JP3042123B2 - Method for producing N-cyanoacetamidine derivative - Google Patents
Method for producing N-cyanoacetamidine derivativeInfo
- Publication number
- JP3042123B2 JP3042123B2 JP35682891A JP35682891A JP3042123B2 JP 3042123 B2 JP3042123 B2 JP 3042123B2 JP 35682891 A JP35682891 A JP 35682891A JP 35682891 A JP35682891 A JP 35682891A JP 3042123 B2 JP3042123 B2 JP 3042123B2
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Description
【０００１】[0001]
【産業上の利用分野】本発明は、BACKGROUND OF THE INVENTION
【０００２】[0002]
【化４】 （式中、Ｒ2 は低級アルキル基を示し、Ｘは水素又はハ
ロゲンを示す。）Embedded image (In the formula, R 2 represents a lower alkyl group, and X represents hydrogen or halogen.)
【０００３】で表わされるＮ−シアノアセトアミジン誘
導体の製造方法に関するものであり、本化合物（III)は
殺虫剤又は殺虫剤の中間体としてきわめて有用な化合物
である。[0003] The present compound (III) is an extremely useful compound as an insecticide or an intermediate of an insecticide.
【０００４】[0004]
【従来の技術と問題点】一般式（Ｉ）BACKGROUND OF THE INVENTION General formula (I)
【０００５】[0005]
【化５】 （式中、Ｒ1 、Ｒ2 は、各々同一又は異なって、低級ア
ルキル基を示す。）Embedded image (Wherein, R 1 and R 2 are the same or different and each represents a lower alkyl group.)
【０００６】で表わされるＮ−シアノアセトアミデート
と、N-cyanoacetamidodate represented by the formula:
【０００７】[0007]
【化６】 （式中、Ｘは、前記と同じ意味を有する。）Embedded image (In the formula, X has the same meaning as described above.)
【０００８】で表わされるアミン誘導体とを反応させ、
式(III)Reacting with an amine derivative represented by the formula:
Formula (III)
【０００９】[0009]
【化７】 （式中、Ｒ2 、Ｘは、前記と同じ意味を有する。）Embedded image (In the formula, R 2 and X have the same meanings as described above.)
【００１０】で表わされるＮ−シアノアセトアミジン誘
導体を製造する一般的方法として、メタノール、エタノ
ール等の低級アルコール中で反応させる方法が知られて
おり、これらに関してはＷＯ９１／０４９６５に記載が
ある。しかしながら、類似化合物についての実施例の記
載はあるが、本発明に係る化合物(III）の製造実施例は
具体的記載がない。As a general method for producing an N-cyanoacetamidine derivative represented by the following formula, a method of reacting in a lower alcohol such as methanol or ethanol is known, and these are described in WO91 / 04965. However, although there is a description of an example for a similar compound, there is no specific description for a production example of the compound (III) according to the present invention.
【００１１】本発明者等は、前記文献の方法に従い、化
合物（Ｉ）と化合物（II）の反応をメタノール、エタノ
ール等の低級アルコール中で検討したところ、化合物
（Ｉ）の１当量に対し、化合物（II）が２当量反応して
いる、下に示した副生物（以下副生物Ａという）。The present inventors have studied the reaction of compound (I) with compound (II) in a lower alcohol such as methanol or ethanol according to the method described in the above-mentioned literature. A by-product shown below (hereinafter referred to as "by-product A"), in which 2 equivalents of the compound (II) are reacted.
【００１２】[0012]
【化８】 （式中、Ｒ2 、Ｘは、前記と同じ意味を有する。）Embedded image (In the formula, R 2 and X have the same meanings as described above.)
【００１３】が比較的多く生成し、化合物(III) の収率
は充分に満足されるものではない事が判った。It was found that the yield of compound (III) was not sufficiently satisfactory.
【００１４】[0014]
【発明が解決しようとする課題】本発明は、化合物
（Ｉ）と化合物（II）を反応させて化合物(III) を製造
する際に、前記副生物Ａの生成をできるだけおさえ、化
合物(III）の収率を上げる事を目的とする。SUMMARY OF THE INVENTION The present invention relates to a method for producing a compound (III) by reacting a compound (I) with a compound (II) to minimize the formation of the by-product A, The purpose is to increase the yield of.
【００１５】[0015]
【課題を解決するための手段】本発明者等は、上記課題
を解決するため鋭意検討を重ねた結果、アルコール類を
溶媒とした場合に比べ、水又は水〜低級アルコール混合
溶媒中で化合物（Ｉ）と化合物（II）を反応させる事に
より、前記副生物Ａの生成がおさえられ、化合物(III)
が著しく好効率で得られることを知るに至り、本発明を
完成した。又、本発明の方法によれば、化合物（Ｉ）が
反応中加水分解で消費される事が予想されたが、化合物
（II）との反応速度が非常に速いため、化合物（Ｉ）と
化合物（II）はほぼ等モルを使用すれば良い事も見出し
た。Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, compared with the case where alcohols were used as a solvent, the compounds ( By reacting I) with compound (II), the formation of by-product A is suppressed, and compound (III)
Have been found to be obtained with extremely good efficiency, and the present invention has been completed. According to the method of the present invention, compound (I) was expected to be consumed by hydrolysis during the reaction. However, since the reaction rate of compound (II) is very high, compound (I) and compound (I) It was also found that (II) should be used in approximately equimolar amounts.
【００１６】即ち、本発明は一般式（Ｉ）That is, the present invention provides a compound represented by the general formula (I)
【００１７】[0017]
【化９】 （式中、Ｒ1 、Ｒ2 は前記と同じ意味を有する。）Embedded image (In the formula, R 1 and R 2 have the same meaning as described above.)
【００１８】で表わされるＮ−シアノアセトアミデート
と、式（II）N-cyanoacetamidodate represented by the formula (II):
【００１９】[0019]
【化１０】 （式中、Ｘは、前記と同じ意味を有する。）Embedded image (In the formula, X has the same meaning as described above.)
【００２０】で表わされるアミン誘導体を、水又は水〜
低級アルコール混合溶媒中で反応させる事を特徴とす
る、式(III) 。The amine derivative represented by the formula
Formula (III), characterized in that the reaction is carried out in a lower alcohol mixed solvent.
【００２１】[0021]
【化１１】 （式中、Ｒ2 、Ｘは、は前記と同じ意味を有する。）Embedded image (Wherein, R 2 and X have the same meaning as described above.)
【００２２】で表わされるＮ−シアノアセトアミジン誘
導体の製法である。This is a method for producing an N-cyanoacetamidine derivative represented by the formula:
【００２３】つぎに、本発明は、例えば化合物（II）を
水又は水〜低級アルコール混合溶媒中に溶解させた溶液
中に、化合物（Ｉ）を滴下して反応させる事により、従
来の方法に比べ好効率で化合物(III) を得る事ができ
る。反応溶媒として水〜低級アルコール混合溶媒を用い
る場合、水１００部に対し低級アルコール４０部以下の
比率で混合した溶媒を用いる事で好結果が得られる。
又、低級アルコールとしてはメタノール、エタノール等
が使用できるが、工業的には安価なメタノールの使用が
望ましい。Next, the present invention provides a method according to the prior art, for example, by dropping compound (I) into a solution obtained by dissolving compound (II) in water or a mixed solvent of water and lower alcohol. Compound (III) can be obtained with higher efficiency. When a mixed solvent of water and a lower alcohol is used as a reaction solvent, good results can be obtained by using a solvent in which 100 parts of water and 40 parts or less of a lower alcohol are mixed.
As the lower alcohol, methanol, ethanol and the like can be used, but it is desirable to use inexpensive methanol industrially.
【００２４】化合物（Ｉ）は化合物（II）の１当量に対
し、１〜1.０５当量を用いる事で充分好結果が得られ
る。反応温度は−２０℃〜５０℃、好ましくは０℃〜３
０℃が良く、反応温度が高いと副生物Ａの生成量が増加
して収率が低下する傾向があり、反応温度が低いと反応
に長時間を要する。反応終了後、析出した結晶を濾過並
びに水洗処理を行う事により化合物(III)を得る事もで
きるが、反応後のスラリー溶液中の水と低級アルコール
の割合を適度に調整した後、昇温溶解し再結晶する事に
より、高純度の化合物(III) を好収率で得る事ができ
る。The use of 1 to 1.05 equivalents of the compound (I) to 1 equivalent of the compound (II) can give satisfactory results. The reaction temperature is -20 ° C to 50 ° C, preferably 0 ° C to 3 ° C.
0 ° C. is good. If the reaction temperature is high, the yield of by-product A tends to increase and the yield tends to decrease. If the reaction temperature is low, the reaction requires a long time. After completion of the reaction, the precipitated crystals can be filtered and washed with water to obtain compound (III) .However, after appropriately adjusting the ratio of water and lower alcohol in the slurry solution after the reaction, the mixture is heated and dissolved. By recrystallization, high purity compound (III) can be obtained in good yield.
【００２５】[0025]
【実施例】以下に示す実施例は、本発明を説明するもの
であって、本発明は何らこれに限定されるものではな
い。The following examples illustrate the present invention and do not limit the present invention in any way.
【００２６】実施例１ Ｎ−シアノ−Ｎ’−（２−クロル−５−ピリジンメチ
ル）アセトアミジンExample 1 N-cyano-N '-(2-chloro-5-pyridinemethyl) acetamidine
【００２７】[0027]
【化１２】 Embedded image
【００２８】水２３０mlに純度９7.５％の２−クロル−
５−ピリジルメチルアミン５8.５ｇ（0.４mol ）を加
え、冷却攪拌下に２５℃を保ちながら純度９７％のメチ
ル Ｎ−シアノアセトアミド４1.６ｇ（0.４１２mol ）
を４５分かけて滴下し、同温度で３０分攪拌した。反応
終了後、得られた目的物のスラリー液にメタノール８１
mlを加え、８０℃に加温して析出している結晶を溶解さ
せた後、１５℃迄徐冷して再結晶し、濾過、水洗、乾燥
して融点１４１〜１４３℃の目的物結晶７9.１ｇを得
た。高速液体クロマトグラフィーにて分析した結果、目
的物の純度は９9.３％であった。収率９4.１％。 1 Ｈ−ＮＭＲスペクトル（ＣＤＣｌ3 ）δｐｐｍ：2.３
５（３Ｈ、ｓ、ＣＨ3 ）4.５０（２Ｈ、ｄ、ＮＨＣ
Ｈ2 ）6.６０（１Ｈ、ｂｒｏａｄ、ＮＨ）7.２６〜8.３
２（３Ｈ、ｍ、ａｒｏｍａｔｉｃ）2-chloro- having a purity of 97.5% in 230 ml of water
58.5 g (0.4 mol) of 5-pyridylmethylamine was added.
And maintaining the temperature at 25 ° C under cooling and stirring.
N-cyanoacetamide 41.6 g (0.412 mol)
Was added dropwise over 45 minutes, and the mixture was stirred at the same temperature for 30 minutes. reaction
After completion, methanol 81 was added to the obtained slurry liquid of the target substance.
Add the solution and heat to 80 ° C to dissolve the precipitated crystals.
After cooling, slowly cool to 15 ° C to recrystallize, filter, wash and dry.
To give 79.1 g of the target crystal having a melting point of 141 to 143 ° C.
Was. As a result of analysis by high performance liquid chromatography,
The purity of the target was 99.3%. Yield 94.1%.1 H-NMR spectrum (CDClThree) Δ ppm: 2.3
5 (3H, s, CHThree) 4.50 (2H, d, NHC
H 2 ) 6.60 (1H, broad, NH) 7.26-8.3
2 (3H, m, aromatic)
【００２９】実施例２ Ｎ−シアノ−Ｎ’−（２−クロル−５−ピリジルメチ
ル）アセトアミジン 水２３０mlとメタノール８１mlとの混合溶媒に純度９7.
５％の２−クロル−５−ピリジルメチルアミン５8.５ｇ
（0.４mol ）を加え、冷却攪拌下に２０℃を保ちながら
純度９７％のメチル Ｎ−シアノアセトアミジン４1.６
ｇ（0.４１２mol ）を４５分かけて滴下し、同温度で３
０分攪拌した。反応後、８０℃に加温して析出している
結晶を溶解させた後、１５℃迄徐冷して再結晶し、濾
過、水洗、乾燥して融点１４１〜１４３℃の目的物結晶
７9.７ｇを得た。高速液体クロマトグラフィーにて分析
した結果、目的物の純度は９9.６％であった。収率９5.
１％。又、濾過母液を高速液体クロマトグラフィーにて
分析した結果、副生物Ａはわずか0.２３ｇ（0.００１２
mol ）しか生成していない事が判った。Example 2 N-cyano-N '-(2-chloro-5-pyridylmethyl) acetamidine Purity of 97 in a mixed solvent of 230 ml of water and 81 ml of methanol.
58.5 g of 5% 2-chloro-5-pyridylmethylamine
(0.4 mol) and methyl N-cyanoacetamidine having a purity of 97% while maintaining the temperature at 20 ° C. under cooling and stirring.
g (0.412 mol) was added dropwise over 45 minutes.
Stirred for 0 minutes. After the reaction, the mixture was heated to 80 ° C. to dissolve the precipitated crystals, then gradually cooled to 15 ° C., recrystallized, filtered, washed with water, and dried to obtain the target crystal having a melting point of 141 to 143 ° C. 79. 7 g were obtained. As a result of analysis by high performance liquid chromatography, the purity of the target product was 99.6%. Yield 95.
1%. Further, as a result of analyzing the filtered mother liquor by high performance liquid chromatography, only 0.23 g (0.000012) of by-product A was found.
mol).
【００３０】参考例１ Ｎ−シアノ−Ｎ’−（２−クロル−５−ピリジルメチ
ル）アセトアミジン メタノール２００mlに純度９７％のメチル Ｎ−シアノ
アセトアミド４1.６ｇ（0.４１２mol ）を加え、冷却攪
拌下に２０℃を保ちながら純度９7.５％の２−クロル−
５−ピリジルメチルアミン５8.５ｇ（0.４mol ）を４５
分かけて滴下し、同温度で１時間攪拌した。反応終了
後、得られた目的物のスラリー液に水４００mlを加えて
さらに結晶を析出させた後、濾過水洗乾燥して融点１４
１〜１４２℃の目的物結晶７6.１ｇを得た。高速液体ク
ロマトグラフィーにて分析した結果、純度は９9.２％で
あった。収率９0.４％。又、濾過母液を高速液体クロマ
トグラフィーで分析した結果、副生物Ａの生成量は1.８
７ｇ（0.００４５mol ）と実施例に比べ多く生成してい
る事が判った。Reference Example 1 N-cyano-N '-(2-chloro-5-pyridylmethyl) acetamidine To 200 ml of methanol was added 41.6 g (0.412 mol) of methyl N-cyanoacetamide having a purity of 97%, followed by cooling and stirring. 2-chloro- having a purity of 97.5% while maintaining the temperature at 20 ° C.
58.5 g (0.4 mol) of 5-pyridylmethylamine was added to 45
The mixture was added dropwise over a minute, and the mixture was stirred at the same temperature for 1 hour. After completion of the reaction, 400 ml of water was added to the obtained slurry of the target substance to precipitate further crystals.
There were obtained 76.1 g of the target crystal at 1-142 ° C. As a result of analysis by high performance liquid chromatography, the purity was 99.2%. 90.4% yield. Further, as a result of analyzing the filtered mother liquor by high performance liquid chromatography, the amount of by-product A produced was 1.8.
It turned out that 7 g (0.0045 mol) was produced in a larger amount than in the examples.
【００３１】参考例２ Ｎ，Ｎ’−ビス（２−クロル−ピリジルメチル）アセト
アミジン（副生物Ａ）Reference Example 2 N, N'-bis (2-chloro-pyridylmethyl) acetamidine (by-product A)
【００３２】[0032]
【化１３】 Embedded image
【００３３】Ｎ−シアノ−Ｎ’−（２−クロル−５−ピ
リジルメチル）アセトアミジン2.１０ｇと２−クロル−
５−ピリジルメチルアミン1.４３ｇを混合し、９０℃で
２４時間攪拌した。反応後、反応液をカラムクロマトグ
ラフィにより分離精製し、目的物結晶0.５４ｇを得た。
融点１０９〜１１１℃。 1 Ｈ−ＮＭＲスペクトル（ＣＤＣｌ3 ）δｐｐｍ：1.９
４（３Ｈ、ｓ、ＣＨ3 ）4.４１（４Ｈ、ｓ、ＣＨ2 ）7.
２４〜8.３２（６Ｈ、ｍ、ａｒｏｍａｔｉｃ）。N-cyano-N '-(2-chloro-5-pyridylmethyl) acetamidine 2.10 g and 2-chloro-
1.43 g of 5-pyridylmethylamine was mixed and stirred at 90 ° C. for 24 hours. After the reaction, the reaction solution was separated and purified by column chromatography to obtain 0.54 g of the target crystal.
109-111 ° C. 1 H-NMR spectrum (CDCl 3 ) δ ppm: 1.9
4 (3H, s, CH 3 ) 4.41 (4H, s, CH 2) 7.
24-8.32 (6H, m, aromatic).
【００３４】[0034]
【発明の効果】本発明によれば、化合物（Ｉ）と化合物
（II）を反応させて化合物(III) を製造する際に、従来
の方法に比べ、副生物の生成がおさえられ、化合物(II
I）が好収率で得られた。According to the present invention, when the compound (I) is reacted with the compound (II) to produce the compound (III), the production of by-products is suppressed as compared with the conventional method, and the compound ( II
I) was obtained in good yield.
フロントページの続き (72)発明者 川原 典明 新潟県中頸城郡中郷村大字藤沢950 日 本曹達株式会社 二本木工場内 (72)発明者 小島 篤 新潟県中頸城郡中郷村大字藤沢950 日 本曹達株式会社 二本木工場内 (56)参考文献 特開 平５−178833（ＪＰ，Ａ) 国際公開91／4965（ＷＯ，Ａ１) (58)調査した分野(Int.Cl.7，ＤＢ名) C07D 213/00 - 213/61 ＣＡ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)Continuing on the front page (72) Inventor Noriaki Kawahara Niigata Pref., Nakazawa-mura, Nakago-mura, Osamu Fujisawa 950 Nihon Soda Co., Ltd. Nihon Soda Co., Ltd. Company Nihongi Plant (56) References JP-A-5-178833 (JP, A) International Publication No. 91/4965 (WO, A1) (58) Fields investigated (Int. Cl. 7 , DB name) C07D 213/00 -213/61 CA (STN) REGISTRY (STN)
Claims (1)
ルキル基を示す。）で表わされるＮ−シアノアセトアミ
デートと、式（II） 【化２】 （式中、Ｘは、水素又はハロゲンを示す。）で表わされ
るアミン誘導体を、水又は水〜低級アルコール混合溶媒
中で反応させる事を特徴とする式（III) 【化３】 （式中、Ｒ2 、Ｘは、前記と同じ意味を有する。）で表
わされるＮ−シアノアセトアミジン誘導体の製法。1. A compound of the general formula (I) (Wherein R 1 and R 2 are the same or different and each represents a lower alkyl group), and an N-cyanoacetamidomate represented by the formula (II): (Wherein X represents hydrogen or halogen), wherein an amine derivative represented by the formula (III) is reacted in water or a mixed solvent of water and a lower alcohol. (Wherein, R 2 and X have the same meanings as described above.) A method for producing an N-cyanoacetamidine derivative represented by the formula:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35682891A JP3042123B2 (en) | 1991-12-26 | 1991-12-26 | Method for producing N-cyanoacetamidine derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35682891A JP3042123B2 (en) | 1991-12-26 | 1991-12-26 | Method for producing N-cyanoacetamidine derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05178834A JPH05178834A (en) | 1993-07-20 |
| JP3042123B2 true JP3042123B2 (en) | 2000-05-15 |
Family
ID=18450980
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP35682891A Expired - Lifetime JP3042123B2 (en) | 1991-12-26 | 1991-12-26 | Method for producing N-cyanoacetamidine derivative |
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| Country | Link |
|---|---|
| JP (1) | JP3042123B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4708548B2 (en) * | 2000-11-06 | 2011-06-22 | 日本曹達株式会社 | Method for removing basic impurities of 6-chloronicotine derivative |
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1991
- 1991-12-26 JP JP35682891A patent/JP3042123B2/en not_active Expired - Lifetime
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| Publication number | Publication date |
|---|---|
| JPH05178834A (en) | 1993-07-20 |
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