CN103319421B - The preparation method of a kind of pyrimidinylthiobenzoate herbicides pyribenzoxim - Google Patents
The preparation method of a kind of pyrimidinylthiobenzoate herbicides pyribenzoxim Download PDFInfo
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- CN103319421B CN103319421B CN201310228135.9A CN201310228135A CN103319421B CN 103319421 B CN103319421 B CN 103319421B CN 201310228135 A CN201310228135 A CN 201310228135A CN 103319421 B CN103319421 B CN 103319421B
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Abstract
The preparation method of a kind of pyrimidinylthiobenzoate herbicides pyribenzoxim of the present invention, belongs to agrochemicals field. Carry out according to following step: taking another kind of pyrimidine Whitfield's ointment herbicide bispyribac-sodium as raw material, reaction flask adds two grass ether, organic solvent, basic catalyst, dewatering agent, diphenylketoxime, 6-36 hour is reacted under conventional temperature, TLC follows the tracks of reaction, react completely and filter after terminating, filtrate is under reduced pressure steamed except reclaiming organic solvent, obtains white solid pyribenzoxim weedicide with toluene recrystallization. One provided by the invention is with pyrimidine Whitfield's ointment herbicide bispyribac-sodium and diphenylketoxime raw material; the preparation method that dehydration reaction carries out safety broad-spectrum pyrimidine salicylic acid pyribenzoxim weedicide is carried out under efficient acylation catalyst and condensing agent effect; this preparation technology's receipts rate height (more than 90.4%); this technology is green process for cleanly preparing technology, is suitable for preparing safe and efficient wide spectrum pyrimidine salicylic acid pyribenzoxim weedicide in a large number.
Description
Technical field
The present invention relates to a kind of safe and efficient wide spectrum paddy field pyrimidinylthiobenzoate herbicides---the preparation method of pyribenzoxim (Pyribenzoxim), it is specifically related to one and under katalysis, prepares the method for pyribenzoxim with diphenylketoxime single stage method as raw material taking pyrimidinylthiobenzoate herbicides two grass ether (Bispyribac), belong to agrochemicals field.
Background technology
Pyrimidinylthiobenzoate herbicides is class acetolactate synthestase (ALS) inhibitor again succeeded in developing in the 90's of last century, can preventing and treating multiple intractable weeds, such weedicide is efficient with it, safety, wide spectrum, selectivity height and environmental friendliness etc. receive very big concern. It researchs and develops on sulfonylurea herbicide composition optimizes basis, and its herbicide spectrum and activity are all better than sulfonylurea herbicide, overcome sulfonylurea herbicide degradation speed slow, and succession crop produces the shortcomings such as poisoning. Current main products has two grass ether, pyrithiobacsodium, pyribenzoxims etc.
Pyribenzoxim is by the paddy field broad spectrum pyrimidinylthiobenzoate herbicides of Korea S LG chemical company exploitation, has and tags and systemic action, is mainly used in preventing and kill off rice terrace barnyard grass, nutgrass flatsedge and multiple annual grassy weeds. the existing LG of its preparation method chemical company report, with 2, 6-resorcylic acid, 2-methylsulfonyl-4, 6-bis-first pyrimidine etc. is prepared through polystep reaction for raw material, its reactions steps is many, complex process, total recovery low (38%), (1. KooSJ, et.al., PesticideScience, 1997, 51 (2), 109 114. 2. KimKT, et.al., Processforpreparing2, 6-di (4, 6-dimethoxypyrimidin-2-yl) oxybenzoicacidoximeesterderivativesasherbicides.Can.Pat. Appl., (1997), 2194080. 3. HurCU, et.al., Pyrimidinederivatives, processfortheirpreparation, andtheiruseasherbicides.Eur.Pat.Appl. (1995), EP658549A1).
The pyrimidinylthiobenzoate herbicides of Shuan Caomishi combinatorial chemistry company exploitation, can effectively prevent and kill off the barnyard grass in rice field and other gramineous weedss, we prepare two grass ether herbicide (Xu Defeng etc. in a large number by green cleaning procedure production technology, the preparation method of herbicide bispyribac-sodium, Chinese invention patent, CN101265235). This patent is on former patent basis, take herbicide bispyribac-sodium as starting raw material, safe and efficient wide spectrum pyrimidinylthiobenzoate herbicides pyribenzoxim is prepared by single stage method, namely prepare pyribenzoxim taking two grass ether as raw material enters dehydration condensation single stage method under catalyst action with diphenylketoxime, solve the complicated technology problem that LG chemical company multistep processes prepares pyribenzoxim. The method is cleaning procedure production technology, can be mass pyribenzoxim weedicide, and its preparation technology is as follows.
Summary of the invention
Object: for solving the deficiencies in the prior art, the present invention provides a kind of taking another kind of pyrimidine Whitfield's ointment herbicide bispyribac-sodium as raw material, under catalyst action, react single stage method with diphenylketoxime prepare pyribenzoxim, the method is cleaning procedure production technology, concise in technology, is applicable to batch production safety broad-spectrum pyrimidine salicylic acid pyribenzoxim weedicide.
Technical scheme: for solving the problems of the technologies described above, the technical solution used in the present invention is:
A preparation method for pyrimidinylthiobenzoate herbicides pyribenzoxim, carries out according to following step:
Taking another kind of pyrimidine Whitfield's ointment herbicide bispyribac-sodium as raw material, reaction flask adds two grass ether, organic solvent, basic catalyst, dewatering agent, diphenylketoxime, 6-36 hour is reacted under conventional temperature, TLC follows the tracks of reaction, react completely and filter after terminating, filtrate is under reduced pressure steamed except reclaiming organic solvent, obtains white solid pyribenzoxim weedicide with toluene recrystallization.
Described organic solvent is methylene dichloride, trichloromethane, 1,2-ethylene dichloride, dioxane, tetrahydrofuran (THF), N, dinethylformamide etc., and it is 50-100:1 with the mol ratio of two grass ether.
Described basic catalyst is: DMAP (DMAP), 4-(1'-Pyrrolidine) pyridine (4-PPY), I-hydroxybenzotriazole (HOBt), and it is 0.1-0.3:1 with the mol ratio of two grass ether.
Described dewatering agent: N, N'-dicyclohexylcarbodiimide (DCC), N, N'-di-isopropyl carbon imide (DIC), 1-ethyl-3 (3-dimethyl propylamine) carbodiimide (EDCI), it is 1-1.5:1 with the mol ratio of two grass ether.
Described diphenylketoxime is 1-1.5:1 with the mol ratio of two grass ether.
One provided by the invention is with pyrimidine Whitfield's ointment herbicide bispyribac-sodium and diphenylketoxime raw material; the preparation method that dehydration reaction carries out safety broad-spectrum pyrimidine salicylic acid pyribenzoxim weedicide is carried out under efficient acylation catalyst and condensing agent effect; this preparation technology's receipts rate height (more than 90.4%); this technology is green process for cleanly preparing technology, is suitable for preparing safe and efficient wide spectrum pyrimidine salicylic acid pyribenzoxim weedicide in a large number.
This patent main innovate point:
1) adopting cleaning procedure technology of preparing, can prepare new type of safe high-efficiency broad spectrum pyrimidinylthiobenzoate herbicides pyribenzoxim in a large number, be applicable to batch production, receipts rate height, purity is good.
2) wastewater flow rate is few, and catalyzer and organic solvent are all recyclable.
3) reaction temperature and, receipts rate height
Embodiment
Below in conjunction with example, the present invention done concrete explanation:
Example one: the preparation of pyribenzoxim
1L reaction flask adds two grass ether (43.0g; 100mmol), diphenylketoxime (20.8g; 107mmol), DCC(22.5g; 107mmol), DMAP(1.25g; 10mmol), methylene dichloride 500 milliliters; under nitrogen protection, react 20 hours under room temperature, after reaction result; filter; filtrate is concentration and recovery methylene dichloride under reduced pressure, obtains pyribenzoxim product, then carries out recrystallization with toluene and obtain white crystal pyribenzoxim (56.01g; 91.9%); fusing point: 128.5��130.5 DEG C, purity 98.2%1HNMR (CDCl3,300MHz): ��: 7.10-7.50 (m, 13H), 5.75 (s, 2H), 3.78 (s, 12H).
Example two: the preparation of pyribenzoxim
1L reaction flask adds two grass ether (43.0g, 100mmol), diphenylketoxime (19.5g, 100mmol), DIC(12.6g; 100mmol), HOBt(1.62g, 12mmol), 1,2-ethylene dichloride 395 milliliters; under nitrogen protection, react 24 hours under room temperature, after reaction result; filter; filtrate is concentration and recovery 1,2-ethylene dichloride under reduced pressure, obtains pyribenzoxim product; carry out recrystallization with toluene again and obtain white crystal pyribenzoxim (55.1g, 90.4%).
Example three: the preparation of pyribenzoxim
1.5L reaction flask adds two grass ether (43.0g, 100mmol), diphenylketoxime (29.1g, 150mmol), EDCI(23.3g; 150mmol), 4-PPY(2.53g, 30mmol), 1,2-ethylene dichloride 788 milliliters; under nitrogen protection, react 18 hours under room temperature, after reaction result; filter; filtrate is concentration and recovery 1,2-ethylene dichloride under reduced pressure, obtains pyribenzoxim product; carry out recrystallization with toluene again and obtain white crystal pyribenzoxim (55.3g, 90.7%).
Claims (2)
1. the preparation method of a pyrimidinylthiobenzoate herbicides pyribenzoxim, it is characterised in that carry out according to following step:
1L reaction flask adds two grass ether 100mmol, diphenylketoxime 107mmol, N; N'-dicyclohexylcarbodiimide 107mmol, DMAP 10mmol, methylene dichloride 500 milliliters; under nitrogen protection, react 20 hours under room temperature, after reaction terminates; filter; filtrate is concentration and recovery methylene dichloride under reduced pressure, obtains pyribenzoxim product, then carries out recrystallization with toluene and obtain white crystal pyribenzoxim 56.01g; fusing point: 128.5��130.5 DEG C, purity 98.2%.
2. the preparation method of a pyrimidinylthiobenzoate herbicides pyribenzoxim, it is characterized in that carrying out according to following step: in 1.5L reaction flask, add two grass ether 100mmol, diphenylketoxime 150mmol, 1-ethyl-3 (3-dimethyl propylamine) carbodiimide 150mmol, 4-(1'-Pyrrolidine) pyridine 30mmol, 1, 2-ethylene dichloride 788 milliliters, under nitrogen protection, react 18 hours under room temperature, after reaction terminates, filter, filtrate is concentration and recovery 1 under reduced pressure, 2-ethylene dichloride, obtain pyribenzoxim product, carry out recrystallization with toluene again and obtain white crystal pyribenzoxim 55.3g.
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| CN107652242B (en) * | 2017-10-09 | 2020-07-31 | 中国农业大学 | Synthesis of pyrimidine salicylic acid oxime ester and application of pyrimidine salicylic acid oxime ester as herbicide |
| CN109081792A (en) * | 2018-07-23 | 2018-12-25 | 常州大学 | A kind of preparation method of pyribenzoxim by-product of dicyclohexylurea recovery |
| CN108558777B (en) * | 2018-07-31 | 2021-01-26 | 河北大学 | Pyrimidine salicylic acid derivative and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2194080A1 (en) * | 1995-12-28 | 1997-06-29 | Kun-Tai Kim | Novel process for preparing 2,6-di(4,6-dimethoxypyrimidin-2-yl) oxybenzoic acid oxime ester derivatives |
| CN1043885C (en) * | 1993-11-13 | 1999-06-30 | 株式会社乐喜 | Novel herbicidal pyrimidine derivatives, process for preparation thereof and their use as herbicide |
| CN101265235A (en) * | 2008-05-08 | 2008-09-17 | 上海交通大学 | Method for preparing herbicide bispyribac-sodium |
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| AU5415899A (en) * | 1998-07-16 | 2000-02-07 | Aventis Agriculture Ltd. | Aryl vinyl ether derivatives and their use as herbicides |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1043885C (en) * | 1993-11-13 | 1999-06-30 | 株式会社乐喜 | Novel herbicidal pyrimidine derivatives, process for preparation thereof and their use as herbicide |
| CA2194080A1 (en) * | 1995-12-28 | 1997-06-29 | Kun-Tai Kim | Novel process for preparing 2,6-di(4,6-dimethoxypyrimidin-2-yl) oxybenzoic acid oxime ester derivatives |
| CN101265235A (en) * | 2008-05-08 | 2008-09-17 | 上海交通大学 | Method for preparing herbicide bispyribac-sodium |
Non-Patent Citations (2)
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| Facile Detosylatjpn of Cyclic Peptides. An Effective Synthesis of platelet glycoprotein IIb/IIIa inhibitors;Lin-hua Zhang，Philip Ma;《Tetrahedron Letters.》;19941231;第35卷(第32期);第5766页图示1 * |
| 新型除草剂嘧啶肟草醚的合成研究;田志高 等;《现代农药》;20110831;第10卷(第4期);第27-29页 * |
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Effective date of registration: 20190520 Address after: 318000 No. 218-1 Waisha Road, Jiaojiang District, Taizhou City, Zhejiang Province Patentee after: Taizhou Yunong Biotechnology Co., Ltd. Address before: No. 1, Wujin District, Wujin District, Changzhou, Jiangsu Patentee before: Changzhou University |