JP4876476B2 - Chloroalkoxystyrene and process for producing the same - Google Patents

Description

  The present invention relates to a novel chloroalkoxystyrene useful as a raw material for medical and agricultural chemicals, functional polymers, and the like, and a method for producing the same.

  The compound of the present invention, chloroalkoxystyrene, is a novel compound. However, styrene compounds having a halogen-substituted alkyl group such as 3-bromopropylstyrene, 4-bromobutylstyrene, and 2- (4-bromomethylcyclohexylene) -ethylstyrene are proposed as raw materials for heat-resistant anion exchange resins. The same effect is expected for this compound (see, for example, Patent Document 1).

Moreover, it is not known also about the manufacturing method of the chloroalkoxy styrene which is a compound of this invention because of a novel compound. On the other hand, the following production methods are known for similar styrene derivatives. For example, (1) a method in which para-hydroxystyrene is used as a raw material and reacted with 1,12-dibromododecane in the presence of an alkali (see, for example, Non-Patent Document 1), (2) para-hydroxyacetophenone in the presence of an alkali , 4-dibromobutane to convert to para- (4-bromobutyloxy) acetophenone, followed by reduction with NaBH ₄ to give 1- (1-hydroxyethyl) -4-bromobutyloxyacetophenone. Induction and further dehydration reaction (for example, see Non-Patent Document 2), (3) A method in which para-acetoxystyrene is saponified with potassium hydroxide and then reacted with dibromoalkane (for example, Non-Patent Document 3) Etc.

However, with respect to the method (1), since para-hydroxystyrene as a raw material is an unstable and extremely easy compound, there is a problem that it is extremely difficult to handle in large quantities. In addition to the large number of operations, the operation is complicated and NaBH ₄ that is a water-inhibiting and self-igniting substance has to be handled in large quantities. Furthermore, in the method (3), it is necessary to use para-acetoxystyrene which is expensive and difficult to obtain as a raw material. As described above, there are many problems in applying the above-described conventional synthesis methods to the chloroalkoxystyrene which is the compound of the present invention.

JP-A-4-349994 (Example) "Journal of Organic Chemistry" (USA), 1989, Vol. 54, p3106-3113 (Experimental section) “Polymer Journal” (Japan), 1991, Vol. 23, p1225-1241 (Scheme 2, experimental section) “Polymer Preprints”. (USA), 2003, 44, 346-347 (Experimental section, Fig. 1)

  An object of the present invention is to provide a novel chloroalkoxystyrene useful as a raw material for medical and agricultural chemicals, functional polymers, and the like, and an efficient production method thereof.

  As a result of intensive studies to solve the conventional problems, the present inventors have found that a chloroalkoxyphenylmagnesium halide represented by the following formula (3) and a vinyl halide represented by the following formula (4) are present in the presence of a catalyst. It was found that by reacting with chloroalkoxystyrene, chloroalkoxystyrene can be easily obtained, and the present invention has been completed.

（式中、ｎは３〜５の整数を表し、Ｘはハロゲン原子を表す）
すなわち本発明は、下記式（１）で示されるクロロアルコキシスチレン、及び下記式（３）で示されるクロロアルコキシフェニルマグネシウムハライドと下記式（４）で示されるビニルハライドとを触媒の存在下に反応させることを特徴とする、クロロアルコキシスチレンの製造方法に関する。

(In the formula, n represents an integer of 3 to 5, and X represents a halogen atom)
That is, the present invention reacts chloroalkoxystyrene represented by the following formula (1), chloroalkoxyphenylmagnesium halide represented by the following formula (3) and vinyl halide represented by the following formula (4) in the presence of a catalyst. The present invention relates to a method for producing chloroalkoxystyrene.

（式中、ｎは３〜５の整数を表し、Ｘはハロゲン原子を表す）
以下、本発明について詳細に説明する。

(In the formula, n represents an integer of 3 to 5, and X represents a halogen atom)
Hereinafter, the present invention will be described in detail.

  The chloroalkoxystyrene in the present invention is a compound having a structure represented by the following formula (1). Specifically, o- (3-chloropropoxy) styrene, o- (4-chlorobutoxy) styrene, o- (5-chloropentoxy) styrene, m- (3-chloropropoxy) styrene, m- (4-chlorobutoxy) styrene, m- (5-chloropentoxy) styrene, p- (3-chloropropoxy) styrene, Examples include p- (4-chlorobutoxy) styrene, p- (5-chloropentoxy) styrene, and one or a mixture of two or more of these compound groups may be used.

（式中、ｎは３〜５の整数を表す）
本発明において、下記式（３）で示されるクロロアルコキシフェニルマグネシウムハライドと下記式（４）で示されるビニルハライドとを触媒の存在下に反応させることにより、クロロアルコキシスチレンを効率的に製造することができる。

(In the formula, n represents an integer of 3 to 5)
In the present invention, chloroalkoxystyrene is efficiently produced by reacting a chloroalkoxyphenylmagnesium halide represented by the following formula (3) with a vinyl halide represented by the following formula (4) in the presence of a catalyst. Can do.

（式中、ｎは３〜５の整数を表し、Ｘはハロゲン原子を表す）
式（３）で示される化合物の具体例としては、ｏ−（３−クロロプロポキシ）フェニルマグネシウムフルオライド、ｏ−（３−クロロプロポキシ）フェニルマグネシウムクロライド、ｏ−（３−クロロプロポキシ）フェニルマグネシウムブロマイド、ｏ−（３−クロロプロポキシ）フェニルマグネシウムヨーダイド、ｏ−（４−クロロブトキシ）フェニルマグネシウムフルオライド、ｏ−（４−クロロブトキシ）フェニルマグネシウムクロライド、ｏ−（４−クロロブトキシ）フェニルマグネシウムブロマイド、ｏ−（４−クロロブトキシ）フェニルマグネシウムヨーダイド、ｏ−（５−クロロペンチルオキシ）フェニルマグネシウムフルオライド、ｏ−（５−クロロペンチルオキシ）フェニルマグネシウムクロライド、ｏ−（５−クロロペンチルオキシ）フェニルマグネシウムブロマイド、ｏ−（５−クロロペンチルオキシ）フェニルマグネシウムヨーダイド、ｍ−（３−クロロプロポキシ）フェニルマグネシウムフルオライド、ｍ−（３−クロロプロポキシ）フェニルマグネシウムクロライド、ｍ−（３−クロロプロポキシ）フェニルマグネシウムブロマイド、ｍ−（３−クロロプロポキシ）フェニルマグネシウムヨーダイド、ｍ−（４−クロロブトキシ）フェニルマグネシウムフルオライド、ｍ−（４−クロロブトキシ）フェニルマグネシウムクロライド、ｍ−（４−クロロブトキシ）フェニルマグネシウムブロマイド、ｍ−（４−クロロブトキシ）フェニルマグネシウムヨーダイド、ｍ−（５−クロロペンチルオキシ）フェニルマグネシウムフルオライド、ｍ−（５−クロロペンチルオキシ）フェニルマグネシウムクロライド、ｍ−（５−クロロペンチルオキシ）フェニルマグネシウムブロマイド、ｍ−（５−クロロペンチルオキシ）フェニルマグネシウムヨーダイド、ｐ−（３−クロロプロポキシ）フェニルマグネシウムフルオライド、ｐ−（３−クロロプロポキシ）フェニルマグネシウムクロライド、ｐ−（３−クロロプロポキシ）フェニルマグネシウムブロマイド、ｐ−（３−クロロプロポキシ）フェニルマグネシウムヨーダイド、ｐ−（４−クロロブトキシ）フェニルマグネシウムフルオライド、ｐ−（４−クロロブトキシ）フェニルマグネシウムクロライド、ｐ−（４−クロロブトキシ）フェニルマグネシウムブロマイド、ｐ−（４−クロロブトキシ）フェニルマグネシウムヨーダイド、ｐ−（５−クロロペンチルオキシ）フェニルマグネシウムフルオライド、ｐ−（５−クロロペンチルオキシ）フェニルマグネシウムクロライド、ｐ−（５−クロロペンチルオキシ）フェニルマグネシウムブロマイド、ｐ−（５−クロロペンチルオキシ）フェニルマグネシウムヨーダイド等が挙げられる。

(In the formula, n represents an integer of 3 to 5, and X represents a halogen atom)
Specific examples of the compound represented by the formula (3) include o- (3-chloropropoxy) phenylmagnesium fluoride, o- (3-chloropropoxy) phenylmagnesium chloride, o- (3-chloropropoxy) phenylmagnesium bromide. O- (3-chloropropoxy) phenylmagnesium iodide, o- (4-chlorobutoxy) phenylmagnesium fluoride, o- (4-chlorobutoxy) phenylmagnesium chloride, o- (4-chlorobutoxy) phenylmagnesium bromide O- (4-chlorobutoxy) phenylmagnesium iodide, o- (5-chloropentyloxy) phenylmagnesium fluoride, o- (5-chloropentyloxy) phenylmagnesium chloride, o- (5-chlorope Tiloxy) phenylmagnesium bromide, o- (5-chloropentyloxy) phenylmagnesium iodide, m- (3-chloropropoxy) phenylmagnesium fluoride, m- (3-chloropropoxy) phenylmagnesium chloride, m- (3- Chloropropoxy) phenylmagnesium bromide, m- (3-chloropropoxy) phenylmagnesium iodide, m- (4-chlorobutoxy) phenylmagnesium fluoride, m- (4-chlorobutoxy) phenylmagnesium chloride, m- (4- Chlorobutoxy) phenyl magnesium bromide, m- (4-chlorobutoxy) phenyl magnesium iodide, m- (5-chloropentyloxy) phenyl magnesium fluoride, m- (5-chloro) Pentyloxy) phenylmagnesium chloride, m- (5-chloropentyloxy) phenylmagnesium bromide, m- (5-chloropentyloxy) phenylmagnesium iodide, p- (3-chloropropoxy) phenylmagnesium fluoride, p- ( 3-chloropropoxy) phenylmagnesium chloride, p- (3-chloropropoxy) phenylmagnesium bromide, p- (3-chloropropoxy) phenylmagnesium iodide, p- (4-chlorobutoxy) phenylmagnesium fluoride, p- ( 4-chlorobutoxy) phenyl magnesium chloride, p- (4-chlorobutoxy) phenyl magnesium bromide, p- (4-chlorobutoxy) phenyl magnesium iodide, p- (5-chloro) Lopentyloxy) phenylmagnesium fluoride, p- (5-chloropentyloxy) phenylmagnesium chloride, p- (5-chloropentyloxy) phenylmagnesium bromide, p- (5-chloropentyloxy) phenylmagnesium iodide, etc. Can be mentioned.

  Although it does not specifically limit as a preparation method of the chloroalkoxyphenyl magnesium halide mentioned above, For example, after reacting halophenol and a halochloroalkane and inducing | guiding | deriving to chloroalkoxyphenyl halide, it shows. It can be easily prepared by reacting with metallic magnesium.

（式中、ｎはいずれも３〜５の整数を表し、Ｘはいずれもハロゲン原子を表す）
上記反応式（Ａ）の方法において用いられるハロフェノールの具体例としては、ｏ−フルオロフェノール、ｏ−クロロフェノール、ｏ−ブロモフェノール、ｏ−ヨードフェノール、ｍ−フルオロフェノール、ｍ−クロロフェノール、ｍ−ブロモフェノール、ｍ−ヨードフェノール、ｐ−フルオロフェノール、ｐ−クロロフェノール、ｐ−ブロモフェノール、ｐ−ヨードフェノール等が挙げられる。

(Wherein n represents an integer of 3 to 5 and X represents a halogen atom)
Specific examples of the halophenol used in the method of the above reaction formula (A) include o-fluorophenol, o-chlorophenol, o-bromophenol, o-iodophenol, m-fluorophenol, m-chlorophenol, m -Bromophenol, m-iodophenol, p-fluorophenol, p-chlorophenol, p-bromophenol, p-iodophenol and the like.

  Specific examples of the halochloroalkane used in the method of the reaction formula (A) include 1-chloro-3-fluoropropane, 1,3-dichloropropane, 1-bromo-3-chloropropane, 1-chloro-3- Iodopropane, 1-chloro-4-fluorobutane, 1,4-dichlorobutane, 1-bromo-4-chlorobutane, 1-chloro-4-iodopropane, 1-chloro-5-fluoropentane, 1,5-dichloro Pentane, 1-bromo-5-chloropentane, 1-chloro-5-iodopentane and the like can be mentioned.

  In the method of the present invention, the desired chloroalkoxystyrene can be synthesized by reacting the chloroalkoxyphenylmagnesium halide prepared in the above reaction formula (A) with a vinyl halide in the presence of a catalyst.

  The catalyst used in the method of the present invention is not particularly limited. For example, one or two selected from the group consisting of a palladium catalyst, a nickel catalyst, a manganese catalyst, an iron catalyst, a cobalt catalyst, and a rhodium catalyst. More than species.

  The palladium-based catalyst used in the method of the present invention is a catalyst containing palladium element as an active ingredient, and is not particularly limited. For example, palladium powder, palladium (II) chloride, palladium (II) bromide. , Palladium (II) iodide, palladium (II) acetate, palladium (II) nitrate, palladium (II) sulfate, palladium (II) cyanide, palladium (II) acetylacetonate, palladium (II) trifluoroacetate, palladium Examples thereof include compounds such as carbon, hydrates of these compounds, and various complex catalysts derived from these compounds.

  The nickel-based catalyst used in the method of the present invention is a catalyst containing nickel element as an active ingredient and is not particularly limited. For example, nickel powder, nickel fluoride (II), nickel chloride (II) , Nickel bromide (II), nickel iodide (II), nickel sulfate (II), nickel nitrate (II), nickel perchlorate (II), nickel sulfide (II), nickel formate (II), nickel oxalate (II), nickel (II) acetate, nickel (II) fumarate, nickel (II) lactate, nickel (II) gluconate, nickel (II) benzoate, nickel (II) stearate, nickel (II) sulfamate , Nickel amidosulfate (II), nickel carbonate (II), nickel (II) acetylacetonate, nickel carbon, etc. , Hydrates of these compounds or various complex catalysts derived from these compounds, and the like.

  The manganese-based catalyst used in the method of the present invention is a catalyst containing manganese element as an active ingredient, and is not particularly limited. For example, manganese (II) chloride, manganese (II) bromide, iodide Manganese (II), manganese fluoride (II), manganese acetate (II), manganese acetate (III), manganese formate (II), manganese oxalate (II), manganese benzoate (II), manganese stearate (II) , Manganese (II) borate, manganese (II) acetylacetonate, manganese (III) acetylacetonate, manganese carbonate (II), manganese sulfate (II), manganese nitrate (II), manganese phosphate (II), manganese Examples thereof include powders, hydrates of these compounds, and various complex catalysts derived from these compounds.

  The iron-based catalyst used in the method of the present invention is a catalyst containing iron element as an active ingredient, and is not particularly limited. For example, iron (II) chloride, iron (III) chloride, iron bromide. (II), iron bromide (III), iron (II) iodide, iron (II) fluoride, iron (III) fluoride, iron (II) acetate, iron (II) oxalate, iron (III) oxalate (III) ), Iron (III) citrate, iron (III) perchlorate, iron (III) acetylacetonate, iron (III) nitrate, iron (III) phosphate, iron (II) sulfate, iron (III) sulfate, Or compounds such as iron powder, hydrates of these compounds, or various complex catalysts derived from these compounds can be mentioned.

  The cobalt-based catalyst used in the method of the present invention is a catalyst containing cobalt element as an active ingredient, and is not particularly limited. For example, cobalt (II) chloride, cobalt (II) bromide, iodide Cobalt (II), cobalt fluoride (II), cobalt acetate (II), cobalt acetate (III), cobalt formate (II), cobalt oxalate (II), cobalt benzoate (II), cobalt stearate (II) , Cobalt (II) borate, cobalt (II) acetylacetonate, cobalt (III) acetylacetonate, cobalt (II) carbonate, cobalt (II) sulfate, cobalt (II) nitrate, cobalt (II) phosphate, or Examples include compounds such as cobalt powder, hydrates of these compounds, and various complex catalysts derived from these compounds. That.

  The rhodium-based catalyst used in the method of the present invention is a catalyst containing a rhodium element as an active ingredient, and is not particularly limited. For example, rhodium (II) chloride, rhodium bromide (II), rhodium acetate (II), rhodium acetate (III), rhodium (II) acetylacetonate, rhodium (III) acetylacetonate, rhodium powder, rhodium carbon, etc., hydrates of these compounds, or various compounds derived from these compounds Examples include complex catalysts.

  In the method of the present invention, the above-described catalysts can be used alone or as a mixture.

In addition, although there is no special limitation about the usage-amount of the catalyst used for the method of this invention, the usage-amount of about 1 * 10 < ^-4 > ^-1 * 10 <^-1> times mole is normally selected with respect to chloroalkoxyphenyl magnesium halide. It is. When the amount used is less than 1 × 10 ⁻⁴ times mole, the reaction does not proceed smoothly, and when the amount used exceeds 1 × 10 ⁻¹ times mole, the yield is in proportion to the amount used. It does not improve, but it is economically disadvantageous.

  In the method of the present invention, chloroalkoxyphenylmagnesium halide and vinyl halide are usually reacted in the presence of the catalyst described above in an inert gas atmosphere such as nitrogen and / or argon.

  Specific examples of the vinyl halide used in the method of the present invention include vinyl fluoride, vinyl chloride, vinyl bromide and vinyl iodide, and these can be used alone or as a mixture. Usually, vinyl chloride and / or vinyl bromide are selected in consideration of economy and availability.

  Although there is no special limitation about the usage-amount of the vinyl halide used in the method of this invention, the usage-amount of about 1.0-10.0 times mole is normally selected with respect to chloroalkoxyphenyl magnesium halide. When the amount used is less than 1.0 times mol, the reaction does not proceed smoothly, and when the amount used exceeds 10.0 times mol, the yield does not improve for the amount used, On the contrary, it becomes economically disadvantageous.

  The method of the present invention is usually carried out in the presence of a solvent. The reaction solvent used in the method of the present invention is not particularly limited as long as it does not inhibit the reaction. For example, ether solvents, oxygen-containing solvents, nitrogen-containing solvents, aromatic hydrocarbon solvents And aliphatic hydrocarbon solvents. Usually, these solvents can be used alone or in combination.

  Moreover, as reaction temperature in the method of this invention, the range of -10 degreeC-solvent recirculation | reflux temperature is normally used.

  After completion of the reaction, by appropriately combining acid washing, water washing, alkali washing, etc., by-product inorganic substances and unreacted raw materials are removed, and further by ordinary purification techniques such as chromatography, distillation, recrystallization, The intended chloroalkoxystyrene can be obtained.

  As is clear from the above description, according to the method of the present invention, a novel compound, chloroalkoxystyrene, can be efficiently produced.

  EXAMPLES The method of the present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

  Various analysis / measurement methods in the present invention are shown below.

[Elemental analysis]
Element analyzer: Perkin Elmer fully automatic element analyzer 2400II
Oxygen flask combustion-IC measurement method: Tosoh ion chromatograph IC-2001
[Mass spectrometry]
Mass spectrometer: JMS-K9
Measuring method: DI-MS (EI) analysis [NMR measurement]
NMR measuring apparatus: VARIAN Gemini-200
Example 1 Synthesis of p- (3-chloropropoxy) styrene

１）ｐ−（３−クロロプロポキシ）ブロモベンゼンの合成
攪拌装置を備えた１Ｌフラスコ中に、ｐ−ブロモフェノール １７３．０ｇ（１．０ｍｏｌ）［東京化成品］、水酸化ナトリウム４８．０ｇ（１．２ｍｏｌ）［和光純薬品］、１−ブロモ−３−クロロプロパン １８８．９ｇ（１．２ｍｏｌ）［東京化成品］、水３００ｇを仕込み、１００℃にて４時間加熱した。その後、反応液を室温まで冷却し、析出した副生ＮａＢｒをろ過して、さらに有機層を分液した。得られた有機層を減圧蒸留に付し、目的のｐ−（３−クロロプロポキシ）ブロモベンゼン ２１２．１ｇを得た（収率８２％、純度９６％）。

1) Synthesis of p- (3-chloropropoxy) bromobenzene In a 1-L flask equipped with a stirrer, 173.0 g (1.0 mol) of p-bromophenol (Tokyo Chemicals), 48.0 g of sodium hydroxide (1 0.2 mol) [Wako Pure Chemical Industries], 1-bromo-3-chloropropane 188.9 g (1.2 mol) [Tokyo Chemicals] and water 300 g were charged and heated at 100 ° C. for 4 hours. Thereafter, the reaction solution was cooled to room temperature, the precipitated by-product NaBr was filtered, and the organic layer was further separated. The obtained organic layer was subjected to vacuum distillation to obtain 212.1 g of the target p- (3-chloropropoxy) bromobenzene (yield 82%, purity 96%).

<P- (3-chloropropoxy) bromobenzene>
(1) Mass spectrometry (m / z): 249 (m +)
(2) Elemental analysis
Calculated values: C = 43.3%, H = 4.0%, Br = 32.0%, Cl = 14.2%, O = 4.0%
Found: C = 43.4%, H = 4.1%, Br = 31.8%, Cl = 14.1%, O = 3.6%
2) Synthesis of p- (3-chloropropoxy) styrene In a 300 mL flask equipped with a stirrer and a reflux device under a nitrogen atmosphere, 2.7 g (0.11 mol) of metallic magnesium (cut shape, 20 to 50 mesh) [ Yamastone Metal Co., Ltd.], tetrahydrofuran 50.0 g [Kanto Chemical Co., Ltd.], ethyl bromide 0.7 g (0.006 mol) [Kanto Chemical Co., Ltd.] were charged, and the mixture was heated and stirred for 30 minutes under solvent reflux conditions. Thereafter, the solution was cooled to 10 ° C., and a solution prepared by dissolving 24.9 g (0.10 mol) of p- (3-chloropropoxy) bromobenzene synthesized above in 50.0 g of tetrahydrofuran was added at 10 ° C. over 2 hours. It was dripped. The mixture was further stirred at the same temperature for 1 hour to obtain a target tetrahydrofuran solution of p- (3-chloropropoxy) phenylmagnesium bromide.

Subsequently, 16 mg (0.001 mol) of anhydrous iron chloride (FeCl ₃ ) [Wako Pure Chemical Industries] was added to this solution, and then 6.3 g (0.10 mol) of vinyl chloride gas was blown in at 10 ° C. over 1 hour. The mixture was further stirred at the same temperature for 0.5 hour. After completion of the reaction, a saturated aqueous ammonium chloride solution was added to dissolve and remove unreacted raw materials and by-product Mg salts, and the resulting organic layer was subjected to vacuum distillation to obtain a 125 ° C./0.4 kPa fraction. As a result, 14.4 g of a colorless liquid compound was obtained. As a result of analysis, this compound was identified as the desired p- (3-chloropropoxy) styrene (yield 72% (p- (3-chloropropoxy) bromobenzene reference, purity 94%)).

<P- (3-chloropropoxy) styrene>
(1) Mass spectrometry (m / z): 196 (m +)
(2) Elemental analysis
Calculated values: C = 67.2%, H = 6.7%, Cl = 18.0%, O = 8.1%
Found: C = 67.4%, H = 6.5%, Cl = 17.9%, O = 8.2%
(3) ¹ H-NMR (CDCl ₃ ): 2.31 (2H), 3.82 (2H), 4.20 (2H), 5.21 (1H), 5.69 (1H), 6.75 (1H), 6.95 (2H), 7.43 (2H) [ppm]
(4) ¹³ C-NMR (CDCl ₃ ): 32.40, 41.63, 64.41. 111.72, 114.54, 127.44, 130.68, 136.21, 158.49 [ppm]
Example 2 Synthesis of m- (3-chloropropoxy) styrene

１）ｍ−（３−クロロプロポキシ）ブロモベンゼンの合成
実施例１で用いたｐ−ブロモフェノール １７３．０ｇ（１．０ｍｏｌ）の代わりに、ｍ−ブロモフェノール １７３．０ｇ（１．０ｍｏｌ）［和光純薬品］を用いた以外は、実施例１の方法に準じて反応を行ったところ、目的のｍ−（３−クロロプロポキシ）ブロモベンゼン １９６．６ｇが得られた（収率７５％、純度９５％）。

1) Synthesis of m- (3-chloropropoxy) bromobenzene 17-3.0 g (1.0 mol) of m-bromophenol instead of 173.0 g (1.0 mol) of p-bromophenol used in Example 1 The reaction was carried out in accordance with the method of Example 1 except that [Optical Pure Chemical] was used, and 196.6 g of the target m- (3-chloropropoxy) bromobenzene was obtained (yield 75%, purity 95). %).

2) Synthesis of m- (3-chloropropoxy) styrene In a 300 mL flask equipped with a stirrer and a reflux device in a nitrogen atmosphere, 1.4 g (0.06 mol) of metallic magnesium (cut, 20 to 50 mesh) [ Yamastone Metal Co., Ltd.], tetrahydrofuran 25.0 g [Kanto Chemical Co., Ltd.], ethyl bromide 0.4 g (0.003 mol) [Kanto Chemical Co., Ltd.] were charged, and the mixture was heated and stirred for 30 minutes under solvent reflux conditions. Thereafter, the liquid was cooled to 10 ° C., and a solution prepared by dissolving 12.5 g (0.05 mol) of m- (3-chloropropoxy) bromobenzene synthesized above in 25.0 g of tetrahydrofuran was added at 10 ° C. over 2 hours. It was dripped. The mixture was further stirred at the same temperature for 1 hour to obtain a target tetrahydrofuran solution of m- (3-chloropropoxy) phenylmagnesium bromide.

Subsequently, 16 mg (0.001 mol) of anhydrous iron chloride (FeCl ₃ ) [Wako Pure Chemical Industries] was added to this solution, and then 3.2 g (0.05 mol) of vinyl chloride gas was blown in at 5 ° C. over 1 hour. The mixture was further stirred at the same temperature for 0.5 hour. After completion of the reaction, a saturated aqueous ammonium chloride solution is added to dissolve and remove unreacted raw materials and by-product Mg salts, and the obtained organic layer is subjected to silica gel column chromatography to obtain the desired m- (3-chloropropoxy). ) 6.2 g of styrene was obtained (yield 60% (based on m- (3-chloropropoxy) bromobenzene), purity 95%).

<M- (3-Chloropropoxy) styrene>
(1) Mass spectrometry (m / z): 196 (m +)
(2) Elemental analysis
Calculated values: C = 67.2%, H = 6.7%, Cl = 18.0%, O = 8.1%
Found: C = 67.3%, H = 6.8%, Cl = 17.8%, O = 8.1%
Example 3 Synthesis of p- (4-chlorobutoxy) styrene

１）ｐ−（４−クロロブトキシ）ブロモベンゼンの合成
攪拌装置を備えた１Ｌフラスコ中に、ｐ−ブロモフェノール １７３．０ｇ（１．０ｍｏｌ）［東京化成品］、水酸化カリウム８４．２ｇ（１．５ｍｏｌ）［和光純薬品］、１，４−ジクロロブタン ２２６．０ｇ（２．０ｍｏｌ）［関東化学品］、水２００ｇを仕込み、１００℃にて６時間加熱した。その後、反応液を室温まで冷却し、析出した副生ＫＢｒをろ過して、さらに有機層を分液した。得られた有機層を減圧蒸留に付し、目的のｐ−（４−クロロブトキシ）ブロモベンゼン １９７．０ｇを得た（収率７１％、純度９５％）。

1) Synthesis of p- (4-chlorobutoxy) bromobenzene In a 1 L flask equipped with a stirrer, 173.0 g (1.0 mol) of p-bromophenol [Tokyo Chemicals], 84.2 g of potassium hydroxide (1 0.5 mol) [Wako Pure Chemicals], 1,4-dichlorobutane 226.0 g (2.0 mol) [Kanto Chemicals], and water 200 g were charged and heated at 100 ° C. for 6 hours. Thereafter, the reaction solution was cooled to room temperature, the precipitated by-product KBr was filtered, and the organic layer was further separated. The obtained organic layer was subjected to distillation under reduced pressure to obtain 197.0 g of the target p- (4-chlorobutoxy) bromobenzene (yield 71%, purity 95%).

<P- (4-chlorobutoxy) bromobenzene>
(1) Mass spectrometry (m / z): 264 (m +)
(2) Elemental analysis
Calculated values: C = 45.6%, H = 4.6%, Br = 30.3%, Cl = 13.5%, O = 6.0%
Found: C = 45.4%, H = 4.4%, Br = 30.6%, Cl = 13.8%, O = 5.8%
2) Synthesis of p- (4-chlorobutoxy) styrene In a 200 mL flask equipped with a stirrer and a reflux apparatus under a nitrogen atmosphere, 2.4 g (0.10 mol) of metallic magnesium (cut shape, 20 to 50 mesh) [ Yamastone Metal Co., Ltd.], tetrahydrofuran 50.0 g [Kanto Chemical Co., Ltd.], ethyl bromide 0.7 g (0.006 mol) [Kanto Chemical Co., Ltd.] were charged, and the mixture was heated and stirred for 30 minutes under solvent reflux conditions. Thereafter, the liquid was cooled to 5 ° C., and a solution prepared by dissolving 26.4 g (0.10 mol) of p- (4-chlorobutoxy) bromobenzene synthesized in 30.0 g of tetrahydrofuran over 5 hours at 5 ° C. It was dripped. The mixture was further stirred at the same temperature for 2 hours to obtain a target tetrahydrofuran solution of p- (4-chlorobutoxy) phenylmagnesium bromide.

  Subsequently, 1.1 g (0.002 mol) [Aldrich product] of 1,3-bis (diphenylphosphino) propane-dichloronickel was added to this solution, and then 16.0 g (0.15 mol) of vinyl bromide gas was added to 5 g. The mixture was blown at 2 ° C. over 2 hours, and further stirred at the same temperature for 1 hour. After completion of the reaction, a saturated aqueous ammonium chloride solution is added to dissolve and remove unreacted raw materials and by-product Mg salts, and the obtained organic layer is subjected to silica gel column chromatography to obtain the desired p- (4-chlorobutoxy). ) 14.1 g of styrene was obtained (yield 65% (based on p- (4-chlorobutoxy) bromobenzene), purity 94%).

<P- (4-chlorobutoxy) styrene>
(1) Mass spectrometry (m / z): 211 (m +)
(2) Elemental analysis
Calculated values: C = 68.4%, H = 7.2%, Cl = 16.8%, O = 7.6%
Found: C = 68.4%, H = 7.0%, Cl = 16.9%, O = 7.7%
Example 4 Synthesis of p- (5-chloropentoxy) styrene

１）ｐ−（５−クロロペントキシ）ブロモベンゼンの合成
攪拌装置を備えた５００ｍＬフラスコ中に、ｐ−ブロモフェノール ８６．５ｇ（０．５ｍｏｌ）［東京化成品］、水酸化ナトリウム３２．０ｇ（０．８ｍｏｌ）［和光純薬品］、１−ブロモ−５−クロロペンタン １７１．５ｇ（１．０ｍｏｌ）［和光純薬品］、水１５０ｇを仕込み、８０℃にて３時間加熱した。その後、反応液を室温まで冷却し、析出した副生ＮａＢｒをろ過して、さらに有機層を分液した。得られた有機層を減圧蒸留に付し、目的のｐ−（５−クロロペンチロキシ）ブロモベンゼン １１５．７ｇを得た（収率８０％、純度９６％）。

1) Synthesis of p- (5-chloropentoxy) bromobenzene In a 500 mL flask equipped with a stirrer, 86.5 g (0.5 mol) [Tokyo Chemicals] p-bromophenol, 32.0 g sodium hydroxide ( 0.8 mol) [Wako Pure Chemical Industries], 1-bromo-5-chloropentane 171.5 g (1.0 mol) [Wako Pure Chemical Industries], and 150 g of water were charged and heated at 80 ° C. for 3 hours. Thereafter, the reaction solution was cooled to room temperature, the precipitated by-product NaBr was filtered, and the organic layer was further separated. The obtained organic layer was subjected to distillation under reduced pressure to obtain 115.7 g of the target p- (5-chloropentyloxy) bromobenzene (yield 80%, purity 96%).

<P- (5-chloropentyloxy) bromobenzene>
(1) Mass spectrometry (m / z): 278 (m +)
2) Synthesis of p- (5-chloropentyloxy) styrene 2.4 g (0.10 mol) of metallic magnesium (cut shape, 20-50 mesh) in a 200 mL flask equipped with a stirrer and a reflux device under a nitrogen atmosphere [Yamaishi Metal], tetrahydrofuran 50.0 g [Kanto Chemicals], toluene 10.0 g [Kanto Chemicals], ethyl bromide 0.7 g (0.005 mol) [Kanto Chemicals] were charged under solvent reflux conditions. The mixture was heated and stirred for 30 minutes. Thereafter, the liquid was cooled to 0 ° C., and a solution prepared by dissolving 27.8 g (0.10 mol) of p- (5-chloropentyloxy) bromobenzene synthesized above in 50.0 g of tetrahydrofuran was added at 0 ° C. for 2 hours. And dripped. The mixture was further stirred at the same temperature for 1 hour to obtain the target p- (5-chloropentyloxy) phenylmagnesium bromide in tetrahydrofuran / toluene.

Subsequently, 32 mg (0.002 mol) of anhydrous cobalt chloride (CoCl ₂ ) [Wako Pure Chemical Industries] was added to this solution, and then 7.6 g (0.12 mol) of vinyl chloride gas was blown in at 0 ° C. over 1 hour. The mixture was further stirred at the same temperature for 1 hour. After completion of the reaction, a saturated aqueous ammonium chloride solution is added to dissolve and remove unreacted raw materials and by-product Mg salts, and the obtained organic layer is subjected to silica gel column chromatography to obtain the desired p- (5-chloropentyl). 15.8 g of (roxy) styrene was obtained (yield 68% (based on p- (5-chloropentyloxy) bromobenzene, purity 96%)).

<P- (5-chloropentyloxy) styrene>
(1) Mass spectrometry (m / z): 225 (m +)
(2) Elemental analysis
Calculated values: C = 69.5%, H = 7.6%, Cl = 15.8%, O = 7.1%
Found: C = 69.4%, H = 7.5%, Cl = 15.8%, O = 7.3%

Claims (3)

Chloroalkoxystyrene represented by the following formula (1).

(In the formula, n represents an integer of 3 to 5) Chloroalkoxystyrene represented by the following formula (2).

(In the formula, n represents an integer of 3 to 5) A chloroalkoxyphenyl magnesium halide represented by the following formula (3) and a vinyl halide represented by the following formula (4) are mixed with anhydrous iron chloride (FeCl ₃ ), 1,3-bis (diphenylphosphino) propane-dichloronickel, The method for producing chloroalkoxystyrene according to claim 1, wherein the reaction is performed in the presence of a catalyst selected from anhydrous cobalt chloride (CoCl ₂ ) .

(In the formula, n represents an integer of 3 to 5, and X represents a halogen atom)