CN114891039B - Preparation method of Dufulin compound - Google Patents

Preparation method of Dufulin compound Download PDF

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CN114891039B
CN114891039B CN202210535185.0A CN202210535185A CN114891039B CN 114891039 B CN114891039 B CN 114891039B CN 202210535185 A CN202210535185 A CN 202210535185A CN 114891039 B CN114891039 B CN 114891039B
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toxic
phosphorus
mixed solution
dufulin
solvent
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CN114891039A (en
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邹西红
黄发声
石吉祥
李现玲
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Guangxi Tianyuan Biochemical Co Ltd
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Guangxi Tianyuan Biochemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6536—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having nitrogen and sulfur atoms with or without oxygen atoms, as the only ring hetero atoms
    • C07F9/6539—Five-membered rings
    • C07F9/6541—Five-membered rings condensed with carbocyclic rings or carbocyclic ring systems
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
    • A01N57/24—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing heterocyclic radicals

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Biochemistry (AREA)
  • Molecular Biology (AREA)
  • Agronomy & Crop Science (AREA)

Abstract

The invention relates to a preparation method of a toxic fluorine phosphorus compound, which comprises the following steps: (1) Reflux reaction is carried out on 2-ammonia-4-methylbenzothiazole and o-fluorobenzaldehyde to generate Schiff base; (2) Carrying out reflux reaction on diethyl phosphite and the Schiff base prepared in the step (1) to generate a toxic fluorine-phosphorus-containing mixed solution; (3) Crystallizing the mixed solution containing the toxic fluorine and phosphorus prepared in the step (2) to obtain a mixed solution containing the toxic fluorine and phosphorus crystal; (4) And (3) carrying out azeotropic distillation on the mixed solution of the toxic fluorine-phosphorus-containing crystal obtained in the step (3), and separating to obtain the toxic fluorine-phosphorus compound. The preparation method has the advantages of simple process, low cost and high reaction yield, and is suitable for industrial production.

Description

Preparation method of Dufulin compound
Technical Field
The invention belongs to the technical field of pesticides, and particularly relates to a preparation method of a toxic fluorine phosphorus compound.
Background
Plant virus diseases are called plant "cancers", and are diseases which are difficult to control and easy to spread. The virus disease mainly damages the economic crops such as tobacco, vegetables, fruit trees and the like and the grain crops such as rice, corn and the like, seriously affects the yield and the quality of the crops, even leads to the sterilization, and affects the income of peasants and the national grain safety. The chemical name of the Dufulin is N- [2- (4-methylbenzothiazolyl) ] -2-amino-2-fluorophenyl-O, O-diethyl phosphonate, belongs to an antiviral compound with independent intellectual property rights, is a new generation of efficient, broad-spectrum and low-toxicity antiviral preparation which is independently and successfully innovated by the university of Guizhou fine chemical research center, and is a new variety of domestic independent and pioneering pesticides. The Dufulin has the characteristics of outstanding effect of preventing and treating viral diseases and low cost, and can forcefully promote the increase of production and income of farmers.
The patent with publication number of CN1687088A reports N-substituted benzothiazolyl-1-substituted phenyl-O, O-dialkyl-alpha-amino phosphonate derivatives, a preparation method and application thereof, but the synthesis method has great defects, in particular to a crystallization method for distilling benzene, toluene and dimethylbenzene under reduced pressure, and the crystal size is different, the content is unstable and the yield is low. Secondly, the solvent is required to be distilled off under reduced pressure in the synthesis process of the Dufulin, and benzene, toluene and xylene which are solvents are recovered by distillation under reduced pressure cannot be completely brought into crystallization, and the smell of the solvent is too large, so that the operation environment of workers is influenced.
Patent publication No. CN102807585A discloses a method for crystallizing Dufulin by using ultrasonic auxiliary technique, in which the toxic Dufulin is crystallized by using ultrasonic auxiliary technique, and laboratory synthesis is easy to operate but not suitable for ton industrial production.
In the past, those skilled in the art have been working on developing new, more advanced, rational, more suitable for industrial production methods to obtain toxic fluorophosphorus compounds with simpler preparation process, higher yields and lower prices.
Disclosure of Invention
The invention aims to solve the technical problems of overcoming the defects in the prior art and providing the preparation method of the toxic fluorine phosphorus compound, which has the advantages of simple preparation process, low cost, high reaction yield and suitability for industrial production.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of a Dufulin compound comprises the following steps:
(1) Reflux reaction of 2-ammonia-4-methylbenzothiazole and o-fluorobenzaldehyde to generate Schiff base (Schiff base);
(2) Carrying out reflux reaction on diethyl phosphite and the Schiff base prepared in the step (1) to generate a toxic fluorine-phosphorus-containing mixed solution;
(3) Crystallizing the mixed solution containing the toxic fluorine and phosphorus prepared in the step (2) to obtain a mixed solution containing the toxic fluorine and phosphorus crystal;
(4) And (3) carrying out azeotropic distillation on the mixed solution of the toxic fluorine-phosphorus-containing crystal obtained in the step (3), and separating to obtain the toxic fluorine-phosphorus compound.
Preferably, steps (1), (2), (3) and (4) are carried out in the same reaction vessel.
Preferably, the temperature of the reflux reaction in the step (1) is 110-150 ℃ and the reaction time is 2-6 h;
preferably, in step (1), 2-amino-4-methylbenzothiazole: the mass ratio of the o-fluorobenzaldehyde is 1-1.10: 0.73 to 0.78;
preferably, the reflux reaction in step (1) is carried out in a first solvent selected from one or a mixture of two or more of benzene, toluene, xylene, trimethylbenzene, cyclohexanone, chloroform, etc.;
preferably, in step (1), 2-amino-4-methylbenzothiazole: o-fluorobenzaldehyde: the mass ratio of the first solvent is 1-1.10: 0.73 to 0.78:3.00 to 5.00;
optionally, adding a catalyst to the reflux reaction of step (1);
preferably, the catalyst is p-toluene sulfonic acid.
Preferably, the reflux reaction temperature in the step (2) is 110-150 ℃ and the reaction time is 2-6 h.
Preferably, the temperature of the azeotropic distillation in step (4) is 85 to 110 ℃.
Preferably, in the step (3), the second solvent is added to the mixed solution containing toxic fluorine and phosphorus prepared in the step (2) and then crystallized, wherein the second solvent is selected from one or more of methanol, ethanol, n-butanol, tert-butyl methyl ether, water, isopropyl ether, cyclohexanone, diethylene glycol butyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ether, tetrahydrofuran and the like;
preferably, the crystallization temperature in step (3) is below 95 ℃.
Further preferred, 2-amino-4-methylbenzothiazole: o-fluorobenzaldehyde: diethyl phosphite: a first solvent: the mass ratio of the second solvent is 1-1.10: 0.73 to 0.78:0.95 to 1.10: 3.00-5.00: 3.00 to 5.00;
preferably, 2-amino-4-methylbenzothiazole: o-fluorobenzaldehyde: diethyl phosphite: a first solvent: the mass ratio of the second solvent is 1-1.05: 0.73 to 0.78:1.00 to 1.05: 3.00-5.00: 3.00-5.00.
In order to solve the technical problems, the invention adopts the following technical scheme:
a pesticide preparation comprises the toxic fluorine phosphorus compound prepared by the preparation method and a carrier and/or an auxiliary agent acceptable in pesticide.
Preferably, the pesticide formulation includes solid formulations and liquid formulations;
preferably, the solid preparation is selected from one of water dispersible granules, wettable powder and granules;
preferably, the liquid formulation is selected from one of a suspending agent, a microcapsule suspending agent, and a microemulsion.
Preferably, the auxiliary agent comprises one or more of a stabilizer, a dispersant, a surfactant, and a solvent.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following advantages:
1. the yield of the toxic fluorophosphorus compound is high, the average yield reaches 93.96 percent, and the yield of the compound (toxic fluorophosphorus compound) in the example 10 in the patent with the publication number of CN1687088A is 85.7 percent, compared with the yield of the compound, the yield of the compound is improved by 8.26 percent;
2. the preparation method of the Dufulin of the invention greatly improves the yield and ensures that each ton of product creates direct economic benefit exceeding 3 ten thousand yuan (RMB)/ton relative to the preparation method of the example 10 in the patent with the publication number of CN 1687088A;
3. according to the preparation method, the azeotropic distillation is adopted, so that the solvent residue in the product is greatly reduced, the smell is obviously reduced during discharging, and the operation environment can be greatly improved;
4. after the process is adjusted, the generated impurity amount is greatly reduced, the blocking phenomenon caused by sticky materials is reduced, and suction filtration is smoother;
5. the residue (liquid) amount of the invention is reduced from the original 250kg/T product to 75kg/T product, thus greatly reducing the environmental protection pressure;
6. the preparation method of the toxic fluorine phosphorus compound has reasonable design, mild reaction conditions, easily obtained raw materials, convenient operation, high product yield, suitability for large-scale production and good industrial reproducibility.
Detailed Description
In order to make the technical scheme and the beneficial effects of the invention more obvious and understandable, the following detailed description is given by way of example. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. The experimental procedure, in which specific conditions are not noted in the examples below, generally follows conventional experimental conditions. The reagents and materials used in the present invention are commercially available unless otherwise specified. The pesticide raw materials, the solvent, the surfactant, the stabilizer, the dispersing agent, the catalyst and the carrier used in the invention are all purchased from chemical and agricultural raw material companies at home and abroad and can be directly utilized. The percentages in the following examples are mass percentages unless otherwise indicated.
The invention relates to a preparation method of a toxic fluorine phosphorus compound, which comprises the following steps:
(1) Reflux reaction is carried out on 2-ammonia-4-methylbenzothiazole and o-fluorobenzaldehyde to generate Schiff base;
in some embodiments, the temperature of the reflux reaction in step (1) is 110 to 150 ℃, preferably 110 to 130 ℃, more preferably 110 to 120 ℃, and more particularly may be 110 ℃,111 ℃,112 ℃,113 ℃,115 ℃,116 ℃,118 ℃,120 ℃,126 ℃,135 ℃.
In some embodiments, the reaction time of the reflux reaction in step (1) is 2 to 6 hours, preferably 4 to 6 hours, more specifically may be 4 hours, 5 hours, 6 hours.
In some embodiments, 2-amino-4-methylbenzothiazole in step (1): the mass ratio of the o-fluorobenzaldehyde is 1-1.10: 0.73 to 0.78.
In some embodiments, the reflux reaction in step (1) is performed in a first solvent selected from the group consisting of benzene, toluene, xylene, trimethylbenzene, cyclohexanone, and a mixture of two or more of trichloromethane, more preferably benzene, toluene, trichloromethane, xylene, and trimethylbenzene.
In some embodiments, 2-amino-4-methylbenzothiazole in step (1): o-fluorobenzaldehyde: the mass ratio of the first solvent is 1-1.10: 0.73 to 0.78: 3.00-5.00.
In some embodiments, a catalyst is added in the reflux reaction of step (1); preferably, the catalyst is p-toluene sulfonic acid.
In some specific embodiments, the specific operations of step (1) are:
adding 2-ammonia-4-methylbenzothiazole, o-fluorobenzaldehyde and a first solvent with prescribed amounts into a reaction kettle, stirring, heating until reflux occurs, starting timing, controlling the reaction temperature to be 110-150 ℃, carrying out reflux reaction for 2-6H to generate Schiff base, and separating H 2 O。
(2) Carrying out reflux reaction on diethyl phosphite and the Schiff base prepared in the step (1) to generate a toxic fluorine-phosphorus-containing mixed solution;
in some embodiments, the temperature of the reflux reaction in step (2) is from 110 to 150 ℃, preferably from 110 to 130 ℃, more preferably from 110 to 120 ℃.
In some embodiments, the reaction time of the reflux reaction in step (2) is 2 to 6 hours, preferably 3 to 5 hours.
In some embodiments, the vapor pressure of the reflux reaction in step (2) is <0.2Mpa.
In some specific embodiments, the specific operations of step (2) are:
after the step (1) is completed, adding the diethyl phosphite with the prescription amount into a reaction kettle, heating until reflux occurs, starting timing at the moment, controlling the reaction temperature to be 110-150 ℃, controlling the steam pressure to be less than 0.2Mpa, and carrying out reflux reaction on the diethyl phosphite and the Schiff base prepared in the step (1) for 2-6 h to generate the mixed solution containing the toxic fluorine and phosphorus.
(3) Crystallizing the mixed solution containing the toxic fluorine and phosphorus prepared in the step (2) to obtain the mixed solution containing the toxic fluorine and phosphorus crystals.
In some embodiments, in step (3), the second solvent is added to the mixed solution containing toxic fluorine and phosphorus prepared in step (2) and then crystallization is performed, wherein the second solvent is selected from one or more of methanol, ethanol, n-butanol, tert-butyl methyl ether, water, isopropyl ether, cyclohexanone, diethylene glycol butyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ether, tetrahydrofuran and the like, and preferably one or more of ethanol, methanol, n-butanol and water.
In some embodiments, the crystallization temperature in step (3) is below 95 ℃, preferably 90-95 ℃.
In some specific embodiments, the specific operations of step (3) are:
cooling the mixed solution containing the toxic fluorine and phosphorus in the reaction kettle to below 95 ℃, and adding a second solvent for crystallization to obtain the mixed solution containing the toxic fluorine and phosphorus crystals.
(4) And (3) carrying out azeotropic distillation on the mixed solution of the toxic fluorine-phosphorus-containing crystal obtained in the step (3), and separating to obtain the toxic fluorine-phosphorus compound.
In some embodiments, the temperature of the azeotropic distillation in step (4) is from 85 to 110 ℃, preferably from 85 to 100 ℃.
In some specific embodiments, the specific operations of step (4) are:
heating all materials in a reaction kettle (the mixed solution of the toxic fluorine-containing phosphorus crystals obtained in the step (3)) to 85-110 ℃, separating the first solvent through azeotropic distillation, and finally separating the second solvent and H 2 And (3) centrifugally filtering the mixture of O and the Dufulin to obtain Dufulin wet powder, and drying the Dufulin wet powder to obtain the Dufulin compound original drug.
In some embodiments, steps (1), (2), (3) and (4) are performed in the same reaction vessel.
In some embodiments, 2-amino-4-methylbenzothiazole: o-fluorobenzaldehyde: diethyl phosphite: a first solvent: the mass ratio of the second solvent is 1-1.10: 0.73 to 0.78:0.95 to 1.10: 3.00-5.00: 3.00 to 5.00;
preferably, 2-amino-4-methylbenzothiazole: o-fluorobenzaldehyde: diethyl phosphite: a first solvent: the mass ratio of the second solvent is 1-1.05: 0.73 to 0.78:1.00 to 1.05: 3.00-5.00: 3.00-5.00.
The invention also provides a pesticide preparation, which comprises the toxic fluorine phosphorus compound prepared by the preparation method and a carrier and/or an auxiliary agent acceptable in pesticide.
In some embodiments, the pesticide formulation includes a solid formulation and a liquid formulation.
In some embodiments, the solid formulation is selected from one of water dispersible granules, wettable powders, and granules.
In some embodiments, the liquid formulation is selected from one of a suspending agent, a microcapsule suspending agent, and a microemulsion.
In some embodiments, the adjuvant includes one or more of a stabilizer, a dispersant, a surfactant, and a solvent.
In some specific embodiments, the carrier is one or both of white carbon black and kaolin.
In some specific embodiments, the stabilizer is one or both of sodium lignosulfonate and magnesium aluminum silicate.
In some embodiments, the dispersant is selected from alkyl naphthalene sulfonates.
In some specific embodiments, the surfactant is selected from one or more of alkylphenol ethoxylates, polyoxyethylene fatty alcohol ethers, and sodium dodecyl sulfate.
In some embodiments, the solvent is one or both of ethylene glycol and water.
Example 1
(1) Adding 105kg of 98% 2-ammonia-4-methylbenzothiazole, 75kg of 99% o-fluorobenzaldehyde, 400kg of 98% toluene and 4kg of 98% p-toluenesulfonic acid into a 1000L enamel reactor, stirring and heating to reflux, and starting the first step of reactionHeating to 110deg.C, reacting for 4 hr to obtain Schiff base, separating 10.5kg of H 2 O。
(2) After the step (1) is completed, 102kg of 99% diethyl phosphite is put into a reaction kettle, heated to reflux, counted at the moment, and reacted with Schiff base in the reaction kettle for 3 hours under the condition that the steam pressure is less than 0.2MPa and the temperature is 120 ℃ to generate the toxic fluorine-phosphorus mixed solution.
(3) And cooling the mixed solution containing the toxic fluorine phosphorus to 90 ℃, adding 300kg of 75% ethanol for crystallization, and obtaining the mixed solution containing the toxic fluorine phosphorus crystals.
(4) Heating all materials in a reaction kettle to 92 ℃, separating toluene by an azeotropic distillation method, and finally adding ethanol and H 2 And (3) centrifugally filtering the mixture of O and the Dufulin to obtain Dufulin wet powder, and drying the Dufulin wet powder to obtain 243.03kg of Dufulin compound raw medicine, wherein the content is 92.65%, and the yield is 92.15%.
Example 2
(1) Adding 105kg of 98% 2-ammonia-4-methylbenzothiazole, 75kg of 99% o-fluorobenzaldehyde, 350kg of 98% toluene and 4kg of 98% p-toluenesulfonic acid into a 1000L enamel reaction kettle, stirring and heating to reflux, starting the first step of reaction, heating to 113 ℃, reacting for 4 hours to generate Schiff base, and separating 11kg of H at the moment 2 O。
(2) After the step (1) is completed, 102kg of 99% diethyl phosphite is put into a reaction kettle, heated to reflux, counted at the moment, and reacted with Schiff base in the reaction kettle for 3 hours under the condition that the steam pressure is less than 0.2MPa and the temperature is 120 ℃ to generate the toxic fluorine-phosphorus mixed solution.
(3) And cooling the mixed solution containing the toxic fluorine phosphorus to 90 ℃, adding 300kg of 75% ethanol for crystallization, and obtaining the mixed solution containing the toxic fluorine phosphorus crystals.
(4) Heating all materials in a reaction kettle to 92 ℃, separating toluene by an azeotropic distillation method, and finally adding ethanol and H 2 The mixture of O and Dufulin is centrifugally filtered to obtain Dufulin wet powder, and the Dufulin wet powder is dried to obtain 240.37kg of Dufulin compound raw drug with 93.88% content and yield92.35％。
Example 3
(1) Adding 105kg of 98% 2-ammonia-4-methylbenzothiazole, 75kg of 99% o-fluorobenzaldehyde, 400kg of 98% benzene and 4kg of 98% p-toluenesulfonic acid into a 1000L enamel reaction kettle, stirring and heating to reflux, starting the first step of reaction, heating to 113 ℃, reacting for 5H to generate Schiff base, and separating 10kg of H at the moment 2 O。
(2) After the step (1) is completed, 100kg of 99% diethyl phosphite is put into a reaction kettle, heated to reflux, counted at the moment, and reacted with Schiff base in the reaction kettle for 4 hours under the condition that the steam pressure is less than 0.2MPa and the temperature is 115 ℃ to generate the toxic fluorine-phosphorus mixed solution.
(3) And cooling the mixed solution containing the toxic fluorine phosphorus to 95 ℃, adding 400kg of 75% ethanol for crystallization, and obtaining the mixed solution containing the toxic fluorine phosphorus crystals.
(4) Heating all materials in a reaction kettle to 92 ℃, separating benzene by using an azeotropic distillation method, and azeotropically adding ethanol and H 2 And (3) centrifugally filtering the mixture of O and the Dufulin to obtain Dufulin wet powder, and drying the Dufulin wet powder to obtain 240.19kg of Dufulin compound raw medicine, wherein the content is 94.00%, and the yield is 92.40%.
Example 4
(1) Adding 105kg of 98% 2-ammonia-4-methylbenzothiazole, 75kg of 99% o-fluorobenzaldehyde, 350kg of 98% benzene and 4kg of 98% p-toluenesulfonic acid into a 1000L enamel reaction kettle, stirring and heating to reflux, starting the first step, heating to 115 ℃ for 4 hours, reacting to generate Schiff base, and separating 12kg of H at the moment 2 O。
(2) After the step (1) is completed, 100kg of 99% diethyl phosphite is put into a reaction kettle, heated to reflux, counted at the moment, and reacted with Schiff base in the reaction kettle for 5 hours under the condition that the steam pressure is less than 0.2MPa and the temperature is 115 ℃ to generate the toxic fluorine-phosphorus mixed solution.
(3) And cooling the mixed solution containing the toxic fluorine and phosphorus to 95 ℃, adding 350kg of 75% methanol for crystallization, and obtaining the mixed solution containing the toxic fluorine and phosphorus crystal.
(4) Heating all materials in a reaction kettle to 98 ℃ to separate benzene by an azeotropic distillation method, and separating methanol and H 2 And (3) centrifugally filtering the mixture of O and the Dufulin to obtain Dufulin wet powder, and drying the Dufulin wet powder to obtain 241.74kg of Dufulin compound raw medicine, wherein the content is 93.80%, and the yield is 92.80%.
Example 5
(1) Adding 100kg of 98% 2-ammonia-4-methylbenzothiazole, 75kg of 99% o-fluorobenzaldehyde, 400kg of 98% benzene and 4kg of 98% p-toluenesulfonic acid into a 1000L enamel reaction kettle, stirring and heating to reflux, starting the first step, heating to 110 ℃ for 5H, and generating Schiff base, wherein 9kg of H is separated 2 O。
(2) After the step (1) is completed, 102kg of 99% diethyl phosphite is put into a reaction kettle, heated to reflux, counted at the moment, and reacted with Schiff base in the reaction kettle for 4 hours under the condition that the steam pressure is less than 0.2MPa and the temperature is 130 ℃ to generate the toxic fluorine-phosphorus mixed solution.
(3) And cooling the mixed solution containing the toxic fluorine and phosphorus to 90 ℃, adding 400kg of 65% methanol for crystallization, and obtaining the mixed solution containing the toxic fluorine and phosphorus crystal.
(4) Heating all materials in a reaction kettle to 93 ℃, separating benzene by using an azeotropic distillation method, and azeotropically adding methanol and H 2 And (3) centrifugally filtering the mixture of O and the Dufulin to obtain Dufulin wet powder, and drying the Dufulin wet powder to obtain 246.55kg of Dufulin compound raw medicine, wherein the content is 92.15%, and the yield is 92.98%.
Example 6
(1) Adding 100kg of 98% 2-ammonia-4-methylbenzothiazole, 75kg of 99% o-fluorobenzaldehyde, 350kg of 99% trichloromethane and 4kg of 98% p-toluenesulfonic acid into a 1000L enamel reaction kettle, stirring and heating to reflux, starting the first step of reaction, heating to 120 ℃ for 4 hours, and generating Schiff base, wherein 9.6kg of H is separated 2 O。
(2) After the step (1) is completed, 100kg of 99% diethyl phosphite is put into a reaction kettle, heated to reflux, counted at the moment, and reacted with Schiff base in the reaction kettle for 4 hours under the condition that the steam pressure is less than 0.2MPa and the temperature is 116 ℃ to generate the toxic fluorine-phosphorus mixed solution.
(3) And cooling the mixed solution containing the toxic fluorine and phosphorus to 95 ℃, adding 350kg of 100% n-butanol for crystallization, and obtaining the mixed solution containing the toxic fluorine and phosphorus crystals.
(4) Heating all materials in a reaction kettle to 93 ℃, separating chloroform by using an azeotropic distillation method, and azeotropically adding n-butanol and H 2 And (3) centrifugally filtering the mixture of O and the Dufulin to obtain Dufulin wet powder, and drying the Dufulin wet powder to obtain 246.78kg of Dufulin compound raw medicine, wherein the content is 94.56%, and the yield is 95.50%.
Example 7
(1) Adding 100kg of 98% 2-ammonia-4-methylbenzothiazole, 75kg of 99% o-fluorobenzaldehyde, 400kg of 98% dimethylbenzene and 4kg of 98% p-toluenesulfonic acid into a 1000L enamel reaction kettle, stirring and heating to reflux, starting the first step of reaction, heating to 111 ℃, reacting for 5H to generate Schiff base, and separating 11kg of H at the moment 2 O。
(2) After the step (1) is completed, 102kg of 99% diethyl phosphite is put into a reaction kettle, heated to reflux, counted at the moment, and reacted with Schiff base in the reaction kettle for 4 hours under the condition that the steam pressure is less than 0.2MPa and the temperature is 120 ℃ to generate the toxic fluorine-phosphorus mixed solution.
(3) And cooling the mixed solution containing the toxic fluorine and phosphorus to 90 ℃, adding 350kg of 70% n-butanol for crystallization, and obtaining the mixed solution containing the toxic fluorine and phosphorus crystals.
(4) Heating all materials in a reaction kettle to 95 ℃, separating dimethylbenzene by utilizing an azeotropic distillation method, and azeotropically adding n-butanol and H 2 And (3) centrifugally filtering the mixture of O and the Dufulin to obtain Dufulin wet powder, and drying the Dufulin wet powder to obtain 241.18kg of Dufulin compound raw medicine, wherein the content is 94.02%, and the yield is 92.80%.
Example 8
(1) Adding 100kg of 98% 2-ammonia-4-methylbenzothiazole, 75kg of 99% o-fluorobenzaldehyde, 450kg of 98% toluene and 4kg of 98% p-toluenesulfonic acid into a 1000L enamel reactor, stirring and heating to reflux, and reacting in the first stepStarting timing, heating to 115 deg.C, reacting for 5 hr to obtain Schiff base, separating 10kg of H 2 O。
(2) After the step (1) is completed, 105kg of 99% diethyl phosphite is put into a reaction kettle, heated to reflux, counted at the moment, and reacted with Schiff base in the reaction kettle for 3 hours under the condition that the steam pressure is less than 0.2MPa and the temperature is 120 ℃ to generate the toxic fluorine-phosphorus mixed solution.
(3) Cooling the mixed solution containing the toxic fluorine phosphorus to 95 ℃, adding 200kg of water and 200kg of 75% ethanol for crystallization, and obtaining the mixed solution containing the toxic fluorine phosphorus crystal.
(4) Heating all materials in a reaction kettle to 98 ℃, separating toluene by azeotropic distillation, and azeotropically adding ethanol and H 2 And (3) centrifugally filtering the mixture of O and the Dufulin to obtain Dufulin wet powder, and drying the Dufulin wet powder to obtain 239.97kg of Dufulin compound raw medicine, wherein the content is 93.66%, and the yield is 91.98%.
Example 9
(1) Adding 105kg of 98% 2-ammonia-4-methylbenzothiazole, 75kg of 99% o-fluorobenzaldehyde, 400kg of 98% benzene and 4kg of 98% p-toluenesulfonic acid into a 1000L enamel reaction kettle, stirring and heating to reflux, starting the first step of reaction, heating to 110 ℃, reacting for 5H to generate Schiff base, and separating 11kg of H at the moment 2 O。
(2) After the step (1) is completed, 100kg of 99% diethyl phosphite is put into a reaction kettle, heated to reflux, counted at the moment, and reacted with Schiff base in the reaction kettle for 3 hours under the condition that the steam pressure is less than 0.2MPa and the temperature is 125 ℃ to generate the toxic fluorine-phosphorus mixed solution.
(3) Cooling the mixed solution containing the toxic fluorine phosphorus to 95 ℃, adding 300kg of water and 200kg of 75% ethanol for crystallization, and obtaining the mixed solution containing the toxic fluorine phosphorus crystal.
(4) Heating all materials in a reaction kettle to 95 ℃, separating benzene by azeotropic distillation, and azeotropically adding ethanol and H 2 The mixture of O and Dufulin is centrifugally filtered to obtain Dufulin wet powder, and the Dufulin wet powder is dried to obtain 246.96kg of Dufulin compound raw drug with 92.66% content and yield93.65%.
Example 10
(1) Adding 105kg of 98% 2-ammonia-4-methylbenzothiazole, 75kg of 99% o-fluorobenzaldehyde and 400kg of 98% toluene into a 1000L enamel reaction kettle, stirring and heating to reflux, starting the first step of reaction, heating to 116 ℃ for 5H, reacting to generate Schiff base, and separating 9kg of H at the moment 2 O。
(2) After the step (1) is completed, 100kg of 99% diethyl phosphite is put into a reaction kettle, heated to reflux, counted at the moment, and reacted with Schiff base in the reaction kettle for 5 hours under the condition that the steam pressure is less than 0.2MPa and the temperature is 118 ℃ to generate the toxic fluorine-phosphorus mixed solution.
(3) Cooling the mixed solution containing the toxic fluorine and phosphorus to 95 ℃, adding 450kg of water for crystallization, and obtaining the mixed solution containing the toxic fluorine and phosphorus crystal.
(4) Heating all materials in a reaction kettle to 96 ℃, separating toluene by azeotropic distillation, and azeotroping H 2 And (3) centrifugally filtering the mixture of O and the Dufulin to obtain Dufulin wet powder, and drying the Dufulin wet powder to obtain 245.54kg of Dufulin compound raw medicine, wherein the content is 92.55%, and the yield is 93.00%.
Example 11
(1) Adding 105kg of 98% 2-ammonia-4-methylbenzothiazole, 75kg of 99% o-fluorobenzaldehyde and 400kg of 99% chloroform into a 1000L enamel reaction kettle, stirring and heating to reflux, starting the first step of reaction, timing, heating to 118 ℃, reacting for 2H to generate Schiff base, and separating 9.7kg of H at the moment 2 O。
(2) After the step (1) is completed, 95kg of 99% diethyl phosphite is put into a reaction kettle, heated to reflux, counted at the moment, and reacted with Schiff base in the reaction kettle for 3 hours under the condition that the steam pressure is less than 0.2MPa and the temperature is 120 ℃ to generate the toxic fluorine-phosphorus mixed solution.
(3) And cooling the mixed solution containing the toxic fluorine and phosphorus to 95 ℃, adding 450kg of 100% n-butanol for crystallization, and obtaining the mixed solution containing the toxic fluorine and phosphorus crystals.
(4) Heating all materials in the reaction kettle to 90 ℃ and steaming by azeotropyDistilling, separating chloroform, azeotroping n-butanol and H 2 And (3) centrifugally filtering the mixture of O and the Dufulin to obtain Dufulin wet powder, and drying the Dufulin wet powder to obtain 248.27kg of Dufulin compound raw medicine, wherein the content is 96.50%, and the yield is 98.05%.
Example 12
(1) Adding 110kg of 98% 2-ammonia-4-methylbenzothiazole, 75kg of 99% o-fluorobenzaldehyde, 200kg of 98% benzene, 200kg of 98% toluene and 4kg of 98% p-toluenesulfonic acid into a 1000L enamel reaction kettle, stirring and heating to reflux, starting the first step of reaction, heating to 126 ℃ for 6 hours, and generating Schiff base, wherein 9.6kg of H is separated out 2 O。
(2) After the step (1) is completed, 100kg of 99% diethyl phosphite is put into a reaction kettle, heated to reflux, counted at the moment, and reacted with Schiff base in the reaction kettle for 4 hours under the condition that the steam pressure is less than 0.2MPa and the temperature is 112 ℃ to generate the toxic fluorine-phosphorus mixed solution.
(3) And cooling the mixed solution containing the toxic fluorine and phosphorus to 95 ℃, adding 400kg of water for crystallization, and obtaining the mixed solution containing the toxic fluorine and phosphorus crystal.
(4) Heating all materials in a reaction kettle to 96 ℃, separating benzene and toluene through azeotropic distillation, centrifugally filtering a mixture of water and Dufulin after azeotropy to obtain Dufulin wet powder, and drying the Dufulin wet powder to obtain 245.23kg of Dufulin compound raw material with the content of 0.96.80% and the yield of 97.15%.
Example 13
(1) Adding 100kg of 98% 2-ammonia-4-methylbenzothiazole, 75kg of 99% o-fluorobenzaldehyde, 200kg of 98% benzene and 200kg of 98% xylene into a 1000L enamel reaction kettle, stirring and heating to reflux, starting the first step, timing, heating to 136 ℃, reacting for 5H to generate Schiff base, and separating 9.5kg of H at the moment 2 O。
(2) After the step (1) is completed, 105kg of 99% diethyl phosphite is put into a reaction kettle, heated to reflux, counted at the moment, and reacted with Schiff base in the reaction kettle for 5 hours under the condition that the steam pressure is less than 0.2MPa and the temperature is 110 ℃ to generate the toxic fluorine-phosphorus mixed solution.
(3) And cooling the mixed solution containing the toxic fluorine and phosphorus to 95 ℃, adding 400kg of water for crystallization, and obtaining the mixed solution containing the toxic fluorine and phosphorus crystal.
(4) Heating all materials in a reaction kettle to 98 ℃, separating benzene and dimethylbenzene through azeotropic distillation, centrifugally filtering a mixture of water and Dufulin after azeotropy to obtain Dufulin wet powder, and drying the Dufulin wet powder to obtain 243.83kg of Dufulin compound raw material, wherein the content is 94.35%, and the yield is 94.15%.
Example 14
(1) Adding 105kg of 98% 2-ammonia-4-methylbenzothiazole, 75kg of 99% o-fluorobenzaldehyde, 200kg of 98% toluene, 200kg of 98% trimethylbenzene and 4kg of 98% p-toluenesulfonic acid into a 1000L enamel reaction kettle, stirring and heating to reflux, starting the first step of reaction, heating to 135 ℃, reacting for 4H to generate Schiff base, and separating 9.6kg of H at the moment 2 O。
(2) After the step (1) is completed, 100kg of 99% diethyl phosphite is put into a reaction kettle, heated to reflux, counted at the moment, and reacted with Schiff base in the reaction kettle for 2 hours under the condition that the steam pressure is less than 0.2MPa and the temperature is 116 ℃ to generate the toxic fluorine-phosphorus mixed solution.
(3) And cooling the mixed solution containing the toxic fluorine and phosphorus to 95 ℃, adding 400kg of 100% n-butanol for crystallization, and obtaining the mixed solution containing the toxic fluorine and phosphorus crystals.
(4) Heating all materials in a reaction kettle to 85 ℃, separating toluene and trimethylbenzene through azeotropic distillation, centrifugally filtering a mixture of n-butanol, water and Dufulin after azeotropy to obtain Dufulin wet powder, and drying the Dufulin wet powder to obtain 244.61kg of Dufulin compound raw material with the content of 94.20 percent and the yield of 94.30 percent.
Example 15
(1) Adding 105kg of 98% 2-ammonia-4-methylbenzothiazole, 75kg of 99% o-fluorobenzaldehyde and 450kg of 98% toluene into a 1000L enamel reaction kettle, stirring and heating to reflux, starting the first step of reaction, heating to 116 ℃ for 5H, and reacting to generate Schiff base, wherein 11.9kg of H is separated out 2 O。
(2) After the step (1) is completed, 95kg of 99% diethyl phosphite is put into a reaction kettle, heated to reflux, counted at the moment, and reacted with Schiff base in the reaction kettle for 3 hours under the condition that the steam pressure is less than 0.2MPa and the temperature is 126 ℃ to generate the toxic fluorine-phosphorus mixed solution.
(3) Cooling the mixed solution containing toxic fluorine and phosphorus to 95 ℃, and adding H 2 And (3) crystallizing by using 450kg of O to obtain a mixed solution of toxic fluorine-phosphorus crystals.
(4) Heating all materials in a reaction kettle to 96 ℃, separating toluene by azeotropic distillation, and azeotroping H 2 And (3) centrifugally filtering the mixture of O and the Dufulin to obtain Dufulin wet powder, and drying the Dufulin wet powder to obtain 246.92kg of Dufulin compound raw medicine, wherein the content is 95.12%, and the yield is 96.12%.
EXAMPLE 16 20% Dufulin suspension
Taking 21.7kg of 92.15% of profenofos original drug, 4kg of alkylphenol ethoxylates, 3.5kg of polyoxyethylene fatty alcohol ether, 2kg of sodium lignin sulfonate, 0.5kg of ethylene glycol, 1kg of magnesium aluminum silicate and 100kg of water, mixing the above materials, uniformly shearing and mixing the materials at a high speed, and grinding the materials in a ball grinding machine for 2-3 hours to ensure that the particle diameters are below 5mm, thereby preparing the 20% profenofos suspending agent (medicament 1).
The same processing method was used to obtain the medicines 2 to 9, and the medicines 2 to 9 were different from the medicines 1 in that the profenofos crude drug prepared in example 1 was replaced with the profenofos crude drug prepared in example 2 to 9, and a 20% profenofos suspending agent (medicine 2 to medicine 9) was obtained by processing.
EXAMPLE 17 30% Dufulin wettable powder
32.3kg of 93% of the crude Dufulin prepared in example 10, 3kg of alkyl naphthalene sulfonate, 3.5kg of sodium dodecyl sulfate, 2kg of white carbon black and 100kg of kaolin are taken. The materials are uniformly mixed, and then crushed into a certain particle size by air flow, thus obtaining 30% of Dufulin wettable powder (medicament 10).
The same processing method is used to obtain the medicaments 11-15, and the medicaments 11-15 are different from the medicament 10 in that the toxic fluorine phosphorus crude drug prepared in the example 10 is replaced by the toxic fluorine phosphorus crude drug prepared in the example 11-15, and 30% toxic fluorine phosphorus wettable powder (the medicaments 11-15) is obtained by processing.
Application example 1
Test agent: medicament 1-medicament 9, wherein the medicament 1-medicament 9 is 20% of Dufulin suspending agent
Control agent 1:20% Dufulin suspension (accession number PD 20211999), 80-100 ml/mu, guangxi Garden Biochemical Co., ltd
Control agent 2:2% lentinan aqueous solution (accession number PD 20130717), 100-120 ml/mu, heilongjiang province Dadofeng agricultural technology development Co., ltd
The test method comprises the following steps: the test is carried out for 2 times, the first time of taking medicine 10 days after transplanting the rice of 8 months and 20 days of 2021, the second time of taking medicine 3 days of 9 months of 2021, 15 days after taking medicine for the second time and the investigation result of 18 days of 9 months of 2021. Five samples were taken from the diagonal line of each cell, 20 clusters were investigated per spot (i.e., 100 clusters were investigated per cell), and total plant numbers and plant numbers of each stage were recorded. The incidence and severity of southern black-streaked dwarf disease is graded as follows:
level 0: the whole plant is free from diseases;
stage 1: the dwarf is lighter, and the height is within 20% shorter than that of the healthy plant;
3 stages: the dwarf is obvious, and the height is 20 to 35 percent shorter than that of the healthy plant;
5 stages: the dwarf is serious, and the height is 25% -50% shorter than that of the healthy plant;
7 stages: dwarfing is serious, the height is 50% shorter than that of the healthy plant, or the healthy plant dies.
TABLE 1 control effects of treatments on black streaked dwarf of Rice
Note that: the values in the table are the average of 4 replicates
The test result shows that the average prevention and control effect of the medicament 1-medicament 9 on the southern rice black-streaked dwarf is 90.31 percent, which is equivalent to that of a 20 percent Dufulin suspending agent (registration formula) of a control medicament 1 and is greatly higher than that of a control medicament 2 (2 percent lentinan aqua). After each application, 3d, 5d and 10d of the rice is observed, and the rice in each district has better growth vigor, no phytotoxicity and good safety.
Application example 2
Test agent: the medicament 10-medicament 15 is 30% of Dufulin wettable powder
Control agent 3:30% Dufulin suspension (accession number PD 20160338), guangxi Garden Biochemical Co., ltd
Control agent 4:8% Ningnanmycin (accession number PD 20097122), desmothers BioCo., ltd
The test method comprises the following steps: the test is carried out for 3 times, the spraying is carried out for 8 months and 15 days in 2021, the rice is sprayed for two leaves and one heart period, the spraying is carried out again before the transplanting in the seedling bed of 24 days in 2021, the transplanting is carried out for 27 days in 2021, the pesticide is carried out for 3 rd times after the transplanting is carried out for 15 days in 2021, the pesticide is carried out for 20 days after the pesticide is carried out for 3 rd, five diagonal points of each cell are sampled, 20 clusters are surveyed for each point (namely 100 clusters are surveyed for each cell), and the total plant number and the plant number of each level are recorded.
Classification of southern rice orange leaf disease: reference is made to southern black-streaked dwarf disease occurrence and morbidity classification.
Table 2 field efficacy test of treatments on southern rice orange leaf disease
The test result shows that the average control effect of the medicament 10-medicament 15 on southern rice orange leaf disease 20 days after the third medicament is 80.94 percent, which is equivalent to the control effect of 30 percent of the Dufulin wettable powder (registered formula) of the control medicament 3. After the application, the rice growth vigor of each treated rice is observed 5d and 10d, and the rice growth vigor of each district is good after the field treatment, so that no phytotoxicity occurs. Indicating good safety of the applied medicament.
It should be understood that the above examples are illustrative and are not intended to encompass all possible implementations encompassed by the claims. Various modifications and changes may be made in the above embodiments without departing from the scope of the disclosure. Likewise, the individual features of the above embodiments can also be combined arbitrarily to form further embodiments of the invention which may not be explicitly described. Therefore, the above examples merely represent several embodiments of the present invention and do not limit the scope of protection of the patent of the present invention.

Claims (12)

1. A preparation method of a Dufulin compound is characterized in that: the method comprises the following steps:
(1) Reflux reaction is carried out on 2-ammonia-4-methylbenzothiazole and o-fluorobenzaldehyde to generate Schiff base;
(2) Carrying out reflux reaction on diethyl phosphite and the Schiff base prepared in the step (1) to generate a toxic fluorine-phosphorus-containing mixed solution;
(3) Crystallizing the mixed solution containing the toxic fluorine and phosphorus prepared in the step (2) to obtain a mixed solution containing the toxic fluorine and phosphorus crystal;
(4) Carrying out azeotropic distillation on the mixed solution of the toxic fluorine-phosphorus-containing crystal obtained in the step (3), and separating to obtain a toxic fluorine-phosphorus compound;
in the step (3), adding a second solvent into the mixed solution containing toxic fluorine and phosphorus prepared in the step (2) and crystallizing; the second solvent is selected from one or more than two of methanol, ethanol, n-butanol and water;
wherein the temperature of the azeotropic distillation in the step (4) is 85-100 ℃.
2. The method for preparing a toxic fluorophosphorus compound according to claim 1, characterized by: the steps (1), (2), (3) and (4) are carried out in the same reaction kettle.
3. The method for preparing a toxic fluorophosphorus compound according to claim 1, characterized by: the temperature of the reflux reaction in the step (1) is 110-150 ℃ and the reaction time is 2-6 h.
4. The method for preparing a toxic fluorophosphorus compound according to claim 1, characterized by: 2-amino-4-methylbenzothiazole in step (1): the mass ratio of the o-fluorobenzaldehyde is 1-1.10: 0.73 to 0.78.
5. The method for preparing a toxic fluorophosphorus compound according to claim 1, characterized by: the reflux reaction in the step (1) is performed in a first solvent, and the first solvent is selected from one or a mixture of more than two of benzene, toluene, xylene, trimethylbenzene, cyclohexanone and chloroform.
6. The method for producing a toxic fluorophosphorus compound according to claim 5, characterized by: 2-amino-4-methylbenzothiazole in step (1): o-fluorobenzaldehyde: the mass ratio of the first solvent is 1-1.10: 0.73 to 0.78: 3.00-5.00.
7. The method for preparing a toxic fluorophosphorus compound according to claim 1, characterized by: and (3) adding a catalyst into the reflux reaction in the step (1).
8. The method for producing a toxic fluorophosphorus compound according to claim 7, characterized by: the catalyst is p-toluenesulfonic acid.
9. The method for preparing a toxic fluorophosphorus compound according to claim 1, characterized by: the temperature of the reflux reaction in the step (2) is 110-150 ℃ and the reaction time is 2-6 h.
10. The method for producing a toxic fluorophosphorus compound according to any one of claims 3 to 8, characterized by: the crystallization temperature in the step (3) is below 95 ℃.
11. The method for preparing a toxic fluorophosphorus compound according to claim 10, characterized by: the 2-ammonia-4-methylbenzothiazole: o-fluorobenzaldehyde: diethyl phosphite: a first solvent: the mass ratio of the second solvent is 1-1.10: 0.73 to 0.78:0.95 to 1.10: 3.00-5.00: 3.00-5.00.
12. The method for preparing a toxic fluorophosphorus compound according to claim 10, characterized by: the 2-ammonia-4-methylbenzothiazole: o-fluorobenzaldehyde: diethyl phosphite: a first solvent: the mass ratio of the second solvent is 1-1.05: 0.73 to 0.78:1.00 to 1.05: 3.00-5.00: 3.00-5.00.
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CN1687088A (en) * 2005-04-04 2005-10-26 贵州大学 N-substituted benzothiazolyl-1-substituted phenyl-0,0-dialkyl-alpha-amino phosphonate ester derivatives preparation and application
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Publication number Priority date Publication date Assignee Title
CN1687088A (en) * 2005-04-04 2005-10-26 贵州大学 N-substituted benzothiazolyl-1-substituted phenyl-0,0-dialkyl-alpha-amino phosphonate ester derivatives preparation and application
CN102391307A (en) * 2011-11-04 2012-03-28 广西田园生化股份有限公司 Synthesization method of Dufulin

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