JPH01125354A - 4-acetylamino-3-fluorophenoxyacetic acid and its production - Google Patents
4-acetylamino-3-fluorophenoxyacetic acid and its productionInfo
- Publication number
- JPH01125354A JPH01125354A JP28480987A JP28480987A JPH01125354A JP H01125354 A JPH01125354 A JP H01125354A JP 28480987 A JP28480987 A JP 28480987A JP 28480987 A JP28480987 A JP 28480987A JP H01125354 A JPH01125354 A JP H01125354A
- Authority
- JP
- Japan
- Prior art keywords
- acetylamino
- acid
- fluorophenol
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- BKWLNJCWKBFINN-UHFFFAOYSA-N 2-(4-acetamido-3-fluorophenoxy)acetic acid Chemical compound CC(=O)NC1=CC=C(OCC(O)=O)C=C1F BKWLNJCWKBFINN-UHFFFAOYSA-N 0.000 title 1
- 239000002253 acid Substances 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 abstract description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 abstract description 2
- WBJINCZRORDGAQ-UHFFFAOYSA-N ethyl formate Chemical compound CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 abstract description 2
- 230000002363 herbicidal effect Effects 0.000 abstract description 2
- 239000004009 herbicide Substances 0.000 abstract description 2
- BYKUYCWZSGDEFL-UHFFFAOYSA-N n-(2-fluoro-4-hydroxyphenyl)acetamide Chemical compound CC(=O)NC1=CC=C(O)C=C1F BYKUYCWZSGDEFL-UHFFFAOYSA-N 0.000 abstract 2
- 239000000463 material Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229940106681 chloroacetic acid Drugs 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 239000012345 acetylating agent Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- JDNTWHVOXJZDSN-UHFFFAOYSA-N iodoacetic acid Chemical compound OC(=O)CI JDNTWHVOXJZDSN-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- LCPDWSOZIOUXRV-UHFFFAOYSA-N phenoxyacetic acid Chemical class OC(=O)COC1=CC=CC=C1 LCPDWSOZIOUXRV-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
Abstract
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およびその製造法
に関するものである。さらに詳しくは、特開昭６１−７
６４８６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−８−フルオロフェ
ノキシ酢酸（以下、本発明化合物と記す）およびその製
造法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 and a method for producing the same. For more details, please refer to JP-A-61-7
The present invention provides 4-acetylamino-8-fluorophenoxyacetic acid (hereinafter referred to as the compound of the present invention), which is a useful raw material for producing the herbicides and the like described in JP-A No. 6486, and a method for producing the same.
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 explained.
本発明化合物は、４−アセチルアミノ−８−フルオロフ
ェノールとクロロ酢酸、ブロモ酢酸、ヨード酢酸等のハ
ロ酢酸とを、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製造される。The compound of the present invention is produced by reacting 4-acetylamino-8-fluorophenol with a haloacetic acid such as chloroacetic acid, bromoacetic acid, or iodoacetic acid, usually in the presence of a dehydrohalogenating agent.
該反応に使用される脱ハロゲン化水素剤としては水酸化
リチウム、水酸化ナトリウム、水酸化カリウム、水酸化
テトラメチルアンモニウム等の水酸化物、炭酸ナトリウ
ム、炭酸カリウム等の炭酸塩、炭酸水素ナトリウム、炭
酸水素カリウム等の炭酸水素塩、水素化ナトリウムなど
があげられる。The dehydrohalogenating agent used in the reaction includes hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and tetramethylammonium hydroxide, carbonates such as sodium carbonate and potassium carbonate, sodium hydrogen carbonate, Examples include hydrogen carbonates such as potassium hydrogen carbonate, sodium hydride, and the like.
反応に供せられる試剤の量は、通常、４−アセチルアミ
ノ−８−フルオロフェノール１当量に対して、ハロ酢酸
は１〜５当量であり、脱ハロゲン化水素剤は１〜５当聞
である。反応に用いられる溶媒としては例えば、ジオキ
サン、テトラヒドロフラン等のエーテル類、アセトン等
のケトン類、Ｎ、Ｎ−ジメチルホルムアミド等のアミド
類、ジメチルスルホキシド、スルホラン等の硫黄化合物
、ヘキサメチルホスホルトリアミド等のリン化合物、水
などあるいはそれらの混合物があげられる。The amount of reagents used in the reaction is usually 1 to 5 equivalents of haloacetic acid and 1 to 5 equivalents of dehydrohalogenation agent per equivalent of 4-acetylamino-8-fluorophenol. . Examples of solvents used in the reaction include ethers such as dioxane and tetrahydrofuran, ketones such as acetone, amides such as N,N-dimethylformamide, sulfur compounds such as dimethyl sulfoxide and sulfolane, and hexamethylphosphorotriamide. Examples include phosphorus compounds, water, etc., or mixtures thereof.
反応温度は通常２０〜２００℃、好ましくは６０〜１２
０℃の範囲である。反応終了後、反応液は酸性下で有機
溶媒抽出、濃縮等の通常の後処理を行い、必要ならば、
再結晶、クロマトグラフィー等の操作を行う。The reaction temperature is usually 20-200°C, preferably 60-12°C.
It is in the range of 0°C. After the reaction is completed, the reaction solution is subjected to conventional post-treatments such as organic solvent extraction and concentration under acidic conditions, and if necessary,
Perform operations such as recrystallization and chromatography.
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−８−フルオロフェノールは４−アミ
ノ−８−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反応させることにより得ることがで
きる。In addition, 4, which is a raw material compound when producing the compound of the present invention,
-Acetylamino-8-fluorophenol can be obtained by reacting 4-amino-8-fluorophenol with an acetylating agent such as acetyl chloride or acetic anhydride.
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−８（４Ｈ）−一オン−６−イル）−
４，５，６，７−テトラヒドロ−２Ｈ−イソインドール
−１，８−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-8(4H)-mono-6-yl)-
This leads to 4,5,6,7-tetrahydro-2H-isoindole-1,8-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, specific examples of manufacturing the compounds of the present invention will be shown, but the present invention is not limited to the following examples.
製造例
４−アセチルアミノ−８−フルオロフェノールを、重曹
１．２６ｆを水５．８８ｆに溶かした液に加え、８０〜
４０°Ｃで１時間撹拌した。Production Example 4 - Acetylamino-8-fluorophenol was added to a solution of 1.26 f of baking soda dissolved in 5.88 f of water, and
Stirred at 40°C for 1 hour.
これに、水酸化ナトリウム１．１０ｆ＄クロロ酢酸２．
２８＾水６．８１Ｆに溶かした液を加え、９０″Ｃで２
時間撹拌した。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−８−フルオロフェノ
キシ酢酸２．Ｏｆを得た。Add to this 1.10 f of sodium hydroxide and 2.0 f of chloroacetic acid.
28^ Add the solution dissolved in water 6.81F and heat at 90″C for 2
Stir for hours. After cooling the reaction mixture, the pH was adjusted to 2 with concentrated hydrochloric acid.
After extracting with ethyl acetate and drying the extract, the solvent was distilled off under reduced pressure to obtain 4-acetylamino-8-fluorophenoxyacetic acid. I got Of.
ｍｐ １５２〜１５８℃
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−８−フルオロフェノールの製造例を
参考例として示す。mp 152-158°C Next, 4 which is a raw material compound when producing the compound of the present invention
A production example of -acetylamino-8-fluorophenol is shown as a reference example.
参考例
４−アミノ−８−フルオロフェノール
１０．１Ｆを酢酸８１．４９ｆに溶かし、無水酢酸８．
９２ｆを加え７５°Ｃで２時間加熱撹拌した。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−８−フルオロフェ
ノール６．８１を得た。Reference Example 4-Amino-8-fluorophenol 10.1F was dissolved in 81.49F of acetic acid, and 8.1F of acetic anhydride was dissolved.
92f was added, and the mixture was heated and stirred at 75°C for 2 hours. After cooling the reaction solution, it was poured into ice water, extracted with ethyl acetate, washed with water, dried,
Then, the solvent was distilled off under reduced pressure, and the residue was subjected to silica gel chromatography (developing solvent: ethyl acetate:hexane = 1
:1) to obtain 6.81 of 4-acetylamino-8-fluorophenol.
ｍｐ １１４〜１１５℃ （６完）mp 114~115℃ (6 complete)
Claims (2)
酸。(1) 4-acetylamino-8-fluorophenoxyacetic acid.
ハロ酢酸とを反応させることを特徴とする４−アセチル
アミノ−８−フルオロフェノキシ酢酸の製造法。(2) A method for producing 4-acetylamino-8-fluorophenoxyacetic acid, which comprises reacting 4-acetylamino-8-fluorophenol and haloacetic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62284809A JP2517991B2 (en) | 1987-11-10 | 1987-11-10 | 4-acetylamino-3-fluorophenoxyacetic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62284809A JP2517991B2 (en) | 1987-11-10 | 1987-11-10 | 4-acetylamino-3-fluorophenoxyacetic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01125354A true JPH01125354A (en) | 1989-05-17 |
| JP2517991B2 JP2517991B2 (en) | 1996-07-24 |
Family
ID=17683293
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62284809A Expired - Lifetime JP2517991B2 (en) | 1987-11-10 | 1987-11-10 | 4-acetylamino-3-fluorophenoxyacetic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2517991B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5166401A (en) * | 1991-06-25 | 1992-11-24 | Pfizer Inc | Intermediates for 5-fluoro-6-chlorooxindole |
| US5210212A (en) * | 1991-06-25 | 1993-05-11 | Pfizer Inc | Process for 5-fluoro-6-chlorooxindole |
-
1987
- 1987-11-10 JP JP62284809A patent/JP2517991B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5166401A (en) * | 1991-06-25 | 1992-11-24 | Pfizer Inc | Intermediates for 5-fluoro-6-chlorooxindole |
| US5210212A (en) * | 1991-06-25 | 1993-05-11 | Pfizer Inc | Process for 5-fluoro-6-chlorooxindole |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2517991B2 (en) | 1996-07-24 |
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