CN102329255A - Process for synthesizing fomesafen through directional nitration - Google Patents
Process for synthesizing fomesafen through directional nitration Download PDFInfo
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- CN102329255A CN102329255A CN201110337238A CN201110337238A CN102329255A CN 102329255 A CN102329255 A CN 102329255A CN 201110337238 A CN201110337238 A CN 201110337238A CN 201110337238 A CN201110337238 A CN 201110337238A CN 102329255 A CN102329255 A CN 102329255A
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Abstract
The invention relates to a method for synthesizing weedicide fomesafen with high efficiency, low toxicity and low residue. The method comprises the following steps of: reacting 3-(2-chlorine-a,a,a-trifluoro para-tolyloxy)-benzoic acid serving as a raw material with mixed acid (nitric acid and sulfuric acid) under the conditions of a mixed solvent (methylbenzene and acetic ether) serving as a solvent and a novel directional catalyst (aluminum silicon complex) to obtain 5-(2-chlorine-2,2,2-trifluoro-para-tolyloxy)-2-nitrobenzoic acid; and synthesizing the fomesafen.
Description
Technical field
The present invention relates to the new synthesis technology of agricultural herbicide fomesafen.
Background technology
A kind of soybean, peanut field herbicide after seedling of fomesafen with high selectivity; Can prevent and kill off soybean, peanut field broadleaf weeds and Rhizoma Cyperi effectively; Gramineous weeds is also had certain preventive effect, have broad weed-killing spectrum, active high, miscibility is strong, toxicity is low, environmentally friendly, to characteristics such as succession crop safety.The operational path of report mainly is so that 3-(2-chloro-a, a, a-trifluoro p-methoxyphenyl)-phenylformic acid is raw material and nitric acid reaction at present; Synthetic 5-(2-chloro-2; 2,2-three fluoro-are to tolyloxy)-the 2-nitrobenzoic acid, synthetic then fomesafen; Wherein nitrated yield generally about 75-78%, needs further to improve.
Summary of the invention
The object of the invention is to invent a kind of synthetic fomesafen technology of directional nitrification that improves nitrated yield.
The technical scheme of the present invention's employing is for this reason: the present invention is so that 3-(2-chloro-a, a, a-trifluoro p-methoxyphenyl)-phenylformic acid is a raw material; React under the condition of mixed solvent and aluminium Si catalyst with nitration mixture; Temperature is controlled at-5 ℃-0 ℃, and a reaction times 5-6 hour aftertreatment gets 5-(2-chloro-2,2; 2-three fluoro-are to tolyloxy)-the 2-nitrobenzoic acid, and then synthetic fomesafen.
Aluminium, silicon weight ratio are 1:4 in the described aluminium Si catalyst.
Described nitration mixture is nitric acid and sulfuric acid, and the weight ratio of 3-(2-chloro-a, a, a-trifluoro p-methoxyphenyl)-phenylformic acid and nitration mixture is 1:0.9.
Said nitric acid and vitriolic weight ratio are 1:2.5-3.
Used mixed solvent is toluene or vinyl acetic monomer or both mixtures.
The weight ratio of said toluene and vinyl acetic monomer is 1:2.
The present invention is with 3-(2-chloro-a; A, the a-trifluoro p-methoxyphenyl)-phenylformic acid is a raw material, adopts synthetic 5-(the 2-chloro-2 of directional nitrification technology; 2; 2-three fluoro-are to tolyloxy)-2-nitrobenzoic acid and fomesafen, the synthetic total recovery of nitrated yield and fomesafen is all increased, nitrated yield can bring up to 85% from 75%.
Embodiment:
Example 1:
One is equipped with in the 1000ml four-hole boiling flask of stirring, TM and device for absorbing tail gas and adds 3-(2-chloro-a; A; The a-trifluoro p-methoxyphenyl)-phenylformic acid 150 grams; Aluminium Si catalyst 0.5 gram and mixed solvent (toluene and vinyl acetic monomer) 200 grams, wherein aluminium silicon weight ratio is 1:4 in the aluminium Si catalyst, the weight ratio of toluene and vinyl acetic monomer is 1:2; Cooling keeps temperature-5 ℃, drips nitration mixture 135 grams, and nitric acid and vitriolic weight ratio are 1:3.Reacted 5 hours, and got 5-(2-chloro-2,2,2-three fluoro-are to tolyloxy)-2-nitrobenzoic acid after the aftertreatment, synthetic then fomesafen, nitrated yield 85%.
Example 2:
One is equipped with and adds 3-(2-chloro-a, a, a-trifluoro p-methoxyphenyl)-phenylformic acid 150 grams in the 1000ml four-hole boiling flask of stirring, TM and device for absorbing tail gas; Mixed solvent (toluene and vinyl acetic monomer) 200 gram, cooling keep temperature-5 ℃-0 ℃, drip nitration mixture 135 grams; Reacted 5 hours, and got 5-(2-chloro-2,2 after the aftertreatment; 2-three fluoro-are to tolyloxy)-the 2-nitrobenzoic acid, synthetic then fomesafen, nitrated yield 55%-60%.
Example 3:
One is equipped with in the 1000ml four-hole boiling flask of stirring, TM and device for absorbing tail gas and adds 3-(2-chloro-a; A; The a-trifluoro p-methoxyphenyl)-phenylformic acid 150 grams; Aluminium Si catalyst 0.5 gram and mixed solvent (toluene and vinyl acetic monomer) 200 grams, wherein aluminium silicon weight ratio is 1:3.5 in the aluminium Si catalyst, the weight ratio of toluene and vinyl acetic monomer is 1:2.5; Cooling keeps 0 ℃ of temperature, drips nitration mixture 135 grams, and nitric acid and vitriolic weight ratio are 1:, 2.5, reacted 5 hours, get 5-(2-chloro-2,2,2-three fluoro-are to tolyloxy)-2-nitrobenzoic acid after the aftertreatment, synthetic then fomesafen, nitrated yield 82%.
Example 4:
One is equipped with and adds 3-(2-chloro-a, a, a-trifluoro p-methoxyphenyl)-phenylformic acid 150 grams in the 1000ml four-hole boiling flask of stirring, TM and device for absorbing tail gas; Aluminium Si catalyst 0.5 gram and toluene 200 grams, cooling keep temperature-5 ℃-0 ℃, drip nitration mixture 135 and restrain; Reacted 5 hours, and got 5-(2-chloro-2,2 after the aftertreatment; 2-three fluoro-are to tolyloxy)-the 2-nitrobenzoic acid, synthetic then fomesafen, nitrated yield 70%-75%.
Claims (7)
1. the synthetic fomesafen technology of directional nitrification is characterized in that, with 3-(2-chloro-a; A, a-trifluoro p-methoxyphenyl)-and phenylformic acid is a raw material, reacts under condition with nitration mixture with the mixed solvent of toluene, vinyl acetic monomer and aluminium Si catalyst; Temperature is controlled at-5 ℃-0 ℃, and a reaction times 5-6 hour aftertreatment gets 5-(2-chloro-2,2; 2-three fluoro-are to tolyloxy)-the 2-nitrobenzoic acid, and then synthetic fomesafen.
2. directional nitrification according to claim 1 synthesizes fomesafen technology, it is characterized in that, aluminium, silicon weight ratio are 1:4 in the described aluminium Si catalyst.
3. directional nitrification according to claim 1 and 2 synthesizes fomesafen technology, it is characterized in that, described nitration mixture is nitric acid and sulfuric acid, and the weight ratio of 3-(2-chloro-a, a, a-trifluoro p-methoxyphenyl)-phenylformic acid and nitration mixture is 1:0.9.
4. directional nitrification according to claim 3 synthesizes fomesafen technology, it is characterized in that, said nitric acid and vitriolic weight ratio are 1:2.5-3.
5. directional nitrification according to claim 1 and 2 synthesizes fomesafen technology, it is characterized in that, the weight ratio of said toluene and vinyl acetic monomer is 1:2.
6. directional nitrification according to claim 3 synthesizes fomesafen technology, it is characterized in that, the weight ratio of said toluene and vinyl acetic monomer is 1:2.
7. directional nitrification according to claim 4 synthesizes fomesafen technology, it is characterized in that, the weight ratio of said toluene and vinyl acetic monomer is 1:2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201110337238XA CN102329255B (en) | 2011-10-31 | 2011-10-31 | Process for synthesizing fomesafen through directional nitration |
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| CN201110337238XA CN102329255B (en) | 2011-10-31 | 2011-10-31 | Process for synthesizing fomesafen through directional nitration |
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| CN102329255B CN102329255B (en) | 2013-11-13 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112279790A (en) * | 2019-07-23 | 2021-01-29 | 佳木斯市恺乐农药有限公司 | Preparation method of fomesafen original drug |
| CN114887563A (en) * | 2022-06-08 | 2022-08-12 | 江苏长青农化南通有限公司 | Micro-channel reactor for improving nitration yield and process thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4046798A (en) * | 1973-02-12 | 1977-09-06 | Rohm And Haas Company | Herbicidal 4-trifluoromethyl-4'nitrodiphenyl ethers |
| WO1996036587A1 (en) * | 1995-05-19 | 1996-11-21 | Zeneca Limited | Catalytic nitration |
| US5946638A (en) * | 1997-08-22 | 1999-08-31 | Jayasuriya; Keerthi | Regioselective nitration of aromatic compounds and the reaction products thereof |
| CN1266422A (en) * | 1997-07-28 | 2000-09-13 | 曾尼卡有限公司 | Nitration process for diphenyl ethers |
| CN1463962A (en) * | 2002-06-04 | 2003-12-31 | 高俊 | Aromatic compound nitration manufacturing process |
| CN1182110C (en) * | 1999-12-22 | 2004-12-29 | 辛甄塔有限公司 | Process for preparation of diphenyl ether compounds |
| CN101033192A (en) * | 2006-03-06 | 2007-09-12 | 北京夏一催化技术有限公司 | Method of preparing nitrobenzene from benzene by nitric acid nitrating |
-
2011
- 2011-10-31 CN CN201110337238XA patent/CN102329255B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4046798A (en) * | 1973-02-12 | 1977-09-06 | Rohm And Haas Company | Herbicidal 4-trifluoromethyl-4'nitrodiphenyl ethers |
| WO1996036587A1 (en) * | 1995-05-19 | 1996-11-21 | Zeneca Limited | Catalytic nitration |
| CN1266422A (en) * | 1997-07-28 | 2000-09-13 | 曾尼卡有限公司 | Nitration process for diphenyl ethers |
| US5946638A (en) * | 1997-08-22 | 1999-08-31 | Jayasuriya; Keerthi | Regioselective nitration of aromatic compounds and the reaction products thereof |
| CN1182110C (en) * | 1999-12-22 | 2004-12-29 | 辛甄塔有限公司 | Process for preparation of diphenyl ether compounds |
| CN1463962A (en) * | 2002-06-04 | 2003-12-31 | 高俊 | Aromatic compound nitration manufacturing process |
| CN101033192A (en) * | 2006-03-06 | 2007-09-12 | 北京夏一催化技术有限公司 | Method of preparing nitrobenzene from benzene by nitric acid nitrating |
Non-Patent Citations (1)
| Title |
|---|
| 李彦龙，徐威: "氟磺胺草醚硝化工艺改进", 《农药研究与应用》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112279790A (en) * | 2019-07-23 | 2021-01-29 | 佳木斯市恺乐农药有限公司 | Preparation method of fomesafen original drug |
| CN114887563A (en) * | 2022-06-08 | 2022-08-12 | 江苏长青农化南通有限公司 | Micro-channel reactor for improving nitration yield and process thereof |
| CN114887563B (en) * | 2022-06-08 | 2023-07-14 | 江苏长青农化南通有限公司 | Microchannel reactor for improving nitration yield and process thereof |
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| CN102329255B (en) | 2013-11-13 |
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