JP2016169192A - Method of producing 7-octenyl halide - Google Patents
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Abstract
Description
本発明は、７−オクテニルハライドの製造方法に関する。 The present invention relates to a method for producing 7-octenyl halide.
７−オクテニルハライドの製造方法としては、例えば
（１）１，７−オクタジエンを塩素化または臭素化またはヨウ素化する方法（特許文献１、非特許文献１、２参照）、
（２）８−クロロ−１−オクチンをリンドラー触媒存在下水添し、７−オクテニルクロリドを製造する方法（非特許文献３参照）、
（３）７−オクテニルブロミドとテトラメチルアンモニウムクロリドより７−オクテニルクロリドを製造する方法（特許文献１参照）、
（４）アリルマグネシウムブロミドと１−ブロモ−５−クロロペンタンを反応させる方法（非特許文献４、５参照）、
（５）アリルマグネシウムクロリドと１，５−ジクロロペンタンを反応させる方法（非特許文献６参照）、
（６）アリルマグネシウムブロミドと１，５−ジブロモペンタンを反応させる方法（特許文献３参照）、
（７）メチルトリ（５−クロロペンタン）ホウ素銅とアリルクロリドを反応させる方法（非特許文献７参照）
などが挙げられる。
As a manufacturing method of 7-octenyl halide, for example, (1) 1,7-octadiene is chlorinated or brominated or iodinated (see Patent Document 1, Non-Patent Documents 1 and 2),
(2) A method of producing 7-octenyl chloride by hydrogenating 8-chloro-1-octyne in the presence of a Lindlar catalyst (see Non-Patent Document 3),
(3) A method for producing 7-octenyl chloride from 7-octenyl bromide and tetramethylammonium chloride (see Patent Document 1),
(4) A method of reacting allylmagnesium bromide and 1-bromo-5-chloropentane (see Non-Patent Documents 4 and 5),
(5) A method of reacting allylmagnesium chloride and 1,5-dichloropentane (see Non-Patent Document 6),
(6) A method of reacting allylmagnesium bromide with 1,5-dibromopentane (see Patent Document 3),
(7) Method of reacting methyltri (5-chloropentane) boron copper with allyl chloride (see Non-Patent Document 7)
Etc.
しかしながら、上記（１）の方法では、両末端へのハロゲン化が進行し生成物の選択性が低く、（２）や（３）の方法では、原料となる８−クロロ−１−オクチンあるいは７−オクテニルブロミドの入手が困難であり、（４）〜（６）の方法では、いずれも高価な反応剤を用いる必要があると共に、反応後処理後に廃棄物が大量に発生し、加えて（５）の方法では収率２９％と低く工業的に製造することは困難である。また、（７）の方法では、メチルトリ（５−クロロペンタン）ホウ素銅を得るまでに多工程を要し、反応処理後の廃棄物も大量に発生するという問題があった。このため、上記（１）〜（８）の方法では７−オクテニルハライドを工業的に安価に製造することは困難であった。 However, in the method (1), halogenation at both ends proceeds and the selectivity of the product is low. In the methods (2) and (3), 8-chloro-1-octyne or 7 as a raw material is used. -Octenyl bromide is difficult to obtain, and in any of the methods (4) to (6), it is necessary to use an expensive reagent, and a large amount of waste is generated after the post-reaction treatment. In the method 5), the yield is as low as 29% and it is difficult to produce it industrially. Further, the method (7) has a problem that many steps are required until methyltri (5-chloropentane) boron copper is obtained, and a large amount of waste is generated after the reaction treatment. For this reason, it has been difficult to produce 7-octenyl halide industrially at low cost by the methods (1) to (8).
しかして、本発明の目的は、７−オクテニルハライドを、好収率かつ安価に、工業的に有利に製造し得る方法を提供することにある。 Accordingly, an object of the present invention is to provide a method capable of industrially advantageously producing 7-octenyl halide at a good yield and low cost.
本発明者らは、鋭意検討した結果、工業的に入手しやすい７−オクテン−１−オールとハロゲン化チオニルを反応させると、驚くべきことに、末端二重結合へハロゲン化水素が付加した副生成物の生成が抑制され、目的生成物である７−オクテニルハライドが高収率で得られることを見出し、本発明を完成した。 As a result of intensive studies, the present inventors have surprisingly found that when 7-octen-1-ol, which is industrially available, is reacted with thionyl halide, a hydrogen halide is added to the terminal double bond. The production of the product was suppressed, and it was found that the target product, 7-octenyl halide, was obtained in high yield, and the present invention was completed.
すなわち、本発明は、
［１］７−オクテン−１−オールを、下記一般式（Ｉ）
[1] 7-octen-1-ol is represented by the following general formula (I)
（式中、Ｘは、塩素原子、臭素原子またはヨウ素原子を表す）
で示されるハロゲン化チオニルと反応させることを特徴とする７−オクテニルハライドの製造方法。
［２］Ｘが塩素原子であることを特徴とする、［１］の製造方法。
［３］塩基の存在下に行う、［１］または［２］の製造方法。
［４］反応温度が２０〜２００℃である、［１］〜［３］のいずれかの製造方法。
を提供する。
(In the formula, X represents a chlorine atom, a bromine atom or an iodine atom)
A process for producing a 7-octenyl halide, characterized by reacting with a thionyl halide represented by the formula:
[2] The production method of [1], wherein X is a chlorine atom.
[3] The production method of [1] or [2], which is carried out in the presence of a base.
[4] The production method of any one of [1] to [3], wherein the reaction temperature is 20 to 200 ° C.
I will provide a.
本発明によれば、医薬品、農薬、各種化学品、樹脂などの原料として有用である７−オクテニルハライドを、好収率かつ安価に、工業的に有利に製造することができる。 According to the present invention, 7-octenyl halide, which is useful as a raw material for pharmaceuticals, agricultural chemicals, various chemicals, resins and the like, can be industrially advantageously produced in good yield and low cost.
式（Ｉ）中のＸは、塩素原子、臭素原子またはヨウ素原子を表す。これらのうち、塩素原子が好ましい。式（Ｉ）で表されるハロゲン化チオニルの使用量は、７−オクテン−１−オールに対して通常０．８〜５モル倍の範囲が好ましく、経済性および後処理の容易さの観点から、１〜３モル倍の範囲がより好ましい。 X in the formula (I) represents a chlorine atom, a bromine atom or an iodine atom. Of these, a chlorine atom is preferred. The amount of thionyl halide represented by the formula (I) is preferably in the range of 0.8 to 5 mol times based on 7-octen-1-ol, from the viewpoint of economy and ease of post-treatment. The range of 1-3 mole times is more preferable.
本発明の製造方法は、塩基の存在下または非存在下で実施できるが、塩基の存在下で実施するのが好ましい。塩基の存在下に反応を実施する場合に使用できる塩基としては、例えばトリエチルアミン、トリブチルアミン、ジイソプロピルエチルアミン、１，４−ジアザビシクロ［２．２．２］オクタンなどの三級アミン；ピリジン、２−ピコリン、２，６−ルチジンなどの含窒素複素環式芳香族化合物；炭酸ナトリウム、炭酸カリウムなどのアルカリ金属炭酸塩；炭酸マグネシウム、炭酸カルシウムなどのアルカリ土類金属炭酸塩；炭酸水素ナトリウム、炭酸水素カリウムなどのアルカリ金属炭酸水素塩；水素化ナトリウム、水素化カリウムなどのアルカリ金属水素化物；水素化マグネシウム、水素化カルシウムなどのアルカリ土類金属水素化物；ナトリウムメトキシド、ナトリウムエトキシドなどのアルコラートなどが挙げられる。中でも、三級アミンや含窒素複素環式芳香族化合物が好ましく、含窒素複素環式芳香族化合物がより好ましく、ピリジンが特に好ましい。
本発明の製造方法を塩基の存在下で実施することにより、副生成物、特に７−オクテン−１−オールの末端二重結合へハロゲン化水素が付加した副生成物の生成をより効果的に抑制できる。末端二重結合へのハロゲン化水素付加の抑制効果は塩基が三級アミンや含窒素複素環式芳香族化合物である場合に特に顕著であり、特にピリジンを用いるのが効果的である。
塩基の使用量は、７−オクテン−１−オールに対して通常０．００１〜５モル倍の範囲が好ましく、経済性および後処理の容易さの観点から、０．０１〜３モル倍の範囲がより好ましい。
The production method of the present invention can be carried out in the presence or absence of a base, but is preferably carried out in the presence of a base. Examples of bases that can be used when the reaction is carried out in the presence of a base include tertiary amines such as triethylamine, tributylamine, diisopropylethylamine, 1,4-diazabicyclo [2.2.2] octane; pyridine, 2-picoline Nitrogen-containing heterocyclic aromatic compounds such as 2,6-lutidine; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkaline earth metal carbonates such as magnesium carbonate and calcium carbonate; sodium hydrogen carbonate and potassium hydrogen carbonate Alkali metal hydrogencarbonates such as sodium hydride and potassium hydride; alkaline earth metal hydrides such as magnesium hydride and calcium hydride; alcoholates such as sodium methoxide and sodium ethoxide Can be mentioned. Of these, tertiary amines and nitrogen-containing heterocyclic aromatic compounds are preferred, nitrogen-containing heterocyclic aromatic compounds are more preferred, and pyridine is particularly preferred.
By carrying out the production method of the present invention in the presence of a base, by-products, in particular, by-products in which hydrogen halide is added to the terminal double bond of 7-octen-1-ol are more effectively produced. Can be suppressed. The effect of suppressing the addition of hydrogen halide to the terminal double bond is particularly remarkable when the base is a tertiary amine or a nitrogen-containing heterocyclic aromatic compound, and it is particularly effective to use pyridine.
The amount of base used is preferably in the range of usually 0.001 to 5 mol times relative to 7-octen-1-ol, and in the range of 0.01 to 3 mol times from the viewpoint of economy and ease of post-treatment. Is more preferable.
本発明の製造方法は、溶媒の存在下または非存在下で実施できる。溶媒の存在下に反応を実施する場合に使用できる溶媒としては、反応に関与しないものであれば特に制限されず、例えばペンタン、ヘキサン、ヘプタン、オクタンなどの脂肪族炭化水素；ベンゼン、トルエン、キシレン、メシチレンなどの芳香族炭化水素；クロロベンゼン、フルオロベンゼンなどのハロゲン化芳香族炭化水素；ジエチルエーテル、ジイソプロピルエーテル、ジブチルエーテル、テトラヒドロフラン、ジオキサン、１，２−ジメトキシエタン、ジグライム、トリグライム、テトラグライムなどのエーテル；ジクロロメタン、クロロホルム、１，２−ジクロロエタンなどのハロゲン化脂肪族炭化水素などが挙げられる。これらの溶媒は、1種類を単独で使用しても良いし、２種類以上を混合して使用しても良い。溶媒の存在下に反応を実施する場合、溶媒の使用量に特に制限はないが、通常７−オクテン−１−オールに対して、通常、０．１〜１００質量倍の範囲が好ましく、０．５〜１０質量倍の範囲であるのがより好ましく、１〜５質量倍の範囲であるのがさらに好ましい。なお、７−オクテニルハライドの生産性の観点からは、溶媒を使用せずに本発明の製造方法を実施することが好ましい。 The production method of the present invention can be carried out in the presence or absence of a solvent. The solvent that can be used when the reaction is carried out in the presence of a solvent is not particularly limited as long as it does not participate in the reaction. For example, aliphatic hydrocarbons such as pentane, hexane, heptane, and octane; benzene, toluene, xylene , Aromatic hydrocarbons such as mesitylene; halogenated aromatic hydrocarbons such as chlorobenzene and fluorobenzene; diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, diglyme, triglyme, tetraglyme, etc. Ether; Halogenated aliphatic hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane and the like. These solvents may be used alone or in combination of two or more. When the reaction is carried out in the presence of a solvent, the amount of the solvent used is not particularly limited, but is usually preferably in the range of 0.1 to 100 times by mass with respect to 7-octen-1-ol. It is more preferably in the range of 5 to 10 times by mass, and further preferably in the range of 1 to 5 times by mass. In addition, it is preferable to implement the manufacturing method of this invention, without using a solvent from a viewpoint of productivity of 7-octenyl halide.
本発明の製造方法において、反応温度は、２０〜２００℃の範囲であるのが好ましく、５０〜１５０℃の範囲であるのがより好ましい。２０℃より低い場合、反応中間体であるクロロ亜硫酸エステルから目的物への反応速度が非常に遅く、２００℃より高い場合は、二重結合への塩素付加による不純物増加が著しい。反応時間は、７−オクテン−１−オール、塩基、ハロゲン化チオニル（Ｉ）及び溶媒の種類や使用量などにより異なるが、通常５分間〜４８時間の範囲である。 In the production method of the present invention, the reaction temperature is preferably in the range of 20 to 200 ° C, more preferably in the range of 50 to 150 ° C. When the temperature is lower than 20 ° C., the reaction rate from the reaction intermediate chlorosulfite ester to the target product is very slow. When the temperature is higher than 200 ° C., the increase in impurities due to the addition of chlorine to the double bond is remarkable. While the reaction time varies depending on the type and amount of 7-octen-1-ol, base, thionyl halide (I) and solvent used, it is generally in the range of 5 minutes to 48 hours.
本発明の製造方法においては、例えば、回分式反応器に７−オクテン−１−オール、塩基、及び溶媒を混合し、ハロゲン化チオニル（Ｉ）を滴下し所定温度で攪拌することにより行う。また、反応圧力に特に制限はなく、減圧下、常圧下、加圧下のいずれでも実施できるが、反応により発生する塩酸および亜硫酸ガス等の除外を行う上では、減圧下または常圧下であることが好ましい。 In the production method of the present invention, for example, 7-octen-1-ol, a base, and a solvent are mixed in a batch reactor, and thionyl (I) halide is added dropwise and stirred at a predetermined temperature. The reaction pressure is not particularly limited and can be performed under reduced pressure, normal pressure, or increased pressure. However, in order to exclude hydrochloric acid and sulfurous acid gas generated by the reaction, the reaction pressure may be under reduced pressure or normal pressure. preferable.
反応終了後に得られる７−オクテニルハライドは、有機化合物の単離・精製において通常用いられる方法により単離することができる。例えば、反応混合物を中和および水洗した後、減圧蒸留およびシリカゲルクロマトグラフィーなどにより精製することで、目的とする７−オクテニルハライドを得ることができる。 The 7-octenyl halide obtained after completion of the reaction can be isolated by a method usually used in the isolation and purification of organic compounds. For example, the target 7-octenyl halide can be obtained by neutralizing and washing the reaction mixture and then purifying it by distillation under reduced pressure or silica gel chromatography.
なお、本発明において使用される７−オクテン−１−オールは、例えば、ブタジエンの水和二量化により工業的に製造される２，７−オクタジエン−１−オールを銅系触媒またはクロム系触媒の存在下に異性化させることによって得られる７−オクテン−１−アールを、クロムの酸化物からなる触媒またはクロム、銅及び亜鉛からなる群から選ばれる少なくとも二種の金属の組み合わせからなる金属酸化物触媒の存在下７０〜１５０℃の温度で水素化する方法（特開昭５８−２２５０３３号参照）または７−オクテン−１−アールを、銅系触媒の存在下１５０℃より高く２００℃以下の温度でかつ転化率を９５％以下に水素化する方法（特開平１０−２２６６５９号参照）により容易に入手できる。 The 7-octen-1-ol used in the present invention is, for example, 2,7-octadien-1-ol produced industrially by hydration dimerization of butadiene as a copper catalyst or a chromium catalyst. 7-octen-1-al obtained by isomerization in the presence of a catalyst comprising a chromium oxide or a metal oxide comprising a combination of at least two metals selected from the group consisting of chromium, copper and zinc A method of hydrogenating at a temperature of 70 to 150 ° C. in the presence of a catalyst (see JP-A-58-225033) or 7-octen-1-al at a temperature higher than 150 ° C. and not higher than 200 ° C. in the presence of a copper-based catalyst And can be easily obtained by a method of hydrogenating the conversion to 95% or less (see JP-A-10-226659).
以下、実施例により本発明を具体的に説明するが、本発明はこれらの実施例に限定されない。 EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples.
＜実施例１＞
攪拌機、冷却管、温度計、滴下ロートを備えた５００ｍｌ反応器に７−オクテン−１−オール１４０．１ｇ（純度９２．１％；１．０１ｍｏｌ）、ピリジン３．２４ｇ（０．０４１ｍｏｌ）を投入し、内部の混合物の温度を攪拌下に３℃まで冷却した。ついで、塩化チオニル１３７．７ｇ（１．１０ｍｏｌ）を内温１０℃以下を保ちながら２時間かけて滴下した。滴下終了後、内温６０〜７０℃に加熱し、４時間加熱攪拌を行った。冷却後、水７０ｇを加え攪拌静置ののち、水相を分離し、さらに有機相を、５％炭酸水素ナトリウム水溶液１３３ｇ、次いで水７０ｇで洗浄した。分離した有機相をガスクロマトグラフィーで分析した結果、７−オクテニルクロリド１３８．５ｇ（０．９４４ｍｏｌ；収率９４％）が生成していることがわかった。該反応液を蒸留精製することにより、７−オクテニルクロリド１３１．６ｇ（０．８９７ｍｏｌ；累計収率８９％）を得た。
<Example 1>
Into a 500 ml reactor equipped with a stirrer, a condenser, a thermometer and a dropping funnel, 140.1 g of 7-octen-1-ol (purity 92.1%; 1.01 mol) and 3.24 g (0.041 mol) of pyridine were charged. The temperature of the internal mixture was cooled to 3 ° C. with stirring. Next, 137.7 g (1.10 mol) of thionyl chloride was added dropwise over 2 hours while maintaining the internal temperature at 10 ° C. or lower. After completion of dropping, the internal temperature was heated to 60 to 70 ° C., and the mixture was heated and stirred for 4 hours. After cooling, 70 g of water was added and the mixture was allowed to stand for stirring. The aqueous phase was separated, and the organic phase was washed with 133 g of 5% aqueous sodium hydrogen carbonate solution and then with 70 g of water. As a result of analyzing the separated organic phase by gas chromatography, it was found that 138.5 g (0.944 mol; yield 94%) of 7-octenyl chloride was produced. The reaction solution was purified by distillation to obtain 131.6 g (0.897 mol; cumulative yield 89%) of 7-octenyl chloride.
＜実施例２＞
攪拌機、冷却管、温度計、滴下ロートを備えた５０ｍｌ反応器に７−オクテン−１−オール１３．８ｇ（純度９２．９％；０．１０ｍｏｌ）、トリエチルアミン０．４０ｇ（４．０ｍｍｏｌ）を投入し、内部の混合物の温度を攪拌下に２℃まで冷却した。ついで、塩化チオニル１３．２ｇ（０．１１ｍｏｌ）を内温１０℃以下を保ちながら０．５時間かけて滴下した。滴下終了後、内温６０〜７０℃に加熱し、３時間加熱攪拌を行った。冷却後、トルエン６０ｇ、水２２ｇを加え攪拌静置ののち、水相を分離し、さらに有機相を、５％炭酸水素ナトリウム水溶液２２ｇ、次いで水２０ｇで洗浄した。分離した有機相を濃縮し、ガスクロマトグラフィーで分析した結果、７−オクテニルクロリド１３．０ｇ（０．０８８ｍｏｌ；収率８８％）が生成していることがわかった。該反応液を蒸留精製することにより、７−オクテニルクロリド１２．３ｇ（０．０８４ｍｏｌ；累計収率８４％）を得た。
<Example 2>
7-octen-1-ol 13.8 g (purity 92.9%; 0.10 mol) and triethylamine 0.40 g (4.0 mmol) were charged into a 50 ml reactor equipped with a stirrer, a condenser, a thermometer and a dropping funnel. The temperature of the internal mixture was cooled to 2 ° C. with stirring. Subsequently, thionyl chloride (13.2 g, 0.11 mol) was added dropwise over 0.5 hours while maintaining the internal temperature at 10 ° C. or lower. After completion of the dropping, the mixture was heated to an internal temperature of 60 to 70 ° C. and stirred for 3 hours. After cooling, 60 g of toluene and 22 g of water were added and the mixture was allowed to stand, and then the aqueous phase was separated. The organic phase was washed with 22 g of 5% aqueous sodium hydrogen carbonate solution and then with 20 g of water. The separated organic phase was concentrated and analyzed by gas chromatography. As a result, it was found that 13.0 g (0.088 mol; yield 88%) of 7-octenyl chloride was produced. The reaction solution was purified by distillation to obtain 12.3 g (0.084 mol; cumulative yield 84%) of 7-octenyl chloride.
＜実施例３＞
攪拌機、冷却管、温度計、滴下ロートを備えた５０ｍｌ反応器に７−オクテン−１−オール１３．９ｇ（純度９２．９％；０．１０ｍｏｌ）を投入し、２５℃で攪拌を行った。ついで、塩化チオニル１３．１ｇ（０．１１ｍｏｌ）を内温４０℃以下を保ちながら０．５時間かけて滴下した。滴下終了後、内温９０〜１００℃に加熱し、６時間加熱攪拌を行った。冷却後、トルエン６０ｇ、水２０ｇを加え攪拌静置ののち、水相を分離し、さらに有機相を５％炭酸水素ナトリウム水溶液２５ｇ、次いで水２０ｇで洗浄した。分離した有機相を濃縮し、ガスクロマトグラフィーで分析した結果、７−オクテニルクロリド１２．４ｇ（０．０８５ｍｏｌ；収率８５％）が生成していることがわかった。該反応液を蒸留精製することにより、７−オクテニルクロリド１１．７ｇ（０．０８０ｍｏｌ；累計収率８０％）を得た。
<Example 3>
To a 50 ml reactor equipped with a stirrer, a condenser, a thermometer, and a dropping funnel, 13.9 g (purity 92.9%; 0.10 mol) of 7-octen-1-ol was charged and stirred at 25 ° C. Next, 13.1 g (0.11 mol) of thionyl chloride was added dropwise over 0.5 hours while maintaining the internal temperature at 40 ° C. or lower. After completion of dropping, the internal temperature was heated to 90 to 100 ° C., and the mixture was heated and stirred for 6 hours. After cooling, 60 g of toluene and 20 g of water were added and the mixture was allowed to stand, and the aqueous phase was separated. The organic phase was washed with 25 g of a 5% aqueous sodium hydrogen carbonate solution and then with 20 g of water. The separated organic phase was concentrated and analyzed by gas chromatography. As a result, it was found that 12.4 g (0.085 mol; yield 85%) of 7-octenyl chloride was produced. The reaction solution was purified by distillation to obtain 11.7 g (0.080 mol; cumulative yield 80%) of 7-octenyl chloride.
＜実施例４＞
攪拌機、冷却管、温度計、滴下ロートを備えた５０ｍｌ反応器に７−オクテン−１−オール６．９９ｇ（純度９１．７％；０．０５ｍｏｌ）、ピリジン５．９３ｇ（０．０７５ｍｏｌ）、トルエン１５ｍｌを投入し、内部の混合物の温度を攪拌下に５℃まで冷却した。ついで、塩化チオニル６．６５ｇ（０．０５５ｍｏｌ）を内温１５℃以下を保ちながら０．５時間かけて滴下した。滴下終了後、内温６０℃に加熱し、１０時間加熱攪拌を行った。冷却後、水３０ｇを加え攪拌静置ののち、水相を分離し、さらに有機相を、５％炭酸水素ナトリウム水溶液３０ｇ、次いで水３０ｇで洗浄した。分離した有機相をガスクロマトグラフィーで分析した結果、７−オクテニルクロリド６．９７ｇ（０．０４７５ｍｏｌ；収率９５％）が生成していることがわかった。該反応液を蒸留精製することにより、７−オクテニルクロリド６．６１ｇ（０．０４５１ｍｏｌ；累計収率９０％）を得た。
<Example 4>
In a 50 ml reactor equipped with a stirrer, a condenser, a thermometer, and a dropping funnel, 7.99 g of 7-octen-1-ol (purity 91.7%; 0.05 mol), 5.93 g (0.075 mol) of pyridine, toluene 15 ml was charged and the temperature of the internal mixture was cooled to 5 ° C. with stirring. Subsequently, 6.65 g (0.055 mol) of thionyl chloride was added dropwise over 0.5 hours while maintaining the internal temperature at 15 ° C. or lower. After completion of dropping, the mixture was heated to an internal temperature of 60 ° C. and stirred for 10 hours. After cooling, 30 g of water was added and the mixture was allowed to stand for stirring. The aqueous phase was separated, and the organic phase was washed with 30 g of 5% aqueous sodium hydrogen carbonate solution and then with 30 g of water. As a result of analyzing the separated organic phase by gas chromatography, it was found that 6.97 g (0.0475 mol; yield 95%) of 7-octenyl chloride was produced. The reaction solution was purified by distillation to obtain 6.61 g (0.0451 mol; cumulative yield 90%) of 7-octenyl chloride.
＜実施例５＞
実施例１において、塩化チオニルのかわりに臭化チオニルを用いる以外は同様に実施し、蒸留精製後の収率８６％で７−オクテニルブロミドを得た。
<Example 5>
The same procedure as in Example 1 was carried out except that thionyl bromide was used in place of thionyl chloride to obtain 7-octenyl bromide in a yield of 86% after purification by distillation.
本発明の方法により得られる７−オクテニルハライドは、反応性に富む末端ビニル基および第一級ハロゲン基を有していることから工業的に極めて有用な化合物であり、医薬品、農薬、各種化学品、樹脂などの原料として有用である。 The 7-octenyl halide obtained by the method of the present invention is an industrially extremely useful compound because it has a highly reactive terminal vinyl group and primary halogen group. It is useful as a raw material for products and resins.
Claims (4)
で示されるハロゲン化チオニルと反応させることを特徴とする７−オクテニルハライドの製造方法。 7-octen-1-ol is represented by the following general formula (I)
A process for producing a 7-octenyl halide, characterized by reacting with a thionyl halide represented by the formula:
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