JP3951018B2 - Method for producing N-acylsulfenamide compound - Google Patents

Description

【非特許文献７】
V. A. Ignatov, R. A. Akchuria, I. V. Volkov, and P. A. Pirogov, J. Gen. Chem. USSR, 47, 1004-1010 (1977); Zh. Obshch. Khim., 47, 1096-1103 (1977).
【非特許文献８】
Y. Miura, Y. Katsura, and M. Kinoshita, Bull. Chem. Soc. Jpn., 51, 3004-3007 (1978).
【０００５】
【発明が解決しようとする課題】
本発明の課題は、Ｎ - アシルスルフェンアミド化合物を製造するにあたり、塩素ガスを用いて合成されている塩化スルフェニル化合物を原料に用いることなく、Ｎ - アシルスルフェンアミド化合物を製造するための新規な製造方法を提供することである。
【０００６】
【課題を解決するための手段】
本発明者らは、Ｎ-アシルスルフェンアミド化合物及びその製造方法について鋭意研究を重ねた結果、Ｎ-スルフェナモイルベンゾイミダゾール化合物とアミド化合物を反応させると、Ｎ-スルフェナモイルベンゾイミダゾールの硫黄原子上でアミド化合物がベンゾイミダゾール環と置換反応を起こすことによりＮ-アシルスルフェンアミド化合物を得ることができる反応を新たに見いだし、この知見に基づいて本発明を完成するに至った。
【０００７】
すなわち、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Ｎ-スルフェニルベンゾイミダゾール化合物と下記一般式（ハ）で表されるアミド化合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５】

（式中、Ｒ^１は、炭素数１〜１２のアルキル基、炭素数３〜８のシクロアルキル基、炭素数１〜１２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、ニトロ基から選ばれる基又は原子を示す。Ｒ^１が複数ある場合は、各Ｒ^１は互いに同一であっても、異なっていてもよい。
ｎは、０または１〜４の整数である。
Ｒ^２は、炭素数１〜１２のアルキル基、炭素数３〜８のシクロアルキル基、炭素数６〜１２の芳香族基から選ばれる基を示す。
Ｒ^３は、水素原子、炭素数１〜１２のアルキル基、炭素数３〜８のシクロアルキル基、炭素数６〜１２の芳香族基、炭素数１〜８のアシル基から選ばれる基を示す。
Ｒ^４は、水素原子、炭素数１〜１２のアルキル基、炭素数３〜８のシクロアルキル基、炭素数６〜１２の芳香族基、炭素数１〜８の複素環基から選ばれる基又は原子を示す。）
【化６】

（式中、Ｒ^１は、炭素数１〜１２のアルキル基、炭素数３〜８のシクロアルキル基、炭素数１〜１２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、ニトロ基から選ばれる基又は原子を示す。Ｒ^１が複数ある場合は、各Ｒ^１は、互いに同一であっても、異なっていてもよい。
ｎは、０または１〜４の整数である。
Ｒ^２は、炭素数１〜１２のアルキル基、炭素数３〜８のシクロアルキル基、炭素数６〜１２の芳香族基から選ばれる基を示す。
Ｒ^５は、炭素数１〜１２のアルキル基、炭素数３〜８のシクロアルキル基、炭素数１〜１２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、ニトロ基から選ばれる基又は原子を示す。Ｒ^５が複数ある場合は、各Ｒ^５は互いに同一であっても、異なっていてもよい。
ｍは、０または１〜４の整数である。）
【化７】

（式中、Ｒ^３は、水素原子、炭素数１〜１２のアルキル基、炭素数３〜８のシクロアルキル基、炭素数６〜１２の芳香族基、炭素数１〜８のアシル基から選ばれる基を示す。
Ｒ^４は、水素原子、炭素数１〜１２のアルキル基、炭素数３〜８のシクロアルキル基、炭素数６〜１２の芳香族基、炭素数１〜８の複素環基から選ばれる基又は原子を示す。）
【０００９】
【発明実施の形態】
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１〜１２のアルキル基、炭素数３〜８のシクロアルキル基、炭素数１〜１２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、デシル基、ドデシル基等が挙げられる。
前記シクロアルキル基の具体例を示すと、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。
ハロゲン原子には、塩素、フッ素、ヨウ素、臭素から選ばれる原子が用いられる。
ｎは０または１〜４の整数を示す。
【００１０】
式中、Ｒ^２は、炭素数１〜１２のアルキル基、炭素数３〜８のシクロアルキル基、炭素数６〜１２の芳香族基を示す。
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、デシル基、ドデシル基等が挙げられる。
前記シクロアルキル基の具体例を示すと、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基等が挙げられる。
前記芳香族基の具体例を示すと、フェニル基、トリル基、アニシル基、ナフチル基、メチルナフチル基等が挙げられ、これらの芳香族基にはメチル基、エチル基、プロピル基などのアルキル基、メトキシ基、エトキシ基、プロピオキシなどのアルコキシ基、ハロゲン原子、ニトロ基等の置換基により置換されていてもよい。
ｎは、０又は１〜４の整数を表す。
【００１１】
Ｒ^３は、水素原子、炭素数１〜１２のアルキル基、炭素数３〜８のシクロアルキル基、炭素数６〜１２の芳香族基、炭素数１〜８のアシル基を示す。
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、デシル基、ドデシル基等が挙げられる。
前記シクロアルキル基の具体例を示すと、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基等が挙げられる。
前記芳香族基の具体例を示すと、フェニル基、トリル基、アニシル基、ナフチル基、メチルナフチル基等が挙げられる。これらの芳香族基にはメチル基、エチル基、プロピル基、イソプロピル基などのアルキル基、メトキシ基、エトキシ基、プロピロキシ基、ブトキシ基などのアルコキシ基、塩素、フッ素、臭素及びヨウ素からなるハロゲン原子、ニトロ基等の基により置換されていてもよい。
前記アシル基の具体例を示すと、ホルミル基、アセチル基、プロピオニル基、ブチリル基、イソブチリル基、バレリル基、イソバレリル基、ベンゾイル基、シクロヘキシルカルボニル基等が挙げられる。
【００１２】
Ｒ^４は、水素原子、炭素数１〜１２のアルキル基、炭素数３〜８のシクロアルキル基、炭素数６〜１２の芳香族基、炭素数１〜８の複素環基を示す。
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、デシル基、ドデシル基等が挙げられる。
前記シクロアルキル基の具体例を示すと、シクロプロピル基、シクロブチル基、シクロヘキシル基、シクロヘプチル基等が挙げられる。
前記複素環基の具体例を示すと、フリル基、ピリジル基、キノリル基、チエニル基、ピペリジル基、イソキノリル基、ピロリル基、トリアジニル基、イミダゾリル基、トリアゾリル基、テトラゾリル基等が挙げられる。
【００１３】
前記化合物は、ゴムの加硫化剤、殺菌剤、殺虫剤、除草剤として用いることができる。
【００１９】
本発明のＮ-アシルスルフェンアミド化合物に含まれる具体的な化合物を挙げると、以下の化合物（１）から（７）に示されるフェンアミド化合物が挙ることができる。これらは、以下に述べる実施例中でその製造方法及び特性値を明らかにする。
本発明に含まれるＮ-アシルスルフェンアミド化合物は、前記一般式（イ）に包含されるものであり、この具体例に限定されるものではない。
【化１１】

【００２０】
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１２】

（式中、Ｒ^１は、炭素数１〜１２のアルキル基、炭素数３〜８のシクロアルキル基、炭素数１〜１２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、ニトロ基から選ばれる基又は原子を示す。Ｒ^１が複数ある場合は、各Ｒ^１は互いに同一であっても、異なっていてもよい。
ｎは０または１〜４の整数である。
Ｒ^２は、炭素数１〜１２のアルキル基、炭素数３〜８のシクロアルキル基、炭素数６〜１２の芳香族基から選ばれる基を示す。
Ｒ^３は、水素原子、炭素数１〜１２のアルキル基、炭素数３〜８のシクロアルキル基、炭素数６〜１２の芳香族基、炭素数１〜８のアシル基から選ばれる基を示す。
Ｒ^４は、水素原子、炭素数１〜１２のアルキル基、炭素数３〜８のシクロアルキル基、炭素数６〜１２の芳香族基、炭素数１〜８の複素環基から選ばれる基又は原子を示す。）
【００２１】
原料物質である下記一般式（ロ）で表されるＮ-スルフェニルベンゾイミダゾール化合物と、下記一般式（ハ）で表されるアミド化合物を反応させる。
【化１３】

（式中、Ｒ^１は、炭素数１〜１２のアルキル基、炭素数３〜８のシクロアルキル基、炭素数１〜１２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のアルキル基、炭素数３〜８のシクロアルキル基、炭素数６〜１２の芳香族基を示す。Ｒ^５は炭素数１〜１２のアルキル基、炭素数３〜８のシクロアルキル基、炭素数１〜１２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^５が複数ある場合は、各Ｒ^５は互いに同一であっても、異なっていてもよく、ｍは０または１〜４の整数である。）
【化１４】

（式中、Ｒ^３は、水素原子、炭素数１〜１２のアルキル基、炭素数３〜８のシクロアルキル基、炭素数６〜１２の芳香族基、炭素数１〜８のアシル基を示す。Ｒ^４は水素原子、炭素数１〜１２のアルキル基、炭素数３〜８のシクロアルキル基、炭素数６〜１２の芳香族基、炭素数１〜８の複素環基を示す。）
【００２２】
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、テトラヒドロフラン、ジエチルエーテル、ジオキサン、ジメトキシエタン、ジエトキシエタン、N,N-ジメチルホルムアミド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。
添加する塩基性物質としては、水素化ナトリウム、n-ブチルリチウム、s-ブチルリチウム、t-ブチルリチウム、リチウムジイソプロピルアミド、ナトリウムアミド等が用いられる。
反応温度は、−７８℃から１０℃、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、副反応が生起するので、好ましくない。
【００２３】
前記原料物質である一般式（ロ）で表されるＮ-スルフェニルベンゾイミダゾール化合物は、Ｎ-無置換スルフェンアミド化合物とベンゾイミダゾール化合物を加熱させ、アミン交換反応を起こさせるという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）で表されるアミド化合物は、カルボン酸をアミン化合物と反応させて製造される。
反応時間は、５分から１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。
【００２４】
【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。
下記実施例によって製造される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）である。この化合物の各種スペクトルデータを測定し、その結果を主要な判定基準として同定を行った。
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。
【００２５】
実施例１
内容積３０ｍｌのガラス製容器中にアセトアミド（７２ｍｇ，１．０ｍｍｏｌ）をＴＨＦ１０ｍｌに溶かし、０℃において水素化ナトリウム２ｍｍｏｌを加えた。１５分後、N-(2-メトキシカルボニルベンゼンスルフェニル)ベンゾイミダゾール（１００ｍｇ，０．３５ｍｍｏｌ）を加え、０℃で３０分撹拌を行った。反応溶液に水を加え、生成物を塩化メチレンで抽出し、溶液を硫酸マグネシウムで乾燥させた。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：アセトン：メタノール＝１００：５：１）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３３ｍｇ、収率４２％で得た。
この化合物は酢酸エチル−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 129-130 ℃. ¹H NMR (CD₃OD) d 2.21 (3H, s), 3.91 (3H, s), 7.22 (1H, td, J = 7.6, 1.0 Hz), 7.28 (1H, dd, J = 8.3, 1.0 Hz), 7.54 (1H, ddd, J = 8.3, 7.6, 1.2 Hz), 8.02 (1H, dd, J = 7.6, 1.2 Hz). ¹³C NMR (CD₃OD) d 23.0, 52.8, 123.1, 125.3, 125.5, 132.1, 134.2, 146.5, 168.3, 175.8. IR (KBr) v_max 3264, 2957, 1703, 1667, 1439, 1314, 1290, 1242, 1148, 747 cm^-1. 元素分析 C₁₀H₁₁NO₃S としての計算値: C, 53.32; H, 4.92; N, 6.22. 実測値: C, 53.44; H, 4.65; N, 6.11.
【００２６】
実施例２
内容積３０ｍｌのガラス製容器中にベンズアミド（１２１ｍｇ，１．０ｍｍｏｌ）をＴＨＦ１０ｍｌに溶かし、０℃において水素化ナトリウム２ｍｍｏｌを加えた。１５分後N-(2-メトキシカルボニルベンゼンスルフェニル)ベンゾイミダゾール（１００ｍｇ，０．３５ｍｍｏｌ）を加え、０℃で１０分撹拌を行った。反応溶液に水を加え、生成物を塩化メチレンで抽出し、溶液を硫酸マグネシウムで乾燥させた。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：アセトン：メタノール＝１００：５：１）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量６３ｍｇ、収率６２％で得た。
この化合物は酢酸エチル−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 156-158 ℃. ¹H NMR (CDCl₃) d 3.92 (3H, s), 7.16 (1H, t, J = 7.6 Hz), 7.30 (1H, d, J = 7.9 Hz), 7.41-7.45 (3H, m), 7.54 (1H, d, J = 7.9 Hz), 7.56 (1H, s), 7.91 (2H, d, J = 7.7 Hz), 7.99 (1H, d, J = 7.7 Hz). ¹³C NMR (CDCl₃) d 52.4, 122.1, 124.2, 124.6, 127.7, 128.8, 131.1, 132.4, 133.1, 144.9, 167.1, 169.0. IR (KBr) v_max 3264, 3063, 2951, 1701, 1663, 1453, 1433, 1312, 1256, 1105, 745, 693 cm^-1. 元素分析 C₁₅H₁₃NO₃S としての計算値: C, 62.70; H, 4.56; N, 4.87. 実測値: C, 62.68; H, 4.27; N, 4.76.
【００２７】
実施例３
内容積３０ｍｌのガラス製容器中にアセトアミド（７２ｍｇ，１．０ｍｍｏｌ）をＴＨＦ１０ｍｌに溶かし、０℃において水素化ナトリウム２ｍｍｏｌを加えた。１５分後、N-(2-エトキシカルボニルベンゼンスルフェニル)ベンゾイミダゾール（１００ｍｇ，０．３４ｍｍｏｌ）を加え、０℃で３０分撹拌を行った。反応溶液に水を加え、生成物を塩化メチレンで抽出し、溶液を硫酸マグネシウムで乾燥させた。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：アセトン：メタノール＝１００：５：１）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量６３ｍｇ、収率７８％で得た。
この化合物は酢酸エチル−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 122.0-123.0 ℃. ¹H NMR (CD₃OD) d 1.29 (3H, t, J = 7.0 Hz), 2.21 (3H, s), 4.37 (2H, q, J = 7.0 Hz), 7.23 (1H, ddd, J = 7.9, 7.3, 1.2 Hz), 7.28 (1H, d, J = 7.9 Hz), 7.54 (1H, ddd, J = 7.9, 7.3, 1.5 Hz), 8.02 (1H, dd, J = 7.9, 1.2 Hz). ¹³C NMR (CD₃OD) d 14.6, 23.0, 62.6, 123.1, 125.5, 125.6, 132.1, 134.1, 146.5, 167.9, 175.8. IR (KBr) v_max 3231, 2986, 1682, 1439, 1370, 1277, 1240, 1148, 1107, 1059, 1011, 752 cm^-1. 元素分析 C₁₁H₁₃NO₃S としての計算値: C, 55.21; H, 5.48; N, 5.85. 実測値: C, 55.57; H, 5.39; N, 5.73.
【００２８】
実施例４
実施例３において、アセトアミドの代わりにベンズアミド（１２１ｍｇ，１．０ｍｏｌ）を用いることにより、化合物（４）のＮ−アシルスルフェンアミドを収量７１ｍｇ、収率７０％で得た。
この化合物は酢酸エチル−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 146.0-147.0 ℃. ¹H NMR (CDCl₃) d 1.40 (3H, t, J = 7.0 Hz), 4.38 (2H, q, J = 7.0 Hz), 7.16 (1H, td, J = 8.2, 1.2 Hz), 7.30 (1H, d, J = 8.2 Hz), 7.41-7.45 (3H, m), 7.55 (1H, t, J = 7.6 Hz), 7.61 (1H, brs), 7.92 (1H, d, J = 7.6 Hz), 8.01 (1H, dd, J = 7.6, 1.2 Hz). ¹³C NMR (CDCl₃) d 14.3, 61.6, 122.1, 124.6, 127.7, 128.8, 131.1, 132.5, 133.1, 144.8, 166.7, 169.1. IR (KBr) v_max 3281, 3223, 1688, 1661, 1453, 1426, 1256, 1150, 1105, 1057, 1020, 756, 689 cm^-1. 元素分析 C₁₆H₁₄NO₃S としての計算値: C, 63.77; H, 5.02; N, 4.65. 実測値: C, 63.79; H, 4.89; N, 4.56.
【００２９】
実施例５
実施例４において、アセトアミドの代わりにp-メチルベンズアミド（１３５ｍｇ，１．０ｍｏｌ）を用いることにより、化合物（５）のＮ−アシルスルフェンアミドを収量９６ｍｇ、収率９０％で得た。
この化合物は酢酸エチル−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 138.4-139.5 ℃. ¹H NMR (CDCl₃) d 1.40 (3H, t, J = 7.3 Hz), 2.41 (1H, s), 4.39 (2H, q, J = 7.3 Hz), 7.16 (1H, ddd, J = 7.9, 7.0, 1.2 Hz), 7.24 (2H, d, J = 7.9 Hz), 7.29 (1H, d, J = 7.9 Hz), 7.42 (1H, ddd, J = 7.9, 7.0, 1.5 Hz), 7.82 (2H, d, J = 8.2 Hz), 8.01 (1H, dd, J = 7.9, 1.2 Hz). ¹³C NMR (CDCl₃) d 14.3, 21.6, 61.5, 122.1, 124.5, 124.6, 127.7, 129.4, 130.3, 131.1, 133.0, 143.1, 145.0, 166.7. IR (KBr) v_max 3227, 2978, 1696, 1657, 1437, 1254, 1148, 1101, 1059, 748 cm^-1. 元素分析 C₁₇H₁₇NO₃Sとしての計算値: C, 64.74; H, 5.43; N, 4.44. 実測値: C, 64.51; H, 5.29; N, 4.32.
【００３０】
実施例６
実施例３において、アセトアミドの代わりにN-メチルアセトアミド（７３ｍｇ，１．０ｍｏｌ）を用いることにより、化合物（６）のＮ−アシルスルフェンアミドを収量５１．５ｍｇ、収率６０％で得た。
この化合物は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 81.2-82.2 ℃. ¹H NMR (CDCl₃) d 1.43 (3H, t, J = 7.0 Hz), 2.29 (3H, s), 3.29 (3H, s), 4.42 (2H, q, J = 7.0 Hz), 7.07 (1H, d, J = 7.9 Hz), 7.27 (1H, td, J = 7.6, 1.2 Hz), 7.57 (1H, td, J = 8.2, 1.2 Hz), 8.12 (1H, dd, J = 7.6, 1.2 Hz). ¹³C NMR (CDCl₃) d 14.2, 21.5, 38.8, 61.6, 121.0, 124.2, 124.9, 131.5, 133.5, 144.3, 166.6, 176.7. IR (KBr) v_max 1678, 1368, 1308, 1148, 1101, 965, 918, 748, 509 cm^-1. 元素分析 C₁₂H₁₅NO₃S としての計算値: C, 56.90; H, 5.97; N, 5.53. 実測値: C, 57.32; H, 5.99; N, 5.35.
【００３１】
実施例７
実施例３において、アセトアミドの代わりにN-メチルベンズアミド（１３５ｍｇ，１．０ｍｏｌ）を用いることにより、化合物（７）のＮ−アシルスルフェンアミドを収量７４ｍｇ、収率７０％で得た。
この化合物は酢酸エチル−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108.2-109.9 ℃. ¹H NMR (CDCl₃) d 1.36 (3H, t, J = 7.0 Hz), 3.43 (3H, s), 4.33 (2H, q, J = 7.0 Hz), 7.23-7.28 (4H, m), 7.34 (1H, t, J = 7.3 Hz), 7.48 (2H, m), 7.62 (1H, ddd, J = 8.5, 7.3, 1.5 Hz), 8.05 (1H, dd, J = 7.9, 1.2 Hz). ¹³C NMR (CDCl₃) d 14.2, 39.7, 61.6, 103.2, 121.6, 124.2, 124.8, 127.3, 127.8, 130.3, 131.5, 133.5, 135.0, 144.7, 166.5, 190.3. IR (KBr) v_max 1686, 1649, 1462, 1331, 1281, 1256, 1144, 1103, 1061, 1009, 747, 714, 696, 538 cm^-1.
【００３２】
【発明の効果】
本発明によれば、塩素ガスや塩素化合物を用いることなく、Ｎ-スルフェニルベンゾイミダゾール化合物とアミド化合物を反応させる新規な方法が得られる。その際に、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。
本発明により得られる、前記一般式（ニ）で表される新規Ｎ-アシルスルフェンアミド化合物は、ゴムの加硫化剤、殺菌剤、殺虫剤、除草剤として用いることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention, N - a process for producing an acyl sulfenamide compound.
[0002]
[Prior art]
It is known that some sulfenamide compounds have functions as rubber vulcanizing agents, fungicides, insecticides, and herbicides (Non-Patent Document 1), and particularly N-benzoyl-4. -Chlorobenzenesulfenamide has been reported to have a plant growth regulating function (Non-patent Document 2). Thus, a group of N-acylsulfenamide compounds are industrially important compounds, and the creation of new compounds and the development of safer production methods are required.
[0003]
Amide compounds are generally produced by acylation of amine compounds. Similarly, a paper at the beginning of the 20th century reports that N-acylsulfenamide compounds can be obtained by acylation of sulfenamide (Non-patent Document 3, Non-patent Document 4, Non-patent Document 5, Non-patent Document 5). Patent Document 6), and thereafter, acylation of sulfenamide compounds did not proceed by the usual reaction with acid chlorides or acid anhydrides, and it was reported that disulfide compounds and disulfenylamine compounds were obtained. (Non-patent Document 7).
Therefore, in order to produce an N-acylsulfenamide compound, it has been produced by a reaction between a chlorinated sulfenyl compound and an amide compound (for example, Non-Patent Document 8).
However, since chlorinated sulfenyl compounds are conventionally produced by reaction of thiol compounds or disulfide compounds with chlorine gas, chlorine gas must be used to produce N-acylsulfenamide compounds. It has been said that. For these reasons, it has been desired to develop a method that does not use a sulfenyl chloride compound in order to produce an N-acylsulfenamide compound.
[0004]
[Non-Patent Document 1]
L. Craine and M. Raban, Chem. Rev., 89, 689-712 (1989).
[Non-Patent Document 2]
NP Pel'kis, YV Karabanov, VP Borisenko, and ES Levchenko, Fiziol. Akt. Veshch., 16, 47-49 (1984); Chem. Abstr., 103, 18314 (1985).
[Non-Patent Document 3]
Th. Zincke and Fr. Farr, Ann., 391, 57-88 (1912).
[Non-Patent Document 4]
Th. Zincke and S. Lenhardt, Ann., 400, 2-27 (1913).

[Non-Patent Document 7]
VA Ignatov, RA Akchuria, IV Volkov, and PA Pirogov, J. Gen. Chem. USSR, 47, 1004-1010 (1977); Zh. Obshch. Khim., 47, 1096-1103 (1977).
[Non-Patent Document 8]
Y. Miura, Y. Katsura, and M. Kinoshita, Bull. Chem. Soc. Jpn., 51, 3004-3007 (1978).
[0005]
[Problems to be solved by the invention]
An object of the present invention, N - in producing the acyl sulfenamide compound, a sulfenyl chloride compound is synthesized by using chlorine gas without using a raw material, N - for the production of acyl sulfenamide compound It is to provide a new manufacturing method.
[0006]
[Means for Solving the Problems]
As a result of extensive research on the N-acylsulfenamide compound and the production method thereof, the present inventors have found that when N-sulfenamoylbenzimidazole compound and amide compound are reacted, sulfur of N-sulfenamoylbenzimidazole is obtained. A new reaction has been found that allows an N-acylsulfenamide compound to be obtained by causing a substitution reaction of an amide compound with a benzimidazole ring on an atom, and the present invention has been completed based on this finding.
[0007]
That is, according to the present invention, in a method for producing an N-acylsulfenamide compound represented by the following general formula (I), an N-sulfenylbenzimidazole compound represented by the following general formula (B) and Provided is a method for producing an N-acylsulfenamide compound, which comprises reacting an amide compound represented by the general formula (c).
[Chemical formula 5]

(In the formula, R ¹ is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxyl group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a halogen atom, or a nitro group. If .R ¹ showing a group or atom selected from the group have more than one, even each R ¹ is the same as each other or may be different.
n is 0 or an integer of 1 to 4.
R ² represents a group selected from an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and an aromatic group having 6 to 12 carbon atoms.
R ³ represents a group selected from a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aromatic group having 6 to 12 carbon atoms, and an acyl group having 1 to 8 carbon atoms. .
R ⁴ is a group selected from a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aromatic group having 6 to 12 carbon atoms, and a heterocyclic group having 1 to 8 carbon atoms, or Indicates an atom. )
[Chemical 6]

(In the formula, R ¹ is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxyl group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a halogen atom, or a nitro group. If .R ¹ showing a group or atom selected from the group there are a plurality, each R ¹ may be the same or may be different from one another.
n is 0 or an integer of 1 to 4.
R ² represents a group selected from an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and an aromatic group having 6 to 12 carbon atoms.
R ⁵ is selected from an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxyl group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a halogen atom, and a nitro group. Indicates a group or atom. If R ⁵ have multiple, even each R ⁵ is the same as each other or may be different.
m is 0 or an integer of 1-4. )
[Chemical 7]

(In the formula, R ³ is selected from a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aromatic group having 6 to 12 carbon atoms, and an acyl group having 1 to 8 carbon atoms. Represents a group.
R ⁴ is a group selected from a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aromatic group having 6 to 12 carbon atoms, and a heterocyclic group having 1 to 8 carbon atoms, or Indicates an atom. )
[0009]
DETAILED DESCRIPTION OF THE INVENTION
The N-acylsulfenamide compound of the present invention is a compound represented by the following general formula (I).
[Chemical 9]

In the formula, R ¹ is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxyl group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a halogen atom, or a nitro group. Indicates.
Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, isopentyl group, 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 Group, 3-octyl group, 4-octyl group, decyl group, dodecyl 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.
As the halogen atom, an atom selected from chlorine, fluorine, iodine and bromine is used.
n shows 0 or the integer of 1-4.
[0010]
Wherein, ^{R 2} represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aromatic group having 6 to 12 carbon atoms.
Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, isopentyl group, 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 Group, 3-octyl group, 4-octyl group, decyl group, dodecyl group and the like.
Specific examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.
Specific examples of the aromatic group include phenyl group, tolyl group, anisyl group, naphthyl group, methylnaphthyl group and the like, and these aromatic groups include alkyl groups such as methyl group, ethyl group and propyl group. , An alkoxy group such as a methoxy group, an ethoxy group, or propioxy, a halogen atom, or a substituent such as a nitro group.
n represents 0 or an integer of 1 to 4.
[0011]
R ³ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aromatic group having 6 to 12 carbon atoms, or an acyl group having 1 to 8 carbon atoms.
Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, isopentyl group, 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 Group, 3-octyl group, 4-octyl group, decyl group, dodecyl group and the like.
Specific examples of the cycloalkyl group include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like.
Specific examples of the aromatic group include phenyl group, tolyl group, anisyl group, naphthyl group, methylnaphthyl group and the like. These aromatic groups include alkyl groups such as methyl, ethyl, propyl, and isopropyl groups, alkoxy groups such as methoxy, ethoxy, propyloxy, and butoxy groups, and halogen atoms composed of chlorine, fluorine, bromine, and iodine. And may be substituted with a group such as a nitro group.
Specific examples of the acyl group include formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, benzoyl group, cyclohexylcarbonyl group and the like.
[0012]
R ⁴ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aromatic group having 6 to 12 carbon atoms, or a heterocyclic group having 1 to 8 carbon atoms.
Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, isopentyl group, 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 Group, 3-octyl group, 4-octyl group, decyl group, dodecyl group and the like.
Specific examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclohexyl group, and a cycloheptyl group.
Specific examples of the heterocyclic group include furyl group, pyridyl group, quinolyl group, thienyl group, piperidyl group, isoquinolyl group, pyrrolyl group, triazinyl group, imidazolyl group, triazolyl group, tetrazolyl group and the like.
[0013]
The compounds can be used as rubber vulcanizing agents, fungicides, insecticides, and herbicides.
[0019]
Specific examples of the compound included in the N-acylsulfenamide compound of the present invention include the following phenamide compounds represented by the compounds (1) to (7). These will clarify the manufacturing method and characteristic values in the examples described below.
The N-acylsulfenamide compounds included in the present invention are included in the general formula (A), and are not limited to these specific examples.
Embedded image

[0020]
The method for producing the N-acylsulfenamide compound of the present invention represented by the general formula (A) is as follows.
Embedded image

(In the formula, R ¹ is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxyl group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a halogen atom, or a nitro group. If .R ¹ showing a group or atom selected from the group have more than one, even each R ¹ is the same as each other or may be different.
n is 0 or an integer of 1-4.
R ² represents a group selected from an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and an aromatic group having 6 to 12 carbon atoms.
R ³ represents a group selected from a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aromatic group having 6 to 12 carbon atoms, and an acyl group having 1 to 8 carbon atoms. .
R ⁴ is a group selected from a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aromatic group having 6 to 12 carbon atoms, and a heterocyclic group having 1 to 8 carbon atoms, or Indicates an atom. )
[0021]
An N-sulfenylbenzimidazole compound represented by the following general formula (B), which is a raw material, is reacted with an amide compound represented by the following general formula (C).
Embedded image

(In the formula, R ¹ is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxyl group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a halogen atom, or a nitro group. In the case where a plurality of R ¹ are present, each R ¹ may be the same as or different from each other, and n is 0 or an integer of 1 to 4. R ² has 1 to 12 carbon atoms An alkyl group, a cycloalkyl group having 3 to 8 carbon atoms, and an aromatic group having 6 to 12 carbon atoms, R ⁵ represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and 1 carbon atom. 12 alkoxyl group, an alkoxycarbonyl group having 2 to 8 carbon atoms, a halogen atom, a nitro group, if R ⁵ have multiple, even each R ⁵ is the same as each other or different, m Is 0 or an integer of 1 to 4.)
Embedded image

(In the formula, R ³ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aromatic group having 6 to 12 carbon atoms, or an acyl group having 1 to 8 carbon atoms. R ⁴ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aromatic group having 6 to 12 carbon atoms, or a heterocyclic group having 1 to 8 carbon atoms.
[0022]
The raw material is preferably dissolved in a solvent and reacted in the presence of a basic substance.
The reaction solvent is used in a solvent such as tetrahydrofuran, diethyl ether, dioxane, dimethoxyethane, diethoxyethane, N, N-dimethylformamide and the like. These solvents are used alone or in the form of a mixed solvent.
As the basic substance to be added, sodium hydride, n-butyllithium, s-butyllithium, t-butyllithium, lithium diisopropylamide, sodium amide or the like is used.
The reaction temperature is in the range of −78 ° C. to 10 ° C., preferably −30 ° C. to 0 ° C. Below this temperature, the reaction is slow and it is difficult to proceed. If this range is exceeded, side reactions occur, which is not preferable.
[0023]
The N-sulfenylbenzimidazole compound represented by the general formula (b) as the raw material is a known method in which an N-unsubstituted sulfenamide compound and a benzimidazole compound are heated to cause an amine exchange reaction. Produced by reaction.
The amide compound represented by the general formula (c), which is another raw material, is produced by reacting a carboxylic acid with an amine compound.
The reaction time is 5 minutes to 1 hour. After completion of the reaction, the solvent is removed and the target product is taken out.
[0024]
【Example】
Next, the present invention will be described in detail with reference to examples. In addition, the Example of this invention gave the typical thing in order to make an understanding of this invention easy, and this invention is not limited only to this.
N-acylsulfenamide compounds (1) to (7) produced by the following examples are the compounds (1) to (7) shown above. Various spectrum data of this compound was measured, and the result was identified using it as a main criterion.
For other N-acylsulfenamide compounds, the melting point and various spectrum data were compared for known ones, and for various unknown N-acylsulfenamide compounds, the various spectra were identified as the main criteria.
[0025]
Example 1
Acetamide (72 mg, 1.0 mmol) was dissolved in 10 ml of THF in a glass container having an internal volume of 30 ml, and 2 mmol of sodium hydride was added at 0 ° C. After 15 minutes, N- (2-methoxycarbonylbenzenesulfenyl) benzimidazole (100 mg, 0.35 mmol) was added, and the mixture was stirred at 0 ° C. for 30 minutes. Water was added to the reaction solution, the product was extracted with methylene chloride, and the solution was dried over magnesium sulfate. The crude product was purified by silica gel chromatography (elution solvent methylene chloride: acetone: methanol = 100: 5: 1) to obtain 33 mg of N-acylsulfenamide of compound (1) in a yield of 42%. It was.
This compound could be further purified by recrystallization using ethyl acetate-hexane.
Melting point 129-130 ° C. ¹ H NMR (CD ₃ OD) d 2.21 (3H, s), 3.91 (3H, s), 7.22 (1H, td, J = 7.6, 1.0 Hz), 7.28 (1H, dd, J = 8.3, 1.0 Hz), 7.54 (1H, ddd, J = 8.3, 7.6, 1.2 Hz), 8.02 (1H, dd, J = 7.6, 1.2 Hz). 13 C NMR (CD 3 OD) d 23.0, 52.8, 123.1, 125.3, 125.5, 132.1, 134.2, 146.5, 168.3, 175.8. IR (KBr) v _max 3264, 2957, 1703, 1667, 1439, 1314, 1290, 1242, 1148, 747 cm ^-1 . Elemental analysis C ₁₀ H ₁₁ Calculated as NO ₃ S: C, 53.32; H, 4.92; N, 6.22. Found: C, 53.44; H, 4.65; N, 6.11.
[0026]
Example 2
Benzamide (121 mg, 1.0 mmol) was dissolved in 10 ml of THF in a glass container having an internal volume of 30 ml, and 2 mmol of sodium hydride was added at 0 ° C. After 15 minutes, N- (2-methoxycarbonylbenzenesulfenyl) benzimidazole (100 mg, 0.35 mmol) was added, and the mixture was stirred at 0 ° C. for 10 minutes. Water was added to the reaction solution, the product was extracted with methylene chloride, and the solution was dried over magnesium sulfate. The crude product was purified by silica gel chromatography (elution solvent methylene chloride: acetone: methanol = 100: 5: 1) to obtain N-acylsulfenamide of compound (2) in a yield of 63 mg and a yield of 62%. It was.
This compound could be further purified by recrystallization using ethyl acetate-hexane.
Melting point 156-158 ° C. ¹ H NMR (CDCl ₃ ) d 3.92 (3H, s), 7.16 (1H, t, J = 7.6 Hz), 7.30 (1H, d, J = 7.9 Hz), 7.41-7.45 (3H , m), 7.54 (1H, d, J = 7.9 Hz), 7.56 (1H, s), 7.91 (2H, d, J = 7.7 Hz), 7.99 (1H, d, J = 7.7 Hz). ¹³ C NMR (CDCl ₃ ) d 52.4, 122.1, 124.2, 124.6, 127.7, 128.8, 131.1, 132.4, 133.1, 144.9, 167.1, 169.0.IR (KBr) v _max 3264, 3063, 2951, 1701, 1663, 1453, 1433, 1312 , 1256, 1105, 745, 693 cm ^-1 . Elemental analysis Calculated as C ₁₅ H ₁₃ NO ₃ S: C, 62.70; H, 4.56; N, 4.87. Found: C, 62.68; H, 4.27; N , 4.76.
[0027]
Example 3
Acetamide (72 mg, 1.0 mmol) was dissolved in 10 ml of THF in a glass container having an internal volume of 30 ml, and 2 mmol of sodium hydride was added at 0 ° C. After 15 minutes, N- (2-ethoxycarbonylbenzenesulfenyl) benzimidazole (100 mg, 0.34 mmol) was added, and the mixture was stirred at 0 ° C. for 30 minutes. Water was added to the reaction solution, the product was extracted with methylene chloride, and the solution was dried over magnesium sulfate. The crude product was purified by silica gel chromatography (elution solvent: methylene chloride: acetone: methanol = 100: 5: 1) to obtain 63 mg of N-acylsulfenamide of compound (3) in a yield of 78%. It was.
This compound could be further purified by recrystallization using ethyl acetate-hexane.
Melting point 122.0-123.0 ° C. ¹ H NMR (CD ₃ OD) d 1.29 (3H, t, J = 7.0 Hz), 2.21 (3H, s), 4.37 (2H, q, J = 7.0 Hz), 7.23 (1H, ddd, J = 7.9, 7.3, 1.2 Hz), 7.28 (1H, d, J = 7.9 Hz), 7.54 (1H, ddd, J = 7.9, 7.3, 1.5 Hz), 8.02 (1H, dd, J = 7.9, 1.2 C) ¹³ C NMR (CD ₃ OD) d 14.6, 23.0, 62.6, 123.1, 125.5, 125.6, 132.1, 134.1, 146.5, 167.9, 175.8. IR (KBr) v _max 3231, 2986, 1682, 1439, 1370 , 1277, 1240, 1148, 1107, 1059, 1011, 752 cm ^-1 . Elemental analysis Calculated as C ₁₁ H ₁₃ NO ₃ S: C, 55.21; H, 5.48; N, 5.85. Found: C, 55.57 ; H, 5.39; N, 5.73.
[0028]
Example 4
In Example 3, by using benzamide (121 mg, 1.0 mol) instead of acetamide, 71 mg of N-acylsulfenamide of compound (4) was obtained in a yield of 70%.
This compound could be further purified by recrystallization using ethyl acetate-hexane.
Melting point 146.0-147.0 ℃. ¹ H NMR (CDCl ₃ ) d 1.40 (3H, t, J = 7.0 Hz), 4.38 (2H, q, J = 7.0 Hz), 7.16 (1H, td, J = 8.2, 1.2 Hz ), 7.30 (1H, d, J = 8.2 Hz), 7.41-7.45 (3H, m), 7.55 (1H, t, J = 7.6 Hz), 7.61 (1H, brs), 7.92 (1H, d, J = 7.6 Hz), 8.01 (1H, dd, J = 7.6, 1.2 Hz). 13 C NMR (CDCl 3) d 14.3, 61.6, 122.1, 124.6, 127.7, 128.8, 131.1, 132.5, 133.1, 144.8, 166.7, 169.1. IR (KBr) v _max 3281, 3223, 1688, 1661, 1453, 1426, 1256, 1150, 1105, 1057, 1020, 756, 689 cm ^-1 . Elemental analysis Calculated as C ₁₆ H ₁₄ NO ₃ S: C , 63.77; H, 5.02; N, 4.65. Found: C, 63.79; H, 4.89; N, 4.56.
[0029]
Example 5
In Example 4, by using p-methylbenzamide (135 mg, 1.0 mol) instead of acetamide, N-acylsulfenamide of Compound (5) was obtained in a yield of 96 mg and a yield of 90%.
This compound could be further purified by recrystallization using ethyl acetate-hexane.
Melting point 138.4-139.5 ℃. ¹ H NMR (CDCl ₃ ) d 1.40 (3H, t, J = 7.3 Hz), 2.41 (1H, s), 4.39 (2H, q, J = 7.3 Hz), 7.16 (1H, ddd , J = 7.9, 7.0, 1.2 Hz), 7.24 (2H, d, J = 7.9 Hz), 7.29 (1H, d, J = 7.9 Hz), 7.42 (1H, ddd, J = 7.9, 7.0, 1.5 Hz) , 7.82 (2H, d, J = 8.2 Hz), 8.01 (1H, dd, J = 7.9, 1.2 Hz). 13 C NMR (CDCl 3) d 14.3, 21.6, 61.5, 122.1, 124.5, 124.6, 127.7, 129.4 , 130.3, 131.1, 133.0, 143.1, 145.0, 166.7. IR (KBr) v _max 3227, 2978, 1696, 1657, 1437, 1254, 1148, 1101, 1059, 748 cm ^-1 .Elemental analysis C ₁₇ H ₁₇ NO ₃ Calculated as S: C, 64.74; H, 5.43; N, 4.44. Found: C, 64.51; H, 5.29; N, 4.32.
[0030]
Example 6
In Example 3, N-methylacetamide (73 mg, 1.0 mol) was used instead of acetamide to obtain N-acylsulfenamide of compound (6) in a yield of 51.5 mg and a yield of 60%.
This compound could be further purified by recrystallization using hexane.
Melting point 81.2-82.2 ℃. ¹ H NMR (CDCl ₃ ) d 1.43 (3H, t, J = 7.0 Hz), 2.29 (3H, s), 3.29 (3H, s), 4.42 (2H, q, J = 7.0 Hz ), 7.07 (1H, d, J = 7.9 Hz), 7.27 (1H, td, J = 7.6, 1.2 Hz), 7.57 (1H, td, J = 8.2, 1.2 Hz), 8.12 (1H, dd, J = ^{7.6, 1.2 Hz). 13 C} NMR (CDCl 3) d 14.2, 21.5, 38.8, 61.6, 121.0, 124.2, 124.9, 131.5, 133.5, 144.3, 166.6, 176.7. IR (KBr) v max 1678, 1368, 1308, 1148, 1101, 965, 918, 748, 509 cm ^-1 . Elemental analysis Calculated as C ₁₂ H ₁₅ NO ₃ S: C, 56.90; H, 5.97; N, 5.53. Found: C, 57.32; H, 5.99; N, 5.35.
[0031]
Example 7
In Example 3, N-methylbenzamide (135 mg, 1.0 mol) was used instead of acetamide, whereby N-acylsulfenamide of compound (7) was obtained in a yield of 74 mg and a yield of 70%.
This compound could be further purified by recrystallization using ethyl acetate-hexane.
Melting point 108.2-109.9 ° C. ¹ H NMR (CDCl ₃ ) d 1.36 (3H, t, J = 7.0 Hz), 3.43 (3H, s), 4.33 (2H, q, J = 7.0 Hz), 7.23-7.28 (4H , m), 7.34 (1H, t, J = 7.3 Hz), 7.48 (2H, m), 7.62 (1H, ddd, J = 8.5, 7.3, 1.5 Hz), 8.05 (1H, dd, J = 7.9, 1.2 ¹³ C NMR (CDCl ₃ ) d 14.2, 39.7, 61.6, 103.2, 121.6, 124.2, 124.8, 127.3, 127.8, 130.3, 131.5, 133.5, 135.0, 144.7, 166.5, 190.3. IR (KBr) v _max 1686 , 1649, 1462, 1331, 1281, 1256, 1144, 1103, 1061, 1009, 747, 714, 696, 538 cm ^-1 .
[0032]
【The invention's effect】
According to the present invention, a novel method of reacting an N-sulfenylbenzimidazole compound with an amide compound can be obtained without using chlorine gas or a chlorine compound. At that time, the N-acylsulfenamide compound can be produced with high yield.
The novel N-acylsulfenamide compounds represented by the general formula (d) obtained by the present invention can be used as rubber vulcanizing agents, fungicides, insecticides, and herbicides.

Claims (2)

In the method for producing an N-acylsulfenamide compound represented by the following general formula (I), an N-sulfenylbenzimidazole compound represented by the following general formula (B) and the following general formula (C) A method for producing an N-acylsulfenamide compound represented by the following general formula (I), comprising reacting a general formula amide compound.

(In the formula, R ¹ is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxyl group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a halogen atom, or a nitro group. If .R ¹ showing a group or atom selected from the group have more than one, even each R ¹ is the same as each other or may be different.
n is 0 or an integer of 1-4.
R ² represents a group selected from an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and an aromatic group having 6 to 12 carbon atoms.
R ³ represents a group selected from a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aromatic group having 6 to 12 carbon atoms, and an acyl group having 1 to 8 carbon atoms. .
R ⁴ is a group selected from a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aromatic group having 6 to 12 carbon atoms, and a heterocyclic group having 1 to 8 carbon atoms, or Indicates an atom. )

(In the formula, R ¹ is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxyl group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a halogen atom, or a nitro group. If .R ¹ showing a group or atom selected from the group there are a plurality, each R ¹ may be the same or may be different from one another.
n is 0 or an integer of 1 to 4.
R ² represents a group selected from an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and an aromatic group having 6 to 12 carbon atoms.
R ⁵ is selected from an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxyl group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a halogen atom, and a nitro group. Indicates a group or atom. If R ⁵ is more, each R ⁵ may be identical to each other or may be different.
m is 0 or an integer of 1-4. )

(In the formula, R ³ is selected from a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aromatic group having 6 to 12 carbon atoms, and an acyl group having 1 to 8 carbon atoms. Represents a group.
R ⁴ is a group selected from a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aromatic group having 6 to 12 carbon atoms, and a heterocyclic group having 1 to 8 carbon atoms, or Indicates an atom. )   The method for producing an N-acylsulfenamide compound according to claim 1, wherein the reaction is carried out in the presence of a base.