JP7753950B2 - Method for producing cyclic sulfite ester - Google Patents
Method for producing cyclic sulfite esterInfo
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Description
本発明は、環状亜硫酸エステルの製造方法に関する。 The present invention relates to a method for producing cyclic sulfite esters.
環状亜硫酸エステルは、非水電解液の添加物として用いられている。非水電解液は、優れた電池特性を高い安定性で示すリチウム二次電池に供するため、一般的に、有機塩素化合物含有量を低減することを求められる。よって環状亜硫酸エステルにおいても、有機塩素化合物を含んでいると非水電解液の添加物として避けられる。 Cyclic sulfites are used as additives in non-aqueous electrolytes. To provide non-aqueous electrolytes with excellent battery characteristics and high stability in lithium secondary batteries, they are generally required to contain a low amount of organic chlorine compounds. Therefore, even cyclic sulfites containing organic chlorine compounds are avoided as additives in non-aqueous electrolytes.
特許文献１には、ジオール化合物とハロゲン化チオニルとを反応させ、環状亜硫酸エステルとすることが記載されている。 Patent Document 1 describes reacting a diol compound with a thionyl halide to produce a cyclic sulfite ester.
しかしながら、これら従前知られた環状亜硫酸エステルの製造方法では、原料比率を制御しておらず、環状亜硫酸エステルの反応収率が満足いくものではなく、且つ、副生物として、環状亜硫酸エステルとは沸点が近似した有機塩素化合物が多く生成されるものであり、結果として、製造された環状亜硫酸エステルを非水電解液の添加物とするためには、該有機塩素化合物を除去するために生産性の低下した蒸留等による精製を必要としていた。すなわち、該有機塩素化合物を含む環状亜硫酸エステルを蒸留により精製するためには、有機塩素化合物を多量の環状亜硫酸エステルと共に除去しなければならず、歩留まり悪化の原因となっていた。 However, these previously known methods for producing cyclic sulfite esters do not control the raw material ratios, resulting in unsatisfactory reaction yields of cyclic sulfite esters. Furthermore, large amounts of organic chlorine compounds with boiling points similar to those of cyclic sulfite esters are produced as by-products. As a result, in order to use the produced cyclic sulfite esters as an additive for non-aqueous electrolytes, purification by distillation or other methods, which reduces productivity, is required to remove the organic chlorine compounds. In other words, in order to purify cyclic sulfite esters containing the organic chlorine compounds by distillation, the organic chlorine compounds must be removed along with a large amount of cyclic sulfite ester, resulting in a decrease in yield.
本発明は上記問題点を解決するためになされたものである。すなわち、反応収率に優れ、且つ、目的生成物と沸点が近似した有機塩素化合物の副生を抑制することが可能となる、環状亜硫酸エステル化合物の製造方法を提供することを目的とする。 The present invention was made to solve the above problems. Specifically, the objective is to provide a method for producing a cyclic sulfite ester compound that has an excellent reaction yield and can suppress the by-production of organic chlorine compounds that have a boiling point similar to that of the target product.
本発明者らは上記課題を解決すべく鋭意研究を重ねた結果、環状亜硫酸エステルの製造おいて、ジオール化合物とハロゲン化チオニルとを特定のモル比率で反応させることにより、反応収率に優れ、且つ、目的生成物と沸点が近似した特定の有機塩素化合物の副生を抑制することが可能となることを見いだし、本発明に至った。 As a result of extensive research to solve the above-mentioned problems, the inventors discovered that, in the production of cyclic sulfite esters, reacting a diol compound with a thionyl halide in a specific molar ratio can achieve excellent reaction yields and suppress the by-production of specific organic chlorine compounds with boiling points similar to those of the target product, leading to the present invention.
即ち、本発明は、以下である。
［１］一般式（１）で表される化合物とハロゲン化チオニルとを１：０．８以上２以下のモル比で反応させる、一般式（２）で表される化合物を製造する方法。
That is, the present invention is as follows.
[1] A method for producing a compound represented by general formula (2), which comprises reacting a compound represented by general formula (1) with a thionyl halide in a molar ratio of 1:0.8 or more and 1:2 or less.
（式中、Ｒ１及びＲ２はそれぞれ互いに独立し、炭素数１から４の炭化水素基又は水素である。） (In the formula, R1 and R2 are each independently a hydrocarbon group having 1 to 4 carbon atoms or hydrogen.)
（式中、Ｒ１及びＲ２は前記に同じ。）
［２］前記反応が、前記ハロゲン化チオニルが存在する反応系に、前記一般式（１）で表される化合物を連続的又は間欠的に導入してなり、前記一般式（１）で表される化合物の導入時の反応温度を０℃以下とする、［１］に記載の製造方法。
［３］前記反応が、前記一般式（１）で表される化合物が存在する反応系に、前記ハロゲン化チオニルを反応系に連続的又は間欠的に導入してなり、前記ハロゲン化チオニルの導入時の反応温度を０℃以下とする、［１］に記載の製造方法。
［４］前記反応が、前記ハロゲン化チオニルと前記一般式（１）で表される化合物とを、それぞれ同時に反応系に導入してなり、前記ハロゲン化チオニル及び前記一般式（１）で表される化合物の導入時の反応温度を０℃以下とする、［１］に記載の製造方法。
(wherein R1 and R2 are the same as above.)
[2] The production method according to [1], wherein the reaction comprises continuously or intermittently introducing the compound represented by the general formula (1) into a reaction system in which the thionyl halide is present, and the reaction temperature during the introduction of the compound represented by the general formula (1) is 0°C or lower.
[3] The production method according to [1], wherein the reaction comprises continuously or intermittently introducing the thionyl halide into a reaction system in which the compound represented by the general formula (1) is present, and the reaction temperature during the introduction of the thionyl halide is 0°C or lower.
[4] The production method according to [1], wherein the reaction comprises simultaneously introducing the thionyl halide and the compound represented by the general formula (1) into a reaction system, and the reaction temperature during the introduction of the thionyl halide and the compound represented by the general formula (1) is 0°C or lower.
本発明によれば、環状亜硫酸エステルの製造において、反応収率に優れ、且つ、有機ハロゲン化物の副生、特にハロゲンが塩素の場合は、目的生成物と沸点が近似した特定の有機塩素化合物の副生を抑制することが可能となった。 The present invention achieves excellent reaction yields in the production of cyclic sulfite esters, while also making it possible to suppress the by-production of organic halides, particularly when the halogen is chlorine, which can suppress the by-production of specific organic chlorine compounds with boiling points similar to those of the target product.
［ジオール化合物Ａ］
本発明は下記一般式（１）で表される化合物（以下「ジオール化合物Ａ」と称する場合がある。）とハロゲン化チオニルとを特定のモル比で反応させ、下記一般式（２）で表される化合物（以下「環状亜硫酸エステルＡ」と称する場合がある。）を製造する方法の発明である。
[Diol compound A]
The present invention relates to a method for producing a compound represented by the following general formula (2) (hereinafter may be referred to as "cyclic sulfite A") by reacting a compound represented by the following general formula (1) (hereinafter may be referred to as "diol compound A") with a thionyl halide in a specific molar ratio.
（式中、Ｒ１及びＲ２はそれぞれ互いに独立し、炭素数１から４の炭化水素基又は水素である。）
該炭素数１から４の炭化水素基としては、メチル基、エチル基、ビニル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔ－ブチル基等が挙げられ、メチル基、エチル基、ビニル基、ｎ－プロピル基及びｎ－ブチル基からなる群より選ばれた少なくともの一つの基が好ましく、エチル基及び／又はビニル基がより好ましく、ビニル基がさらに好ましい。又、Ｒ１及びＲ２の片方が水素であることが好ましい。Ｒ１及びＲ２を前記した好ましい基とすることにより、反応収率に優れ、且つ、有機ハロゲン化物の副生、特にハロゲンが塩素の場合は、目的生成物と沸点が近似した有機塩素化合物の副生を抑制することが可能となる。
(In the formula, R1 and R2 are each independently a hydrocarbon group having 1 to 4 carbon atoms or hydrogen.)
Examples of the hydrocarbon group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a vinyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group. At least one group selected from the group consisting of a methyl group, an ethyl group, a vinyl group, an n-propyl group, and an n-butyl group is preferred, an ethyl group and/or a vinyl group is more preferred, and a vinyl group is even more preferred. It is also preferred that one of R1 and R2 is hydrogen. By selecting the preferred groups as R1 and R2 , the reaction yield is excellent and it is possible to suppress the by-production of an organic halide, particularly, when the halogen is chlorine, the by-production of an organic chlorine compound having a boiling point similar to that of the target product.
（式中、Ｒ１及びＲ２は前記に同じ。） (wherein R1 and R2 are the same as above.)
［ハロゲン化チオニル］
ハロゲン化チオニルとしては、フッ化チオニル、塩化チオニル、臭化チオニルが挙げられるが、副生するハロゲン化水素の取り扱いの容易さから、塩化チオニルが好ましい。
[Thionyl halide]
Examples of the thionyl halide include thionyl fluoride, thionyl chloride, and thionyl bromide, with thionyl chloride being preferred because the hydrogen halide produced as a by-product is easy to handle.
ジオール化合物Ａとハロゲン化チオニルとの反応における特定のモル比とは、ジオール化合物Ａとハロゲン化チオニルとを１：０．８以上２以下のモル比とすることであり、モル比の下限は１：０．８５が好ましく、１：０．９がより好ましい。モル比の上限は１：１．５が好ましく、１：１．２がより好ましい。前記範囲とすることにより、反応収率に優れ、且つ、有機ハロゲン化物の副生、特にハロゲンが塩素の場合は、目的生成物と沸点が近似した有機塩素化合物の副生を抑制することが可能となる。 The specific molar ratio in the reaction between diol compound A and thionyl halide is a molar ratio of diol compound A to thionyl halide of 1:0.8 or greater and 1:2 or less, with the lower molar ratio preferably being 1:0.85, and more preferably 1:0.9. The upper molar ratio is preferably 1:1.5, and more preferably 1:1.2. By maintaining the molar ratio within this range, the reaction yield is excellent and it is possible to suppress the by-production of organic halides, particularly when the halogen is chlorine, and the by-production of organic chlorine compounds with boiling points similar to that of the target product.
環状亜硫酸エステルＡは、前記ハロゲン化チオニルが存在する反応系に、前記ジオール化合物Ａを導入して反応させて製造しても、前記ジオール化合物Ａが存在する反応系に、前記ハロゲン化チオニルを導入して反応させて製造しても構わない。さらに、前記のハロゲン化チオニルとジオール化合物Ａとを、それぞれを同時に反応系に導入して製造してもよい。 Cyclic sulfite A may be produced by introducing the diol compound A into a reaction system in which the thionyl halide is present and reacting them, or by introducing the thionyl halide into a reaction system in which the diol compound A is present and reacting them. Furthermore, the thionyl halide and diol compound A may be simultaneously introduced into the reaction system to produce the cyclic sulfite A.
前記ハロゲン化チオニルが存在する反応系に、前記ジオール化合物Ａを導入して反応させる場合には、前記ジオール化合物Ａ導入時の反応温度は０℃以下が好ましく、－１０℃以下がより好ましく、－２０℃以下がさらに好ましい。該反応温度の下限は特に制限はないが、－５０℃が好ましい。前記範囲とすることにより、反応収率に優れ、且つ、目的生成物と沸点が近似した有機塩素化合物の副生を抑制することが可能となる。尚、前記ジオール化合物Ａの反応系への導入の形態は連続的でも間欠的でも構わない。 When the diol compound A is introduced into a reaction system containing the thionyl halide and reacted, the reaction temperature during the introduction of the diol compound A is preferably 0°C or lower, more preferably -10°C or lower, and even more preferably -20°C or lower. There is no particular lower limit to the reaction temperature, but -50°C is preferred. By keeping the reaction temperature within this range, the reaction yield is excellent and it is possible to suppress the by-production of organic chlorine compounds with boiling points similar to those of the target product. The diol compound A may be introduced into the reaction system continuously or intermittently.
前記ジオール化合物Ａが存在する反応系に、前記ハロゲン化チオニルを導入して反応させる場合も同様であり、前記ハロゲン化チオニル導入時の反応温度は０℃以下が好ましく、－１０℃以下がより好ましく、－２０℃以下がさらに好ましい。該反応温度の下限は特に制限はないが、－５０℃が好ましい。前記範囲とすることにより、反応収率に優れ、且つ、目的生成物と沸点が近似した有機塩素化合物の副生を抑制することが可能となる。尚、前記ハロゲン化チオニルの反応系への導入の形態は連続的でも間欠的でも構わない。 The same applies when the thionyl halide is introduced into a reaction system containing the diol compound A and reacted. The reaction temperature when the thionyl halide is introduced is preferably 0°C or lower, more preferably -10°C or lower, and even more preferably -20°C or lower. There is no particular lower limit to the reaction temperature, but -50°C is preferred. By keeping the reaction temperature within this range, it is possible to achieve an excellent reaction yield and suppress the by-production of organic chlorine compounds with boiling points similar to those of the target product. The thionyl halide may be introduced into the reaction system continuously or intermittently.
前記ハロゲン化チオニル、前記ジオール化合物Ａそれぞれを同時に反応系に導入する場合も、ハロゲン化チオニルが導入された時点で、ジオール化合物Ａは反応系に存在し、ジオール化合物Ａが導入された時点で、ハロゲン化チオニルは反応系に存在する。よって、前記ハロゲン化チオニル、前記ジオール化合物Ａそれぞれの反応系への導入時の反応温度は、前記した温度範囲とすることが好ましい。 Even when the thionyl halide and diol compound A are introduced into the reaction system simultaneously, diol compound A is present in the reaction system when the thionyl halide is introduced, and the thionyl halide is present in the reaction system when diol compound A is introduced. Therefore, the reaction temperatures when the thionyl halide and diol compound A are introduced into the reaction system are preferably within the above-mentioned temperature ranges.
反応系にはさらに、反応で副生するハロゲン化水素を吸収する化合物（以下「吸収化合物」と称する場合がある。）を導入してもよい。導入量としては、特に制限はないが、目的生成物の精製の観点から、ジオール化合物Ａ量に対して、０．０１モル％以下が好ましい。吸収化合物の種類としては、ジメチルフォルムアミド（以下「ＤＭＦ」と称する場合がある。）等のＮ，Ｎ－二置換アミド、トリエチルアミン等の３級アミン、ピリジン等の含窒素複素環化合物等が挙げられ、ＤＭＦ、ピリジンが好ましい。 A compound that absorbs hydrogen halide produced as a by-product in the reaction (hereinafter sometimes referred to as "absorbing compound") may also be introduced into the reaction system. There are no particular restrictions on the amount introduced, but from the perspective of purifying the target product, an amount of 0.01 mol % or less relative to the amount of diol compound A is preferred. Examples of absorbing compounds include N,N-disubstituted amides such as dimethylformamide (hereinafter sometimes referred to as "DMF"), tertiary amines such as triethylamine, and nitrogen-containing heterocyclic compounds such as pyridine, with DMF and pyridine being preferred.
以下、実施例により本発明を更に詳細に説明するが、本発明の要旨を越えない限り以下の実施例に限定されるものではない。
なお、以下の実施例及び比較例において、各反応原料、反応により得られた生成物の分析は、内部標準法によるガスクロマトグラフィーにより、内部標準物質としてトリデカンを使用し、実施した。生成物中、目的物質であるビニルエチレンサルファイトと沸点が近似した副生物である有機塩素化合物は４－アセトキシ－３－クロロ－１－ブテン（以下「ＡＣＬ」と称する場合がある。）であった。
The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded.
In the following examples and comparative examples, the analysis of each reaction raw material and the product obtained by the reaction was carried out by gas chromatography using an internal standard method, with tridecane as the internal standard. Among the products, the organochlorine compound, which was a by-product with a boiling point similar to that of the target substance, vinylethylene sulfite, was 4-acetoxy-3-chloro-1-butene (hereinafter sometimes referred to as "ACL").
（実施例１）
１００ｍｌのガラス製容器に塩化チオニル１５．１ｇ（０．１２８ｍｏｌ）を導入し、－４０℃に冷却し、反応液とした。該反応液の温度を－４０℃に保持したまま、１，２－ジヒドロキシ－３－ブテン１０．１ｇ（０．１１５ｍｏｌ）を少量ずつ、該反応液に導入し、反応を行った。次いで、－４０℃で４時間攪拌して反応を続行した。その後、室温で反応液に窒素を連続的に導入しながら３０分撹拌した後、反応液を氷冷し、反応液に７．８２質量％の炭酸水素ナトリウム水溶液を２４．０ｇ加えて３０分撹拌し、反応を停止した。その後、水相と有機相の２相に分離した。該有機相をガスクロマトグラフィーにより分析したところ、ビニルエチレンサルファイト重量は１３．７ｇ（０．１０３ｍｏｌ、反応収率９０．０％）であり、ＡＣＬ重量は０．００３６８ｇであった。製造されたビニルエチレンサルファイト１００重量％に対してＡＣＬが０．０２６９重量％副生していた。
Example 1
15.1 g (0.128 mol) of thionyl chloride was introduced into a 100 ml glass vessel and cooled to -40°C to form a reaction solution. While maintaining the temperature of the reaction solution at -40°C, 10.1 g (0.115 mol) of 1,2-dihydroxy-3-butene was introduced into the reaction solution in small portions to carry out the reaction. The reaction was then continued with stirring at -40°C for 4 hours. After that, the reaction solution was stirred for 30 minutes at room temperature while continuously introducing nitrogen into the reaction solution. The reaction solution was then ice-cooled, and 24.0 g of a 7.82% by mass aqueous solution of sodium bicarbonate was added to the reaction solution and stirred for 30 minutes to terminate the reaction. The reaction solution was then separated into two phases: an aqueous phase and an organic phase. Analysis of the organic phase by gas chromatography revealed that the weight of vinyl ethylene sulfite was 13.7 g (0.103 mol, reaction yield 90.0%) and the weight of ACL was 0.00368 g. Based on 100% by weight of the produced vinyl ethylene sulfite, 0.0269% by weight of ACL was produced as a by-product.
（実施例２）
５００ｍｌのガラス製容器に塩化チオニル７４．１ｇ（０．６２８ｍｏｌ）を導入し、－２０℃に冷却し、反応液とした。該反応液を－２０℃に保持したまま、１，２－ジヒドロキシ－３－ブテン５０．２ｇ（０．５７０ｍｏｌ）を少量ずつ、該反応液に導入し、反応を行った。次いで、－２０℃で３時間攪拌して反応を続行した。その後、室温で反応液に窒素を連続的に導入しながら３０分撹拌した後、反応液を氷冷し、反応液に７．８２質量％の炭酸水素ナトリウム水溶液を１１５ｇ加えて３０分撹拌し、反応を停止した。その後、水相と有機相の２相に分離した。該有機相をガスクロマトグラフィーにより分析したところ、ビニルエチレンサルファイト重量は６８．０ｇ（０．５１１ｍｏｌ、反応収率８９．６％）であり、ＡＣＬ重量は０．０３３６ｇであった。製造されたビニルエチレンサルファイト１００重量％に対してＡＣＬが０．０４９４重量％副生していた。
Example 2
74.1 g (0.628 mol) of thionyl chloride was introduced into a 500 ml glass vessel and cooled to -20°C to form a reaction solution. While maintaining the reaction solution at -20°C, 50.2 g (0.570 mol) of 1,2-dihydroxy-3-butene was introduced into the reaction solution in small portions to carry out the reaction. The reaction was then continued with stirring at -20°C for 3 hours. After stirring for 30 minutes while continuously introducing nitrogen into the reaction solution at room temperature, the reaction solution was ice-cooled, and 115 g of a 7.82% by mass aqueous solution of sodium bicarbonate was added to the reaction solution and stirred for 30 minutes to terminate the reaction. The reaction was then separated into two phases: an aqueous phase and an organic phase. Analysis of the organic phase by gas chromatography revealed that the weight of vinyl ethylene sulfite was 68.0 g (0.511 mol, reaction yield 89.6%) and the weight of ACL was 0.0336 g. Based on 100% by weight of the produced vinyl ethylene sulfite, 0.0494% by weight of ACL was produced as a by-product.
（参考例１）
１００ｍｌのガラス製容器に塩化チオニル６．４２ｇ（０．０５４４ｍｏｌ）を導入し、－５℃に冷却し、反応液とした。該反応液を－５℃に保持したまま、１，２－ジヒドロキシ－３－ブテン４．２３ｇ（０．０４８１ｍｏｌ）を少量ずつ、該反応液に導入し、反応を行った。次いで、－５℃で２時間攪拌して反応を続行した。その後、室温で反応液に窒素を連続的に導入しながら３０分撹拌した後、反応液を氷冷し、反応液に７．８２質量％の炭酸水素ナトリウム水溶液を７．４０ｇ加えて３０分撹拌し、反応を停止した。その後、水相と有機相の２相に分離した。該有機相をガスクロマトグラフィーにより分析したところ、ビニルエチレンサルファイト重量は５．４２ｇ（０．０４０７ｍｏｌ、反応収率８４．７％）であり、ＡＣＬ重量は０．００２８０ｇであった。製造されたビニルエチレンサルファイト１００重量％に対してＡＣＬが０．０５１６重量％副生していた。
( Reference example 1 )
6.42 g (0.0544 mol) of thionyl chloride was introduced into a 100 ml glass vessel and cooled to -5°C to form a reaction solution. While maintaining the reaction solution at -5°C, 4.23 g (0.0481 mol) of 1,2-dihydroxy-3-butene was introduced into the reaction solution in small portions to carry out the reaction. The reaction was then continued with stirring at -5°C for 2 hours. After that, the reaction solution was stirred for 30 minutes at room temperature while continuously introducing nitrogen into the reaction solution. The reaction solution was then ice-cooled, and 7.40 g of a 7.82% by mass aqueous solution of sodium bicarbonate was added to the reaction solution and stirred for 30 minutes to terminate the reaction. The reaction was then separated into two phases: an aqueous phase and an organic phase. Analysis of the organic phase by gas chromatography revealed that the weight of vinyl ethylene sulfite was 5.42 g (0.0407 mol, reaction yield 84.7%) and the weight of ACL was 0.00280 g. The amount of ACL produced as a by-product was 0.0516% by weight based on 100% by weight of the produced vinyl ethylene sulfite.
（実施例３）
１００ｍｌのガラス製容器に１，２－ジヒドロキシ－３－ブテン９．９９ｇ（０．１１３ｍｏｌ）を導入し、－２０℃に冷却し、反応液とした。該反応液を－２０℃に保持したまま、塩化チオニル１４．９ｇ（０．１２６ｍｏｌ）を少量ずつ、該反応液に導入し、反応を行った。次いで、－２０℃で３時間攪拌して反応を続行した。その後、室温で反応液に窒素を連続的に導入しながら３０分撹拌した後、反応液を氷冷し、反応液に７．８２質量％の炭酸水素ナトリウム水溶液を２８．２ｇ加えて３０分撹拌し、反応を停止した。その後、水相と有機相の２相に分離した。該有機相をガスクロマトグラフィーにより分析したところ、ビニルエチレンサルファイト重量は１３．３ｇ（０．１００ｍｏｌ、反応収率８８．２％）であり、ＡＣＬ重量は０．００７５４ｇであった。製造されたビニルエチレンサルファイト１００重量％に対してＡＣＬが０．０５６７重量％副生していた。
Example 3
9.99 g (0.113 mol) of 1,2-dihydroxy-3-butene was introduced into a 100 ml glass vessel and cooled to -20°C to form a reaction solution. While maintaining the reaction solution at -20°C, 14.9 g (0.126 mol) of thionyl chloride was introduced into the reaction solution in small portions to carry out the reaction. The reaction was then continued with stirring at -20°C for 3 hours. After that, the reaction solution was stirred for 30 minutes at room temperature while continuously introducing nitrogen into the reaction solution. The reaction solution was then ice-cooled, and 28.2 g of a 7.82% by mass aqueous solution of sodium bicarbonate was added to the reaction solution and stirred for 30 minutes to terminate the reaction. The reaction solution was then separated into two phases: an aqueous phase and an organic phase. Analysis of the organic phase by gas chromatography revealed that the weight of vinyl ethylene sulfite was 13.3 g (0.100 mol, reaction yield 88.2%) and the weight of ACL was 0.00754 g. Based on 100% by weight of the produced vinyl ethylene sulfite, 0.0567% by weight of ACL was produced as a by-product.
（比較例１）
３００ｍｌのガラス製容器に塩化チオニル１５．０ｇ（０．１２７ｍｏｌ）を導入し、－２０℃に冷却し、反応液とした。該反応液を－２０℃に保持したまま、１，２－ジヒドロキシ－３－ブテン３．６６ｇ（０．０４１５ｍｏｌ）を少量ずつ、該反応液に導入し反応を行った。次いで、－２０℃で３時間攪拌して反応を続行した。その後、室温で反応液に窒素を連続的に導入しながら３０分撹拌した後、反応液を氷冷し、反応液に７．８２質量％の炭酸水素ナトリウム水溶液を８０ｇ加えて３０分撹拌し、反応を停止した。その後、水相と有機相の２相に分離した。該有機相をガスクロマトグラフィーにより分析したところ、ビニルエチレンサルファイト重量は１．３８ｇ（０．０２５８ｍｏｌ、反応収率６２．２％）であり、ＡＣＬ重量は０．００１４５ｇであった。製造されたビニルエチレンサルファイト１００重量％に対してＡＣＬが０．１０５１重量％副生していた。
(Comparative Example 1)
15.0 g (0.127 mol) of thionyl chloride was introduced into a 300 ml glass vessel and cooled to -20°C to form a reaction solution. While maintaining the reaction solution at -20°C, 3.66 g (0.0415 mol) of 1,2-dihydroxy-3-butene was introduced into the reaction solution in small portions to carry out the reaction. The reaction was then continued with stirring at -20°C for 3 hours. After that, the reaction solution was stirred for 30 minutes at room temperature while continuously introducing nitrogen into the reaction solution. The reaction solution was then ice-cooled, and 80 g of a 7.82% by mass aqueous solution of sodium bicarbonate was added to the reaction solution and stirred for 30 minutes to terminate the reaction. The reaction was then separated into two phases: an aqueous phase and an organic phase. Analysis of the organic phase by gas chromatography revealed that the weight of vinyl ethylene sulfite was 1.38 g (0.0258 mol, reaction yield 62.2%) and the weight of ACL was 0.00145 g. The amount of ACL produced as a by-product was 0.1051% by weight based on 100% by weight of the vinyl ethylene sulfite produced.
（比較例２）
３００ｍｌのガラス製容器に塩化チオニル１５．０ｇ（０．１２７ｍｏｌ）を導入し、－２０℃に冷却し、反応液とした。該反応液に、ＤＭＦ０．１５０ｇ（０．００２０５ｍｏｌ）と１，２－ジヒドロキシ－３－ブテン３．８６ｇ（０．０４３８ｍｏｌ）の混合溶液を少量ずつ、該反応液に導入し、反応を行った。次いで、－２０℃で３時間攪拌して反応を続行した。その後、室温で反応液に窒素を連続的に導入しながら３０分撹拌し、反応を停止した。その後、反応液を氷冷し、７．８２質量％の炭酸水素ナトリウム水溶液を５６．６ｇ加えて３０分撹拌し、反応を停止した。その後、水相と有機相の２相に分離した。該有機相をガスクロマトグラフィーにより分析したところ、ビニルエチレンサルファイト重量は０．７４５ｇ（０．００５５９ｍｏｌ、反応収率１２．８％）であり、ＡＣＬ重量は０．００３１６ｇであった。製造されたビニルエチレンサルファイト１００重量％に対してＡＣＬが０．４２４１重量％副生していた。
(Comparative Example 2)
15.0 g (0.127 mol) of thionyl chloride was introduced into a 300 ml glass vessel and cooled to -20°C to form a reaction solution. A mixed solution of 0.150 g (0.00205 mol) of DMF and 3.86 g (0.0438 mol) of 1,2-dihydroxy-3-butene was introduced little by little into the reaction solution, and the reaction was carried out. The reaction was then continued with stirring at -20°C for 3 hours. Thereafter, the reaction was terminated by stirring for 30 minutes while continuously introducing nitrogen into the reaction solution at room temperature. Thereafter, the reaction solution was ice-cooled, and 56.6 g of a 7.82 mass% aqueous sodium bicarbonate solution was added and stirred for 30 minutes to terminate the reaction. The reaction was then separated into two phases: an aqueous phase and an organic phase. The organic phase was analyzed by gas chromatography, and the weight of vinyl ethylene sulfite was 0.745 g (0.00559 mol, reaction yield 12.8%), and the weight of ACL was 0.00316 g. The amount of ACL produced as a by-product was 0.4241 wt% based on 100 wt% of vinyl ethylene sulfite produced.
以上より、本発明の製造方法により、環状亜硫酸エステルＡを製造すると、反応収率が向上し、該環状亜硫酸エステルＡと沸点が近似した有機塩素化合物の副生を抑制できるとこが明らかである。 From the above, it is clear that producing cyclic sulfite ester A using the production method of the present invention improves the reaction yield and suppresses the by-production of organic chlorine compounds with boiling points similar to those of cyclic sulfite ester A.
Claims (1)
前記ハロゲン化チオニルは、フッ化チオニル、塩化チオニル及び臭化チオニルからなる群より選ばれた少なくとも一つの化合物であり、
前記反応が、下記の３つから選ばれるいずれかの反応である、一般式（２）で表される化合物を製造する方法。
・前記ハロゲン化チオニルが存在する反応系に、前記一般式（１）で表される化合物を連続的又は間欠的に導入してなる反応であり、前記一般式（１）で表される化合物の導入時の反応温度を－２０℃以下とする。
・前記一般式（１）で表される化合物が存在する反応系に、前記ハロゲン化チオニルを反応系に連続的又は間欠的に導入してなる反応であり、前記ハロゲン化チオニルの導入時の反応温度を－２０℃以下とする。
・前記ハロゲン化チオニルと前記一般式（１）で表される化合物とを、それぞれ同時に反応系に導入してなる反応であり、前記ハロゲン化チオニル及び前記一般式（１）で表される化合物の導入時の反応温度を－２０℃以下とする。
the thionyl halide is at least one compound selected from the group consisting of thionyl fluoride, thionyl chloride, and thionyl bromide;
A method for producing a compound represented by general formula (2), wherein the reaction is any one of the following three reactions :
A reaction in which the compound represented by the general formula (1) is continuously or intermittently introduced into a reaction system in which the thionyl halide is present, and the reaction temperature during the introduction of the compound represented by the general formula (1) is set to −20° C. or lower.
A reaction in which the thionyl halide is continuously or intermittently introduced into a reaction system in which the compound represented by the general formula (1) is present, and the reaction temperature during the introduction of the thionyl halide is set to −20° C. or lower.
A reaction in which the thionyl halide and the compound represented by the general formula (1) are simultaneously introduced into a reaction system, and the reaction temperature during the introduction of the thionyl halide and the compound represented by the general formula (1) is set to −20° C. or lower.
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