CN104262285A - Method for synthesizing intermediate of agricultural insecticide indoxacarb - Google Patents
Method for synthesizing intermediate of agricultural insecticide indoxacarb Download PDFInfo
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Abstract
The invention discloses a method for synthesizing an intermediate of agricultural insecticide indoxacarb. The method comprises the following steps: (1) putting YCW-4, Lewis acid and methylbenzene into a reaction container according to a proportion, stirring, heating to a reacting temperature of 105-110 DEG C, dripping a methylbenzene solution of diethoxymethane, adding benzyl carbazate, and reacting at the reacting temperature until the reaction is carried out completely, wherein azeotrope of ethanol and diethoxymethane serving as a byproduct is constantly vaporized and eliminated in the reacting process; (2) stopping heating after the reaction is finished, cooling to room temperature under a stirring condition, concentrating at reduced pressure to reclaim methylbenzene, cooling and crystallizing the concentrate at low temperature by using a crystallization solvent, suction-filtering, washing, and baking to obtain light yellow crystal which is a target product, namely the intermediate of agricultural insecticide indoxacarb. The synthesizing method has the technical advantage of high yield.
Description
Technical field
The invention belongs to organic synthesis field, relate to the new synthetic process of agricultural insecticide indoxacarb intermediate.
Background technology
Indoxacarb (structural formula is shown in formula 1); chemical name: 7-chloro-2; 3; 4a; 5-tetrahydrochysene-2 (methoxycarbonyl (4-Trifluoromethoxyphen-l) formamyl) indeno (1; 2-e) oxadiazine-4a-carboxylate methyl ester, popular name: indoxacarb, trade(brand)name: Ammate, Avatar etc.This product is du pont company's calendar year 2001 listing oxadiazine class novel chiral sterilant, is also first business-like sodium channel blocking-up type sterilant.Indoxacarb has novel structure, the mechanism of action is unique, consumption is low, all effective to nearly all lepidoptera pest, to people and animals, environment, crop, non-target organism and the beneficial organism feature such as safely, the favourable agents substituting high poison, high residue and resistance sterilant, market and having a extensive future.
The chemical structural formula (YCW) of formula 1 indoxacarb
Indoxacarb is a complex structure oxadiazine compounds, and containing a chiral centre in structure, there are R and S two isomer, wherein only S isomer has activity, and R isomer does not have activity.Commercialization indoxacarb commercially available is at present the safety hit (ee=50%) of E.I.Du Pont Company and triumphant grace (smart indoxacarb, ee=100%) mainly.Because the compound patent of indoxacarb will expire in April, 2015, therefore domestic agricultural chemicals enterprise more and more payes attention to optimization and the innovation of its synthesis technique.
Patent WO09211249 and WO9319045 once disclosed 2-(phenmethyl)-7-chlorine indeno [1, the 2-e] [synthesis technique of 1,3,4] oxadiazines-2,4a (3H, 5H)-dicarboxylic acid-4a-methyl ester (YCW-5).But it is low that the major defect of this technique is reaction yield, raw material easily resolves into MCIC (structural formula is shown in formula 2).
The structural formula of formula 2 MCIC
The present invention early stage literature survey and indoxacarb synthesising process research basis on (synthetic route is shown in formula 3), primary study and optimize cyclization (YCW-5) reaction, its be synthesis indoxacarb (YCW) committed step.But when carrying out cyclization according to the method for reported in literature, yield is on the low side, when major cause is cyclization, raw material hydrazone (YCW-4) easily resolves into MCIC (YCW-3), and the temperature of reaction of the method is 80-85 DEG C.The industry urgently wishes effectively to solve the problem; Therefore the synthesis method of agricultural insecticide indoxacarb intermediate of the present invention is devised.
The synthetic route of formula 3 indoxacarb
Summary of the invention
The technical problem to be solved in the present invention is to provide 2-(the phenmethyl)-7-chlorine indeno [1 of the high and operational safety of a kind of efficiency, 2-e] [1,3,4] oxadiazines-2,4a (3H, the new synthesis process of 5H)-dicarboxylic acid-4a-methyl ester (YCW-5), with applicable suitability for industrialized production.
In order to solve the problems of the technologies described above, the invention provides a kind of synthesis method of agricultural insecticide indoxacarb intermediate (YCW-5), comprising the following steps:
1), by (5-chloro-2,3-dihydro-2-hydroxyl-2-methoxycarbonyl-1H-indenes-subunit) hydrazine carboxylic acid's benzyl esters (YCW-4), Lewis acid, toluene drops in reaction vessel in proportion, stir, be warming up to the temperature of reaction of 105 ~ 110 DEG C (being preferably 106 ~ 108 DEG C), drip the toluene solution of methylene diethyl ether and react until reaction is carried out completely after adding hydrazine benzyl formate under above-mentioned temperature of reaction; Constantly steam in reaction process and remove as the ethanol of by product and the azeotrope of methylene diethyl ether;
The mol ratio of described hydrazine benzyl formate and YCW-4 is 0.1 ~ 1:1 (being preferably 0.15 ~ 0.55:1); The mol ratio of Lewis acid and YCW-4 is 0.02 ~ 0.2:1 (being preferably 0.1:1); The mol ratio of methylene diethyl ether and YCW-4 is 3 ~ 10:1 (being preferably 4.6 ~ 4.7:1);
Remarks illustrate: ethanol is the by product that reaction produces; There is adverse influence to reaction after generation, remove so will steam;
2), react and terminate rear stopping heating, be cooled to room temperature under stirring, concentration and recovery toluene under reduced pressure, concentrated solution recrystallisation solvent crystallisation by cooling at low temperatures, suction filtration, washing, dry, obtain light yellow crystal, be target product--agricultural insecticide indoxacarb intermediate.
Improvement as the synthesis method of agricultural insecticide indoxacarb intermediate of the present invention: the toluene solution of described methylene diethyl ether drips at twice, dropwises rear interpolation hydrazine benzyl formate first, and then carries out secondary dropping; React under temperature of reaction until reaction is carried out completely after second time dropwises.
Remarks illustrate:
Generally speaking, the toluene solution accounting for the methylene diethyl ether of total amount 2/3 is dripped first; Second time drips the toluene solution of remaining methylene diethyl ether.
Need control temperature can not lower than 92 DEG C when dripping the toluene solution of methylene diethyl ether, the mode that therefore drips be intermittent dropping, that is, when temperature is lower than 92 DEG C, stop dropping; When temperature recovery to 92 DEG C, recover to drip.Therefore, the time dripped first is about 2 ~ 2.6 hours, dropwises rear interpolation hydrazine benzyl formate reaction 1 ~ 1.5 hour first; The time that second time drips the toluene solution of methylene diethyl ether is about 1 ~ 1.3 hour; After second time dropwises, under temperature of reaction, reaction is until reaction is carried out completely, that is, this reaction process is followed the tracks of with thin-layer chromatography (TLC), and YCW-4 reacts completely and is reaction end; Therefore the reaction times is about 2 ~ 2.5 hours.
The decomposition amount of YCW-4 is between 10%-50%, the amount of the hydrazine benzyl formate added can be decomposed by the YCW-4 measured the amount generating YCW-3 and be determined, in order to cost-saving, the hydrazine benzyl formate added only needs the amount of skipping over, therefore, the mol ratio of general hydrazine benzyl formate and YCW-4 is 0.15 ~ 0.55:1.
Further improvement as the synthesis method of agricultural insecticide indoxacarb intermediate of the present invention:
Lewis acid is boron trifluoride, Vanadium Pentoxide in FLAKES, sulphur trioxide, tosic acid or diphenylsulfonium methylsulphonic acid ammonium.Preferred Lewis acids is tosic acid, diphenylsulfonium methylsulphonic acid ammonium.Most preferably Lewis acid is tosic acid.
Further improvement as the synthesis method of agricultural insecticide indoxacarb intermediate of the present invention: described step 2) in recrystallisation solvent be lower alcohol containing 1 ~ 4 carbon atom.
Further improvement as the synthesis method of agricultural insecticide indoxacarb intermediate of the present invention: the described lower alcohol containing 1 ~ 4 carbon atom is methyl alcohol, ethanol, Virahol, propyl carbinol or isopropylcarbinol.Particular methanol.
Further improvement as the synthesis method of agricultural insecticide indoxacarb intermediate of the present invention: under room temperature, YCW-4, Lewis acid, toluene are dropped in reaction vessel in proportion.
Usual room temperature is 15 ~ 25 DEG C.
In the present invention, step 2) with reference to carrying out with Publication about Document: Wang Min. the synthetic route pre-test [D] of new and effective sterilant indoxacarb. Beijing: China Agricultural University, 2007.Stephen F M, Gary D A, Rafael S, et al.The discovery of indoxacarb:oxadiazine as a new class of pyrazoline-type insecticides.Pest Management Science, 2001,57:153-164.
In the present invention, step 1) in reaction solvent used be toluene.The amount ranges of toluene is the solubleness of YCW-4 at visual response temperature and determines, that is, minimum the wanting of its consumption can make YCW-4 dissolve.Therefore, generally speaking, under temperature of reaction of the present invention, the toluene of the YCW-4 adapted 50 ~ 60mL of every 0.026mol.
Methylene diethyl ether in the toluene solution of methylene diethyl ether: the volume ratio of toluene is 1:2 ~ 4 (being preferably 1:3)
Step 2) in the amount ranges of recrystallisation solvent be at a reflux temperature, consumption when YCW-5 can dissolve completely.The solvent of Separation and Recovery---toluene can recycled in lower batch produce in.
In sum, agricultural insecticide indoxacarb intermediate of the present invention, that is, 2-(phenmethyl)-7-chlorine indeno [1,2-e] [1,3, the synthesis of 4] oxadiazines-2,4a (3H, 5H)-dicarboxylic acid-4a-methyl ester (YCW-5) take YCW-4 as raw material, under lewis acidic catalysis, generate YCW-5 with methylene diethyl ether generation condensation reaction.
Synthesis route is as follows:
The preparation method of YCW-5 of the present invention, suitability for industrialized production, reacts raw materials used and reagent is commercially available.Product yield is more than 80%, content more than 95%.
The present invention relates to the preparation method of YCW-5, there is following beneficial effect: in reaction process, add hydrazine benzyl formate, reaction can not only be completed fast, and effectively inhibit the decomposition of YCW-4.
In sum, the present invention passes through Optimization Technology, improve temperature of reaction, especially appropriate interpolation hydrazine benzyl formate in reaction process, have found the factor and preferred process parameter that affect ring-closure reaction, significantly reduce the decomposition of YCW-4, improve the overall yield of ring-closure reaction and the former medicine of indoxacarb, for the industrialization of this project lays a solid foundation.
Embodiment
Following examples are for further describing the present invention, but the present invention is only limitted to this absolutely not.
The synthesis method of embodiment 1, a kind of agricultural insecticide indoxacarb intermediate, carry out following steps successively:
1), in the 250mL four-hole bottle with fractionation plant, 10gYCW-4 (0.026mol), 0.45g tosic acid (0.0026mol), 50mL toluene (through Non-aqueous processing) is added, reflux has drop formation, now temperature T in four-hole bottle to thorn shape fractional column
lbe 108 DEG C, thorn shape post tip temperature T
2when being 106 DEG C, start the mixed solution that intermittent dropping is made up of 10mL methylene diethyl ether (0.08mol) and 30mL toluene, in dropping process, the reflux temperature of reaction solution can reduce, as thorn shape post tip temperature T
2during lower than 92 DEG C, stop dripping, start to separate partially liq to thorn shape post tip temperature T
2go back up to 92 DEG C, stop distillation procedure, continue to drip, cyclical operation like this, after dropwising in 2h, reaction condition is checked by TLC, the amount of the YCW-3 that estimation feed material degradation produces, after adding the hydrazine benzyl formate reaction 1h of appropriate (0.0143mol), then adds methylene diethyl ether 5ml, (dripping control mode the same) is dripped complete in toluene 15ml, 1h.Carry out completely (about 2 hours) in 106 ~ 108 DEG C of insulations to reaction.
2), react and terminate rear stopping heating, be cooled to room temperature, after concentrated, obtain brown viscous liquid, add 30mL methyl alcohol and carry out recrystallization, have solid to separate out, suction filtration, cold methanol washs, and dries to obtain faint yellow solid 8.45g (content >=95%), with the YCW-4 rate of collecting for 83%.
Embodiment 2: a kind of synthesis method of agricultural insecticide indoxacarb intermediate, carry out following steps successively:
1), in the 250mL four-hole bottle with fractionation plant, 10g YCW-4 (0.026mol), 0.83g diphenylsulfonium methylsulphonic acid ammonium (0.0026mol), 50mL toluene (through Non-aqueous processing) is added, reflux has drop formation to thorn type reflux column, now temperature T in four-hole bottle
lbe 108 DEG C, thorn shape post tip temperature T
2when being 106 DEG C, start the mixed solution that intermittent dropping is made up of 10mL methylene diethyl ether and 30mL toluene, in dropping process, the reflux temperature of reaction solution can reduce, as thorn shape post tip temperature T
2during lower than 92 DEG C, stop dripping, start to separate partially liq to thorn shape post tip temperature T
2go back up to 92 DEG C, stop distillation procedure, continue to drip, cyclical operation like this, after dropwising in 2h, reaction condition is checked by TLC, the amount of the YCW-3 that estimation feed material degradation produces, after adding the hydrazine benzyl formate reaction 1h of appropriate (0.0143mol), then adds methylene diethyl ether 5ml, (dripping control mode the same) is dripped complete in toluene 15ml, 1h.Carry out completely (about 2 hours) in 106 ~ 108 DEG C of insulations to reaction.
2), react and terminate rear stopping heating, be cooled to room temperature, after concentrated, obtain brown viscous liquid, add 30mL methyl alcohol and carry out recrystallization, have solid to separate out, suction filtration, cold methanol washs, and dries to obtain faint yellow solid 7.32g (content >=95%), with the YCW-4 rate of collecting for 71%.
Comparative example 1-1, cancel the use (but the reaction times of 1h still retains) of " hydrazine benzyl formate " in embodiment 1, all the other are equal to embodiment 1.Final faint yellow solid 5.8g, with the YCW-4 rate of collecting for 58%.
In comparative example 1-2, change embodiment 1, the consumption of " hydrazine benzyl formate " makes 0.006mol into; All the other are equal to embodiment 1.Final faint yellow solid 8.4g, with the YCW-4 rate of collecting for 84%.
In comparative example 1-3, change embodiment 1, the consumption of " hydrazine benzyl formate " is 0.020mol; All the other are equal to embodiment 1.Final faint yellow solid 8.3g, with the YCW-4 rate of collecting for 83%.
Comparative example 2, by embodiment 1 step 1) in the temperature of reaction temperature 80-85 DEG C that makes the document described in above-mentioned formula 3 into inform by 106 ~ 108 DEG C; All the other are with embodiment 1.Final faint yellow solid 5.4g, with the YCW-4 rate of collecting for 54%.
Finally, it is also to be noted that what enumerate above is only several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be had.All distortion that those of ordinary skill in the art can directly derive from content disclosed by the invention or associate, all should think protection scope of the present invention.
Claims (6)
1. the synthesis method of agricultural insecticide indoxacarb intermediate, is characterized in that comprising the following steps:
1), YCW-4, Lewis acid, toluene are dropped in reaction vessel in proportion, stir, be warming up to the temperature of reaction of 105 ~ 110 DEG C, drip the toluene solution of methylene diethyl ether and react until reaction is carried out completely after adding hydrazine benzyl formate under above-mentioned temperature of reaction; Constantly steam in reaction process and remove as the ethanol of by product and the azeotrope of methylene diethyl ether;
Described YCW-4 is (chloro-2, the 3-dihydro-2-hydroxyl-2-methoxycarbonyl-1H-indenes-subunits of 5-) hydrazine carboxylic acid's benzyl esters;
The mol ratio of described hydrazine benzyl formate and YCW-4 is 0.1 ~ 1:1; The mol ratio of Lewis acid and YCW-4 is 0.02 ~ 0.2:1; The mol ratio of methylene diethyl ether and YCW-4 is 3 ~ 10:1;
2), react and terminate rear stopping heating, be cooled to room temperature under stirring, concentration and recovery toluene under reduced pressure, concentrated solution recrystallisation solvent crystallisation by cooling at low temperatures, suction filtration, washing, dry, obtain light yellow crystal, be target product--agricultural insecticide indoxacarb intermediate.
2. the synthesis method of agricultural insecticide indoxacarb intermediate according to claim 1, is characterized in that: the toluene solution of described methylene diethyl ether drips at twice, dropwises rear interpolation hydrazine benzyl formate first, and then carries out secondary dropping; React under temperature of reaction until reaction is carried out completely after second time dropwises.
3. the synthesis method of agricultural insecticide indoxacarb intermediate according to claim 1 and 2, is characterized in that:
Described Lewis acid is boron trifluoride, Vanadium Pentoxide in FLAKES, sulphur trioxide, tosic acid or diphenylsulfonium methylsulphonic acid ammonium.
4. the synthesis method of agricultural insecticide indoxacarb intermediate according to claim 3, is characterized in that: described step 2) in recrystallisation solvent be lower alcohol containing 1 ~ 4 carbon atom.
5. the synthesis method of agricultural insecticide indoxacarb intermediate according to claim 4, is characterized in that: the described lower alcohol containing 1 ~ 4 carbon atom is methyl alcohol, ethanol, Virahol, propyl carbinol or isopropylcarbinol.
6., according to the synthesis method of the arbitrary described agricultural insecticide indoxacarb intermediate of claim 5, it is characterized in that: under room temperature, YCW-4, Lewis acid, toluene are dropped in reaction vessel in proportion.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106397351A (en) * | 2016-08-31 | 2017-02-15 | 京博农化科技股份有限公司 | Preparation method of indoxacarb intermediate |
| CN109651288A (en) * | 2018-12-29 | 2019-04-19 | 京博农化科技有限公司 | A kind of preparation method of indoxacarb intermediate |
| CN110527646A (en) * | 2019-08-20 | 2019-12-03 | 浙江工业大学 | Tropical bacillus WZZ018 and its application |
| EP3804853A4 (en) * | 2018-06-08 | 2021-08-04 | Jingbo Agrochemicals Technology Co., Ltd | Preparation method for s-indoxacarb |
| CN113607833A (en) * | 2021-07-08 | 2021-11-05 | 京博农化科技有限公司 | Content analysis method of indoxacarb intermediate |
| CN113607836A (en) * | 2021-07-23 | 2021-11-05 | 京博农化科技有限公司 | Method for analyzing content of indoxacarb key intermediate |
| CN114957158A (en) * | 2022-05-31 | 2022-08-30 | 浙江禾本科技股份有限公司 | Method for preparing indoxacarb intermediate |
| CN115974808A (en) * | 2022-12-21 | 2023-04-18 | 大连奇凯医药科技有限公司 | Preparation method of 2-benzyl-7-chlorine [1,2-e ] indeno [1,3,4] oxadiazine methyl diformate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1226891A (en) * | 1996-08-05 | 1999-08-25 | 纳幕尔杜邦公司 | Processes for preparing indeno [1,2-E] (1,3,4) oxadiazine-dicarboxylates |
| CN1282739A (en) * | 1994-04-20 | 2001-02-07 | 纳幕尔杜邦公司 | Intermediate used in preparing oxdiazine and its manufacturing method |
| MY141190A (en) * | 2005-05-02 | 2010-03-31 | Gharda Chemicals Ltd | A process for the large scale manufacture of indoxacarb and associated 1, 3, 4 oxadiazines |
-
2014
- 2014-09-09 CN CN201410453895.4A patent/CN104262285B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1282739A (en) * | 1994-04-20 | 2001-02-07 | 纳幕尔杜邦公司 | Intermediate used in preparing oxdiazine and its manufacturing method |
| CN1226891A (en) * | 1996-08-05 | 1999-08-25 | 纳幕尔杜邦公司 | Processes for preparing indeno [1,2-E] (1,3,4) oxadiazine-dicarboxylates |
| MY141190A (en) * | 2005-05-02 | 2010-03-31 | Gharda Chemicals Ltd | A process for the large scale manufacture of indoxacarb and associated 1, 3, 4 oxadiazines |
Non-Patent Citations (2)
| Title |
|---|
| 杨丙连，等: "茚虫威合成方法述评", 《农药》, vol. 51, no. 10, 31 October 2012 (2012-10-31), pages 774 - 779 * |
| 陈锦露，等: "新颖氨基甲酸酯类杀虫剂茚虫威的合成与应用", 《浙江化工》, vol. 36, no. 1, 31 December 2005 (2005-12-31), pages 30 - 41 * |
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| CN106397351A (en) * | 2016-08-31 | 2017-02-15 | 京博农化科技股份有限公司 | Preparation method of indoxacarb intermediate |
| CN106397351B (en) * | 2016-08-31 | 2018-10-30 | 京博农化科技股份有限公司 | A kind of preparation method of indoxacarb intermediate |
| EP3804853A4 (en) * | 2018-06-08 | 2021-08-04 | Jingbo Agrochemicals Technology Co., Ltd | Preparation method for s-indoxacarb |
| CN109651288A (en) * | 2018-12-29 | 2019-04-19 | 京博农化科技有限公司 | A kind of preparation method of indoxacarb intermediate |
| CN110527646A (en) * | 2019-08-20 | 2019-12-03 | 浙江工业大学 | Tropical bacillus WZZ018 and its application |
| CN110527646B (en) * | 2019-08-20 | 2021-05-11 | 浙江工业大学 | Tropical bacillus WZZ018 and application thereof |
| CN113607833A (en) * | 2021-07-08 | 2021-11-05 | 京博农化科技有限公司 | Content analysis method of indoxacarb intermediate |
| CN113607833B (en) * | 2021-07-08 | 2023-10-31 | 山东京博农化科技股份有限公司 | Content analysis method of indoxacarb intermediate |
| CN113607836A (en) * | 2021-07-23 | 2021-11-05 | 京博农化科技有限公司 | Method for analyzing content of indoxacarb key intermediate |
| CN113607836B (en) * | 2021-07-23 | 2023-10-31 | 山东京博农化科技股份有限公司 | Analysis method for content of indoxacarb key intermediate |
| CN114957158A (en) * | 2022-05-31 | 2022-08-30 | 浙江禾本科技股份有限公司 | Method for preparing indoxacarb intermediate |
| CN115974808A (en) * | 2022-12-21 | 2023-04-18 | 大连奇凯医药科技有限公司 | Preparation method of 2-benzyl-7-chlorine [1,2-e ] indeno [1,3,4] oxadiazine methyl diformate |
| CN115974808B (en) * | 2022-12-21 | 2024-03-12 | 大连奇凯医药科技有限公司 | Preparation method of 2-benzyl-7-chloro [1,2-e ] indeno [1,3,4] oxadiazine dimethyl ester |
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