CN104876916A - Preparation method of difenoconazole - Google Patents
Preparation method of difenoconazole Download PDFInfo
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- CN104876916A CN104876916A CN201510063421.3A CN201510063421A CN104876916A CN 104876916 A CN104876916 A CN 104876916A CN 201510063421 A CN201510063421 A CN 201510063421A CN 104876916 A CN104876916 A CN 104876916A
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- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
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Abstract
The invention belongs to the field of pesticide original drugs and relates to a preparation technology of a pesticide original drug, especially to a preparation method of difenoconazole. The preparation method provided by the invention comprises steps of acylation reaction, cyclization synthesis and condensed difenoconazole synthesis. In comparison with the prior art, the invention has the following advantages and positive effects: by changing the condensed difenoconazole synthesis step in previous technologies, reactants are minimized, the bromination process is omitted, reaction time is shortened, crystallization speed is raised, and production time is saved; yield of products is high, quality is good, and viscosity is moderate; and wastes are reduced, and clean and environmentally friendly production is realized.
Description
Technical field
The invention belongs to pesticide original medicine field, relate to a kind of preparation technology of pesticide original medicine, particularly relate to a kind of preparation method of difenoconazole.
Background technology
Difenoconazole is a kind of sterilant of broad-spectrum high efficacy, the main biosynthesizing suppressing germ cell ergosterol, thus destroys membrane structure and function, thus reaches and have well protection and therapeutic action to the multiple fungal disease such as vegetables and melon and fruit.
The ISO common name of difenoconazole: Difenoconazole
Its chemical name: suitable, the chloro-4-of trans-3-[4-methyl-2-(1H-1,2,4-triazole-1-ylmethyl)-1,3-bis-Evil pentane-2-base] phenyl 4-chloro-phenyl-ether (suitable, reverse proportionality is about 45:55)
CAS registration number: 119446-68-3
Molecular formula: C19H17Cl2N3O3
Chemical formula is:
Difenoconazole is white solid, fusing point 76 ° of C, boiling point 220 ° of C/0.03mmHg, vapour pressure 120mPa (20 ° of C).Solvability (20 ° of C): water 3.3mg/l, be soluble in organic solvent, be mainly used in preventing and treating pear scab, alternaria leaf spot of apple, tomato drought epidemic disease, watermelon grafting, pepper anthracnose, powdery mildew of strawberry, bitter rot or anthracnose of grape, black Ya disease, citrus scab etc.
Due to difenoconazole site of action accurately, the multiple fungal disease such as vegetables and melon and fruit has good therapeutic action, simultaneously to the safety of crop, that difenoconazole is played in the development of present green agriculture, pollution-less agriculture is crucial and irreplaceable effect.
In order to improve quality and the yield of difenoconazole coarse fodder, applicant have submitted a patent application on 07 23rd, 2010 to State Intellectual Property Office, its grant number is CN101899040B, a kind of preparation technology of difenoconazole is disclosed in invention file, use the preparation technology that this patent provides, although improve the rewinding rate of difenoconazole to a certain extent, reduce the loss of material of reaction, but the speed of its crystallization is excessively slow, strengthen+production time, reduce production efficiency, add production cost.
Summary of the invention
The crystallization velocity that the present invention is directed to above-mentioned difenoconazole crosses the technical problems such as slow, proposes a kind of preparation method of reasonable in design, crystallization velocity is fast, yield is high, loss of material is few difenoconazole.
In order to achieve the above object, the technical solution used in the present invention is, the invention provides a kind of preparation method of difenoconazole, comprises acidylate synthesis, Cyclization, condensation difenoconazole synthesize three processing steps, specific as follows:
A. acidylate synthesis step: first by phenyl ether (3,4'-dichloro-diphenyl ether), bromoacetyl chloride, aluminum chloride and additive add in reactor in 10 DEG C-15 DEG C reaction 5h, be added dropwise to hydrochloric acid again, then spent acid layer, additive layer is divided, precipitation reclaims additive and applies mechanically, obtain bromoketone (chloro-3, the 4'-dichloro phenylate ethyl ketones of the bromo-2-of w-);
B. Cyclization step: the bromoketone obtain upper step and propylene glycol, catalyzer p-methyl benzenesulfonic acid, toluene add in reactor and reacts 4h in 105 DEG C-110 DEG C, reaction terminates the removing of rear material oil reservoir, toluene layer, precipitation obtains bromination ketal (3-chloro-4 (4-methyl-2-brooethyl-1,3 one dioxin-pentane-2 one base) phenyl-4 '-chloro-phenyl-ether);
C. condensation difenoconazole synthesis step: bromination ketal, 1-Sodium-1,2,4-Triazole, solvent added in difenoconazole synthesis reactor and carry out back flow reaction, the material obtained after reaction, through suction filtration, removes the sodium salt that reaction generates.Then vacuum distillation recovered solvent.Add water and toluene after distillation terminates to stir and leave standstill, then divide water-yielding stratum, water layer toluene extracts.After washing terminates, precipitation obtains difenoconazole crude product.
In the preparation method of above-mentioned difenoconazole, described solvent is toluene, acetone, DMSO(dimethyl sulfoxide (DMSO)) or DMF(dimethyl formamide).
As preferably, described solvent is DMF.
As preferably, the proportioning between described bromination ketal and 1-Sodium-1,2,4-Triazole is 1.14:1.
As preferably, described bromination ketal and 1-Sodium-1,2,4-Triazole, the reaction times of DMF in synthesis reactor are 8 ~ 12h.
In the preparation method of above-mentioned difenoconazole, the method also comprises purification step, described purification step is: condensation difenoconazole synthesis step is obtained difenoconazole crude product adds toluene, ethanol dissolves, then temperature-fall period adds linking agent, freezing and crystallizing, suction filtration, obtains refining difenoconazole.
In the preparation method of above-mentioned difenoconazole, described linking agent is vinylbenzene, methacrylic acid or aziridine.
As preferably, described linking agent is aziridine.
In the preparation method of above-mentioned difenoconazole, described additive is methylene dichloride, trichloromethane or tetrachloromethane.
As preferably, described additive is methylene dichloride.
Compared with prior art, advantage of the present invention and positively effect are,
The present invention is by condensation difenoconazole synthesis step in technique before change, decrease reactant, save bromination operation, shorten the reaction times, improve the speed of crystallization, save the production time, and the yield rate of producing product is high, quality better, viscosity is moderate, and waste product is few simultaneously, achieves clean environment firendly and produces.
Embodiment
In order to more clearly understand above-mentioned purpose of the present invention, feature and advantage, below in conjunction with embodiment, the present invention will be further described.It should be noted that, when not conflicting, the feature in the embodiment of the application and embodiment can combine mutually.
Set forth a lot of detail in the following description so that fully understand the present invention, but the present invention can also adopt and be different from other modes described here and implement, and therefore, the present invention is not limited to the restriction of the specific embodiment of prospectus below.
Embodiment 1: the present embodiment provides the preparation method of a kind of preparation method of difenoconazole, comprises acidylate synthesis, Cyclization, condensation difenoconazole synthesizes three processing steps, specific as follows:
A. acidylate synthesis step: first by phenyl ether (3,4'-dichloro-diphenyl ether), bromoacetyl chloride, aluminum chloride and additive add in reactor in 10 DEG C-15 DEG C reaction 5h, be added dropwise to hydrochloric acid again, then spent acid layer, additive layer is divided, precipitation reclaims additive and applies mechanically, obtain bromoketone (chloro-3, the 4'-dichloro phenylate ethyl ketones of the bromo-2-of w-);
B. Cyclization step: the bromoketone obtain upper step and propylene glycol, catalyzer p-methyl benzenesulfonic acid, toluene add in reactor and reacts 4h in 105 DEG C-110 DEG C, reaction terminates the removing of rear material oil reservoir, toluene layer, precipitation obtains bromination ketal (3-chloro-4 (4-methyl-2-brooethyl-1,3 one dioxin-pentane-2 one base) phenyl-4 '-chloro-phenyl-ether);
C. condensation difenoconazole synthesis step: bromination ketal, 1-Sodium-1,2,4-Triazole, solvent added in difenoconazole synthesis reactor and carry out back flow reaction, the material obtained after reaction, through suction filtration, removes the sodium salt that reaction generates.Then vacuum distillation recovered solvent.Add water and toluene after distillation terminates to stir and leave standstill, then divide water-yielding stratum, water layer toluene extracts.After washing terminates, precipitation obtains difenoconazole crude product.
The reaction equation of above-mentioned steps is:
Acidylate is synthesized:
Cyclization:
C. condensation difenoconazole synthesis:
First from the detailed description of acidylate synthesis step:
Acidylate synthesis step--bromoketone synthesizes
In the reactor with stirring, thermometer, add phenyl ether 0.1mol, aluminum chloride 0.1mol, additive 100ml, 10 DEG C of-20 DEG C of temperature controls, dripped bromoacetyl chloride in 1-2 hour, after dripping off, insulation for some time, to reacting complete, is added dropwise in 0.11mol hydrochloric acid/100ml water, temperature 5-10 DEG C.Then spent acid layer, additive layer is divided, (note: this is said point and goes spent acid layer, additive layer to be the routine techniques means of the industry, therefore be not described in detail at this) precipitation reclaim additive apply mechanically, obtain bromoketone (chloro-3, the 4'-dichloro phenylate ethyl ketones of the bromo-2-of w-);
The data of screening proportioning raw materials, additive, reaction times are as follows:
The proportioning (phenyl ether: bromoacetyl chloride, mol ratio) of phenyl ether, bromoacetyl chloride
Table 1 Data Comparison form
| Experiment lot number | Material proportion | Product must be measured | Content | Yield |
| 1 | 1∶0.9 | 32.06g | 96.7% | 85.5% |
| 2 | 1∶1.0 | 35.1g | 97.6% | 93.5% |
| 3 | 1∶1.05 | 35.5g | 97.8% | 95.0% |
| 4 | 1∶1.1 | 35.3g | 97.5% | 94.2% |
As can be seen from the above, phenyl ether and bromoacetyl chloride proportioning are 1: 1.05 is the best.
(2) screening of additive
Select trichloromethane, methylene dichloride, tetrachloromethane as additive, result is as follows:
Table 2 Data Comparison form
| Experiment lot number | Solvent | Must measure | Content | Yield |
| 5 | Methylene dichloride | 35.5g | 97.8% | 95.0% |
| 6 | Trichloromethane | 35.0g | 97.6% | 93.3% |
| 7 | Tetrachloromethane | 35.1g | 97.3% | 92% |
As can be seen from the above, methylene dichloride is used to make additive effect best.
(3) screening in reaction times
Table 3 Data Comparison form
| Experiment lot number | Reaction times | Must measure | Content | Yield |
| 8 | 2h | 28.3g | 88% | 70% |
| 9 | 4h | 33.8g | 94% | 88.2% |
| 10 | 5h | 35.5g | 97.8% | 95.0% |
| 11 | 6h | 35.6g | 96.9% | 94.8% |
Therefore 5 hours reaction times was best.
Cyclization step--the synthesis of bromination ketal
In the reactor with stirring, thermometer, add bromoketone, propylene glycol 0.13mol, CAT(toluene sulfonic acide) and toluene 200mL, heat 105-110 DEG C of back flow reaction 3-5 hour, after reaction, be cooled to 20 DEG C, removing oil reservoir, toluene layer (note: the routine techniques means that this is said removing oil reservoir, toluene layer is the industry, therefore be not described in detail at this), precipitation obtains bromination ketal.
The data of screening the proportioning of reaction mass, reaction times, catalyst levels are as follows:
The proportioning (bromination ketal: propylene glycol, mol ratio) of bromination ketal and propylene glycol
Table 4 Data Comparison form
| Experiment lot number | Material proportion | Must measure | Content | Yield |
| 12 | 1∶1.5 | 29.2g | 91% | 63.7% |
| 13 | 1∶1 | 35.6g | 94% | 80% |
| 14 | 1∶2 | 38g | 95% | 86% |
| 15 | 1∶3 | 40.1g | 98.5% | 94.5% |
| 16 | 1∶4 | 39g | 97.3% | 90.7% |
As can be seen from the above, propylene glycol consumption is too low then to be transformed not exclusively, and too high then side reaction increases, and yield is all undesirable, for best when proportioning is 1: 3.
The screening in reaction times
Table 5 Data Comparison form
| Experiment lot number | Reaction times | Must measure | Content | Yield |
| 17 | 3h | 38.5g | 95% | 87.5% |
| 18 | 4h | 40.1g | 98.5% | 94.5% |
| 19 | 5h | 39.5g | 97% | 91.6% |
Can find out reaction 4 hours the bests from experimental result, then the time that increases do not have effect yet.
CAT(toluene sulfonic acide) consumption
Table 6 Data Comparison form
| Experiment lot number | Catalyst levels | Must measure | Content | Yield |
| 20 | 1g | 40.1g | 98.5% | 94.5% |
| 21 | 0.5g | 39.1g | 95% | 88.8% |
| 22 | 1.2g | 39.8g | 97.5% | 92.8% |
As seen from the above table, the consumption of catalyzer p-methyl benzenesulfonic acid is the 1-2% accounting for bromoketone weight.
Condensation difenoconazole synthesis step
0.14mol 1-Sodium-1,2,4-Triazole, 200ml solvent, bromination ketal 0.1mol is added in the synthesis reactor with stirring, water trap, reflux exchanger, thermometer.Be warmed up to 120 ~ 125 degree of insulations 10h, then cool to room temperature, filter the sodium salt removed reaction and generate.Then vacuum distillation recovered solvent.Add 100ml water and 200ml toluene, then divide water-yielding stratum, water layer 50ml toluene extracts.Merge organic layer, the crude product of the difenoconazole of precipitation.
Mainly experiment screening is carried out to the selection of solvent, the proportioning of material
(1) screening of solvent
Have chosen toluene, acetone, DMSO, DMF be solvent.The selection result
Table 7 Data Comparison form
| Solvent (ml) | Difenoconazole (g) | Content (%) | Yield (%) |
| Toluene 200ml | 40.6 | 80.0 | 78.4 |
| Acetone 200ml | 41.2 | 0 | 0 |
| DMSO200ml | 40.2 | 50.2 | 49.7 |
| DMF200ml | 39.5 | 85.0 | 82.6 |
From then on table can find out that solvent is very large, wherein better with the effect of DMF on the impact of reaction.
(2) proportioning of 1-Sodium-1,2,4-Triazole and bromination ketal is screened
Table 8 Data Comparison table
| 1-Sodium-1,2,4-Triazole: bromination ketal (m/m) | Difenoconazole (g) | Content (%) | Yield (%) |
| 1:1.12 | 38.2 | 85.4 | 80.2 |
| 1:1.13 | 38.85 | 91.1 | 87.1 |
| 1:1.14 | 40.24 | 95.2 | 94.3 |
| 1:1.15 | 40.3 | 95.0 | 94.2 |
Coupon results shows, in proportioning screening, when material proportion is 1:1.14, result is more reasonable.
(1) from technical process, reaction conditions is gentle, simple to operate, and removing bromination operation, produces cheap property and greatly strengthen.
(2) decrease production link, solvent is applied mechanically, and without useless, cleanly production, decreases pollution, reduces cost.
Four, purification step
The crude product that upper step obtains is added in solvating agent and dissolves, then add linking agent, freezing and crystallizing in temperature-fall period, suction filtration, obtain refining difenoconazole.
Table 9 Data Comparison form
| Experiment lot number | Solvating agent class | Must measure | Content | Yield |
| 32 | Virahol (99%, 200g) | 75.4g | 97% | 70.6% |
| 33 | Toluene (99%, 200g) | 67.4g | 94% | 64% |
| 34 | Ethanol (anhydrous, 200g) | 70.5g | 94.6% | 65.8% |
| 35 | Ethanol, toluene Mixed Solvent | 80g | 96.2% | 85.1% |
As can be seen from the above, ethanol, toluene Mixed Solvent are best solvating agent.
The screening of linking agent
Table 10 Data Comparison form
| Experiment lot number | Kind | Must measure | Content | Yield |
| 35 | Vinylbenzene | 75.5g | 90% | 71% |
| 36 | Methacrylic acid | 77.4g | 93.9% | 73% |
| 37 | Aziridine | 83g | 97% | 86.5% |
As can be seen from the above, aziridine crosslinker is best.
The Data Comparison of the product that the difenoconazole product adopting purification step of the present invention to obtain and the last patent application of the applicant (201010234679.2) obtain is as follows:
The 1st batch, table 13
| Experiment lot number | Reaction times | Must measure | Content | Yield |
| Former patent solvent | 41 hours | 70.1g | 95% | 65.2% |
| Adopt novel solvent | 10 hours | 75.6g | 98% | 77.2% |
The 2nd batch, table 14
| Experiment lot number | Reaction times | Must measure | Content | Yield |
| Former patent solvent | 42 hours | 71.4g | 95% | 65.6% |
| Adopt novel solvent | 10.3 hours | 76.6g | 98% | 78.8% |
The 3rd batch, table 15
| Experiment lot number | Reaction times | Must measure | Content | Yield |
| Former patent solvent | 40 hours | 71.2g | 95% | 66.6% |
| Adopt novel solvent | 10.7 hours | 77.6g | 98% | 79.1% |
This reaction times refers to crystallization time; Must measure the actual mass referring to the product obtained, content refers to: the purity of product after refining.
The above; it is only preferred embodiment of the present invention; it is not restriction the present invention being made to other form; the Equivalent embodiments that any those skilled in the art may utilize the technology contents of above-mentioned announcement to be changed or be modified as equivalent variations is applied to other field; but everyly do not depart from technical solution of the present invention content; according to any simple modification, equivalent variations and remodeling that technical spirit of the present invention is done above embodiment, still belong to the protection domain of technical solution of the present invention.
Claims (10)
1. a preparation method for difenoconazole, comprise acidylate synthesis step, Cyclization step and condensation difenoconazole synthesis step, concrete operation step is as follows:
A. acidylate synthesis step: first phenyl ether, bromoacetyl chloride, aluminum chloride and additive are added reaction kettle for reaction, then be added dropwise to hydrochloric acid, obtain bromoketone;
B. Cyclization step: the bromoketone obtain acidylate synthesis step and propylene glycol, catalyzer p-methyl benzenesulfonic acid, toluene add reaction kettle for reaction, obtains bromination ketal after reaction terminates, it is characterized in that:
C. condensation difenoconazole synthesis step is: the bromination ketal obtained in Cyclization step, 1-Sodium-1,2,4-Triazole added in synthesis reactor together with solvent and react, reacting rear material is through suction filtration, remove the sodium salt that reaction generates, then vacuum distillation recovered solvent, add water and toluene after distillation terminates to stir and leave standstill, then divide water-yielding stratum, water layer toluene extracts, after washing terminates, precipitation obtains difenoconazole crude product.
2. the preparation method of difenoconazole according to claim 1, is characterized in that, described solvent is toluene, acetone, DMSO or DMF.
3. the preparation method of difenoconazole according to claim 2, is characterized in that, described solvent is DMF.
4. the preparation method of difenoconazole according to claim 3, is characterized in that, the proportioning between bromination ketal and 1-Sodium-1,2,4-Triazole is 1.14:1.
5. the preparation method of difenoconazole according to claim 4, is characterized in that, described bromination ketal and 1-Sodium-1,2,4-Triazole, the reaction times of DMF in synthesis reactor are 8 ~ 12h.
6. the preparation method of difenoconazole according to claim 1, it is characterized in that, the method also comprises purification step, described purification step is: condensation difenoconazole synthesis step is obtained difenoconazole crude product adds toluene, ethanol dissolves, then temperature-fall period adds linking agent, freezing and crystallizing, suction filtration, obtains refining difenoconazole.
7. the preparation method of difenoconazole according to claim 6, is characterized in that, described linking agent is vinylbenzene, methacrylic acid or aziridine.
8. the preparation method of difenoconazole according to claim 7, is characterized in that, described linking agent is aziridine.
9. the preparation method of difenoconazole according to claim 1, is characterized in that, described additive is methylene dichloride, trichloromethane or tetrachloromethane.
10. the preparation method of difenoconazole according to claim 9, is characterized in that, described additive is methylene dichloride.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112300137A (en) * | 2020-08-24 | 2021-02-02 | 江苏禾本生化有限公司 | Synthetic method of high-purity difenoconazole |
| CN113861004A (en) * | 2021-11-03 | 2021-12-31 | 山东潍坊双星农药有限公司 | Catalytic synthesis method of difenoconazole intermediate difenone |
| CN116041309A (en) * | 2023-01-17 | 2023-05-02 | 浙江宇龙生物科技股份有限公司 | Continuous extraction synthesis method of substituted ketal |
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| CN116041309A (en) * | 2023-01-17 | 2023-05-02 | 浙江宇龙生物科技股份有限公司 | Continuous extraction synthesis method of substituted ketal |
| CN116041309B (en) * | 2023-01-17 | 2023-11-14 | 浙江宇龙生物科技股份有限公司 | Continuous extraction synthesis method of substituted ketal |
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Application publication date: 20150902 |