CN116354850A - Preparation method of fenpropathrin - Google Patents
Preparation method of fenpropathrin Download PDFInfo
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- CN116354850A CN116354850A CN202310286177.1A CN202310286177A CN116354850A CN 116354850 A CN116354850 A CN 116354850A CN 202310286177 A CN202310286177 A CN 202310286177A CN 116354850 A CN116354850 A CN 116354850A
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- fenpropathrin
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- phenoxy
- organic solvent
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- XQUXKZZNEFRCAW-UHFFFAOYSA-N fenpropathrin Chemical compound CC1(C)C(C)(C)C1C(=O)OC(C#N)C1=CC=CC(OC=2C=CC=CC=2)=C1 XQUXKZZNEFRCAW-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- -1 m-phenoxyl-2-oxo-phenylacetaldehyde oxime Chemical compound 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 17
- FZCDBGYCFVKRDV-UHFFFAOYSA-N 1-(3-phenoxyphenyl)ethanone Chemical compound CC(=O)C1=CC=CC(OC=2C=CC=CC=2)=C1 FZCDBGYCFVKRDV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 238000010992 reflux Methods 0.000 claims abstract description 6
- IOGXOCVLYRDXLW-UHFFFAOYSA-N tert-butyl nitrite Chemical group CC(C)(C)ON=O IOGXOCVLYRDXLW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000012414 tert-butyl nitrite Substances 0.000 claims abstract description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 6
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical group FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 claims description 5
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 3
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- OWFXIOWLTKNBAP-UHFFFAOYSA-N isoamyl nitrite Chemical compound CC(C)CCON=O OWFXIOWLTKNBAP-UHFFFAOYSA-N 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 6
- 230000018044 dehydration Effects 0.000 abstract description 4
- 238000006297 dehydration reaction Methods 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 3
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract description 2
- 238000005837 enolization reaction Methods 0.000 abstract description 2
- 239000000543 intermediate Substances 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000004128 high performance liquid chromatography Methods 0.000 description 8
- 239000012074 organic phase Substances 0.000 description 6
- 239000000575 pesticide Substances 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 5
- 238000004537 pulping Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002728 pyrethroid Substances 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- 241000607479 Yersinia pestis Species 0.000 description 3
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 3
- 230000002147 killing effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- DSQFSFBBPSALMS-UHFFFAOYSA-N 2-bromo-2-(3-phenoxyphenyl)acetonitrile Chemical compound N#CC(Br)C1=CC=CC(OC=2C=CC=CC=2)=C1 DSQFSFBBPSALMS-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- GXUQMKBQDGPMKZ-UHFFFAOYSA-N 2-hydroxy-2-(3-phenoxyphenyl)acetonitrile Chemical compound N#CC(O)C1=CC=CC(OC=2C=CC=CC=2)=C1 GXUQMKBQDGPMKZ-UHFFFAOYSA-N 0.000 description 1
- MRLGCTNJRREZHZ-UHFFFAOYSA-N 3-phenoxybenzaldehyde Chemical compound O=CC1=CC=CC(OC=2C=CC=CC=2)=C1 MRLGCTNJRREZHZ-UHFFFAOYSA-N 0.000 description 1
- 241000238876 Acari Species 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- VXSIXFKKSNGRRO-MXOVTSAMSA-N [(1s)-2-methyl-4-oxo-3-[(2z)-penta-2,4-dienyl]cyclopent-2-en-1-yl] (1r,3r)-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropane-1-carboxylate;[(1s)-2-methyl-4-oxo-3-[(2z)-penta-2,4-dienyl]cyclopent-2-en-1-yl] (1r,3r)-3-[(e)-3-methoxy-2-methyl-3-oxoprop-1-enyl Chemical class CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)O[C@@H]1C(C)=C(C\C=C/C=C)C(=O)C1.CC1(C)[C@H](/C=C(\C)C(=O)OC)[C@H]1C(=O)O[C@@H]1C(C)=C(C\C=C/C=C)C(=O)C1 VXSIXFKKSNGRRO-MXOVTSAMSA-N 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000003169 central nervous system Anatomy 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- DMQSHEKGGUOYJS-UHFFFAOYSA-N n,n,n',n'-tetramethylpropane-1,3-diamine Chemical compound CN(C)CCCN(C)C DMQSHEKGGUOYJS-UHFFFAOYSA-N 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 230000001546 nitrifying effect Effects 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 210000001428 peripheral nervous system Anatomy 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 1
- 229940074439 potassium sodium tartrate Drugs 0.000 description 1
- HYJYGLGUBUDSLJ-UHFFFAOYSA-N pyrethrin Natural products CCC(=O)OC1CC(=C)C2CC3OC3(C)C2C2OC(=O)C(=C)C12 HYJYGLGUBUDSLJ-UHFFFAOYSA-N 0.000 description 1
- 229940070846 pyrethrins Drugs 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
-
- 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
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
- C07C249/06—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes by nitrosation of hydrocarbons or substituted hydrocarbons
-
- 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
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
- C07C249/12—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes by reactions not involving the formation of oxyimino groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Abstract
The invention discloses a preparation method of fenpropathrin, and belongs to the technical field of medical intermediates. The method is characterized in that m-phenoxyacetophenone is used as a raw material, is subjected to enolization under an acidic condition, is substituted with tert-butyl nitrite alpha to obtain m-phenoxyl-2-oxo-phenylacetaldehyde oxime, is subjected to carbonyl reduction to obtain m-phenoxyl-2-hydroxy-phenylacetaldehyde oxime, and is subjected to reflux dehydration with 2, 3-tetramethyl cyclopropane carboxylic acid under the action of a catalyst to obtain fenpropathrin.
Description
Technical Field
The invention relates to a preparation method of fenpropathrin, belonging to the technical field of chemical synthesis in medical intermediates.
Background
Pyrethroid is an important bionic pesticide, is a pesticide product advocated to be popularized by China, wherein fenpropathrin is a pyrethroid pesticide, has strong contact killing, repelling and stomach poisoning effects on pests, has good effects even at low temperature, overcomes the characteristic that other pyrethroid pesticides do not kill mites, has toxicity to people and livestock, and is called a third-generation new pesticide.
Fenpropathrin, CAS:64257-84-7, english name: fenppropatrin, a typical pesticide for pyrethrins. The fenpropathrin has the advantages of low toxicity, wide insecticidal spectrum, small dosage, no residual toxicity, no public hazard, good light stability and special mite killing effect, can be used in farmlands on a large scale, and can also be used for preventing and controlling indoor pests, and the fenpropathrin can block the conduction of stimulus and play a role in rapidly killing the pests through the functions of a central nervous system and a peripheral nervous system, so that the fenpropathrin has good quick acting property.
The difficulty of fenpropathrin is often that cyano is introduced, as in patent US4254050,1981, a, 3-phenoxybenzaldehyde, 2, 6-dimethyl-2, 6-diazaheptane, sodium cyanide and 2, 3-tetramethyl cyclopropane acyl chloride are adopted for one-pot synthesis to prepare fenpropathrin, and the method is convenient to synthesize and operate, but uses sodium cyanide which is a highly toxic product, so that great hidden danger is generated to safety production, and industrial scale production is not facilitated. The reaction equation is as follows:
patent US4061664,1977, a reports that alpha-cyano-3-phenoxybenzyl bromide and 2, 3-tetramethyl cyclopropane carboxylic acid are adopted to synthesize fenpropathrin in potassium carbonate aqueous solution under the action of a phase transfer catalyst, and the method has high cost of raw material alpha-cyano-3-phenoxybenzyl bromide and is not beneficial to large-scale production. The reaction equation is as follows:
the report of the literature [ Journal ofAgricultural and Food Chemistry,1998, vol.46, #6, p.2211-2221] discloses that alpha-cyano-3-phenoxy benzyl alcohol and 2, 3-tetramethyl cyclopropane acyl chloride are reacted to prepare fenpropathrin, the reaction effect is particularly good, but the raw material cost is higher, and the industrial scale production is not favored. The reaction equation is as follows:
aiming at the defects of the method, the synthesis process is necessary to be optimized, the searching process is simpler, more convenient and more effective, the preparation method with low potential safety hazard and higher total yield can be avoided from introducing cyano groups by cyanide, so that the method is suitable for industrial production and meets the increasing market demands.
Disclosure of Invention
In order to overcome the technical defects, the invention discloses a preparation method of fenpropathrin. The method is characterized in that m-phenoxyacetophenone is used as a raw material, is subjected to enolization under an acidic condition, is substituted with tert-butyl nitrite alpha to obtain m-phenoxyl-2-oxo-phenylacetaldehyde oxime, is reduced by using a reducing agent on carbonyl to obtain m-phenoxyl-2-hydroxy-phenylacetaldehyde oxime, and is subjected to reflux dehydration with 2, 3-tetramethyl cyclopropane carboxylic acid under the action of a catalyst to obtain fenpropathrin.
The preparation method of fenpropathrin comprises the following steps:
the first step: mixing m-phenoxy acetophenone, hydrochloric acid and an organic solvent, and adding nitrous acid ester for reaction to obtain m-phenoxy-2-oxo-phenylacetaldehyde oxime;
and a second step of: reacting m-phenoxy-2-oxo-phenylacetaldehyde oxime with a reducing agent in an organic solvent to obtain m-phenoxy-2-hydroxy-phenylacetaldehyde oxime;
and a third step of: and (3) heating, refluxing and water diversion of m-phenoxy-2-hydroxy-phenethyl aldoxime and 2, 3-tetramethyl cyclopropane carboxylic acid in an organic solvent in the presence of a catalyst to obtain fenpropathrin.
Further, in the above technical scheme, in the first step, the organic solvent is selected from tetrahydrofuran or 2-methyltetrahydrofuran, and the hydrochloric acid is selected from 25-36% hydrochloric acid.
Further, in the above technical scheme, in the first step, the nitrite is selected from tert-butyl nitrite or isoamyl nitrite.
Further, in the technical scheme, in the first step, the molar ratio of the m-phenoxyacetophenone, the hydrochloric acid and the nitrous acid ester is 1:0.03-0.05:1.15-1.20.
Further, in the above technical solution, in the second step, the reducing agent is selected from sodium borohydride, potassium borohydride, or aluminum isopropoxide.
Further, in the above technical scheme, in the second step, the molar ratio of the m-phenoxy-2-oxo-phenylacetaldehyde oxime to the reducing agent is 1:1.05-1.20.
Further, in the above technical scheme, in the third step, the catalyst is selected from tris (pentafluorophenyl) borane.
Further, in the above technical scheme, in the third step, the organic solvent is selected from a mixed solvent consisting of 1, 4-dioxane/toluene or 1, 4-dioxane/n-heptane.
Further, in the above technical scheme, in the third step, the molar ratio of the m-phenoxy-2-hydroxyphenylaldoxime, 2, 3-tetramethylcyclopropane carboxylic acid and the catalyst is 1:0.95-1.02:0.01-0.05.
Advantageous effects of the invention
1. The green nitrifying agent nitrite is adopted, so that the activity is high, the price is low, and the compatibility of functional groups is good.
2. The condensation and the dehydration are completed simultaneously by the non-traditional Lewis acid catalyst such as tris (pentafluorophenyl) borane, and the dehydration efficiency is high.
3. The use of the highly toxic potassium cyanide or sodium cyanide is avoided, the complicated certificate-handling purchasing process is omitted, and the potential safety hazard is greatly reduced.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The invention is further illustrated by the following specific examples. These examples should be construed as merely illustrative of the present invention and not limiting the scope of the present invention. Various changes and modifications to the present invention may be made by one skilled in the art after reading the description herein, and such equivalent changes and modifications are intended to fall within the scope of the present invention as defined in the appended claims.
Example 1
Under the protection of nitrogen, 212g (1.0 mol) of m-phenoxyacetophenone, 5g of concentrated hydrochloric acid and 210mL of 2-methyltetrahydrofuran are added into a reaction bottle at room temperature, after being stirred uniformly, the temperature is reduced to 0-5 ℃, 140.6g (1.20 mol) of isoamyl nitrite is added dropwise at the temperature of 0-10 ℃, after the dropwise addition is finished, the temperature is slowly increased to 35-38 ℃ for reaction for 2 hours, and the remainder of HPLC raw materials is sampled<4%, cooling to 0 ℃, adding water for quenching, standing for layering, extracting the water phase with 2-methyltetrahydrofuran, merging the organic phases, concentrating under reduced pressure at 30 ℃ until no-flowing liquid is obtained, adding n-heptane for pulping, and filtering to obtain 196.9g of m-phenoxy-2-oxo-phenylacetaldehyde oxime, wherein the yield is 81.6%. 1 HNMR(400MHz,CDCl 3 ):8.56(s,1H),8.09-7.75(m,8H),7.48(dd,2H).
Example 2
Under the protection of nitrogen, 212g (1.0 mol) of m-phenoxyacetophenone, 5g of concentrated hydrochloric acid and 200mL of tetrahydrofuran are added into a reaction bottle at room temperature, after being stirred uniformly, the temperature is reduced to 0-5 ℃, 118.6g (1.15 mol) of tert-butyl nitrite is added dropwise at the temperature of 0-10 ℃, after the dropwise addition is finished, the temperature is slowly increased to 35-38 ℃ for 2 hours, the residual 3% of the sample HPLC raw material is cooled to 0 ℃, water quenching is added, methyl tert-butyl ether is added, standing and layering are carried out, the aqueous phase is extracted by methyl tert-butyl ether, the organic phases are combined, the mixture is concentrated to no-flow liquid at 30 ℃ under reduced pressure, n-heptane is added for beating, and the m-phenoxyl-2-oxo-phenylacetaldehyde oxime 203.4g is obtained after filtration, HPLC 99.4% and the yield is 84.3%.
Example 3
In a reaction flask, 48.3g (0.2 mol) of m-phenoxy-2-oxo-phenylacetaldehyde oxime and 300mL of isopropyl alcohol were dissolved under stirring under nitrogen, and then 49g (0.24 mol) of aluminum isopropoxide/240 mL of toluene mixed solution was added dropwise. After the dripping is finished, the temperature is raised to 50-55 ℃ for reaction for 4 hours, then the temperature is reduced to 0 ℃, 8% potassium sodium tartrate aqueous solution is added for quenching, standing and layering are carried out, isopropanol is removed by distillation, aqueous phase dichloromethane extraction is carried out, organic phases are combined, saturated saline water is used for washing, the organic phases are decompressed and concentrated to no-flow liquid, n-heptane is added for hot pulping purification, and thus 41.6g of m-phenoxy-2-hydroxyphenylglyoxime is obtained, HPLC (high performance liquid chromatography) 97.8% and the yield is 85.5%. 1 HNMR(400MHz,CDCl 3 ):10.98(s,1H),7.76-7.24(m,10H),6.79(dd,2H).
Example 4
Under the protection of nitrogen, 48.3g (0.2 mol) of M-phenoxy-2-oxo-phenylacetaldehyde oxime and 350mL of tetrahydrofuran are added into a reaction bottle to be mixed, the temperature is reduced to 0 ℃, 7.9g (0.21 mol) of sodium borohydride is added in batches, then the reaction is carried out for 1.5 hours at room temperature, 0.5M hydrochloric acid is added for quenching, methyl tertiary butyl ether is added for extraction, standing and layering are carried out, an organic phase is reserved, a water phase is extracted by methylene dichloride, an organic phase is combined, reduced pressure concentration is carried out, normal heptane is added, hot pulping and purification are carried out, and 44.1g of M-phenoxy-2-hydroxy-phenylacetaldehyde oxime is obtained, HPLC 96.1% and the yield is 90.6%.
Example 5
Into the reaction flask, 24.3g (0.1 mol) of m-phenoxy-2-hydroxyphenylglyoxime, 13.9g (0.098 mol) of 2, 3-tetramethylcyclopropanecarboxylic acid, 2.6g (0.005 mol) of tris (pentafluorophenyl) borane, 100mL of 1, 4-dioxane and 130mL of toluene were added and mixed, and the mixture was heated to 60℃to react for 1 hourAnd then continuously heating to reflux and water diversion for 7 hours, reducing the temperature, concentrating under reduced pressure and distilling until the mass is 3.0-3.5 times that of the residual, adding n-heptane, pulping and purifying to obtain 31.9g of fenpropathrin, the yield is 91.2%, and the HPLC is 99.8%. 1 HNMR(400MHz,CDCl 3 ):7.42-7.01(m,9H),6.36(s,1H),1.27(s,3H),1.26(s,1H),1.22(s,3H),1.21(s,3H),1.18(s,3H).
Example 6
To the reaction flask, 24.3g (0.1 mol) of m-phenoxy-2-hydroxyphenylglyoxime, 13.9g (0.098 mol) of 2, 3-tetramethyl cyclopropanecarboxylic acid, 2.6g (0.005 mol) of tris (pentafluorophenyl) borane, 140mL of 1, 4-dioxane and 140mL of n-heptane were added and mixed, the temperature was raised to 60℃for reaction for 1 hour, then the mixture was continuously raised to reflux and water separation for 10 hours, the mixture was cooled, concentrated under reduced pressure and distilled to 3.5 to 4.0 times the mass, and 32g of fenpropathrin was obtained by pulping and purifying with n-heptane, the yield was 91.6%, and HPLC was 99.4%.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should be covered by the protection scope of the present invention by making equivalents and modifications to the technical solution and the inventive concept thereof.
Claims (9)
1. The preparation method of fenpropathrin is characterized by comprising the following steps:
the first step: mixing m-phenoxy acetophenone, hydrochloric acid and an organic solvent, and adding nitrous acid ester for reaction to obtain m-phenoxy-2-oxo-phenylacetaldehyde oxime;
and a second step of: reacting m-phenoxy-2-oxo-phenylacetaldehyde oxime with a reducing agent in an organic solvent to obtain m-phenoxy-2-hydroxy-phenylacetaldehyde oxime;
and a third step of: and (3) heating, refluxing and water diversion of m-phenoxy-2-hydroxy-phenethyl aldoxime and 2, 3-tetramethyl cyclopropane carboxylic acid in an organic solvent in the presence of a catalyst to obtain fenpropathrin.
2. The process for the preparation of fenpropathrin according to claim 1, wherein: in the first step, the organic solvent is selected from tetrahydrofuran or 2-methyltetrahydrofuran, and the hydrochloric acid is selected from 25-36% hydrochloric acid.
3. The process for the preparation of fenpropathrin according to claim 1, wherein: in the first step, the nitrite is selected from tert-butyl nitrite or isoamyl nitrite.
4. The process for the preparation of fenpropathrin according to claim 1, wherein: in the first step, the molar ratio of the m-phenoxyacetophenone, the hydrochloric acid and the nitrous acid ester is 1:0.03-0.05:1.15-1.20.
5. The process for the preparation of fenpropathrin according to claim 1, wherein: in the second step, the reducing agent is selected from sodium borohydride, potassium borohydride or aluminum isopropoxide.
6. The process for the preparation of fenpropathrin according to claim 1, wherein: in the second step, the molar ratio of the m-phenoxy-2-oxo-phenylacetaldehyde oxime to the reducing agent is 1:1.05-1.20.
7. The process for the preparation of fenpropathrin according to claim 1, wherein: in a third step, the catalyst is selected from tris (pentafluorophenyl) borane.
8. The process for the preparation of fenpropathrin according to claim 1, wherein: in the third step, the organic solvent is selected from a mixed solvent consisting of 1, 4-dioxane/toluene or 1, 4-dioxane/n-heptane.
9. The process for the preparation of fenpropathrin according to claim 1, wherein: in the third step, the molar ratio of the m-phenoxy-2-hydroxy-phenethyl aldoxime to the 2, 3-tetramethyl cyclopropane carboxylic acid to the catalyst is 1:0.95-1.02:0.01-0.05.
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Citations (4)
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|---|---|---|---|---|
| US3835176A (en) * | 1971-06-29 | 1974-09-10 | Sumitomo Chemical Co | Alpha-cyanobenzyl cyclopropanecarboxylates |
| JPH093029A (en) * | 1995-06-21 | 1997-01-07 | Sumitomo Chem Co Ltd | Production of alpha-cyanobenzyl ester derivative |
| CN1357538A (en) * | 2000-12-06 | 2002-07-10 | 南开大学 | Prepn. of fenpropathrin |
| CN104513178A (en) * | 2013-09-29 | 2015-04-15 | 青岛好利特生物农药有限公司 | Fenpropathrin preparation method |
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| US3835176A (en) * | 1971-06-29 | 1974-09-10 | Sumitomo Chemical Co | Alpha-cyanobenzyl cyclopropanecarboxylates |
| JPH093029A (en) * | 1995-06-21 | 1997-01-07 | Sumitomo Chem Co Ltd | Production of alpha-cyanobenzyl ester derivative |
| CN1357538A (en) * | 2000-12-06 | 2002-07-10 | 南开大学 | Prepn. of fenpropathrin |
| CN104513178A (en) * | 2013-09-29 | 2015-04-15 | 青岛好利特生物农药有限公司 | Fenpropathrin preparation method |
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