JP2561471B2 - Method for producing 5-fluoro-2-nitrophenol - Google Patents
Method for producing 5-fluoro-2-nitrophenolInfo
- Publication number
- JP2561471B2 JP2561471B2 JP62147351A JP14735187A JP2561471B2 JP 2561471 B2 JP2561471 B2 JP 2561471B2 JP 62147351 A JP62147351 A JP 62147351A JP 14735187 A JP14735187 A JP 14735187A JP 2561471 B2 JP2561471 B2 JP 2561471B2
- Authority
- JP
- Japan
- Prior art keywords
- fluoro
- nitrophenol
- added
- producing
- mixture
- 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
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 <産業上の利用分野> 本発明は5−フルオロ−2−ニトロフェノールの製造
法に関する。さらに詳しくは、特開昭61−79486号公報
に記載の除草剤である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−ジオンを製造する際の中間体である5−フルオロ
−2−ニトロフェノールの製造法に関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention relates to a method for producing 5-fluoro-2-nitrophenol. More specifically, 2- [4-substituted-7-fluoro-, which is a herbicide described in JP-A No. 61-79486, is disclosed.
2H-1,4-benzoxazin-3 (4H) -one-6-yl] -4,5,6,7-tetrahydro-2H-isoindole-
The present invention relates to a method for producing 5-fluoro-2-nitrophenol, which is an intermediate in producing 1,3-dione.
<従来の技術> 従来5−フルオロ−2−ニトロフェノールの製造法と
しては、3−フルオロフェノールを発煙硝酸でニトロ化
する方法(J.Chem.Soc.,1928,1880)および2,4−ジフル
オロニトロベンゼンを水酸化ナトリウム水溶液と反応さ
せた後、酸性下に水蒸気蒸留を行う方法(工業化学雑誌
73巻3号513頁、1970年)が知られている。<Prior Art> Conventionally, as a method for producing 5-fluoro-2-nitrophenol, a method of nitrating 3-fluorophenol with fuming nitric acid (J. Chem. Soc., 1928 , 1880) and 2,4-difluorophenol were used. After reacting nitrobenzene with sodium hydroxide solution, steam distillation under acidic condition
73, No. 3, 513, 1970) is known.
<発明が解決しようとする問題点> しかしながら、前者の方法は、ニトロ化の配向性の異
なる3−フルオロ−4−ニトロフェノールやジニトロ体
である2,4−ジニトロフェノールを副生するという問題
点があり、また、後者の方法は3−フルオロ−4−ニト
ロフェノールが副生するため水蒸気蒸留等の分離操作が
必要なことや収率が必ずしも充分とは言えないことなど
の問題点があった。<Problems to be Solved by the Invention> However, the former method has a problem in that 3-fluoro-4-nitrophenol and dinitro 2,4-dinitrophenol, which are different in orientation of nitration, are by-produced. In addition, the latter method has a problem that a separation operation such as steam distillation is necessary because 3-fluoro-4-nitrophenol is by-produced and the yield is not always sufficient. .
<問題点を解決するための手段> 本発明者らは、5−フルオロ−2−ニトロフェノール
の製造法につき鋭意検討した結果、2,4−ジフルオロニ
トロベンゼンと水酸化物とを1,4−ジオキサン中で反応
させることにより、容易に高収率で、しかも3−フルオ
ロ−4−ニトロフェノールの副生もなく5−フルオロ−
2−ニトロフェノールが製造できることを見出し本発明
に至った。<Means for Solving Problems> The inventors of the present invention have diligently studied a method for producing 5-fluoro-2-nitrophenol, and as a result, have determined that 2,4-difluoronitrobenzene and hydroxide are combined with 1,4-dioxane. By reacting in the medium, 5-fluoro- can be easily obtained in high yield and without by-product of 3-fluoro-4-nitrophenol.
The present invention has been accomplished by finding that 2-nitrophenol can be produced.
本反応は、通常0〜200℃の温度で行い、用いられる
水酸化物としては、水酸化リチウム、水酸化ナトリウ
ム、水酸化カリウム、水酸化ルビジウム、水酸化セシウ
ム、水酸化カルシウム、水酸化バリウム、水酸化テトラ
アルキルアンモニウム(例えば水酸化ベンジルトリメチ
ルアンモニウム)等が挙げられる。また、必要により塩
化ベンジルトリメチルアンモニウム、塩化ベンジルトリ
エチルアンモニウム、臭化テトラブチルアンモニウム、
クラウンテーテル類、トリス〔2−(2−メトキシエト
キシ)エチル〕アミン等の相関移動触媒を加えることも
できる。本反応に要する時間は、通常4時間〜10日間で
あり、反応温度を挙げるうことにより反応時間を短縮す
ることができる。This reaction is usually carried out at a temperature of 0 to 200 ° C., and hydroxides used include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, calcium hydroxide, barium hydroxide, Examples thereof include tetraalkylammonium hydroxide (eg, benzyltrimethylammonium hydroxide). If necessary, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, tetrabutylammonium bromide,
A phase transfer catalyst such as crown theteres and tris [2- (2-methoxyethoxy) ethyl] amine can also be added. The time required for this reaction is usually 4 hours to 10 days, and the reaction time can be shortened by raising the reaction temperature.
反応終了後は、反応液を水に加え、必要により有機溶
媒で抽出し濃縮等の通常の後処理を行うことにより、5
−フルオロ−2−ニトロフェノールが製造できる。After completion of the reaction, the reaction solution is added to water, extracted with an organic solvent if necessary, and subjected to usual post-treatments such as concentration to obtain 5
-Fluoro-2-nitrophenol can be produced.
<実施例> 次に、製造例および比較例を挙げて本発明をより詳し
く説明する。<Examples> Next, the present invention will be described in more detail with reference to production examples and comparative examples.
製造例 水酸化ナトリウム(フレーク状、95%品)32.00gおよ
びトリス〔2−(2メトキシエトキシ)エチル〕アミン
3.20gを1,4−ジオキサン200gに懸濁させ、30℃で2,4−
ジフルオロニトロベンゼン31.82gを加え、同温で32時間
撹拌した。反応液に水を加え、1,2−ジクロロエタンで
水層を洗浄した後、水層に濃塩酸72gを加え、1,2−ジク
ロロエタンで抽出した。抽出液を希塩酸で洗浄し、乾燥
後減圧下に溶媒を留去して5−フルオロ−2−ニトロフ
ェノール27.61gを得た。Production Example 32.00 g of sodium hydroxide (flakes, 95% product) and tris [2- (2methoxyethoxy) ethyl] amine
3.20 g was suspended in 200 g of 1,4-dioxane, and 2,4-
31.82 g of difluoronitrobenzene was added, and the mixture was stirred at the same temperature for 32 hours. Water was added to the reaction solution, the aqueous layer was washed with 1,2-dichloroethane, 72 g of concentrated hydrochloric acid was added to the aqueous layer, and the mixture was extracted with 1,2-dichloroethane. The extract was washed with dilute hydrochloric acid, dried and the solvent was distilled off under reduced pressure to obtain 27.61 g of 5-fluoro-2-nitrophenol.
収率 88% 融点 35−37℃ 比較例1 水酸化ナトリウム(95%品)32.00gおよび塩化ベンジ
ルトリエチルアンモニウム2.28gを水200gに溶解し、40
℃で2,4−ジフルオロニトロベンゼン31.82gを加え、同
温で27時間撹拌した。反応液に水800gを加え、1,2−ジ
クロロエタンで水層を洗浄した後、水層に濃塩酸72gを
加え、1,2−ジクロロエタンで抽出した。抽出液を希塩
酸で洗浄し、乾燥後減圧下に溶媒を留去して5−フルオ
ロ−2−ニトロフェノールと3−フルオロ−4−ニトロ
フェノールとの混合物(混合比 87:13)27.24gを得
た。Yield 88% Melting point 35-37 ° C Comparative Example 1 32.00 g of sodium hydroxide (95% product) and 2.28 g of benzyltriethylammonium chloride were dissolved in 200 g of water, and 40
31.82 g of 2,4-difluoronitrobenzene was added at 0 ° C, and the mixture was stirred at the same temperature for 27 hours. 800 g of water was added to the reaction solution, the aqueous layer was washed with 1,2-dichloroethane, 72 g of concentrated hydrochloric acid was added to the aqueous layer, and the mixture was extracted with 1,2-dichloroethane. The extract was washed with diluted hydrochloric acid, dried and the solvent was distilled off under reduced pressure to obtain 27.24 g of a mixture of 5-fluoro-2-nitrophenol and 3-fluoro-4-nitrophenol (mixing ratio 87:13). It was
比較例2 水酸化カリウム(85.5%品)2.49gを水47.31gに溶解
し、40℃で2,4−ジフルオロニトロベンゼン1.59gを加
え、同温で22時間撹拌した。反応液に水40gを加え、1,2
−ジクロロエタンで水層を洗浄した後、水層に濃塩酸3.
6gを加え、1,2−ジクロロエタンで抽出した。抽出液を
希塩酸で洗浄し、乾燥後減圧下に溶媒を留去して5−フ
ルオロ−2−ニトロフェノールと3−フルオロ−4−ニ
トロフェノールとの混合物(混合比 90:10)1.26gを得
た。Comparative Example 2 2.49 g of potassium hydroxide (85.5% product) was dissolved in 47.31 g of water, 1.59 g of 2,4-difluoronitrobenzene was added at 40 ° C., and the mixture was stirred at the same temperature for 22 hours. 40 g of water was added to the reaction solution,
-After washing the aqueous layer with dichloroethane, concentrated hydrochloric acid in the aqueous layer 3.
6 g was added and extracted with 1,2-dichloroethane. The extract was washed with diluted hydrochloric acid, dried and the solvent was distilled off under reduced pressure to obtain 1.26 g of a mixture of 5-fluoro-2-nitrophenol and 3-fluoro-4-nitrophenol (mixing ratio 90:10). It was
比較例3 水酸化カリウム(85.5%品)2.49gおよび臭化テトラ
ブチルアンモニウム0.16gをN,N−ジメチルホルムアミド
47.31gに懸濁させ、40℃で2,4−ジフルオロニトロベン
ゼン1.59gを加え、同温で12時間撹拌した。反応液に水4
0gを加え、1,2−ジクロロエタンで水層を洗浄した後、
水層に濃塩酸3.6gを加え、1,2−ジクロロエタンで抽出
した。抽出液を希塩酸で洗浄し、乾燥後減圧下に溶媒を
留去して5−フルオロ−2−ニトロフェノールと3−フ
ルオロ−4−ニトロフェノールとの混合物(混合比 9
0:10)1.46gを得た。Comparative Example 3 2.49 g of potassium hydroxide (85.5% product) and 0.16 g of tetrabutylammonium bromide were added to N, N-dimethylformamide.
The suspension was suspended in 47.31 g, 1,59 g of 2,4-difluoronitrobenzene was added at 40 ° C., and the mixture was stirred at the same temperature for 12 hours. Water 4 in the reaction solution
After adding 0 g and washing the aqueous layer with 1,2-dichloroethane,
Concentrated hydrochloric acid (3.6 g) was added to the aqueous layer, and the mixture was extracted with 1,2-dichloroethane. The extract was washed with diluted hydrochloric acid, dried and the solvent was distilled off under reduced pressure to give a mixture of 5-fluoro-2-nitrophenol and 3-fluoro-4-nitrophenol (mixing ratio 9
0:10) 1.46 g was obtained.
比較例4 水酸化カリウム(85.5%品)2.49gおよび臭化テトラ
ブチルアンモニウム0.16gをトルエン47.31gに懸濁さ
せ、40℃で2,4−ジフルオロニトロベンゼン1.59gを加
え、同温で38時間撹拌したが反応の進行が遅く、5−フ
ルオロ−2−ニトロフェノールと3−フルオロ−4−ニ
トロフェノールの混合物は25%しか生成していないこと
が液体クロマトグラムで確認された。Comparative Example 4 2.49 g of potassium hydroxide (85.5% product) and 0.16 g of tetrabutylammonium bromide were suspended in 47.31 g of toluene, 1.59 g of 2,4-difluoronitrobenzene was added at 40 ° C., and the mixture was stirred at the same temperature for 38 hours. However, the progress of the reaction was slow, and it was confirmed in the liquid chromatogram that only 25% of the mixture of 5-fluoro-2-nitrophenol and 3-fluoro-4-nitrophenol was produced.
比較例5 水酸化カリウム(85.5%品)2.49gおよび臭化テトラ
ブチルアンモニウム0.16gを1,2−ジクロロエタン47.31g
に懸濁させ、40℃で2,4−ジフルオロニトロベンゼン1.5
9gを加え、同温で18時間撹拌したが反応の進行が遅く、
5−フルオロ−2−ニトロフェノールと3−フルオロ−
4−ニトロフェノールの混合物は4%しか生成していな
いことが液体クロマトグラムで確認された。Comparative Example 5 2.49 g of potassium hydroxide (85.5% product) and 0.16 g of tetrabutylammonium bromide were added to 47.31 g of 1,2-dichloroethane.
Suspended in 2,4-difluoronitrobenzene 1.5 at 40 ℃
9g was added and stirred at the same temperature for 18 hours, but the reaction progressed slowly,
5-fluoro-2-nitrophenol and 3-fluoro-
The liquid chromatogram confirmed that the mixture of 4-nitrophenol produced only 4%.
<発明の効果> 本発明の製造法によれば、5−フルオロ−2−ニトロ
フェノールを高収率で、しかも3−フルオロ−4−ニト
ロフェノールで副生することなく製造できる。<Effects of the Invention> According to the production method of the present invention, 5-fluoro-2-nitrophenol can be produced in a high yield without producing by-product of 3-fluoro-4-nitrophenol.
フロントページの続き (72)発明者 田部井 伸昭 大阪市此花区春日出中3丁目1番98号 住友化学工業株式会社内 (72)発明者 船木 雄司 大阪市此花区春日出中3丁目1番98号 住友化学工業株式会社内Front page continued (72) Inventor Nobuaki Tabei 3-1-198 Kasugade, Konohana-ku, Osaka Sumitomo Chemical Co., Ltd. (72) Inventor Yuji Funaki 3-1-1, Kasugade, Konohana-ku, Osaka Sumitomo Chemical Co., Ltd.
Claims (2)
物とを、相間移動触媒の存在下または非存在下に、1,4
−ジオキサン中で反応させることを特徴とする5−フル
オロ−2−ニトロフェノールの製造法。1. A method comprising the steps of adding 1,4-difluoronitrobenzene and hydroxide in the presence or absence of a phase transfer catalyst to give 1,4
-A method for producing 5-fluoro-2-nitrophenol, characterized by reacting in dioxane.
項に記載の製造法。2. A method according to claim 1, wherein a phase transfer catalyst is used.
The production method described in the section.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62147351A JP2561471B2 (en) | 1987-06-12 | 1987-06-12 | Method for producing 5-fluoro-2-nitrophenol |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62147351A JP2561471B2 (en) | 1987-06-12 | 1987-06-12 | Method for producing 5-fluoro-2-nitrophenol |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS63310851A JPS63310851A (en) | 1988-12-19 |
JP2561471B2 true JP2561471B2 (en) | 1996-12-11 |
Family
ID=15428222
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP62147351A Expired - Lifetime JP2561471B2 (en) | 1987-06-12 | 1987-06-12 | Method for producing 5-fluoro-2-nitrophenol |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2561471B2 (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3936826A1 (en) * | 1989-11-04 | 1991-05-08 | Bayer Ag | N-ARYL NITROGEN HETEROCYCLES |
CN102285888A (en) * | 2010-11-15 | 2011-12-21 | 江苏威凯尔医药科技有限公司 | New preparation method of 2-fluoro-4-nitrophenol |
CN102766053B (en) * | 2012-07-17 | 2014-08-27 | 成都百事兴科技实业有限公司 | Production method of 3-fluoro-4-nitrophenol |
CN106045861B (en) * | 2016-05-26 | 2019-04-19 | 山东润博生物科技有限公司 | A kind of method and its system of the fluoro- 2- nitrophenol of continuous production 5- |
CN107935858B (en) * | 2016-10-12 | 2020-09-08 | 利尔化学股份有限公司 | Preparation method of 5-fluoro-2-nitrophenol |
CN116514662A (en) * | 2022-12-12 | 2023-08-01 | 山东京博农化科技股份有限公司 | Preparation method of 5-fluoro-2-nitrophenol |
-
1987
- 1987-06-12 JP JP62147351A patent/JP2561471B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JPS63310851A (en) | 1988-12-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Grundmann et al. | Nitrile oxides. X. Improved method for the prepared of nitrile oxides from aldoximes | |
US7265251B2 (en) | Process for the preparation of nitroalkenes | |
JP4872668B2 (en) | Process for producing 2-amino-5-iodobenzoic acid | |
JP2021066723A (en) | Preparation method for m-diamide compounds | |
JP2561471B2 (en) | Method for producing 5-fluoro-2-nitrophenol | |
CN109897006B (en) | Preparation method of mesosulfuron-methyl | |
JP2003292476A (en) | Method for producing diaminoresorcinol compound | |
JP2000319209A (en) | Production of iodinated aromatic compound | |
JPS5840545B2 (en) | Method for producing 2-(4'amino-phenyl)-5-aminobenzimidazole | |
KR950013107B1 (en) | Process for the preparatio of 2-nitro-5-phenoxy-n-alkylsulfonyl benzamides by nitration | |
JPH0390057A (en) | Chlorofluorobenzonitrile and production thereof | |
JP2021195320A (en) | Method for producing 5-bromo-2-halogenated benzoic acid | |
JP2002255954A (en) | METHOD FOR PRODUCING 2-n-BUTYL-5-NITROBENZOFURAN | |
JPS60152449A (en) | 3-amino-4-fluorophenyl ether and its preparation | |
US4165268A (en) | Process for the production of substituted toluene compounds | |
WO2023029235A1 (en) | Method for preparing sacubitril intermediate | |
JP3193421B2 (en) | Method for producing 2-amino-4-fluorobenzoic acid | |
JP4956760B2 (en) | Method for producing 3-bromobenzoic acid or alkyl ester thereof | |
JPS6054948B2 (en) | Method for producing aromatic amines from α,β↓-unsaturated cycloaliphatic ketoxime | |
PL86547B1 (en) | ||
JPS5821616B2 (en) | Amine manufacturing method | |
EP0596130B1 (en) | Production of 2-halo-3,5-difluoroaniline, intermediate for producing the same, and production of said intermediate | |
JP2517990B2 (en) | 4-acetylamino-5-fluoro-2-nitrophenoxyacetic acid | |
JPS6216445A (en) | Intermediate for manufacture of asymmetric hydantoin | |
JPH08169868A (en) | Production of 4-cyano-4'-hydroxybiphenyl |