CN114989040A - Synthetic method of mefenpyr-diethyl intermediate - Google Patents
Synthetic method of mefenpyr-diethyl intermediate Download PDFInfo
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- CN114989040A CN114989040A CN202210802810.3A CN202210802810A CN114989040A CN 114989040 A CN114989040 A CN 114989040A CN 202210802810 A CN202210802810 A CN 202210802810A CN 114989040 A CN114989040 A CN 114989040A
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- mefenpyr
- nitrite
- diethyl
- solvent
- ethyl
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- OPGCOAPTHCZZIW-UHFFFAOYSA-N diethyl 1-(2,4-dichlorophenyl)-5-methyl-4h-pyrazole-3,5-dicarboxylate Chemical group CCOC(=O)C1(C)CC(C(=O)OCC)=NN1C1=CC=C(Cl)C=C1Cl OPGCOAPTHCZZIW-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000010189 synthetic method Methods 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- OHLRLMWUFVDREV-UHFFFAOYSA-N ethyl 4-chloro-3-oxobutanoate Chemical compound CCOC(=O)CC(=O)CCl OHLRLMWUFVDREV-UHFFFAOYSA-N 0.000 claims abstract description 12
- IAWHNGSIQZYZQB-UHFFFAOYSA-N (2,4-dichlorophenyl)azanium;chloride Chemical compound Cl.NC1=CC=C(Cl)C=C1Cl IAWHNGSIQZYZQB-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 10
- -1 2-chloro-2- [2- (2, 4-dichlorophenyl) hydrazino ] ethyl Chemical group 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 7
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims abstract description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 235000011054 acetic acid Nutrition 0.000 claims description 5
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- OWFXIOWLTKNBAP-UHFFFAOYSA-N isoamyl nitrite Chemical compound CC(C)CCON=O OWFXIOWLTKNBAP-UHFFFAOYSA-N 0.000 claims description 4
- 238000001308 synthesis method Methods 0.000 claims description 4
- IOGXOCVLYRDXLW-UHFFFAOYSA-N tert-butyl nitrite Chemical compound CC(C)(C)ON=O IOGXOCVLYRDXLW-UHFFFAOYSA-N 0.000 claims description 4
- 239000012414 tert-butyl nitrite Substances 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- SKRDXYBATCVEMS-UHFFFAOYSA-N isopropyl nitrite Chemical compound CC(C)ON=O SKRDXYBATCVEMS-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 3
- XEJNEDVTJPXRSM-UHFFFAOYSA-N 1-(2,4-dichlorophenyl)-5-methyl-4,5-dihydro-1H-pyrazole-3,5-dicarboxylic acid Chemical compound OC(=O)C1(C)CC(C(O)=O)=NN1C1=CC=C(Cl)C=C1Cl XEJNEDVTJPXRSM-UHFFFAOYSA-N 0.000 claims 2
- 238000005580 one pot reaction Methods 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 10
- 239000004009 herbicide Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000002363 herbicidal effect Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- KQCMTOWTPBNWDB-UHFFFAOYSA-N 2,4-dichloroaniline Chemical compound NC1=CC=C(Cl)C=C1Cl KQCMTOWTPBNWDB-UHFFFAOYSA-N 0.000 description 3
- 241000209140 Triticum Species 0.000 description 3
- 235000021307 Triticum Nutrition 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- ZTPAUBJZUBGGEY-UHFFFAOYSA-N (2,4-dichlorophenyl)hydrazine Chemical compound NNC1=CC=C(Cl)C=C1Cl ZTPAUBJZUBGGEY-UHFFFAOYSA-N 0.000 description 2
- 239000012954 diazonium Substances 0.000 description 2
- 150000001989 diazonium salts Chemical class 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 231100000674 Phytotoxicity Toxicity 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000000729 antidote Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- QJXMXLMJPBEVGC-UHFFFAOYSA-N ethyl 2-chloro-2-[2-(2,4-dichlorophenyl)hydrazinyl]acetate Chemical compound CCOC(=O)C(Cl)NNC1=CC=C(Cl)C=C1Cl QJXMXLMJPBEVGC-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Substances ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000009333 weeding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/16—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of hydrazones
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthetic method of a mefenpyr-diethyl intermediate, which comprises the following steps: 2, 4-dichloroaniline hydrochloride, ethyl chloroacetoacetate and nitrite are reacted in a solvent to obtain the 2-chloro-2- [2- (2, 4-dichlorophenyl) hydrazino ] ethyl acetate. The method synthesizes the mefenpyr-diethyl intermediate 2-chloro-2- [2- (2, 4-dichlorophenyl) hydrazino ] ethyl acetate through one-step reaction, has simple reaction operation, high safety and less three wastes, and simultaneously the yield of the mefenpyr-diethyl intermediate obtained by preparation reaches more than 81.2 percent and the purity is more than 98 percent.
Description
Technical Field
The invention relates to the technical field of organic chemical synthesis, in particular to a synthetic method of a mefenpyr-diethyl intermediate.
Background
Chemical weeding in farmland is one of essential measures for controlling weed growth and improving grain yield in recent years. However, because of the close relationship between many grassy weeds in wheat fields and wheat crops, the selectivity of common herbicides between wheat crops and grassy weeds is poor, and phytotoxicity is easy to generate. The herbicide safener is added into the herbicide, so that the selectivity of the herbicide can be increased, and the weed control effect is improved.
Mefenpyr-diethyl is a novel herbicide safener published by the britton plant protection agency, 1999. The pyrazole antidote is developed by the company Antonter, and can protect crops from being damaged by herbicide when being used together with the herbicide.
The following methods are mainly reported in the literature for preparing mefenpyr-diethyl:
patent WO9107874 discloses: 2, 4-dichloroaniline is used as a raw material, diazotization is firstly carried out to prepare 2, 4-dichlorophenylhydrazine, then the 2, 4-dichlorophenylhydrazine reacts with oxalyl chloride monoethyl ester, phosphorus pentachloride chloride is used to prepare 2-chlorine-2- [2- (2, 4-dichlorophenyl) hydrazino ] ethyl acetate, and finally the ethyl pentachloride chloride and ethyl methacrylate are cyclized to prepare a target product, wherein the reaction formula is as follows:
the process has long route, complex reaction, low yield and more three wastes.
Secondly, patent CN102816118 discloses: taking 2, 4-dichloroaniline as a raw material, firstly reacting with sodium nitrite to prepare diazonium salt, then condensing with chloroacetoacetic acid ethyl ester to obtain 2-chloro-2- [2- (2, 4-dichlorophenyl) hydrazino ] acetic acid ethyl ester, and finally cyclizing with ethyl methacrylate to prepare a target product, wherein the reaction formula is as follows:
the process uses a large amount of hydrochloric acid and sodium acetate, has high cost, has a large amount of three wastes, and the diazonium salt prepared by the reaction of 2, 4-dichloroaniline and sodium nitrite has poor stability under a neutral condition, and is easy to bring potential safety hazards in industrial production.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects of long synthetic route, low yield, high cost, large amount of three wastes and the like of the mefenpyr-diethyl intermediate in the prior art, so that the synthetic method of the mefenpyr-diethyl intermediate is mild in condition, high in safety, less in three wastes and high in purity.
Therefore, the invention provides a synthetic method of a mefenpyr-diethyl intermediate, which comprises the following steps:
reacting 2, 4-dichloroaniline hydrochloride, ethyl chloroacetoacetate and nitrite in a solvent to obtain 2-chloro-2- [2- (2, 4-dichlorophenyl) hydrazino ] ethyl acetate.
The reaction route is as follows:
preferably, the solvent is at least one of methanol, ethanol, isopropanol, tert-butanol, tetrahydrofuran, 1, 4-dioxane, benzene, toluene, xylene, formamide, acetamide, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, sulfolane, formic acid, acetic acid, propionic acid, and butyric acid.
Preferably, the nitrite is at least one of isopropyl nitrite, tert-butyl nitrite or isoamyl nitrite.
Preferably, the molar ratio of the 2, 4-dichloroaniline hydrochloride, the ethyl chloroacetoacetate and the nitrite is 1.0 (0.9-1.5) to 1.05-2.0.
Preferably, the ratio of the 2, 4-dichloroaniline hydrochloride to the solvent is 0.1mol (40-250) mL.
Preferably, the reaction temperature is-10 to 100 ℃, and the reaction time is 1 to 16 hours.
The technical scheme of the invention has the following advantages:
1. the synthetic method of the mefenpyr-diethyl intermediate is characterized in that 2, 4-dichloroaniline hydrochloride, ethyl chloroacetoacetate and nitrite ester are used as raw materials, and the mefenpyr-diethyl intermediate 2-chloro-2- [2- (2, 4-dichlorophenyl) hydrazino ] ethyl acetate is synthesized through one-step reaction, so that the reaction is simple to operate, high in safety and less in three wastes, the yield of the mefenpyr-diethyl intermediate obtained by preparation is more than 81.2%, and the purity of the mefenpyr-diethyl intermediate is more than 98%;
2. according to the synthesis method of the mefenpyr-diethyl intermediate, a reagent which is extremely toxic, flammable and explosive or difficult to store and is used in the existing synthesis method is not used in the reaction process, so that the harm to operators and the environment is avoided, the industrial prospect is good, and a new thought suitable for industrial large-scale production is provided for the synthesis of the mefenpyr-diethyl intermediate and the mefenpyr-diethyl.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1
The synthesis of the mefenpyr-diethyl intermediate comprises the following steps:
mixing 19.9g of 2, 4-dichloroaniline hydrochloride, 16.5g of ethyl chloroacetoacetate, 20g of formic acid and 20mL of N, N-dimethylacetamide, stirring and heating to 30 ℃, slowly dripping 10.3g of isopropyl nitrite into the mixture, heating to 80 ℃ after dripping to react for 5 hours, cooling the reaction solution to 0 ℃, performing suction filtration, washing with water, and drying to obtain 23.8g of orange solid, wherein the yield is 80.5%, and the purity is higher than 98% by HPLC (high performance liquid chromatography).
Example 2
The synthesis of the mefenpyr-diethyl intermediate comprises the following steps:
mixing 19.9g of 2, 4-dichloroaniline hydrochloride, 18.1g of ethyl chloroacetoacetate and 48g of acetic acid, slowly dripping 11.9g of tert-butyl nitrite into the mixture under stirring at room temperature, cooling the reaction solution to 0 ℃ after dripping off and heating to 70 ℃ for reaction for 6 hours, carrying out suction filtration, washing with water, and drying to obtain 24.5g of orange solid, wherein the yield is 82.9%, and the purity is more than 98% by HPLC (high performance liquid chromatography).
Example 3
The synthesis of the mefenpyr-diethyl intermediate comprises the following steps:
mixing 19.9g of 2, 4-dichloroaniline hydrochloride, 19.6g of ethyl chloroacetoacetate, 30g of butyric acid and 50mL of tetrahydrofuran, slowly dripping 10.3g of isoamyl nitrite into the mixture under room temperature stirring, heating to 60 ℃ after dripping, reacting for 6 hours, decompressing, steaming to remove a low-boiling-point solvent, cooling the reaction solution to 0 ℃, performing suction filtration, washing with water, and drying to obtain 25.3g of orange solid, wherein the yield is 85.6%, and the purity is higher than 98% by HPLC (high performance liquid chromatography).
Example 4
The synthesis of the mefenpyr-diethyl intermediate comprises the following steps:
19.9g of 2.4-dichloroaniline hydrochloride and 19.6g of ethyl chloroacetoacetate were mixed with 25g of acetic acid and 100mL of toluene, and 20g of isoamyl nitrite was slowly added dropwise thereto with stirring at room temperature. After dropping, heating to 100 ℃ for reaction for 3h, decompressing and steaming to remove the low-boiling-point solvent, cooling the reaction liquid to 0 ℃, performing suction filtration, washing with water, and drying to obtain 24.9g of orange solid, wherein the yield is 84.3%, and the purity is higher than 95% by HPLC (high performance liquid chromatography).
Example 5
The synthesis of the mefenpyr-diethyl intermediate comprises the following steps:
mixing 19.9g of 2.4-dichloroaniline hydrochloride, 19.6g of ethyl chloroacetoacetate, 25g of acetic acid and 100mL of tert-butyl alcohol, slowly dripping 20g of tert-butyl nitrite into the mixture under stirring at room temperature, stirring the mixture at room temperature after dripping to react for 16 hours, evaporating the solvent with low boiling point under reduced pressure, cooling the reaction solution to 0 ℃, performing suction filtration, washing with water, and drying to obtain 24.0g of orange solid, wherein the yield is 81.2 percent, and the purity is over 95 percent by HPLC (high performance liquid chromatography).
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (6)
1. A synthetic method of a mefenpyr-diethyl intermediate is characterized by comprising the following steps:
reacting 2, 4-dichloroaniline hydrochloride, ethyl chloroacetoacetate and nitrite in a solvent to obtain 2-chloro-2- [2- (2, 4-dichlorophenyl) hydrazino ] ethyl acetate.
2. The method for synthesizing a mefenpyr intermediate according to claim 1, wherein the solvent is at least one of methanol, ethanol, isopropanol, tert-butanol, tetrahydrofuran, 1, 4-dioxane, benzene, toluene, xylene, formamide, acetamide, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, sulfolane, formic acid, acetic acid, propionic acid, and butyric acid.
3. The method for synthesizing a mefenpyr intermediate according to claim 1, wherein the nitrite ester is at least one of isopropyl nitrite, tert-butyl nitrite or isoamyl nitrite.
4. The method for synthesizing the mefenpyr-diethyl intermediate as claimed in claim 1, wherein the molar ratio of the 2, 4-dichloroaniline hydrochloride, the ethyl chloroacetoacetate and the nitrite is 1.0 (0.9-1.5) to 1.05-2.0.
5. The synthesis method of the mefenpyr-diethyl intermediate according to claim 1 or 2, wherein the ratio of the 2, 4-dichloroaniline hydrochloride to the solvent is 0.1mol (40-250) mL.
6. The synthesis method of the mefenpyr-diethyl intermediate as claimed in claim 1, wherein the reaction temperature is-10-100 ℃ and the reaction time is 1-16 h.
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2022
- 2022-07-07 CN CN202210802810.3A patent/CN114989040A/en active Pending
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