CN116514688A - Synthesis process of tribenuron-methyl - Google Patents

Synthesis process of tribenuron-methyl Download PDF

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CN116514688A
CN116514688A CN202310492677.0A CN202310492677A CN116514688A CN 116514688 A CN116514688 A CN 116514688A CN 202310492677 A CN202310492677 A CN 202310492677A CN 116514688 A CN116514688 A CN 116514688A
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methyl
tribenuron
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mass ratio
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芦虹
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Fuxin Qianyi Fine Chemical Industry Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
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    • C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
    • C07C303/40—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids by reactions not involving the formation of sulfonamide groups
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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    • B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
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    • B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
    • B01J2531/36—Yttrium
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Abstract

The invention discloses a synthesis process of tribenuron-methyl, which comprises the following steps: (1) Weighing and uniformly mixing methyl o-formate benzenesulfonamide and dimethylbenzene, adding triphosgene, fully mixing, adding a catalyst, heating to reflux, and obtaining an intermediate reactant after the reaction is finished; (2) Mixing the intermediate reactant with dichloromethane, fully stirring, adding N-methyltriazine, heating to reflux, carrying out heat preservation reaction, and removing dichloromethane under reduced pressure to obtain a reaction crude product; (3) The reaction crude product is washed by methanol and dried to obtain the tribenuron-methyl. The invention designs a novel tribenuron-methyl synthesis process, which combines a triphosgene method with a novel catalyst to synthesize tribenuron-methyl.

Description

Synthesis process of tribenuron-methyl
Technical Field
The invention relates to the field of synthesis of tribenuron-methyl, in particular to a synthesis process of tribenuron-methyl.
Background
The tribenuron-methyl herbicide has the characteristics of high weeding activity, wide weeding spectrum, strong selectivity and the like, can inhibit the synthesis of side chain amino acid, the synthesis of acetolactate, the cell division, the growth of bud tips and roots and promote the death of weeds after being applied to the soil and entering the root and leaf absorber of weed plants, and can be metabolized into inactive substances for normal growth by cereal crops, so that the tribenuron-methyl herbicide is particularly suitable for weeding in wheat fields.
The synthesis process of tribenuron-methyl adopts an isocyanate route, and methyl orthoformate benzenesulfonamide and oxalyl chloride react to obtain 2-methyl formate-3-benzenesulfonyl isocyanate or methyl orthoformate benzenesulfonamide reacts with phosgene or diphosgene to obtain 2-methyl formate-3-benzenesulfonyl isocyanate; and the generated 2-methyl formate-3-benzenesulfonyl isocyanate reacts with methyl triazine to generate tribenuron-methyl. However, considering that phosgene or diphosgene has great danger, the existing synthesis process of tribenuron-methyl selects triphosgene to replace phosgene or diphosgene, and the triphosgene method is obviously superior to the phosgene or diphosgene method in the aspects of safety, quality, cost and the like, thereby becoming the main production process in China at present.
However, the condition for synthesizing tribenuron-methyl by using the triphosgene method has higher requirements, needs to react for a longer time in a closed system and needs a higher reaction temperature, which clearly increases the cost and the operation difficulty of the synthesis process greatly. Therefore, a process for synthesizing tribenuron-methyl herbicide under milder and more efficient conditions needs to be mentioned.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide a synthesis process of tribenuron-methyl.
The aim of the invention is realized by adopting the following technical scheme:
a synthesis process of tribenuron-methyl comprises the following steps:
(1) Weighing and uniformly mixing methyl o-formate benzenesulfonamide and dimethylbenzene, adding triphosgene, fully mixing, adding a catalyst, heating to reflux, and obtaining an intermediate reactant after the reaction is finished;
(2) Mixing the intermediate reactant with dichloromethane, fully stirring, adding N-methyltriazine, heating to reflux, carrying out heat preservation reaction, and removing dichloromethane under reduced pressure to obtain a reaction crude product;
(3) The reaction crude product is washed by methanol and dried to obtain the tribenuron-methyl.
Preferably, in the step (1), the mass ratio of the methyl phthalate benzenesulfonamide to the triphosgene is 1:1.6-1.8.
Preferably, in the step (1), the mass-volume ratio of the methyl o-formate benzenesulfonamide to the xylene is 1g: (3.5-5.5) mL.
Preferably, in step (1), the catalyst is NCO-SCA/Zn-Y-MOFs, and the mass ratio of the catalyst to the methyl orthoformate benzenesulfonamide is 1.2-2.4:1.
Preferably, in step (1), the reaction temperature is 120-140℃and the reaction time is 1-3 hours.
Preferably, in step (1), the catalyst is separated after the reaction is completed and xylene is removed under reduced pressure.
Preferably, in step (2), the mass to volume ratio of intermediate reactant to dichloromethane is 1g: (3-5) mL.
Preferably, in step (2), the mass ratio of N-methyltriazine to intermediate reactants is from 1.3 to 1.7:2.4 to 2.8.
Preferably, in step (2), the reaction temperature is 38-42℃and the reaction time is 1-2h.
Preferably, in the step (3), the washing process of the reaction crude product by using methanol is that the reaction crude product is firstly added into 5-10 times of methanol by mass, the reaction crude product is sufficiently stirred for 1-2 hours, liquid is removed by filtration, and then the collected product is washed for at least three times by using methanol again and then dried under reduced pressure.
Preferably, the preparation method of the catalyst NCO-SCA/Zn-Y-MOFs comprises the following steps:
s1, weighing zinc nitrate hexahydrate and yttrium nitrate hexahydrate, dissolving in deionized water, and uniformly stirring to form a first mixed solution; weighing 2-methylimidazole, mixing with deionized water, and fully stirring to form a second mixed solution;
s2, dropwise adding the first mixed solution into the second mixed solution at room temperature, continuously stirring the reaction solution, transferring the reaction solution into a reaction kettle after the dropwise adding is finished, carrying out heat preservation reaction, cooling to room temperature, filtering out precipitate, washing three times by using pure water, and drying in an oven to obtain Zn-Y-MOFs;
s3, weighing isocyanatosilane, mixing with toluene, fully stirring until the isocyanatosilane is dissolved, adding Zn-Y-MOFs, carrying out ultrasonic homogenization, heating to reflux in a reflux condensing device, carrying out heat preservation reaction, then removing the solvent under reduced pressure, washing three times by using acetone, and carrying out vacuum drying to obtain the NCO-SCA/Zn-Y-MOFs.
Preferably, in the first mixed solution of S1, the mass ratio of the zinc nitrate hexahydrate, the yttrium nitrate hexahydrate and the deionized water is 0.6-1:0.2-0.4:10-20.
Preferably, in the second mixed solution of S1, the mass ratio of the 2-methylimidazole to the deionized water is 1.3-1.5:10-20.
Preferably, in the step S2, the mass ratio of the first mixed solution to the second mixed solution is 1:1.1-1.3.
Preferably, in the step S2, the dropping speed is 20-30 drops/min, and the stirring speed is 200-300rpm.
Preferably, in the step S2, the reaction temperature in the reaction kettle is 160-180 ℃ and the reaction time is 3-5h.
Preferably, in S3, the isocyanatosilane includes 3-isocyanatopropyl trimethoxysilane.
Preferably, in the step S3, the reaction temperature is 110-120 ℃ and the reaction time is 5-8h.
Preferably, in the S3, the mass ratio of the isocyanatosilane, the Zn-Y-MOFs and the toluene is 0.8-1.6:2-4:20-30.
The beneficial effects of the invention are as follows:
1. the invention designs a novel tribenuron-methyl synthesis process, which combines a triphosgene method with a novel catalyst to synthesize tribenuron-methyl.
2. According to the invention, the methyl o-formate benzenesulfonamide is used to react with triphosgene in dimethylbenzene, and the self-developed catalyst NCO-SCA/Zn-Y-MOFs is used in the reaction process, so that the reaction is quicker in the process, the defects of high cost and high danger caused by long-time high temperature in the triphosgene reaction process are overcome, the reaction time is shortened, but the yield is increased, and the purity is higher.
3. The catalyst NCO-SCA/Zn-Y-MOFs used in the invention is prepared by taking zinc and yttrium co-doped organometallic framework ligand Zn-Y-MOFs as a carrier and isocyanatosilane as a carrier. The prepared catalyst has high activity and strong reusability.
4. In the catalyst NCO-SCA/Zn-Y-MOFs, isocyanate silane NCO-SCA is used as a carrier, and isocyanate groups in the catalyst NCO-SCA/Zn-Y-MOFs can be used as a reaction transfer body to be combined with reactants, so that the reaction is accelerated. The metal framework ligand Zn-Y-MOFs belongs to alkaline ligands, has certain catalytic activity, and can be combined with reaction byproduct hydrogen chloride, so that the reaction process is further accelerated.
Detailed Description
The technical features, objects and advantages of the present invention will be more clearly understood from the following detailed description of the technical aspects of the present invention, but should not be construed as limiting the scope of the invention.
The invention is further described with reference to the following examples.
Example 1
A synthesis process of tribenuron-methyl comprises the following steps:
(1) Weighing methyl o-formate benzenesulfonamide and dimethylbenzene, uniformly mixing, adding triphosgene, fully mixing, adding a catalyst NCO-SCA/Zn-Y-MOFs, heating to 130 ℃, refluxing, reacting for 2 hours, separating the catalyst after the reaction is finished, and removing dimethylbenzene under reduced pressure to obtain an intermediate reactant;
wherein, the mass ratio of the methyl phthalate benzenesulfonamide to the triphosgene is 1:1.7, the mass-volume ratio of the methyl o-formate benzenesulfonamide to the dimethylbenzene is 1g:4.5mL of catalyst to methyl orthoformate benzenesulfonamide mass ratio was 1.8:1.
(2) Mixing the intermediate reactant with dichloromethane, fully stirring, adding N-methyltriazine, heating to 40 ℃ and refluxing for 1.5h, and removing the dichloromethane under reduced pressure to obtain a reaction crude product;
wherein the mass volume ratio of the intermediate reactant to the dichloromethane is 1g: the mass ratio of N-methyltriazine to intermediate reactant was 1.5:2.6 in 4 mL.
(3) And washing the reaction crude product by using methanol, namely adding the reaction crude product into methanol with the mass being 8 times that of the reaction crude product, fully stirring for 1.5 hours, filtering to remove liquid, washing the collected product by using methanol for at least three times again, and drying under reduced pressure to obtain the tribenuron-methyl.
The preparation method of the catalyst NCO-SCA/Zn-Y-MOFs in the step (1) comprises the following steps:
s1, weighing zinc nitrate hexahydrate and yttrium nitrate hexahydrate, dissolving in deionized water, and uniformly stirring to form a first mixed solution, wherein the mass ratio of the zinc nitrate hexahydrate to the yttrium nitrate hexahydrate to the deionized water is 0.8:0.3:15; weighing 2-methylimidazole and deionized water, mixing, and fully stirring to form a second mixed solution, wherein the mass ratio of the 2-methylimidazole to the deionized water is 1.4:15;
s2, dropwise adding the first mixed solution into the second mixed solution at room temperature, continuously stirring the reaction solution at the dropwise speed of 25 drops/min and the stirring speed of 250rpm, transferring the reaction solution into a reaction kettle after the dropwise addition is finished, keeping the reaction temperature at 170 ℃, reacting for 4 hours at the temperature, cooling to room temperature, filtering out precipitate, washing three times by using pure water, and drying in an oven to obtain Zn-Y-MOFs;
wherein the mass ratio of the first mixed solution to the second mixed solution is 1:1.2;
s3, weighing 3-isocyanatopropyl trimethoxy silane, mixing with toluene, fully stirring until the mixture is dissolved, adding Zn-Y-MOFs, carrying out ultrasonic homogenization, heating to 115 ℃ in a reflux condensing device for reflux reaction, carrying out heat preservation and stirring for 6 hours, then removing the solvent under reduced pressure, washing for three times by using acetone, and carrying out vacuum drying to obtain NCO-SCA/Zn-Y-MOFs;
wherein the mass ratio of 3-isocyanatopropyl trimethoxysilane, zn-Y-MOFs and toluene is 1.2:3:25.
Example 2
A synthesis process of tribenuron-methyl comprises the following steps:
(1) Weighing methyl o-formate benzenesulfonamide and dimethylbenzene, uniformly mixing, adding triphosgene, fully mixing, adding a catalyst NCO-SCA/Zn-Y-MOFs, heating to 120 ℃, refluxing, reacting for 3 hours, separating the catalyst after the reaction is finished, and removing dimethylbenzene under reduced pressure to obtain an intermediate reactant;
wherein, the mass ratio of the methyl phthalate benzenesulfonamide to the triphosgene is 1:1.6, the mass-volume ratio of the methyl o-formate benzenesulfonamide to the xylene is 1g:3.5mL of catalyst to methyl orthoformate benzenesulfonamide mass ratio was 1.2:1.
(2) Mixing the intermediate reactant with dichloromethane, fully stirring, adding N-methyltriazine, heating to 38 ℃, refluxing for 2 hours, and removing the dichloromethane under reduced pressure to obtain a reaction crude product;
wherein the mass volume ratio of the intermediate reactant to the dichloromethane is 1g:3mL, the mass ratio of N-methyltriazine to intermediate was 1.3:2.4.
(3) And washing the reaction crude product by using methanol, namely adding the reaction crude product into methanol with the mass of 5 times, fully stirring for 1h, filtering to remove liquid, washing the collected product by using methanol for at least three times again, and drying under reduced pressure to obtain the tribenuron-methyl.
The preparation method of the catalyst NCO-SCA/Zn-Y-MOFs in the step (1) comprises the following steps:
s1, weighing zinc nitrate hexahydrate and yttrium nitrate hexahydrate, dissolving in deionized water, and uniformly stirring to form a first mixed solution, wherein the mass ratio of the zinc nitrate hexahydrate to the yttrium nitrate hexahydrate to the deionized water is 0.6:0.2:10; weighing 2-methylimidazole and deionized water, mixing, and fully stirring to form a second mixed solution, wherein the mass ratio of the 2-methylimidazole to the deionized water is 1.3:10;
s2, dropwise adding the first mixed solution into the second mixed solution at room temperature, continuously stirring the reaction solution at the dropwise speed of 20 drops/min and the stirring speed of 200rpm, transferring the reaction solution into a reaction kettle after the dropwise addition is finished, keeping the reaction temperature at 160 ℃, reacting for 5 hours at the temperature, cooling to room temperature, filtering out precipitate, washing three times by using pure water, and drying in an oven to obtain Zn-Y-MOFs;
wherein the mass ratio of the first mixed solution to the second mixed solution is 1:1.1;
s3, weighing 3-isocyanatopropyl trimethoxy silane, mixing with toluene, fully stirring until the mixture is dissolved, adding Zn-Y-MOFs, carrying out ultrasonic homogenization, heating to 110 ℃ in a reflux condensing device for reflux reaction, carrying out heat preservation and stirring for 5 hours, then removing the solvent under reduced pressure, washing for three times by using acetone, and carrying out vacuum drying to obtain NCO-SCA/Zn-Y-MOFs;
wherein the mass ratio of 3-isocyanatopropyl trimethoxysilane, zn-Y-MOFs and toluene is 0.8:2:20.
Example 3
A synthesis process of tribenuron-methyl comprises the following steps:
(1) Weighing methyl o-formate benzenesulfonamide and dimethylbenzene, uniformly mixing, adding triphosgene, fully mixing, adding a catalyst NCO-SCA/Zn-Y-MOFs, heating to 140 ℃, refluxing, reacting for 1h, separating the catalyst after the reaction is finished, and removing dimethylbenzene under reduced pressure to obtain an intermediate reactant;
wherein, the mass ratio of the methyl phthalate benzenesulfonamide to the triphosgene is 1:1.8, the mass-volume ratio of the methyl o-formate benzenesulfonamide to the dimethylbenzene is 1g: the mass ratio of catalyst to methyl orthoformate benzenesulfonamide was 2.4:1, 5.5 mL.
(2) Mixing the intermediate reactant with dichloromethane, fully stirring, adding N-methyltriazine, heating to 42 ℃, refluxing for 1h, and removing dichloromethane under reduced pressure to obtain a reaction crude product;
wherein the mass volume ratio of the intermediate reactant to the dichloromethane is 1g: the mass ratio of N-methyltriazine to intermediate reactant is 1.7:2.8 in 5 mL.
(3) And washing the reaction crude product by using methanol, namely adding the reaction crude product into 10 times of methanol by mass, fully stirring for 2 hours, filtering to remove liquid, washing the collected product by using methanol for at least three times again, and drying under reduced pressure to obtain the tribenuron-methyl.
The preparation method of the catalyst NCO-SCA/Zn-Y-MOFs in the step (1) comprises the following steps:
s1, weighing zinc nitrate hexahydrate and yttrium nitrate hexahydrate, dissolving in deionized water, and uniformly stirring to form a first mixed solution, wherein the mass ratio of the zinc nitrate hexahydrate to the yttrium nitrate hexahydrate to the deionized water is 1:0.4:20; weighing 2-methylimidazole and deionized water, mixing, and fully stirring to form a second mixed solution, wherein the mass ratio of the 2-methylimidazole to the deionized water is 1.5:20;
s2, dropwise adding the first mixed solution into the second mixed solution at room temperature, continuously stirring the reaction solution at the dropwise speed of 30 drops/min and the stirring speed of 300rpm, transferring the reaction solution into a reaction kettle after the dropwise addition is finished, keeping the reaction temperature at 180 ℃, reacting for 3 hours at the temperature, cooling to room temperature, filtering out precipitate, washing three times by using pure water, and drying in an oven to obtain Zn-Y-MOFs;
wherein the mass ratio of the first mixed solution to the second mixed solution is 1:1.1;
s3, weighing 3-isocyanatopropyl trimethoxy silane, mixing with toluene, fully stirring until the mixture is dissolved, adding Zn-Y-MOFs, carrying out ultrasonic homogenization, heating to reflux at 120 ℃ in a reflux condensing device for reflux reaction, carrying out heat preservation and stirring for 8 hours, then decompressing to remove the solvent, washing with acetone for three times, and carrying out vacuum drying to obtain NCO-SCA/Zn-Y-MOFs;
wherein the mass ratio of 3-isocyanatopropyl trimethoxysilane, zn-Y-MOFs and toluene is 1.6:4:30.
Comparative example 1
The synthesis process of tribenuron-methyl differs from example 1 only in that the catalyst is different.
The catalyst of this comparative example was n-butyl isocyanate.
Comparative example 2
The synthesis process of tribenuron-methyl differs from example 1 only in that the catalyst is different.
The catalyst of this comparative example was 3-isocyanatopropyl trimethoxysilane.
Comparative example 3
The synthesis process of tribenuron-methyl differs from example 1 only in that the catalyst is different.
The catalyst of the comparative example is conventional MOFs, and the preparation method comprises the following steps:
s1, weighing zinc nitrate hexahydrate, dissolving in deionized water, and uniformly stirring to form a first mixed solution, wherein the mass ratio of the zinc nitrate hexahydrate to the deionized water is 0.8:15; weighing 2-methylimidazole and deionized water, mixing, and fully stirring to form a second mixed solution, wherein the mass ratio of the 2-methylimidazole to the deionized water is 1.4:15;
s2, dropwise adding the first mixed solution into the second mixed solution at room temperature, continuously stirring the reaction solution at the dropwise speed of 25 drops/min and the stirring speed of 250rpm, transferring the reaction solution into a reaction kettle after the dropwise addition is finished, keeping the reaction temperature at 170 ℃, reacting for 4 hours at the temperature, cooling to room temperature, filtering out precipitate, washing three times by using pure water, and drying in an oven to obtain the conventional MOFs;
wherein the mass ratio of the first mixed solution to the second mixed solution is 1:1.2.
Comparative example 4
The synthesis process of tribenuron-methyl differs from example 1 only in that the catalyst is different.
The catalyst of the comparative example is Zn-Y-MOFs, and the preparation method comprises the following steps:
s1, weighing zinc nitrate hexahydrate and yttrium nitrate hexahydrate, dissolving in deionized water, and uniformly stirring to form a first mixed solution, wherein the mass ratio of the zinc nitrate hexahydrate to the yttrium nitrate hexahydrate to the deionized water is 0.8:0.3:15; weighing 2-methylimidazole and deionized water, mixing, and fully stirring to form a second mixed solution, wherein the mass ratio of the 2-methylimidazole to the deionized water is 1.4:15;
s2, dropwise adding the first mixed solution into the second mixed solution at room temperature, continuously stirring the reaction solution at the dropwise speed of 25 drops/min and the stirring speed of 250rpm, transferring the reaction solution into a reaction kettle after the dropwise addition is finished, keeping the reaction temperature at 170 ℃, reacting for 4 hours at the temperature, cooling to room temperature, filtering out precipitate, washing three times by using pure water, and drying in an oven to obtain Zn-Y-MOFs;
wherein the mass ratio of the first mixed solution to the second mixed solution is 1:1.2.
Experimental example
The reaction conditions for synthesizing tribenuron-methyl in example 1 and comparative examples 1 to 4 were examined and compared, and the yields of the finally obtained products and the activity of recycling the catalyst were shown in Table 1.
Table 1 comparison of the results of different methods for synthesizing tribenuron-methyl herbicide
As can be seen from Table 1, the yield of example 1 of the present invention is as high as 98.9%, the purity is as high as 98.5%, and the yield can still reach 97.2% after repeated use for 5 times; whereas the yield and purity of comparative example 1 were lower; comparative example 2, although having higher yield and purity than comparative example 1, is still inferior to example 1 and is relatively difficult to reuse; comparative example 3 and comparative example 4 are conventional carriers and carriers prepared by the present invention, and it can be seen that the carriers prepared by the present invention are more catalytic, and can be used not only as carriers, but also for improving catalytic performance.
From the above, it can be seen that the process for synthesizing tribenuron-methyl of example 1 of the present invention performs better and can follow the concept of green chemistry.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.

Claims (10)

1. The synthesis process of tribenuron-methyl is characterized by comprising the following steps:
(1) Weighing and uniformly mixing methyl o-formate benzenesulfonamide and dimethylbenzene, adding triphosgene, fully mixing, adding a catalyst, heating to reflux, and obtaining an intermediate reactant after the reaction is finished;
(2) Mixing the intermediate reactant with dichloromethane, fully stirring, adding N-methyltriazine, heating to reflux, carrying out heat preservation reaction, and removing dichloromethane under reduced pressure to obtain a reaction crude product;
(3) The reaction crude product is washed by methanol and dried to obtain the tribenuron-methyl.
2. The synthesis process of tribenuron-methyl according to claim 1, wherein in the step (1), the mass ratio of methyl orthoformate benzenesulfonamide to triphosgene is 1:1.6-1.8; the mass volume ratio of the methyl o-formate benzenesulfonamide to the dimethylbenzene is 1g: (3.5-5.5) mL; the mass ratio of the catalyst to the methyl o-formate benzenesulfonamide is 1.2-2.4:1.
3. The process for synthesizing tribenuron-methyl according to claim 1, wherein in the step (1), the reaction temperature is 120-140 ℃ and the reaction time is 1-3h; after the reaction was completed, the catalyst was separated, and xylene was removed under reduced pressure.
4. The process for synthesizing tribenuron-methyl according to claim 1, wherein in the step (2), the mass-volume ratio of the intermediate reactant to dichloromethane is 1g: (3-5) mL; the mass ratio of the N-methyltriazine to the intermediate reactant is 1.3-1.7:2.4-2.8.
5. The process for synthesizing tribenuron-methyl according to claim 1, wherein in the step (2), the reaction temperature is 38-42 ℃ and the reaction time is 1-2h.
6. The process for synthesizing tribenuron-methyl according to claim 1, wherein in the step (3), the washing process of the reaction crude product by using methanol is that the reaction crude product is firstly added into 5-10 times of methanol by mass, the mixture is sufficiently stirred for 1-2 hours, the liquid is removed by filtration, and then the collected product is washed for at least three times by using methanol again, and then the product is dried under reduced pressure.
7. The synthesis process of tribenuron-methyl according to claim 3, wherein the catalyst is NCO-SCA/Zn-Y-MOFs, and the preparation method of the catalyst comprises the following steps:
s1, weighing zinc nitrate hexahydrate and yttrium nitrate hexahydrate, dissolving in deionized water, and uniformly stirring to form a first mixed solution; weighing 2-methylimidazole, mixing with deionized water, and fully stirring to form a second mixed solution;
s2, dropwise adding the first mixed solution into the second mixed solution at room temperature, continuously stirring the reaction solution, transferring the reaction solution into a reaction kettle after the dropwise adding is finished, carrying out heat preservation reaction, cooling to room temperature, filtering out precipitate, washing three times by using pure water, and drying in an oven to obtain Zn-Y-MOFs;
s3, weighing isocyanatosilane, mixing with toluene, fully stirring until the isocyanatosilane is dissolved, adding Zn-Y-MOFs, carrying out ultrasonic homogenization, heating to reflux in a reflux condensing device, carrying out heat preservation reaction, then removing the solvent under reduced pressure, washing three times by using acetone, and carrying out vacuum drying to obtain the NCO-SCA/Zn-Y-MOFs.
8. The synthesis process of tribenuron-methyl according to claim 1, wherein in the first mixed solution of S1, the mass ratio of zinc nitrate hexahydrate, yttrium nitrate hexahydrate and deionized water is 0.6-1:0.2-0.4:10-20;
in the second mixed solution of the S1, the mass ratio of the 2-methylimidazole to the deionized water is 1.3-1.5:10-20.
9. The synthesis process of tribenuron-methyl according to claim 1, wherein in the step S2, the mass ratio of the first mixed solution to the second mixed solution is 1:1.1-1.3; in the step S2, the dropping speed is 20-30 drops/min, and the stirring speed is 200-300rpm; the reaction temperature in the reaction kettle is 160-180 ℃ and the reaction time is 3-5h.
10. The synthesis process of tribenuron-methyl according to claim 1, wherein in the step S3, the reaction temperature is 110-120 ℃ and the reaction time is 5-8h; the isocyanatosilane includes 3-isocyanatopropyl trimethoxysilane; the mass ratio of the isocyanatosilane, the Zn-Y-MOFs and the toluene is 0.8-1.6:2-4:20-30.
CN202310492677.0A 2023-05-05 2023-05-05 Synthesis process of tribenuron-methyl Pending CN116514688A (en)

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