JP2004051599A - N-acylsulfenamide compound and method for manufacturing n-acylsulfenamide compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an N-acylsulfenamide compound having physiological activities and a method for manufacturing the same. <P>SOLUTION: The method for manufacturing the N-acylsulfenamide compound represented by general formula (1) in comprises reacting a compound of formula (2) with an acid anhydride of formula (3). In the general formula, R<SP>1</SP>is a 1-8C alkyl group, a 3-8C cycloalkyl group, a 1-8C alkoxyl group, a 2-8C alkoxycarbonyl group, a halogen atom or a nitro group, and when a plurality of R<SP>1</SP>exist, each R<SP>1</SP>may be the same or different; n is an integer of 0-4; and R<SP>2</SP>is a 1-12C perfluoroalkyl group. <P>COPYRIGHT: (C)2004,JPO

Description

（式中、Ｒ^１は炭素数１〜８のアルキル基、炭素数３〜８のシクロアルキル基、炭素数１〜８のアルコキシル基、炭素数２〜８のアルコキシカルボニル基、ハロゲン原子、ニトロ基を示し、Ｒ^１が複数ある場合は、各Ｒ^１は互いに同一であっても異なっていてもよく、ｎは０または１〜４の整数である。Ｒ^２は炭素数１〜１２のペルフルオロアルキル基を示す。）
【０００７】
また、本発明によれば、下記一般式（イ）で表されるＮ−アシルスルフェンアミド化合物を製造する方法において、下記一般式（ロ）で表されるスルフェンアミド化合物と、下記一般式（ハ）で表される酸無水物を反応させることを特徴とするＮ−アシルスルフェンアミド化合物の製造方法が提供される。
【化６】

（式中、Ｒ^１は炭素数１〜８のアルキル基、炭素数３〜８のシクロアルキル基、炭素数１〜８のアルコキシル基、炭素数２〜８のアルコキシカルボニル基、ハロゲン原子、ニトロ基を示し、Ｒ^１が複数ある場合は、各Ｒ^１は互いに同一であっても異なっていてもよく、ｎは０または１〜４の整数である。Ｒ^２は炭素数１〜１２のペルフルオロアルキル基を示す。）
【化７】

（式中、Ｒ^１は炭素数１〜８のアルキル基、炭素数３〜８のシクロアルキル基、炭素数１〜８のアルコキシル基、炭素数２〜８のアルコキシカルボニル基、ハロゲン原子、ニトロ基を示し、Ｒ^１が複数ある場合は、各Ｒ^１は互いに同一であっても異なっていてもよく、ｎは０または１〜４の整数である。）
【化８】

（式中、Ｒ^２は炭素数１〜１２のペルフルオロアルキル基を示す。）
【０００８】
【発明の実施の形態】
本発明のＮ−アシルスルフェンアミド化合物は、以下の一般式（イ）で示される化合物である。
【化９】

式中、Ｒ^１は、炭素数１〜８のアルキル基、炭素数３〜８のシクロアルキル基、炭素数１〜８のアルコキシル基、炭素数２〜８のアルコキシカルボニル基、ハロゲン原子、ニトロ基を示す。
前記アルキル基の具体例を示すと、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｓ−ブチル基、ｔ−ブチル基、ｎ−ペンチル基、イソペンチル基、ネオペンチル基、ｔ−ペンチル基、ｎ−ヘキシル基、イソヘキシル基、２−ヘキシル、３−ヘキシル基、ｎ−ヘプチル基、２−ヘプチル基、３−ヘプチル基、４−ヘプチル基、ｎ−オクチル基、２−オクチル基、３−オクチル基、４−オクチル基等が挙げられる。
前記シクロアルキル基具体例を示すと、シクロプロピル基、シクロブチル基、シクロヘキシル基等が挙げられる。
前記アルコキシル基の具体例を示すと、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ヘキシロキシ基等が挙げられる。
前記アルコキシカルボニル基の具体例を示すと、メトキシカルボニル基、エトキシカルボニル基、プロポキシカルボニル基、ヘキシロキシカルボニル基、ベンジロキシカルボニル基等が挙げられる。
ｎは０または１〜４の整数を示す。
【０００９】
また、Ｒ^２は、炭素数１〜１２のペルフルオロアルキル基を示す。前記ペルフルオロアルキル基の具体例を示すと、トリフルオロメチル基、ペンタフルオロエチル基、ペルフルオロプロピル基、ペルフルオロイソプロピル基、ペルフルオロブチル基、ペルフルオロイソブチル基、ペルフルオロ−ｓ−ブチル基，ペルフルオロ−ｔ−ブチル基、ペルフルオロヘキシル基等が挙げられる。
【００１０】
本発明のＮ−アシルスルフェンアミド化合物の具体的な化合物を挙げると、化合物（１）から（７）に示されるＮ−アシルスルフェンアミド化合物が挙げられる。これらの化合物は、ゴムの加硫化剤、殺菌剤、殺虫剤、除草剤の出発原料としての用途がある。
【化１０】

【００１１】
前記一般式（イ）で表される本発明のＮ−アシルスルフェンアミド化合物
の製造方法は以下の通りである。
【化１１】

（式中、Ｒ^１は炭素数１〜８のアルキル基、炭素数３〜８のシクロアルキル基、炭素数１〜８のアルコキシル基、炭素数２〜８のアルコキシカルボニル基、ハロゲン原子、ニトロ基を示し、Ｒ^１が複数ある場合は、各Ｒ^１は互いに同一であっても、異なっていてもよく、ｎは０または１〜４の整数である。Ｒ^２は炭素数１〜１２のペルフルオロアルキル基を示す。）
【００１２】
原料物質である下記一般式（ロ）で表されるスルフェンアミド化合物と、下記一般式（ハ）で表される酸無水物を反応させる。
【化１２】

（式中、Ｒ^１は炭素数１〜８のアルキル基、炭素数３〜８のシクロアルキル基、炭素数１〜８のアルコキシル基、炭素数２〜８のアルコキシカルボニル基、ハロゲン原子、ニトロ基を示し、Ｒ^１が複数ある場合は、各Ｒ^１は互いに同一であっても異なっていてもよく、ｎは０または１〜４の整数である。）
【化１３】

（式中、Ｒ^２は炭素数１〜１２のペルフルオロアルキル基を示す。）
【００１３】
前記原料物質を、好ましくは溶剤に溶解させ、　塩基性物質の存在下に反応させる。
反応溶媒は、塩化メチレン、クロロホルム、１，２−ジクロロエタン、アセトニトリル、テトラヒドロフラン、ジオキサン、ベンゼン、トルエン、キシレン、クロロベンゼン、ジクロロベンゼン、アニソール等の溶媒中で行われる。
また、これらの溶媒は単独または混合溶媒の形で使用される。
添加する塩基物質としては、第三級アミン類が用いられる。このアミン類として、ピリジン、メチルピリジン、ジメチルピリジン、トリエチルアミン、トリブチルアミン等が用いられる。
反応温度は、−７８℃から０℃、好ましくは、−３０℃から０℃の範囲である。この温度未満では、反応は遅く、反応の進行が困難となる。この範囲を超える場合には、副反応が生起し、好ましくない。
なお、前記原料物質である一般式（ロ）で表されるスルフェンアミド化合物は、チオール化合物とヒドロキシルアミン−Ｏ−スルホン酸を公知の方法で反応させて製造される。もう一方の原料物質である一般式（ハ）で表される酸無水物は、カルボン酸を脱水反応させることにより製造される。
反応時間は、５分から５時間である。反応終了後、溶剤を除去し、目的生成物を取り出す。
【００１４】
【実施例】
次に、本発明を実施例により詳細に説明する。なお、本発明の実施例は本発明の理解を容易にするために代表的な物をあげたものであり、本発明はこれだけに限定されるものではない。なお、下記実施例によって製造される新規なＮ−アシルスルフェンアミド化合物（１）〜（７）は、前記で示した化合物（１）〜（７）であり、各種スペクトルデータを主要な判定基準として同定した。他のＮ−アシルスルフェンアミド化合物は、既知のものについては融点および各種スペクトルデータを比較することより、未知のものについては各種スペクトルを主要な判定基準として同定した。
【００１５】
実施例１
内容積３０ｍｌのガラス製容器中に２−メトキシカルボニルベンゼンスルフェンアミド（９１．５ｍｇ，０．５ｍｍｏｌ）を塩化メチレン５ｍｌに溶かし、無水トリフルオロ酢酸（２１０ｍｇ，１．０ｍｍｏｌ）とピリジン（８０μｌ）を加えた。０℃で３０分撹拌させた後、溶媒を減圧下留去させ、粗生成物をシリカゲルクロマトグラフィー（溶出溶媒　塩化メチレン）で精製することにより、化合物（１）のＮ−アシルスルフェンアミドを収量１０２ｍｇ、収率７３％で得た。
この化合物は塩化メチレン−ヘキサンを用いて再結晶することによりさらに精製することができた。
融点：１２７−１２８　°Ｃ．　^１Ｈ　ＮＭＲ　（５００　ＭＨｚ，　ＣＤＣｌ_３）：　ｄ　８．０４　（ｄｄ，　Ｊ　＝　７．６，　１．２　Ｈｚ，１Ｈ），　７．５４　（ｄｄｄ，　Ｊ　＝　８．６，　７．３，　１．５　Ｈｚ，　１Ｈ），　７．５０　（ｓ，　１Ｈ），　７．２７　（ｄｄｄ，　Ｊ　＝７．０，　７．０，　１．３　Ｈｚ，　１Ｈ），　７．１７　（ｄｄ，　Ｊ　＝　８．０，　０．６　Ｈｚ，　１Ｈ），　３．９６　（ｓ，　３Ｈ）；　^１３Ｃ　ＮＭＲ　（１２５　ＭＨｚ，　ＣＤＣｌ_３）：　ｄ　１６７．４，　１５９．２　（ｑ，　Ｊ_ＣＦ　＝　３７．０　Ｈｚ，　Ｃ＝Ｏ），　１４２．４，　１３３．６，　１３１．３，　１２５．５，　１２４．５，　１２１．５，　１１５．７　（ｑ，　Ｊ_ＣＦ　＝　２８７．４　Ｈｚ，　ＣＦ_３），　５２．８；　ＩＲ　（ＫＢｒ）：　３２２３，　３０９０，　２９５９，　１７１３，　１６９６，　１４６８，　１４４１，　１３１９，　１２０６，　１１６３，　７４７　ｃｍ^−１；　高分解能マス：計算値　Ｃ_１０Ｈ_８Ｆ_３ＮＯ_３Ｓ：２７９．０１７７，　実測値　２７９．０１４１．
【００１６】
実施例２
実施例１において、２−メトキシカルボニルベンゼンスルフェンアミドの代わりに、２−ブロモベンゼンスルフェンアミド（１０２ｍｇ，０．５ｍｍｏｌ）を用いて同様な反応を行い、粗生成物をシリカゲルクロマトグラフィー（溶出溶媒　塩化メチレン：ヘキサン＝２：１）で精製することにより、化合物（２）のＮ−アシルスルフェンアミドを収率１４４ｍｇ、収率８０％で得た。
融点：８９−９０　°Ｃ．　^１Ｈ　ＮＭＲ　（５００　ＭＨｚ，　ＣＤＣｌ_３）：　ｄ　７．５６　（ｓ，　１Ｈ），　７．５４　（ｄｄ，　Ｊ　＝　８．６，　１．６　Ｈｚ，　１Ｈ），　７．３３　（ｄｄｄ，　Ｊ　＝　８．６，　７．３，　１．２　Ｈｚ，　１Ｈ），　７．１６−７．１３　（ｍ，　２Ｈ）；　^１３Ｃ　ＮＭＲ　（１２５　ＭＨｚ，　ＣＤＣｌ_３）：　ｄ　１５９．０　（ｑ，　Ｊ_ＣＦ　＝　３８．１　Ｈｚ，　Ｃ＝Ｏ），　１３６．１，　１３３．２，　１２８．８，　１２８．３，　１２６．３，　１１９．９，　１１５．５　（ｑ，　Ｊ_ＣＦ　＝　２８８．４　Ｈｚ，　ＣＦ_３）；　ＩＲ　（ＫＢｒ）：　３２２５，　１７２３，　１４６８，　１４４７，　１２１１，　１１６７，　１１５０，　７４１　ｃｍ^−１；　高分解能マス：計算値　Ｃ_８Ｈ_５ＢｒＦ_３ＮＯＳ：　２９８．９２２７，　３００．９２０７，　実測値２９８．９２１０，　３００．９２１６．
【００１７】
実施例３
実施例１において、２−メトキシカルボニルベンゼンスルフェンアミドの代わりに、４−ニトロベンゼンスルフェンアミド（８５ｍｇ，０．５ｍｍｏｌ）を用いて同様な反応を行い、粗生成物をシリカゲルクロマトグラフィー（溶出溶媒　塩化メチレン）で精製することにより、化合物（３）のＮ−アシルスルフェンアミドを収率９０ｍｇ、収率８２％で得た。
融点：１１１−１１３　°Ｃ．　^１Ｈ　ＮＭＲ　（５００　ＭＨｚ，　ＣＤＣｌ_３）：　ｄ　８．２２　（ｄｄｄ，　Ｊ　＝　９．２，　２．５，　２．５　Ｈｚ，　２Ｈ　），　７．７４　（ｓ，　１Ｈ），　７．３４　（ｄｄｄ，　Ｊ　＝　９．２，　２．５，　２．５　Ｈｚ，　２Ｈ）；　^１３Ｃ　ＮＭＲ（１２５　ＭＨｚ，　ＣＤＣｌ_３）：　ｄ　１５９．０　（ｑ，　Ｊ_ＣＦ　＝　３９．１　Ｈｚ，　Ｃ＝Ｏ），　１４６．８，　１４４．８，　１２４．６，１２４．４，　１１５．４　（ｑ，　Ｊ_ＣＦ　＝　２８８．４　Ｈｚ，　ＣＦ_３）；　ＩＲ　（ＫＢｒ）：　３２７４，　１７２６，　１５８０，　１５２２，　１４５８，　１３４１，　１２１１，　１１６９，　１１３２　ｃｍ^−１；　高分解能マス：計算値　Ｃ_８Ｈ_５Ｆ_３Ｎ_２Ｏ_３Ｓ：　２６５．９９７３，　実測値２６５．９９５３．
【００１８】
実施例４
実施例１において、２−メトキシカルボニルベンゼンスルフェンアミドの代わりに、ベンゼンスルフェンアミド（６３ｍｇ，０．５ｍｍｏｌ）を用い、同様な反応を行い、粗生成物をシリカゲルクロマトグラフィー（溶出溶媒　塩化メチレン：ヘキサン２：１）で精製することにより、化合物（４）のＮ−アシルスルフェンアミドを収率８６ｍｇ、収率７８％で得た。
融点：７０−７２　°Ｃ．　^１Ｈ　ＮＭＲ　（５００　ＭＨｚ，　ＣＤＣｌ_３）：　ｄ　７．５３　（ｓ，　１Ｈ），　７．４６−７．４３　（ｍ，　２Ｈ），　７．３９−７．３２　（ｍ，　３Ｈ）；　^１３Ｃ　ＮＭＲ　（１２５　ＭＨｚ，　ＣＤＣｌ_３）：　ｄ　１５９．１　（ｑ，　Ｊ_ＣＦ　＝　３７．１Ｈｚ，　Ｃ＝Ｏ），　１３５．５，　１２９．５，　１２９．１，　１２９．０，　１１５．６　（ｑ，　Ｊ_ＣＦ　＝　２８７．４　Ｈｚ，　ＣＦ_３）；　ＩＲ　（ＫＢｒ）：　３２４５，　１７１７，　１４４１，　１３２１，　１１８６，　７４０，　６８９　ｃｍ^−１；　高分解能マス：計算値Ｃ_８Ｈ_６Ｆ_３ＮＯＳ：　２２１．０１２２，　実測値　２２１．０１４５．
【００１９】
実施例５
実施例１において、２−メトキシカルボニルベンゼンスルフェンアミドの代わりに、４−メチルベンゼンスルフェンアミド（７０ｍｇ，０．５ｍｍｏｌ）を用いて同様な反応を行い、粗生成物をシリカゲルクロマトグラフィー（溶出溶媒　塩化メチレン：ヘキサン＝２：１）で精製することにより、化合物（５）のＮ−アシルスルフェンアミドを収率７４ｍｇ、収率６３％で得た。
融点：８４−８６　°Ｃ．　^１Ｈ　ＮＭＲ　（５００　ＭＨｚ，　ＣＤＣｌ_３）：　ｄ　７．５３　（ｓ，　１Ｈ），　７．４３　（ｄ，　Ｊ　＝　８．３　Ｈｚ，　２Ｈ），　７．１８　（ｄ，　Ｊ　＝　８．０Ｈｚ，　２Ｈ），　２．３６　（ｓ，　３Ｈ）；　^１３Ｃ　ＮＭＲ　（１２５　ＭＨｚ，　ＣＤＣｌ_３）：　ｄ　１５９．１　（ｑ，　Ｊ_ＣＦ　＝　３８．１　Ｈｚ，　Ｃ＝Ｏ），　１４０．１，　１３１．９，　１３０．９，　１３０．２，　１１５．６　（ｑ，　Ｊ_ＣＦ　＝　２８７．４　Ｈｚ，　ＣＦ_３），　２１．３；　ＩＲ　（ＫＢｒ）：　３２８９，　３２３９，　２９２６，　１７２５，　１４６８，　１３２１，　１１６３，　８０４　ｃｍ^−１；　高分解能マス：計算値Ｃ_９Ｈ_８Ｆ_３ＮＯＳ：　２３５．０２７９，　実測値２３５．０２９１．
【００２０】
実施例６
内容積３０ｍｌのガラス製容器中に２−メトキシカルボニルベンゼンスルフェンアミド（９１．５ｍｇ，０．５ｍｍｏｌ）を塩化メチレン５ｍｌに溶かし、無水ペンタフルオロプロピオン酸（３１０ｍｇ，１．０ｍｍｏｌ）とピリジン（８０μｌ，１．０ｍｍｏｌ）を加えた。０℃で１５分撹拌させた後、溶媒を減圧下留去させ、粗生成物をシリカゲルクロマトグラフィー（溶出溶媒　塩化メチレン）で精製することにより、化合物（６）のＮ−アシルスルフェンアミドを収量１４８ｍｇ、収率９０％で得た。この化合物は塩化メチレン−ヘキサンを用いて再結晶することによりさらに精製することができた。
融点：１１７−１１８　°Ｃ．　^１Ｈ　ＮＭＲ　（５００　ＭＨｚ，　ＣＤＣｌ_３）：　ｄ　８．０４　（ｄｄ，　Ｊ　＝　８．０，　１．６　Ｈｚ，１Ｈ），　７．５５−７．５２　（ｍ，　２Ｈ），　７．２６　（ｄｄｄ，　Ｊ　＝　７．３，　７．３，　１．２　Ｈｚ，　１Ｈ），　７．１４　（ｄｄ，Ｊ　＝　８．２，　０．６　Ｈｚ，　１Ｈ），　３．９６　（ｓ，　３Ｈ）；　^１３Ｃ　ＮＭＲ　（１２５　ＭＨｚ，　ＣＤＣｌ_３）：　ｄ　１６７．４，　１５９．８　（ｔ，　Ｊ_ＣＦ　＝　２６．８　Ｈｚ，　Ｃ＝Ｏ），　１４２．４，　１３３．６，　１３１．８，　１２５．５，　１２４．５，　１２１．５，１１７．７　（ｑｔ，　Ｊ_ＣＦ　＝　２８５．４，　３４．０　Ｈｚ，　ＣＦ_３），　１０７．１　（ｔｑ，　Ｊ_ＣＦ　＝　２６６．８，　３９．３　Ｈｚ，ＣＦ_２），　５２．８；　ＩＲ　（ＫＢｒ）：　３２５２，　１７０７，　１４４３，　１３１９，　１２１３，　１１４８，　１０３２，　７４７　ｃｍ^−１；　高分解能マス：計算値Ｃ_１１Ｈ_８Ｆ_５ＮＯ_３Ｓ：　３２９．０１４５，　実測値３２９．００９４．
【００２１】
実施例７
実施例６において、２−メトキシカルボニルベンゼンスルフェンアミドの代わりに、４−ニトロベンゼンスルフェンアミド（８５ｍｇ，０．５ｍｍｏｌ）を用いて同様な反応を行い、粗生成物をシリカゲルクロマトグラフィー（溶出溶媒　塩化メチレン）で精製することにより、化合物（７）のＮ−アシルスルフェンアミドを収率１１９ｍｇ、収率８５％で得た。
融点：８８−８９　°Ｃ．　^１Ｈ　ＮＭＲ　（５００　ＭＨｚ，　ＣＤＣｌ_３）：　ｄ　８．２４　（ｄｄｄ，　Ｊ　＝　９．２，　２．５，　２．５Ｈｚ，　２Ｈ　），　７．６７　（ｓ，　１Ｈ），　７．３４　（ｄｄｄ，　Ｊ　＝　９．２，　２．５，　２．５　Ｈｚ，　２Ｈ）；　^１３Ｃ　ＮＭＲ　（１２５　ＭＨｚ，　ＣＤＣｌ_３）：　ｄ　１５９．８　（ｔ，　Ｊ_ＣＦ　＝　２６．８　Ｈｚ，　Ｃ＝Ｏ），　１４６．８，　１４４．７，　１２４．６，　１２４．４，　１１７．５　（ｑｔ，　Ｊ_ＣＦ　＝　２８５．４，　３４．０　Ｈｚ，　ＣＦ_３），　１０７．０　（ｔｑ，　Ｊ_ＣＦ　＝　２６６．８，　４０．３　Ｈｚ，　ＣＦ_２）；　ＩＲ　（ＫＢｒ）：　３２６０，　１７２１，　１５１２，　１４５１，　１３４６，　１２０８，　１１８１，　１１５７，　１０３０，　８５５　ｃｍ^−１；　高分解能マス：計算値Ｃ_９Ｈ_５Ｆ_５Ｎ_２Ｏ_３Ｓ：　３１５．９９４１，　実測値３１５．９９３０．
【００２２】
【発明の効果】
本発明によれば、スルフェンアミド化合物と酸無水物を反応させることにより、新規なＮ−アシルスルフェンアミド化合物を収率よく製造することができる。しかも、有毒な塩素ガスを用いることなく安全に製造できるので、工業的なＮ−アシルスルフェンアミド化合物の合成法として最適である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a novel N-acylsulfenamide compound and a method for producing an N-acylsulfenamide compound. More specifically, the present invention relates to a novel N-acylsulfenamide compound and a method for efficiently producing an N-acylsulfenamide compound by reacting a sulfenamide compound with an acid anhydride.
[0002]
[Prior art]
It has been known that some sulfenamide compounds have functions as rubber vulcanizing agents, fungicides, insecticides, and herbicides (Chem. Rev., 89 , 689 (1989)). In particular, it has been reported that N-benzoyl-4-chlorobenzenesulfenamide has a plant growth regulating function (Fiziol. Akt. Veshch, 16 , 47 (1984); Chem. Abstr., 103 , 18314 ( 1985).).
As described above, a group of N-acylsulfenamide compounds are industrially important compounds, and there is a need for the development of new compounds and safer production methods.
[0003]
Amide compounds are generally produced by acylation of an amine compound. Similarly, there is a report in the early 20th century that an N-acylsulfenamide compound can be obtained by acylation of sulfenamide (Ann. 391 , 55 (1912), Ann., 400 , 1 ( 1913), Ann., 406 , 103 (1914), Ber., 72 , 663 (1939).) Then, acylation of a sulfenamide compound is performed by a conventional method using an acid chloride or an acid anhydride. It has been reported that a disulfide compound or a disulfenylamine compound was obtained without progress (J. Gen. Chem. USSR, 47 , 1004 (1977); Zh. Obshch. Khim., 47 , 1096 (1977)). .).
Therefore, in order to produce an N-acylsulfenamide compound, it has been produced by reacting a sulfenyl chloride compound with an amide compound (for example, Bull. Chem. Soc. Jpn., 51 , 3004 (1978)).
However, since the sulfenyl chloride compound had to be produced conventionally by reacting a thiol compound or a disulfide compound with chlorine gas, it was necessary to supply toxic chlorine gas to the reaction system as a gas. Handling is often difficult, and a safe manufacturing method is desired.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide a novel N-acylsulfenamide compound and, in producing an N-acylsulfenamide compound, using a sulfenyl chloride compound synthesized using toxic chlorine gas as a raw material. It is an object of the present invention to overcome the disadvantages of the use and to provide an industrially advantageous method for producing an N-acylsulfenamide compound.
[0005]
[Means for Solving the Problems]
The present inventors have conducted extensive studies on N-acylsulfenamide compounds and methods for producing the same, and as a result, a novel N-acylsulfenamide compound was obtained by reacting a sulfenamide compound with perfluorocarboxylic anhydride. Have been found to be able to safely and easily obtain an N-acylsulfenamide compound without using chlorine gas, and have completed the present invention based on this finding.
[0006]
That is, according to the present invention, a novel N-acylsulfenamide compound represented by the following general formula (A) is provided.
Embedded image

(Wherein, R ¹ is an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a halogen atom, a nitro group are shown, when R ¹ are a plurality, each R ¹ may be the being the same or different, n is an integer of 0 or 1 to 4 .R ² is perfluoroalkyl of 1 to 12 carbon atoms Represents a group.)
[0007]
Further, according to the present invention, in a method for producing an N-acylsulfenamide compound represented by the following general formula (A), a sulfenamide compound represented by the following general formula (B): A method for producing an N-acylsulfenamide compound, characterized by reacting the acid anhydride represented by (c), is provided.
Embedded image

(Wherein, R ¹ is an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a halogen atom, a nitro group are shown, when R ¹ are a plurality, each R ¹ may be the being the same or different, n is an integer of 0 or 1 to 4 .R ² is perfluoroalkyl of 1 to 12 carbon atoms Represents a group.)
Embedded image

(Wherein, R ¹ is an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a halogen atom, a nitro group are shown, when R ¹ are a plurality, each R ¹ may be the being the same or different, n is an integer of 0 or 1 to 4.)
Embedded image

(In the formula, R ² represents a C 1-12 perfluoroalkyl group.)
[0008]
BEST MODE FOR CARRYING OUT THE INVENTION
The N-acylsulfenamide compound of the present invention is a compound represented by the following general formula (A).
Embedded image

In the formula, R ¹ is an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a halogen atom, and a nitro group. Is shown.
Illustrative examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an s-butyl group, a t-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, t-pentyl group, n-hexyl group, isohexyl group, 2-hexyl, 3-hexyl group, n-heptyl group, 2-heptyl group, 3-heptyl group, 4-heptyl group, n-octyl group, 2-octyl Group, 3-octyl group, 4-octyl group and the like.
Specific examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group.
Specific examples of the alkoxyl group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a hexyloxy group.
Specific examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a hexyloxycarbonyl group, and a benzyloxycarbonyl group.
n shows 0 or the integer of 1-4.
[0009]
R ² represents a C 1-12 perfluoroalkyl group. Specific examples of the perfluoroalkyl group include a trifluoromethyl group, a pentafluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluoroisobutyl group, a perfluoro-s-butyl group, and a perfluoro-t-butyl group. And a perfluorohexyl group.
[0010]
Specific examples of the N-acylsulfenamide compound of the present invention include the N-acylsulfenamide compounds represented by the compounds (1) to (7). These compounds find use as starting materials for rubber vulcanizing agents, fungicides, insecticides and herbicides.
Embedded image

[0011]
The method for producing the N-acylsulfenamide compound of the present invention represented by the general formula (a) is as follows.
Embedded image

(Wherein, R ¹ is an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a halogen atom, a nitro group are shown, ^{when R 1} is more than one be each ^{R 1} is the same as each other or different, .R ² n is 0 or an integer of 1 to 4 1 to 12 carbon atoms perfluoro Represents an alkyl group.)
[0012]
A sulfenamide compound represented by the following general formula (b), which is a raw material, is reacted with an acid anhydride represented by the following general formula (c).
Embedded image

(Wherein, R ¹ is an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a halogen atom, a nitro group are shown, when R ¹ are a plurality, each R ¹ may be the being the same or different, n is an integer of 0 or 1 to 4.)
Embedded image

(In the formula, R ² represents a C 1-12 perfluoroalkyl group.)
[0013]
The raw material is preferably dissolved in a solvent and reacted in the presence of a basic substance.
The reaction solvent is performed in a solvent such as methylene chloride, chloroform, 1,2-dichloroethane, acetonitrile, tetrahydrofuran, dioxane, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, and anisole.
These solvents are used alone or in the form of a mixed solvent.
Tertiary amines are used as the base substance to be added. As the amines, pyridine, methylpyridine, dimethylpyridine, triethylamine, tributylamine and the like are used.
Reaction temperatures range from -78 ° C to 0 ° C, preferably from -30 ° C to 0 ° C. If the temperature is lower than this temperature, the reaction is slow and the progress of the reaction becomes difficult. If it exceeds this range, a side reaction occurs, which is not preferable.
In addition, the sulfenamide compound represented by the general formula (b) as the raw material is produced by reacting a thiol compound with hydroxylamine-O-sulfonic acid by a known method. An acid anhydride represented by the general formula (C), which is another raw material, is produced by subjecting a carboxylic acid to a dehydration reaction.
The reaction time is between 5 minutes and 5 hours. After completion of the reaction, the solvent is removed and the desired product is taken out.
[0014]
【Example】
Next, the present invention will be described in detail with reference to examples. It should be noted that the embodiments of the present invention are representative ones for easy understanding of the present invention, and the present invention is not limited to these. In addition, the novel N-acylsulfenamide compounds (1) to (7) produced by the following Examples are the compounds (1) to (7) shown above, and various spectral data are used as main criteria. As identified. Other N-acylsulfenamide compounds were identified by comparing the melting point and various spectral data of known compounds with various spectra as the main criteria for unknown compounds.
[0015]
Example 1
In a glass container having an inner volume of 30 ml, 2-methoxycarbonylbenzenesulfenamide (91.5 mg, 0.5 mmol) was dissolved in 5 ml of methylene chloride, and trifluoroacetic anhydride (210 mg, 1.0 mmol) and pyridine (80 μl) were added. added. After stirring at 0 ° C. for 30 minutes, the solvent is distilled off under reduced pressure, and the crude product is purified by silica gel chromatography (elution solvent: methylene chloride) to yield the N-acylsulfenamide of compound (1). 102 mg was obtained in a yield of 73%.
This compound could be further purified by recrystallization using methylene chloride-hexane.
Melting point: 127-128 ° C. ¹ H NMR (500 MHz, CDCl ₃ ): d 8.04 (dd, J = 7.6, 1.2 Hz, 1H), 7.54 (ddd, J = 8.6, 7.3, 1.3. 5 Hz, 1H), 7.50 (s, 1H), 7.27 (ddd, J = 7.0, 7.0, 1.3 Hz, 1H), 7.17 (dd, J = 8.0). ^{, 0.6 Hz, 1H), 3.96} (s, 3H); 13 C NMR (125 MHz, CDCl 3): d 167.4, 159.2 (q, J CF = 37.0 Hz, C = O), 142.4, 133.6, 131.3 , 125.5, 124.5, 121.5, 115.7 (q, J CF = 287.4 Hz, CF 3), 52.8; IR (KBr): 3223, 3090, 2959, 1713, 1696, 146 , 1441, 1319, 1206, 1163 , 747 cm -1; High resolution mass: Calculated _{C 10 H 8 F 3 NO 3} S: 279.0177, Found 279.0141.
[0016]
Example 2
In Example 1, the same reaction was carried out using 2-bromobenzenesulfenamide (102 mg, 0.5 mmol) instead of 2-methoxycarbonylbenzenesulfenamide, and the crude product was subjected to silica gel chromatography (elution solvent). By purifying with methylene chloride: hexane = 2: 1), N-acylsulfenamide of the compound (2) was obtained in a yield of 144 mg and a yield of 80%.
Melting point: 89-90 ° C. ¹ H NMR (500 MHz, CDCl ₃ ): d 7.56 (s, 1H), 7.54 (dd, J = 8.6, 1.6 Hz, 1H), 7.33 (ddd, J = 8). .6, 7.3, 1.2 Hz, 1H), 7.16-7.13 (m, 2H); ¹³ C NMR (125 MHz, CDCl ₃ ): d 159.0 (q, J _CF = 38). .1 Hz, C = O), 136.1, 133.2, 128.8, 128.3, 126.3, 119.9, 115.5 (q, J CF = 288.4 Hz, CF 3) ; IR (KBr): 3225, 1723, 1468, 1447, 1211, 1167, 1150, 741 cm -1; high resolution mass: calculated _{C 8 H 5 BrF 3 NOS:} 298.9227, 300.9207, Found 29 8.9210, 300.9216.
[0017]
Example 3
In Example 1, a similar reaction was carried out using 4-nitrobenzenesulfenamide (85 mg, 0.5 mmol) instead of 2-methoxycarbonylbenzenesulfenamide, and the crude product was subjected to silica gel chromatography (elution solvent: chloride By purification with methylene), N-acylsulfenamide of compound (3) was obtained in a yield of 90 mg and 82%.
Melting point: 111-113 ° C. ¹ H NMR (500 MHz, CDCl ₃ ): d 8.22 (ddd, J = 9.2, 2.5, 2.5 Hz, 2H), 7.74 (s, 1H), 7.34 (ddd) , J = 9.2, 2.5, 2.5 Hz, 2H); 13 C NMR (125 MHz, CDCl 3): d 159.0 (q, J CF = 39.1 Hz, C = O), 146.8, 144.8, 124.6, 124.4, 115.4 (q, J _CF = 288.4 Hz, CF ₃ ); IR (KBr): 3274, 1726, 1580, 1522, 1458, 1341 ^{, 1211, 1169, 1132 cm -1} ; high resolution mass: calculated _{C 8 H 5 F 3 N 2} O 3 S: 265.9973, Found 265.9953.
[0018]
Example 4
In Example 1, the same reaction was carried out using benzenesulfenamide (63 mg, 0.5 mmol) instead of 2-methoxycarbonylbenzenesulfenamide, and the crude product was subjected to silica gel chromatography (elution solvent: methylene chloride: By purifying with hexane (2: 1), N-acylsulfenamide of the compound (4) was obtained in a yield of 86 mg and 78%.
Melting point: 70-72 ° C. ¹ H NMR (500 MHz, CDCl ₃ ): d 7.53 (s, 1H), 7.46-7.43 (m, 2H), 7.39-7.32 (m, 3H); ¹³ C NMR. (125 MHz, CDCl ₃ ): d 159.1 (q, J _CF = 37.1 Hz, C = O), 135.5, 129.5, 129.1, 129.0, 115.6 (q, J _{CF = 287.4 Hz, CF 3)} ; IR (KBr): 3245, 1717, 1441, 1321, 1186, 740, 689 cm -1; high resolution mass: calculated _{C 8 H 6 F 3 NOS:} 221.0122 , Measured 221.0145.
[0019]
Example 5
In Example 1, the same reaction was carried out using 4-methylbenzenesulfenamide (70 mg, 0.5 mmol) instead of 2-methoxycarbonylbenzenesulfenamide, and the crude product was subjected to silica gel chromatography (elution solvent). By purifying with methylene chloride: hexane = 2: 1), N-acylsulfenamide of compound (5) was obtained in a yield of 74 mg and 63%.
Melting point: 84-86 ° C. ¹ H NMR (500 MHz, CDCl ₃ ): d 7.53 (s, 1 H), 7.43 (d, J = 8.3 Hz, 2H), 7.18 (d, J = 8.0 Hz, 2H). ), 2.36 (s, 3H); ¹³ C NMR (125 MHz, CDCl ₃ ): d 159.1 (q, J _CF = 38.1 Hz, C = O), 140.1, 131.9, _{130.9, 130.2, 115.6 (q,} J CF = 287.4 Hz, CF 3), 21.3; IR (KBr): 3289, 3239, 2926, 1725, 1468, 1321, 1163, 804 cm ⁻¹ ; high-resolution mass: calculated value C ₉ H ₈ F ₃ NOS: 235.0279, measured value 235.0291.
[0020]
Example 6
In a 30 ml glass container, 2-methoxycarbonylbenzenesulfenamide (91.5 mg, 0.5 mmol) was dissolved in 5 ml of methylene chloride, and pentafluoropropionic anhydride (310 mg, 1.0 mmol) and pyridine (80 μl, 1.0 mmol) was added. After stirring at 0 ° C. for 15 minutes, the solvent is distilled off under reduced pressure, and the crude product is purified by silica gel chromatography (elution solvent: methylene chloride) to obtain the N-acylsulfenamide of compound (6). 148 mg was obtained in a yield of 90%. This compound could be further purified by recrystallization using methylene chloride-hexane.
Melting point: 117-118 ° C. ¹ H NMR (500 MHz, CDCl ₃ ): d 8.04 (dd, J = 8.0, 1.6 Hz, 1H), 7.55-7.52 (m, 2H), 7.26 (ddd) , J = 7.3, 7.3, 1.2 Hz, 1H), 7.14 (dd, J = 8.2, 0.6 Hz, 1H), 3.96 (s, 3H); ¹³ C _{NMR (125 MHz, CDCl 3)} : d 167.4, 159.8 (t, J CF = 26.8 Hz, C = O), 142.4, 133.6, 131.8, 125.5, 124 _{.5, 121.5,117.7 (qt, J CF} = 285.4, 34.0 Hz, CF 3), 107.1 (tq, J CF = 266.8, 39.3 Hz, CF 2) , 52.8; IR (KBr): 3252, 1707, 1443, 1 319, 1213, 1148, 1032, 747 cm -1; High resolution mass: Calculated _{C 11 H 8 F 5 NO 3} S: 329.0145, Found 329.0094.
[0021]
Example 7
In Example 6, the same reaction was carried out using 4-nitrobenzenesulfenamide (85 mg, 0.5 mmol) instead of 2-methoxycarbonylbenzenesulfenamide, and the crude product was subjected to silica gel chromatography (elution solvent: chloride By purifying with methylene), 119 mg of the N-acylsulfenamide of the compound (7) was obtained at a yield of 85%.
Melting point: 88-89 ° C. ¹ H NMR (500 MHz, CDCl ₃ ): d 8.24 (ddd, J = 9.2, 2.5, 2.5 Hz, 2H), 7.67 (s, 1H), 7.34 (ddd, J = 9.2, 2.5, 2.5 Hz, 2H); ¹³ C NMR (125 MHz, CDCl ₃ ): d 159.8 (t, J _CF = 26.8 Hz, C = O), 146 .8, 144.7, 124.6, 124.4, 117.5 (qt, J CF = 285.4, 34.0 Hz, CF 3), 107.0 (tq, J CF = 266.8, 40.3 Hz, CF ₂ ); IR (KBr): 3260, 1721, 1512, 1451, 1346, 1208, 1181, 1157, 1030, 855 cm ⁻¹ ; high-resolution mass: calculated value C ₉ H ₅ F ₅ N _{2 3} S: 315.9941, Found 315.9930.
[0022]
【The invention's effect】
According to the present invention, a novel N-acylsulfenamide compound can be produced with high yield by reacting a sulfenamide compound with an acid anhydride. Moreover, since it can be produced safely without using toxic chlorine gas, it is most suitable as an industrial method for synthesizing N-acylsulfenamide compounds.

Claims (2)

An N-acylsulfenamide compound, which is a compound represented by the following general formula (A).

(Wherein, R ¹ is an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a halogen atom, a nitro group are shown, ^{when R 1} is more than one be each ^{R 1} is the same as each other or different, .R ² n is 0 or an integer of 1 to 4 1 to 12 carbon atoms perfluoro Represents an alkyl group.) In a method for producing an N-acylsulfenamide compound represented by a sulfenamide compound represented by the following general formula (A), an acid anhydride represented by the following general formula (B) and the following general formula (C) A method for producing an N-acylsulfenamide compound, comprising reacting a product.

(Wherein, R ¹ is an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a halogen atom, a nitro group are shown, ^{when R 1} is more than one be each ^{R 1} is the same as each other or different, .R ² n is 0 or an integer of 1 to 4 1 to 12 carbon atoms perfluoro Represents an alkyl group.)

(Wherein, R ¹ is an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a halogen atom, a nitro group are shown, when R ¹ are a plurality, each R ¹ may be the being the same or different, n is an integer of 0 or 1 to 4.)

(In the formula, R ² represents a C 1-12 perfluoroalkyl group.)