JP2008063320A - Method for producing dithiol compound - Google Patents
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本発明は、高収率で工業的に安価で簡便なジチオール化合物の新規な製造方法に関する。 The present invention relates to a novel method for producing a dithiol compound that is industrially inexpensive and simple with a high yield.
ジチオール化合物は、医薬、農薬およびゴム薬品の原料および中間体、高屈折率用プラスチックの原料モノマーとしても有用である。
従来、ジチオール化合物を製造する方法としては、以下の方法が知られている。例えば、特許文献１には１，５−ヘキサジエンと硫化水素から触媒の存在下において光照射を行なうことにより１，６−ヘキサンジチオールを得る方法が記載されている。しかし、この本方法は、高価な光照射装置を必要とする。また、反応圧力が１２から１４ｂａｒと高圧であり大掛かりな装置を必要とする。また、非特許文献１には１，５−ジブロモペンタンと水硫化ナトリウムにより１，５−ペンタンジチオールを製造する方法が記載されている。しかし、１，５−ペンタンジチオールの収率が低い。従って、工業的に安価で簡便なジチオール化合物を製造するための方法の開発が待望されている。
Conventionally, the following methods are known as methods for producing dithiol compounds. For example, Patent Document 1 describes a method of obtaining 1,6-hexanedithiol by irradiating light from 1,5-hexadiene and hydrogen sulfide in the presence of a catalyst. However, this method requires an expensive light irradiation device. Further, the reaction pressure is as high as 12 to 14 bar, and a large apparatus is required. Non-Patent Document 1 describes a method for producing 1,5-pentanedithiol using 1,5-dibromopentane and sodium hydrosulfide. However, the yield of 1,5-pentanedithiol is low. Therefore, development of a method for producing an industrially inexpensive and simple dithiol compound is awaited.
本発明は、大掛かりな装置を用いることなく高収率で、工業的に安価で簡便なジチオール化合物の製造方法を提供することを課題とする。 An object of the present invention is to provide a method for producing a dithiol compound that is high in yield, industrially inexpensive and simple without using a large-scale apparatus.
本発明者らは、前記課題を解決するため鋭意研究を行った結果、相間移動触媒を用いることにより、ジハロゲン化合物から高収率で工業的に安価で簡便にジチオール化合物を製造する方法を見出し、本発明を完成するに至った。
即ち、本発明は一般式（１）で表されるジハロゲン化合物と下記一般式（２）で表される水硫化物を相間移動触媒の存在下で反応させることを特徴とする、下記一般式（３）で表されるジチオール化合物の製造方法である。（式中、Ｘはハロゲン原子を表し、Ｙはヘテロ原子及び／又は反応に関与しない炭化水素基であり、その炭素水素基中にヘテロ原子又は環構造を含有していてもよい、Ｍはアルカリ金属を表す。）
Ｘ−ＣＨ２−Ｙ−ＣＨ２−Ｘ・・・（１）
ＭＳＨ・・・（２）
ＨＳ−ＣＨ２−Ｙ−ＣＨ２−ＳＨ・・・（３）
As a result of intensive studies to solve the above problems, the present inventors have found a method for producing a dithiol compound easily from a dihalogen compound in a high yield at an industrially low cost by using a phase transfer catalyst, The present invention has been completed.
That is, the present invention is characterized by reacting a dihalogen compound represented by the general formula (1) and a hydrosulfide represented by the following general formula (2) in the presence of a phase transfer catalyst. It is a manufacturing method of the dithiol compound represented by 3). (In the formula, X represents a halogen atom, Y is a heteroatom and / or a hydrocarbon group that does not participate in the reaction, and the carbon-hydrogen group may contain a heteroatom or a ring structure. M is an alkali. Represents metal.)
X-CH 2 -Y-CH 2 -X ··· (1)
MSH (2)
HS-CH 2 -Y-CH 2 -SH ··· (3)
本発明により、大掛かりな装置を用いることなく医薬、農薬およびゴム薬品の原料および中間体、高屈折率用プラスチックの原料モノマーとしても有用であるジチオール化合物を、高収率で、工業的に安価で簡便に製造することができる。また、安価なチオール化剤を用い、１つの工程によりジチオール化合物を得ることができ、経済的、工業的価値が極めて大きい。 According to the present invention, dithiol compounds that are useful as raw materials and intermediates for pharmaceuticals, agricultural chemicals and rubber chemicals, and as raw material monomers for plastics for high refractive index without using a large-scale apparatus can be obtained in a high yield and industrially inexpensively. It can be easily manufactured. Moreover, a dithiol compound can be obtained by one process using an inexpensive thiolating agent, and the economic and industrial value is extremely high.
本発明でいうジハロゲン化合物とは、炭素鎖の両末端にハロゲン原子を有するものをいう。ジハロゲン化合物のＸにあたるハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられ、好ましくは、塩素原子、臭素原子、特に好ましくは塩素原子である。 The dihalogen compound as used in the field of this invention means what has a halogen atom in both ends of a carbon chain. Examples of the halogen atom corresponding to X of the dihalogen compound include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a chlorine atom and a bromine atom, particularly preferably a chlorine atom.
一般式（１）で表されるジハロゲン化合物のＹとしては、酸素原子、硫黄原子、窒素原子などのヘテロ原子及び／又は脂肪族（脂環式を含む）又は芳香族（芳香脂肪族を含む）の炭化水素基が挙げられる。炭化水素基は、反応に関与しない置換基、例えばアルキル基等を有していてもよく、その炭素鎖中にヘテロ原子（硫黄原子、酸素原子、窒素原子）や環構造（脂環構造、芳香環構造、複素環構造等）などの反応に関与しない原子又は原子団を含有していてもよい。 Y of the dihalogen compound represented by the general formula (1) is a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom and / or aliphatic (including alicyclic) or aromatic (including araliphatic). These hydrocarbon groups are mentioned. The hydrocarbon group may have a substituent that does not participate in the reaction, such as an alkyl group, and has a heteroatom (sulfur atom, oxygen atom, nitrogen atom) or ring structure (alicyclic structure, aromatic group) in its carbon chain. An atom or atomic group that does not participate in the reaction such as a ring structure or a heterocyclic structure may be contained.
前記炭化水素基としては、具体的には、例えば、メチレン基、エチレン基、プロパン−１，３−ジイル基、ブタン−１，４−ジイル基、ペンタン−１，５−ジイル基、ヘキサン−１，６−ジイル基、ヘプタン−１，７−ジイル基、オクタン−１，８−ジイル基、ノナン−１，９−ジイル基、デカン−１，１０−ジイル基、ウンデカン−１，１１−ジイル基、ドデカン−１，１２−ジイル基、シクロヘキサン−１，１−ジイル基、シクロヘキサン−１，２−ジイル基、シクロヘキサン−１，４−ジイル基等のアルキレン基や、２−メチルプロパン−１，３−ジイル基、３−メチルペンタン−１，５−ジイル基、ジメチルメチレン基、２，２−ジメチルプロパン−１，３−ジイル基等の置換基を有するアルキレン基や、シクロへキサン−１，４−ジメチル基（位置異性体を含む）等の炭素鎖中に環構造を有するアルキレン基や、２−チアプロパン−１，３−ジイル基、３−チアペンタン−１，５−ジイル基、４−チアヘプタン−１，７−ジイル基、１，３−ジチアプロパン−１，３−ジイル基、２，４−ジチアペンタン−１，５−ジイル基、２，３−ジチアブタン−１，４−ジイル基、３，４−ジチアヘキサン−１，６−ジイル基、３，５−ジチアヘプタン−１，７−ジイル基、２，５−ジチアヘキサン−１，６−ジイル基、３，６−ジチアオクタン−１，８−ジイル基、４，５−ジチアオクタン−１，８−ジイル基、４，６−ジチアノナン−１，９−ジイル基、４，７−ジチアデカン−１，１０−ジイル基、３，７−ジチアノナン−１，９−ジイル基、４，８−ジチアウンデカン−１，１１−ジイル基、２−オキサプロパン−１，３−ジイル基、３−オキサペンタン−１，５−ジイル基、４−オキサヘプタン−１，７−ジイル基、１，３−ジオキサプロパン−１，３−ジイル基、２，４−ジオキサペンタン−１，５−ジイル基、３，５−ジオキサヘプタン−１，７−ジイル基、２，５−ジオキサヘキサン−１，６−ジイル基、３，６−ジオキサオクタン−１，８−ジイル基、４，６−ジオキサノナン−１，９−ジイル基、４，７−ジオキサデカン−１，１０−ジイル基、３，７−ジオキサノナン−１，９−ジイル基、４，８−ジオキサウンデカン−１，１１−ジイル基、１，４−ジチアン−２，５−ジイル基、１，４−ジオキサン−２，５−ジイル基等の炭素鎖中にヘテロ原子を有するアルキレン基や、１，４−ジチアン−２，５−ジメチル基（前記シクロへキサン−１，４−ジメチル基に対応する；位置異性体を含む）、１，４−ジオキサン−２，５−ジメチル基（前記シクロへキサン−１，４−ジメチル基に対応する；位置異性体を含む）等の炭素鎖中にヘテロ原子及び環構造を有するアルキレン基や、１，２−フェニレン基、１，３−フェニレン基、１，４−フェニレン基、２，５−トリレン基、３，４−トリレン基、１，２−キシリレン基、１，３−キシリレン基、１，４−キシリレン基、１，４−ナフチレン基、４，４‘−ビフェニレン基等のアリーレン基や、ピリジン−２，５−ジイル基、３，４−チエニレン基、１，３，４−チアジアゾール−２，５−ジイル基、１，３，４−チアジアゾール−２，５−ジメチル基等の炭素鎖中にヘテロ原子を有するアリーレン基などが挙げられる。 Specific examples of the hydrocarbon group include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and hexane-1. , 6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group , Alkylene groups such as dodecane-1,12-diyl group, cyclohexane-1,1-diyl group, cyclohexane-1,2-diyl group, cyclohexane-1,4-diyl group, and 2-methylpropane-1,3 -An alkylene group having a substituent such as a diyl group, 3-methylpentane-1,5-diyl group, dimethylmethylene group, 2,2-dimethylpropane-1,3-diyl group, or cyclohexane-1,4 − An alkylene group having a ring structure in a carbon chain such as a methyl group (including positional isomers), 2-thiapropane-1,3-diyl group, 3-thiapentane-1,5-diyl group, 4-thiaheptane-1 , 7-diyl group, 1,3-dithiapropane-1,3-diyl group, 2,4-dithiapentane-1,5-diyl group, 2,3-dithiabutane-1,4-diyl group, 3,4-dithiahexane -1,6-diyl group, 3,5-dithiaheptane-1,7-diyl group, 2,5-dithiahexane-1,6-diyl group, 3,6-dithiaoctane-1,8-diyl group, 4,5 -Dithiaoctane-1,8-diyl group, 4,6-dithianonane-1,9-diyl group, 4,7-dithiadecane-1,10-diyl group, 3,7-dithianonane-1,9-diyl group, 4 , 8-dithiaundecane-1 11-diyl group, 2-oxapropane-1,3-diyl group, 3-oxapentane-1,5-diyl group, 4-oxaheptane-1,7-diyl group, 1,3-dioxapropane-1 , 3-diyl group, 2,4-dioxapentane-1,5-diyl group, 3,5-dioxaheptane-1,7-diyl group, 2,5-dioxahexane-1,6-diyl group 3,6-dioxaoctane-1,8-diyl group, 4,6-dioxanonane-1,9-diyl group, 4,7-dioxadecane-1,10-diyl group, 3,7-dioxanonane-1, In carbon chain such as 9-diyl group, 4,8-dioxaundecane-1,11-diyl group, 1,4-dithian-2,5-diyl group, 1,4-dioxane-2,5-diyl group An alkylene group having a heteroatom or 1,4-dithian-2 , 5-dimethyl group (corresponding to the cyclohexane-1,4-dimethyl group; including regioisomers), 1,4-dioxane-2,5-dimethyl group (the cyclohexane-1,4- An alkylene group having a heteroatom and a ring structure in a carbon chain such as a dimethyl group (including positional isomers), a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group, 2,5-tolylene group, 3,4-tolylene group, 1,2-xylylene group, 1,3-xylylene group, 1,4-xylylene group, 1,4-naphthylene group, 4,4'-biphenylene group, etc. Arylene group, pyridine-2,5-diyl group, 3,4-thienylene group, 1,3,4-thiadiazole-2,5-diyl group, 1,3,4-thiadiazole-2,5-dimethyl group Having a heteroatom in the carbon chain such as Such as arylene group, and the like.
また、前記炭化水素基中の炭素数は１〜２０、好ましくは３〜１０である。本発明において用いられるジハロゲン化合物の具体例としては、１，６−ジクロロヘキサン、１，５−ジクロロペンタン、１，５−ジクロロ−３−メチルペンタン、１，４−ビス（クロロメチル）シクロヘキサン、１,１０−ジクロロデカン、１,１２−ジブロモドデカン又は１，２−ビス（２−クロロエトキシ）エタンなどが挙げられる。 Moreover, carbon number in the said hydrocarbon group is 1-20, Preferably it is 3-10. Specific examples of the dihalogen compound used in the present invention include 1,6-dichlorohexane, 1,5-dichloropentane, 1,5-dichloro-3-methylpentane, 1,4-bis (chloromethyl) cyclohexane, , 10-dichlorodecane, 1,12-dibromododecane, 1,2-bis (2-chloroethoxy) ethane and the like.
一般式（２）で表される水硫化物のＭにあたるアルカリ金属としては、カリウム、ナトリウムなどが挙げられる。 Examples of the alkali metal corresponding to M of the hydrosulfide represented by the general formula (2) include potassium and sodium.
本発明で用いられる相間移動触媒としては、１５−クラウン５エーテル、１８−クラウン６−エーテルなどの環状ポリエーテル類、ポリエチレングリコールジアルキルエーテルなどの非環状ポリエーテル類、テトラブチルホスホニウムクロリド、テトラフェニルホスホニウムクロリド、テトラフェニルホスホニウムブロミドなどのホスホニウム塩、クリプタンド〔２．２．１〕、クリプタンド〔２．２．２〕等の環状ポリエーテルアミン類、テトラメチルアンモニウムクロリド、テトラエチルアンモニウムクロリド、テトラブチルアンモニウムブロミド、テトラブチルアンモニウムヨーダイド、ベンジルトリメチルアンモニウムクロリド、アリコート３３６などの四級アンモニウム塩などが挙げられる。この中で、四級アンモニウム塩が好ましく用いられる。 Examples of the phase transfer catalyst used in the present invention include cyclic polyethers such as 15-crown 5 ether and 18-crown 6-ether, acyclic polyethers such as polyethylene glycol dialkyl ether, tetrabutylphosphonium chloride, and tetraphenylphosphonium. Phosphonium salts such as chloride and tetraphenylphosphonium bromide, cyclic polyetheramines such as cryptand [2.2.1] and cryptand [2.2.2], tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium bromide, And quaternary ammonium salts such as tetrabutylammonium iodide, benzyltrimethylammonium chloride, and aliquot 336. Of these, quaternary ammonium salts are preferably used.
本発明において用いられる水硫化物の使用量は、ジハロゲン化合物１モルに対して１．５モルから１０モル、更には２モルから５モルであることが好ましい。また、相間移動触媒の使用量は、ジハロゲン化合物１モルに対して０．００１モルから０．５モル、更には０．０１モルから０．２モルが好ましい。 The amount of hydrosulfide used in the present invention is preferably 1.5 to 10 mol, more preferably 2 to 5 mol, per 1 mol of the dihalogen compound. The amount of the phase transfer catalyst used is preferably from 0.001 to 0.5 mol, more preferably from 0.01 to 0.2 mol, based on 1 mol of the dihalogen compound.
ジハロゲン化合物と水硫化物の混合方法に特に制限はない。すなわち、ジハロゲン化合物に水硫化物を少量ずつ加えることもできるし、水硫化物にジハロゲン化合物を少量ずつ加えることも可能である。また、ジハロゲン化合物と水硫化物は、溶媒に溶解したものを加えることもできるし、溶媒に溶解せず、そのまま加えることもできる。 There are no particular restrictions on the method of mixing the dihalogen compound and hydrosulfide. That is, the hydrosulfide can be added to the dihalide compound little by little, or the dihalogen compound can be added to the hydrosulfide little by little. In addition, the dihalogen compound and hydrosulfide can be added in a form dissolved in a solvent, or can be added as it is without being dissolved in the solvent.
本発明における反応温度は、０℃〜１２０℃、更には１０℃〜１００℃の範囲が好ましい。また、反応は大気圧下において行なうことができる。本発明においては、反応の進行を妨げない程度において水を用いることができる。水の使用量は、ジハロゲン化合物１重量部に対して１〜１０重量部程度である。また、反応系を希釈するために有機溶媒を適宜用いることができる。有機溶媒としては、アルコール（メタノール、エタノール、ブタノール等）、脂肪族炭化水素（ヘキサン、ヘプタン等）、芳香族炭化水素（トルエン、キシレン等）、脂肪族エーテル（ジエチルエーテル、ジイソプロピルエーテル、テトラヒドロフラン等）、脂肪族アミド（Ｎ，Ｎ−ジメチルホルムアミド、Ｎ−メチルピロリドン等）、脂肪族スルホキシド（ジメチルスルホキシド等）などが挙げられる。有機溶媒は、単独でまたは２種類以上を混合して用いることができる。 The reaction temperature in the present invention is preferably in the range of 0 ° C to 120 ° C, more preferably 10 ° C to 100 ° C. The reaction can be carried out under atmospheric pressure. In the present invention, water can be used as long as it does not hinder the progress of the reaction. The amount of water used is about 1 to 10 parts by weight per 1 part by weight of the dihalogen compound. In addition, an organic solvent can be appropriately used to dilute the reaction system. Organic solvents include alcohol (methanol, ethanol, butanol, etc.), aliphatic hydrocarbons (hexane, heptane, etc.), aromatic hydrocarbons (toluene, xylene, etc.), aliphatic ethers (diethyl ether, diisopropyl ether, tetrahydrofuran, etc.) , Aliphatic amides (N, N-dimethylformamide, N-methylpyrrolidone, etc.), aliphatic sulfoxides (dimethylsulfoxide, etc.) and the like. An organic solvent can be used individually or in mixture of 2 or more types.
反応によって得られたジチオール化合物は、反応後、例えば、洗浄、中和、抽出、濃縮、ろ過等の後処理を行う。更に、蒸留、カラムクロマトグラフィー、再結晶等により精製されたジチオール化合物を得ることができる。本発明においては蒸留精製が好ましく用いられる。 The dithiol compound obtained by the reaction is subjected to post-treatment such as washing, neutralization, extraction, concentration, and filtration after the reaction. Furthermore, a dithiol compound purified by distillation, column chromatography, recrystallization or the like can be obtained. In the present invention, distillation purification is preferably used.
以下、実施例を挙げて本発明を具体的に説明するが、本発明は、これら実施例に制限されるものではない。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not restrict | limited to these Examples.
［実施例１］
１，６−ジクロロヘキサン（１８６ｇ，１．２ｍｏｌ）に水（１００ｍｌ）、テトラブチルアンモニウムブロミド（７．７４ｇ，０．０２４ｍｏｌ）を加えた。窒素雰囲気下、混合液を５０℃に加熱し、４４重量％水硫化カリウム（ＫＳＨ）水溶液（５９０ｇ，３．６ｍｏｌ）を３時間かけて滴下した。反応混合液を５０℃でさらに３時間攪拌混合した。
反応液を室温（２５℃）まで冷却した。冷却した後の反応液を分液し、下層（水層）を除去した。油層（上層）に、２Ｍ−ＨＣｌ水溶液（６１．８ｇ）に食塩（１０．５ｇ）を溶解したものを加えて、室温で１５分間攪拌した。混合液を分液し、下層（水層）を除去することにより、粗１，６−ヘキサンジチオール（１７７．４ｇ）を得た。高速液体クロマトグラフィー（ＨＰＬＣ）（株式会社島津製作所製ＬＣ−１０）で定量を行った結果、１，６−ヘキサンジチオールの純度は、８５％であり、反応収率は８３％（１，６−ジクロロヘキサン基準）であった。次いで、減圧蒸留を行い、１，６−ヘキサンジチオールを１４５ｇで得た（ｂｐ.１２２−１２３℃／２０ｔｏｒｒ）。ＨＰＬＣで定量を行った結果、１，６−ヘキサンジチオールの純度は９９．４％であり、蒸留単離収率は８０％（１，６−ジクロロヘキサン基準）であった。
[Example 1]
Water (100 ml) and tetrabutylammonium bromide (7.74 g, 0.024 mol) were added to 1,6-dichlorohexane (186 g, 1.2 mol). Under a nitrogen atmosphere, the mixture was heated to 50 ° C., and a 44 wt% aqueous potassium hydrosulfide (KSH) solution (590 g, 3.6 mol) was added dropwise over 3 hours. The reaction mixture was stirred and mixed at 50 ° C. for an additional 3 hours.
The reaction solution was cooled to room temperature (25 ° C.). The reaction liquid after cooling was separated, and the lower layer (aqueous layer) was removed. A solution obtained by dissolving sodium chloride (10.5 g) in 2M HCl aqueous solution (61.8 g) was added to the oil layer (upper layer), and the mixture was stirred at room temperature for 15 minutes. The mixed solution was separated, and the lower layer (aqueous layer) was removed to obtain crude 1,6-hexanedithiol (177.4 g). As a result of quantification by high performance liquid chromatography (HPLC) (LC-10 manufactured by Shimadzu Corporation), the purity of 1,6-hexanedithiol was 85%, and the reaction yield was 83% (1,6- (Based on dichlorohexane). Subsequently, vacuum distillation was performed to obtain 145 g of 1,6-hexanedithiol (bp. 122-123 ° C./20 torr). As a result of quantification by HPLC, the purity of 1,6-hexanedithiol was 99.4%, and the distillation isolation yield was 80% (1,6-dichlorohexane standard).
［実施例２］
１，５−ジクロロペンタン（７．０５ｇ，５０ｍｍｏｌ）に水（３．８ｍｌ）、テトラブチルアンモニウムブロミド（０．８１ｇ、２.５ｍｍｏｌ）を加えた。窒素雰囲気下、反応混合液を５０℃に加熱し、４４重量％水硫化カリウム水溶液（２４．６ｇ，１５０ｍｍｏｌ）を２時間かけて滴下した。反応混合液を５０℃でさらに３時間攪拌した。反応液を室温まで冷却した後、分液し、１，５−ペンタンジチオールを反応収率８２％（１，５−ジクロロペンタン基準）で得た。
[Example 2]
Water (3.8 ml) and tetrabutylammonium bromide (0.81 g, 2.5 mmol) were added to 1,5-dichloropentane (7.05 g, 50 mmol). Under a nitrogen atmosphere, the reaction mixture was heated to 50 ° C., and a 44 wt% aqueous potassium hydrosulfide solution (24.6 g, 150 mmol) was added dropwise over 2 hours. The reaction mixture was stirred at 50 ° C. for a further 3 hours. The reaction solution was cooled to room temperature and then separated to obtain 1,5-pentanedithiol in a reaction yield of 82% (based on 1,5-dichloropentane).
［実施例３］
１，５−ジクロロ−３−メチルペンタン（１１４．８ｇ，０．７４０ｍｏｌ）に水（６１．８ｍｌ）、テトラブチルアンモニウムブロミド（１１．９３ｇ，０．０３７ｍｏｌ）を加えた。窒素雰囲気下、混合液を５０℃に加熱し、４４重量％水硫化カリウム（ＫＳＨ）水溶液（３６４．３ｇ，２．２２ｍｏｌ）を３時間かけて滴下した。反応混合液を５０℃でさらに４時間攪拌混合した。
反応液を室温（２５℃）まで冷却した。冷却した後の反応液を分液し、下層（水層）を除去した。油層（上層）に、２Ｍ−ＨＣｌ水溶液（３８．１ｇ）に食塩（６．４９ｇ）を溶解したものを加えて、室温で１５分間攪拌した。混合液を分液し、下層（水層）を除去することにより、粗１，５−ジメルカプト−３−メチルペンタン（１０４．５ｇ）を得た。高速液体クロマトグラフィー（ＨＰＬＣ）（株式会社島津製作所製ＬＣ−１０）で定量を行った結果、１，５−ジメルカプト−３−メチルペンタンの純度は、７８％であり、反応収率は７３％（１，５−ジクロロ−３−メチルペンタン基準）であった。次いで、減圧蒸留を行い、１，５−ジメルカプト−３−メチルペンタンを７５．０ｇで得た（ｂｐ.１０６−１０７℃／１２ｔｏｒｒ）。ＨＰＬＣで定量を行った結果、１，５−ジメルカプト−３−メチルペンタンの純度は９９．４％であり、蒸留単離収率は６７％（１，５−ジクロロ−３−メチルペンタン基準）であった。
[Example 3]
Water (61.8 ml) and tetrabutylammonium bromide (11.93 g, 0.037 mol) were added to 1,5-dichloro-3-methylpentane (114.8 g, 0.740 mol). Under a nitrogen atmosphere, the mixture was heated to 50 ° C., and a 44 wt% aqueous potassium hydrosulfide (KSH) solution (364.3 g, 2.22 mol) was added dropwise over 3 hours. The reaction mixture was stirred and mixed at 50 ° C. for an additional 4 hours.
The reaction solution was cooled to room temperature (25 ° C.). The reaction liquid after cooling was separated, and the lower layer (aqueous layer) was removed. A solution obtained by dissolving sodium chloride (6.49 g) in a 2M HCl aqueous solution (38.1 g) was added to the oil layer (upper layer) and stirred at room temperature for 15 minutes. The mixed solution was separated, and the lower layer (aqueous layer) was removed to obtain crude 1,5-dimercapto-3-methylpentane (104.5 g). As a result of quantification by high performance liquid chromatography (HPLC) (LC-10 manufactured by Shimadzu Corporation), the purity of 1,5-dimercapto-3-methylpentane was 78%, and the reaction yield was 73% ( 1,5-dichloro-3-methylpentane). Next, vacuum distillation was performed to obtain 1,5-dimercapto-3-methylpentane at 75.0 g (bp. 106-107 ° C./12 torr). As a result of quantification by HPLC, the purity of 1,5-dimercapto-3-methylpentane was 99.4%, and the distillation isolation yield was 67% (based on 1,5-dichloro-3-methylpentane). there were.
［実施例４］
１，４−ビス（クロロメチル）シクロヘキサン（１０．９ｇ，６０ｍｍｏｌ）に水（５ｍｌ）、テトラブチルアンモニウムブロミド（１．９４ｇ，６ｍｍｏｌ）を加えた。窒素雰囲気下、反応混合液を７０℃に加熱し、４４重量％水硫化カリウム水溶液（２９．５ｇ，１８０ｍｍｏｌ）を２時間かけて滴下した。反応混合液を７０℃でさらに３時間攪拌した。反応液を室温まで冷却した後、分液し、１，４−ビス（メルカプトメチル）シクロヘキサンを反応収率８０％（１，４−ビス（クロロメチル）シクロヘキサン基準）で得た。
[Example 4]
Water (5 ml) and tetrabutylammonium bromide (1.94 g, 6 mmol) were added to 1,4-bis (chloromethyl) cyclohexane (10.9 g, 60 mmol). Under a nitrogen atmosphere, the reaction mixture was heated to 70 ° C., and a 44 wt% aqueous potassium hydrosulfide solution (29.5 g, 180 mmol) was added dropwise over 2 hours. The reaction mixture was stirred at 70 ° C. for a further 3 hours. The reaction solution was cooled to room temperature and then separated to obtain 1,4-bis (mercaptomethyl) cyclohexane with a reaction yield of 80% (based on 1,4-bis (chloromethyl) cyclohexane).
［実施例５］
１，４−ビス（クロロメチル）シクロヘキサン（１０．９ｇ，６０ｍｍｏｌ）に水（５ｍｌ）、テトラブチルアンモニウムブロミド（１．９４ｇ，６ｍｍｏｌ）を加えた。窒素雰囲気下、２０℃で反応混合液に４４重量％水硫化カリウム水溶液（２９．５ｇ，１８０ｍｍｏｌ）を０．５時間かけて滴下した。反応混合液を２０℃で２０時間攪拌後、反応液を分液し、１，４−ビス（メルカプトメチル）シクロヘキサンを反応収率８５％（１，４−ビス（クロロメチル）シクロヘキサン基準）で得た。
[Example 5]
Water (5 ml) and tetrabutylammonium bromide (1.94 g, 6 mmol) were added to 1,4-bis (chloromethyl) cyclohexane (10.9 g, 60 mmol). Under a nitrogen atmosphere, a 44 wt% aqueous potassium hydrosulfide solution (29.5 g, 180 mmol) was added dropwise to the reaction mixture at 20 ° C. over 0.5 hour. After stirring the reaction mixture at 20 ° C. for 20 hours, the reaction mixture was separated to obtain 1,4-bis (mercaptomethyl) cyclohexane in a reaction yield of 85% (based on 1,4-bis (chloromethyl) cyclohexane). It was.
［実施例６］
１，４−ビス（クロロメチル）シクロヘキサン（１０．９ｇ，６０ｍｍｏｌ）に水（５ｍｌ）、テトラブチルアンモニウムブロミド（１．９４ｇ，６ｍｍｏｌ）を加えた。窒素雰囲気下、反応混合液を７０℃に加熱し、３４重量％水硫化ナトリウム水溶液（２９．７ｇ，１８０ｍｍｏｌ）を２時間かけて滴下した。反応混合液を７０℃で４時間攪拌した。反応液を室温まで冷却した後、分液し、１，４−ビス（メルカプトメチル）シクロヘキサンを反応収率８０％（１，４−ビス（クロロメチル）シクロヘキサン基準）で得た。
[Example 6]
Water (5 ml) and tetrabutylammonium bromide (1.94 g, 6 mmol) were added to 1,4-bis (chloromethyl) cyclohexane (10.9 g, 60 mmol). Under a nitrogen atmosphere, the reaction mixture was heated to 70 ° C., and a 34 wt% aqueous sodium hydrosulfide solution (29.7 g, 180 mmol) was added dropwise over 2 hours. The reaction mixture was stirred at 70 ° C. for 4 hours. The reaction solution was cooled to room temperature and then separated to obtain 1,4-bis (mercaptomethyl) cyclohexane in a reaction yield of 80% (based on 1,4-bis (chloromethyl) cyclohexane).
［実施例７］
１，４−ビス（クロロメチル）シクロヘキサン（１０．９ｇ，６０ｍｍｏｌ）に水（５ｍｌ）、アリコート３３６（１．７７ｇ，４．４ｍｍｏｌ）を加えた。窒素雰囲気下、反応混合液を７０℃に加熱し、３４重量％水硫化ナトリウム水溶液（２９．７ｇ，１８０ｍｍｏｌ）を２時間かけて滴下した。反応混合液を７０℃で４時間攪拌した。反応液を室温まで冷却した後、分液し、１，４−ビス（メルカプトメチル）シクロヘキサンを反応収率７７％（１，４−ビス（クロロメチル）シクロヘキサン基準）で得た。
[Example 7]
Water (5 ml) and aliquot 336 (1.77 g, 4.4 mmol) were added to 1,4-bis (chloromethyl) cyclohexane (10.9 g, 60 mmol). Under a nitrogen atmosphere, the reaction mixture was heated to 70 ° C., and a 34 wt% aqueous sodium hydrosulfide solution (29.7 g, 180 mmol) was added dropwise over 2 hours. The reaction mixture was stirred at 70 ° C. for 4 hours. The reaction solution was cooled to room temperature and then separated to obtain 1,4-bis (mercaptomethyl) cyclohexane in a reaction yield of 77% (based on 1,4-bis (chloromethyl) cyclohexane).
［実施例８］
１,１０−ジクロロデカン（１２．７ｇ，６０ｍｍｏｌ）に水（５ｍｌ）、テトラブチルアンモニウムブロミド（０．９７ｇ，３ｍｍｏｌ）を加えた。窒素雰囲気下、反応混合液を７０℃に加熱し、３４重量％水硫化ナトリウム水溶液（２９．７ｇ，１８０ｍｍｏｌ）を２時間かけて滴下した。反応混合液を７０℃で５時間攪拌した。反応液を室温まで冷却した後、分液し、１，１０−デカンジチオールを反応収率７７％（１，１０−ジクロロデカン基準）で得た。
[Example 8]
Water (5 ml) and tetrabutylammonium bromide (0.97 g, 3 mmol) were added to 1,10-dichlorodecane (12.7 g, 60 mmol). Under a nitrogen atmosphere, the reaction mixture was heated to 70 ° C., and a 34 wt% aqueous sodium hydrosulfide solution (29.7 g, 180 mmol) was added dropwise over 2 hours. The reaction mixture was stirred at 70 ° C. for 5 hours. The reaction solution was cooled to room temperature and then separated to obtain 1,10-decanedithiol in a reaction yield of 77% (based on 1,10-dichlorodecane).
［実施例９］
１,１２−ジブロモドデカン（１９．７ｇ，６０ｍｍｏｌ）に水（５ｍｌ）、テトラブチルアンモニウムブロミド（０．９７ｇ，３ｍｍｏｌ）を加えた。窒素雰囲気下、反応混合液を７０℃に加熱し、３４重量％水硫化ナトリウム水溶液（２９．７ｇ，１８０ｍｍｏｌ）を２時間かけて滴下した。反応混合液を７０℃で５時間攪拌した。反応液を室温まで冷却した後、分液し、１，１２−ドデカンジチオールを反応収率７７％（１,１２−ジブロモドデカン基準）で得た。
[Example 9]
Water (5 ml) and tetrabutylammonium bromide (0.97 g, 3 mmol) were added to 1,12-dibromododecane (19.7 g, 60 mmol). Under a nitrogen atmosphere, the reaction mixture was heated to 70 ° C., and a 34 wt% aqueous sodium hydrosulfide solution (29.7 g, 180 mmol) was added dropwise over 2 hours. The reaction mixture was stirred at 70 ° C. for 5 hours. The reaction solution was cooled to room temperature and then separated to obtain 1,12-dodecanedithiol in a reaction yield of 77% (based on 1,12-dibromododecane).
［実施例１０］
１，２−ビス（２−クロロエトキシ）エタン（２２．５ｇ，１２０ｍｍｏｌ）に水（１０ｍｌ）、テトラブチルアンモニウムブロミド（１．９４ｇ，６ｍｍｏｌ）を加えた。窒素雰囲気下、反応混合液を５０℃に加熱し、３４重量％水硫化ナトリウム水溶液（５９．４ｇ，３６０ｍｍｏｌ）を２時間かけて滴下した。反応混合液を５０℃で５時間攪拌した。反応液を室温まで冷却した後、分液し、１，２−ビス（２−メルカプトエトキシ）エタンを反応収率７０％（１，２−ビス（２−クロロエトキシ）エタン基準）で得た。
[Example 10]
Water (10 ml) and tetrabutylammonium bromide (1.94 g, 6 mmol) were added to 1,2-bis (2-chloroethoxy) ethane (22.5 g, 120 mmol). Under a nitrogen atmosphere, the reaction mixture was heated to 50 ° C., and a 34 wt% aqueous sodium hydrosulfide solution (59.4 g, 360 mmol) was added dropwise over 2 hours. The reaction mixture was stirred at 50 ° C. for 5 hours. The reaction solution was cooled to room temperature and then separated to obtain 1,2-bis (2-mercaptoethoxy) ethane at a reaction yield of 70% (based on 1,2-bis (2-chloroethoxy) ethane).
［実施例１１］
１,６−ジクロロヘキサン（９．３０ｇ，６０ｍｍｏｌ）にトルエン（９．３０ｍｌ）、水（５ｍｌ）、テトラブチルアンモニウムブロミド（０．９７ｇ，３ｍｍｏｌ）を加えた。窒素雰囲気下、反応混合液を５０℃に加熱し、３４重量％水硫化ナトリウム水溶液（２９．７ｇ，１８０ｍｍｏｌ）を２時間かけて滴下した。反応混合液を５０℃で７時間攪拌した。反応液を室温まで冷却した後、分液し、１，６−ヘキサンジチオールを反応収率８３％（１,６−ジクロロヘキサン基準）で得た。
[Example 11]
Toluene (9.30 ml), water (5 ml) and tetrabutylammonium bromide (0.97 g, 3 mmol) were added to 1,6-dichlorohexane (9.30 g, 60 mmol). Under a nitrogen atmosphere, the reaction mixture was heated to 50 ° C., and a 34 wt% aqueous sodium hydrosulfide solution (29.7 g, 180 mmol) was added dropwise over 2 hours. The reaction mixture was stirred at 50 ° C. for 7 hours. The reaction solution was cooled to room temperature and then separated to obtain 1,6-hexanedithiol in a reaction yield of 83% (1,6-dichlorohexane standard).
［比較例１］
テトラブチルアンモニウムブロミドを加えない以外は、全て実施例３と同様に操作を行った。得られた反応液を分析した結果、１，４−ビス（メルカプトメチル）シクロヘキサンは全く生成していないことが確認された。
[Comparative Example 1]
All operations were performed in the same manner as in Example 3 except that tetrabutylammonium bromide was not added. As a result of analyzing the obtained reaction solution, it was confirmed that 1,4-bis (mercaptomethyl) cyclohexane was not produced at all.
Claims (4)
Ｘ−ＣＨ２−Ｙ−ＣＨ２−Ｘ・・・（１）
ＭＳＨ・・・（２）
ＨＳ−ＣＨ２−Ｙ−ＣＨ２−ＳＨ・・・（３） A dihalogen compound represented by the following general formula (1) and a hydrosulfide represented by the following general formula (2) are reacted in the presence of a phase transfer catalyst, represented by the following general formula (3) A method for producing a dithiol compound. (In the formula, X represents a halogen atom, Y is a heteroatom and / or a hydrocarbon group that does not participate in the reaction, and the carbon-hydrogen group may contain a heteroatom or a ring structure. M is an alkali. Represents metal.)
X-CH 2 -Y-CH 2 -X ··· (1)
MSH (2)
HS-CH 2 -Y-CH 2 -SH ··· (3)
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| CN109503549A (en) * | 2018-11-27 | 2019-03-22 | 山东益丰生化环保股份有限公司 | A kind of preparation method and applications of the multi-thioalcohol compound of the structure of trithiane containing 1,3,5- |
| CN111072532A (en) * | 2019-12-04 | 2020-04-28 | 山东益丰生化环保股份有限公司 | Preparation method of 1,2, 3-trimercapto propane |
| EP4242251A1 (en) * | 2022-03-11 | 2023-09-13 | Nouryon Chemicals International B.V. | Production of bis-thiol compounds and use thereof in the production of liquid polysulfide polymers |
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| CN109503549A (en) * | 2018-11-27 | 2019-03-22 | 山东益丰生化环保股份有限公司 | A kind of preparation method and applications of the multi-thioalcohol compound of the structure of trithiane containing 1,3,5- |
| CN109503549B (en) * | 2018-11-27 | 2020-09-22 | 山东益丰生化环保股份有限公司 | Preparation method and application of polythiol compound containing 1,3, 5-trithiane structure |
| CN111072532A (en) * | 2019-12-04 | 2020-04-28 | 山东益丰生化环保股份有限公司 | Preparation method of 1,2, 3-trimercapto propane |
| CN111072532B (en) * | 2019-12-04 | 2020-09-25 | 山东益丰生化环保股份有限公司 | Preparation method of 1,2, 3-trimercapto propane |
| WO2021109754A1 (en) * | 2019-12-04 | 2021-06-10 | 山东益丰生化环保股份有限公司 | Preparation method for 1,2,3-trimercaptopropane |
| EP4242251A1 (en) * | 2022-03-11 | 2023-09-13 | Nouryon Chemicals International B.V. | Production of bis-thiol compounds and use thereof in the production of liquid polysulfide polymers |
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