JP2517990B2 - 4-acetylamino-5-fluoro-2-nitrophenoxyacetic acid - Google Patents
4-acetylamino-5-fluoro-2-nitrophenoxyacetic acidInfo
- Publication number
- JP2517990B2 JP2517990B2 JP62284808A JP28480887A JP2517990B2 JP 2517990 B2 JP2517990 B2 JP 2517990B2 JP 62284808 A JP62284808 A JP 62284808A JP 28480887 A JP28480887 A JP 28480887A JP 2517990 B2 JP2517990 B2 JP 2517990B2
- Authority
- JP
- Japan
- Prior art keywords
- acetylamino
- acid
- fluoro
- compound
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- Plural Heterocyclic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 本発明は新規なフェノキシ酢酸誘導体に関するもので
ある。さらに詳しくは、特開昭61−76486号公報に記載
の除草剤等を製造する上で有用な製造原料である４−ア
セチルアミノ−５−フルオロ−２−ニトロフェノキシ酢
酸（以下、本発明化合とと記す）を提供するものであ
る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel phenoxyacetic acid derivative. More specifically, 4-acetylamino-5-fluoro-2-nitrophenoxyacetic acid (hereinafter referred to as "the compound of the present invention", which is a raw material useful for producing the herbicides described in JP-A-61-76486) It is provided.
まず、本発明化合物の製造法について説明する。 First, the method for producing the compound of the present invention will be described.
本発明化合物は４−アセチルアミノ−３−フルオロフ
ェノキシ酢酸をニトロ化することによって製造される。The compounds of the present invention are prepared by nitrating 4-acetylamino-3-fluorophenoxyacetic acid.
該ニトロ化反応は硝酸や硝酸ナトリウム、硝酸カリウ
ム等の硝酸塩あるいはこれらと硫酸との混合物などのニ
トロ化剤を反応させることによって行われる。The nitration reaction is carried out by reacting a nitrating agent such as nitric acid, a nitrate such as sodium nitrate or potassium nitrate, or a mixture of these with sulfuric acid.
反応に用いられる試剤の量は、４−アセチルアミノ−
３−フルオロフェノキシ酢酸１当量に対して、通常、ニ
トロ化剤は１〜５当量である。反応に用いられる溶媒と
しては、例えば、ジクロロメタン、クロロホルム、1,2
−ジクロロエタン、1,1,1−トリクロロエタン等のハロ
ゲン化炭化水素類、水、硫酸、酢酸などあるいはそれら
の混合物があげられる。反応温度は通常−10〜30℃、好
ましくは０〜10℃の範囲であり、反応に要する時間は30
分〜24時間程度が標準的である。The amount of reagent used in the reaction is 4-acetylamino-
Usually, the nitrating agent is used in an amount of 1 to 5 equivalents based on 1 equivalent of 3-fluorophenoxyacetic acid. As the solvent used in the reaction, for example, dichloromethane, chloroform, 1,2
Examples thereof include halogenated hydrocarbons such as -dichloroethane and 1,1,1-trichloroethane, water, sulfuric acid, acetic acid and the like, or a mixture thereof. The reaction temperature is usually -10 to 30 ° C, preferably 0 to 10 ° C, and the reaction time is 30
Minutes to 24 hours is standard.
反応終了後の反応液は氷水にあけ、生成した結晶を
取するか、有機溶媒抽出および濃縮などの通常の後処理
を行う。さらに必要により、再結晶、クロマトグラフィ
ー等の操作を行う。After completion of the reaction, the reaction solution is poured into ice water and the resulting crystals are removed or subjected to usual post-treatments such as extraction with an organic solvent and concentration. If necessary, operations such as recrystallization and chromatography are performed.
なお、本発明化合物を製造する際の原料化合物である
４−アセチルアミノ−３−フルオロフェノキシ酢酸は次
式に示される経路により得ることができる。In addition, 4-acetylamino-3-fluorophenoxyacetic acid, which is a starting material compound for producing the compound of the present invention, can be obtained by the route shown by the following formula.
即ち、４−アミノ−３−フルオロフェノールを塩化ア
セチル、無水酢酸等のアセチル化剤と必要により塩基の
存在下に反応させて４−アミノ−３−フルオロフェノー
ルに導き、これをクロロ酢酸、ブロモ酢酸、ヨード酢酸
等のハロ酢酸と、通常脱ハロゲン化水素剤の存在下に反
応させることによって得ることができる。 That is, 4-amino-3-fluorophenol is reacted with an acetylating agent such as acetyl chloride or acetic anhydride in the presence of a base as necessary to give 4-amino-3-fluorophenol, which is then converted into chloroacetic acid or bromoacetic acid. , Iodoacetic acid and the like, and usually can be obtained by reacting with a haloacetic acid in the presence of a dehydrohalogenating agent.
本発明化合物は下記の経路により、有用な除草性化合
物である２−〔４−置換−７−フルオロ−2H−1,4−ベ
ンゾオキサジン−３（4H）−オン−６−イル〕−4,5,6,
7−テトラヒドロ−2H−イソインドール−1,3−ジオンに
導かれる。The compound of the present invention is a useful herbicidal compound, 2- [4-substituted-7-fluoro-2H-1,4-benzoxazin-3 (4H) -on-6-yl] -4, by the following route. 5,6,
Directed to 7-tetrahydro-2H-isoindole-1,3-dione.
〔式中、Ｒはアルキル基、アルケニル基、アルキニル
基またはアルコキシアルキル基を表わし、Ｒ′はアルキ
ル基を表わす。〕 以下、本発明化合物の製造例を具体例にて示すが、本
発明は下記の例のみに限定されるものではない。 [In the formula, R represents an alkyl group, an alkenyl group, an alkynyl group or an alkoxyalkyl group, and R'represents an alkyl group. Hereinafter, production examples of the compound of the present invention will be shown in specific examples, but the present invention is not limited to the following examples.
製造例 ４−アセチルアミノ−３−フルオロフェノキシ酢酸0.
92gを96％硫酸14.24gに懸濁させ、０℃で61％硝酸0.44g
を滴下し、さらに２時間０℃で攪拌した。次いで反応混
合物を氷水に加え、結晶を取して水洗、乾燥し、４−
アセチルアミノ−５−フルオロ−２−ニトロフェノキシ
酢酸1.25gを得た。Production Example 4-Acetylamino-3-fluorophenoxyacetic acid 0.
Suspend 92g in 96% sulfuric acid 14.24g, 0.4% g 61% nitric acid at 0 ℃
Was added dropwise, and the mixture was further stirred at 0 ° C. for 2 hours. Then, the reaction mixture was added to ice water, crystals were taken, washed with water, dried, and
1.25 g of acetylamino-5-fluoro-2-nitrophenoxyacetic acid was obtained.
mp 238〜239℃ 次に、本発明化合物を製造する際の原料化合物である
４−アセチルアミノ−３−フルオロフェノキシ酢酸の製
造例を参考例にて示す。mp 238 to 239 [deg.] C. Next, Reference Examples show Production Examples of 4-acetylamino-3-fluorophenoxyacetic acid, which is a starting material compound for producing the compound of the present invention.
参考例 （ｉ） ４−アセチルアミノ−３−フルオロフェノール
の製造 ４−アミノ−３−フルオロフェノール10.1gを酢酸81.
49gに溶かし、無水酢酸8.92gを加え75℃で２時間加熱攪
拌した。反応液を放冷後氷水にあけ、酢酸エチルで抽出
し、水洗後乾燥、次いで減圧下に溶媒を留去して、残渣
をシリカゲルクロマトグラフィー（展開溶媒；酢酸エチ
ル：ヘキサン＝1:1）に付し、４−アセチルアミノ−３
−フルオロフェノール6.3gを得た。Reference Example (i) Production of 4-acetylamino-3-fluorophenol 10.1 g of 4-amino-3-fluorophenol was added to 81.
It was dissolved in 49 g, 8.92 g of acetic anhydride was added, and the mixture was heated with stirring at 75 ° C. for 2 hours. The reaction solution is allowed to cool, then poured into ice water, extracted with ethyl acetate, washed with water, dried, and then the solvent is distilled off under reduced pressure, and the residue is subjected to silica gel chromatography (developing solvent; ethyl acetate: hexane = 1: 1). Attached, 4-acetylamino-3
-6.3 g of fluorophenol are obtained.
mp 114〜115℃ （ii） ４−アセチルアミノ−３−フルオロフェノキシ
酢酸の製造 ４−アセチルアミノ−３−フルオロフェノールを、重
曹1.26gを水5.33gに溶かした液に加え、30〜40℃で１時
間攪拌した。これに、水酸化ナトリウム1.10gとクロロ
酢酸2.28gとを水6.81gに溶かした液を加え、90℃で２時
間攪拌した。反応混合物を放冷した後濃塩酸でpH2と
し、酢酸エチルで抽出、抽出液を乾燥後減圧下に溶媒を
留去して４−アセチルアミノ−３−フルオロフェノキシ
酢酸2.0gを得た。mp 114-115 ° C (ii) Production of 4-acetylamino-3-fluorophenoxyacetic acid 4-Acetylamino-3-fluorophenol was added to a solution prepared by dissolving 1.26 g of baking soda in 5.33 g of water at 30-40 ° C. Stir for 1 hour. To this was added a solution prepared by dissolving 1.10 g of sodium hydroxide and 2.28 g of chloroacetic acid in 6.81 g of water, and the mixture was stirred at 90 ° C for 2 hours. The reaction mixture was allowed to cool, adjusted to pH 2 with concentrated hydrochloric acid, extracted with ethyl acetate, the extract was dried and the solvent was evaporated under reduced pressure to give 2.0 g of 4-acetylamino-3-fluorophenoxyacetic acid.
mp 152〜153℃mp 152-153 ℃
Claims (1)
ニトロフェノキシ酢酸。1. 4-Acetylamino-5-fluoro-2-
Nitrophenoxyacetic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62284808A JP2517990B2 (en) | 1987-11-10 | 1987-11-10 | 4-acetylamino-5-fluoro-2-nitrophenoxyacetic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62284808A JP2517990B2 (en) | 1987-11-10 | 1987-11-10 | 4-acetylamino-5-fluoro-2-nitrophenoxyacetic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01125356A JPH01125356A (en) | 1989-05-17 |
| JP2517990B2 true JP2517990B2 (en) | 1996-07-24 |
Family
ID=17683280
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62284808A Expired - Lifetime JP2517990B2 (en) | 1987-11-10 | 1987-11-10 | 4-acetylamino-5-fluoro-2-nitrophenoxyacetic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2517990B2 (en) |
-
1987
- 1987-11-10 JP JP62284808A patent/JP2517990B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01125356A (en) | 1989-05-17 |
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