JPH09165367A - Production of hydroxyl-containing aliphatic mercapto compound - Google Patents
Production of hydroxyl-containing aliphatic mercapto compoundInfo
- Publication number
- JPH09165367A JPH09165367A JP7347832A JP34783295A JPH09165367A JP H09165367 A JPH09165367 A JP H09165367A JP 7347832 A JP7347832 A JP 7347832A JP 34783295 A JP34783295 A JP 34783295A JP H09165367 A JPH09165367 A JP H09165367A
- Authority
- JP
- Japan
- Prior art keywords
- general formula
- compound
- reaction
- ethylene sulfide
- mercapto compound
- 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.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、脂肪族メルカプト
化合物の製造方法、特に、水酸基を有する脂肪族メルカ
プト化合物の製造方法に関する。TECHNICAL FIELD The present invention relates to a method for producing an aliphatic mercapto compound, and more particularly to a method for producing an aliphatic mercapto compound having a hydroxyl group.
【０００２】[0002]
【従来の技術】下記の一般式（ＩＩ）で示される、水酸
基を有する脂肪族メルカプト化合物である１−ヒドロキ
シ−５−メルカプト−３−チアペンタン（ｎが２の化合
物）の合成方法としては、例えば下記の２種類の方法が
知られている。2. Description of the Related Art As a method for synthesizing 1-hydroxy-5-mercapto-3-thiapentane (a compound in which n is 2), which is an aliphatic mercapto compound having a hydroxyl group, represented by the following general formula (II), The following two types of methods are known.
【０００３】[0003]
【化３】 Embedded image
【０００４】（方法Ａ）下記の反応式（Ａ）に示すよう
に、エチレンオキシドにエタンジチオールを反応させる
方法（Ｊ．Ｃｈｅｍ．Ｓｏｃ．，８１７〜８２６、１９
５２）。(Method A) A method of reacting ethylene oxide with ethanedithiol as shown in the following reaction formula (A) (J. Chem. Soc., 817-826, 19)
52).
【０００５】[0005]
【化４】 Embedded image
【０００６】（方法Ｂ）下記の反応式（Ｂ）に示すよう
に、クロロエタノールにエタンジチオールを反応させる
方法（Ｃａｎｃｅｒ，１０、９７１〜９７５、１９５
７）。(Method B) As shown in the following reaction formula (B), a method for reacting ethanedithiol with chloroethanol (Cancer, 10 , 971-975, 195).
7).
【０００７】[0007]
【化５】 Embedded image
【０００８】上述の方法Ａおよび方法Ｂに従って上述の
一般式（ＩＩ）中のｎが３以上の化合物を製造する場合
は、例えば下記の一般式（ＩＩＩ）で示されるジメルカ
プト化合物を製造し、このジメルカプト化合物を原料と
して上述の方法Ａおよび方法Ｂを実施する。In the case of producing a compound in which n in the above general formula (II) is 3 or more according to the above method A and method B, for example, a dimercapto compound represented by the following general formula (III) is produced, and The above method A and method B are carried out using a dimercapto compound as a raw material.
【０００９】[0009]
【化６】 [Chemical 6]
【００１０】なお、一般式（ＩＩＩ）で示されるジメル
カプト化合物は、チオール類にエチレンスルフィドを付
加反応させることにより製造することができる。例え
ば、一般式（ＩＩＩ）中のｎが２の化合物であるジメル
カプトジエチルスルフィドは、下記の反応式（Ｃ）に示
すように、エタンジチオールにエチレンスルフィドを反
応させることにより製造することができる（Ｊ．Ｃｈｅ
ｍ．Ｓｏｃ．，１８９４、１９４８）。因に、一般式
（ＩＩＩ）中のｎが３以上の化合物は、この反応により
得られた生成物を原料として、同様の反応を段階的に繰
り返すことにより得ることができる。The dimercapto compound represented by the general formula (III) can be produced by the addition reaction of thiols with ethylene sulfide. For example, dimercaptodiethyl sulfide, which is a compound in which n is 2 in the general formula (III), can be produced by reacting ethanedithiol with ethylene sulfide as shown in the following reaction formula (C) ( J. Che
m. Soc. , 1894, 1948). Incidentally, the compound in which n in the general formula (III) is 3 or more can be obtained by repeating the same reaction stepwise using the product obtained by this reaction as a raw material.
【００１１】[0011]
【化７】 Embedded image
【００１２】[0012]
【発明が解決しようとする課題】上述の方法Ａおよび方
法Ｂは、いずれも収率が４０％以下と低く、工業性の点
で有効ではない。また、一般式（ＩＩ）中のｎが３以上
の化合物を製造する場合は、先ず上述の反応式（Ｃ）に
従って、エチレンスルフィドを用いて一般式（ＩＩＩ）
において（−ＳＣＨ2ＣＨ2）基がｎ−１で示される化合
物を製造し、こうして得られた化合物に最終工程でエチ
レンオキシドまたはクロロエタノールを反応させる必要
がある。この場合は、目的とする化合物の収率が低いだ
けではなく、数種類の原料、すなわちエチレンスルフィ
ドおよびエチレンオキシドまたはクロロエタノールを用
いる必要があるので、原料効率上も有利な製造方法とは
言いにくい。The above-mentioned method A and method B are both ineffective in terms of industrial property since the yield is low at 40% or less. In the case of producing a compound in which n in the general formula (II) is 3 or more, first, according to the above reaction formula (C), ethylene sulfide is used to prepare the general formula (III)
It is necessary to prepare a compound in which the (-SCH 2 CH 2 ) group is represented by n-1 and to react the compound thus obtained with ethylene oxide or chloroethanol in the final step. In this case, not only is the yield of the target compound low, but it is necessary to use several kinds of raw materials, that is, ethylene sulfide and ethylene oxide or chloroethanol, so it is difficult to say that the production method is advantageous in terms of raw material efficiency.
【００１３】本発明の目的は、上述の一般式（ＩＩ）で
示される、水酸基を有する脂肪族メルカプト化合物を効
率的に製造することにある。An object of the present invention is to efficiently produce an aliphatic mercapto compound having a hydroxyl group, which is represented by the above general formula (II).
【００１４】[0014]
【課題を解決するための手段】本発明者らは、上述の状
況に鑑み、水酸基を有する脂肪族メルカプト化合物を効
率的に製造する方法を提供すべく鋭意検討した。そのた
めに、同一分子内にメルカプト基と水酸基とを有する化
合物にエチレンスルフィドを付加させる方法を想定し
た。[Means for Solving the Problems] In view of the above situation, the present inventors have made earnest studies to provide a method for efficiently producing an aliphatic mercapto compound having a hydroxyl group. Therefore, a method of adding ethylene sulfide to a compound having a mercapto group and a hydroxyl group in the same molecule was assumed.
【００１５】しかしながら、同一分子内にメルカプト基
と水酸基とを有する化合物にエチレンスルフィドを付加
させようとした場合、化学量論量のエチレンスルフィド
を用いると、エチレンスルフィドの自己重合、あるいは
目的とする化合物にさらにエチレンスルフィドが付加し
たりする副反応が起こり、目的とする化合物を選択的に
しかも効率的に製造するのは困難であった。However, when ethylene sulfide is added to a compound having a mercapto group and a hydroxyl group in the same molecule, if ethylene stoichiometric amount is used, the ethylene sulfide self-polymerizes or the desired compound is obtained. In addition, side reactions such as the addition of ethylene sulfide occur, which makes it difficult to selectively and efficiently produce the desired compound.
【００１６】そこで、エチレンスルフィドと、一般式
（Ｉ）で示される、同一分子内にメルカプト基および水
酸基を有する化合物との反応について種々検討した結
果、一般式（Ｉ）で示される化合物とエチレンスルフィ
ドとを塩基触媒の存在下で反応させた場合、特に、一般
式（Ｉ）で示される化合物に対してエチレンスルフィド
を１／２倍モル以下用いた場合に、目的とする水酸基を
有する脂肪族メルカプト化合物が選択的にかつ効率的に
得られることを見いだし本発明を完成するに至った。Then, as a result of various studies on the reaction between ethylene sulfide and the compound represented by the general formula (I) having a mercapto group and a hydroxyl group in the same molecule, the compound represented by the general formula (I) and the ethylene sulfide were investigated. In the presence of a base catalyst, particularly when ethylene sulfide is used in an amount of 1/2 times or less the amount of the compound represented by the general formula (I), an aliphatic mercapto having a desired hydroxyl group. The inventors have found that the compound can be obtained selectively and efficiently, and have completed the present invention.
【００１７】すなわち、本発明に係る、下記の一般式
（ＩＩ）で示される、水酸基を有する脂肪族メルカプト
化合物の製造方法は、下記の一般式（Ｉ）で示される脂
肪族メルカプト化合物とエチレンスルフィドとを塩基触
媒の存在下で反応させる工程を含んでいる。That is, according to the present invention, a method for producing an aliphatic mercapto compound having a hydroxyl group, which is represented by the following general formula (II), is carried out by using an aliphatic mercapto compound represented by the following general formula (I) and ethylene sulfide. And reacting in the presence of a base catalyst.
【００１８】[0018]
【化８】 Embedded image
【００１９】[0019]
【化９】 Embedded image
【００２０】このような本発明の製造方法において、エ
チレンスルフィドは、通常、一般式（Ｉ）で示される脂
肪族メルカプト化合物に対して１／２倍モル以下用いら
れる。また、塩基触媒としては、脂肪族アミンが好まし
く用いられる。In such a production method of the present invention, ethylene sulfide is usually used in an amount of 1/2 times or less the molar amount of the aliphatic mercapto compound represented by the general formula (I). An aliphatic amine is preferably used as the base catalyst.
【００２１】[0021]
【発明の実施の態様】本発明の製造方法は、下記の一般
式（ＩＩ）で示される、水酸基を有する脂肪族メルカプ
ト化合物の製造方法である。BEST MODE FOR CARRYING OUT THE INVENTION The production method of the present invention is a production method of an aliphatic mercapto compound having a hydroxyl group represented by the following general formula (II).
【００２２】[0022]
【化１０】 Embedded image
【００２３】このような脂肪族メルカプト化合物は、例
えば、加硫剤、架橋剤、エポキシ樹脂硬化剤、重合調整
剤、酸化防止剤などの広範囲な分野において有用性を有
している。Such aliphatic mercapto compounds have utility in a wide range of fields such as vulcanizing agents, cross-linking agents, epoxy resin curing agents, polymerization regulators and antioxidants.
【００２４】本発明の方法により上述の脂肪族メルカプ
ト化合物を製造する場合は、下記の一般式（Ｉ）で示さ
れる脂肪族メルカプト化合物とエチレンスルフィドとを
塩基触媒の存在下で反応させる。When the above-mentioned aliphatic mercapto compound is produced by the method of the present invention, the aliphatic mercapto compound represented by the following general formula (I) is reacted with ethylene sulfide in the presence of a base catalyst.
【００２５】[0025]
【化１１】 Embedded image
【００２６】このような一般式（Ｉ）で示される脂肪族
メルカプト化合物のうち、ｎが２の化合物は、市販のも
のを用いることができる。具体的には、関東化学株式会
社製の２−メルカプトエタノールなどを用いることがで
きる。Among the aliphatic mercapto compounds represented by the general formula (I), the compound in which n is 2 may be a commercially available one. Specifically, 2-mercaptoethanol manufactured by Kanto Chemical Co., Inc. can be used.
【００２７】塩基触媒としては、無機系の塩基触媒また
は有機系の塩基触媒のいずれが用いられてもよい。無機
系の塩基触媒としては、水酸化ナトリウムや水酸化カリ
ウムなどの水酸化アルカリ金属類、炭酸ナトリウムや炭
酸カリウムなどの炭酸アルカリ金属類が例示できる。一
方、有機系の塩基触媒としては、トリエチルアミン、ｎ
−ブチルアミンなどの脂肪族アミンを例示することがで
きる。なお、塩基触媒としては、分離・回収が容易であ
る点で脂肪族アミンを用いるのが好ましい。As the base catalyst, either an inorganic base catalyst or an organic base catalyst may be used. Examples of the inorganic base catalyst include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and alkali metal carbonates such as sodium carbonate and potassium carbonate. On the other hand, as the organic base catalyst, triethylamine, n
Examples thereof include aliphatic amines such as butylamine. As the base catalyst, it is preferable to use an aliphatic amine because it is easy to separate and collect.
【００２８】本発明では、一般式（Ｉ）で示される脂肪
族メルカプト化合物に対してエチレンスルフィドを１／
２倍モル以下反応させるのが好ましく、１／２〜１／２
０倍モル、さらに１／３〜１／１０倍モル反応させるの
がより好ましい。エチレンスルフィドの使用量が１／２
倍モルより多い場合は、エチレンスルフィドが自己重合
したり、付加反応の選択性が低下するために、目的とす
る脂肪族メルカプト化合物の収率が低下するおそれがあ
る。一方、エチレンスルフィドの使用量が１／２０倍モ
ルより少ない場合は、反応性が低下し、同様に目的とす
る脂肪族メルカプト化合物の収率が低下する。In the present invention, ethylene sulfide is added to the aliphatic mercapto compound represented by the general formula (I) in an amount of 1 /
It is preferable to carry out the reaction in an amount of 2 times or less,
It is more preferable to carry out a 0-fold molar reaction, and further a 1/3 to 1 / 10-fold molar reaction. 1/2 the amount of ethylene sulfide used
If the amount is more than twice, the yield of the target aliphatic mercapto compound may decrease because ethylene sulfide self-polymerizes or the selectivity of the addition reaction decreases. On the other hand, when the amount of ethylene sulfide used is less than 1/20 times the molar amount, the reactivity lowers and the yield of the desired aliphatic mercapto compound also lowers.
【００２９】また、塩基触媒の使用量は、使用するエチ
レンスルフィドのモル数の０．０１〜１倍モルに設定す
るのが好ましい。塩基触媒の使用量がこの範囲よりも少
ない場合は、反応速度が遅くなる。逆に、この範囲より
も多い場合は、使用量に見合う経済的な効果が得られな
い。The amount of the base catalyst used is preferably set to 0.01 to 1 times the molar number of ethylene sulfide used. When the amount of the base catalyst used is less than this range, the reaction rate becomes slow. On the contrary, if the amount is larger than this range, the economical effect corresponding to the amount used cannot be obtained.
【００３０】一般式（Ｉ）で示される脂肪族メルカプト
化合物とエチレンスルフィドとを反応させる際には、反
応溶媒を用いることができる。反応溶媒としては、本発
明で反応原料として用いるものと同様の脂肪族メルカプ
ト化合物やベンゼン，トルエン，キシレンなどの芳香族
炭化水素溶媒などを用いることができる。このような反
応溶媒のうち、経済性の点で原料である脂肪族メルカプ
ト化合物を反応溶媒として用いるのが特に好ましい。When the aliphatic mercapto compound represented by the general formula (I) is reacted with ethylene sulfide, a reaction solvent can be used. As the reaction solvent, the same aliphatic mercapto compounds as those used as the reaction raw material in the present invention, aromatic hydrocarbon solvents such as benzene, toluene, and xylene can be used. Among such reaction solvents, it is particularly preferable to use the aliphatic mercapto compound as a raw material as a reaction solvent from the viewpoint of economy.
【００３１】一般式（Ｉ）で示される脂肪族メルカプト
化合物とエチレンスルフィドとを反応させる際には、前
者に対して後者を滴下する。この際の反応温度は、通
常、−５０〜１００℃に設定するのが好ましく、０〜６
０℃に設定するのがより好ましい。反応温度が１００℃
を超える場合は、副反応が発生しやすくなり、目的とす
る脂肪族メルカプト化合物の収率が低下するおそれがあ
る。逆に、反応温度が−５０℃未満の場合は、反応速度
が遅くなり過ぎ、実用的ではない。When the aliphatic mercapto compound represented by the general formula (I) is reacted with ethylene sulfide, the latter is added dropwise to the former. The reaction temperature at this time is usually preferably set to -50 to 100 ° C, and 0 to 6
It is more preferable to set it to 0 ° C. Reaction temperature is 100 ℃
If it exceeds, side reactions are likely to occur and the yield of the target aliphatic mercapto compound may be reduced. On the contrary, when the reaction temperature is less than -50 ° C, the reaction rate becomes too slow, which is not practical.
【００３２】上述の反応は、常圧、すなわち大気圧で進
行させることができるが、加圧下で進行させることもで
きる。加圧下で反応を行う場合、圧力範囲は１〜１５気
圧に設定するのが好ましく、１〜１０気圧に設定するの
がより好ましい。The above reaction can be carried out at normal pressure, that is, atmospheric pressure, but it can also be carried out under pressure. When the reaction is carried out under pressure, the pressure range is preferably set to 1 to 15 atmospheres, more preferably 1 to 10 atmospheres.
【００３３】反応の進行は、高速液体クロマトグラフィ
ーにより確認することができる。反応の完結に要する時
間は、反応温度により異なるが、通常、１〜２０時間で
ある。The progress of the reaction can be confirmed by high performance liquid chromatography. The time required for completion of the reaction varies depending on the reaction temperature, but is usually 1 to 20 hours.
【００３４】反応終了後の反応液には、原料である一般
式（Ｉ）で示される脂肪族メルカプト化合物、生成物で
ある一般式（ＩＩ）で示される脂肪族メルカプト化合物
および塩基触媒などが含まれる。生成物である一般式
（ＩＩ）で示される脂肪族メルカプト化合物は、この反
応液を濃縮して蒸留すると、容易に取得することができ
る。因みに、収率は、通常、使用したエチレンスルフィ
ドに対して８５〜９５％程度である。The reaction liquid after completion of the reaction contains an aliphatic mercapto compound represented by the general formula (I) as a raw material, an aliphatic mercapto compound represented by the general formula (II) as a product, and a base catalyst. Be done. The product, the aliphatic mercapto compound represented by the general formula (II), can be easily obtained by concentrating and distilling the reaction solution. Incidentally, the yield is usually about 85 to 95% based on the ethylene sulfide used.
【００３５】なお、原料である一般式（Ｉ）で示される
脂肪族メルカプト化合物は、生成物である一般式（Ｉ
Ｉ）で示される脂肪族メルカプト化合物と分離された後
に反応原料として繰り返し用いることができる。このよ
うにすれば、目的とする一般式（ＩＩ）で示される脂肪
族メルカプト化合物は、より高収率で得られることにな
る。The aliphatic mercapto compound represented by the general formula (I) as a raw material is a product of the general formula (I).
It can be repeatedly used as a reaction raw material after being separated from the aliphatic mercapto compound represented by I). By doing so, the desired aliphatic mercapto compound represented by the general formula (II) can be obtained in a higher yield.
【００３６】参考として、一般式（ＩＩ）中のｎが２の
脂肪族メルカプト化合物を製造する場合の反応式を下記
に示す。As a reference, the reaction formula in the case of producing an aliphatic mercapto compound in which n in the general formula (II) is 2 is shown below.
【００３７】[0037]
【化１２】 Embedded image
【００３８】なお、一般式（ＩＩ）中のｎが３の脂肪族
メルカプト化合物は、上記反応式により得られた一般式
（ＩＩ）中のｎが２の脂肪族メルカプト化合物を原料と
し、これにエチレンスルフィドを反応させると製造する
ことができる。また、一般式（ＩＩ）中のｎが４または
５の脂肪族メルカプト化合物も、同様に一般式（ＩＩ）
中のｎが１つ少ない脂肪族メルカプト化合物を原料とし
て、反応を段階的に繰り返すことにより製造することが
できる。The aliphatic mercapto compound having n of 3 in the general formula (II) is prepared by using the aliphatic mercapto compound having n of 2 in the general formula (II) as a raw material. It can be produced by reacting ethylene sulfide. Further, an aliphatic mercapto compound in which n in the general formula (II) is 4 or 5 is also represented by the general formula (II).
It can be produced by repeating the reaction stepwise by using an aliphatic mercapto compound having n smaller by 1 as a raw material.
【００３９】上述のように、本発明の製造方法では、目
的とする脂肪族メルカプト化合物を選択的にかつ高収率
で製造することができ、また、反応原料としては一般式
（Ｉ）で示される脂肪族メルカプト化合物以外にエチレ
ンスルフィドを用いるだけでよいので、目的とする脂肪
族メルカプト化合物を効率的に製造することができる。As described above, according to the production method of the present invention, the desired aliphatic mercapto compound can be produced selectively and in high yield, and the reaction raw material is represented by the general formula (I). Since it is only necessary to use ethylene sulfide in addition to the aliphatic mercapto compound described above, the desired aliphatic mercapto compound can be efficiently produced.
【００４０】[0040]
【実施例】以下、実施例により本発明をさらに詳しく説
明するが、本発明はこれらの実施例により何等限定され
るものではない。実施例１ 撹拌機、温度計および冷却管を備えた容量が３リットル
の四つ口フラスコを用意し、これに窒素雰囲気下で２−
メルカプトエタノール（一般式（Ｉ）中のｎが２の化合
物）７８２．５ｇ（１０モル）とトリエチルアミン３．
０ｇ（０．０３モル）とを仕込んだ。これに、反応温度
を室温から５０℃に保ちながら、２時間かけてエチレン
スルフィド１８０．９ｇ（３．０モル）を滴下した。滴
下終了後、室温で３時間撹拌し、高速液体クロマトグラ
フィーによりエチレンスルフィドの消失および１−ヒド
ロキシ−５−メルカプト−３−チアペンタン（一般式
（ＩＩ）中のｎが２の化合物）の生成を確認した。な
お、一般式（ＩＩ）中のｎが３以上の化合物の生成は認
められなかった。The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Example 1 A three-liter four-necked flask equipped with a stirrer, a thermometer, and a cooling tube was prepared, and the flask was charged with 2-
782.5 g (10 mol) of mercaptoethanol (a compound of which n is 2 in the general formula (I)) and triethylamine
0 g (0.03 mol) was charged. While maintaining the reaction temperature from room temperature to 50 ° C., 180.9 g (3.0 mol) of ethylene sulfide was added dropwise over 2 hours. After completion of dropping, the mixture was stirred at room temperature for 3 hours, and disappearance of ethylene sulfide and formation of 1-hydroxy-5-mercapto-3-thiapentane (a compound of which n is 2 in the general formula (II)) were confirmed by high performance liquid chromatography. did. In addition, formation of a compound in which n in the general formula (II) was 3 or more was not observed.
【００４１】次に、反応液を加熱濃縮し、原料である２
−メルカプトエタノールを留去した。その後、濃縮液を
５ｔｏｒｒの減圧下、１３１〜１４０℃で蒸留したとこ
ろ、無色透明液体の１−ヒドロキシ−５−メルカプト−
３−チアペンタンが３８９．９ｇ得られた。収率は、エ
チレンスルフィドに対して９４％であった。Next, the reaction solution was heated and concentrated to obtain the raw material 2
-The mercaptoethanol was distilled off. Then, the concentrated solution was distilled at 131 to 140 ° C. under a reduced pressure of 5 torr to give 1-hydroxy-5-mercapto-colorless transparent liquid.
389.9 g of 3-thiapentane was obtained. The yield was 94% based on ethylene sulfide.
【００４２】実施例２ 撹拌機、温度計および冷却管を備えた容量が０．５リッ
トルの四つ口フラスコを用意し、これに実施例１で得ら
れた１−ヒドロキシ−５−メルカプト−３−チアペンタ
ン（一般式（Ｉ）中のｎが３の化合物）１３８ｇ（１．
０モル）とトリエチルアミン１．０ｇ（０．０１モル）
とを窒素雰囲気下で仕込んだ。これに、反応温度を室温
から５０℃に保ちながら、２時間かけてエチレンスルフ
ィド９．０ｇ（０．１５モル）を滴下し、その後室温で
３時間撹拌した。 Example 2 A four-necked flask having a capacity of 0.5 liter equipped with a stirrer, a thermometer and a cooling tube was prepared, and the 1-hydroxy-5-mercapto-3 obtained in Example 1 was placed therein. -138 g (1. thiapentane (a compound in which n in the general formula (I) is 3))
0 mol) and triethylamine 1.0 g (0.01 mol)
And were prepared under a nitrogen atmosphere. While maintaining the reaction temperature from room temperature to 50 ° C., 9.0 g (0.15 mol) of ethylene sulfide was added dropwise over 2 hours, and then stirred at room temperature for 3 hours.
【００４３】次に、反応液を減圧下で濃縮し、得られた
濃縮液を５ｔｏｒｒの減圧下、１４０〜１６０℃で蒸留
したところ、無色透明液体の１−ヒドロキシ−８−メル
カプト−３，６−ジチアオクタン（一般式（ＩＩ）中の
ｎが３の化合物）が２６．８ｇ得られた。収率は、エチ
レンスルフィドに対して９０％であった。Next, the reaction solution was concentrated under reduced pressure, and the resulting concentrated solution was distilled under reduced pressure of 5 torr at 140 to 160 ° C. to obtain 1-hydroxy-8-mercapto-3,6 as a colorless transparent liquid. 26.8 g of dithiaoctane (a compound in which n in the general formula (II) is 3) was obtained. The yield was 90% based on ethylene sulfide.
【００４４】実施例３ 撹拌機、温度計および冷却管を備えた容量が０．５リッ
トルの四つ口フラスコを用意し、これに実施例２で得ら
れた１−ヒドロキシ−８−メルカプト−３，６−ジチア
オクタン（一般式（Ｉ）中のｎが４の化合物）１６８ｇ
（１．０モル）とトリエチルアミン１．０ｇ（０．０１
モル）とを窒素雰囲気下で仕込んだ。これに、反応温度
を室温から５０℃に保ちながら、２時間かけてエチレン
スルフィド９．０ｇ（０．１５モル）を滴下し、その後
室温で３時間撹拌した。 Example 3 A four-necked flask having a volume of 0.5 liter equipped with a stirrer, a thermometer and a cooling tube was prepared, and the 1-hydroxy-8-mercapto-3 obtained in Example 2 was prepared therein. 168 g of 6, -dithiaoctane (a compound in which n in the general formula (I) is 4)
(1.0 mol) and triethylamine 1.0 g (0.01
Mol) and were charged under a nitrogen atmosphere. While maintaining the reaction temperature from room temperature to 50 ° C., 9.0 g (0.15 mol) of ethylene sulfide was added dropwise over 2 hours, and then stirred at room temperature for 3 hours.
【００４５】次に、反応液を減圧下で濃縮し、得られた
濃縮液を５ｔｏｒｒの減圧下、１６０〜１８０℃で蒸留
したところ、無色透明液体の１−ヒドロキシ−１１−メ
ルカプト−３，６，９−トリチアウンデカン（一般式
（ＩＩ）中のｎが４の化合物）が３４．１ｇ得られた。
収率は、エチレンスルフィドに対して８８％であった。Next, the reaction solution was concentrated under reduced pressure, and the obtained concentrated solution was distilled under reduced pressure of 5 torr at 160 to 180 ° C. to obtain 1-hydroxy-11-mercapto-3,6 as a colorless transparent liquid. , 9-Trithiaundecane (a compound in which n is 4 in the general formula (II)) was obtained in an amount of 34.1 g.
The yield was 88% based on ethylene sulfide.
【００４６】実施例４ 撹拌機、温度計および冷却管を備えた容量が０．５リッ
トルの四つ口フラスコを用意し、これに実施例３で得ら
れた１−ヒドロキシ−１１−メルカプト−３，６，９−
トリチアウンデカン（一般式（Ｉ）中のｎが５の化合
物）２２８ｇ（１．０モル）とトリエチルアミン１．０
ｇ（０．０１モル）とを窒素雰囲気下で仕込んだ。これ
に、反応温度を室温から５０℃に保ちながら、２時間か
けてエチレンスルフィド９．０ｇ（０．１５モル）を滴
下し、その後室温で３時間撹拌した。 Example 4 A four-necked flask having a capacity of 0.5 liter equipped with a stirrer, a thermometer and a cooling tube was prepared, and the 1-hydroxy-11-mercapto-3 obtained in Example 3 was placed therein. , 6, 9-
228 g (1.0 mol) of trithiaundecane (a compound in which n is 5 in the general formula (I)) and 1.0 of triethylamine
and g (0.01 mol) were charged under a nitrogen atmosphere. While maintaining the reaction temperature from room temperature to 50 ° C., 9.0 g (0.15 mol) of ethylene sulfide was added dropwise over 2 hours, and then stirred at room temperature for 3 hours.
【００４７】次に、トリエチルアミンおよび未反応の１
−ヒドロキシ−１１−メルカプト−３，６，９−トリチ
アウンデカンを５ｔｏｒｒの減圧下、１６０〜１８０℃
で留去したところ、無色透明液体の１−ヒドロキシ−１
４−メルカプト−３，６，９，１２−テトラチアテトラ
デカン（一般式（ＩＩ）中のｎが５の化合物）が４３．
５ｇ得られた。収率は、エチレンスルフィドに対して９
１％であった。Next, triethylamine and unreacted 1
-Hydroxy-11-mercapto-3,6,9-trithiaundecane under reduced pressure of 5 torr at 160 to 180 ° C.
When distilled off, 1-hydroxy-1 was obtained as a colorless transparent liquid.
4-mercapto-3,6,9,12-tetrathiatetradecane (a compound in which n in the general formula (II) is 5) is 43.
5 g was obtained. The yield is 9 based on ethylene sulfide.
1%.
【００４８】実施例５ 実施例１において反応液を加熱濃縮して得られた留分
を、１５５〜１６５℃で蒸留し、原料として用いた２−
メルカプトエタノール５２５ｇを回収した。 Example 5 The fraction obtained by heating and concentrating the reaction solution in Example 1 was distilled at 155 to 165 ° C. and used as a raw material.
525 g of mercaptoethanol was recovered.
【００４９】この２−メルカプトエタノール５２２ｇ
（６．７モル）およびトリエチルアミン２．０ｇ（０．
０２モル）を、撹拌機、温度計および冷却管を備えた容
量が１リットルの四つ口フラスコに窒素雰囲気下で仕込
んだ。これに、反応温度を室温から５０℃に保ちなが
ら、２時間かけてエチレンスルフィド１２０．４ｇ
（２．０モル）を滴下した。滴下終了後、室温で３時間
撹拌し、高速液体クロマトグラフィーによりエチレンス
ルフィドの消失および１−ヒドロキシ−５−メルカプト
−３−チアペンタン（一般式（ＩＩ）中のｎが２の化合
物）の生成を確認した。522 g of this 2-mercaptoethanol
(6.7 mol) and 2.0 g of triethylamine (0.
(02 mol) was charged to a four-necked flask having a capacity of 1 liter equipped with a stirrer, a thermometer and a condenser under a nitrogen atmosphere. While maintaining the reaction temperature from room temperature to 50 ° C, 120.4 g of ethylene sulfide was added over 2 hours.
(2.0 mol) was added dropwise. After completion of dropping, the mixture was stirred at room temperature for 3 hours, and disappearance of ethylene sulfide and formation of 1-hydroxy-5-mercapto-3-thiapentane (a compound of which n in the general formula (II) is 2) were confirmed by high performance liquid chromatography. did.
【００５０】次に、反応液を加熱濃縮し、得られた濃縮
液を５ｔｏｒｒの減圧下、１３１〜１４０℃で蒸留した
ところ、無色透明液体の１−ヒドロキシ−５−メルカプ
ト−３−チアペンタンが２５１．２ｇ得られた。収率
は、エチレンスルフィドに対して９１％であった。Then, the reaction solution was concentrated by heating, and the obtained concentrated solution was distilled at 131 to 140 ° C. under a reduced pressure of 5 torr to give 251 of 1-hydroxy-5-mercapto-3-thiapentane as a colorless transparent liquid. 0.2 g was obtained. The yield was 91% based on ethylene sulfide.
【００５１】続いて、上述の反応液を加熱濃縮して得ら
れた留分を１５５〜１６５℃で蒸留し、原料として用い
た２−メルカプトエタノールを３０２ｇ回収した。そし
て、回収した２−メルカプトエタノール２９７．２ｇ
（３．８モル）を、撹拌機、温度計および冷却管を備え
た容量が１リットルの四つ口フラスコに窒素雰囲気下で
仕込んだ。これに、トリエチルアミン１．０ｇ（０．０
１モル）を添加し、さらに反応温度を室温から５０℃に
保ちながら、２時間かけてエチレンスルフィド６０．２
ｇ（１．０モル）を滴下した。滴下終了後、室温で３時
間撹拌し、高速液体クロマトグラフィーによりエチレン
スルフィドの消失および１−ヒドロキシ−５−メルカプ
ト−３−チアペンタンの生成を確認した。Subsequently, the fraction obtained by heating and concentrating the above reaction solution was distilled at 155 to 165 ° C., and 302 g of 2-mercaptoethanol used as a raw material was recovered. And 297.2 g of recovered 2-mercaptoethanol
(3.8 mol) was charged into a four-necked flask having a capacity of 1 liter equipped with a stirrer, a thermometer and a condenser under a nitrogen atmosphere. To this, 1.0 g of triethylamine (0.0
1 mol), and while maintaining the reaction temperature from room temperature to 50 ° C., ethylene sulfide 60.2 was added over 2 hours.
g (1.0 mol) was added dropwise. After completion of dropping, the mixture was stirred at room temperature for 3 hours, and disappearance of ethylene sulfide and production of 1-hydroxy-5-mercapto-3-thiapentane were confirmed by high performance liquid chromatography.
【００５２】次に、反応液を加熱濃縮し、得られた濃縮
液を５ｔｏｒｒの減圧下、１３１〜１４０℃で蒸留した
ところ、無色透明液体の１−ヒドロキシ−５−メルカプ
ト−３−チアペンタンが１２０．２ｇ得られた。収率
は、エチレンスルフィドに対して８７％であった。Next, the reaction solution was concentrated by heating, and the obtained concentrated solution was distilled at 131 to 140 ° C. under a reduced pressure of 5 torr to give 120 mg of 1-hydroxy-5-mercapto-3-thiapentane as a colorless transparent liquid. 0.2 g was obtained. The yield was 87% based on ethylene sulfide.
【００５３】本実施例では、上述のように原料となる２
−メルカプトエタノールを回収して繰り返し使用するこ
とにより、合計で７６１．３ｇの１−ヒドロキシ−５−
メルカプト−３−チアペンタンが得られた。この収率
は、原料である２−メルカプトエタノールに対して５
５．１％であった。In this embodiment, as the raw material, 2
-By collecting and repeatedly using mercaptoethanol, a total of 761.3 g of 1-hydroxy-5-
Mercapto-3-thiapentane was obtained. This yield is 5 with respect to 2-mercaptoethanol as a raw material.
It was 5.1%.
【００５４】比較例 撹拌機、温度計および冷却管を備えた容量が０．５リッ
トルの四つ口フラスコを用意し、これに２−メルカプト
エタノール７８．１ｇ（１．０モル）とトリエチルアミ
ン１．０ｇ（０．０１モル）とを窒素雰囲気下で仕込ん
だ。これに、反応温度を室温から５０℃に保ちながら、
２時間かけてエチレンスルフィド６０．１ｇ（１．０モ
ル）を滴下し、その後室温で３時間撹拌した。 Comparative Example A four-necked flask having a capacity of 0.5 liter, equipped with a stirrer, a thermometer and a cooling tube, was prepared, and 78.1 g (1.0 mol) of 2-mercaptoethanol and 1. 0 g (0.01 mol) was charged under a nitrogen atmosphere. While keeping the reaction temperature from room temperature to 50 ° C,
60.1 g (1.0 mol) of ethylene sulfide was added dropwise over 2 hours, and then the mixture was stirred at room temperature for 3 hours.
【００５５】次に、反応液を加熱濃縮し、得られた濃縮
液を５ｔｏｒｒの減圧下、１３１〜１４０℃で蒸留した
ところ、無色透明液体の１−ヒドロキシ−５−メルカプ
ト−３−チアペンタン（一般式（ＩＩ）中のｎが２の化
合物）が３８．７ｇ得られた。収率は、エチレンスルフ
ィドに対して２８％であった。Next, the reaction solution was concentrated by heating, and the resulting concentrated solution was distilled under reduced pressure of 5 torr at 131 to 140 ° C. to obtain 1-hydroxy-5-mercapto-3-thiapentane (general) as a colorless transparent liquid. 38.7 g of a compound in which n in the formula (II) is 2 was obtained. The yield was 28% based on ethylene sulfide.
【００５６】なお、上述の反応液をガスクロマトグラフ
ィーにより分析したところ、一般式（ＩＩ）中のｎが３
〜５の脂肪族メルカプト化合物が副生物として生成して
いることが確認できた。また、反応液をゲルパーミエー
ションクロマトグラフィーにより分析したところ、エチ
レンスルフィドの自己重合物の生成が確認された。When the above reaction solution was analyzed by gas chromatography, n in the general formula (II) was 3
It was confirmed that the aliphatic mercapto compound of ~ 5 was produced as a by-product. In addition, when the reaction solution was analyzed by gel permeation chromatography, formation of a self-polymerized product of ethylene sulfide was confirmed.
【００５７】[0057]
【発明の効果】本発明に係る脂肪族メルカプト化合物の
製造方法では、上述の一般式（Ｉ）で示される脂肪族メ
ルカプト化合物とエチレンスルフィドとを塩基触媒の存
在下で反応させているので、上述の一般式（ＩＩ）で示
される、水酸基を有する脂肪族メルカプト化合物を効率
的にかつ選択的に製造することができる。In the method for producing an aliphatic mercapto compound according to the present invention, the aliphatic mercapto compound represented by the above general formula (I) is reacted with ethylene sulfide in the presence of a base catalyst. The aliphatic mercapto compound having a hydroxyl group represented by the general formula (II) can be efficiently and selectively produced.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 鈴木 道夫 兵庫県加古郡播磨町宮西346番地の１ 住 友精化株式会社第１研究所内 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Michio Suzuki 1 346 Miyanishi, Harima-cho, Kako-gun, Hyogo Prefecture Sumitomo Seika Chemical Co., Ltd.
Claims (3)
カプト化合物とエチレンスルフィドとを塩基触媒の存在
下で反応させる工程を含む、下記の一般式（ＩＩ）で示
される、水酸基を有する脂肪族メルカプト化合物の製造
方法。 【化１】 【化２】 1. A hydroxyl group represented by the following general formula (II), which comprises a step of reacting an aliphatic mercapto compound represented by the following general formula (I) with ethylene sulfide in the presence of a base catalyst. Process for producing aliphatic mercapto compound. Embedded image Embedded image
プト化合物に対して、前記エチレンスルフィドを１／２
倍モル以下用いる、請求項１に記載の水酸基を有する脂
肪族メルカプト化合物の製造方法。2. The ethylene sulfide is added to 1/2 of the aliphatic mercapto compound represented by the general formula (I).
The method for producing an aliphatic mercapto compound having a hydroxyl group according to claim 1, which is used in an amount not more than 2 times the molar amount.
る、請求項１または２に記載の水酸基を有する脂肪族メ
ルカプト化合物の製造方法。3. The method for producing an aliphatic mercapto compound having a hydroxyl group according to claim 1, wherein an aliphatic amine is used as the base catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34783295A JP3794650B2 (en) | 1995-12-14 | 1995-12-14 | Method for producing aliphatic mercapto compound having hydroxyl group |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34783295A JP3794650B2 (en) | 1995-12-14 | 1995-12-14 | Method for producing aliphatic mercapto compound having hydroxyl group |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09165367A true JPH09165367A (en) | 1997-06-24 |
| JP3794650B2 JP3794650B2 (en) | 2006-07-05 |
Family
ID=18392912
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34783295A Expired - Fee Related JP3794650B2 (en) | 1995-12-14 | 1995-12-14 | Method for producing aliphatic mercapto compound having hydroxyl group |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3794650B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002226453A (en) * | 2001-01-30 | 2002-08-14 | Mitsui Chemicals Inc | Method for producing thiol compound and polymerizable composition containing the resultant thiol compound |
| CN107082755A (en) * | 2017-03-03 | 2017-08-22 | 河北科技大学 | A kind of preparation method of diethylamino ethanethiol impurity |
-
1995
- 1995-12-14 JP JP34783295A patent/JP3794650B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002226453A (en) * | 2001-01-30 | 2002-08-14 | Mitsui Chemicals Inc | Method for producing thiol compound and polymerizable composition containing the resultant thiol compound |
| JP4684426B2 (en) * | 2001-01-30 | 2011-05-18 | 三井化学株式会社 | Polythiol and polymerizable composition containing the polythiol |
| CN107082755A (en) * | 2017-03-03 | 2017-08-22 | 河北科技大学 | A kind of preparation method of diethylamino ethanethiol impurity |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3794650B2 (en) | 2006-07-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5702887B2 (en) | Method for preparing polysulfide | |
| US5078980A (en) | Process for the removal of isocyanic acid from a mixture of isocyanic acid and ammonia | |
| JP4596663B2 (en) | Bis (hydroxyphenylthio) fluorene compound and method for producing the same | |
| JPH09165367A (en) | Production of hydroxyl-containing aliphatic mercapto compound | |
| IE60623B1 (en) | Synthesis of perfluoroalkyl bromides | |
| US20160002373A1 (en) | Preparation of polyisobutylene-based polymer networks by thiol-ene chemistry | |
| AU703677B2 (en) | Process for the preparation of organic disulphides and polysulphides | |
| JP2002338540A (en) | Bisthiophenolfluorene compounds and method for producing the same | |
| CN110615750B (en) | Synthetic method of fluorine-containing disulfide | |
| JP3794651B2 (en) | Mercapto compound, method for producing mercapto compound, tetraol compound, and method for producing tetraol compound | |
| US3914252A (en) | Preparation of N-iodocompounds | |
| JPH1025258A (en) | Alkylation of cyclopentadiene-based compound | |
| EP0395103B1 (en) | Process for preparing perfluoroalkenyl sulfonyl fluorides | |
| CN1307165C (en) | 4-methyl-5-formylthiazole preparation method | |
| CN111808114A (en) | Compound based on cascade sulfydryl/bromomaleimide Michael addition and application thereof | |
| JP2008044896A (en) | Method for producing fluoroolefin | |
| JPH0578308A (en) | Production of 4-phenylthiobenzenethiol | |
| JPH085849B2 (en) | Method for producing tertiary aralkyl monourethane | |
| JPH0469358A (en) | Asymmetric diacetylene compound | |
| JPH04145039A (en) | Production of 4,4'-(1-phenylethylidene)bisphenol | |
| Khan et al. | Improved Preparation and Application of Poly (Ethylene Glycol) Vinyl Sulfone | |
| CN115490717A (en) | Synthetic method of N- (trimethylsilyl) morpholine | |
| CN112441991A (en) | Synthetic method of nitrogen oxide sulfur cyclopentane compound | |
| JPS6270341A (en) | Production of glycidol ester unsaturated monomer | |
| US7645798B2 (en) | N-(2-hydroxyalkanoyl)-N,N′-dialkylureas and a process for their preparation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20051101 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20051228 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20060404 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20060410 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| LAPS | Cancellation because of no payment of annual fees |