CN113845451B - Method for preparing trione herbicide - Google Patents
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- CN113845451B CN113845451B CN202010599783.5A CN202010599783A CN113845451B CN 113845451 B CN113845451 B CN 113845451B CN 202010599783 A CN202010599783 A CN 202010599783A CN 113845451 B CN113845451 B CN 113845451B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
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- 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
- A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
- A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
- A01N41/10—Sulfones; Sulfoxides
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- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
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Abstract
The invention belongs to the field of organic synthesis, and particularly relates to a method for preparing a trione herbicide. The method is characterized in that the substituted benzoic acid is used as a raw material to obtain an acylation reaction system after acyl chlorination and esterification, and then the trione herbicide is prepared through rearrangement reaction, and the method is characterized in that: the rearrangement reaction is to add a rearrangement catalyst into an acylation reaction system, and react at 0-50 ℃ for 0.5-12 hours at a constant temperature to obtain a trione herbicide; the method of the invention avoids using a highly toxic acetone cyanohydrin catalyst, has low reaction temperature, short reaction time and cyclic solvent, can achieve 90 percent of total yield of the prepared trione herbicide product, has 98 percent of content, is safe and environment-friendly, has small three wastes and is suitable for industrial production.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a method for preparing a trione herbicide.
Background
Triones herbicides are a class of highly effective, broad-spectrum, safe herbicides that are widely used.
US 4921526 discloses a method for the trans-rearrangement of enol esters into acylated cyclic 1, 3-dione herbicidal compounds, i.e. triones, under the catalysis of acetone cyanohydrin.
WO 94045524, EP 666254, WO 9903845 and the like also disclose methods for the trans-rearrangement of enol esters to triones under the action of acetone cyanohydrin rearrangement catalysts.
Since acetone cyanohydrin belongs to a highly toxic chemical, the safety risks for human, livestock and environment are great, and research on safer rearrangement catalysts is needed to prepare triones.
Disclosure of Invention
The object of the present invention is to provide a process for preparing triones.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a method for preparing trione herbicide, take substituted benzoic acid (v) as raw materials, get the acylation reaction system after the acyl chlorination, then prepare the trione herbicide through the rearrangement reaction, characterized by that: the rearrangement reaction is to add a rearrangement catalyst (formula III) into an acylation reaction system, and react for 0.5-12 hours at the temperature of 0-50 ℃ under the condition of heat preservation to obtain the trione herbicide;
the molar ratio of the rearrangement catalyst (formula III) to the raw material is (0.0005-1): 1; wherein the structure of formula III is as follows,
Preferably, in the rearrangement catalyst (formula III) formula, G is selected from C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, cyclopropane, phenyl and pyridyl optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C 1 -C 3 Alkyl, halogenated C 1 -C 3 Alkyl, cyclopropane, C 1 -C 3 Alkoxy, halo C 1 -C 3 Alkoxy, C 1 -C 3 Alkoxymethylene, halogenated C 1 -C 3 Alkoxymethylene, tetrahydrofuranyl C 1 -C 3 Alkoxymethylene, C 1 -C 3 Alkylthio, halo C 1 -C 3 Alkylthio, C 1 -C 3 Alkylamino, C 1 -C 3 Dialkylamino, cyclopropylamino, C 1 -C 3 Alkylsulfonyl or C 1 -C 3 Alkyl sulfamoyl.
Preferably, the rearrangement catalyst has the formula (formula III)Wherein G is selected from C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, cyclopropane, phenyl and pyridyl optionally substituted by fluorine, chlorine, bromine, nitro, C 1 -C 3 Alkyl, halogenated C 1 -C 3 Alkyl, C 1 -C 3 Alkoxy, halo C 1 -C 3 Alkoxy, C 1 -C 3 Alkoxymethylene, halogenated C 1 -C 3 Alkoxymethylene, tetrahydrofuranyl C 1 -C 3 Alkoxymethylene, C 1 -C 3 An alkylsulfonyl group.
Further preferably, in the rearrangement catalyst (formula III), G is selected from methyl, chloromethyl, cyclopropenyl, phenyl and pyridyl optionally substituted with fluorine, chlorine, bromine, nitro, methyl, trifluoromethyl, methoxy, trifluoromethoxy, ethoxymethylene, trifluoroethoxymethylene, tetrahydrofuranylmethyleneoxymethylene, methylsulfonyl,
still more preferably, the rearrangement catalyst (formula III) wherein G is selected from the group consisting of methyl, chloromethyl, cyclopropane, phenyl, 3-pyridyl, 4-chlorophenyl, 2-methylphenyl, 3-methoxyphenyl, 4-trifluoromethoxyphenyl,
More preferably, in the rearrangement catalyst (formula III), G is selected from the group consisting of methyl, phenyl, 2-tolyl,
most preferably, in the rearrangement catalyst (formula III), G is selected from phenyl, 2-tolyl.
Further, the reaction temperature of the acylation reaction system is 10-40 ℃ and the reaction time is 0.5-10 hours.
The rearrangement reaction temperature is 20-40 ℃ and the reaction time is 0.5-8; wherein the molar ratio of the rearrangement catalyst (formula III) to the starting material is (0.001-1): 1.
The rearrangement reaction temperature is 25-35 ℃ and the reaction time is 0.5-6; wherein the molar ratio of the rearrangement catalyst (formula III) to the starting material is (0.005-1): 1.
The rearrangement reaction temperature is 25-35 ℃ and the reaction time is 0.5-5; wherein the molar ratio of the rearrangement catalyst (formula III) to the starting material is (0.01-1): 1.
The rearrangement reaction temperature is 30-35 ℃ and the reaction time is 0.5-4; wherein the molar ratio of the rearrangement catalyst (formula III) to the starting material is (0.01-1): 1.
And (3) regulating the temperature of the acylation reaction system to room temperature, adding a rearrangement catalyst, reacting at the rearrangement temperature, regulating the pH value of the system to be alkaline, cooling, standing at room temperature, layering, collecting upper-layer feed liquid for extraction, collecting upper-layer feed liquid, regulating the pH value to be acidic, and filtering and washing to obtain the trione herbicide.
The acylation reaction system is characterized in that a solvent is added into a product carried by the reaction of acyl chloride by taking the substituted benzoic acid (v) as a raw material, then 1, 3-cyclohexanedione is added, an organic base is dropwise added at the temperature of between 0 and 10 ℃, and the thermal insulation reaction is continuously carried out for 0.5 to 1.5 hours after the dropwise addition, so that the enol ester of the substituted benzoic acid of the acylation reaction product is obtained.
The method comprises the steps of adding raw material substituted benzoic acid (v) into a solvent, heating to 50-55 ℃, dropwise adding thionyl chloride, continuously carrying out reflux reaction for 1.5-2.5 hours after dropwise adding, and evaporating the solvent and the excessive thionyl chloride under reduced pressure to obtain the substituted benzoyl chloride of the general formula IV.
Further, a method for preparing the trione herbicide has the following reaction formula,
1) Acyl chlorination reaction type
2) Acylation reaction type
3) Rearrangement reaction type
In the reaction formula:
R 1 selected from chlorine, nitro, preferably nitro;
R 2 selected from hydrogen,
Preferably hydrogen, & gt>
More preferably hydrogen;
g is selected from the same as described above.
1) Acyl chlorination reaction
Dissolving the substituted benzoic acid of the general formula V in toluene or 1, 2-dichloroethane, heating to 50-55 ℃, dropwise adding thionyl chloride, continuously carrying out reflux reaction for 1.5-2.5 hours after dropwise adding, and evaporating the solvent and the excessive thionyl chloride under reduced pressure to obtain the substituted benzoyl chloride of the general formula IV. The solvent is preferably 1, 2-dichloroethane.
2) Acylation reaction
Adding toluene or 1, 2-dichloroethane as solvent into the product of the step 1), namely the substituted benzoyl chloride of the general formula IV, adding 1, 3-cyclohexanedione, dropwise adding organic base trimethylamine, triethylamine, diisopropylethylamine, pyridine or 4-dimethylaminopyridine at 0-10 ℃, and continuously carrying out heat preservation reaction for 0.5-1.5 hours after dropwise adding to obtain the compound of the general formula II, namely (3-oxo-cyclohex-1-en-1-yl) substituted benzoate. The solvent is preferably 1, 2-dichloroethane; the organic base is preferably selected from trimethylamine, triethylamine and diisopropylethylamine, and more preferably triethylamine.
3) Rearrangement reaction
Adding a rearrangement catalyst, namely a compound III in the general formula, into the reaction solution after the acylation reaction in the step 2).
Wherein the molar ratio of thionyl chloride to substituted benzoic acid of the general formula V is (1-3): 1, preferably (1-1.5): 1, a step of; the molar ratio of the organic base to the substituted benzoic acid of the formula V is (1-5): 1, preferably (1-3): 1, more preferably (2-3): 1.
In the definitions of the compounds of the general formula given above, the terms used in the collection generally represent the following substituents:
halogen: refers to fluorine, chlorine, bromine or iodine.
Alkyl: straight or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl or the different butyl, pentyl or hexyl isomers.
Haloalkyl: straight or branched alkyl groups, the hydrogen atoms on these alkyl groups may be partially or fully substituted with halogen, such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, heptafluoroisopropyl, and the like.
Cycloalkyl: a substituted or unsubstituted cyclic alkyl group such as cyclopropyl, cyclopentyl or cyclohexyl; substituents such as methyl, halogen, and the like.
Unsubstituted means that all substituents are hydrogen.
An alkoxy group: a linear or branched alkyl group, linked to the structure via an oxygen atom bond, such as methoxy, ethoxy, t-butoxy, and the like.
Haloalkoxy: straight-chain or branched alkoxy groups, the hydrogen atoms on these alkoxy groups may be partially or completely substituted with halogen, such as chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, trifluoroethoxy, and the like.
Alkoxymethylene: alkyl-O-CH 2 -, e.g. CH 3 OCH 2 -。
Haloalkoxymethylene: haloalkyl-O-CH 2 -, e.g. CF 3 CH 2 OCH 2 -。
Tetrahydrofuranylalkoxymethylene: tetrahydrofuranyl-alkyl-O-CH 2 -, e.g.
Alkylthio: a linear or branched alkyl group linked to the structure via a sulfur atom bond, such as methylthio, ethylthio, and the like.
Haloalkylthio: straight-chain or branched alkylthio groups, the hydrogen atoms on these alkylthio groups may be partially or wholly substituted with halogen, such as difluoromethylthio, trifluoroethylthio and the like.
Alkylamino: a linear or branched alkyl group linked to the structure via a nitrogen atom bond, such as methylamino, ethylamino, n-propylamino, isopropylamino or isomerised butylamine.
Dialkylamino group: two identical or different linear or branched alkyl groups are bonded to the structure via a nitrogen atom bond, such as dimethylamino, methylethylamino, and the like.
Cycloalkylamino group: cycloalkyl-NH-, such as cyclopropylamino.
Alkylsulfonyl: alkyl-S (O) 2 -, for example methylsulfonyl.
Alkyl sulfamoyl: alkyl-NH-S (O) 2 -, e.g. CH 3 NH S(O) 2 -。
Compared with the prior art, the invention has the advantages that:
the transposition catalyst overcomes the risk brought by acetone cyanohydrin drastic drugs, and has mild reaction conditions and high yield. The invention provides an effective preparation method for industrial production of triones herbicide.
Detailed Description
The following examples serve to further illustrate the invention but are not meant to limit it.
Preparation of compound V-substituted benzoic acid in each example was performed as in references US4780127a and CN109678767, or commercially available intermediates were purchased.
Example 1
1) Preparation of 4-methanesulfonyl-2-nitrobenzoyl chloride by acid chlorination reaction:
to the dried reaction flask were added 4-methanesulfonyl-2-nitrobenzoic acid (14.9 g,0.06 mol), DMF (0.2 g) and 1, 2-dichloroethane (80 g), and the mixture was stirred and warmed to 50-55℃and thionyl chloride (9.4 g,0.078 mol) was added dropwise, and after completion of the dropwise reaction, the solvent and excess thionyl chloride were distilled off under reduced pressure at reflux temperature for 2 hours to give 15.8g of 4-methanesulfonyl-2-nitrobenzoyl chloride.
2) Preparation of (3-oxocyclohex-1-en-1-yl) -4-methanesulfonyl-2-nitrobenzoate:
1, 2-dichloroethane (160 g) and 1, 3-cyclohexanedione (7.2 g,0.063 mol) were added to the 4-methanesulfonyl-2-nitrobenzoyl chloride obtained above, triethylamine (18.4 g,0.18 mol) was added dropwise at 2 to 10℃for 1.5 to 2 hours, and the mixture was incubated at 5 to 10℃for 0.5 hour to give an intermediate (3-oxocyclohex-1-en-1-yl) -4-methanesulfonyl-2-nitrobenzoate.
3) Rearrangement reaction preparation of 2- (4-methanesulfonyl-2-nitrobenzoyl) -1, 3-cyclohexanedione (mesotrione):
the reaction solution was rapidly warmed to 25℃and then was reacted with o-methylbenzonitrile (0.2 g,1.35 mmol), a rearrangement catalyst, at 33-35℃for 4 hours. Adding water (60 g), dropwise adding 20% potassium hydroxide solution to pH=10-11, stirring at room temperature for 0.5 hours, standing, layering, collecting a lower organic phase, adding 1, 2-dichloroethane into an upper feed liquid for extraction once, combining the organic phase to be recovered solvent and triethylamine, adding 10% hydrochloric acid into the upper feed liquid for acidification to pH=1-2, stirring at room temperature for 2 hours, filtering, washing a filter cake with water twice, discharging to obtain light yellow wet product 20.6g, and drying at 40-50 ℃ to obtain mesotrione original drug product 18.9g, wherein the quantitative content is 98.0%, and the yield is 90.9% (calculated by 4-methanesulfonyl-2-nitrobenzoic acid).
Example 2
1) Preparation of 4-methanesulfonyl-2-nitrobenzoyl chloride by acid chlorination reaction:
to the dried reaction flask were added 4-methanesulfonyl-2-nitrobenzoic acid (14.9 g,0.06 mol), DMF (0.2 g) and 1, 2-dichloroethane (80 g), and the mixture was stirred and warmed to 50-55℃and thionyl chloride (14.5 g,0.12 mol) was added dropwise, and after completion of the dropwise reaction, the reaction was carried out at reflux temperature for 2 hours, the solvent and excess thionyl chloride were distilled off under reduced pressure to give 15.9g of 4-methanesulfonyl-2-nitrobenzoyl chloride.
2) Preparation of (3-oxocyclohex-1-en-1-yl) -4-methanesulfonyl-2-nitrobenzoate:
1, 2-dichloroethane (160 g) and 1, 3-cyclohexanedione (7.2 g,0.063 mol) were added to the 4-methanesulfonyl-2-nitrobenzoyl chloride obtained above, triethylamine (18.4 g,0.18 mol) was added dropwise at 5-8℃for 1.5-2 hours, and the mixture was incubated at 5-8℃for 0.5 hour to give an intermediate (3-oxocyclohex-1-en-1-yl) -4-methanesulfonyl-2-nitrobenzoate.
3) Rearrangement reaction preparation of 2- (4-methanesulfonyl-2-nitrobenzoyl) -1, 3-cyclohexanedione (mesotrione):
the reaction solution was rapidly warmed to 25℃and a rearrangement catalyst, benzoylnitrile (0.2 g,1.5 mmol), was added thereto, and the reaction solution was warmed to 30 to 33℃and allowed to react for 3.5 hours. Adding water (60 g), dropwise adding 20% potassium hydroxide solution to pH=10-11, stirring at room temperature for 0.5 hours, standing, layering, collecting a lower organic phase, adding 1, 2-dichloroethane into an upper feed liquid for extraction once, combining the organic phase to be recovered solvent and triethylamine, adding 10% hydrochloric acid into the upper feed liquid for acidification to pH=1-2, stirring at room temperature for 2 hours, filtering, washing a filter cake with water twice, discharging to obtain light yellow wet product 20.7g, and drying at 40-50 ℃ to obtain mesotrione original drug product 18.8g, wherein the quantitative content is 98.2%, and the yield is 90.6% (calculated by 4-methanesulfonyl-2-nitrobenzoic acid).
Example 3
1) Preparation of 2-chloro-4-methanesulfonyl benzoyl chloride by acid chlorination reaction:
to a dry reaction flask were added 2-chloro-4-methylsulfonylbenzoic acid (14.4 g,0.06 mol), DMF (0.2 g) and 1, 2-dichloroethane (80 g), stirred and warmed to 50-55℃and thionyl chloride (9.4 g,0.078 mol) was added dropwise, and after completion of the dropwise reaction, the solvent and excess thionyl chloride were distilled off under reduced pressure at reflux temperature for 2 hours to give 15.2g of 2-chloro-4-methylsulfonylbenzoyl chloride.
2) Preparation of (3-oxocyclohex-1-en-1-yl) -2-chloro-4-methanesulfonyl benzoate:
1, 2-dichloroethane (160 g) and 1, 3-cyclohexanedione (7.2 g,0.063 mol) were added to the above-obtained 2-chloro-4-methanesulfonyl benzoyl chloride, triethylamine (18.4 g,0.18 mol) was added dropwise at a temperature of 2 to 10℃for 1.5 to 2 hours, and the mixture was kept at a temperature of 5 to 10℃for 0.5 hour to give an intermediate (3-oxocyclohex-1-en-1-yl) -2-chloro-4-methanesulfonyl benzoate.
3) Rearrangement reaction preparation of 2- (2-chloro-4-methylsulfonylbenzoyl) -1, 3-cyclohexanedione (sulcotrione):
the reaction solution was rapidly warmed to 25℃and then was reacted with o-methylbenzonitrile (0.2 g,1.35 mmol), a rearrangement catalyst, at 33-35℃for 4 hours. Adding water (60 g), dropwise adding 20% potassium hydroxide solution to pH=10-11, stirring at room temperature for 0.5 hours, standing, layering, collecting a lower organic phase, adding 1, 2-dichloroethane into an upper feed liquid for extraction once, combining the organic phase to be recovered solvent and triethylamine, adding 10% hydrochloric acid into the upper feed liquid for acidification to pH=1-2, stirring at room temperature for 2 hours, filtering, washing a filter cake with water twice, discharging to obtain light yellow wet product 20.2g, and drying at 40-50 ℃ to obtain 18.3g of sulcotrione technical product with a quantitative content of 97.8% and a yield of 90.7% (calculated by 2-chloro-4-methanesulfonyl benzoic acid).
Example 4
1) Preparation of 2-chloro-4-methanesulfonyl-3- ((2, 2-trifluoroethoxy) methyl) benzoyl chloride:
to the dried reaction flask were added 2-chloro-4-methanesulfonyl-3- ((2, 2-trifluoroethoxy) methyl) benzoic acid (21.3 g,0.06 mol), DMF (0.2 g) and 1, 2-dichloroethane (80 g), stirred and warmed to 50-55 ℃, thionyl chloride (9.4 g,0.078 mol) was added dropwise, and after completion of the dropwise addition, the solvent and excess thionyl chloride were distilled off under reduced pressure at reflux temperature for 2 hours to give 22.0g of 2-chloro-4-methanesulfonyl-3- ((2, 2-trifluoroethoxy) methyl) benzoyl chloride.
2) Preparation of acylation reaction (3-oxocyclohex-1-en-1-yl) -2-chloro-4-methanesulfonyl-3- ((2, 2-trifluoroethoxy) methyl) benzoate:
1, 2-dichloroethane (160 g) and 1, 3-cyclohexanedione (7.2 g,0.063 mol) were added to the above-obtained 2-chloro-4-methanesulfonyl-3- ((2, 2-trifluoroethoxy) methyl) benzoyl chloride, and triethylamine (18.4 g,0.18 mol) was added dropwise at a temperature of 2 to 10℃for 1.5 to 2 hours, followed by incubation at 5 to 10℃for 0.5 hours to obtain an intermediate (3-oxocyclohex-1-en-1-yl) -2-chloro-4-methanesulfonyl-3- ((2, 2-trifluoroethoxy) methyl) benzoate.
3) Rearrangement reaction preparation of 2- (2-chloro-4-methanesulfonyl-3- ((2, 2-trifluoroethoxy) methyl) benzoyl) -1, 3-cyclohexanedione (cyclosulfamide):
the reaction mixture was rapidly warmed to 25℃and o-methylbenzoyl nitrile (0.2 g,1.35 mmol) was added thereto, and the mixture was warmed to 33-35℃and reacted for 4 hours. Adding water (60 g), dropwise adding 20% potassium hydroxide solution to pH=10-11, stirring at room temperature for 0.5 hours, standing, layering, collecting a lower organic phase, adding 1, 2-dichloroethane into an upper feed liquid for extraction once, combining an organic phase to be recovered solvent and triethylamine, adding 10% hydrochloric acid into the upper feed liquid for acidification to pH=1-2, stirring at room temperature for 2 hours, filtering, washing a filter cake twice with water, discharging to obtain a pale yellow wet product, and drying at 40-50 ℃ to obtain 24.1g of a benzoyl ketone raw material product, wherein the quantitative content is 97.6%, and the yield is 88.9% (calculated by 2-chloro-4-methanesulfonyl-3- ((2, 2-trifluoroethoxy) methyl) benzoic acid).
Example 5
To replace o-methylbenzoyl nitrile with 4-methanesulfonyl-2-nitrobenzonitrile (0.2 g,0.79 mmol) as in example 1, the quantitative content of mesotrione was 98.2% and the yield was 90.3% (based on 4-methanesulfonyl-2-nitrobenzoic acid).
Example 6
To the mixture was reacted at 60 to 65℃for 4 hours after the addition of o-methylbenzonitrile in accordance with the method of example 1, the quantitative content of mesotrione was 92.5% and the yield was 78.2% (based on 4-methanesulfonyl-2-nitrobenzoic acid).
Comparative example 1
To replace o-methylbenzonitrile with acetone cyanohydrin (0.2 g,2.33 mmol) as in example 1, the quantitative content of mesotrione was 95.6% and the yield was 83.8% (based on 4-methanesulfonyl-2-nitrobenzoic acid).
Comparative example 2
The o-methylbenzonitrile was replaced by acetone cyanohydrin (0.4 g,4.65 mmol) as in example 1 to give a quantitative content of mesotrione of 97.2% and a yield of 85.6% (calculated as 4-methanesulfonyl-2-nitrobenzoic acid).
As can be seen from the above examples, the conversion efficiency of the catalyst of the present invention is higher, and the yield of the rearrangement catalyst of the present invention is higher, and the obtained product has a higher content than that of acetone cyanohydrin of the prior art, and is safer and more environment-friendly.
Claims (10)
1. A method for preparing trione herbicide, take substituted benzoic acid as raw materials, get the acylation reaction system after acyl chlorination, then prepare trione herbicide through the rearrangement reaction, characterized by that: the rearrangement reaction is to add a rearrangement catalyst (formula III) into an acylation reaction system, and react for 0.5-12 hours at the temperature of 0-50 ℃ under the condition of heat preservation to obtain the trione herbicide;
the molar ratio of the rearrangement catalyst (formula III) to the raw material is (0.0005-1): 1; wherein the structure of formula III is as follows,
2. A process for preparing a trione herbicide as claimed in claim 1, wherein: the reaction temperature of the acylation reaction system is 10-40 ℃ and the reaction time is 0.5-10 hours.
3. A process for preparing a trione herbicide as claimed in claim 2, wherein: the rearrangement reaction temperature is 20-40 ℃ and the reaction time is 0.5-8 hours; wherein the molar ratio of the rearrangement catalyst (formula III) to the starting material is (0.001-1): 1.
4. A process for preparing a trione herbicide as claimed in claim 3, wherein: the rearrangement reaction temperature is 25-35 ℃ and the reaction time is 0.5-6 hours; wherein the molar ratio of the rearrangement catalyst (formula III) to the starting material is (0.005-1): 1.
5. A process for preparing a trione herbicide as claimed in any one of claims 1 to 4, characterized in that: and (3) regulating the temperature of the acylation reaction system to room temperature, adding a rearrangement catalyst, reacting at the rearrangement temperature, regulating the pH value of the system to be alkaline after the reaction, cooling to room temperature, standing, extracting and layering, collecting a water phase, regulating the pH value of the water phase feed liquid to be 1-2, and filtering and washing to obtain the trione herbicide.
6. A process for preparing a trione herbicide as claimed in any one of claims 1 to 4, characterized in that: the rearrangement catalyst (formula III) wherein G is selected from the group consisting of C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, cyclopropane, phenyl and pyridyl optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C 1 -C 3 Alkyl, halogenated C 1 -C 3 Alkyl, cyclopropane, C 1 -C 3 Alkoxy, halo C 1 -C 3 Alkoxy, C 1 -C 3 Alkoxymethylene, halogenated C 1 -C 3 Alkoxymethylene, tetrahydrofuranyl C 1 -C 3 Alkoxymethylene, C 1 -C 3 Alkylthio, halo C 1 -C 3 Alkylthio, C 1 -C 3 Alkylamino, C 1 -C 3 Dialkylamino, cyclopropylamino, C 1 -C 3 Alkylsulfonyl or C 1 -C 3 Alkyl sulfamoyl.
7. A process for preparing a trione herbicide as claimed in claim 1, wherein: the acylation reaction system is characterized in that a solvent is added into a product obtained by acyl chloride reaction with substituted benzoic acid as a raw material, then 1, 3-cyclohexanedione is added, the temperature is controlled to be 0-10 ℃, organic base is dropwise added, and the thermal insulation reaction is continued for 0.5-1.5 hours after the dropwise addition, so that enol ester of the substituted benzoic acid of the acylation reaction product is obtained.
8. A process for preparing a trione herbicide as claimed in claim 7, wherein: the solvent is toluene or 1, 2-dichloroethane; the organic base is trimethylamine, triethylamine, diisopropylethylamine, pyridine or 4-dimethylaminopyridine.
9. A process for preparing a trione herbicide as claimed in claim 1 or 7, characterized in that: adding the raw material substituted benzoic acid into a solvent, heating to 50-55 ℃, dropwise adding thionyl chloride, continuously carrying out reflux reaction for 1.5-2.5 hours after dropwise adding, and evaporating the solvent and the excessive thionyl chloride under reduced pressure to obtain substituted benzoyl chloride of the general formula IV;
10. a process for preparing a trione herbicide as claimed in claim 9, wherein: the molar ratio of the thionyl chloride to the raw material is (1-3): 1.
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| CN85109777A (en) * | 1984-12-20 | 1987-02-04 | 斯托弗化学公司 | The preparation method of compound of diketone acylate |
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