JP2004300110A - Method for producing thioester compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for the industrial production of a thioester compound useful as an intermediate for a polythiol having high sulfur content and indispensable for achieving high refractive index in high production efficiency at a low cost. <P>SOLUTION: The thioester compound expressed by general formula (III) (m and n are each 0 or an integer of ≥1 and m+n is an integer of ≥1; and R1 is an aliphatic group, an alicyclic group, a heterocyclic group, an aromatic organic residue or an aliphatic organic residue having sulfur atom in the chain) is produced by reacting a thiocarboxylic acid compound expressed by general formula (I) (R1 is an aliphatic group, an alicyclic group, a heterocyclic group, an aromatic organic residue or an aliphatic organic residue containing sulfur atom) with a halogen compound expressed by general formula (II) (X1 and X2 are each independently a halogen atom; m and n are each 0 or an integer of ≥1 and m+n is an integer of ≥1; and R2 is a univalent or polyvalent organic residue) in the presence of an organic base. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

（式中、 Ｒ１は脂肪族、脂環族、複素環、芳香族有機残基または硫黄原子を有する脂肪族有機残基を示す。）
【００１２】
【化５】

（式中、Ｘ１、Ｘ２はそれぞれ独立にハロゲン原子を表し、ｍ、ｎは０または１以上の整数を示し且つｍ＋ｎは１以上の整数である。 Ｒ２は１価以上の有機残基を示す。）
【００１３】
【化６】

（式中、ｍ、ｎは０または１以上の整数を示し且つｍ＋ｎは１以上の整数である。Ｒ１は脂肪族、脂環族、複素環、芳香族有機残基、もしくは鎖中に硫黄原子を有する脂肪族有機残基を示す。）
【００１４】
〔２〕有機塩基としてトリエチルアミンを使用する〔１〕記載の製造方法。
【００１５】
〔３〕一般式（Ｉ）で表される化合物がチオ酢酸であり、一般式（ＩＩ）で表される化合物が塩化メチレンである〔２〕記載の製造方法。
【００１６】
〔４〕請求項３において、塩化メチレンとトリエチルアミンを装入した後にチオ酢酸を装入する〔３〕記載の製造方法。
【００１７】
〔５〕トリエチルアミンの使用量はチオカルボン酸化合物に対して１．０当量以上２．０当量以下とする〔４〕記載の製造方法
【００１８】
【発明の実施の形態】
以下、本発明を詳細に説明する。
【００１９】
本発明では下記一般式（Ｉ）で表されるチオカルボン酸化合物を塩基存在下で下記一般式（ＩＩ）で表されるハロゲン化合物と反応させる事により一般式（ＩＩＩ）で表されるチオエステル化合物を得る事を特徴としている。
【００２０】
【化７】

（式中、 Ｒ１は脂肪族、脂環族、複素環、芳香族有機残基または硫黄原子を有する脂肪族有機残基を示す。）
【００２１】
【化８】

（式中、Ｘ１、Ｘ２はそれぞれ独立にハロゲン原子を表し、ｍ、ｎは０または１以上の整数を示し且つｍ＋ｎは１以上の整数である。 Ｒ２は１価以上の有機残基をす。）
【００２２】
【化９】

（式中、ｍ、ｎは０または１以上の整数を示し且つｍ＋ｎは１以上の整数である。Ｒ１は脂肪族、脂環族、複素環、芳香族有機残基、もしくは鎖中に硫黄原子を有する脂肪族有機残基を示す。）
【００２３】
一般式（Ｉ）中Ｒ１にあたる有機残基としては、たとえばメタン、エタン、プロパン、ブタン、ペンタン、ヘキサン、エチレン、プロピレン、１−ブテン、２−ブテン、ブタジエン、等の直鎖状脂肪族から誘導される有機残基、シクロペンタン、シクロペンテン、シクロペンタジエン、シクロヘキサン、１，２−ジメチルシクロヘキサン、１，４−ジメチルシクロヘキサン、シクロヘキセン、１，３−シクロヘキサジエン、１，４−シクロヘキサジエン、ノルボルナン、２，３−ジメチルノルボルナン、２，５−ジメチルノルボルナン、２，６−ジメチルノルボルナン等の環状脂肪族から誘導される１価の有機残基、
【００２４】
シクロペンタン、シクロペンテン、シクロペンタジエン、シクロヘキサン、１，２−ジメチルシクロヘキサン、１，４−ジメチルシクロヘキサン、シクロヘキセン、１，３−シクロヘキサジエン、１，４−シクロヘキサジエン、ノルボルナン、２，３−ジメチルノルボルナン、２，５−ジメチルノルボルナン、２，６−ジメチルノルボルナン等の環状脂肪族から誘導される１価の有機残基、
【００２５】
チオラン、２，５−ジメチルチオラン、３，４−ジメチルチオラン、２，３−ジメチルチオラン、２，５−ジエチルチオラン、３，４−ジエチルチオラン、２，３−ジエチルチオラン、１，３−ジチオレン、２，４−ジメチル１，３−ジチオレン、４，５−ジメチル１，３−ジチオレン、２，４−ジエチル１，３−ジチオレン、４，５−ジエチル１，３−ジチオレン、１，３−ジチオラン、２，４−ジメチル１，３−ジチオラン、４，５−ジメチル１，３−ジチオラン、２，４−ジエチル１，３−ジチオラン、４，５−ジエチル１，３−ジチオラン、チオフェン、２，５−ジメチルチオフェン、１，４−ジチアン、２，６−ジメチル１，４−ジチアン、２，３−ジメチル１，４−ジチアン、２，５−ジエチル１，４−ジチアン、２，６−ジエチル１，４−ジチアン、２，３−ジエチル１，４−ジチアン、１，３，５−トリチアン、２，４−ジメチル−１，３，５−トリチアン、２，４−ジエチル−１，３，５−トリチアン、チアゾール、１，３，４−チアジアゾール、１，３−ジチエタン、２，４−ジメチル−１，３−ジチエタン、２，４−ジエチル−１，３−ジチエタン、等の複素環から誘導される１価の有機残基、
【００２６】
ベンゼン、ｏ−キシレン、ｍ−キシレン、ｐ−キシレン、ナフタレン、ビフェニール、アントラセン、ペリレン、スチレン、エチルベンゼン、等の芳香族から誘導される１価の有機残基、
【００２７】
ビス（メルカプトメチル）スルフィド、ビス（メルカプトメチル）ジスルフィド、ビス（メルカプトエチル）スルフィド、ビス（メルカプトエチル）ジスルフィド、ビス（メルカプトプロピル）スルフィド、ビス（メルカプトメチルチオ）メタン、ビス（２−メルカプトエチルチオ）メタン、１，２−ビス（３−メルカプトプロピル）エタン、１，３−ビス（メルカプトエチルチオ）プロパン、１，３−ビス（３−メルカプトプロピルチオ）プロパン、１，２，３−トリス（メルカプトメチルチオ）プロパン、１，２，３−トリス（２−メルカプトエチルチオ）プロパン、１，２，３−トリス（３−メルカプトプロピルチオ）プロパン、１、２−ビス［（２−メルカプトエチル）チオ］−３−メルカプトプロパン、等の硫黄を有する化合物から誘導される一般に入手可能な１価の有機残基等があるが、これらに限定されるものではない。
【００２８】
本発明に使用される一般式（ＩＩ）のＸ１、Ｘ２はフッ素、塩素、臭素、ヨウ素などのハロゲン原子である。Ｒ２としては一価以上の有機残基であり、たとえばメタン、エタン、プロパン、ブタン、ペンタン、ヘキサン、エチレン、プロピレン、１−ブテン、２−ブテン、ブタジエン、等の直鎖状脂肪族から誘導される有機残基、シクロペンタン、シクロペンテン、シクロペンタジエン、シクロヘキサン、１，２−ジメチルシクロヘキサン、１，４−ジメチルシクロヘキサン、シクロヘキセン、１，３−シクロヘキサジエン、１，４−シクロヘキサジエン、ノルボルナン、２，３−ジメチルノルボルナン、２，５−ジメチルノルボルナン、２，６−ジメチルノルボルナン等の環状脂肪族から誘導されるｍ＋ｎ価の有機残基、
【００２９】
チオラン、２，５−ジメチルチオラン、３，４−ジメチルチオラン、２，３−ジメチルチオラン、２，５−ジエチルチオラン、３，４−ジエチルチオラン、２，３−ジエチルチオラン、１，３−ジチオレン、２，４−ジメチル１，３−ジチオレン、４，５−ジメチル１，３−ジチオレン、２，４−ジエチル１，３−ジチオレン、４，５−ジエチル１，３−ジチオレン、１，３−ジチオラン、２，４−ジメチル１，３−ジチオラン、４，５−ジメチル１，３−ジチオラン、２，４−ジエチル１，３−ジチオラン、４，５−ジエチル１，３−ジチオラン、チオフェン、２，５−ジメチルチオフェン、１，４−ジチアン、２，６−ジメチル１，４−ジチアン、２，３−ジメチル１，４−ジチアン、２，５−ジエチル１，４−ジチアン、２，６−ジエチル１，４−ジチアン、２，３−ジエチル１，４−ジチアン、１，３，５−トリチアン、２，４−ジメチル−１，３，５−トリチアン、２，４−ジエチル−１，３，５−トリチアン、チアゾール、１，３，４−チアジアゾール、１，３−ジチエタン、２，４−ジメチル−１，３−ジチエタン、２，４−ジエチル−１，３−ジチエタン、等の複素環から誘導されるｍ＋ｎ価の有機残基、
【００３０】
ベンゼン、ｏ−キシレン、ｍ−キシレン、ｐ−キシレン、ナフタレン、ビフェニール、アントラセン、ペリレン、スチレン、エチルベンゼン、等の芳香族から誘導されるｍ＋ｎ価の有機残基、
【００３１】
ビス（メルカプトメチル）スルフィド、ビス（メルカプトメチル）ジスルフィド、ビス（メルカプトエチル）スルフィド、ビス（メルカプトエチル）ジスルフィド、ビス（メルカプトプロピル）スルフィド、ビス（メルカプトメチルチオ）メタン、ビス（２−メルカプトエチルチオ）メタン、１，２−ビス（３−メルカプトプロピル）エタン、１，３−ビス（メルカプトエチルチオ）プロパン、１，３−ビス（３−メルカプトプロピルチオ）プロパン、１，２，３−トリス（メルカプトメチルチオ）プロパン、１，２，３−トリス（２−メルカプトエチルチオ）プロパン、１，２，３−トリス（３−メルカプトプロピルチオ）プロパン、１、２−ビス［（２−メルカプトエチル）チオ］−３−メルカプトプロパン、等の硫黄原子を有する脂肪族から誘導されるｍ＋ｎ価の有機残基等が挙がられるが、これらは一般に入手可能な試薬である。
【００３２】
本発明における反応は無溶媒、即ち一般式（ＩＩ）で表されるハロゲン化合物を反応基質兼溶媒として使用する事がこのましい。溶媒を使用する場合は反応を阻害しない溶媒であれば特に限定しないが、水、またはメタノール、エタノール、イソプロパノール、ブタノール、メトキシエタノール等アルコール類、トルエン、キシレン等の芳香族炭化水素系溶媒が好ましく用いられる。この内２種以上を混合して使用しても何ら差し支えない。
【００３３】
本発明では、上記一般式（ＩＩ）で表される有機ハロゲン化合物を有機塩基存在下、上記一般式（Ｉ）で表されるチオカルボン酸化合物と反応させるが、その反応方法としては、一般式（ＩＩ）で表されるハロゲン化合物を有機塩基存在下に一般式（Ｉ）で表されるチオカルボン酸化合物を滴下する方法と、一般式（Ｉ）で表されるチオカルボン酸化合物に有機塩基存在下に一般式（ＩＩ）で表されるハロゲン化合物滴下する方法があり、いずれの方法も可能であるが、一般式（ＩＩ）で表されるハロゲン化合物を有機塩基存在下に一般式（Ｉ）で表されるチオカルボン酸化合物を滴下する方法が特に好ましい。
【００３４】
本発明では、上記一般式（ＩＩ）で表される有機ハロゲン化合物を有機塩基存在下、上記一般式（Ｉ）で表されるチオカルボン酸化合物と反応させるがその有機塩基の量はチオカルボン酸化合物に対して１．０〜１．２当量が好ましく、１．０２〜１．１５当量で反応を行う事が更に好ましい。また一般式（ＩＩ）で表されるハロゲン化合物の量は一般式（Ｉ）で表されるチオカルボン酸化合物に対して１．０〜１０．０当量で反応を行う事が好ましく、４．０〜８．０当量で行うの事が更に好ましい。
【００３５】
本発明では、有機塩基存在下一般式（ＩＩ）で表されるハロゲン化合物に上記一般式（Ｉ）で表されるチオカルボン酸化合物を反応させるが、その滴下温度は５〜８０℃の範囲で滴下を行うのが好ましく、１０〜２０℃の範囲で行うのが更に好ましい。更に熟成は３０〜８０℃の範囲で行うのが好ましく、４０〜５０℃の範囲が更に好ましい。熟成時間はチオカルボン酸化合物の消費時間で決めているが、その範囲は滴下終了直後から１００時間の範囲であり、３〜１０時間で終了させるのが更に好ましい。
【００３６】
本発明では後処理方法としては反応マスを酸洗、水洗を行った後、濃縮、トッピングを行うだけで高純度のチオエステル化合物を得たが、もちろんこれら以外の後処理も可能であり、蒸留やカラム精製など一般的な方法を取る事が可能である。
【００３７】
【実施例】
以下本発明を具体的に実施例を用いて示す。
実施例１ チオ酢酸滴下法
攪拌機を備えたガラス製反応容器にトリエチルアミン３３４．３ｇ（３．３ｍｏｌ）と塩化メチレン７６８．２ｇ（９．０ｍｏｌ）を室温約２５℃にて装入した後、攪拌混合し、その還流温度（約４５℃）まで３０分かけて昇温した。この反応混合物にチオ酢酸２２８．８ｇ（３．０ｍｏｌ）を還流下４５℃から４８℃で５時間かけて滴下装入した。更に反応混合物を還流温度（４８℃）で３時間熟成した後、３．１６重量％塩酸水３４４．７ｇを加えて約４０℃で３０分間攪拌して酸洗浄を行い、３０分静置した後分液操作にて有機層と水層を分離した。その有機層を反応器に戻しイオン交換水３１４．４ｇを加え、４０℃で３０分間攪拌して水洗を行った後、３０分静置分液を行い、有機層と水層を分離した。下層の有機層を６０℃／０．６ｋＰａにて減圧濃縮を行った後８０℃／０．６ｋＰａにてトッピングを行い、９９．９重量％のビスアセチルチオメタン２３６．２ｇを得た。収率はチオ酢酸２ｍｏｌに対して９５．６ｍｏｌ％であった。
【００３８】
実施例２ 有機塩基造塩法
攪拌機を備えたガラス製反応容器にチオ酢酸２２８．８ｇ（３．０ｍｏｌ）とシクロヘキサンを室温約２５℃にて装入した後、攪拌混合し、１０℃まで冷却した。そこへトリエチルアミン３３４．３ｇ（３．３ｍｏｌ）を冷却しながら５〜１０℃で２．５時間かけて滴下して造塩を行った。その後温度を２０℃まで昇温しジクロロメタン１０１９．２ｇ（１２．０ｍｏｌ）を２．５時間かけて２０〜２５℃で滴下した。更に３０℃まで昇温を行ない、３０〜３５℃で１０時間熟成した。イオン交換水３８０ｇを加え、約２５℃で３０分間攪拌して水洗を行った後、３０分静置分液を行い、有機層と水層を分離した。下層の有機層を６０℃／０．６ｋＰａにて減圧濃縮を行った後８０℃／０．６ｋＰａにてトッピングを行い、９２．７重量％のビスアセチルチオメタン２１０．８ｇを得た。収率はチオ酢酸２ｍｏｌに対して７９．３ｍｏｌ％であった。
【００３９】
比較例１ ジブロモメタンとチオ酢酸ソーダによる合成法
攪拌機を備えた反応容器にチオ酢酸２２８．８ｇ（３．０ｍｏｌ）とメタノール１００ｍｌ（９２．４ｇ）を２５℃にて装入、攪拌混合し２０℃に冷却した後ナトリウムメトキシドの２８％メタノール溶液を６３６．７（３．３ｍｏｌ）を１５から２５℃の範囲で約３時間かけて滴下した。滴下終了後造塩マスを２０〜３０℃で約１時間造塩して、これを造塩マスとする。これとは別にジブロモメタン５２１．５ｇ（３．０ｍｏｌ）を室温でメタノール１５０ｍｌ（１３８．７ｇ）に溶解したマスに、先程の造塩マスを３時間かけて６０〜６５℃で滴下する。その後昇温を行い、反応マスを６０〜６５℃で４時間熟成を行った後、反応混合物を２５℃まで冷却した後濾過を行い、濾塊をメタノール１００ｇでリンスし、濾塊（ＮａＢｒ）１７０．３ｇを除去し、濾液１１３５．４ｇを得た。濾液を濃縮・脱溶媒を行った後、濃縮マス３６０．２ｇを得た。これを更に純水３００ｍｌにて水洗を行った後、上層の有機層を減圧濃縮して純度９０．４重量％のビスアセチルチオメタン１８９．１ｇを得た。その時の収率はチオ酢酸２当量に対して６９．４ｍｏｌ％であった。
【００４０】
実施例１と比較すると収率、純度は共にややに劣っている上に、工業的にはナトリウムメトキシドの使用が難しく、操作も煩雑であった。
【００４１】
比較例２ 無機塩基造塩法
攪拌機を備えた反応容器にチオ酢酸２２８．８ｇ（３．０ｍｏｌ）とメタノール６００ｍｌを２５℃にて装入した後、攪拌混合し５〜１０℃に冷却した後水酸化カリウム２１７．７ｇ（３．３ｍｏｌ）を５〜１０℃の範囲で約４時間かけて滴下し造塩を行った。その造塩マスを５〜１０℃の範囲で３０分間熟成した後４０℃まで昇温を行い、塩化メチレン７６８．２ｇ（９．０ｍｏｌ）を３５〜４５℃の範囲で約２時間かけて滴下後４０℃で４０時間熟成を行った。その反応混合物を２５℃まで冷却後濾過し水酸化カリウム４１４．１ｇを除去した。濾液を更に濃縮した後、純水５００ｍｌにて水洗を行ったい上層の有機層を減圧濃縮してビスアセチルチオメタンを純度８０．７重量％、１７９．２ｇを得た。収率はチオ酢酸２当量に対して５８．７ｍｏｌ％であった。
【００４２】
実施例１と比較すると収率、純度共に劣っていた上に反応時間も長かった。
【００４３】
【発明の効果】
本発明によりチオエステル化合物を簡便かつ高収率で得る工業的製造が可能となった。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing a thioester compound suitably used as an intermediate in the field of resins such as optical materials that require a high refractive index and high transparency.
[0002]
[Prior art]
Plastic lenses are lighter and harder to break than inorganic glass lenses and can be dyed, and have recently been rapidly used in optical materials such as spectacle lenses and camera lenses. The performances required of these plastic lenses are high refractive index, high Abbe number, high heat resistance and low specific gravity.
[0003]
Among these performances, high heat resistance and low specific gravity have been realized at a high level even with current high refractive index plastic lenses.
[0004]
As a lens giving a high refractive index, a sulfur-containing polyurethane lens has already been disclosed. For example, Patent Document 1 proposes a polyurethane lens made of a polymer of a polyisocyanate compound and a polythiol compound, and is widely used as an optical lens such as an eyeglass lens. Here, they succeeded in improving the refractive index by increasing the sulfur content used in polythiourethane. Further, as a polyurethane lens having a higher refractive index, for example, Patent Document 2 discloses a polyurethane lens obtained from a polymer of a trithiol compound 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane and a polyisocyanate compound. Polyurethane lenses have been proposed.
[0005]
After that, it was required to further increase the refractive index of polythiourethane, and it was necessary to further increase the sulfur content. Therefore, the present inventors have proposed a method for easily producing polythiol having a high sulfur content (Patent Document 3). Among them, a thioester compound is taken up as a useful intermediate, but the production method of the thioester compound has not always been industrially applied. As a method for producing a thioester compound, for example, there is a method of reacting dibromomethane with sodium thioacetate to obtain a thioester compound (Patent Document 3). However, further reduction in selectivity and reaction time has been desired.
[0006]
[Patent Document 1]
JP-A-63-46213 [Patent Document 2]
Japanese Patent Laying-Open No. 2-270859 [Patent Document 3]
JP 2001-342172 A
[Problems to be solved by the invention]
Therefore, it was necessary to develop a method for industrially producing a thioester compound, which is a useful intermediate of polythiol having a high sulfur content, which is indispensable for increasing the refractive index, efficiently and at low cost.
[0008]
[Means for Solving the Problems]
Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-described problems, and as a result, have found that an industrial production method for obtaining a thioester compound in a high yield and simply by reacting a thiocarboxylic acid compound with a halogen compound in the presence of an organic base. And completed the present invention.
[0009]
That is, the present invention has the following configurations.
[0010]
[1] A thiocarboxylic acid compound represented by the following general formula (III), wherein a thiocarboxylic acid compound represented by the following general formula (I) is reacted with a halogen compound represented by the general formula (II) in the presence of an organic base. A method for producing a compound.
[0011]
Embedded image

(In the formula, R1 represents an aliphatic, alicyclic, heterocyclic, aromatic organic residue or an aliphatic organic residue having a sulfur atom.)
[0012]
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(Wherein, X1 and X2 each independently represent a halogen atom, m and n each represent 0 or an integer of 1 or more, and m + n represents an integer of 1 or more. R2 represents an organic residue having a valence of 1 or more. )
[0013]
Embedded image

(In the formula, m and n each represent 0 or an integer of 1 or more, and m + n is an integer of 1 or more. R1 is an aliphatic, alicyclic, heterocyclic, aromatic organic residue, or a sulfur atom in the chain. Represents an aliphatic organic residue having the formula:
[0014]
[2] The production method according to [1], wherein triethylamine is used as the organic base.
[0015]
[3] The production method according to [2], wherein the compound represented by the general formula (I) is thioacetic acid, and the compound represented by the general formula (II) is methylene chloride.
[0016]
[4] The method according to [3], wherein thioacetic acid is charged after charging methylene chloride and triethylamine.
[0017]
[5] The production method according to [4], wherein the amount of triethylamine used is 1.0 equivalent or more and 2.0 equivalents or less based on the thiocarboxylic acid compound.
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail.
[0019]
In the present invention, a thiocarboxylic acid compound represented by the following general formula (I) is reacted with a halogen compound represented by the following general formula (II) in the presence of a base to form a thioester compound represented by the following general formula (III). It is characterized by gaining.
[0020]
Embedded image

(In the formula, R1 represents an aliphatic, alicyclic, heterocyclic, aromatic organic residue or an aliphatic organic residue having a sulfur atom.)
[0021]
Embedded image

(Wherein, X1 and X2 each independently represent a halogen atom, m and n each represent 0 or an integer of 1 or more, and m + n is an integer of 1 or more. R2 represents a monovalent or more organic residue. )
[0022]
Embedded image

(In the formula, m and n each represent 0 or an integer of 1 or more, and m + n is an integer of 1 or more. R1 is an aliphatic, alicyclic, heterocyclic, aromatic organic residue, or a sulfur atom in the chain. Represents an aliphatic organic residue having the formula:
[0023]
Examples of the organic residue corresponding to R1 in the general formula (I) include those derived from straight-chain aliphatics such as methane, ethane, propane, butane, pentane, hexane, ethylene, propylene, 1-butene, 2-butene, and butadiene. Organic residues, cyclopentane, cyclopentene, cyclopentadiene, cyclohexane, 1,2-dimethylcyclohexane, 1,4-dimethylcyclohexane, cyclohexene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, norbornane, 2, A monovalent organic residue derived from a cycloaliphatic such as 3-dimethylnorbornane, 2,5-dimethylnorbornane, 2,6-dimethylnorbornane,
[0024]
Cyclopentane, cyclopentene, cyclopentadiene, cyclohexane, 1,2-dimethylcyclohexane, 1,4-dimethylcyclohexane, cyclohexene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, norbornane, 2,3-dimethylnorbornane, 2 Monovalent organic residues derived from cycloaliphatic groups such as 2,5-dimethylnorbornane and 2,6-dimethylnorbornane;
[0025]
Thiolane, 2,5-dimethylthiolane, 3,4-dimethylthiolane, 2,3-dimethylthiolane, 2,5-diethylthiolane, 3,4-diethylthiolane, 2,3-diethylthiolane, 1,3-dithiolene, 2,4-dimethyl-1,3-dithiolene, 4,5-dimethyl-1,3-dithiolene, 2,4-diethyl-1,3-dithiolene, 4,5-diethyl-1,3-dithiolene, 1,3-dithiolane, 2,4-dimethyl-1,3-dithiolane, 4,5-dimethyl-1,3-dithiolane, 2,4-diethyl-1,3-dithiolane, 4,5-diethyl-1,3-dithiolane, Thiophene, 2,5-dimethylthiophene, 1,4-dithiane, 2,6-dimethyl-1,4-dithiane, 2,3-dimethyl-1,4-dithiane, 2,5-diethyl-1,4-dithiane, 2, 6-je 1,4-dithiane, 2,3-diethyl-1,4-dithiane, 1,3,5-trithiane, 2,4-dimethyl-1,3,5-trithiane, 2,4-diethyl-1,3 Derived from heterocycles such as 5-trithiane, thiazole, 1,3,4-thiadiazole, 1,3-dithiethane, 2,4-dimethyl-1,3-dithiethane, 2,4-diethyl-1,3-dithiethane, and the like. A monovalent organic residue,
[0026]
Monovalent organic residues derived from aromatics such as benzene, o-xylene, m-xylene, p-xylene, naphthalene, biphenyl, anthracene, perylene, styrene, ethylbenzene,
[0027]
Bis (mercaptomethyl) sulfide, bis (mercaptomethyl) disulfide, bis (mercaptoethyl) sulfide, bis (mercaptoethyl) disulfide, bis (mercaptopropyl) sulfide, bis (mercaptomethylthio) methane, bis (2-mercaptoethylthio) Methane, 1,2-bis (3-mercaptopropyl) ethane, 1,3-bis (mercaptoethylthio) propane, 1,3-bis (3-mercaptopropylthio) propane, 1,2,3-tris (mercapto Methylthio) propane, 1,2,3-tris (2-mercaptoethylthio) propane, 1,2,3-tris (3-mercaptopropylthio) propane, 1,2-bis [(2-mercaptoethyl) thio] -3- Compounds having sulfur such as mercaptopropane There is generally a monovalent organic residue available such induced, but not limited thereto.
[0028]
X1 and X2 in the general formula (II) used in the present invention are halogen atoms such as fluorine, chlorine, bromine and iodine. R2 is a monovalent or higher valent organic residue, and is derived from a linear aliphatic group such as methane, ethane, propane, butane, pentane, hexane, ethylene, propylene, 1-butene, 2-butene, butadiene and the like. Organic residues, cyclopentane, cyclopentene, cyclopentadiene, cyclohexane, 1,2-dimethylcyclohexane, 1,4-dimethylcyclohexane, cyclohexene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, norbornane, 2,3 An m + n-valent organic residue derived from a cycloaliphatic such as dimethylnorbornane, 2,5-dimethylnorbornane, 2,6-dimethylnorbornane,
[0029]
Thiolane, 2,5-dimethylthiolane, 3,4-dimethylthiolane, 2,3-dimethylthiolane, 2,5-diethylthiolane, 3,4-diethylthiolane, 2,3-diethylthiolane, 1,3-dithiolene, 2,4-dimethyl-1,3-dithiolene, 4,5-dimethyl-1,3-dithiolene, 2,4-diethyl-1,3-dithiolene, 4,5-diethyl-1,3-dithiolene, 1,3-dithiolane, 2,4-dimethyl-1,3-dithiolane, 4,5-dimethyl-1,3-dithiolane, 2,4-diethyl-1,3-dithiolane, 4,5-diethyl-1,3-dithiolane, Thiophene, 2,5-dimethylthiophene, 1,4-dithiane, 2,6-dimethyl-1,4-dithiane, 2,3-dimethyl-1,4-dithiane, 2,5-diethyl-1,4-dithiane, 2, 6-je 1,4-dithiane, 2,3-diethyl-1,4-dithiane, 1,3,5-trithiane, 2,4-dimethyl-1,3,5-trithiane, 2,4-diethyl-1,3 Derived from heterocycles such as 5-trithiane, thiazole, 1,3,4-thiadiazole, 1,3-dithiethane, 2,4-dimethyl-1,3-dithiethane, 2,4-diethyl-1,3-dithiethane, and the like. M + n-valent organic residues to be
[0030]
M + n-valent organic residues derived from aromatics such as benzene, o-xylene, m-xylene, p-xylene, naphthalene, biphenyl, anthracene, perylene, styrene and ethylbenzene;
[0031]
Bis (mercaptomethyl) sulfide, bis (mercaptomethyl) disulfide, bis (mercaptoethyl) sulfide, bis (mercaptoethyl) disulfide, bis (mercaptopropyl) sulfide, bis (mercaptomethylthio) methane, bis (2-mercaptoethylthio) Methane, 1,2-bis (3-mercaptopropyl) ethane, 1,3-bis (mercaptoethylthio) propane, 1,3-bis (3-mercaptopropylthio) propane, 1,2,3-tris (mercapto Methylthio) propane, 1,2,3-tris (2-mercaptoethylthio) propane, 1,2,3-tris (3-mercaptopropylthio) propane, 1,2-bis [(2-mercaptoethyl) thio] Fat having sulfur atom such as -3-mercaptopropane Although m + n valent organic residue such as is derived is diminishing return from, which are commonly available reagents.
[0032]
The reaction in the present invention preferably uses no solvent, that is, a halogen compound represented by the general formula (II) is used as a reaction substrate and a solvent. When a solvent is used, the solvent is not particularly limited as long as the solvent does not inhibit the reaction, but water or an alcohol such as methanol, ethanol, isopropanol, butanol, methoxyethanol, an alcohol such as toluene, or xylene is preferably used. Can be Two or more of these may be used in combination.
[0033]
In the present invention, the organic halogen compound represented by the general formula (II) is reacted with the thiocarboxylic acid compound represented by the general formula (I) in the presence of an organic base. A method of dropping a thiocarboxylic acid compound represented by the general formula (I) into a halogen compound represented by the formula (I) in the presence of an organic base; There is a method of dropping a halogen compound represented by the general formula (II), and any of the methods is possible. However, the halogen compound represented by the general formula (II) is represented by the general formula (I) in the presence of an organic base. The method of dropping the thiocarboxylic acid compound to be used is particularly preferred.
[0034]
In the present invention, the organic halogen compound represented by the general formula (II) is reacted with the thiocarboxylic acid compound represented by the general formula (I) in the presence of an organic base. The reaction is preferably performed in an amount of 1.0 to 1.2 equivalents, more preferably 1.02 to 1.15 equivalents. The amount of the halogen compound represented by the general formula (II) is preferably 1.0 to 10.0 equivalents to the thiocarboxylic acid compound represented by the general formula (I), and it is preferably 4.0 to 10.0. More preferably, the reaction is carried out at 8.0 equivalents.
[0035]
In the present invention, the thiocarboxylic acid compound represented by the general formula (I) is reacted with the halogen compound represented by the general formula (II) in the presence of an organic base. And more preferably in the range of 10 to 20 ° C. Further, the aging is preferably performed in the range of 30 to 80 ° C, more preferably in the range of 40 to 50 ° C. The aging time is determined by the consumption time of the thiocarboxylic acid compound, but the range is from immediately after the completion of the dropping to 100 hours, more preferably 3 to 10 hours.
[0036]
In the present invention, as a post-treatment method, a high-purity thioester compound is obtained simply by performing acid washing, water washing, concentration and topping of the reaction mass, but of course, other post-treatments are also possible, such as distillation and General methods such as column purification can be used.
[0037]
【Example】
Hereinafter, the present invention will be specifically described with reference to Examples.
Example 1 Thioacetic acid dropping method In a glass reactor equipped with a stirrer, 334.3 g (3.3 mol) of triethylamine and 768.2 g (9.0 mol) of methylene chloride were charged at room temperature of about 25 ° C. Thereafter, the mixture was stirred and mixed, and the temperature was raised to the reflux temperature (about 45 ° C.) over 30 minutes. To this reaction mixture, 228.8 g (3.0 mol) of thioacetic acid was added dropwise at 45 ° C. to 48 ° C. under reflux over 5 hours under reflux. The reaction mixture was further aged at reflux temperature (48 ° C.) for 3 hours, added with 344.7 g of 3.16% by weight hydrochloric acid aqueous solution, stirred at about 40 ° C. for 30 minutes, washed with acid, and allowed to stand for 30 minutes. An organic layer and an aqueous layer were separated by a liquid separation operation. The organic layer was returned to the reactor, 314.4 g of ion-exchanged water was added, and the mixture was stirred at 40 ° C. for 30 minutes, washed with water, and allowed to stand still for 30 minutes to separate the organic layer from the aqueous layer. The lower organic layer was concentrated under reduced pressure at 60 ° C./0.6 kPa and then topped at 80 ° C./0.6 kPa to obtain 236.2 g of 99.9% by weight bisacetylthiomethane. The yield was 95.6 mol% based on 2 mol of thioacetic acid.
[0038]
Example 2 Organic base salt formation method 228.8 g (3.0 mol) of thioacetic acid and cyclohexane were charged into a glass reactor equipped with a stirrer at room temperature of about 25 ° C, and then stirred and mixed. Cooled to ° C. 334.3 g (3.3 mol) of triethylamine was added dropwise thereto at 5 to 10 ° C. over 2.5 hours while cooling to form a salt. Thereafter, the temperature was raised to 20 ° C, and 1019.2 g (12.0 mol) of dichloromethane was added dropwise at 20 to 25 ° C over 2.5 hours. The temperature was further raised to 30 ° C., and the mixture was aged at 30 to 35 ° C. for 10 hours. After adding 380 g of ion-exchanged water and stirring at about 25 ° C. for 30 minutes to wash with water, the liquid was allowed to stand for 30 minutes to separate the organic layer and the aqueous layer. The lower organic layer was concentrated under reduced pressure at 60 ° C./0.6 kPa and then topped at 80 ° C./0.6 kPa to obtain 210.8 g of 92.7% by weight of bisacetylthiomethane. The yield was 79.3 mol% based on 2 mol of thioacetic acid.
[0039]
Comparative Example 1 Synthesis method using dibromomethane and sodium thioacetate In a reaction vessel equipped with a stirrer, 228.8 g (3.0 mol) of thioacetic acid and 100 ml (92.4 g) of methanol were charged at 25 ° C and stirred. After mixing and cooling to 20 ° C., 636.7 (3.3 mol) of a 28% methanol solution of sodium methoxide was added dropwise over a period of about 3 hours in the range of 15 to 25 ° C. After completion of the dropping, the salt-forming mass is subjected to salt formation at 20 to 30 ° C. for about 1 hour, and this is used as a salt-forming mass. Separately, the salt-forming mass is dropped at 60 to 65 ° C. over 3 hours to a mass in which 521.5 g (3.0 mol) of dibromomethane is dissolved in 150 ml (138.7 g) of methanol at room temperature. Thereafter, the temperature was raised, and the reaction mass was aged at 60 to 65 ° C for 4 hours. After cooling the reaction mixture to 25 ° C, filtration was performed. The filter cake was rinsed with 100 g of methanol, and the filter cake (NaBr) 170 was removed. 0.3 g was removed to obtain 1135.4 g of a filtrate. After the filtrate was concentrated and desolvated, 360.2 g of a concentrated mass was obtained. This was further washed with 300 ml of pure water, and the upper organic layer was concentrated under reduced pressure to obtain 189.1 g of bisacetylthiomethane having a purity of 90.4% by weight. The yield at that time was 69.4 mol% based on 2 equivalents of thioacetic acid.
[0040]
Compared with Example 1, both the yield and the purity were somewhat inferior, and industrially it was difficult to use sodium methoxide, and the operation was complicated.
[0041]
Comparative Example 2 Inorganic base salt- forming method 228.8 g (3.0 mol) of thioacetic acid and 600 ml of methanol were charged into a reaction vessel equipped with a stirrer at 25 ° C, followed by stirring and mixing to 5 to 10 ° C. After cooling, 217.7 g (3.3 mol) of potassium hydroxide was added dropwise at a temperature in the range of 5 to 10 ° C. over about 4 hours to form a salt. After aging the salt-forming mass in the range of 5 to 10 ° C. for 30 minutes, the temperature was raised to 40 ° C., and 768.2 g (9.0 mol) of methylene chloride was dropped in the range of 35 to 45 ° C. over about 2 hours. Aging was performed at 40 ° C. for 40 hours. The reaction mixture was cooled to 25 ° C. and filtered to remove 414.1 g of potassium hydroxide. After further concentrating the filtrate, the upper organic layer to be washed with 500 ml of pure water was concentrated under reduced pressure to obtain bisacetylthiomethane having a purity of 80.7% by weight and 179.2 g. The yield was 58.7 mol% based on 2 equivalents of thioacetic acid.
[0042]
Compared with Example 1, both the yield and the purity were inferior and the reaction time was longer.
[0043]
【The invention's effect】
INDUSTRIAL APPLICABILITY The present invention has enabled industrial production of a thioester compound to be easily and in high yield.

Claims (5)

A thioester compound represented by the general formula (III), characterized by reacting a thiocarboxylic acid compound represented by the following general formula (I) with a halogen compound represented by the following general formula (II) in the presence of an organic base. Manufacturing method.

(In the formula, R1 represents an aliphatic, alicyclic, heterocyclic, aromatic organic residue or an aliphatic organic residue having a sulfur atom.)

(Wherein, X1 and X2 each independently represent a halogen atom, m and n each represent 0 or an integer of 1 or more, and m + n is an integer of 1 or more. R2 represents an organic residue having a valence of 1 or more. )

(In the formula, m and n each represent 0 or an integer of 1 or more, and m + n is an integer of 1 or more. R1 is an aliphatic, alicyclic, heterocyclic, aromatic organic residue, or a sulfur atom in the chain. Represents an aliphatic organic residue having the formula: 2. The method according to claim 1, wherein triethylamine is used as the organic base. The method according to claim 2, wherein the compound represented by the general formula (I) is thioacetic acid, and the compound represented by the general formula (II) is methylene chloride. 4. The process according to claim 3, wherein thioacetic acid is added dropwise after charging methylene chloride and triethylamine. 4. The method according to claim 3, wherein the amount of triethylamine is from 1.0 to 2.0 equivalents based on the thiocarboxylic acid compound.