ for 72 hours, the yield was 5%.
p-TFDVB was obtained. Application example 1 A solution of 1.0 g of p-TFDVB dissolved in 2 ml of carbon tetrachloride is dropped onto a glass plate. When left in the air for one hour at room temperature, carbon tetrachloride evaporates and at the same time absorbs oxygen from the air, forming a slightly yellowish film-like polymer compound on the glass plate. The obtained polymer compound has excellent acid resistance and alkali resistance, is insoluble in most organic solvents, and contains carboxylic acid in the molecule. The properties of the polymer compound are shown below. (1) 35%-HCl or 30%-H ₂ SO ₄ , 60%-HNO ₃
Even if immersed in water for 60 minutes at 50℃, the appearance or
As a result of EA, there is almost no change. (2) Even when immersed in 6N-NaOH at 55℃ for 90 minutes, there is almost no change in appearance or EA results. (3) Insoluble or sparingly soluble in n-hexane, benzene, chloroform, diethyl ether, methanol, tetraglyme, and dimethylformamide. (4) In IR, carboxylic acid absorption is seen at 1730 cm ^-1 , and this absorption changes to ammonium salt absorption at 1585 cm ^-1 by NH ₃ treatment. (5) EA was found; H2.8%, C50.2%, F25.0%.

Claims (1)

[Claims] 1 β, β, β', β'-tetrafluorodivinylbenzene represented by the general formula [Formula]. 2 (a) Phthaldialdehyde, ( _b ) a difluoromethane compound represented by the general formula CF ₂ c) Reducing metal,
β, β, β′, β′-tetra characterized by reacting with at least one compound selected from the group consisting of alkali metal iodide or alkaline earth metal iodide and tertiary phosphine. Method for producing fluorodivinylbenzene. 3 (a) Phthaldialdehyde, (b) General formula CF ₂ HX
(where X is a halogen atom selected from the group consisting of chlorine, bromine, and iodine), (c) a tertiary phosphine, and (d) a basic compound are reacted. , β,
A method for producing β′,β′-tetrafluorodivinylbenzene.