JP2015042621A - Method of producing vinylbenzyl(fluoroalkyl) ether - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of producing a vinylbenzyl(fluoroalkyl) ether industrially at low costs.SOLUTION: A method of producing a vinylbenzyl(fluoroalkyl) ether of formula (1) (in the formula, Ris a fluoroalkyl group, and n is an integer of 1-3) comprises reacting a fluoroalkyl alcohol of formula (2) (in the formula, Ris a fluoroalkyl group, and n is an integer of 1-3) with chloromethylstyrene in a solvent selected from tertiary alcohols, nitrogen-containing organic solvents and sulfur-containing organic solvents in the presence of a solid alkali.

Description

  The present invention relates to a novel method for producing vinylbenzyl (-fluoroalkyl) ether useful as a gas separation membrane, a monomer for a surface treatment agent having water repellency, and the like.

  Vinyl benzyl (fluoroalkyl) ether is a gas separation membrane (see Patent Document 1), a surface treatment agent having water repellency (see Non-Patent Document 1), an organic field-effect transistor (see Non-Patent Document 2), It is known that it can be used as a monomer for a combined film (see Patent Document 2), a photosensitive composition for a color filter and a photosensitive transfer material (see Patent Document 3), a contact lens (see Patent Document 4), and the like.

In general, an example of synthesizing an alkyl (fluoroalkyl) ether by reacting an alkyl chloride with a fluoroalkyl alcohol is known. When the boiling point of the alkyl chloride is low, the alkyl chloride is excessively added to the fluoroalkyl alcohol. And an alkyl (fluoroalkyl) ether is synthesized using an excess of aqueous sodium hydroxide in the presence of a phase transfer catalyst (see Patent Document 5: Example 1 shows a production method represented by the following general formula) Have been described).

An example of synthesizing vinylbenzyl (fluoroalkyl) ether using an aqueous sodium hydroxide solution in the presence of a phase transfer catalyst using chloromethylstyrene and fluoroalkyl alcohol as shown by the following general formula is known. (See Non-Patent Document 1, Patent Documents 1 and 2).

  In this document, when the product is purified by distillation under reduced pressure, if chloromethylstyrene remains, the boiling point is close to that of the product and it is difficult to remove. Therefore, it is necessary to eliminate chloromethylstyrene by using excessive fluoroalkyl alcohol. was there. However, because fluoroalkyl alcohol is expensive, fluoroalkyl alcohol is used in a ratio of approximately 1: 1 with respect to chloromethylstyrene. In general, in a reaction using a phase transfer catalyst, either an alkyl halide or an alcohol is used in excess, so that the yield decreases when used in a ratio of about 1: 1. Therefore, in this document, the yield is increased by using a large excess of about 1 equivalent of phase transfer catalyst and about 5 equivalent of sodium hydroxide. For this reason, in order to produce industrially, there existed a problem that the usage-amount of a chemical | drug | medicine was large, the chemical | medical agent cost was high, production efficiency was bad, and a lot of waste liquid produced.

  In addition, this document has a problem that the reaction time is long. Increasing the reaction temperature to shorten the reaction time has the problem that benzyl chloride is hydrolyzed and by-products such as benzyl alcohol and dibenzyl ether are produced, and it is necessary to react at a low reaction temperature, reducing the reaction time. could not.

  To date, no examples of synthesizing vinylbenzyl (fluoroalkyl) ether without using a phase transfer catalyst and an aqueous sodium hydroxide solution have been known.

On the other hand, examples of synthesizing alkyl (fluoroalkyl) ether from alkyl chloride and fluoroalkyl alcohol using sodium hydride as an alkali are known (see Patent Documents 6 and 7: Example B3 of Patent Document 6 is A production method represented by the following general formula is described).

  However, sodium hydride is expensive and dangerous because it reacts with moisture to produce hydrogen gas, and is difficult to use industrially. This reference only describes expensive and dangerous alkalis such as n-butyllithium, t-butoxypotassium, and sodium amide as other alkalis.

On the other hand, as represented by the following general formula, an example of synthesizing allyl (fluoroalkyl) ether from allyl bromide and fluoroalkyl alcohol using a solid alkali is known (see Patent Documents 8 and 9).

  However, the fluoroalkyl alcohol is only an example of fluoroalkylethanol, and the alkyl chloride does not react because of the weak acidity of the alcohol. Therefore, there is only an example of allyl bromide, and the reaction temperature needs to be as high as 80-100 ° C.

In addition, an example in which ether is synthesized from paramethoxybenzyl chloride and alcohol using a solid alkali is known (see Patent Document 10: Example 2 describes a production method represented by the following general formula). .

  However, since it is a normal alcohol, its acidity is weak, and as alkyl chloride, only paramethoxybenzyl chloride having reactivity equivalent to or higher than that of alkyl iodide reacts. Moreover, the reaction temperature needs to be as high as 150 ° C., and styrene compounds that may be polymerized and fluoroalkyl alcohols having a boiling point of 150 ° C. or less cannot be used.

  Therefore, an inexpensive and industrial method for producing vinylbenzyl (fluoroalkyl) ether from chloromethylstyrene and fluoroalkyl alcohol has not yet been developed.

Japanese Patent Laid-Open No. 5-7748 JP-A-63-97215 JP 2008-203786 A Special table 2007-524870 Japanese Patent Laid-Open No. 11-1450 JP 2007-262070 A International Publication No. 2011/0887717 Japanese Patent Laid-Open No. 11-43457 JP-A-9-208513 JP 2012-201671 A

Polymer Journal, Japan, August 1988, Vol. 45, No. 8, p653 Macromolecular research, Korea, 2009, Vol. 17, No. 9, p646

  An object of the present invention is to provide a method for industrially producing vinylbenzyl (fluoroalkyl) ether at low cost.

（式中、Ｒ_fはフルオロアルキル基を示し、ｎは１から３の整数を示す。）

（式中、Ｒ_fはフルオロアルキル基を示し、ｎは１から３の整数を示す。） That is, the production method of the present invention is a production method of vinylbenzyl (fluoroalkyl) ether represented by the following general formula (1), which comprises fluoroalkyl alcohol represented by the following general formula (2) and chloromethylstyrene. The reaction is carried out in the presence of a solid alkali in a solvent selected from tertiary alcohols, nitrogen-containing organic solvents, and sulfur-containing organic solvents.

(In the formula, R _f represents a fluoroalkyl group, and n represents an integer of 1 to 3.)

(In the formula, R _f represents a fluoroalkyl group, and n represents an integer of 1 to 3.)

  According to the present invention, vinylbenzyl (fluoroalkyl) ether is produced in large quantities at low cost from chloromethylstyrene and fluoroalkyl alcohol by using a solid alkali without using a phase transfer catalyst or an aqueous sodium hydroxide solution. be able to.

（式中、Ｒ_fはフルオロアルキル基を示し、ｎは１から３の整数を示す。）
で表されるフルオロアルキルアルコールのＲ_fは、好ましくは１〜１６個の炭素原子、より好ましくは２〜１４個の炭素原子を有する直鎖状または分枝鎖状のフッ素化アルキルである。Ｒ_fは、アルキル基のすべての水素がフッ素に置換されてもよい。また一部の水素が残ってもよい。特に末端のメチルの水素が１つ残ってもよい。 In the present invention, the following general formula (2)

(In the formula, R _f represents a fluoroalkyl group, and n represents an integer of 1 to 3.)
R _{f of the} fluoroalkyl alcohol represented by the formula is preferably a linear or branched fluorinated alkyl having 1 to 16 carbon atoms, more preferably 2 to 14 carbon atoms. In R _f , all hydrogens of the alkyl group may be substituted with fluorine. Some hydrogen may remain. In particular, one terminal methyl hydrogen may remain.

  Examples of the fluoroalkyl alcohol represented by the general formula (2) include 1H, 1H-trifluoroethanol, 1H, 1H-pentafluoropropanol, 1H, 1H, 3H-tetrafluoropropanol, 1H, 1H, 4H-hexa. Fluorobutanol, 2H-hexafluoro-2-propanol, 1H, 1H-heptafluorobutanol, 1H, 1H, 5H-octafluoropentanol, 1H, 1H-nonafluoropentanol, nonafluoro-t-butanol, 1H, 1H, 7H-dodecafluoroheptanol, 1H, 1H-tridecafluoroheptanol, 1H, 1H-pentadecafluorooctanol, 1H, 1H, 9H-hexadecafluorononanol, 1H, 1H-heptadecafluorononanol and the like are listed. 2H- Kisafuruoro-2-propanol, IH, 1H-heptafluorobutanol, IH, 1H-nonafluorobutyl pentanol, IH, 1H-tridecafluoro-heptanol, IH, 1H-pentadecafluorooctyl octanol and the like are preferable. The fluoroalkyl alcohol is not a single compound but may be a mixture of two or more fluoroalkyl alcohols having different carbon numbers.

  Examples of the chloromethylstyrene used in the present invention include 4-chloromethylstyrene, 3-chloromethylstyrene, a mixture of 4-chloromethylstyrene and 3-chloromethylstyrene, and the like. 4-chloromethylstyrene, 4-chloromethyl A mixture of styrene and 3-chloromethylstyrene is preferred.

（式中、Ｒ_fはフルオロアルキル基、ｎは１から３の整数を示す。）
で表されるビニルベンジル（フルオロアルキル）エーテルとしては、例えばビニルベンジル（１Ｈ，１Ｈ−トリフルオロエチル）エーテル、ビニルベンジル（１Ｈ，１Ｈ,３Ｈ−テトラフルオロプロピル）エーテル、ビニルベンジル（２Ｈ−ヘキサフルオロ−２−プロピル）エーテル、ビニルベンジル（１Ｈ，１Ｈ−ヘプタフルオロブチル）エーテル、ビニルベンジル（１Ｈ，１Ｈ、５Ｈ−オクタフルオロペンチル）エーテル、ビニルベンジル（１Ｈ，１Ｈ、７Ｈ−ドデカフルオロヘプチル）エーテル、ビニルベンジル(１Ｈ，１Ｈ−トリデカフルオロヘプチル）エーテル、ビニルベンジル（１Ｈ,１Ｈ,９Ｈ−ヘキサデカフルオロノニル）エーテル、ビニルベンジル（１Ｈ,１Ｈ-ペンタデカフルオロオクチル）エーテル、４−ビニルベンジル（２Ｈ−ヘキサフルオロ−２−プロピル）エーテル等を好ましく挙げることができる。なおビニルベンジル（フルオロアルキル）エーテルは、ビニルベンジルの異性体について、ビニルとメチレンがメタの関係にあるｍ体、ビニルとメチレンがパラの関係にあるｐ体、及びこれらｍ体／ｐ体の混合物のいずれでもよい。 In the present invention, the following general formula (1)

(In the formula, R _f represents a fluoroalkyl group, and n represents an integer of 1 to 3.)
As vinylbenzyl (fluoroalkyl) ether represented by, for example, vinylbenzyl (1H, 1H-trifluoroethyl) ether, vinylbenzyl (1H, 1H, 3H-tetrafluoropropyl) ether, vinylbenzyl (2H-hexafluoro). -2-propyl) ether, vinylbenzyl (1H, 1H-heptafluorobutyl) ether, vinylbenzyl (1H, 1H, 5H-octafluoropentyl) ether, vinylbenzyl (1H, 1H, 7H-dodecafluoroheptyl) ether, Vinylbenzyl (1H, 1H-tridecafluoroheptyl) ether, vinylbenzyl (1H, 1H, 9H-hexadecafluorononyl) ether, vinylbenzyl (1H, 1H-pentadecafluorooctyl) ether, 4-vinylbenzyl (2 - it can be exemplified preferably hexafluoro-2-propyl) ether. Vinylbenzyl (fluoroalkyl) ether is an m-isomer in which vinyl and methylene have a meta relationship, a p-form in which vinyl and methylene have a para relationship, and a mixture of these m- and p-isomers. Either of these may be used.

  In the present invention, when chloromethylstyrene remains, it is difficult to remove the product when it is purified by distillation under reduced pressure, and there is a problem that corrosion derived from chlorine ions occurs in the polymer, film, etc. For this reason, it is preferable to eliminate chloromethylstyrene by using an excessive amount of fluoroalkyl alcohol. However, since fluoroalkyl alcohol is expensive, it is preferable to use 0.8 to 3 equivalents, more preferably 1.0 to 1.5 equivalents, of fluoroalkyl alcohol with respect to chloromethylstyrene.

  As the solid alkali used in the present invention, an alkali metal hydroxide or an alkali metal carbonate is preferable. As the alkali metal hydroxide, sodium hydroxide, potassium hydroxide and lithium hydroxide are preferable, and sodium hydroxide is more preferable. As the alkali metal carbonate, potassium carbonate, sodium carbonate, sodium hydrogen carbonate, cesium carbonate and the like are preferable, and potassium carbonate is more preferable. Examples of the shape of the solid alkali include a lump shape, a pellet shape, a flake shape, and a granular shape.

  The PKa of the fluoroalkyl alcohol used in the present invention is, for example, 12.4 for 1H, 1H-trifluoroethanol and 9.3 for 2H-hexafluoro-2-propanol, which is close to phenol (pKa = 9.95). It is the strength of the acid (see International Publication No. 2012/118084). Therefore, even solid alkalis such as weakly basic alkali metal hydroxides and alkali metal carbonates function sufficiently as a dehydrochlorinating agent and react.

  In the present invention, an alkali metal iodide may be added to accelerate the reaction. Examples of the alkali metal iodide include potassium iodide, sodium iodide, lithium iodide and the like. The amount of alkali metal iodide to be added is preferably 0.01 to 0.5 equivalent, more preferably 0.1 to 0.3 equivalent, based on chloromethylstyrene.

  The solvent used in the present invention is preferably selected from tertiary alcohols, nitrogen-containing organic solvents, and sulfur-containing organic solvents. As the tertiary alcohol, 2-methyl-2-propanol, 2-methyl-2-butanol, 2-methyl-2-pentanol and the like are preferable, and 2-methyl-2-propanol is more preferable. As the nitrogen-containing organic solvent, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N, N′-dimethylimidazolidone, tetramethylurea and the like are preferable, and N, N-dimethyl is preferred. Formamide is more preferred. As the sulfur-containing organic solvent, dimethyl sulfoxide, sulfolane and the like are preferable, and dimethyl sulfoxide is more preferable.

  There is no restriction | limiting in particular as the usage-amount of a solvent, It is preferable to use 0.5-30 weight times with respect to chloromethylstyrene from the point of manufacturing cost or reaction rate, and it is more preferable to use 0.8-5 weight times.

  In the production method of the present invention, the reaction temperature is preferably from 45 ° C. to the boiling point of the solvent, and preferably from 50 to 90 ° C., since the temperature at which chloromethylstyrene does not polymerize is preferred.

  The reaction time is usually 30 minutes to 24 hours, preferably 30 minutes to 10 hours.

  Since the raw materials and products used in the present invention have a styrene structure, they may be polymerized in the reaction, post-treatment and isolation / purification steps. In order to prevent polymerization, a polymerization inhibitor may be added. As the polymerization inhibitor to be used, hydroquinone, methoquinone, 4-methoxy-1-naphthol, 2-methoxy-1,4-naphthoquinone, phenothiazine, 2-methoxyphenothiazine, t-butylcatechol and the like are preferable.

  After completion of the reaction, the target product is easily isolated from the reaction mixture by distillation, washing, distillation, crystallization, filtration, column chromatography or the like.

  Below, based on an Example, this invention is demonstrated in detail. The scope of the present invention is not limited by these.

In the examples, the identity and purity of the compounds were measured by the following method. Moreover, the raw material used for the Example used the general reagent purchased from the reagent maker (Tokyo Chemical Industry Co., Ltd., Wako Pure Chemical Industries, Ltd., Nacalai Tesque, Tosoh Corp.).
1. Nuclear magnetic resonance spectroscopy (NMR) measurement A 400 MHz NMR measuring instrument (JEOL JNM-LA400) manufactured by JEOL Ltd. was used. 5 mg of the synthesized compound was dissolved in about 1 g of CDCl ₃ (containing tetramethylsilane 0.05% w / w), and a nuclear magnetic resonance spectrum was measured.
2. Infrared spectroscopy (IR) measurement Using an infrared spectrometer (IR Prestige-21) manufactured by Shimadzu Corporation, an infrared spectrum was measured by a liquid film method.
3. Gas Chromatography (GC) Measurement Using a GC measuring instrument (GC-2010 series) manufactured by Shimadzu Corporation, the compound synthesized under the following conditions was measured, and the purity and yield were calculated by area ratio.
Apparatus: GC-2010 series manufactured by Shimadzu Corporation Column: DB-5 (manufactured by Agilent Technologies) L = 30 m, φ = 0.25 mm, D = 0.25 μm
Carrier: helium (column pressure: 139.9 kPa)
Analysis conditions:
Inlet temperature: 250 ° C
Detector temperature: 320 ° C
Temperature program: Oven 50 ° C x 2 minutes,
Rate 15 ℃ / min
Final 300 ° C x 3 minutes SP ratio 20: 1

温度計、撹拌子を取り付けた１００ｍＬ３口フラスコに、９９％粒状固体水酸化ナトリウム（製品名トーソーパール） ５．０ｇ（０．１２４モル）、ｔ−ブタノール ４０ｇ、１Ｈ，１Ｈ，５Ｈ−オクタフルオロペンタノール １６．２ｇ（０．０７０モル）を仕込み、６５℃に加熱し、クロロメチルスチレン（ｍ体／ｐ体混合物） ９．４ｇ（０．０６２モル）を滴下した。滴下後、７０℃で７時間攪拌した後、冷却し反応液を得た。得られた反応液を分析したところ、クロロメチルスチレン基準のＧＣ収率は９６．３％であった。トルエン、水を加えて分液し水相を除去し、有機相を水で２回洗浄した。有機相に４−メトキシ−１−ナフトール ０．０２ｇを加え、溶媒を濃縮し、８７〜８９℃／０．３Ｐａで蒸留した留分を回収しビニルベンジル（１Ｈ，１Ｈ，５Ｈ−オクタフルオロペンチル）エーテル（ｍ体／ｐ体混合物）を収率９０％で得た。 Example 1 Synthesis of vinylbenzyl (1H, 1H, 5H-octafluoropentyl) ether (m-form / p-form mixture) represented by the following general formula

In a 100 mL three-necked flask equipped with a thermometer and a stir bar, 99% granular solid sodium hydroxide (product name Tosoh Pearl) 5.0 g (0.124 mol), t-butanol 40 g, 1H, 1H, 5H-octafluoropen 16.2 g (0.070 mol) of tanol was charged and heated to 65 ° C., and 9.4 g (0.062 mol) of chloromethylstyrene (m-form / p-form mixture) was added dropwise. After dropping, the mixture was stirred at 70 ° C. for 7 hours and then cooled to obtain a reaction solution. When the obtained reaction liquid was analyzed, the GC yield based on chloromethylstyrene was 96.3%. Toluene and water were added for liquid separation, the aqueous phase was removed, and the organic phase was washed twice with water. 0.02 g of 4-methoxy-1-naphthol was added to the organic phase, the solvent was concentrated, and the fraction distilled at 87 to 89 ° C./0.3 Pa was recovered and vinylbenzyl (1H, 1H, 5H-octafluoropentyl) was recovered. Ether (m-isomer / p-isomer mixture) was obtained with a yield of 90%.

The spectrum data of the obtained compound is shown below.
¹ H-NMR (CDCl ₃ , 400 MHz) δ: 3.8 to 4.0 (m, 2H), 4.6 to 4.7 (m, 2H), 5.2 to 5.3 (m, 1H), 5.7 to 5.8 (m, 1H), 6.0 ( m, 1H), 6.6-6.8 (m, 1H), 7.2-7.4 (m, 4H) ppm
IR (neat): 3011, 2930, 2878, 1678, 1169, 1130, 991, 910, 806cm ^-1

Example 2 Synthesis of vinylbenzyl (1H, 1H, 5H-octafluoropentyl) ether (m-form / p-form mixture) Into a 100 mL three-necked flask equipped with a thermometer and a stirrer was placed 9.1 g (0.066 mol) of potassium carbonate. ), N, N-dimethylformamide 19.7 g, 1H, 1H, 5H-octafluoropentanol 8.9 g (0.038 mol) is charged, heated to 65 ° C., and chloromethylstyrene (m-form / p-form mixture) ) 5.2 g (0.034 mol) was added dropwise. After dropping, the mixture was stirred at 70 ° C. for 7 hours and then cooled to obtain a reaction solution. The GC yield of this reaction solution based on chloromethylstyrene was 92.5%. The precipitate was filtered, 0.02 g of 4-methoxy-1-naphthol was added, the solvent was concentrated, and a fraction distilled at 99 to 101 ° C./0.3 Pa was recovered, and vinylbenzyl (1H, 1H in a yield of 76% was recovered. , 5H-octafluoropentyl) ether (m-form / p-form mixture) was obtained.

Example 3 Synthesis of vinylbenzyl (1H, 1H, 5H-octafluoropentyl) ether (m-isomer / p-isomer mixture) 8.5 g (0.062 mol) of potassium carbonate was added to a 100 mL three-necked flask equipped with a thermometer and a stirrer. ), N, N-dimethylformamide 17.1 g, 1H, 1H, 5H-octafluoropentanol 8.1 g (0.035 mol), potassium iodide 0.16 g, and heated to 65 ° C., chloromethylstyrene (M body / p body mixture) 4.7 g (0.031 mol) was added dropwise. After dropping, the mixture was stirred at 70 ° C. for 7 hours and then cooled to obtain a reaction solution. The GC yield of vinylbenzyl (1H, 1H, 5H-octafluoropentyl) ether (m-form / p-form mixture) based on chloromethylstyrene in this reaction solution was 88.1%.

温度計、撹拌子を取り付けた１００ｍＬ３口フラスコに、９９％粒状固体水酸化ナトリウム（製品名トーソーパール） ４．４ｇ（０．１１モル）、ｔ−ブタノール ２６ｇ、１Ｈ，１Ｈ，７Ｈ−ドデカフルオロヘプタノール ２５．２ｇ（０．０７６モル）を仕込み、７０℃に加熱し、クロロメチルスチレン（ｍ体／ｐ体混合物） １０．４ｇ（０．０６８モル）を滴下した。滴下後、７０℃で７時間攪拌した後、冷却し反応液を得た。この反応液のクロロメチルスチレン基準のＧＣ収率は９６．４％であった。トルエン、水を加え分液し水相を除去した。有機相を水で２回洗浄し、４−メトキシ−１−ナフトール ０．０４ｇを加え、溶媒を濃縮し、１０５〜１０７℃／０．３Ｐａで蒸留した留分を回収し収率８８％でビニルベンジル（１Ｈ，１Ｈ，７Ｈ−ドデカフルオロヘプチル）エーテル（ｍ体／ｐ体混合物）を得た。 Example 4 Synthesis of vinylbenzyl (1H, 1H, 7H-dodecafluoroheptyl) ether (m-form / p-form mixture) represented by the following general formula

In a 100 mL three-necked flask equipped with a thermometer and a stirring bar, 99% granular solid sodium hydroxide (product name Tosoh Pearl) 4.4 g (0.11 mol), t-butanol 26 g, 1H, 1H, 7H-dodecafluorohepta 25.2 g (0.076 mol) of diol was charged and heated to 70 ° C., and 10.4 g (0.068 mol) of chloromethylstyrene (m-isomer / p-isomer mixture) was added dropwise. After dropping, the mixture was stirred at 70 ° C. for 7 hours and then cooled to obtain a reaction solution. The GC yield of this reaction solution based on chloromethylstyrene was 96.4%. Toluene and water were added for liquid separation, and the aqueous phase was removed. The organic phase was washed twice with water, 0.04 g of 4-methoxy-1-naphthol was added, the solvent was concentrated, and the fraction distilled at 105-107 ° C./0.3 Pa was recovered and recovered in a yield of 88%. Benzyl (1H, 1H, 7H-dodecafluoroheptyl) ether (m-isomer / p-isomer mixture) was obtained.

The spectrum data of the obtained compound is shown below.
¹ H-NMR (CDCl ₃ , 400 MHz) δ: 3.8 to 4.0 (m, 2H), 4.6 to 4.7 (m, 2H), 5.2 to 5.3 (m, 1H), 5.7 to 5.8 (m, 1H), 6.0 ( m, 1H), 6.6-6.8 (m, 1H), 7.2-7.4 (m, 4H) ppm
IR (neat): 1630, 1610, 1510, 1210cm ^-1

Example 5 Synthesis of vinylbenzyl (1H, 1H, 7H-dodecafluoroheptyl) ether (m-form / p-form mixture) A 100 mL 3-neck flask equipped with a thermometer and a stirrer was charged with 99% granular solid sodium hydroxide (product name). Tosospearl) 1.2 g (0.03 mol), t-butanol 7.9 g, 1H, 1H, 7H-dodecafluoroheptanol 7.0 g (0.021 mol) were charged, heated to 83 ° C., and chloromethyl Styrene (m-form / p-form mixture) 3.6 g (0.024 mol) was added dropwise. After dropping, the mixture was stirred at 83 ° C. for 4 hours and then cooled to obtain a reaction solution. The GC yield of vinylbenzyl (1H, 1H, 7H-dodecafluoroheptyl) ether (m-form / p-form mixture) based on chloromethylstyrene in this reaction solution was 98.3%.

温度計、撹拌子を取り付けた１００ｍＬ３口フラスコに、９９％粒状固体水酸化ナトリウム（製品名トーソーパール） ３．６ｇ（０．０８９モル）、ｔ−ブタノール １３ｇ、１Ｈ，１Ｈ−ヘプタフルオロブタノール １３．０ｇ（０．０６５モル）を仕込み、７０℃に加熱し、クロロメチルスチレン（ｍ体／ｐ体混合物） ９．０ｇ（０．０５９モル）を滴下した。滴下後、７０℃で７時間攪拌した後、冷却し反応液を得た。この反応液のクロロメチルスチレン基準のＧＣ収率は９７．０％であった。トルエン、水を加え分液し水相を除去した。有機相を水で２回洗浄し、４−メトキシ−１−ナフトール ０．０２ｇを加え、溶媒を濃縮し、７２℃／０．７Ｔｏｒｒで蒸留した留分を回収し収率８１％でビニルベンジル（１Ｈ，１Ｈ−ヘプタフルオロブチル）エーテル（ｍ体／ｐ体混合物）を得た。 Example 6 Synthesis of vinylbenzyl (1H, 1H-heptafluorobutyl) ether (m-form / p-form mixture) represented by the following general formula

In a 100 mL three-necked flask equipped with a thermometer and a stirring bar, 99% granular solid sodium hydroxide (product name Tosoh Pearl) 3.6 g (0.089 mol), t-butanol 13 g, 1H, 1H-heptafluorobutanol 13. 0 g (0.065 mol) was charged and heated to 70 ° C., and 9.0 g (0.059 mol) of chloromethylstyrene (m-isomer / p-isomer mixture) was added dropwise. After dropping, the mixture was stirred at 70 ° C. for 7 hours and then cooled to obtain a reaction solution. The GC yield based on chloromethylstyrene in this reaction solution was 97.0%. Toluene and water were added for liquid separation, and the aqueous phase was removed. The organic phase was washed twice with water, 0.02 g of 4-methoxy-1-naphthol was added, the solvent was concentrated, and the fraction distilled at 72 ° C./0.7 Torr was recovered to recover vinylbenzyl (81% yield). 1H, 1H-heptafluorobutyl) ether (m-form / p-form mixture) was obtained.

The spectrum data of the obtained compound is shown below.
¹ H-NMR (CDCl ₃ , 400 MHz) δ: 3.8 to 4.0 (m, 2H), 4.6 to 4.7 (m, 2H), 5.2 to 5.3 (m, 1H), 5.7 to 5.8 (m, 1H), 6.6 to 6.8 (m, 1H), 7.2-7.4 (m, 4H) ppm
IR (neat): 2878, 1344, 1227, 1123, 991, 912, 735cm ^-1

Example 7 Synthesis of 4-vinylbenzyl (1H, 1H-heptafluorobutyl) ether In a 100 mL three-necked flask equipped with a thermometer and a stir bar, 99 g of granular solid sodium hydroxide (product name Tosoh Pearl) 1.7 g (0 0.042), 12 g of dimethyl sulfoxide, 6.0 g (0.030 mol) of 1H, 1H-heptafluorobutanol, and 4.1 g (0.027 mol) of 4-chloromethylstyrene were stirred and heated at 60 ° C. for 4 hours. After cooling. The GC yield of 4-vinylbenzyl (1H, 1H-heptafluorobutyl) ether based on chloromethylstyrene in the obtained reaction solution was 96.1%.

実施例１において、１Ｈ，１Ｈ，５Ｈ−オクタフルオロペンタノールの代わりに１Ｈ，１Ｈ−トリフルオロエタノールを、クロロメチルスチレン（ｍ体／ｐ体混合物）の代わりに４−クロロメチルスチレンを使用する以外は同様にして、４−ビニルベンジル（１Ｈ，１Ｈ−トリフルオロエチル）エーテルを得た。８１℃／５Ｔｏｒｒで蒸留した留分を回収し収率９０％で４−ビニルベンジル（１Ｈ，１Ｈ−トリフルオロエチル）エーテルを得た。 Example 8 Synthesis of 4-vinylbenzyl (1H, 1H-trifluoroethyl) ether represented by the following general formula

In Example 1, 1H, 1H-trifluoroethanol was used in place of 1H, 1H, 5H-octafluoropentanol, and 4-chloromethylstyrene was used in place of chloromethylstyrene (m-form / p-form mixture). In the same manner, 4-vinylbenzyl (1H, 1H-trifluoroethyl) ether was obtained. A fraction distilled at 81 ° C./5 Torr was collected to obtain 4-vinylbenzyl (1H, 1H-trifluoroethyl) ether in a yield of 90%.

The spectrum data of the obtained compound is shown below.
¹ H-NMR (CDCl ₃ , 400 MHz) δ: 3.6 to 4.0 (m, 2H), 4.6 (m, 2H), 5.1 to 5.8 (m, 2H), 6.5 to 6.8 (m, 1H), 6.8 to 7.0 ( m, 2H), 7.1-7.4 (m, 2H) ppm
IR (neat): 1630, 1610, 1510, 1210, 1150cm ^-1

実施例１において、１Ｈ，１Ｈ，５Ｈ−オクタフルオロペンタノールの代わりに１Ｈ,１Ｈ,９Ｈ−ヘキサデカフルオロノナノールを使用する以外は同様にして、ビニルベンジル（１Ｈ,１Ｈ,９Ｈ−ヘキサデカフルオロノニル）エーテルを得た。１２６−１２８℃／０．３Ｔｏｒｒで蒸留した留分を回収し、収率８７％でビニルベンジル（１Ｈ,１Ｈ,９Ｈ−ヘキサデカフルオロノニル）エーテル（ｍ体/ｐ体混合物）を得た。 Example 9 Synthesis of vinylbenzyl (1H, 1H, 9H-hexadecafluorononyl) ether (m-form / p-form mixture) represented by the following general formula

In Example 1, vinylbenzyl (1H, 1H, 9H-hexadecafluoro was similarly used except that 1H, 1H, 9H-hexadecafluorononanol was used instead of 1H, 1H, 5H-octafluoropentanol. Nonyl) ether was obtained. The fraction distilled at 126-128 ° C./0.3 Torr was collected to obtain vinylbenzyl (1H, 1H, 9H-hexadecafluorononyl) ether (m-form / p-form mixture) in a yield of 87%.

The spectrum data of the obtained compound is shown below.
¹ H-NMR (CDCl ₃ , 400 MHz) δ: 3.8 to 4.0 (m, 2H), 4.6 to 4.7 (m, 2H), 5.2 to 5.3 (m, 1H), 5.7 to 5.8 (m, 1H), 6.0 ( m, 1H), 6.6-6.8 (m, 1H), 7.2-7.4 (m, 4H) ppm
IR (neat): 2878, 1404, 1364, 1207, 1146, 991, 914, 802cm ^-1

実施例１において、１Ｈ，１Ｈ，５Ｈ−オクタフルオロペンタノールの代わりに１Ｈ,１Ｈ-ペンタデカフルオロオクタノールを、クロロメチルスチレン（ｍ体／ｐ体混合物）の代わりに４−クロロメチルスチレンを使用する以外は実施例１と同様にして４−ビニルベンジル（１Ｈ,１Ｈ-ペンタデカフルオロオクチル）エーテルの粗生成物を合成した。ただし、沸点が高いので蒸留でなくシリカゲルカラムクロマトグラフィー（溶離液：ｎ−ヘキサン）で精製し、溶媒を留去して収率９０％で４−ビニルベンジル（１Ｈ,１Ｈ-ペンタデカフルオロオクチル）エーテルを得た。 Example 10 Synthesis of 4-vinylbenzyl (1H, 1H-pentadecafluorooctyl) ether represented by the following general formula

In Example 1, 1H, 1H-pentadecafluorooctanol is used in place of 1H, 1H, 5H-octafluoropentanol, and 4-chloromethylstyrene is used in place of chloromethylstyrene (m-form / p-form mixture). A crude product of 4-vinylbenzyl (1H, 1H-pentadecafluorooctyl) ether was synthesized in the same manner as in Example 1 except that. However, since it has a high boiling point, it is purified by silica gel column chromatography (eluent: n-hexane) instead of distillation, and the solvent is distilled off to give 4-vinylbenzyl (1H, 1H-pentadecafluorooctyl) in 90% yield. Ether was obtained.

The spectrum data of the obtained compound is shown below.
¹ H-NMR (CDCl ₃ , 400 MHz) δ: 3.8 to 4.1 (m, 2H), 4.6 (m, 2H), 5.2 to 5.9 (m, 2H), 6.5 to 6.9 (m, 1H), 7.2 to 7.5 ( m, 4H) ppm
IR (neat): 2800-3000, 1630, 1610, 1210, 1150, 1090cm ^-1

温度計、撹拌子を取り付けた１００ｍＬ３口フラスコに、炭酸カリウム ７．３ｇ（０．０４３モル）、Ｎ，Ｎ−ジメチルホルムアミド １４．７ｇ、２Ｈ−ヘキサフルオロ−２−プロパノール ６．２ｇ（０．０３７モル）を仕込み、４−クロロメチルスチレン ５．０ｇ（０．０３３モル）を滴下し，６０℃に加熱した。滴下後、６０℃で７時間攪拌した。冷却後、得られた反応液のクロロメチルスチレン基準のＧＣ収率は９９．６％であった。沈殿をろ過し４−メトキシ−１−ナフトール ０．０２ｇを加え、溶媒を濃縮し、９０℃／３０Ｔｏｒｒで蒸留した留分を回収し収率８８％で４−ビニルベンジル（２Ｈ−ヘキサフルオロ−２−プロピル）エーテルを得た。 Example 11 Synthesis of 4-vinylbenzyl (2H-hexafluoro-2-propyl) ether represented by the following general formula

To a 100 mL three-necked flask equipped with a thermometer and a stirring bar, 7.3 g (0.043 mol) of potassium carbonate, 14.7 g of N, N-dimethylformamide, 6.2 g of 2H-hexafluoro-2-propanol (0.037) Mol) was added dropwise, and 5.0 g (0.033 mol) of 4-chloromethylstyrene was added dropwise and heated to 60 ° C. After dropping, the mixture was stirred at 60 ° C. for 7 hours. After cooling, the GC yield of the obtained reaction liquid based on chloromethylstyrene was 99.6%. The precipitate was filtered, 0.02 g of 4-methoxy-1-naphthol was added, the solvent was concentrated, and the fraction distilled at 90 ° C./30 Torr was recovered, and 4-vinylbenzyl (2H-hexafluoro-2 was obtained in a yield of 88%. -Propyl) ether was obtained.

The spectrum data of the obtained compound is shown below.
¹ H-NMR (CDCl ₃ , 400 MHz) δ: 4.4 (m, 2H), 4.6 (m, 2H), 5.2 to 5.9 (m, 2H), 6.5 to 6.9 (m, 1H), 7.2 to 7.5 (m, 4H) ppm

Comparative Example 1 Synthesis of vinylbenzyl (1H, 1H, 5H-octafluoropentyl) ether (m-form / p-form mixture) (example using methyl ethyl ketone as solvent)
In a 100 mL four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer, 8.5 g (0.037 mol) of 1H, 1H, 5H-octafluoropentanol and 6.6 g (0.048 mol) of potassium carbonate were added. And 22 g of methyl ethyl ketone were charged and heated to 60 ° C. Subsequently, 5.0 g (0.033 mol) of chloromethylstyrene (m-form / p-form mixture) was added dropwise. After stirring at 60 ° C. for 2 hours, a part of the reaction solution was sampled and subjected to GC analysis. As a result, the GC yield based on chloromethylstyrene was as low as 6.7%.

Comparative Example 2 Synthesis of vinylbenzyl (1H, 1H, 5H-octafluoropentyl) ether (m-form / p-form mixture) (example using sodium hydroxide aqueous solution as a base and 0.9-fold mol of phase transfer catalyst)
In a 200 mL four-necked flask equipped with a thermometer and a stirring bar, water 32 g, 48% aqueous sodium hydroxide solution 54.5 g (0.65 mol), tetrabutylammonium hydrogensulfate 19.6 g (0.058 mol), toluene 131 g, 1H, 1H, 5H-octafluoropentanol 17.3 g (0.075 mol) was charged and stirred. It was cooled to 17 ° C. in a water bath, and 10.1 g (0.066 mol) of chloromethylstyrene ((m-form / p-form mixture) was added dropwise. The total charge was 26.2 times by weight of chloromethylstyrene. After the dropwise addition, the mixture was stirred at room temperature for 2.5 days, and the GC yield was 96.7%.

  Since an intermediate phase was formed when liquid separation was attempted after standing, the aqueous phase was removed, and the intermediate phase was extracted by adding toluene and water, and the organic phases were combined and washed with water three times. To the organic phase, 0.02 g of 4-methoxy-1-naphthol and 0.02 g of 2-methoxyphenothiazine were added, the solvent was concentrated, and a fraction of 87-89 ° C./0.3 Pa was recovered and vinylbenzyl was recovered in a yield of 87%. (1H, 1H, 5H-octafluoropentyl) ether (m-form / p-form mixture) was obtained.

Comparative Example 3 Synthesis of vinylbenzyl (1H, 1H, 7H-dodecafluorononyl) ether (m-form / p-form mixture) (reaction without solvent using sodium hydroxide aqueous solution as a base and using a phase transfer catalyst) )
In a 100 mL three-necked flask equipped with a thermometer and a stirring bar, 2.6 g (0.020 mol) of 33% aqueous sodium hydroxide solution, 0.04 g of tetrabutylammonium chloride, 5.1 g of 1H, 1H, 7H-dodecafluoroheptanol (0.015 mol) was charged and heated to 70 ° C., and 2.4 g (0.016 mol) of chloromethylstyrene (m-form / p-form mixture) was added dropwise. During the dropwise addition, crystals precipitated and became a slurry, which was heated to 75 ° C. After stirring at 75 ° C. for 6 hours, a part of the reaction solution was sampled and analyzed by GC. As a result, the GC yield based on chloromethylstyrene was 79.6%, and unreacted chloromethylstyrene was 10.7%. If the solvent remained, the stirring efficiency was poor and the yield was low.

Comparative Example 4 Synthesis of vinylbenzyl (1H, 1H, 7H-dodecafluoroheptyl) ether (m-form / p-form mixture) (example without solvent)
In a 100 mL four-necked flask equipped with a thermometer and a stirring bar, 2.7 g (0.067 mol) of 99% granular solid sodium hydroxide (product name Tosoh Pearl), 12.6 g of 1H, 1H, 7H-dodecafluoroheptanol ( 0.038 mol) was charged and heated to 70 ° C., and 5.2 g (0.034 mol) of chloromethylstyrene (m-isomer / p-isomer mixture) was added dropwise. After the dropwise addition, the mixture was stirred at 70 ° C. for 1 hour. As a result, crystals were precipitated, the whole liquid became a slurry, and stirring became difficult, and the reaction was stopped. It was difficult to continue the reaction without solvent.

Claims (3)

A process for producing a vinylbenzyl (fluoroalkyl) ether represented by the following general formula (1), comprising a fluoroalkyl alcohol represented by the following general formula (2) and chloromethylstyrene, a tertiary alcohol, and a nitrogen-containing compound A method for producing vinylbenzyl (fluoroalkyl) ether, comprising reacting in a solvent selected from an organic solvent and a sulfur-containing organic solvent in the presence of a solid alkali.

(In the formula, R _f represents a fluoroalkyl group, and n represents an integer of 1 to 3.)

(In the formula, R _f represents a fluoroalkyl group, and n represents an integer of 1 to 3.)   The vinylbenzyl (fluoro) according to claim 1, wherein the solid alkali is an alkali metal hydroxide or an alkali metal carbonate, and the solvent is selected from 2-methyl-2-propanol, dimethyl sulfoxide, and N, N-dimethylformamide. Alkyl) ether production process.   The method for producing vinylbenzyl (fluoroalkyl) ether according to claim 1 or 2, wherein the solid alkali is sodium hydroxide or potassium carbonate.