JP2931064B2 - Substituted pyridinesulfonyl carbamate compound, method for producing the same, and method for producing substituted pyridinesulfonamide compound - Google Patents
Substituted pyridinesulfonyl carbamate compound, method for producing the same, and method for producing substituted pyridinesulfonamide compoundInfo
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- JP2931064B2 JP2931064B2 JP26339290A JP26339290A JP2931064B2 JP 2931064 B2 JP2931064 B2 JP 2931064B2 JP 26339290 A JP26339290 A JP 26339290A JP 26339290 A JP26339290 A JP 26339290A JP 2931064 B2 JP2931064 B2 JP 2931064B2
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- substituted
- compound
- producing
- pyridinesulfonyl
- general formula
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- Agricultural Chemicals And Associated Chemicals (AREA)
- Pyridine Compounds (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、除草剤の有効成分として有用な、後記一般
式（IV）で表わされる置換ピリジンスルホンアミド系化
合物（以下置換ピリジンスルホンアミド系化合物と略
す）を製造するための中間体として有用な、後記一般式
（Ｉ）で表わされる置換ピリジンスルホニルカーバメー
ト系化合物及びその製造方法並びに該中間体を用いた前
記置換ピリジンスルホンアミド系化合物の製造方法に関
する。The present invention relates to a substituted pyridinesulfonamide-based compound represented by the following general formula (IV) (hereinafter referred to as a substituted pyridinesulfonamide-based compound) useful as an active ingredient of a herbicide. ), A method for producing the substituted pyridinesulfonyl carbamate-based compound represented by the following general formula (I), and a method for producing the substituted pyridinesulfonamide-based compound using the intermediate: About.
（先行技術及び本発明に至った経緯） 前記置換ピリジンスルホニルカーバメート系化合物に
近接した化合物は、特開昭62−223180号公報に開示され
ている。ここで開示されている化合物は後記一般式
（Ｉ）中、Ｒがフェニル基のもの（R1及びR2はともにメ
チル基である）であるが、このものは、反応条件次第で
は反応中に分解したりして、生成取得できなかったり、
また、たとえ生成取得できたとしても室温における通常
の保存状態でさえ分解するというような種々の問題を有
している。(Prior Art and Background of the Invention) A compound close to the substituted pyridinesulfonyl carbamate compound is disclosed in JP-A-62-223180. The compounds disclosed herein are those in which R is a phenyl group (both R 1 and R 2 are methyl groups) in the general formula (I) described below. Or it could not be generated or acquired
In addition, there are various problems such as decomposition even in a normal storage state at room temperature even if it can be generated and obtained.
このようなことから本発明者等は、後記一般式（Ｉ）
中、Ｒがフェニル基以外のものについて種々検討したと
ころ、Ｒがアルキル基である置換ピリジンスルホニルカ
ーバメート系化合物が高収率かつ安定に生成取得でき、
さらにそれが除草剤の有効成分として有用な置換ピリジ
ンスルホンアミド系化合物を製造するための中間体とし
て非常に有用であることを見出し、本発明を完成した。From these facts, the present inventors have proposed the following general formula (I)
In which, when R was variously examined other than a phenyl group, a substituted pyridinesulfonyl carbamate-based compound in which R was an alkyl group could be produced and obtained in a high yield and stably,
Furthermore, they have found that it is very useful as an intermediate for producing a substituted pyridinesulfonamide compound useful as an active ingredient of a herbicide, and completed the present invention.
（発明の開示） 本発明は、一般式（Ｉ）； （式中、Ｒ、R1及びR2は各々アルキル基である）で表わ
される置換ピリジンスルホニルカーバメート系化合物
（以下ASDM−Ｃと略す）、 一般式（II）； （式中、R1及びR2は前述の通りである）と、 一般式（III）;XCOOR……（III） （式中、Ｒは前述の
通りであり、Ｘはハロゲン原子である）で表わされる化
合物とを反応させること特徴とする、ASDM−Ｃの製造方
法、及びASDM−Ｃと２−アミノ−4,6−ジメトキシピリ
ミジンとを反応させることを特徴とする、 一般式（IV）； （式中、R1及びR2は前述の通りである）で表わされる、
置換ピリジンスルホンアミド系化合物の製造方法に関す
る。(Disclosure of the Invention) The present invention provides a compound represented by the general formula (I): (Wherein R, R 1 and R 2 are each an alkyl group) (hereinafter, abbreviated as ASDM-C) represented by the general formula (II): (Wherein R 1 and R 2 are as described above), and general formula (III); XCOOR (III) (wherein, R is as described above and X is a halogen atom) A method for producing ASDM-C, characterized by reacting the compound represented by the formula (II), and reacting ASDM-C with 2-amino-4,6-dimethoxypyrimidine; general formula (IV); (Wherein R 1 and R 2 are as described above)
The present invention relates to a method for producing a substituted pyridinesulfonamide compound.
前記一般式（Ｉ）〜（IV）中Ｒ、R1及びR2で表わされ
るアルキル基としては、炭素数１〜６を有するもの、例
えばメチル基、エチル基、プロピル基、ブチル基などが
挙げられ、それらは直鎖又は枝分れ脂肪鎖の幾何異性の
ものを含み、なかでもＲとしてはエチル基が望ましい。Examples of the alkyl group represented by R, R 1 and R 2 in the general formulas (I) to (IV) include those having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, a propyl group and a butyl group. These include those having a geometrical isomer of a linear or branched fatty chain, and among them, R is preferably an ethyl group.
前記一般式（III）中Ｘで表わされるハロゲン原子と
しては、塩素原子、臭素原子、沃素原子が挙げられ、な
かでも塩素原子が望ましい。Examples of the halogen atom represented by X in the general formula (III) include a chlorine atom, a bromine atom and an iodine atom, and among them, a chlorine atom is desirable.
本発明に係るASDM−Ｃの製造方法を以下に詳述する。 The method for producing ASDM-C according to the present invention will be described in detail below.
（式中、Ｒ、R1、R2及びＸは前述の通りである）。 (Wherein R, R 1 , R 2 and X are as described above).
一般式（III）で表わされる化合物の使用量は一概に
規定できないが、一般式（II）で表わされる化合物に対
して通常１〜２倍モル、望ましくは1.2〜1.5倍モルであ
る。Although the amount of the compound represented by the general formula (III) cannot be specified unconditionally, it is usually 1 to 2 moles, preferably 1.2 to 1.5 times the mole of the compound represented by the general formula (II).
上記反応で使用される塩基としては例えば、無水炭酸
カリウム、水酸化ナトリウム、水酸化カリウムなどが挙
げられ、その使用量は一概に規定できないが、一般式
（II）で表わされる化合物に対して通常２〜４倍当量、
望ましくは2.4〜3.0倍当量である。As the base used in the above reaction, for example, anhydrous potassium carbonate, sodium hydroxide, potassium hydroxide and the like can be mentioned, and the amount of use can not be specified unequivocally, but it is usually based on the compound represented by the formula (II). 2 to 4 equivalents,
It is desirably 2.4 to 3.0 equivalents.
また、上記反応で使用される溶媒としては例えば、ア
セトンなどのケトン類、アセトニトリルなどのニトリル
類、前記溶媒と水との混合物などが挙げられ、その使用
量は一概に規定できないが、一般式（II）で表わされる
化合物1gに対して通常３〜20ml、望ましくは５〜10mlで
ある。Examples of the solvent used in the above reaction include ketones such as acetone, nitriles such as acetonitrile, a mixture of the solvent and water, and the amount of the solvent cannot be specified unconditionally. The amount is usually 3 to 20 ml, preferably 5 to 10 ml, per 1 g of the compound represented by II).
上記反応の反応条件は一概に規定できないが、反応温
度は通常10〜100℃、反応時間は通常0.5〜10時間であ
る。Although the reaction conditions for the above reaction cannot be specified unconditionally, the reaction temperature is usually 10 to 100 ° C., and the reaction time is usually 0.5 to 10 hours.
上記製造方法で得られるASDM−Ｃを原料として使用し
て、下記製造方法により、一般式（IV）で表わされる置
換ピリジンスルホンアミド系化合物を製造することがで
きる。The substituted pyridinesulfonamide-based compound represented by the general formula (IV) can be produced by the following production method using ASDM-C obtained by the above production method as a raw material.
前記２−アミノ−4,6−ジメトキシピリミジンの使用
量は一概に規定できないが、ASDM−Ｃに対して通常１〜
２モルである。 Although the amount of the 2-amino-4,6-dimethoxypyrimidine used cannot be unconditionally specified, it is usually 1 to 1 with respect to ASDM-C.
2 moles.
上記反応で使用される溶媒としては例えば、ベンゼ
ン、トルエンなどの芳香族炭化水素類が挙げられ、その
使用量は一概に規定できないが、ASDM−C1gに対して通
常３〜30ml、望ましくは５〜15mlである。As the solvent used in the above reaction, for example, aromatic hydrocarbons such as benzene, toluene and the like can be mentioned, and the amount of use thereof cannot be specified unconditionally. 15 ml.
上記反応の反応条件は一概に規定できないが、反応温
度は通常、使用する溶媒の還流温度であり、反応時間は
通常１〜15時間である。Although the reaction conditions for the above reaction cannot be specified unconditionally, the reaction temperature is usually the reflux temperature of the solvent used, and the reaction time is usually 1 to 15 hours.
（実施例） 本発明をより詳しく述べるため、以下に実施例を記載
するが、これらは本発明を限定するものではない。(Examples) In order to describe the present invention in more detail, examples will be described below, but these do not limit the present invention.
実施例1. エチル｛３−〔（N,N−ジメチルアミノカル
ボニル）−２−ピリジニル〕スルホニル｝カーバメート
の合成 ３四つ口フラスコに、２−アミノスルホニル−N,N
−ジメチルニコチンアミド 206.1g（0.9mol）、無水炭
酸カリウム161.5g（1.17mol）及びアセトニトリル２
を仕込み、室温でクロル炭酸エチルエステル122.1g（1.
13mol）を20分間を要して撹拌下に滴下した。Example 1 Synthesis of ethyl {3-[(N, N-dimethylaminocarbonyl) -2-pyridinyl] sulfonyl} carbamate In a three-necked flask, 2-aminosulfonyl-N, N
-Dimethylnicotinamide 206.1 g (0.9 mol), anhydrous potassium carbonate 161.5 g (1.17 mol) and acetonitrile 2
Chlorocarbonate ethyl ester 122.1g (1.
13 mol) was added dropwise with stirring over a period of 20 minutes.
その後、還流温度で１時間反応させ、次いでアセトニ
トリルを留去した。四つ口フラスコに水500mlを加え反
応物を溶解させ、濃塩酸でpH2以下に調整して結晶を析
出させた。Thereafter, the reaction was carried out at a reflux temperature for 1 hour, and then acetonitrile was distilled off. 500 ml of water was added to the four-necked flask to dissolve the reaction product, and the pH was adjusted to 2 or less with concentrated hydrochloric acid to precipitate crystals.
得られた結晶を濾過、水洗後乾燥し、融点160〜164℃
の目的物246gを得た（収率90.8％）。The obtained crystals are filtered, washed with water and dried, melting point 160-164 ° C
246 g of the desired product was obtained (yield 90.8%).
実施例2. Ｎ−〔（4,6−ジメトキシピリミジン−２−
イル）アミノカルボニル〕−３−ジメチルアミノカルボ
ニル−２−ピリジンスルホンアミドの合成 200ml四つ口フラスコに前記実施例１で得た目的物5.1
g（0.017mol）、２−アミノ−4,6−ジメトキシピリミジ
ン2.6g（0.017mol）及びトルエン50mlを仕込み、還流
下、留出物を20ml/時間の割合で留去し、同時に同じ割
合でトルエンを投入しながら５時間反応させた。Example 2. N-[(4,6-dimethoxypyrimidine-2-
Synthesis of yl) aminocarbonyl] -3-dimethylaminocarbonyl-2-pyridinesulfonamide The desired product 5.1 obtained in the above Example 1 was placed in a 200 ml four-necked flask.
g (0.017 mol), 2.6 g (0.017 mol) of 2-amino-4,6-dimethoxypyrimidine and 50 ml of toluene, and distillate was distilled off under reflux at a rate of 20 ml / hour. The reaction was carried out for 5 hours while charging.
反応終了後、20℃まで冷却して1.5％水酸化ナトリウ
ム水溶液を投入し、15分間撹拌した。After completion of the reaction, the mixture was cooled to 20 ° C., and a 1.5% aqueous sodium hydroxide solution was added thereto, followed by stirring for 15 minutes.
その後、水層をトルエン層と分液し、50％硫酸でpH2
に調整して結晶を析出させた。Then, the aqueous layer was separated from the toluene layer, and the pH was adjusted to
And the crystals were precipitated.
得られた結晶を濾取した後、乾燥し目的物6.62gを得
た（収率94.9％）。The obtained crystals were collected by filtration and dried to obtain 6.62 g of the desired product (yield 94.9%).
───────────────────────────────────────────────────── フロントページの続き (72)発明者 田中 敏博 滋賀県草津市西渋川２丁目３番１号 石 原産業株式会社中央研究所内 審査官 齋藤 恵 (56)参考文献 特開 昭62−223180（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) C07D 213/00 - 213/82 ＣＡ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Toshihiro Tanaka 2-3-1 Nishi-Shibukawa, Kusatsu-shi, Shiga Examiner, Central Research Laboratory, Ishihara Sangyo Co., Ltd. Megumi Saito (56) References JP-A-62-223180 JP, A) (58) Fields investigated (Int. Cl. 6 , DB name) C07D 213/00-213/82 CA (STN) REGISTRY (STN)
Claims (6)
される、置換ピリジンスルホニルカーバメート系化合
物。1. A compound of the general formula (I): (In the formula, R, R 1 and R 2 are each an alkyl group.) A substituted pyridinesulfonylcarbamate compound represented by the formula:
チル基である、請求項１に記載の置換ピリジンスルホニ
ルカーバメート系化合物。2. The substituted pyridinesulfonyl carbamate compound according to claim 1 , wherein R is an ethyl group, and R 1 and R 2 are both methyl groups.
る化合物と、一般式（III）； XCOOR ……（III） （式中、Ｒはアルキル基であり、Ｘはハロゲン原子であ
る）で表わされる化合物とを反応させることを特徴とす
る、一般式（Ｉ）； （式中、Ｒ、R1及びR2は前述の通りである）で表わされ
る、置換ピリジンスルホニルカーバメート系化合物の製
造方法。3. A compound of the general formula (II): (Wherein R 1 and R 2 are each an alkyl group) and a compound represented by the general formula (III): XCOOR (III) (wherein R is an alkyl group and X is a halogen atom A) a compound represented by the general formula (I): (Wherein, R, R 1 and R 2 are as described above), and a method for producing a substituted pyridinesulfonyl carbamate compound.
チル基である、請求項３に記載の置換ピリジンスルホニ
ルカーバメート系化合物の製造方法。4. The method for producing a substituted pyridinesulfonyl carbamate compound according to claim 3, wherein R is an ethyl group and R 1 and R 2 are both methyl groups.
される置換ピリジンスルホニルカーバメート系化合物
と、２−アミノ−4,6−ジメトキシピリミジンとを反応
させることを特徴とする、 一般式（IV）； （式中、R1及びR2は前述の通りである）で表わされる、
置換ピリジンスルホンアミド系化合物の製造方法。5. A compound of the general formula (I): Wherein R, R 1 and R 2 are each an alkyl group; and reacting a substituted pyridinesulfonyl carbamate compound represented by the formula: with 2-amino-4,6-dimethoxypyrimidine. Formula (IV); (Wherein R 1 and R 2 are as described above)
A method for producing a substituted pyridinesulfonamide compound.
チル基である、請求項５に記載の置換ピリジンスルホン
アミド系化合物の製造方法。6. The process according to claim 5, wherein R is an ethyl group and R 1 and R 2 are both methyl groups.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26339290A JP2931064B2 (en) | 1990-10-01 | 1990-10-01 | Substituted pyridinesulfonyl carbamate compound, method for producing the same, and method for producing substituted pyridinesulfonamide compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26339290A JP2931064B2 (en) | 1990-10-01 | 1990-10-01 | Substituted pyridinesulfonyl carbamate compound, method for producing the same, and method for producing substituted pyridinesulfonamide compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04139170A JPH04139170A (en) | 1992-05-13 |
| JP2931064B2 true JP2931064B2 (en) | 1999-08-09 |
Family
ID=17388858
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26339290A Expired - Lifetime JP2931064B2 (en) | 1990-10-01 | 1990-10-01 | Substituted pyridinesulfonyl carbamate compound, method for producing the same, and method for producing substituted pyridinesulfonamide compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2931064B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011039276A1 (en) | 2009-10-01 | 2011-04-07 | Bayer Cropscience Ag | Oxathiazinyl(het)arylsulfonylureas, processes and intermediates for preparation thereof and use thereof as crop protection agents and crop growth regulators |
| CN103073488A (en) * | 2012-12-28 | 2013-05-01 | 合肥久易农业开发有限公司 | Synthesis method of sulfonamide formate |
| CN112645930B (en) * | 2020-12-30 | 2022-08-09 | 邯郸市瑞田农药有限公司 | Nicosulfuron water-phase method synthesis process |
-
1990
- 1990-10-01 JP JP26339290A patent/JP2931064B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04139170A (en) | 1992-05-13 |
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