CN100526286C - Method for synthesizing akarol fenisobromolate - Google Patents
Method for synthesizing akarol fenisobromolate Download PDFInfo
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- CN100526286C CN100526286C CNB2007100703844A CN200710070384A CN100526286C CN 100526286 C CN100526286 C CN 100526286C CN B2007100703844 A CNB2007100703844 A CN B2007100703844A CN 200710070384 A CN200710070384 A CN 200710070384A CN 100526286 C CN100526286 C CN 100526286C
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- acetic acid
- diphenyl acetic
- dibromo diphenyl
- bromopropylate
- isopropyl ester
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Abstract
The invention provides a synthesis method of fenisobromolate. The method uses glyoxylate as the starting material, condensation reaction is first carried out between the glyoxylate and bromobenzene in order to generate 4, 4'-dibromodiphenyl acetic acid, 4, 4'-dibromodiphenyl acetic acid isopropyl ester is produced by the esterification reaction between the 4, 4'-dibromodiphenyl acetic acid and isopropyl alcohol, and under the function of catalyzer, the fenisobromolate is produced by the catalytic oxidation reaction between the 4, 4'-dibromodiphenyl acetic acid isopropyl ester and oxygen. The invention is favorable to industrialized production and has the advantages of short synthetic route, high yield rate, low cost and high purity of products.
Description
(1) technical field
The present invention relates to miticide---the synthetic method of bromopropylate, especially a kind of is the synthetic method of the bromopropylate of main raw material with the oxoethanoic acid.
(2) background technology
The bromopropylate chemical name is 4,4 '-dibromo benzilic acid isopropyl ester, structural formula is suc as formula shown in (I), molecular formula: C
17H
16Br
2O
3, be the miticide of a kind of low toxicity, efficient, wide spectrum, tagging property is strong, the lasting period is long, to become, if mite and ovum all have action of contace poison preferably, temperature variation is to the drug effect influence not quite.Be widely used on fruit tree, vegetables, tealeaves, cotton and the field-crop, be used to prevent and treat evil mites such as various tetranychids, goitre mite, palpus mite, line mite.Because the mechanism of action of bromopropylate product uniqueness, its usage quantity progressively enlarge.
What now industrialized synthesis technique mainly contained Switzerland vapour Ba-employings such as Jia Ji company is the operational path of starting raw material with the st-yrax, and obtained relevant patent, and as: CH 471065, US 3,829,496, US 3,639,446, DD 252,292, GB 1,565,999, GB 1,340, and 610 etc.Its synthesis step is: generate 4 by st-yrax (being bitter almond oil camphor) with urea reaction, 5-diphenyl-imidazole-2-ketone, generate corresponding 4 through bromination reaction again, 5-two (4 '-bromophenyl) imidazoles-2-ketone, the latter through oxidizing reaction obtain 4,4 '-the dibromo benzil, generate 4 through rearrangement reaction again, 4 '-the dibromo benzilic acid, make described bromopropylate through esterification then.This synthesis route is long, yield is low, cost is high.
(3) summary of the invention
The objective of the invention is traditional synthesis process to be improved, a kind of new synthetic route is provided, can obtain bromopropylate with short synthesis step, higher yield, relatively low cost in order to address the above problem.
The synthetic method of a kind of bromopropylate that the present invention adopts is: be starting raw material with the oxoethanoic acid, carry out condensation reaction with bromobenzene earlier and obtain 4,4 '-the dibromo diphenyl acetic acid, the latter and Virahol carry out esterification and obtain 4,4 '-dibromo diphenyl acetic acid isopropyl ester, the ester that is generated carries out catalytic oxidation and obtains described bromopropylate with oxygen in the presence of catalyzer.
Reaction equation is as follows:
Concrete, described method comprises following sequential steps:
(1) oxoethanoic acid and bromobenzene carry out condensation reaction under-15～80 ℃ in the presence of the dewatering agent chlorsulfonic acid or the vitriol oil, refining obtain 4,4 '-the dibromo diphenyl acetic acid;
(2) 4,4 '-the dibromo diphenyl acetic acid in the presence of an acidic catalyst, in benzene kind solvent, under refluxad carry out esterification with Virahol, reaction finish after separation and purification obtain 4,4 '-dibromo diphenyl acetic acid isopropyl ester;
(3) 4,4 '-dibromo diphenyl acetic acid isopropyl ester is dissolved in the organic solvent A, at-10～50 ℃ of following aerating oxygens or air, carries out catalytic oxidation under quaternary ammonium hydroxide catalysis, and reaction product obtains described bromopropylate through precipitation, recrystallization.
Benzene kind solvent described in the step (2) is one of following: 1. benzene, 2. toluene, 3. dimethylbenzene.
An acidic catalyst described in the step (2) is one of following: the 1. vitriol oil, 2. trifluoroacetic acid, 3. tosic acid.
In the step (3), described organic solvent A is one of following: 1. pyridine, 2. picoline, 3. 2,4. dimethyl formamide.
In the step (3), described quaternary ammonium hydroxide is one of following: 1. Tetramethylammonium hydroxide, 2. tetraethyl ammonium hydroxide, 3. trimethyl benzyl ammonium hydroxide, 4. triethyl benzylic hydrogens ammonium oxide, 5. trimethylphenyl ammonium hydroxide, 6. triethyl phenyl ammonium hydroxide.
Separation purification method is as follows in the step (2): reaction use the basic cpd solution washing after finishing, the branch water-yielding stratum, and the underpressure distillation precipitation, residual thing is used the organic solvent B recrystallization again, obtain 4,4 '-dibromo diphenyl acetic acid isopropyl ester.Described basic cpd is one of following: 1. Na
2CO
3, 2. NaHCO
3, 3. NaOH, 4. K
2CO
3, 5. KHCO
3, 6. KOH; Described organic solvent B is sherwood oil or ether.
The ratio of the amount of substance of oxoethanoic acid, bromobenzene, dewatering agent is in the described step (1): 1:1.5～2.5:1.5～2.5.
In the described step (2) 4,4 '-ratio of dibromo diphenyl acetic acid, an acidic catalyst, benzene kind solvent, Virahol amount of substance is: 1:0.02～0.2:15～25:2.5～5.0.
In the described step (3) 4,4 '-ratio of the amount of substance of dibromo diphenyl acetic acid isopropyl ester, organic solvent A, quaternary ammonium hydroxide is: 1:3～6:0.03～1.0.
Preferably, described method in the following order step carry out:
(1) oxoethanoic acid is dropped in the reaction vessel, underpressure distillation dehydration postcooling to 0 ℃～5 ℃, add chlorsulfonic acid, stir, add again in 3 hours, (to be preferably about 1.5 hours) behind the bromobenzene and add chlorsulfonic acid once more, be warming up to 10～50 ℃ (being preferably about 30 ℃), insulation reaction 2～40 hours (being preferably about 22 hours).Reaction adds entry after finishing in reaction mixture, the distillation that heats up steams unnecessary bromobenzene.Moisture is absorbed in cooling, residual thing toluene recrystallization, obtain 4,4 '-the dibromo diphenyl acetic acid.The ratio of the amount of substance of oxoethanoic acid, bromobenzene, chlorsulfonic acid (always adding up to twice add-on) is: 1:1.5～2.5:1.5～2.5;
(2) with 4,4 '-dibromo diphenyl acetic acid, toluene, Virahol and the disposable input reaction vessel of the vitriol oil in, open and stir, reflux dehydration 5～10 hours, cooling, wash with aqueous sodium carbonate, divide water-yielding stratum, after the oil reservoir underpressure distillation removes toluene, use the sherwood oil recrystallization, obtain 4,4 '-dibromo diphenyl acetic acid isopropyl ester.4,4 '-ratio of the amount of substance of dibromo diphenyl acetic acid, the vitriol oil, toluene, Virahol is: 1:0.02～0.2:15～25:2.5～5.0;
(3) with 4,4 '-dibromo diphenyl acetic acid isopropyl ester, pyridine drop in the reaction vessel, stirring and dissolving, be cooled to 0～5 ℃, under agitation, be added dropwise to Tetramethylammonium hydroxide simultaneously, continued insulation reaction 2～4 hours with the speed aerating oxygen (or air) of 30～60ml/min, underpressure distillation obtains described bromopropylate with the sherwood oil recrystallization after reclaiming pyridine.4,4 '-ratio of the amount of substance of dibromo diphenyl acetic acid isopropyl ester, pyridine, Tetramethylammonium hydroxide is: 1:3～6:0.03～1.0.
Beneficial effect of the present invention is mainly reflected in: synthetic route is short, the yield height, and cost is low, and the product purity height is beneficial to suitability for industrialized production.
(4) embodiment
Below in conjunction with specific embodiment the present invention is further described, but protection scope of the present invention is not limited in this:
Embodiment 1:4,4 '-preparation of dibromo diphenyl acetic acid
The 72g oxoethanoic acid is dropped into the 500mL four-hole boiling flask, underpressure distillation removes moisture 40g and (contains 60% water in the oxoethanoic acid, down together), be cooled to 0～5 ℃, in 30 minutes, be added dropwise to 45g chlorsulfonic acid (absorption of tail gas water), continue to stir 15 minutes, in 15 minutes, be added dropwise to the 140g bromobenzene, in 2.0 hours, be added dropwise to the 45g chlorsulfonic acid then once more.Be warming up to 25 ℃ of insulation reaction 20 hours.Reaction is added to the 150g water droplet in the reaction mixture after finishing, and heats up to steam unnecessary bromobenzene.Moisture is absorbed in cooling, and residual thing toluene recrystallization obtains 4,4 of 90g '-dibromo diphenyl acetic acid, and content is greater than 95%, yield 59.4%.
Embodiment 2:4,4 '-preparation of dibromo diphenyl acetic acid
The 72g oxoethanoic acid is dropped into the 500ml four-hole boiling flask, and underpressure distillation removes moisture 40g, is cooled to 0～5 ℃, in 30 minutes, is added dropwise to 40ml acetate, continues to stir 15 minutes, adds the 140g bromobenzene in 15 minutes.In 2.0 hours, be added dropwise to the 95g chlorsulfonic acid then.Be warming up to 25 ℃ of insulation reaction 20 hours.After reaction finishes, the water droplet of 150g is added in the reaction mixture, heating up steams unnecessary bromobenzene.Moisture is absorbed in cooling, and residual thing toluene recrystallization obtains 4,4 of 92g '-dibromo diphenyl acetic acid, and content is greater than 95%, yield 60.7%.
Embodiment 3:4,4 '-preparation of dibromo diphenyl acetic acid
The 72g oxoethanoic acid is dropped into the 500ml four-hole boiling flask, and underpressure distillation removes moisture 40g, is cooled to 0～5 ℃, in 30 minutes, is added dropwise to 98% vitriol oil of 50g, continues to stir 15 minutes, adds the 140g bromobenzene in 15 minutes.In 2.0 hours, be added dropwise to the 85g chlorsulfonic acid then.Be warming up to 25 ℃ of insulation reaction 20 hours.After reaction finishes, the water droplet of 160g is added in the reaction mixture, heating up steams unnecessary bromobenzene.Moisture is absorbed in cooling, and residual thing toluene recrystallization obtains 4,4 of 98g '-dibromo diphenyl acetic acid, and content is greater than 95%, yield 64.7%.
Embodiment 4:4,4 '-preparation of dibromo diphenyl acetic acid isopropyl ester
With 36g embodiment 1 make 4,4 '-the dibromo diphenyl acetic acid, 130ml toluene, the 20g Virahol, the 3g vitriol oil joins in the 250ml four-hole boiling flask successively, open and stir, reflux is deviate from about 4ml water and (is contained alcohol, system takes out of because of a small amount of Virahol is arranged in the toluene, and the latter divides soluble in water, down together) after, be cooled to room temperature, with the aqueous sodium carbonate washing of 6% (mass concentration, down with) of 80ml, branch vibration layer, toluene is reclaimed in underpressure distillation, residual thing sherwood oil recrystallization obtains 4,4 of 37g '-dibromo diphenyl acetic acid isopropyl ester, content is greater than 98%, yield 95.2%.
Embodiment 5:4,4 '-preparation of dibromo diphenyl acetic acid isopropyl ester
With 36g embodiment 2 make 4,4 '-dibromo diphenyl acetic acid, 150ml toluene, 20g Virahol, 3.0g tosic acid join successively in the 250ml four-hole boiling flask, open and stir, after temperature rising reflux is deviate from about 4ml water, be cooled to room temperature, with the 6% aqueous sodium carbonate washing of 80ml, branch vibration layer, toluene is reclaimed in underpressure distillation, use the sherwood oil recrystallization, obtain 4,4 of 37.5g '-dibromo diphenyl acetic acid isopropyl ester, content is greater than 98%, yield 96.5%.
Embodiment 6: the preparation of bromopropylate
With 30g embodiment 4 make 4,4 '-dibromo diphenyl acetic acid isopropyl ester, 100ml pyridine join in the 250ml four-hole boiling flask, stirring and dissolving, be cooled to 0～3 ℃ with icy salt solution then, under agitation with the speed aerating oxygen of 30～60ml/min, be added dropwise to the catalyzer Tetramethylammonium hydroxide of 2.5g simultaneously, in 1 hour, add.Maintain 0～2 ℃ and continue logical oxygen reaction after 2 hours, pyridine is reclaimed in underpressure distillation, uses the sherwood oil recrystallization, obtains the 28g bromopropylate, and content is greater than 95%, yield 87.1%.
Embodiment 7: the preparation of bromopropylate
With 30g embodiment 5 make 4,4 '-dibromo diphenyl acetic acid isopropyl ester, 120mlDMF join in the 250ml four-hole boiling flask stirring and dissolving, bubbling air under normal temperature, be added dropwise to the catalyzer tetraethyl ammonium hydroxide of 2.5g simultaneously, added in 1 hour, continue the blowing air normal-temperature reaction after 2 hours, DMF is reclaimed in underpressure distillation, use the sherwood oil recrystallization, obtain the 29g bromopropylate, content is greater than 95%, yield 90.2%.
Claims (7)
1. the synthetic method of a bromopropylate, described method is as follows: be starting raw material with the oxoethanoic acid, carry out condensation reaction with bromobenzene earlier and obtain 4,4 '-the dibromo diphenyl acetic acid, 4,4 '-the dibromo diphenyl acetic acid carries out esterification with Virahol again and obtains 4,4 '-dibromo diphenyl acetic acid isopropyl ester, 4,4 '-dibromo diphenyl acetic acid isopropyl ester carries out catalytic oxidation with oxygen again, obtains described bromopropylate through aftertreatment in the presence of quaternary ammonium hydroxide; Described quaternary ammonium hydroxide is one of following: 1. Tetramethylammonium hydroxide, 2. tetraethyl ammonium hydroxide, 3. trimethyl benzyl ammonium hydroxide, 4. triethyl benzylic hydrogens ammonium oxide, 5. trimethylphenyl ammonium hydroxide, 6. triethyl phenyl ammonium hydroxide.
2. the synthetic method of bromopropylate as claimed in claim 1 is characterized in that described method comprises following sequential steps:
(1) oxoethanoic acid and bromobenzene carry out condensation reaction under-15～80 ℃ in the presence of the dewatering agent chlorsulfonic acid or the vitriol oil, refining obtain 4,4 '-the dibromo diphenyl acetic acid;
(2) 4,4 '-the dibromo diphenyl acetic acid under refluxad carries out esterification with Virahol in the presence of an acidic catalyst, in benzene kind solvent, obtain 4,4 again through separation and purification '-dibromo diphenyl acetic acid isopropyl ester; Described an acidic catalyst is one of following: the 1. vitriol oil, 2. trifluoroacetic acid, 3. tosic acid; Described benzene kind solvent is one of following: 1. benzene, 2. toluene, 3. dimethylbenzene;
(3) 4,4 '-dibromo diphenyl acetic acid isopropyl ester is dissolved in the organic solvent A, and under-10～50 ℃, aerating oxygen or air carry out catalytic oxidation under quaternary ammonium hydroxide catalysis, and reaction product obtains described bromopropylate through distillation precipitation, recrystallization; Described organic solvent A is one of following: 1. pyridine, 2. picoline, 3. 2,4. dimethyl formamide.
3. the synthetic method of bromopropylate as claimed in claim 2, it is characterized in that in the step (2), described separation purification method is as follows: after reaction finishes, use the basic cpd solution washing, behind minute water, underpressure distillation precipitation, again with the organic solvent B recrystallization obtain 4,4 '-dibromo diphenyl acetic acid isopropyl ester; Described basic cpd is one of following: 1. Na
2CO
3, 2. NaHCO
3, 3. NaOH, 4. K
2CO
3, 5. KHCO
3, 6. KOH; Described organic solvent B is sherwood oil or ether.
4. the synthetic method of bromopropylate as claimed in claim 2 is characterized in that the ratio of oxoethanoic acid, bromobenzene, dewatering agent amount of substance in the described step (1) is: 1:1.5～2.5:1.5～2.5.
5. the synthetic method of bromopropylate as claimed in claim 2, it is characterized in that in the described step (2) 4,4 '-ratio of dibromo diphenyl acetic acid, an acidic catalyst, benzene kind solvent, Virahol amount of substance is: 1:0.02～0.2:15～25:2.5～5.0.
6. the synthetic method of bromopropylate as claimed in claim 2, it is characterized in that in the described step (3) 4,4 '-ratio of dibromo diphenyl acetic acid isopropyl ester, organic solvent A, quaternary ammonium hydroxide amount of substance is: 1:3～6:0.03～1.0.
7. the synthetic method of the described bromopropylate of claim 2, it is characterized in that described method in the following order step carry out:
(1) oxoethanoic acid drops in the reaction vessel, underpressure distillation dehydration postcooling to 0～5 ℃, add chlorsulfonic acid, stir, in 3 hours, add chlorsulfonic acid once more after adding bromobenzene again, be warming up to 10～50 ℃, be incubated 2～40 hours, reaction finishes the back and add entry in reaction mixture, and distillation heats up, unnecessary bromobenzene is steamed, behind cooling and the absorption moisture, in residual thing, add the toluene recrystallization, obtain 4,4 '-the dibromo diphenyl acetic acid, wherein the ratio of oxoethanoic acid, bromobenzene, chlorsulfonic acid amount of substance is: 1:1.5～2.5:1.5～2.5;
(2) with 4,4 '-dibromo diphenyl acetic acid, toluene, Virahol and the disposable adding reaction vessel of the vitriol oil in, open and stir, reflux dehydration 5～10 hours, cooling, wash with aqueous sodium carbonate, layering after the oil reservoir underpressure distillation eliminates toluene, is used the sherwood oil recrystallization, obtain 4,4 '-dibromo diphenyl acetic acid isopropyl ester; 4,4 '-ratio of dibromo diphenyl acetic acid, the vitriol oil, toluene, Virahol amount of substance is: 1:0.02～0.2:15～25:2.5～5.0;
(3) with 4,4 '-dibromo diphenyl acetic acid isopropyl ester, pyridine add in the reaction vessel, stirring and dissolving, be cooled to 0～5 ℃, under agitation, be added dropwise to Tetramethylammonium hydroxide simultaneously, continue insulation after 2～4 hours with 30～60mL/min speed aerating oxygen, pyridine is reclaimed in underpressure distillation, obtains described bromopropylate with the sherwood oil recrystallization; 4,4 '-ratio of the amount of substance of dibromo diphenyl acetic acid isopropyl ester, pyridine, Tetramethylammonium hydroxide is: 1:3～6:0.03～1.0.
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| CNB2007100703844A CN100526286C (en) | 2007-07-27 | 2007-07-27 | Method for synthesizing akarol fenisobromolate |
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| CNB2007100703844A CN100526286C (en) | 2007-07-27 | 2007-07-27 | Method for synthesizing akarol fenisobromolate |
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| CN113563193A (en) * | 2020-08-24 | 2021-10-29 | 江苏禾本生化有限公司 | New preparation method of fenisobromolate |
| CN113831233B (en) * | 2021-08-13 | 2022-09-02 | 江苏禾本生化有限公司 | Synthesis method and application of 2, 2-bis (4-bromophenyl) -2-hydroxyacetic acid |
| CN114315558A (en) * | 2021-12-28 | 2022-04-12 | 江苏禾本生化有限公司 | Novel synthesis method of 4,4' -dibromo-diphenylacetic acid |
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Non-Patent Citations (2)
| Title |
|---|
| 杀螨剂溴螨酯的合成研究. 吴奎华等人.农药，第4期. 1987 |
| 杀螨剂溴螨酯的合成研究. 吴奎华等人.农药，第4期. 1987 * |
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Denomination of invention: A Synthetic Method of Bromo Acaride Effective date of registration: 20230921 Granted publication date: 20090812 Pledgee: Industrial and Commercial Bank of China Limited Wenzhou Lucheng Branch Pledgor: Zhejiang Heben Technology Co.,Ltd. Registration number: Y2023980057938 |