CN113480489A - Isoxazole biphenyl compound and preparation method and application thereof - Google Patents

Isoxazole biphenyl compound and preparation method and application thereof Download PDF

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Publication number
CN113480489A
CN113480489A CN202110952919.0A CN202110952919A CN113480489A CN 113480489 A CN113480489 A CN 113480489A CN 202110952919 A CN202110952919 A CN 202110952919A CN 113480489 A CN113480489 A CN 113480489A
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isoxazole
compound
formula
structure shown
biphenyl compound
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鄢龙家
张燕
刘力
乐意
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Guizhou University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
    • C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
    • C07D261/06—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members
    • C07D261/10—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D261/14—Nitrogen atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
    • C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
    • C07D261/06—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members
    • C07D261/08—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
    • C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
    • C07D261/06—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members
    • C07D261/10—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D261/18—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention relates to an isoxazole biphenyl compound, a preparation method and application thereof, and a structural formula of the isoxazole biphenyl compound
Figure DDA0003219233220000011
R1Is selected from
Figure DDA0003219233220000012
Or
Figure DDA0003219233220000013
R2Is selected from
Figure DDA0003219233220000014
Or

Description

Isoxazole biphenyl compound and preparation method and application thereof
Technical Field
The invention belongs to the technical field of pesticides, and particularly relates to an isoxazole biphenyl compound and a preparation method and application thereof.
Background
Plant diseases have long severely threatened global agricultural production. Among them, phytopathogenic bacteria and fungi are difficult to control and cause huge annual loss of crop yield. For example, rice bacterial blight (Xanthomonas oryzae pv. Oryzae, Xoo), Actinidia kiwii canker (Psa) and Citrus canker (Xanthomonas axonono pv. citri, Xac) cause enormous losses to agricultural production each year.
Compared with other methods, the chemical control has some unique points and has the advantages of high efficiency, low cost, convenient use and the like. However, plant pathogens develop resistance to existing antimicrobial agents. Thus, the discovery of new and more effective agricultural fungicides remains a preoccupation in the field of current crop protection.
Disclosure of Invention
In view of the above, the invention provides an isoxazole biphenyl compound, and a preparation method and application thereof, which are used for relieving the drug resistance problem of the existing pesticide to three pathogenic bacteria, namely rice bacterial blight, kiwi fruit ulcer and citrus ulcer.
The specific technical scheme of the invention is as follows:
an isoxazole biphenyl compound has a structural formula shown as a formula (I):
Figure BDA0003219233210000011
wherein R is1Is selected from
Figure BDA0003219233210000012
Is selected from
Figure BDA0003219233210000013
Namely, the isoxazole biphenyls are selected from:
Figure BDA0003219233210000014
Figure BDA0003219233210000021
the invention also provides an intermediate compound for preparing the isoxazole biphenyl compound or the stereoisomer thereof, the salt thereof or the solvate thereof, which is shown as follows:
Figure BDA0003219233210000022
wherein R is1Is selected from
Figure BDA0003219233210000023
The invention also provides a preparation method of the isoxazole biphenyl compound or the stereoisomer thereof, the salt thereof or the solvate thereof in the technical scheme, which comprises the following steps:
carrying out 1, 3-dipolar cycloaddition reaction on a compound with a structure shown in a formula (II) and a commercially available compound with a structure shown in a formula (III) under the action of a halogenating agent and alkali to obtain an isoxazole biphenyl compound;
wherein:
Figure BDA0003219233210000031
R2is selected from
Figure BDA0003219233210000032
In the invention, the compound with the structure shown in the formula (II) is converted into the compound with the structure shown in the formula (III) under the action of a halogenating agent and alkaliIn the 1, 3-dipolar cycloaddition reaction of the compound, the 1, 3-dipolar cycloaddition reaction is carried out in an organic solvent, the organic solvent is selected from DMF, 1,4-Dioxane, THF or dichloromethane, and DMF is preferred; the temperature of the 1, 3-dipolar cycloaddition reaction is 25-100 ℃, and preferably 75 ℃; the time of the 1, 3-dipolar cycloaddition reaction is 9 h; the halogenating agent is selected from N-chlorosuccinimide (NCS), N-bromosuccinimide (NBS), N-iodosuccinimide (NIS), or Chloramine-T (Chloramine-T), preferably NCS; the alkali is selected from DBU, Cs2CO3、TEA、K2CO3、NaOtBu、Na2CO3NaOH, DIEA, DABCO, DMAP, preferably DIEA; the molar ratio of the compound with the structure shown in the formula (II) to the compound with the structure shown in the formula (III) to the halogenating agent to the base is 1: 1.2: (1.2-3): 1, preferably 1: 1.2: 2: 1; after the cycloaddition reaction, the isoxazole biphenyl compound is preferably obtained by silica gel column separation.
The preparation method of the isoxazole biphenyl compound preferably comprises the following steps:
Figure BDA0003219233210000033
wherein R is1Is selected from
Figure BDA0003219233210000034
Figure BDA0003219233210000035
The invention also provides a composition containing the isoxazole biphenyl compound or a stereoisomer thereof, or a salt or a solvate thereof. The compounds are agriculturally useful adjuvants or fungicides, insecticides or herbicides. Preferably, the formulation of the composition is selected from Emulsifiable Concentrates (EC), Dusts (DP), Wettable Powders (WP), Granules (GR), Aqueous Solutions (AS), Suspension Concentrates (SC), ultra low volume sprays (ULV), Soluble Powders (SP), Microcapsules (MC), smoking agents (FU), aqueous Emulsions (EW), water dispersible granules (WG).
The isoxazole biphenyl compound or the stereoisomer thereof, the salt thereof or the solvate thereof, or the isoxazole biphenyl compound can be used for preventing and treating agricultural diseases and insect pests, preferably, the agricultural diseases and insect pests are plant bacterial or fungal diseases; more preferably, the agricultural pests are plant leaf blight and plant canker; most preferably, the agricultural pests are rice bacterial blight, citrus canker pathogen and kiwi canker pathogen.
The term "substituted" as used herein means that any one of the hydrogen atoms on the designated atom or group is replaced with the designated group of choice, provided that the general valence of the designated atom is not exceeded. If not otherwise stated, substituents are named to the central structure. For example, it is understood that when (cycloalkyl) alkyl is a possible substituent, the point of attachment of the substituent to the central structure is in the alkyl moiety.
Combinations of substituents and or variables are permissible only if such combinations result in stable compounds or useful synthetic intermediates. A stable compound or stable structure implies that the compound is sufficiently stable to be isolated in useful purity from the reaction mixture and subsequently formulated to form an effective therapeutic agent.
The term "halogen" or "halogen atom" refers to chlorine, bromine and iodine.
The isoxazole biphenyl compound has a novel structure, good water solubility, strong inhibition effect on three plant germs, and good application prospect in the creation of new pesticides.
By adopting the technical scheme, a series of isoxazole biphenyl compounds are synthesized, and the compounds are found to have good inhibition effect on pathogenic bacteria, have good inhibition effect on pathogenic bacteria [ Xanthomonas oryzae pv. Oryza, Xoo), Actinidia kiwifruit canker (Psa) and Xanthomonas axano (Xanthomonas axano pv. citri, Xac) ], and provide important scientific basis for research and development of new pesticides.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. All the starting materials and solvents used in the examples are commercially available products.
Preparation of 4-nitro-3-m-tolyl isoxazole:
in a 50mL round bottom flask, 3-methylbenzaldoxime (4mmol) was stirred in DMF (6mL) at room temperature followed by NCS (8mmol) and stirring at 75 ℃ for 1h, followed by addition of DIEA (4mmol) and (E) -N, N-dimethyl-2-nitroethen-1-amine (4.8mmol) and stirring at 75 ℃ for 8h to allow 1, 3-dipolar cycloaddition, after TLC monitoring of the reaction completion, then cooling to room temperature, the reaction mixture was extracted with EtOAc (3X 30mL) and washed with saturated brine (2X 30 mL). Na for organic phase2SO4Drying, filtering, concentrating under reduced pressure, and separating with silica gel column to obtain white solid with yield of 30%.
Other target compounds were synthesized using the corresponding starting materials or substituents, according to the methods described above. The structure, nuclear magnetic resonance hydrogen spectrum and carbon spectrum data of the synthesized isoxazole biphenyl compound are shown in table 1, and the physicochemical properties are shown in table 2.
TABLE 1 NMR hydrogen and carbon spectra data for some of the compounds
Figure BDA0003219233210000041
Figure BDA0003219233210000051
Figure BDA0003219233210000061
Figure BDA0003219233210000071
TABLE 2 physicochemical Properties of the target Compounds
Figure BDA0003219233210000072
Figure BDA0003219233210000081
Pharmacological experiments:
in-vitro antibacterial activity tests are carried out by adopting a turbidity method, and the test objects are rice bacterial blight (Xoo), citrus canker pathogen (Xac) and kiwi fruit bacterial canker pathogen (Psa). BMT (bismerthiazol) and TDC (copper thielavide) were used as positive controls. After the germs are activated by the NA culture medium, a single colony is selected to be inoculated in the NB culture medium and is subjected to shake culture in a constant temperature shaking table at 28 ℃ and 180rpm until the logarithmic phase is reached, and a seed solution is obtained for standby. The test compound was dissolved in DMSO, diluted with 2% Tween aqueous solution to a prescribed concentration, and 1mL of the dilution was added to a tube containing 4mL of NB medium to prepare a drug-containing medium at a concentration of 100. mu.g/mL. Blank NB media was prepared with equal volumes of DMSO, and each tube was inoculated with 40 μ L seed solution, three replicates for each sample. Placing in a constant temperature shaking table at 28 deg.C and 180rpm, and performing shaking culture while monitoring OD of blank control group with ultraviolet spectrophotometer595Measuring OD of the culture medium of the sample to be measured at a value of 0.6 to 0.8595The inhibition ratio was calculated as follows.
Correcting OD595(bacterial culture Medium) OD595- (sterile Medium) OD595
Inhibition (%) - (control medium bacterial solution) OD595- (correction of drug-containing Medium) OD595]/(corrected control Medium bacterial solution) OD595×100。
The examples of the present invention are given to illustrate the technical solution of the present invention, but the contents of the examples are not limited thereto, and the experimental results of the target compounds are shown in table 3.
TABLE 3 inhibition rate of isoxazole biphenyl compounds on three plant pathogens at 100 mug/mL
Figure BDA0003219233210000091
Figure BDA0003219233210000101
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (9)

1. An isoxazole biphenyl compound is characterized in that the structural formula of the isoxazole biphenyl compound is shown as a formula (I):
Figure FDA0003219233200000011
wherein R is1Is selected from
Figure FDA0003219233200000012
R2Is selected from
Figure FDA0003219233200000013
2. The preparation method of isoxazole biphenyls according to claim 1, which comprises the following steps:
carrying out 1, 3-dipolar cycloaddition reaction on a compound with a structure shown in a formula (II) and a compound with a structure shown in a formula (III) under the action of a halogenating agent and alkali to obtain an isoxazole biphenyl compound;
a compound having the structure of formula (II);
Figure FDA0003219233200000014
wherein R is1Is selected from
Figure FDA0003219233200000015
Figure FDA0003219233200000016
R2Is selected from
Figure FDA0003219233200000017
3. The process for the preparation of isoxazole biphenyls according to claim 2, wherein the 1, 3-dipolar cycloaddition reaction is carried out in an organic solvent selected from DMF, 1,4-Dioxane, THF or dichloromethane;
the temperature of the 1, 3-dipolar cycloaddition reaction is 25-100 ℃, and the reaction time is 9 h;
the halogenating agent is selected from N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide and chloramine-T;
the alkali is selected from DBU, Cs2CO3、TEA、K2CO3、NaOtBu、Na2CO3、NaOH、DIEA、DABCO、DMAP；
The molar ratio of the compound with the structure shown in the formula (II) to the compound with the structure shown in the formula (III) to the halogenating agent to the base is 1: 1.2: 1.2-3: 1.
4. the method for preparing isoxazole biphenyls according to claim 2, wherein the isoxazole biphenyls are obtained by separating with a silica gel column after the 1, 3-dipolar cycloaddition reaction.
5. The preparation method of isoxazole biphenyls according to claim 2, which comprises the following steps: and (2) carrying out addition-elimination reaction on methyl, methoxy, trifluoromethyl, cyano, nitro and halogen atom substituted or unsubstituted benzaldehyde to obtain the compound with the structure shown in the formula (II).
6. A composition comprising the isoxazole biphenyl compound of claim 1, or a stereoisomer thereof, or a salt or solvate thereof.
7. Use of a composition according to claim 6, as an adjuvant, fungicide, insecticide or herbicide in agriculture.
8. Use of a composition according to claim 7 as a pesticide for controlling agricultural pests.
9. Use of a composition according to claim 7 for controlling bacterial or fungal diseases in plants.
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Citations (6)

* Cited by examiner, † Cited by third party
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US3629430A (en) * 1968-02-13 1971-12-21 Sankyo Co Isoxazole fungicidal compositions and methods of use
US4187099A (en) * 1977-11-16 1980-02-05 Monsanto Company 3-Aryl-4-isothiazolecarboxylic acid and 3-aryl-4-isoxazolecarboxylic acid derivatives and their use as herbicides
US5627131A (en) * 1995-01-09 1997-05-06 Zeneca Limited Herbicidal compositions of 4-benzoylisoxazole and antidotes therefor
WO2003057215A1 (en) * 2001-12-28 2003-07-17 Takeda Chemical Industries, Ltd. Neurotrophic factor production/secretion accelerator
US20100292275A1 (en) * 2008-01-25 2010-11-18 E.I. Du Pont De Nemours And Company Fungicidal heterocyclic compounds
CN107382892A (en) * 2017-08-14 2017-11-24 贵州大学 A kind of preparation technology of the nitro isoxazole compound of 3 aryl 4

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3629430A (en) * 1968-02-13 1971-12-21 Sankyo Co Isoxazole fungicidal compositions and methods of use
US4187099A (en) * 1977-11-16 1980-02-05 Monsanto Company 3-Aryl-4-isothiazolecarboxylic acid and 3-aryl-4-isoxazolecarboxylic acid derivatives and their use as herbicides
US5627131A (en) * 1995-01-09 1997-05-06 Zeneca Limited Herbicidal compositions of 4-benzoylisoxazole and antidotes therefor
WO2003057215A1 (en) * 2001-12-28 2003-07-17 Takeda Chemical Industries, Ltd. Neurotrophic factor production/secretion accelerator
US20100292275A1 (en) * 2008-01-25 2010-11-18 E.I. Du Pont De Nemours And Company Fungicidal heterocyclic compounds
CN107382892A (en) * 2017-08-14 2017-11-24 贵州大学 A kind of preparation technology of the nitro isoxazole compound of 3 aryl 4

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
AKIRA YOSHIMURA，等: "Hypervalent Iodine(III) Reagent Mediated Regioselective Cycloaddition of Aldoximes with Enaminones", 《EUR. J. ORG. CHEM.》 *
BRUCE C.HAMPER，等: "Synthesis and Herbicidal Activity of 3-Aryl-5-(haloalkyl)-4-isoxazolecarboxamides and Their Derivatives", 《J. AGRIE. FOOD CHEM.》 *
HENNING HOPF，等: "A surprising new route to 4-nitro-3-phenylisoxazole", 《BEILSTEIN J. ORG. CHEM.》 *
李倩倩，等: "3-芳基-4-芳胺甲基异噁唑衍生物的合成及其生物活性初探", 《有机化学》 *
齐传民等: "新型异恶唑类化合物的合成及其生物活性的研究", 《北京师范大学学报(自然科学版)》 *

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