CN117551036A - Refining method of 2- (3, 4-dimethyl-1H-pyrazol-1-yl) succinic acid - Google Patents
Refining method of 2- (3, 4-dimethyl-1H-pyrazol-1-yl) succinic acid Download PDFInfo
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- CN117551036A CN117551036A CN202311485167.7A CN202311485167A CN117551036A CN 117551036 A CN117551036 A CN 117551036A CN 202311485167 A CN202311485167 A CN 202311485167A CN 117551036 A CN117551036 A CN 117551036A
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- pyrazol
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- succinic acid
- dimethylpyrazole
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- 238000000034 method Methods 0.000 title claims abstract description 22
- FGIFCVDSYXGMRG-UHFFFAOYSA-N 2-(3,4-dimethylpyrazol-1-yl)butanedioic acid Chemical compound CC1=CN(C(CC(O)=O)C(O)=O)N=C1C FGIFCVDSYXGMRG-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000007670 refining Methods 0.000 title claims abstract description 18
- VQTVFIMEENGCJA-UHFFFAOYSA-N 3,4-dimethyl-1H-pyrazole Chemical compound CC=1C=NNC=1C VQTVFIMEENGCJA-UHFFFAOYSA-N 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- LRVKDKMOGMEZIW-UHFFFAOYSA-N 2-(4,5-dimethylpyrazol-1-yl)butanedioic acid Chemical compound CC=1C=NN(C=1C)C(C(=O)O)CC(=O)O LRVKDKMOGMEZIW-UHFFFAOYSA-N 0.000 claims abstract description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000002386 leaching Methods 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 239000007787 solid Substances 0.000 claims abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 12
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 9
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000001530 fumaric acid Substances 0.000 claims description 4
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 claims description 4
- 229940011051 isopropyl acetate Drugs 0.000 claims description 4
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-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
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 2
- SKTCDJAMAYNROS-UHFFFAOYSA-N methoxycyclopentane Chemical compound COC1CCCC1 SKTCDJAMAYNROS-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims 1
- 229910021641 deionized water Inorganic materials 0.000 claims 1
- 239000012153 distilled water Substances 0.000 claims 1
- 239000008213 purified water Substances 0.000 claims 1
- 239000008399 tap water Substances 0.000 claims 1
- 235000020679 tap water Nutrition 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000012065 filter cake Substances 0.000 description 8
- FFFDQFQUFFUHAL-UHFFFAOYSA-N CC1=C(NN=C1C(CC(=O)O)C(=O)O)C Chemical compound CC1=C(NN=C1C(CC(=O)O)C(=O)O)C FFFDQFQUFFUHAL-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- MKGIQRNAGSSHRV-UHFFFAOYSA-N 1,1-dimethyl-4-phenylpiperazin-1-ium Chemical compound C1C[N+](C)(C)CCN1C1=CC=CC=C1 MKGIQRNAGSSHRV-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- XKVUYEYANWFIJX-UHFFFAOYSA-N 5-methyl-1h-pyrazole Chemical compound CC1=CC=NN1 XKVUYEYANWFIJX-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N DMSO Substances CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- 239000005696 Diammonium phosphate Substances 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- NGLMYMJASOJOJY-UHFFFAOYSA-O azanium;calcium;nitrate Chemical compound [NH4+].[Ca].[O-][N+]([O-])=O NGLMYMJASOJOJY-UHFFFAOYSA-O 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 229940125532 enzyme inhibitor Drugs 0.000 description 1
- 239000002532 enzyme inhibitor Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 230000001546 nitrifying effect Effects 0.000 description 1
- 239000000618 nitrogen fertilizer Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention discloses a refining method of 2- (3, 4-dimethyl-1H-pyrazol-1-yl) succinic acid, which comprises the following steps: adding water and an organic solvent into DMPSA to be refined, stirring for 0.2-3 hours at 60-110 ℃, then cooling to 0-25 ℃, continuously stirring and crystallizing for 0.2-3 hours, filtering, leaching the solid with water and the organic solvent, and drying to obtain the refined 2- (3, 4-dimethyl-1H-pyrazol-1-yl) succinic acid product. The refining method disclosed by the invention is simple to operate and easy to control, is suitable for industrial production and is excellent in removal effect on residues such as 3, 4-dimethylpyrazole and isomer 2- (4, 5-dimethyl-1H-pyrazol-1-yl) succinic acid, and the obtained 2- (3, 4-dimethyl-1H-pyrazol-1-yl) succinic acid is high in purity and the purity is more than 98%.
Description
Technical Field
The invention relates to the technical field of 2- (3, 4-dimethyl-1H-pyrazol-1-yl) succinic acid refining, in particular to a refining method of 2- (3, 4-dimethyl-1H-pyrazol-1-yl) succinic acid.
Background
The mixture of 2- (3, 4-dimethyl-1H-pyrazol-1-yl) succinic acid and 2- (4, 5-dimethyl-1H-pyrazol-1-yl) succinic acid is commonly called DMPSA, is a novel nitrogenous fertilizer nitrifying enzyme inhibitor developed by Germany BASF, and has the characteristics of high efficiency, no toxicity, stability, specificity and the like. The results of the study show that DMPSA shows similar efficacy in inhibiting nitrogen oxide release, grain yield and quality improvement compared to DMPP, but it has better stability properties (Europ.J.Agronomy.2016, 80,78;Atmospheric Environment,2018,187,255). The current research shows that DMPSA can be used by being compounded with fertilizers such as calcium ammonium nitrate, diammonium phosphate and the like, and shows good synergy and emission reduction results.
US5972064 reports in example 1 that the synthesis of DMPSA analogues obtained by reacting 3-methylpyrazole with maleic anhydride in 50% aqueous acetic acid gives 92% yield and the nuclear magnetism shows an isomer ratio of 2/1, but requires further purification using diethyl ether as solvent and is highly dangerous and unsuitable for commercial use.
EP3199508, US201700540894, CN106068252 and WO2015086823 report that DMPSA products are obtained after a reaction of 100 ℃ for 16 hours by using 50% aqueous acetic acid as a reaction solvent and 3, 4-dimethylpyrazole and maleic anhydride as raw materials, and the yield is 92%, and positional isomers exist, but specific proportions are not reported, but diethyl ether which cannot be used commercially is required, and technical transformation is limited.
EP3199508, US201700540894, CN106068252 and WO2015086823 also report similar reaction conditions in example 2, and the target product was obtained after the end of the reaction using seed crystals, with a conversion of 92%, a yield of 90.22% and a purity of 99.9% and NMR showed that the ratio of 2- (3, 4-dimethylpyrazolyl) succinic acid (P1) to 2- (4, 5-dimethylpyrazolyl) succinic acid (P2) was 3.3/1.
CN112321508 reports a pressure-resistant experiment result using 3, 4-dimethylpyrazole and fumaric acid as raw materials, the reaction temperature is 110-160 ℃, the pressure condition is 0.04-0.53MPa, the reaction time is 1-6 hours, a part of water is required to be removed by flash evaporation after the reaction is completed, the product can be obtained in a yield of >94% by cooling, crystallizing and drying, the purity is generally above 99.5%, and the ratio relationship between 2- (3, 4-dimethylpyrazolyl) succinic acid (P1) and 2- (4, 5-dimethylpyrazolyl) succinic acid (P2) is 92.5/7.5-95.0/5.0. The mode adopts a high-voltage supervision process, has potential safety hazards and is complex to operate.
In general, the synthetic method of DMPSA mainly uses 3, 4-dimethylpyrazole and maleic anhydride or fumaric acid as raw materials, and the product can be obtained through Michael addition reaction under heating and even pressure-resistant conditions. It is not difficult to find that the existing synthesis method mainly has the following problems: (1) The need to use reagents or raw materials for safety supervision limits their application and technical transformations; (2) The use of more severe process conditions, such as a pressurization supervision process and the like, has potential safety hazards; (3) Product refining processes are limited, and the product is usually present in the form of isomers, typically 77/23-95/5; (4) There is no clear method to obtain 2- (3, 4-dimethyl-1H-pyrazol-1-yl) succinic acid or 2- (4, 5-dimethyl-1H-pyrazol-1-yl) succinic acid compounds in a single configuration.
Disclosure of Invention
The invention aims at overcoming the defects in the prior art and provides a refining method of 2- (3, 4-dimethyl-1H-pyrazol-1-yl) succinic acid.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
provided is a method for purifying 2- (3, 4-dimethyl-1H-pyrazol-1-yl) succinic acid, comprising the following steps: adding water and an organic solvent into DMPSA to be refined, stirring for 0.2-3 hours at 60-110 ℃, then cooling to 0-25 ℃, continuously stirring and crystallizing for 0.2-3 hours, filtering, leaching the solid with water and the organic solvent, and drying to obtain a refined 2- (3, 4-dimethyl-1H-pyrazol-1-yl) succinic acid product;
wherein the organic solvent is one or more of dichloromethane, chloroform, 1, 2-dichloroethane, chlorobenzene, toluene, xylene, nitrobenzene, anisole, methyl cyclopentyl ether, methyl tertiary butyl ether, isopropyl ether, ethyl acetate, isopropyl acetate and 2-methyltetrahydrofuran; the DMPSA to be refined comprises a mixture of 2- (3, 4-dimethyl-1H-pyrazol-1-yl) succinic acid and 2- (4, 5-dimethyl-1H-pyrazol-1-yl) succinic acid in a molar ratio of (2-19) to (1).
Further, the organic solvent is one or more of ethyl acetate, isopropyl acetate, methyl tertiary butyl ether, chlorobenzene and toluene.
Further, the DMPSA to be refined also comprises a small amount of residues: 3, 4-dimethylpyrazole, maleic acid and fumaric acid.
Further, the DMPSA to be refined is prepared from 3, 4-dimethylpyrazole and maleic anhydride as raw materials.
Further, the amount of the water used in the refining process is 1 to 20 times, preferably 1 to 10 times, more preferably 2 to 6 times the mass of 3, 4-dimethylpyrazole based on 3, 4-dimethylpyrazole; the amount of the organic solvent used in the purification process is 1 to 20 times, preferably 1 to 15 times, more preferably 3 to 8 times the mass of 3, 4-dimethylpyrazole based on 3, 4-dimethylpyrazole.
Compared with the prior art, the invention has the following technical effects:
the refining method disclosed by the invention is simple and easy to control in operation, does not need to use a reagent or a raw material for safety supervision, is suitable for industrial production and has an excellent effect of removing residues such as 3, 4-dimethylpyrazole and the like and isomer 2- (4, 5-dimethyl-1H-pyrazol-1-yl) succinic acid, and the obtained 2- (3, 4-dimethyl-1H-pyrazol-1-yl) succinic acid has high purity and purity of more than 98%.
Drawings
FIG. 1 is a typical liquid spectrum of DMPSA to be purified in example 1;
FIG. 2 is a typical liquid spectrum of the DMPSA to be purified in example 1 after being purified;
FIG. 3 is a nuclear magnetic resonance spectrum of 2- (3, 4-dimethyl-1H-pyrazol-1-yl) succinic acid in example 1.
Detailed Description
The invention is further described below with reference to the drawings and specific examples, which are not intended to be limiting. It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
The DMPSA to be purified in examples 1-5 below was prepared using prior art preparation methods and the present invention is not described in any great detail. Wherein, the dosage of the 3, 4-dimethylpyrazole and the maleic anhydride in the reaction system is shown in the following table 1:
TABLE 1
Example 1
To DMPSA (P1/P2=71:28, P1:2- (3, 4-dimethylpyrazolyl) butanedioic acid, P2:2- (4, 5-dimethylpyrazolyl) butanedioic acid) to be purified of the 1a system were added 40g (4X) of water and 44g (4.4X) of chlorobenzene (all calculated as 3, 4-dimethylpyrazole), the system was stirred at 80℃for 0.5 hour and then cooled to 10-15℃and then stirred and crystallized continuously for 0.5 hour, filtration was carried out, 20ml of water was used to rinse the cake, and the cake was rinsed again with a small amount of chlorobenzene, and after drying, 15.5g of a product was obtained, the yield was 70.2% and the purity was 99.8%.1H NMR (400 MHz, d 6-DMSO). Delta.12.71 (brs, 2H), 7.45 (s, 1H), 5.13 (t, J=7.0 Hz, 1H), 3.07 (dd, J1=16.8 Hz, J2=6.8 Hz, 1H), 2.93 (dd, J1=16.8 Hz, J2=7.6 Hz, 1H), 2.04 (s, 3H), 1.90 (s, 3H).
Example 2
To the DMPSA (P1/P2=71:28) to be purified of the 1a system, 20g (2X) of water and 30g (3X) of methyl tert-butyl ether (all calculated as 3, 4-dimethylpyrazole) are added, the system is stirred at 60 ℃ for 0.5 hours and then cooled to 10-15 ℃, the mixture is continuously stirred and crystallized for 0.5 hours, filtration and 20ml of water are carried out to wash the filter cake, the filter cake is washed again with a small amount of methyl tert-butyl ether, and the product is obtained after drying, 15.4g, the yield is 69.8% and the purity is 99.6%.
Example 3
50g (5X) of water and 30g (3X) of ethyl acetate (calculated as 3, 4-dimethylpyrazole) are added to DMPSA (P1/P2=70:29) to be refined of the 1b system, the system is stirred at 70 ℃ for 0.5 hours and then cooled to 5-10 ℃, the system is continuously stirred and crystallized for 1 hour, filtration is carried out, 20ml of water is used for leaching a filter cake, the filter cake is leached again by a small amount of ethyl acetate, and the product 15.3g is obtained after drying, the yield is 69.3%, and the purity is 99.8%.
Example 4
To the DMPSA to be purified of the 1c system (P1/P2=72:27) 60g (6X) water and 79g (7.9X) toluene (all calculated as 3, 4-dimethylpyrazole) were added, the system was stirred at 100℃for 0.5 hours and then cooled to 5-10℃and the crystallization was continued for 0.5 hours, filtered, 20ml of water was used to rinse the filter cake, the filter cake was rinsed again with a small amount of toluene, and the product was obtained after drying in 13.4g in 60.7% yield and 99.6% purity.
Example 5
In a 1d system, crude solid is obtained after the reaction and is filtered, 80g (8X) of water and 40g (4X) of ethyl acetate (calculated by 3, 4-dimethylpyrazole) are added into a round bottom bottle, the system is heated to 70 ℃ and stirred for 1 hour, then cooled to 0-5 ℃, stirring and crystallization are continued for 1 hour, filtration is carried out, 20ml of water is used for leaching a filter cake, the filter cake is leached again by a small amount of ethyl acetate, and the product is obtained after the drying, 15.7g, the yield is 71.1%, and the purity is 99.8%.
The foregoing is merely illustrative of the preferred embodiments of the present invention and is not intended to limit the embodiments and scope of the present invention, and it should be appreciated by those skilled in the art that equivalent substitutions and obvious variations may be made using the teachings and illustrations of the present invention, and that such variations are intended to be included within the scope of the present invention.
Claims (6)
1. A method for refining 2- (3, 4-dimethyl-1H-pyrazol-1-yl) succinic acid, which is characterized by comprising the following steps: adding water and an organic solvent into DMPSA to be refined, stirring for 0.2-3 hours at 60-110 ℃, then cooling to 0-25 ℃, continuously stirring and crystallizing for 0.2-3 hours, filtering, leaching the solid with water and the organic solvent, and drying to obtain a refined 2- (3, 4-dimethyl-1H-pyrazol-1-yl) succinic acid product;
wherein the organic solvent is one or more of dichloromethane, chloroform, 1, 2-dichloroethane, chlorobenzene, toluene, xylene, nitrobenzene, anisole, methyl cyclopentyl ether, methyl tertiary butyl ether, isopropyl ether, ethyl acetate, isopropyl acetate and 2-methyltetrahydrofuran; the DMPSA to be refined comprises a mixture of 2- (3, 4-dimethyl-1H-pyrazol-1-yl) succinic acid and 2- (4, 5-dimethyl-1H-pyrazol-1-yl) succinic acid in a molar ratio of (2-19) to (1).
2. The refining method according to claim 1, wherein the organic solvent is one or more of ethyl acetate, isopropyl acetate, methyl tert-butyl ether, chlorobenzene, toluene.
3. The refining method as recited in claim 1, wherein the DMPSA to be refined further includes a small amount of residue: 3, 4-dimethylpyrazole, maleic acid and fumaric acid.
4. A refining method according to claim 3, characterized in that the DMPSA to be refined is prepared starting from 3, 4-dimethylpyrazole and maleic anhydride.
5. The refining method according to claim 4, wherein the amount of water used in the refining process is 1 to 20 times the mass of 3, 4-dimethylpyrazole based on 3, 4-dimethylpyrazole; the dosage of the organic solvent in the refining process is 1-20 times of the mass of the 3, 4-dimethylpyrazole based on the 3, 4-dimethylpyrazole.
6. The refining method according to claim 1, wherein the water is purified water, distilled water, deionized water or tap water.
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|---|---|---|---|
| CN202311485167.7A CN117551036A (en) | 2023-11-08 | 2023-11-08 | Refining method of 2- (3, 4-dimethyl-1H-pyrazol-1-yl) succinic acid |
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| CN202311485167.7A CN117551036A (en) | 2023-11-08 | 2023-11-08 | Refining method of 2- (3, 4-dimethyl-1H-pyrazol-1-yl) succinic acid |
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| CN202311485167.7A Pending CN117551036A (en) | 2023-11-08 | 2023-11-08 | Refining method of 2- (3, 4-dimethyl-1H-pyrazol-1-yl) succinic acid |
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| Country | Link |
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| CN (1) | CN117551036A (en) |
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- 2023-11-08 CN CN202311485167.7A patent/CN117551036A/en active Pending
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