CN115650929A - Isoxazoline-containing ester compound, preparation method and application - Google Patents
Isoxazoline-containing ester compound, preparation method and application Download PDFInfo
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- CN115650929A CN115650929A CN202211404419.4A CN202211404419A CN115650929A CN 115650929 A CN115650929 A CN 115650929A CN 202211404419 A CN202211404419 A CN 202211404419A CN 115650929 A CN115650929 A CN 115650929A
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- isoxazoline
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- -1 ester compound Chemical class 0.000 title claims abstract description 73
- WEQPBCSPRXFQQS-UHFFFAOYSA-N 4,5-dihydro-1,2-oxazole Chemical compound C1CC=NO1 WEQPBCSPRXFQQS-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 75
- 239000002917 insecticide Substances 0.000 claims abstract description 14
- 241000253994 Acyrthosiphon pisum Species 0.000 claims abstract description 8
- 241000500437 Plutella xylostella Species 0.000 claims abstract description 7
- 241001477931 Mythimna unipuncta Species 0.000 claims abstract description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 30
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 28
- 125000006710 (C2-C12) alkenyl group Chemical group 0.000 claims description 26
- 125000006711 (C2-C12) alkynyl group Chemical group 0.000 claims description 26
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 claims description 25
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 20
- 125000000623 heterocyclic group Chemical group 0.000 claims description 19
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 14
- 238000006467 substitution reaction Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 claims description 12
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 12
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 12
- 229910052736 halogen Inorganic materials 0.000 claims description 11
- 150000002367 halogens Chemical class 0.000 claims description 11
- 125000001424 substituent group Chemical group 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 150000001555 benzenes Chemical group 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 claims description 3
- ACBQROXDOHKANW-UHFFFAOYSA-N bis(4-nitrophenyl) carbonate Chemical compound C1=CC([N+](=O)[O-])=CC=C1OC(=O)OC1=CC=C([N+]([O-])=O)C=C1 ACBQROXDOHKANW-UHFFFAOYSA-N 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 4
- 241001477928 Mythimna Species 0.000 claims 1
- 241000219843 Pisum Species 0.000 claims 1
- 241000009298 Trigla lyra Species 0.000 claims 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims 1
- 241000238631 Hexapoda Species 0.000 abstract description 19
- 230000000749 insecticidal effect Effects 0.000 abstract description 13
- 241000607479 Yersinia pestis Species 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 5
- 150000002148 esters Chemical group 0.000 abstract description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical group [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 abstract description 5
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical group NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 abstract description 3
- 230000004071 biological effect Effects 0.000 abstract description 3
- 125000003971 isoxazolinyl group Chemical group 0.000 abstract description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 35
- 238000002844 melting Methods 0.000 description 35
- 230000008018 melting Effects 0.000 description 35
- 239000007787 solid Substances 0.000 description 32
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- 238000001228 spectrum Methods 0.000 description 11
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 150000002431 hydrogen Chemical class 0.000 description 8
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 8
- 229920000053 polysorbate 80 Polymers 0.000 description 8
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 6
- 239000003814 drug Substances 0.000 description 6
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- 235000002098 Vicia faba var. major Nutrition 0.000 description 4
- 102000005915 GABA Receptors Human genes 0.000 description 3
- 108010005551 GABA Receptors Proteins 0.000 description 3
- 241000409991 Mythimna separata Species 0.000 description 3
- MLBZKOGAMRTSKP-UHFFFAOYSA-N fluralaner Chemical compound C1=C(C(=O)NCC(=O)NCC(F)(F)F)C(C)=CC(C=2CC(ON=2)(C=2C=C(Cl)C=C(Cl)C=2)C(F)(F)F)=C1 MLBZKOGAMRTSKP-UHFFFAOYSA-N 0.000 description 3
- 229960004498 fluralaner Drugs 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- FLEFKKUZMDEUIP-QFIPXVFZSA-N 1-[6-[(5s)-5-(3,5-dichloro-4-fluorophenyl)-5-(trifluoromethyl)-4h-1,2-oxazol-3-yl]spiro[1h-2-benzofuran-3,3'-azetidine]-1'-yl]-2-methylsulfonylethanone Chemical compound C1N(C(=O)CS(=O)(=O)C)CC21C1=CC=C(C=3C[C@](ON=3)(C=3C=C(Cl)C(F)=C(Cl)C=3)C(F)(F)F)C=C1CO2 FLEFKKUZMDEUIP-QFIPXVFZSA-N 0.000 description 2
- LULAYUGMBFYYEX-UHFFFAOYSA-N 3-chlorobenzoic acid Chemical compound OC(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-N 0.000 description 2
- 102000012440 Acetylcholinesterase Human genes 0.000 description 2
- 108010022752 Acetylcholinesterase Proteins 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical class N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229940022698 acetylcholinesterase Drugs 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 150000002547 isoxazolines Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 2
- MIRAITXRURDOHX-UHFFFAOYSA-N phenyl 2-chlorobenzenesulfonate Chemical compound ClC1=CC=CC=C1S(=O)(=O)OC1=CC=CC=C1 MIRAITXRURDOHX-UHFFFAOYSA-N 0.000 description 2
- XOIJDIYJCTXRQR-UHFFFAOYSA-N phenyl n,n-diethylcarbamate Chemical compound CCN(CC)C(=O)OC1=CC=CC=C1 XOIJDIYJCTXRQR-UHFFFAOYSA-N 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229960005393 sarolaner Drugs 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- NUUBIXUITNNERY-UHFFFAOYSA-N 1,1,1-trifluoropropane-2-sulfonyl chloride Chemical compound FC(F)(F)C(C)S(Cl)(=O)=O NUUBIXUITNNERY-UHFFFAOYSA-N 0.000 description 1
- AFPHTEQTJZKQAQ-UHFFFAOYSA-N 3-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC([N+]([O-])=O)=C1 AFPHTEQTJZKQAQ-UHFFFAOYSA-N 0.000 description 1
- DENKGPBHLYFNGK-UHFFFAOYSA-N 4-bromobenzoyl chloride Chemical compound ClC(=O)C1=CC=C(Br)C=C1 DENKGPBHLYFNGK-UHFFFAOYSA-N 0.000 description 1
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 1
- 241001124076 Aphididae Species 0.000 description 1
- 240000007124 Brassica oleracea Species 0.000 description 1
- 235000003899 Brassica oleracea var acephala Nutrition 0.000 description 1
- 235000011301 Brassica oleracea var capitata Nutrition 0.000 description 1
- 235000001169 Brassica oleracea var oleracea Nutrition 0.000 description 1
- 108010062745 Chloride Channels Proteins 0.000 description 1
- 102000011045 Chloride Channels Human genes 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 206010021033 Hypomenorrhoea Diseases 0.000 description 1
- 102000016913 Voltage-Gated Sodium Channels Human genes 0.000 description 1
- 108010053752 Voltage-Gated Sodium Channels Proteins 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000005557 antagonist Substances 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 150000001559 benzoic acids Chemical class 0.000 description 1
- 239000000073 carbamate insecticide Substances 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
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- 125000005843 halogen group Chemical group 0.000 description 1
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- 230000003020 moisturizing effect Effects 0.000 description 1
- VIJMMQUAJQEELS-UHFFFAOYSA-N n,n-bis(ethenyl)ethenamine Chemical compound C=CN(C=C)C=C VIJMMQUAJQEELS-UHFFFAOYSA-N 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 230000001537 neural effect Effects 0.000 description 1
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- 230000000361 pesticidal effect Effects 0.000 description 1
- 239000002728 pyrethroid Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000003607 serino group Chemical group [H]N([H])[C@]([H])(C(=O)[*])C(O[H])([H])[H] 0.000 description 1
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- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
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- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
The invention discloses an ester compound containing isoxazoline, a preparation method and application. The invention introduces active groups such as ester, sulfonate, carbamate and the like with excellent biological activity into an isoxazoline structure to obtain a compound with a novel structure. The structure of the compound is shown as formula I:
Description
Technical Field
The invention belongs to the technical field of agricultural pest control, and particularly relates to an isoxazoline-containing ester compound, and a preparation method and application thereof.
Background
The traditional chemical pesticide is limited or prohibited due to the problems of high residue, high resistance, high toxicity and the like. How to develop products with high activity, high selectivity, low risk and low residue has become the development direction of green pesticides. New non-competitive antagonists of GABA receptors, isoxazolines, such as Fluralaner, afoxalaner, sarolaner, fluxamide, etc., that may act on the TM1 and TM3 regions of GABA receptors have been reported in recent years (Vet Parasitol,2014,201,179, institute Biochem Mol biol, 2014,45, 111.
The isoxazoline pesticide acts on a GABA receptor chloride ion channel and shows obvious biological activity on agricultural pests and sanitary pests. Fluralaner is used as a classical isoxazoline insecticide, and the development system, the development process and the development mode thereof provide conditions for the successful design and development of the isoxazoline insecticides such as Afoxalaner, sarolaner and Fluxamide. Wherein, 5-trifluoromethyl-3-phenyl-5-substituted phenyl isoxazoline is an isoxazoline insecticide core active structure and is worthy of further research on the derivation thereof. Lahm et al, duPont, USA, reports the insecticidal activity of a series of isoxazoline-containing ester compounds that are structurally similar to Fluralaner (Bioorg Med Chem Lett,2013,23, 3001).
It is well known that carbamates, esters and sulfonates capable of hydrogen bonding are active groups commonly used in pesticides due to their respective advantages. Carbamate insecticides (e.g., meta-tolyl-methylcarbamate) inhibit acetylcholinesterase (AChE) in the insect nervous system by covalently carbamylating serine residues within the insecticidal active site. Many ester insecticides, such as pyrethroid insecticides, bind to voltage-gated sodium channels and alter their gating kinetics, thereby disrupting neural function (pesticide Sci,2008,33, 371). Most of sulfone compounds have excellent biological activity, particularly in the field of pesticides, such as excellent insecticidal activity and antifungal activity, in order to find a novel agricultural pesticide, the inventor introduces active group fragments commonly used in carbamate, ester and sulfonate pesticides capable of forming hydrogen bonds into an isoxazoline core structure to obtain compounds with novel structures shown in formula I, and finds that the compounds have good effect of preventing and controlling plant pests. At present, no report that carbamate, ester and sulfonate are introduced into an isoxazoline core structure exists, and therefore, the invention discloses an isoxazoline-containing ester compound with a novel structure and application of the isoxazoline-containing ester compound as an agricultural pesticide.
Disclosure of Invention
The invention aims to provide an ester compound containing isoxazoline, a preparation method and application.
An ester compound containing isoxazoline is a compound shown as a formula I;
in the formula: a. The 1 One of substituted or unsubstituted benzene ring, nitrogen-containing heterocycle and oxygen-containing heterocycle is selected, the substitution mode is mono-substituted or polysubstituted, and the substituent is as follows: one of hydrogen, C1-C12 alkyl, halogenated C1-C12 alkyl, C1-C12 alkoxy, halogenated C1-C12 alkoxy, C3-C12 cycloalkyl, C1-C12 alkylthio, C2-C12 alkenyl, C2-C12 alkenylthio, halogenated C2-C12 alkenyl, C2-C12 alkynyl, halogenated C2-C12 alkynyl, halogen, cyano, nitro and benzyloxy.
R 1 One selected from the group consisting of hydrogen, C1-C12 alkyl, halogenated C1-C12 alkyl, C1-C12 alkoxy, halogenated C1-C12 alkoxy, C3-C12 cycloalkyl, C1-C12 alkylthio, C2-C12 alkenyl, C2-C12 alkenylthio, halogenated C2-C12 alkenyl, C2-C12 alkynyl, halogenated C2-C12 alkynyl, halogen, cyano, nitro and benzyloxy;
A 2 is one of substituted or unsubstituted benzene ring, nitrogen-containing heterocycle, oxygen-containing heterocycle and sulfur-containing heterocycle, the substitution mode is single substitution or polysubstitution, and the stituent is selected from hydrogen, C1-C12 alkyl, halogenated C1-C12 alkyl, C1-C12 alkoxy, halogenated C1-C12 alkoxy, C3-C12 cycloalkyl, C1-C12 alkylthio, C2-C12 alkenyl, C2-C12 alkenylthioOne of a group, a halogenated C2-C12 alkenyl group, a C2-C12 alkynyl group, a halogenated C2-C12 alkynyl group, a halogen group, a cyano group, a nitro group and a benzyloxy group;
x is C or S;
n is 1 or 2;
R 2 one selected from the group consisting of C1-C12 alkyl, haloC 1-C12 alkyl, C1-C12 alkoxy, haloC 1-C12 alkoxy, C3-C12 cycloalkyl, haloC 3-C12 cycloalkyl, C1-C12 alkylthio, C2-C12 alkenyl, C2-C12 alkenylthio, haloC 2-C12 alkenyl, C2-C12 alkynyl, haloC 2-C12 alkynyl, C1-C12 alkylamino, haloC 1-C12 alkylamino, C1-C12 alkylaminocarbonyl, C1-C12 alkylsulfonyl, C1-C12 alkylsulfinyl, haloC 1-C12 alkylsulfonyl, C1-C12 alkylaminosulfonyl, di (C1-C12 alkyl) aminosulfonyl, acetyl, and formyl;
or, R 2 One of unsubstituted or substituted benzene ring, nitrogen-containing heterocycle, oxygen-containing heterocycle and sulfur-containing heterocycle is selected, the substitution mode is mono-substituted or polysubstituted, and the substituent is as follows: one of hydrogen, C1-C12 alkyl, halogenated C1-C12 alkyl, C1-C12 alkoxy, halogenated C1-C12 alkoxy, C3-C12 cycloalkyl, C1-C12 alkylthio, C2-C12 alkenyl, C2-C12 alkenylthio, halogenated C2-C12 alkenyl, C2-C12 alkynyl, halogenated C2-C12 alkynyl, acetyl, formyl, halogen, cyano, nitro and benzyloxy.
An ester compound containing isoxazoline is a compound shown as a formula I;
specific substituents in formula i are shown in the following table:
the preparation method of the ester compound containing the isoxazoline is characterized in that the ester compound containing the isoxazoline is the ester compound containing the isoxazoline;
the method comprises the following steps: reacting a compound shown in a formula II with a compound shown in a formula III or a compound shown in a formula IV in an organic solvent to obtain a compound shown in a formula I:
optionally, an additive is mixed into the organic solvent, the additive is selected from one or more of triethylamine, pyridine, dicyclohexylcarbodiimide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide, 4-dimethylaminopyridine and bis (4-nitrophenyl) carbonate, and the organic solvent is selected from one of dichloromethane, toluene, ethyl acetate and tetrahydrofuran.
Optionally, the reaction temperature of the reaction is 0-55 ℃, and the reaction time is 5 min-24 h.
Optionally, the molar ratio of the compound shown in the formula III to the compound shown in the formula II is 1 (0.5-1.5); the molar ratio of the compound shown in the formula IV to the compound shown in the formula II is 1 (0.5-1.5).
The use of an isoxazoline-containing ester compound according to any one of the present invention or an isoxazoline-containing ester compound produced by the method for producing an isoxazoline-containing ester compound according to any one of the present invention for producing an insecticide.
Optionally, the pesticide is used for preventing and treating wigglers, armyworms, pea aphids or diamond back moths.
An insecticide containing an isoxazoline-containing ester compound according to any one of the present invention or an isoxazoline-containing ester compound produced by the method for producing an isoxazoline-containing ester compound according to any one of the present invention.
Optionally, the pesticide is used for controlling diamondback moth, armyworm, pea aphid or wiggler.
The invention has the beneficial effects that:
the isoxazoline-containing ester compound disclosed by the invention has a novel structure, has broad-spectrum insecticidal activity, and particularly has an obvious insecticidal effect on pea aphids, armyworms, diamond back moths and wigglers.
Drawings
The accompanying drawings, which are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosure and together with the description serve to explain the disclosure without limiting the disclosure. In the drawings:
FIG. 1 is a hydrogen spectrum of compound I-01 of the present invention;
FIG. 2 is a carbon spectrum of Compound I-01 of the present invention;
FIG. 3 is a hydrogen spectrum of compound I-18 of the present invention;
FIG. 4 is a hydrogen spectrum of compound I-31 of the present invention.
Detailed Description
The present invention will be further described with reference to the following specific examples, but the present invention is not limited to these examples. The methods are conventional methods unless otherwise specified. The materials are commercially available from the open literature unless otherwise specified.
The invention discloses an ester compound containing isoxazoline, which is a compound shown in a formula I;
in the formula: a. The 1 One of substituted or unsubstituted benzene ring, nitrogen-containing heterocycle and oxygen-containing heterocycle is selected, the substitution mode is monosubstituted or polysubstituted, and the substituent is: one of hydrogen, C1-C12 alkyl, halogenated C1-C12 alkyl, C1-C12 alkoxy, halogenated C1-C12 alkoxy, C3-C12 cycloalkyl, C1-C12 alkylthio, C2-C12 alkenyl, C2-C12 alkenylthio, halogenated C2-C12 alkenyl, C2-C12 alkynyl, halogenated C2-C12 alkynyl, halogen, cyano, nitro and benzyloxy.
R 1 Selected from the group consisting of hydrogen, C1-C12 alkyl, haloC 1-C12 alkyl, C1-C12 alkoxy, haloC 1-C12 alkoxy, C3-C12 ringOne of alkyl, C1-C12 alkylthio, C2-C12 alkenyl, C2-C12 alkenylthio, halogenated C2-C12 alkenyl, C2-C12 alkynyl, halogenated C2-C12 alkynyl, halogen, cyano, nitro and benzyloxy;
A 2 the substituted heterocyclic ring is one of substituted or unsubstituted benzene ring, nitrogen-containing heterocyclic ring, oxygen-containing heterocyclic ring and sulfur-containing heterocyclic ring, the substitution mode is single substitution or multiple substitution, and the substituent is selected from one of hydrogen, C1-C12 alkyl, halogenated C1-C12 alkyl, C1-C12 alkoxy, halogenated C1-C12 alkoxy, C3-C12 cycloalkyl, C1-C12 alkylthio, C2-C12 alkenyl, C2-C12 alkenylthio, halogenated C2-C12 alkenyl, C2-C12 alkynyl, halogenated C2-C12 alkynyl, halogen, cyano, nitro and benzyloxy;
x is C or S;
n is 1 or 2;
R 2 one selected from the group consisting of C1-C12 alkyl, haloC 1-C12 alkyl, C1-C12 alkoxy, haloC 1-C12 alkoxy, C3-C12 cycloalkyl, haloC 3-C12 cycloalkyl, C1-C12 alkylthio, C2-C12 alkenyl, C2-C12 alkenylthio, haloC 2-C12 alkenyl, C2-C12 alkynyl, haloC 2-C12 alkynyl, C1-C12 alkylamino, haloC 1-C12 alkylamino, C1-C12 alkylaminocarbonyl, C1-C12 alkylsulfonyl, C1-C12 alkylsulfinyl, haloC 1-C12 alkylsulfonyl, C1-C12 alkylaminosulfonyl, di (C1-C12 alkyl) aminosulfonyl, acetyl, and formyl.
Or, R 2 One selected from unsubstituted or substituted benzene rings, nitrogen-containing heterocycles, oxygen-containing heterocycles, and sulfur-containing heterocycles. The substitution mode is mono-substituted or multi-substituted, and the substituent groups are as follows: one of hydrogen, C1-C12 alkyl, halogenated C1-C12 alkyl, C1-C12 alkoxy, halogenated C1-C12 alkoxy, C3-C12 cycloalkyl, C1-C12 alkylthio, C2-C12 alkenyl, C2-C12 alkenylthio, halogenated C2-C12 alkenyl, C2-C12 alkynyl, halogenated C2-C12 alkynyl, acetyl, formyl, halogen, cyano, nitro and benzyloxy.
In more detail, see table 1 for data:
TABLE 1
The reagent ratios used are volume ratios unless otherwise specified below.
Example 1: preparation of 4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) phenyl-ethyl sulfonate (I-01):
in a 25mL single neck flask was added 1.88g (5 mmol) of 4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) phenol, 0.66g (6.5 mmol) of triethylamine and 20mL of dichloromethane, 0.66g (6 mmol) of ethanesulfonic acid, 1.9g (10 mmol) of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide and 6mg (0.25 mmol) of 4-dimethylaminopyridine, the reaction was stirred at room temperature for 24h, purified by column chromatography (petroleum ether: ethyl acetate = 8) and dried to give 1.25g of a white solid, yield 54%, melting point: 109.2-110.8 ℃ of the total weight, 1 HNMR(500MHz,Chloroform-d)δ7.71(d,J＝8.8Hz,2H),7.50(s,2H),7.43(s,1H),7.35(d,J＝8.8Hz,2H),4.07(d,J＝17.1Hz,1H),3.69(d,J＝17.2Hz,1H),3.32(q,J＝7.4Hz,2H),1.55(t,J＝7.4Hz,3H). 13 C NMR(126MHz,CDCl 3 ) δ 155.06,150.79,138.91,135.67,129.83,128.68,126.66,125.31,122.68,87.41 (q, J =30.4 Hz), 45.66,44.02,8.26. Specific hydrogen spectra and carbon spectra are detailed in figures 1 and 2.
Example 2: preparation of 4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) phenyl-trifluoromethyl-ethyl sulfonate (I-02):
a25 ml single-neck flask was charged with 1.87g (5 mmol) of 4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) phenol, and triethyleneAmine 0.66g (6.5 mmol) and 15mL dichloromethane, then under ice-bath conditions (0 ℃), to which is added dropwise a solution of trifluoromethyl-ethylsulfonyl chloride 1.18g (6 mmol) in 5mL dichloromethane, after which the reaction is stirred at room temperature for 24h, purified by column chromatography (petroleum ether: ethyl acetate = 8), dried to give 0.80g of a white solid, yield 30%, melting point: 99.0-99.8 ℃. 1 HNMR(500MHz,Chloroform-d)δ7.79(d,J＝8.8Hz,2H),7.55(s,2H),7.48(s,1H),7.39(d,J＝8.8Hz,2H),4.12(d,J＝17.2Hz,1H),3.76(s,1H),3.57(d,J＝8.3Hz,2H),2.92–2.78(m,2H).
The corresponding products I-03 to I-17 can be obtained by the same method as the preparation of the compounds I-01 to I-02, wherein the appearance, yield, melting point and melting point of the compounds are as follows, and only the substituted sulfonic acids are replaced to react with 4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) phenol 1 The HNMR spectra data are shown below.
The compound 4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) phenyl-propyl-1-sulfonate (I-03): white solid, yield 32%, melting point: the temperature of the mixture is between 89.9 and 92.3 ℃, 1 HNMR(500MHz,Chloroform-d)δ7.75(d,J＝8.8Hz,2H),7.55(s,2H),7.47(t,J＝1.9Hz,1H),7.38(s,2H),4.11(d,J＝17.2Hz,1H),3.74(d,J＝17.2Hz,1H),3.46–3.17(m,2H),2.16–1.96(m,2H),1.18(t,J＝7.5Hz,3H).
the compound 4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) phenyl-cyclopropyl sulfonate (I-04): white solid, yield 50%, melting point: the temperature of the mixture is between 123.1 and 124.8 ℃, 1 HNMR(500MHz,Chloroform-d)δ7.75(d,J＝8.8Hz,2H),7.55(s,2H),7.47(s,1H),7.41(d,J＝8.8Hz,2H),4.12(d,J＝17.2Hz,1H),3.74(d,J＝17.3Hz,1H),2.66(ddd,J＝12.8,8.0,4.8Hz,1H),1.32(dt,J＝7.1,3.6Hz,2H),1.19(dd,J＝8.0,2.2Hz,2H).
the compound 4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) phenyl-butyl-1-sulfonate (I-05): yellow solid, yield 45%, melting point: the temperature of the mixture is between 83.5 and 84.9 ℃, 1 HNMR(500MHz,Chloroform-d)δ7.62(d,J＝8.8Hz,2H),7.41(s,2H),7.34(s,1H),7.24(d,J＝8.8Hz,2H),3.98(d,J＝17.2Hz,1H),3.60(d,J＝17.2Hz,1H),3.26–3.04(m,2H),1.87(p,J＝7.7Hz,2H),1.43(q,J＝7.5Hz,2H),0.90(t,J＝7.4Hz,3H).
the compound 4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) phenyl-isobutyl-1-sulfonate (I-06): yellow solid, yield 57%, melting point: the temperature of the mixture is between 81.7 and 82.5 ℃, 1 HNMR(500MHz,Chloroform-d)δ7.75(d,J＝6.7Hz,2H),7.55(s,2H),7.47(s,1H),7.38(d,J＝8.7Hz,2H),4.11(d,J＝17.2Hz,1H),3.73(d,J＝17.2Hz,1H),3.23(d,J＝6.6Hz,2H),2.48(dt,J＝13.5,6.7Hz,1H),1.22(d,J＝6.7Hz,6H).
the compound 4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) phenyl-dimethylsulfamate (I-07): yellow solid, yield 48%, melting point: the temperature of the mixture is between 87.9 and 89.1 ℃, 1 HNMR(500MHz,Chloroform-d)δ7.74(d,J＝8.8Hz,2H),7.56(s,2H),7.47(s,1H),7.39(d,J＝8.8Hz,2H),4.12(d,J＝17.2Hz,1H),3.74(d,J＝17.2Hz,1H),3.04(s,6H).
the compound 4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) phenyl-2-fluorobenzenesulfonate (I-08): yellow solid, yield 42%, melting point: 118.7-119.5 deg.c, 1 HNMR(500MHz,Chloroform-d)δ7.90(dd,J＝8.9,4.9Hz,2H),7.67(d,J＝6.8Hz,2H),7.54(s,2H),7.46(s,1H),7.26(t,J＝8.5Hz,2H),7.12(d,J＝8.8Hz,2H),4.10(d,J＝17.2Hz,1H),3.72(d,J＝17.2Hz,1H).
the compound 4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) phenyl-3-fluorobenzenesulfonate (I-09): yellow solid, yield 40%, melting point: 112.5 to 113.8 ℃, 1 HNMR(500MHz,Chloroform-d)δ7.67–7.62(m,3H),7.60–7.54(m,2H),7.51(s,2H),7.46–7.39(m,2H),7.11(d,J＝8.9Hz,2H),4.08(d,J＝17.2Hz,1H),3.70(d,J＝17.2Hz,1H).
the compound 4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) phenyl-4-fluorobenzenesulfonate (I-10): yellow solid, yield 45%, melting point: the temperature of the mixture is between 82.6 and 83.7 ℃, 1 HNMR(500MHz,Chloroform-d)δ7.89(dd,J＝8.9,4.9Hz,2H),7.66(d,J＝8.8Hz,2H),7.53(s,2H),7.46(s,1H),7.26(t,J＝8.5Hz,2H),7.11(d,J＝8.8Hz,2H),4.10(d,J＝17.2Hz,1H),3.71(d,J＝17.2Hz,1H).
the compound 4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl)Yl) -4, 5-dihydroisoxazol-3-yl) phenyl-2-chlorobenzenesulfonate (I-11): yellow solid, yield 38%, melting point: the temperature of the mixture is between 125.6 and 126.5 ℃, 1 HNMR(500MHz,Chloroform-d)δ7.96(dd,J＝7.9,1.6Hz,1H),7.70–7.60(m,4H),7.52(s,2H),7.47–7.38(m,2H),7.24(d,J＝8.8Hz,2H),4.09(d,J＝17.2Hz,1H),3.71(d,J＝17.3Hz,1H).
the compound 4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) phenyl-3-chlorobenzenesulfonate (I-12): yellow solid, yield 38%, melting point: 113.0-114.1 deg.c, 1 HNMR(500MHz,Chloroform-d)δ7.88(s,1H),7.74(d,J＝6.8Hz,1H),7.67(d,J＝8.8Hz,3H),7.53(d,J＝6.7Hz,3H),7.45(t,J＝2.0Hz,1H),7.12(d,J＝8.7Hz,2H),4.10(d,J＝17.2Hz,1H),3.72(d,J＝17.2Hz,1H).
the compound 4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) phenyl-4-chlorobenzenesulfonate (I-13): white solid, yield 43%, melting point: 135.7-136.5 ℃ of water, 1 HNMR(500MHz,Chloroform-d)δ7.80(d,J＝8.7Hz,2H),7.66(d,J＝8.7Hz,2H),7.58–7.51(m,4H),7.46(d,J＝1.8Hz,1H),7.11(d,J＝8.7Hz,2H),4.10(d,J＝17.2Hz,1H),3.72(d,J＝17.2Hz,1H).
the compound 4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) phenyl-4-cyanobenzenesulfonate (I-14): white solid, yield 53%, melting point: 122.6 to 124.1 ℃ of water, 1 HNMR(500MHz,Chloroform-d)δ7.95(d,J＝8.6Hz,2H),7.84(d,J＝6.7Hz,2H),7.63(d,J＝8.8Hz,2H),7.47(s,2H),7.41(s,1H),7.06(d,J＝8.8Hz,2H),4.05(d,J＝17.2Hz,1H),3.67(d,J＝17.3Hz,1H).
the compound 4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) phenyl-4-methylbenzenesulfonate (I-15): yellow solid, yield 60%, melting point: the temperature of the mixture is between 113.6 and 115.1 ℃, 1 HNMR(500MHz,Chloroform-d)δ7.63(d,J＝8.3Hz,2H),7.53(d,J＝8.8Hz,2H),7.43(s,2H),7.36(s,1H),7.26(d,J＝7.9Hz,2H),6.99(d,J＝8.8Hz,2H),3.99(d,J＝17.2Hz,1H),3.60(d,J＝17.2Hz,1H),2.39(s,2H).
the compound 4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) phenyl-4-methoxybenzenesulfonate (I-16): white solid, yield 56%, melting point: the temperature of the mixed solution is between 129.1 and 130.5 ℃, 1 HNMR(500MHz,Chloroform-d)δ7.64(d,J＝8.9Hz,1H),7.50(d,J＝8.8Hz,1H),7.40(s,1H),7.32(t,J＝1.9Hz,1H),6.96(d,J＝8.7Hz,1H),6.88(d,J＝8.8Hz,1H),3.96(d,J＝17.3Hz,1H),3.79(s,2H),3.58(d,J＝17.2Hz,1H).
the compound 4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) phenyl-thiophene-2-sulfonate (I-17): yellow solid, yield 42%, melting point: 124.1 to 125.5 ℃, 1 HNMR(500MHz,Chloroform-d)δ7.68(d,J＝5.0Hz,1H),7.56(d,J＝8.4Hz,2H),7.53(d,J＝3.8Hz,1H),7.43(s,2H),7.36(s,1H),7.06(d,J＝8.3Hz,3H),3.99(d,J＝17.2Hz,1H),3.60(d,J＝17.2Hz,1H).
example 3: preparation of 4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) phenyl-2-methylbenzoate (I-18):
in a 25mL single neck flask were added 1.87g (5 mmol) of 4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) phenol and 15mL of dichloromethane, added 0.82g (6 mmol) of 2-methylbenzoic acid, 0.66g (6.5 mmol) of triethylamine, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide, 1.9g (10 mmol) and 6mg (0.25 mmol) of 4-dimethylaminopyridine, stirred at room temperature for 24h, column chromatographically purified (petroleum ether: ethyl acetate = 16), dried to give a light yellow oily liquid, yield 36%, 1 HNMR (500mhz, chloroform-d) δ 8.22 (d, J =8.7hz, 1h), 7.78 (d, J =6.8hz, 2h), 7.58 (s, 2H), 7.48 (d, J =3.7hz, 1h), 7.42-7.31 (m, 5H), 4.15 (d, J =17.2hz, 1h), 3.77 (d, J =17.2hz, 1h), 2.73 (s, 3H). The specific hydrogen spectrum is shown in FIG. 3.
Example 4: preparation of 4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) phenyl-3-chlorobenzoate (I-22):
in a 25ml single-mouth bottle1.88g (5 mmol) of 4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) phenol and 15mL of ethyl acetate were added, 0.94g (6 mmol) of 3-chlorobenzoic acid, 0.66g (6.5 mmol) of triethylamine, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide, 1.90g (10 mmol) and 6mg (0.25 mmol) of 4-dimethylaminopyridine were added, the reaction was stirred at room temperature for 24h, column chromatography purification (petroleum ether: ethyl acetate = 16) was performed, and drying was carried out to obtain 0.975g of a pale yellow solid, yield 38%, melting point: the temperature of the mixture is between 128.5 and 130.2 ℃, 1 HNMR(500MHz,Chloroform-d)δ8.22(s,1H),8.13(d,J＝6.5Hz,1H),7.79(d,J＝6.6Hz,2H),7.67(d,J＝8.6Hz,1H),7.57(s,2H),7.52(t,J＝7.9Hz,1H),7.47(s,1H),7.35(d,J＝8.7Hz,2H),4.15(d,J＝17.1Hz,1H),3.77(d,J＝17.2Hz,1H).
example 5: preparation of 4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) phenyl-4-bromobenzoate (I-26).
In a 25mL single-neck flask were charged 1.88g (5 mmol) of 4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) phenol, 0.66g (6.5 mmol) of triethylamine and 15mL of dichloromethane, and then under ice-bath conditions (0 ℃), to this was added dropwise a solution of 1.31g (6 mmol) of 4-bromobenzoyl chloride in 5mL of dichloromethane, which was reacted at room temperature for 30min, stirred at room temperature for 24h, purified by column chromatography (petroleum ether: ethyl acetate = 15): the temperature of the mixture is between 137.4 and 139.7 ℃, 1 HNMR(500MHz,Chloroform-d)δ8.10(d,J＝8.5Hz,2H),7.78(d,J＝8.8Hz,2H),7.71(d,J＝8.5Hz,2H),7.57(s,2H),7.47(s,1H),7.33(d,J＝24.3Hz,2H),4.14(d,J＝17.2Hz,1H),3.76(d,J＝17.2Hz,1H).
example 6: preparation of 4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) phenyl-2-nitrobenzoate (I-27).
At 25m1-one-neck flask was charged with 1.9g (5 mmol) of 4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) phenol and 15mL of toluene, added with 1.0g (6 mmol) of 3-nitrobenzoic acid, 0.66g (6.5 mmol) of triethylamine, 1.2g (6 mmol) of dicyclohexylcarbodiimide and 6mg (0.25 mmol) of 4-dimethylaminopyridine and stirred at room temperature for 24h, purified by column chromatography (petroleum ether: ethyl acetate = 16) and dried to give 0.70g of a light yellow solid, yield 28%, melting point: the temperature of the mixture is between 146.8 and 148.5 ℃, 1 HNMR(500MHz,Chloroform-d)δ8.11(d,J＝9.2Hz,1H),7.93(d,J＝9.2Hz,1H),7.81(dd,J＝18.8,8.8Hz,4H),7.57(s,3H),7.47(s,1H),7.39(d,J＝8.7Hz,2H),4.14(d,J＝17.1Hz,1H),3.76(d,J＝17.2Hz,1H).
according to the same method as the method for preparing the compounds such as the compound I-18 and the like, the corresponding products I-19 to I-21, I-23 to I-25 and I-28 to I-30 can be obtained by only replacing various substituted benzoic acids with 4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) phenol 1 The HNMR spectra data are shown below.
The compound 4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) phenyl-3-methylbenzoate (I-19): pale yellow solid, yield 38%, melting point: 99.5 to 101.3 ℃, 1 HNMR(500MHz,Chloroform-d)δ8.21(d,J＝8.9Hz,1H),7.78(d,J＝8.6Hz,2H),7.57(d,J＝15.6Hz,3H),7.42–7.31(m,4H),4.15(d,J＝17.2Hz,1H),3.77(d,J＝17.1Hz,1H),2.73(s,3H).
the compound 4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) phenyl-4-methylbenzoate (I-20): pale yellow solid, yield 40%, melting point: the temperature of the mixture is between 116.2 and 118.3 ℃, 1 HNMR(500MHz,Chloroform-d)δ8.05(d,J＝5.7Hz,2H),7.78(d,J＝8.7Hz,2H),7.58(s,2H),7.51(d,J＝7.9Hz,1H),7.49–7.44(m,2H),7.36(d,J＝8.7Hz,2H),4.15(d,J＝17.1Hz,1H),3.76(d,J＝17.2Hz,1H),2.49(t,J＝13.9Hz,3H).
the compound 4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) phenyl-2-chlorobenzoate (I-21): pale yellow solid, yield 42%, melting point: the temperature of the mixture is between 91.1 and 92.3 ℃, 1 HNMR(500MHz,Chloroform-d)δ8.09(d,J＝7.8Hz,1H),7.78(d,J＝8.7Hz,2H),7.57(d,J＝3.9Hz,4H),7.51–7.42(m,2H),7.38(d,J＝8.7Hz,2H),4.15(d,J＝17.1Hz,1H),3.77(d,J＝17.2Hz,1H).
the compound 4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) phenyl-4-chlorobenzoate (I-23): pale yellow solid, yield 39%, melting point: 119.8-122.1 ℃ of, 1 HNMR(500MHz,Chloroform-d)δ8.18(d,J＝8.6Hz,2H),7.78(s,2H),7.56(d,J＝7.5Hz,4H),7.48(s,1H),7.40–7.28(m,2H),4.15(d,J＝17.2Hz,1H),3.76(d,J＝17.2Hz,1H).
the compound 4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) phenyl-2-bromobenzoate (I-24): white solid, yield 37%, melting point: the temperature of the mixture is between 102.4 and 104.3 ℃, 1 HNMR(500MHz,Chloroform-d)δ8.06(dd,J＝7.4,2.1Hz,1H),7.79(d,J＝8.8Hz,3H),7.57(s,2H),7.53–7.44(m,3H),7.40(d,J＝8.7Hz,2H),4.15(d,J＝17.1Hz,1H),3.76(d,J＝17.2Hz,1H).
the compound 4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) phenyl-3-bromobenzoate (I-25): white solid, yield 32%, melting point: the temperature of the mixture is between 123.3 and 125.6 ℃, 1 HNMR(500MHz,Chloroform-d)δ8.39(d,J＝14.3Hz,1H),8.17(d,J＝7.8Hz,1H),7.80(dd,J＝22.2,8.5Hz,3H),7.57(s,2H),7.51–7.42(m,2H),7.34(d,J＝9.2Hz,2H),4.15(d,J＝17.1Hz,1H),3.77(d,J＝17.2Hz,1H).
the compound 4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) phenyl-3-nitrobenzoate (I-28): pale yellow solid, yield 20%, melting point: 151.2-152.8 ℃ of the total weight of the mixture, 1 HNMR(500MHz,Chloroform-d)δ9.06(s,1H),8.56(t,J＝7.7Hz,2H),7.81(d,J＝8.2Hz,3H),7.57(s,2H),7.47(s,1H),7.38(d,J＝8.3Hz,2H),4.16(d,J＝17.3Hz,1H),3.78(d,J＝17.2Hz,1H).
the compound 4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) phenyl-4-nitrobenzoate (I-29): pale yellow solid, yield 25%, melting point: 196.7 to 198.8 ℃ of pure natural mineral, 1 HNMR(500MHz,Chloroform-d)δ8.42(s,3H),7.90–7.78(m,2H),7.57(d,J＝3.5Hz,2H),7.49(s,1H),7.39(d,J＝8.8Hz,1H),7.31(s,2H),4.15(d,J＝17.2Hz,1H),3.77(d,J＝17.2Hz,1H).
the compound 4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) phenyl-4-trifluoromethyl benzoate (I-30): white solid, yield 34%, melting point: the temperature of the mixture is between 156.3 and 158.7 ℃, 1 HNMR(500MHz,Chloroform-d)δ8.36(d,J＝8.1Hz,2H),7.82(dd,J＝21.1,8.4Hz,4H),7.58(s,2H),7.47(s,1H),7.37(d,J＝8.4Hz,2H),4.16(d,J＝17.2Hz,1H),3.78(d,J＝17.2Hz,1H).
example 7: preparation of 4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) phenyl-propylcarbamate (I-31):
in a 50ml single-necked flask, 1.88g (5 mmol) of 4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) phenol, 1.8g (NPC, 6 mmol) of bis (4-nitrophenyl) carbonate, 59.86mg (0.5 mmol) of DMAP, and 0.33g (5.5 mmol) of propylamine were charged, and the mixture was stirred at room temperature for 2 to 24 hours. Column chromatography purification (petroleum ether: ethyl acetate = 8): the temperature of the mixed solution is between 103.4 and 105.1 ℃, 1 HNMR (500mhz, chloroform-d) δ 7.69 (d, J =8.7hz, 2h), 7.56 (s, 2H), 7.47 (s, 1H), 7.25 (d, J =8.7hz, 2h), 4.11 (d, J =17.2hz, 1h), 3.73 (d, J =17.2hz, 1h), 3.29 (q, J =7.0hz, 2h), 1.65 (q, J =7.3hz, 2h), 1.02 (t, J =7.5hz, 3h). The hydrogen spectrum is shown in detail in FIG. 4.
The corresponding products I-32 to I-35 can be obtained by following the same method as the preparation of the compound I-31 and only replacing the substituted ammonia with 4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) phenol, and the appearance, yield, melting point and content of the compound 1 The HNMR spectra data are shown below.
The compound 4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) phenyl-diisopropylcarbamate (I-32): white solid, yield 38%, melting point: 99.9-102.3 ℃ of the total weight of the mixture, 1 HNMR(500MHz,Chloroform-d)δ8.09(s,2H),7.49(d,J＝8.8Hz,1H),7.34(s,1H),7.13(d,J＝9.2Hz,2H),7.04(d,J＝8.8Hz,1H),3.87(dd,J＝28.7,16.3Hz,4H),1.15(s,12H).
the compound 4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) phenyl-cyclohexanecarbamate (I-33): white solid, yield 45%, melting point: 135.4-136.5 ℃ of water, 1 HNMR(500MHz,Chloroform-d)δ7.69(d,J＝8.4Hz,2H),7.55(s,2H),7.47(s,1H),7.25(d,J＝8.6Hz,2H),4.11(d,J＝17.2Hz,1H),3.73(d,J＝17.2Hz,1H),3.65–3.54(m,1H),1.79(dd,J＝9.6,4.3Hz,2H),1.72–1.60(m,2H),1.48–1.36(m,2H),1.35–1.20(m,4H).
the compound 4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) phenyl-diethyl carbamate (I-34): white solid, yield 44%, melting point: 114.3-115.6 ℃ of the total weight, 1 HNMR(500MHz,Chloroform-d)δ7.69(d,J＝8.7Hz,2H),7.56(s,2H),7.46(s,1H),7.25(d,J＝8.7Hz,2H),4.11(d,J＝17.1Hz,1H),3.73(d,J＝17.2Hz,1H),3.61–3.31(m,4H),1.28(dt,J＝23.7,6.2Hz,6H).
compound 4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) phenyl-buta rbamate (I-35) is a white solid in 52% yield, melting point: the temperature of the mixture is between 96.7 and 97.3 ℃, 1 HNMR(500MHz,Chloroform-d)δ7.68(d,J＝8.5Hz,2H),7.55(s,2H),7.46(s,1H),7.24(d,J＝8.6Hz,2H),4.11(d,J＝17.1Hz,1H),3.72(d,J＝17.3Hz,1H),3.32(q,J＝6.9Hz,2H),1.62(q,J＝7.3Hz,2H),1.44(q,J＝7.4Hz,2H),1.00(t,J＝7.3Hz,3H).
example 8: insecticidal activity of compound against 4 kinds of pests
The insecticidal activity test of the compound of the formula I selects various healthy and consistently-aged pests such as pea aphids, diamond back moths, sticky insects, wigglers and the like as test insects, and is provided by the research center of biological pesticide engineering technology in Shaanxi province. The indoor activity test is carried out by adopting methods such as a spraying method and the like, and the method comprises the following steps:
according to the agricultural industry standard, the synthesized compound is dissolved in a small amount of acetone, and a 200 mu g/mL medicament is prepared by using a 1 per mill tween-80 aqueous solution for later use. Preparing broad bean leaves with the same size, wrapping petioles of the broad bean leaves with absorbent cotton dipped in water for moisturizing, and putting the broad bean leaves into a culture dish with filter paper and the diameter of 9 cm. And taking another empty culture dish with the diameter of 9cm, picking at least 30 heads of the pea aphids by using a small writing brush, placing the culture dish under a Potter spray tower for 1mL of spraying liquid, settling for 5s, and taking out the culture dish. And inoculating the processed aphids into a culture dish with broad bean leaves. Repeating the treatment for 3 times, using a water solvent treatment containing 1 per thousand of Tween-80 as a control, placing the treated product in a constant-temperature illumination incubator with the temperature of 25 +/-1 ℃, the relative humidity of 80% +/-5% and the light cycle of L/D =16/8h for culture, checking treated test insects after 72h treatment, counting the death number of each treatment by touching the treated test insects with a writing brush, calculating the death rate and correcting the death rate, and using the death rate of the control treatment below 10% as an effective test.
Dissolving the synthesized compound in a small amount of acetone, and preparing into 200 μ g/mL medicament with 1 ‰ Tween-80 water solution for use. Cutting fresh corn leaves into small-leaf discs with the diameter of 1 x 1cm, placing the small-leaf discs into a test medicament, soaking for 3 seconds, taking out the small-leaf discs, naturally airing, placing the small-leaf discs into a culture dish (the diameter is 9 cm) containing filter paper for moisture preservation, inoculating 3-year-old armyworms hungry for 4 hours, repeating the treatment for 3 times, repeating 30 times for each treatment, treating the treated test insects by using a water solvent containing 1 per thousand of Tween-80 as a control, placing the treated test insects into an insect-raising room at the temperature of 25 +/-1 ℃, the relative humidity of 75 +/-5% and the light period of L/D =12/12h for feeding, counting the number of dead insects after 48 hours, wherein the death standard is that the test insects cannot be eaten, and the test brushes cannot move by touching lightly. Mortality was calculated according to the following formula, corrected for mortality, and control treatment mortality below 10% was a valid test.
The synthesized compound is dissolved in a small amount of acetone, and a 200 mu g/mL medicament is prepared by using 1 per mill of Tween-80 aqueous solution for standby. Cutting fresh cabbage leaves into small-leaf discs with the diameter of 1 x 1cm, placing the small-leaf discs into a test reagent for dipping for 3 seconds, taking out the small-leaf discs, naturally airing the small-leaf discs, placing the small-leaf discs into a culture dish (the diameter is 9 cm) containing filter paper for moisture preservation, inoculating 3-year-old diamondback moths starved for 4 hours, repeating the treatment for 3 times, repeating 30 times for each treatment, treating the treated test insects by using a water solvent containing 1 per thousand of tween-80 as a control, placing the treated test insects into an insect-raising room at the temperature of 25 +/-1 ℃, the relative humidity of 75 +/-5% and the light cycle of L/D =12/12h for feeding, counting the number of dead insects after 48 hours, wherein the death standard is that the test insects cannot be taken and the test insects cannot move by touching with a writing brush. Mortality was calculated according to the following formula, corrected for mortality, and control treatment mortality below 10% was a valid test.
Dissolving the synthesized compound in a small amount of acetone, preparing a medicament of 50 mu g/mL with a water solution of 1 thousandth Tween-80 for standby, adding 2mL of liquid medicine into each hole of a 24-hole plate, inoculating about 15 wigglers of 3 years old, repeating the treatment for 3 times, placing the treated test insects in an insect room at the temperature of 25 +/-1 ℃, the relative humidity of 75 +/-5% and the photoperiod of L/D =12/12h for feeding, using water containing 1 thousandth Tween-80 as a control, checking the number of dead and live insects under a binocular dissecting mirror after 48h, and calculating the mortality and correcting the mortality, wherein the effective test is that the mortality of the control treatment is below 10%.
The in vitro insecticidal activity data of some compounds are shown in table 2.
Table 2: activity measurement results of isoxazoline ester derivatives: corrected mortality/%
As can be seen from table 2, the compounds of formula I provided by the present invention have a certain pesticidal activity against all 4 pests tested. Wherein, the insecticidal activity of the compounds I-01 to I-07 on oriental armyworm and wiggler is more than 80 percent, and simultaneously, the insecticidal activity on diamond back moth is also excellent.
The data in table 2 show that the compound of formula I has certain insecticidal activity on oriental armyworm, pea aphid, diamond back moth and wiggler, wherein the insecticidal activity on the oriental armyworm, the diamond back moth and the wiggler is most obvious, and the compound can be used as an insecticide for controlling the insect pests.
The preferred embodiments of the present disclosure have been described in detail above, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all fall within the protection scope of the present disclosure.
It should be noted that, in the foregoing embodiments, various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various combinations that are possible in the present disclosure are not described again.
In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure as long as it does not depart from the gist of the present disclosure.
Claims (10)
1. An ester compound containing isoxazoline is characterized by being a compound shown as a formula I;
in the formula: a. The 1 One of substituted or unsubstituted benzene ring, nitrogen-containing heterocycle and oxygen-containing heterocycle is selected, the substitution mode is monosubstituted or polysubstituted, and the substituent is: one of hydrogen, C1-C12 alkyl, halogenated C1-C12 alkyl, C1-C12 alkoxy, halogenated C1-C12 alkoxy, C3-C12 cycloalkyl, C1-C12 alkylthio, C2-C12 alkenyl, C2-C12 alkenylthio, halogenated C2-C12 alkenyl, C2-C12 alkynyl, halogenated C2-C12 alkynyl, halogen, cyano, nitro and benzyloxy.
R 1 One selected from the group consisting of hydrogen, C1-C12 alkyl, haloC 1-C12 alkyl, C1-C12 alkoxy, haloC 1-C12 alkoxy, C3-C12 cycloalkyl, C1-C12 alkylthio, C2-C12 alkenyl, C2-C12 alkenylthio, haloC 2-C12 alkenyl, C2-C12 alkynyl, haloC 2-C12 alkynyl, halogen, cyano, nitro and benzyloxy;
A 2 the substituted heterocyclic ring is one of substituted or unsubstituted benzene ring, nitrogen-containing heterocyclic ring, oxygen-containing heterocyclic ring and sulfur-containing heterocyclic ring, the substitution mode is single substitution or multiple substitution, and the substituent is selected from one of hydrogen, C1-C12 alkyl, halogenated C1-C12 alkyl, C1-C12 alkoxy, halogenated C1-C12 alkoxy, C3-C12 cycloalkyl, C1-C12 alkylthio, C2-C12 alkenyl, C2-C12 alkenylthio, halogenated C2-C12 alkenyl, C2-C12 alkynyl, halogenated C2-C12 alkynyl, halogen, cyano, nitro and benzyloxy;
x is C or S;
n is 1 or 2;
R 2 selected from the group consisting of C1-C12 alkyl, haloC 1-C12 alkyl, C1-C12 alkoxy, haloC 1-C12 alkoxy, C3-C12 cycloalkyl, haloC 3-C12 cycloalkyl, C1-C12 alkylthio, C2-C12 alkenyl, C2-C12 alkenylthio, haloC 2-C12 alkenyl, C2-C12 alkynyl, haloC 2-C12 alkynyl, C1-C12 alkylamino, haloC 1-C12 alkylamino, C1-C12 alkylaminocarbonyl, C1-C12 alkylsulfonyl, C1-C12 alkylsulfinyl, haloC 1-C12 alkylsulfinylOne of sulfonyl, C1-C12 alkylaminosulfonyl, di (C1-C12 alkyl) aminosulfonyl, acetyl and formyl;
or, R 2 One of unsubstituted or substituted benzene ring, nitrogen-containing heterocycle, oxygen-containing heterocycle and sulfur-containing heterocycle is selected, the substitution mode is mono-substituted or polysubstituted, and the substituent is as follows: one of hydrogen, C1-C12 alkyl, halogenated C1-C12 alkyl, C1-C12 alkoxy, halogenated C1-C12 alkoxy, C3-C12 cycloalkyl, C1-C12 alkylthio, C2-C12 alkenyl, C2-C12 alkenylthio, halogenated C2-C12 alkenyl, C2-C12 alkynyl, halogenated C2-C12 alkynyl, acetyl, formyl, halogen, cyano, nitro and benzyloxy.
2. An ester compound containing isoxazoline is characterized by being a compound shown as a formula I;
specific substituents in formula i are shown in the following table:
3. a method for producing an isoxazoline-containing ester compound, characterized in that the isoxazoline-containing ester compound is the isoxazoline-containing ester compound according to claim 1 or 2;
the method comprises the following steps: reacting a compound shown in a formula II with a compound shown in a formula III or a compound shown in a formula IV in an organic solvent to obtain a compound shown in a formula I:
4. the method of preparing isoxazoline-containing ester compounds according to claim 3, wherein the organic solvent is mixed with an additive selected from one or more of triethylamine, pyridine, dicyclohexylcarbodiimide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide, 4-dimethylaminopyridine and bis (4-nitrophenyl) carbonate, and the organic solvent is selected from one of dichloromethane, toluene, ethyl acetate and tetrahydrofuran.
5. The method for preparing an isoxazoline-containing ester compound according to claim 3 or 4, wherein the reaction temperature is 0 to 55 ℃ and the reaction time is 5min to 24 hours.
6. The method for preparing an isoxazoline-containing ester compound according to claim 3 or 4, wherein the molar ratio of the compound represented by the formula III to the compound represented by the formula II is 1 (0.5 to 1.5); the molar ratio of the compound shown in the formula IV to the compound shown in the formula II is 1 (0.5-1.5).
7. Use of the isoxazoline-containing ester compound according to any one of claims 1 to 2 or the isoxazoline-containing ester compound produced by the method for producing the isoxazoline-containing ester compound according to any one of claims 3 to 6 for producing an insecticide.
8. The use as claimed in claim 7, wherein said insecticide is for the control of wigglers, mythimna, piper pisum or Plutella xylostella.
9. An insecticide containing the isoxazoline-containing ester compound according to any one of claims 1 to 2 or the isoxazoline-containing ester compound produced by the method for producing the isoxazoline-containing ester compound according to any one of claims 3 to 6.
10. The insecticide as claimed in claim 9, wherein said insecticide is used for the control of diamondback moth, armyworm, pea aphid or wiggler.
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