JPH03157361A - Organic sulfur compound and production thereof - Google Patents

Organic sulfur compound and production thereof

Info

Publication number
JPH03157361A
JPH03157361A JP29614889A JP29614889A JPH03157361A JP H03157361 A JPH03157361 A JP H03157361A JP 29614889 A JP29614889 A JP 29614889A JP 29614889 A JP29614889 A JP 29614889A JP H03157361 A JPH03157361 A JP H03157361A
Authority
JP
Japan
Prior art keywords
vinylbenzylthio
sulfur
formula
organic sulfur
bis
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP29614889A
Other languages
Japanese (ja)
Inventor
Takeshi Miyazaki
剛 宮崎
Takashige Murata
村田 敬重
Naoyuki Amaya
直之 天谷
Keizo Anami
啓三 阿南
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NOF Corp
Original Assignee
Nippon Oil and Fats Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Oil and Fats Co Ltd filed Critical Nippon Oil and Fats Co Ltd
Priority to JP29614889A priority Critical patent/JPH03157361A/en
Publication of JPH03157361A publication Critical patent/JPH03157361A/en
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C321/00Thiols, sulfides, hydropolysulfides or polysulfides
    • C07C321/12Sulfides, hydropolysulfides, or polysulfides having thio groups bound to acyclic carbon atoms
    • C07C321/20Sulfides, hydropolysulfides, or polysulfides having thio groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing rings

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

NEW MATERIAL:An organic sulfur compound shown by formula I [R is-S (CH2)nS- (n is 1-10),-SCH2CH2SCH2CH2S-, group shown by formula II or formula III]. EXAMPLE:1,2-Bis(p-vinylbenzylthio)ethane. USE:Useful as a raw material for high-performance polymer. Resins obtained by polymerizing this compound have excellent optical characteristics such as high refractive index and are usable as plastic lens, etc. PREPARATION:A sulfur-containing compound shown by formula IV is reacted with chloromethylstyrene in the presence of a dehydrohalogenating agent or chloromethylstyrene with a compound prepared by making the sulfur-containing compound into an alkali metal salt in the molar ratio of 1:0.5-3 at >=60 deg.C, preferably 20-40 deg.C to give a compound shown by formula I.

Description

【発明の詳細な説明】 〈産業上の利用分野〉 本発明は、新規な有機硫黄化合物及びその製造法に関し
、更に詳細には両末端にビニルベンジル基を有し、ラジ
カル単独重合性もしくは共重合性を有する新規な有機硫
黄化合物及びその製造法に関する。
Detailed Description of the Invention <Industrial Application Field> The present invention relates to a novel organic sulfur compound and a method for producing the same, and more specifically, it has a vinylbenzyl group at both ends and is radically homopolymerizable or copolymerizable. This invention relates to a novel organic sulfur compound having properties and a method for producing the same.

〈従来の技術〉 有機硫黄化合物は自然界に多数存在し、特に生体内にお
ける有機硫黄化合物は、生体の構成要素として多量に含
まれるだけでなく、各種の酵素反応や生理作用に関与し
ていることが知られている。
<Conventional technology> Many organic sulfur compounds exist in nature, and in particular, organic sulfur compounds in living organisms are not only contained in large amounts as constituents of living organisms, but are also involved in various enzymatic reactions and physiological effects. It has been known.

一方石炭あるいは石油中にも多量の有機硫黄化合物が含
まれているが、これらの物質は工業的に利用する場合、
公害の発生源となる恐れがある。
On the other hand, coal and petroleum also contain large amounts of organic sulfur compounds, but when these substances are used industrially,
It may become a source of pollution.

近年、各種の高性能プラスチックス、いわゆるエンジニ
アリングプラスチックの構成成分として硫黄化合物が注
目され1例えばポリスルホン、ポリエーテルスルホン、
ポリフェニレンスルフィド等の硫黄原子の特性を十分に
利用した高性能高・分子物質を得るための重合性含硫黄
有機化合物が注目されている。
In recent years, sulfur compounds have attracted attention as constituents of various high-performance plastics, so-called engineering plastics1, such as polysulfone, polyethersulfone,
Polymerizable sulfur-containing organic compounds, such as polyphenylene sulfide, are attracting attention for producing high-performance polymeric and molecular substances that fully utilize the properties of sulfur atoms.

〈発明が解決しようとする課題〉 本発明の目的は、機能性化合物の中間原料として利用可
能な有機硫黄化合物及びその製造法を提供することにあ
る。
<Problems to be Solved by the Invention> An object of the present invention is to provide an organic sulfur compound that can be used as an intermediate raw material for functional compounds and a method for producing the same.

〈課題を解決するための手段〉 本発明によれば、下記−放火(I) [式中Rは、 S (CH2)n S −(但しnは1
〜10の整数を示す) 、−5CH2C)12SCII
2C1125−また本発明によれば、下記−放火(II
)HRH・・ (II) [式中Rは−S (CHz)n S  (但しnは1〜
10の整数を示す) 、 −3CH2CH2SCH2C
H2S−で表わされる含硫黄化合物と、クロロメチルス
チレンとを脱ハロゲン化水素剤の存在下又は前記−放火
(II)で表わされる含硫黄化合物をアルカリ金属塩と
した化合物と、クロロメチルスチレンとを反応させるこ
とを特徴とする前記−放火(1)で表わされる有機硫黄
化合物の製造法が提供される。
<Means for Solving the Problems> According to the present invention, the following - arson (I) [wherein R is S (CH2)n S - (where n is 1
-5CH2C)12SCII
2C1125 - Also according to the invention - Arson (II
) HRH... (II) [In the formula, R is -S (CHz)n S (however, n is 1 to
(indicates an integer of 10), -3CH2CH2SCH2C
A sulfur-containing compound represented by H2S- and chloromethylstyrene in the presence of a dehydrohalogenating agent, or a compound in which the sulfur-containing compound represented by -arson (II) is an alkali metal salt, and chloromethylstyrene. There is provided a method for producing an organic sulfur compound represented by the above-mentioned -arson (1), which is characterized by carrying out a reaction.

以下本発明をさらに詳細に説明する。The present invention will be explained in more detail below.

本発明の有機硫黄化合物は下記−放火(1)で表わすこ
とができ、 で表わされる有機硫黄化合物が提供される。
The organic sulfur compound of the present invention can be represented by the following -arson (1), and an organic sulfur compound represented by the following is provided.

式中Rは、 s (c Hz)rls −(但しnは1
〜10の整数を示す)、−5CH2CH2SCH2CH
2S−放火(りで表わされる有機硫黄化合物としてし±
In the formula, R is s (c Hz) rls - (where n is 1
~10 integer), -5CH2CH2SCH2CH
2S-arson (as an organic sulfur compound represented by ri)
.

例えば1,2−ビス(P−ビニルベンジルチオ)エタン
、1,2−ビス(m−ビニルベンジルチオ)エタン、1
−(m−ビニルベンジルチオ)−2−(p−ビニルベン
ジルチオ)エタン、ビス(p −ビニルベンジルチオエ
チル)スルフィド、ビス(m−ビニルベンジルチオエチ
ル)スルフィド、(m−ビニルベンジルチオエチル)(
p−ビニルベンジルチオエチル)スルフィド、1,3−
ビス(p−ビニルベンジルチオ)ベンゼン、1,3−ビ
ス(m−ビニルベンジルチオ)ベンゼン、1−(m−ビ
ニルベンジルチオ)−3−(p−ビニルベンジルチオ)
ベンゼン、2,5−ビス(p−ビニルベンジルチオ−1
,3,4−チアジアゾール、2.5−ビス(m−ビニル
ベンジルチオ)−1,3゜4−チアゾール、2−(m−
ビニルベンジルチオ)−5−(p−ビニルベンジルチオ
)−1,3,4−チアジアゾール等を好ましく挙げるこ
とができる。
For example, 1,2-bis(P-vinylbenzylthio)ethane, 1,2-bis(m-vinylbenzylthio)ethane, 1
-(m-vinylbenzylthio)-2-(p-vinylbenzylthio)ethane, bis(p-vinylbenzylthioethyl) sulfide, bis(m-vinylbenzylthioethyl) sulfide, (m-vinylbenzylthioethyl) (
p-vinylbenzylthioethyl) sulfide, 1,3-
Bis(p-vinylbenzylthio)benzene, 1,3-bis(m-vinylbenzylthio)benzene, 1-(m-vinylbenzylthio)-3-(p-vinylbenzylthio)
Benzene, 2,5-bis(p-vinylbenzylthio-1
, 3,4-thiadiazole, 2,5-bis(m-vinylbenzylthio)-1,3°4-thiazole, 2-(m-
Preferred examples include vinylbenzylthio)-5-(p-vinylbenzylthio)-1,3,4-thiadiazole.

本発明の有機硫黄化合物は、低比重であり、また、ラジ
カル重合性を有す2)無色透明の物質であって、例えば
単独重合あるいは他の化合物、具体的には例えば、スチ
レン、0−クロロスチレン、m−クロロスチレン、p−
クロロスチレン、酢酸ビニル、安息香酸ビニル、メチル
メタクリレート。
The organic sulfur compound of the present invention has a low specific gravity, and is a colorless and transparent substance having radical polymerizability, such as homopolymerization or other compounds, specifically, for example, styrene, 0-chloro Styrene, m-chlorostyrene, p-
Chlorostyrene, vinyl acetate, vinyl benzoate, methyl methacrylate.

ベンジルメタクリレート等と共重合させることにより光
学的透明性、高屈折率、耐熱性、耐溶剤性、耐衝撃性、
低比重等の諸物性に優れた樹脂等を製造するための中間
体として利用することができる。
By copolymerizing with benzyl methacrylate, etc., optical transparency, high refractive index, heat resistance, solvent resistance, impact resistance,
It can be used as an intermediate for producing resins with excellent physical properties such as low specific gravity.

本発明の有機硫黄化合物を製造するには、特定の含硫黄
化合物と、クロロメチルスチレンとを脱ハロゲン化水素
剤の存在下反応させる方法(以下第1の方法と略す)、
又は前記含硫黄化合物をアルカリ金属塩とした化合物と
クロロスチレンとを反応させる方法(以下第2の方法と
略す)により得ることができる。
To produce the organic sulfur compound of the present invention, a method of reacting a specific sulfur-containing compound and chloromethylstyrene in the presence of a dehydrohalogenating agent (hereinafter abbreviated as the first method);
Alternatively, it can be obtained by a method of reacting the sulfur-containing compound with an alkali metal salt and chlorostyrene (hereinafter abbreviated as the second method).

本発明の第1の方法に用いる含硫黄化合物は、下記−放
火(II)で表わすことができ、HRH・ ・ (n) 式中Rは前記−放火(1)のRと同様である。前記−放
火(n)で表わされる含硫黄化合物としては1例えば1
,2−ジメルカプトエタン、 1”、 3−ジメルカプ
トプロパン、1,4−ジメルカプトブタン、1,5−ジ
メルカプトペンタン、1,6−ジメルカプトヘキサン、
1,9−ジメルカプトノナン、1,10−ジメルカプト
デカン、硫化−2−メルカプトエチル、0−ジメルカプ
トベンゼン、m−ジメルカプトベンゼン、p−ジメルカ
プトベンゼン、2,5−ジメルカプト−1,3,4−チ
アジアゾール等を好ましく挙げることができ。
The sulfur-containing compound used in the first method of the present invention can be represented by the following -Arson (II), HRH. · (n) where R is the same as R in -Arson (1) above. The sulfur-containing compound represented by -arson (n) is 1, e.g. 1
, 2-dimercaptoethane, 1'', 3-dimercaptopropane, 1,4-dimercaptobutane, 1,5-dimercaptopentane, 1,6-dimercaptohexane,
1,9-dimercaptononane, 1,10-dimercaptodecane, 2-mercaptoethyl sulfide, 0-dimercaptobenzene, m-dimercaptobenzene, p-dimercaptobenzene, 2,5-dimercapto-1,3 , 4-thiadiazole and the like can be preferably mentioned.

使用に際しては、単独若しくは混合物として用いること
ができる。また脱ハロゲン化水素剤としては、トリエチ
ルアミン、トリメチルアミン、トリノルマルプロピルア
ミン、トリイソプロピルアミン、トリノルマルブチルア
ミン、トリイソオクチルアミン、トリオクチルアミン、
トリエタノールアミン、トリベンジルアミン、ベンジル
ジメチルアミン、ジベンジルメチルアミン、ベンジルジ
エチルアミン、ジベンジルエチルアミン、ベンジルジノ
ルマルブチルアミン、トリフェニルアミン、各種ナトリ
ウムアルコキシド等からなる群より選択される1種また
は2種以上を用いることができる。
When used, they can be used alone or as a mixture. Examples of dehydrohalogenation agents include triethylamine, trimethylamine, trin-propylamine, triisopropylamine, trin-butylamine, triisooctylamine, trioctylamine,
One or more selected from the group consisting of triethanolamine, tribenzylamine, benzyldimethylamine, dibenzylmethylamine, benzyldiethylamine, dibenzylethylamine, benzyldinormalbutylamine, triphenylamine, various sodium alkoxides, etc. can be used.

一方本発明の第2の方法に用いる含硫黄化合物をアルカ
リ金属塩とした化合物としては、前記−放火(II)で
表わされる含硫黄化合物をナトリウム塩、カリウム塩等
のアルカリ金yt塩とした化合物を挙げることができ、
また溶媒としては、水。
On the other hand, as a compound in which the sulfur-containing compound used in the second method of the present invention is an alkali metal salt, a compound in which the sulfur-containing compound represented by -arson (II) is an alkali gold yt salt such as a sodium salt or a potassium salt can be used. can be mentioned,
Water is also used as a solvent.

アセトニトリル、酢酸エチル、エタノール、メタノール
、テトラヒドロフラン、ジオキサン、クロロホルム、ジ
クロロメタン、1−プロパツール。
Acetonitrile, ethyl acetate, ethanol, methanol, tetrahydrofuran, dioxane, chloroform, dichloromethane, 1-propanol.

2−プロパツール、n−ヘキサン、シクロヘキサン、ベ
ンゼン、トルエン及びこれらの混合物から成る群より選
択される溶媒を好ましく挙げることができる。
Preferable mention may be made of solvents selected from the group consisting of 2-propatol, n-hexane, cyclohexane, benzene, toluene and mixtures thereof.

更にまた本発明の製造法に用いるクロロメチルスチレン
は、パラ体のみ又はパラ体とメタ体との混合物を用いる
のが好ましく、例えばp−クロロスチレンを用いる場合
、高融点を有する単結晶物等が得られ、またp−クロロ
スチレンとm−クロロスチレンとの混合物を用いる場合
には、常温で液体又はワセリン状の物質が得られる。
Furthermore, the chloromethylstyrene used in the production method of the present invention is preferably used in the form of only the para form or a mixture of the para form and the meta form. For example, when p-chlorostyrene is used, a single crystal having a high melting point or the like is used. When a mixture of p-chlorostyrene and m-chlorostyrene is used, a liquid or vaseline-like substance can be obtained at room temperature.

本発明の製造法において、前記各成分を反応させる際の
仕込み割合は、経済性を鑑みて、クロロメチルスチレン
と、含硫黄化合物又は含硫黄化合物をアルカリ金属塩と
した化合物とを1モル比で1:0.5〜3の範囲とする
のが好ましい。
In the production method of the present invention, the charging ratio when reacting each of the above components is determined from the viewpoint of economical efficiency. 1: It is preferable to set it as the range of 0.5-3.

本発明の第1及び第2の方法において、前記各成分を反
応させる際の反応温度は、好ましくは一60℃以上、特
に好ましくは、20〜40℃であり、また反応時間は、
30分以上、特に6〜24時間であるのが好ましい。更
に反応は、前記含硫黄化合物又は含硫黄化合物をアルカ
リ金属塩とした化合物の酸化を防止するために、窒素、
アルゴン等の不活性ガスの雰囲気下で行うのが好ましい
In the first and second methods of the present invention, the reaction temperature when reacting each component is preferably -60°C or higher, particularly preferably 20 to 40°C, and the reaction time is
Preferably, the time is 30 minutes or more, particularly 6 to 24 hours. Furthermore, in order to prevent the oxidation of the sulfur-containing compound or the alkali metal salt of the sulfur-containing compound,
It is preferable to carry out under an atmosphere of an inert gas such as argon.

また例えば水とトルエンのような二相系の混合溶媒を用
いる際には、ヘキサデシルトリブチルホスホニウムブロ
マイドのような相関移動触媒を用いることもできる。
Furthermore, when a two-phase mixed solvent such as water and toluene is used, a phase transfer catalyst such as hexadecyltributylphosphonium bromide can also be used.

本発明の製造法により得られる反応混合物は、抽出、減
圧、濃縮、蒸留、カラム等により精製することによって
、前記−放火(I)で表わされる有機硫黄化合物を得る
ことができる。
The reaction mixture obtained by the production method of the present invention can be purified by extraction, reduced pressure, concentration, distillation, column, etc. to obtain the organic sulfur compound represented by -arson (I) above.

〈発明の効果〉 本発明の有機硫黄化合物は1重合性を有する新規な化合
物であり、高性能高分子の原料として有用である。また
、本発明の製造法では、前記有機硫黄化合物を高収率で
容易に合成することができる。さらに本発明の有機硫黄
化合物を重合して得られる樹脂は、高屈折率など光学性
特性に優れており、プラスチックレンズなどに利用可能
である。
<Effects of the Invention> The organic sulfur compound of the present invention is a novel monopolymerizable compound and is useful as a raw material for high-performance polymers. Furthermore, in the production method of the present invention, the organic sulfur compound can be easily synthesized in high yield. Furthermore, the resin obtained by polymerizing the organic sulfur compound of the present invention has excellent optical properties such as a high refractive index, and can be used for plastic lenses and the like.

〈実施例〉 以下実施例により本発明を更に詳細に説明するが、これ
らは本発明の範囲を限定するものではない。
<Examples> The present invention will be explained in more detail with reference to Examples below, but these are not intended to limit the scope of the present invention.

失f 脱塩化水素剤を用いた1、2−ビス(p−ビニルベンジ
ルチオ)エタンの製造 滴下ロート、窒素導入管及び撹拌機を付したIQの3つ
ロフラスコにおいて、窒素気流下、トルエン500mQ
、1,2−ジメルカプトエタン94.20g (1mo
12) 、脱ハロゲン化水素剤としてトリエチルアミン
202g(2moQ)を添加した。一方、滴下ロートよ
りp−クロロメチルスチレン305.24g (2mo
n)を徐々に加え、室温で6時間撹拌反応させた。生成
したトリエチルアミン塩酸塩を濾過した後、濾液を1Ω
の分液ロートに移し替え、5wt%水酸化ナトリウム溶
液300mQで3回、蒸留水300mQで3回洗浄し、
有機層を硫酸ナトリウムで乾燥後、減圧濃縮した。得ら
れた残虐を、n−ヘキサンにより再結晶し、1,2−ビ
ス(p−ビニルベンジルチオ)エタン277.1g (
収率85%)を得た。
Production of 1,2-bis(p-vinylbenzylthio)ethane using a dehydrochlorination agent In an IQ three-bottle flask equipped with a dropping funnel, a nitrogen inlet tube, and a stirrer, 500 mQ of toluene was added under a nitrogen stream.
, 1,2-dimercaptoethane 94.20g (1mo
12) 202 g (2 moQ) of triethylamine was added as a dehydrohalogenating agent. Meanwhile, 305.24 g of p-chloromethylstyrene (2 mo
n) was gradually added, and the mixture was stirred and reacted at room temperature for 6 hours. After filtering the generated triethylamine hydrochloride, the filtrate was
Transfer to a separating funnel, wash 3 times with 300 mQ of 5 wt% sodium hydroxide solution and 3 times with 300 mQ of distilled water,
The organic layer was dried over sodium sulfate and then concentrated under reduced pressure. The resulting residue was recrystallized from n-hexane to yield 277.1 g of 1,2-bis(p-vinylbenzylthio)ethane (
A yield of 85% was obtained.

得られた生成物の融点、状態、IRスペクトル、NMR
スペクトル及び元素分析を測定した。その結果を下記に
示す。
Melting point, state, IR spectrum, NMR of the obtained product
Spectra and elemental analysis were measured. The results are shown below.

・mp ; 100〜105℃  白色針状結晶・IR
((!l−”);2900,1420.980(−CH
=CH,)。
・mp; 100-105℃ White needle-like crystals・IR
((!l-”);2900,1420.980(-CH
=CH,).

−NMR(δ; p pm) + ’!−1〜7.5 
(rr+、 8H) t6.5〜6.9 (q、2H)
-NMR(δ; pp pm) + '! -1 to 7.5
(rr+, 8H) t6.5~6.9 (q, 2H)
.

5.1〜5.9 (m、4H)。5.1-5.9 (m, 4H).

3.65 (s、4H)。3.65 (s, 4H).

2.50 (s、4H) ・元素分析(CzoHzz S2) 計算値C;73.57.H;6.80.  S;19.
64測定値C;73.52.H;6.78.  S;1
9.70ス蛎LLL 1.2−ジメルカプトエタンナトリウム塩を用いた1、
2−ビス(p−ビニルベンジルチオ)エタンの製造 滴下ロート、窒素導入管及び撹拌機を付したIQの3つ
ロフラスコに、水酸化ナトリウム80g(2moQ)、
蒸留水500mQを添加溶解させた後、窒素気流下で1
,2−ジメルカプトエタン94.20g (1mo12
)を添加して30分間撹拌し、1,2−ジメルカプトエ
タンナトリウム塩を調製した。次いで1滴下ロートより
P−クロロメチルスチレン305.24g (2moQ
)とトルエン500mQとを徐々に加え、室温で6時r
JJ撹拌反応させた。次に得られた生成物をIQの分液
ロートに移し替え、有機層を5wt%水酸化ナトリウム
溶液300mQで3回、蒸留水300mQで3回洗浄し
、硫酸ナトリウムで乾燥後、減圧濃縮した。得られた残
渣を、n−ヘキサンに加熱溶解させた後、商品名「ワー
コーゲル C−fool(和光純薬株式会社JJI)5
0gを加え50℃で30分間撹拌し、これを濾過した後
、室温まで冷却し析出した結晶をn−ヘキサンより再結
晶し、1.2−ビス(p−ビニルベンジルチオ)エタン
270.8g (収率83%)を得た。得られた生成物
の融点、状態、IRスペクトル、NMRスペクトル及び
元素分析を測定した。その結果を下記に示す。
2.50 (s, 4H) Elemental analysis (CzoHz S2) Calculated value C; 73.57. H; 6.80. S;19.
64 measurement value C; 73.52. H; 6.78. S;1
9.70 S. LLL 1.1 using 2-dimercaptoethane sodium salt,
Production of 2-bis(p-vinylbenzylthio)ethane In an IQ three-bottle flask equipped with a dropping funnel, nitrogen inlet tube, and stirrer, 80 g (2moQ) of sodium hydroxide,
After adding and dissolving 500 mQ of distilled water, 1
,2-dimercaptoethane 94.20g (1mol12
) was added and stirred for 30 minutes to prepare 1,2-dimercaptoethane sodium salt. Next, 305.24 g of P-chloromethylstyrene (2moQ
) and 500 mQ of toluene were gradually added, and the mixture was heated at room temperature for 6 hours.
The reaction was carried out with JJ stirring. Next, the obtained product was transferred to an IQ separating funnel, and the organic layer was washed three times with 300 mQ of 5 wt% sodium hydroxide solution and three times with 300 mQ of distilled water, dried over sodium sulfate, and concentrated under reduced pressure. After heating and dissolving the obtained residue in n-hexane, the product name "Wakogel C-fool (Wako Pure Chemical Industries, Ltd. JJI) 5" was prepared.
0g was added and stirred at 50°C for 30 minutes, filtered, cooled to room temperature, and the precipitated crystals were recrystallized from n-hexane to obtain 270.8g of 1.2-bis(p-vinylbenzylthio)ethane ( A yield of 83% was obtained. The melting point, state, IR spectrum, NMR spectrum and elemental analysis of the obtained product were measured. The results are shown below.

・mp;100〜105℃  白色針状結晶IR(aa
″”);2900,1420,980(−CH=CH,
)。
・mp; 100-105℃ White needle crystal IR (aa
"");2900,1420,980(-CH=CH,
).

820 (−QO−) −NMR(δ:PPm)  盲7−1〜7.5 (m+
 8H)+6.5〜6.9 (q、2H)。
820 (-QO-) -NMR (δ:PPm) Blind 7-1 to 7.5 (m+
8H)+6.5-6.9 (q, 2H).

5.1〜5.9 (m、4H)。5.1-5.9 (m, 4H).

3.65 (s、4H)。3.65 (s, 4H).

2.50 (s、4H) ・元素分析(C2,H2−s2) 計算値Cニア3.57.H;6.80.  S;19.
64測定値C;73.52.H:6.78.  S;1
9.70スJIIJLジ 1.2−ビス(p−ビニルベンジルチオ)エタン、1,
2−ビス(m−ビニルベンジルチオ)エタンおよび1−
(m−ビニルベンジルチオ)−2−(p−ビニルベンジ
ルチオ)エタン混合物の製造 クロロメチルスチレンとしてパラ体及びメタ体混合物(
バラ体60wt%、メタ体40wt%)を用いた以外は
実施例2と同様に反応を行って。
2.50 (s, 4H) ・Elemental analysis (C2, H2-s2) Calculated value C near 3.57. H; 6.80. S;19.
64 measurement value C; 73.52. H:6.78. S;1
9.70s JIIJL di-1,2-bis(p-vinylbenzylthio)ethane, 1,
2-bis(m-vinylbenzylthio)ethane and 1-
Production of (m-vinylbenzylthio)-2-(p-vinylbenzylthio)ethane mixture As chloromethylstyrene, para and meta mixture (
The reaction was carried out in the same manner as in Example 2 except that 60 wt% of bulk body and 40 wt% of meta body were used.

前記混合物を製造した。得られた生成物の状態、IRス
ペクトル、NMRスペクトル及び元素分析を測定した。
The mixture was prepared. The state, IR spectrum, NMR spectrum and elemental analysis of the obtained product were measured.

その結果を下記に示す。The results are shown below.

・白色ワセリン状物質 ・IR(国−”);2900,1420.980(−C
H=CH,)。
・White vaseline-like substance ・IR (Country-”); 2900, 1420.980 (-C
H=CH,).

・元素分析(CZ。HiaS2) 計算値Cフッ3.5フ、Hフロ、80.S;19.64
測定値C;73.51.H;6.74.  S:19.
75ス】nt先 ビス(p−ビニルベンジルチオエチル)スルフィド、ビ
ス(m−ビニルベンジルチオエチル)スルフィドおよび
(m−ビニルベンジルチオエチル)(p−ビニルベンジ
ルチオエチル)スルフィド混合物の製造 クロロメチルスチレンとしてパラ体及びメタ体混合物(
パラ体60wt%、メタ体40wt%)を、また1、2
−ジメルカプトエタンの代わりに、硫化−2−メルカプ
トエチルを用いた以外は実施例2と同様に反応を行って
、前記混合物製造した。
・Elemental analysis (CZ. HiaS2) Calculated value Cfu 3.5fu, H flo, 80. S; 19.64
Measured value C; 73.51. H; 6.74. S:19.
75 S] Preparation of nt-pre-bis(p-vinylbenzylthioethyl) sulfide, bis(m-vinylbenzylthioethyl) sulfide and (m-vinylbenzylthioethyl)(p-vinylbenzylthioethyl) sulfide mixture Chloromethylstyrene as a mixture of para and meta bodies (
60 wt% of para form, 40 wt% of meta form), and 1 or 2
The above mixture was prepared by carrying out the reaction in the same manner as in Example 2, except that -2-mercaptoethyl sulfide was used instead of -dimercaptoethane.

得られた生成物の状態、IRスペクトル、NMRスペク
トル及び元素分析を測定した。その結果を下記に示す。
The state, IR spectrum, NMR spectrum and elemental analysis of the obtained product were measured. The results are shown below.

・白色ワセリン状物質 ・IR(ニー”):2900,1420,980(CH
=CH,)。
・White vaseline-like substance ・IR (knee): 2900, 1420, 980 (CH
=CH,).

820 (−QO−) ・元素分析(C2□H2−83) 計算値C:68.34.H;6.78.S;24.88
測定値C:68.30.H;6.75.  S;24.
91ス】111 1.3−ビス(p−ビニルベンジルチオ)ベンゼン、1
.3−ビス(m−ビニルベンジルチオ)ベンゼンおよび
1−(m−ビニルベンジルチオ)−3−(p−ビニルベ
ンジルチオ)ベンゼン混合物の製造 クロロメチルスチレンとしてパラ体及びメタ体混合物(
バラ体60wt%、メタ体40wt%)を、また1、2
−ジメルカプトエタンの代わりにm−ジメルカプトベン
ゼンを用いた以外は、実施例2と同様に反応を行って前
記混合物を得た。得られた生成物の状態、IRスペクト
ル、NMRスペクトル及び元素分析を測定した。その結
果を下記に示す。
820 (-QO-) Elemental analysis (C2□H2-83) Calculated value C: 68.34. H; 6.78. S; 24.88
Measured value C: 68.30. H; 6.75. S;24.
91st] 111 1.3-bis(p-vinylbenzylthio)benzene, 1
.. Production of 3-bis(m-vinylbenzylthio)benzene and 1-(m-vinylbenzylthio)-3-(p-vinylbenzylthio)benzene mixtures As chloromethylstyrene, para and meta mixtures (
60 wt% of loose body, 40 wt% of meta body), and 1 or 2
The reaction was carried out in the same manner as in Example 2 except that m-dimercaptobenzene was used instead of -dimercaptoethane to obtain the above mixture. The state, IR spectrum, NMR spectrum and elemental analysis of the obtained product were measured. The results are shown below.

・白色ワセリン状物質 ・IR(dll−”); 1600,780,790゜
2900.1420,980 (cH=cHa)− 820(−〇−) ・元素分析(C24H22SJ 計算値C;76.96.H;5.92.  S;17.
12測定値C;76.91.H;5.88.S;17.
16去]1」」 2.5−ビス(p−ビニルベンジルチオ)−1゜3.4
−チアジアゾール、2,5−ビス(m−ビニルベンジル
チオ)−1,3,4−チアジアゾールおよび2−(m−
ビニルベンジルチオ)−5−(p−ビニルベンジルチオ
)−1,3,4−チアジアゾール混合物の製造 クロロメチルスチレンとしてパラ体及びメタ体混合物(
パラ体60wt%、メタ体40wt%)を、また1、2
−ジメルカプトエタンの代わりに、2.5−ジメルカプ
ト−1,3,4−チアジアゾールを用いた以外は、実施
例2と同様に反応を行って、前記混合物を得た。得られ
た生成物の状態、IRスペクトル、NMRスペクトル及
び元素分析を測定した。その結果を下記に示す。
・White petrolatum-like substance ・IR (dll-”); 1600,780,790゜2900.1420,980 (cH=cHa)- 820 (-〇-) ・Elemental analysis (C24H22SJ calculated value C; 76.96.H ;5.92.S;17.
12 Measured value C; 76.91. H; 5.88. S;17.
16 left] 1'' 2.5-bis(p-vinylbenzylthio)-1゜3.4
-thiadiazole, 2,5-bis(m-vinylbenzylthio)-1,3,4-thiadiazole and 2-(m-
Preparation of a mixture of para- and meta-isomers (vinylbenzylthio)-5-(p-vinylbenzylthio)-1,3,4-thiadiazole as chloromethylstyrene (
60 wt% of para form, 40 wt% of meta form), and 1 or 2
The reaction was carried out in the same manner as in Example 2 except that 2,5-dimercapto-1,3,4-thiadiazole was used instead of -dimercaptoethane to obtain the mixture. The state, IR spectrum, NMR spectrum and elemental analysis of the obtained product were measured. The results are shown below.

白色ワセリン状物質 2900.1420.980 (−CH=CH2) 820 ( 0− ) ・元素分析(C2゜H工、N2S、) 計算値C;62.79.H;4.74゜S;25.15 測定値C;62.81.H;4.72゜S;25.13 N;7゜ N;7゜ 32゜ 34゜ 特許呂原人white petrolatum-like substance 2900.1420.980 (-CH=CH2) 820 ( 0- ) ・Elemental analysis (C2°H engineering, N2S,) Calculated value C; 62.79. H; 4.74°S; 25.15 Measured value C; 62.81. H; 4.72°S; 25.13 N; 7゜ N; 7゜ 32° 34° Patent Rogenjin

Claims (1)

【特許請求の範囲】 1)下記一般式( I ) ▲数式、化学式、表等があります▼・・( I ) [式中Rは、−S(CH_2)_nS−(但しnは1〜
10の整数を示す)、−SCH_2CH_2SCH_2
CH_2S−、▲数式、化学式、表等があります▼、▲
数式、化学式、表等があります▼を示す] で表わされる有機硫黄化合物。 2)下記一般式(II) HRH・・(II) [式中Rは−S(CH_2)_nS−(但しnは1〜1
0の整数を示す)、−SCH_2CH_2SCH_2C
H_2S−、▲数式、化学式、表等があります▼、▲数
式、化学式、表等があります▼を示す] で表わされる含硫黄化合物と、クロロメチルスチレンと
を脱ハロゲン化水素剤の存在下又は前記一般式(II)で
表わされる含硫黄化合物をアルカリ金属塩とした化合物
と、クロロスチレンとを反応させることを特徴とする請
求項1記載の有機硫黄化合物の製造法。
[Claims] 1) The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) [In the formula, R is -S(CH_2)_nS- (where n is 1 to
(indicates an integer of 10), -SCH_2CH_2SCH_2
CH_2S-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ is an organic sulfur compound represented by . 2) The following general formula (II) HRH...(II) [In the formula, R is -S(CH_2)_nS- (where n is 1 to 1
(indicates an integer of 0), -SCH_2CH_2SCH_2C
A sulfur-containing compound represented by H_2S-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼] A sulfur-containing compound represented by and chloromethylstyrene are treated in the presence of a dehydrohalogenating agent or as described above. 2. The method for producing an organic sulfur compound according to claim 1, which comprises reacting a sulfur-containing compound represented by general formula (II) with an alkali metal salt and chlorostyrene.
JP29614889A 1989-11-16 1989-11-16 Organic sulfur compound and production thereof Pending JPH03157361A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP29614889A JPH03157361A (en) 1989-11-16 1989-11-16 Organic sulfur compound and production thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP29614889A JPH03157361A (en) 1989-11-16 1989-11-16 Organic sulfur compound and production thereof

Publications (1)

Publication Number Publication Date
JPH03157361A true JPH03157361A (en) 1991-07-05

Family

ID=17829774

Family Applications (1)

Application Number Title Priority Date Filing Date
JP29614889A Pending JPH03157361A (en) 1989-11-16 1989-11-16 Organic sulfur compound and production thereof

Country Status (1)

Country Link
JP (1) JPH03157361A (en)

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