JP5315866B2 - Triphenylmethyl mercaptan and process for producing the same - Google Patents
Triphenylmethyl mercaptan and process for producing the same Download PDFInfo
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Description
本発明は、トリフェニルメチルメルカプタンとその製造方法とに関する。 The present invention relates to triphenylmethyl mercaptan and a method for producing the same.
従来、トリフェニルメチルメルカプタンの製造方法としては、トリフェニルメタノールと硫化水素とを濃硫酸を触媒として、メタノール溶媒中で反応させる方法が知られている（特許文献１参照）。 Conventionally, as a method for producing triphenylmethyl mercaptan, a method is known in which triphenylmethanol and hydrogen sulfide are reacted in a methanol solvent using concentrated sulfuric acid as a catalyst (see Patent Document 1).
また、トリフェニルメチルクロリドと硫化水素とを、酸化アルミニウム（Ａｌ２Ｏ３）の存在下、１，４−ジオキサン溶媒中で反応させる方法が知られている（非特許文献１参照）。
しかしながら、上記従来の特許文献１の製法においては、次の（１）〜（４）のような不都合を生じる。 However, the conventional manufacturing method of Patent Document 1 has the following problems (1) to (4).
（１）濃硫酸を大量（三級アルコールに対して０．１〜０．８モル）に使用しなければならない。
（２）反応中に硫酸濃度の管理が必要となる。
（３）硫酸イオンが残存するため、充分な安定性が得られない。すなわち、得られたトリフェニルメチルメルカプタンの管理状態が良くないと、空気中の水分などを介して加水分解を起こし、結晶が着色し、変質してしまうことが懸念される。
（４）原料のトリフェニルメタノールは、化審法の新規化学物質であるので市販品として大量に入手することが困難である。
(1) Concentrated sulfuric acid must be used in a large amount (0.1 to 0.8 mol with respect to tertiary alcohol).
(2) It is necessary to control the sulfuric acid concentration during the reaction.
(3) Sufficient stability cannot be obtained because sulfate ions remain. That is, if the obtained triphenylmethyl mercaptan is not well managed, there is a concern that hydrolysis will occur via moisture in the air, and the crystals will be colored and altered.
(4) Since the starting material triphenylmethanol is a new chemical substance of the Chemical Substances Control Law, it is difficult to obtain a large amount as a commercial product.
また、上記従来の非特許文献１の製法においては、次の（１）〜（２）のような不都合を生じる。 Moreover, in the manufacturing method of the said conventional nonpatent literature 1, the following problems (1)-(2) arise.
（１）トリフェニルメチルクロリドからトリフェニルメタノールを経由してトリフェニルメチルメルカプタンを合成するには単離工程が必要となる。
（２）アルミニウムイオンが残存するため、トリフェニルメチルメルカプタンを使用した後工程でアルミニウムイオンが溶け残り、濁りの原因となることが懸念される。
(1) An isolation step is required to synthesize triphenylmethyl mercaptan from triphenylmethyl chloride via triphenylmethanol.
(2) Since aluminum ions remain, there is a concern that aluminum ions remain undissolved in the post-process using triphenylmethyl mercaptan, causing turbidity.
本発明は、上記した従来技術の課題を解決し、トリフェニルメチルクロリドから容易にしかも安全に高収率で、高品質のトリフェニルメチルメルカプタンを製造する方法と、これによって得られる高品質のトリフェニルメチルメルカプタンとを提供することを目的としている。 The present invention solves the above-mentioned problems of the prior art, and a method for producing high-quality triphenylmethyl mercaptan easily and safely in high yield from triphenylmethyl chloride, and the high-quality triphenyl obtained thereby. It aims to provide phenylmethyl mercaptan.
上記の課題を解決するために、本発明者らは鋭意研究したところ、低級アルコールの存在下で副生する塩化水素を触媒として硫化水素と反応させてトリフェニルメチルメルカプタンを工業的に安全に効率良く製造できることを見出し、本発明を完成するに至った。 In order to solve the above-mentioned problems, the present inventors have intensively researched, and made triphenylmethyl mercaptan industrially safe and efficient by reacting with hydrogen sulfide using hydrogen chloride by-produced in the presence of a lower alcohol as a catalyst. The inventors have found that it can be manufactured well, and have completed the present invention.
すなわち、上記課題を解決するための本発明のトリフェニルメチルメルカプタンの製造方法は、トリフェニルメチルクロリドと低級アルコールとを混合してトリフェニルアルコールを生成させた後、硫化水素と反応させるものである。 That is, the method for producing triphenylmethyl mercaptan of the present invention for solving the above-mentioned problem is to produce triphenyl alcohol by mixing triphenylmethyl chloride and lower alcohol, and then react with hydrogen sulfide. .
また、上記課題を解決するための本発明のトリフェニルメチルメルカプタンは、上記製造方法によって得られるものである。 Moreover, the triphenylmethyl mercaptan of this invention for solving the said subject is obtained by the said manufacturing method.
以下に本発明を詳細に説明する。 The present invention is described in detail below.
本発明の製造方法において用い得る低級アルコールの具体例としては、メタノール、エタノール、１−プロパノール、イソプロパノール等が挙げられるが、これらに限定されるものではない。好ましくはメタノール、エタノール、イソプロパノールが工業的に好適である。 Specific examples of the lower alcohol that can be used in the production method of the present invention include methanol, ethanol, 1-propanol, isopropanol, and the like, but are not limited thereto. Methanol, ethanol and isopropanol are preferred industrially.
反応に際しては、トリフェニルメチルクロリド、低級アルコールを仕込んだ後、硫化水素を吹き込むことで反応することができるが、好ましくは、あらかじめ低級アルコールを仕込んだ中に、トリフェニルメチルクロリドを添加し、硫化水素を吹き込むことにより攪拌起動時の負荷を低減することができ、さらには添加速度を制御することにより、反応に伴う発熱を制御することができる。 In the reaction, triphenylmethyl chloride and lower alcohol can be charged, and then hydrogen sulfide can be blown into the reaction. Preferably, triphenylmethyl chloride is added to the sulfur alcohol in advance while lower alcohol is charged. By blowing in hydrogen, the load at the start of stirring can be reduced. Furthermore, by controlling the addition rate, the exotherm accompanying the reaction can be controlled.
反応温度は、通常３０〜８０℃、好ましくは４０〜６０℃の範囲である。反応時間は吹込み圧力、反応温度により影響を受けるが、通常１〜２０時間、好ましくは４〜１０時間である。 The reaction temperature is usually in the range of 30 to 80 ° C, preferably 40 to 60 ° C. The reaction time is affected by the blowing pressure and the reaction temperature, but is usually 1 to 20 hours, preferably 4 to 10 hours.
吹込み圧力は、通常０〜０．５ＭＰａ、好ましくは０．０５〜０．２ＭＰａの範囲である。 The blowing pressure is usually in the range of 0 to 0.5 MPa, preferably 0.05 to 0.2 MPa.
本発明の製造方法は、従来の１，４−ジオキサン溶媒を用いる方法や、硫酸を用いる方法に比べて、汎用な溶媒を用いるのみで、触媒を使用することなく安全に効率良くトリフェニルメチルメルカプタンを製造することができる。また、上記した反応温度等の反応条件によって、純度９８％以上のトリフェニルメチルメルカプタンの製造が可能となる。 Compared with the conventional method using 1,4-dioxane solvent and the method using sulfuric acid, the production method of the present invention uses only a general-purpose solvent and safely and efficiently uses triphenylmethyl mercaptan without using a catalyst. Can be manufactured. Further, it is possible to produce triphenylmethyl mercaptan having a purity of 98% or more depending on the reaction conditions such as the reaction temperature described above.
また、仮に純度が９８％以上でなかったとしても、その他の残成分は、トリフェニルメチルクロリド、トリフェニルアルコール、低級アルコール、塩素イオンなどの原料物質または中間物質であって、従来の方法のように、アルミニウムイオンや、硫酸イオンが残存しないので、変色による劣化や、溶解時の濁りなどを生じることもない。したがって、本発明によって得られるトリフェニルメチルメルカプタンは、製造直後の粗品の状態でも安定性に優れたものが得られ、後工程で所望の純度に精製することで、より一層安定性があり、優れた高品質のトリフェニルメチルメルカプタンを得ることができる。 Further, even if the purity is not 98% or more, the other remaining components are raw materials or intermediates such as triphenylmethyl chloride, triphenyl alcohol, lower alcohol, chloride ion, and the like in the conventional method. In addition, since no aluminum ions or sulfate ions remain, neither deterioration due to discoloration nor turbidity during dissolution occurs. Therefore, the triphenylmethyl mercaptan obtained by the present invention is excellent in stability even in the state of a crude product immediately after production, and is more stable and refined by purifying it to a desired purity in a subsequent process. High quality triphenylmethyl mercaptan can be obtained.
以上述べたように、本発明によると、トリフェニルメチルクロリドから容易にしかも安全に高収率で、高品質のトリフェニルメチルメルカプタンを製造することができる。 As described above, according to the present invention, high-quality triphenylmethyl mercaptan can be easily and safely produced in high yield from triphenylmethyl chloride.
以下の実施例により本発明を更に具体的に説明するが、本発明はこれらの実施例に何ら限定されるものではない。 The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these examples.
実施例１
内容量２００ｍｌのテフロンオートクレーブにメタノール１０６．７ｇ（トリフェニルメチルクロリドに対して５．３ｗ／ｗ）を仕込み、これにトリフェニルメチルクロリド（０．００７１７モル）を加え、密閉下、硫化水素３．４ｇ（１．４モル）を加えた。
Example 1
A Teflon autoclave with an internal volume of 200 ml was charged with 106.7 g of methanol (5.3 w / w with respect to triphenylmethyl chloride), triphenylmethyl chloride (0.00717 mol) was added thereto, and hydrogen sulfide 3. 4 g (1.4 mol) was added.
オートクレーブを６５℃のオイルバス中に保ち、回転子を用いて内容物を攪拌しながら８時間反応させ、その後、室温に冷却し、過剰の硫化水素を放出させた後、濾過により生成物を分離した。その結果、トリフェニルメチルメルカプタン１８．７ｇを得た（収率８４．１％）。液体クロマトグラフィー（ＬＣ）分析による純度は９８．０％であった。 The autoclave is kept in an oil bath at 65 ° C., and the contents are reacted for 8 hours with stirring using a rotor, then cooled to room temperature, excess hydrogen sulfide is released, and the product is separated by filtration. did. As a result, 18.7 g of triphenylmethyl mercaptan was obtained (yield 84.1%). The purity by liquid chromatography (LC) analysis was 98.0%.
なお、トリフェニルメタノールの残存量は１．８％であった。 The residual amount of triphenylmethanol was 1.8%.
このようにして得られた試料２０．５ｍｇを１００ミリリットルのメタノールに投入し、６４℃（還流）にて加熱したときの１時間毎の純度の低下率を液体クロマトグラフィー（ＬＣ）分析によって測定した。その結果、純度低下率が１％／ｈｒ以下の高い熱安定性が確認できた。 20.5 mg of the sample thus obtained was put into 100 ml of methanol and the rate of decrease in purity every hour when heated at 64 ° C. (reflux) was measured by liquid chromatography (LC) analysis. . As a result, high thermal stability with a purity reduction rate of 1% / hr or less could be confirmed.
本発明に係るトリフェニルメチルメルカプタンは、保護剤、チオール基導入剤として使用される。 The triphenylmethyl mercaptan according to the present invention is used as a protective agent and a thiol group introducing agent.
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