CN109553605B - Pyrazole amide compound containing tetrazole biphenyl structure and preparation method and application thereof - Google Patents
Pyrazole amide compound containing tetrazole biphenyl structure and preparation method and application thereof Download PDFInfo
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- CN109553605B CN109553605B CN201811480609.8A CN201811480609A CN109553605B CN 109553605 B CN109553605 B CN 109553605B CN 201811480609 A CN201811480609 A CN 201811480609A CN 109553605 B CN109553605 B CN 109553605B
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 title claims abstract description 32
- -1 Pyrazole amide compound Chemical class 0.000 title claims abstract description 19
- 239000004305 biphenyl Substances 0.000 title claims abstract description 16
- 235000010290 biphenyl Nutrition 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 150000003536 tetrazoles Chemical class 0.000 title claims description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- 239000000575 pesticide Substances 0.000 claims abstract description 17
- 241000238631 Hexapoda Species 0.000 claims abstract description 9
- 230000000749 insecticidal effect Effects 0.000 claims description 9
- 239000004480 active ingredient Substances 0.000 claims description 8
- 239000002917 insecticide Substances 0.000 claims description 7
- 241001477931 Mythimna unipuncta Species 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000003814 drug Substances 0.000 claims description 5
- 239000000839 emulsion Substances 0.000 claims description 5
- 239000004562 water dispersible granule Substances 0.000 claims description 3
- 239000004495 emulsifiable concentrate Substances 0.000 claims description 2
- 239000000375 suspending agent Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 4
- 238000003898 horticulture Methods 0.000 abstract description 4
- 125000003831 tetrazolyl group Chemical group 0.000 abstract 3
- ZLIZZDCWMOGEGA-UHFFFAOYSA-N 1h-pyrazole-5-carbonyl chloride Chemical class ClC(=O)C=1C=CNN=1 ZLIZZDCWMOGEGA-UHFFFAOYSA-N 0.000 abstract 2
- YHXKXVFQHWJYOD-UHFFFAOYSA-N 1-biphenyl-2-ylmethanamine Chemical compound NCC1=CC=CC=C1C1=CC=CC=C1 YHXKXVFQHWJYOD-UHFFFAOYSA-N 0.000 abstract 1
- 238000009833 condensation Methods 0.000 abstract 1
- 230000005494 condensation Effects 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 241000607479 Yersinia pestis Species 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000012295 chemical reaction liquid Substances 0.000 description 8
- 239000000543 intermediate Substances 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical group CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 238000004440 column chromatography Methods 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 238000002390 rotary evaporation Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 241000258937 Hemiptera Species 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 240000008042 Zea mays Species 0.000 description 3
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 3
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 3
- 230000004071 biological effect Effects 0.000 description 3
- 235000005822 corn Nutrition 0.000 description 3
- 230000002147 killing effect Effects 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 241000238814 Orthoptera Species 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- WHJMGMTWMIGGQF-UHFFFAOYSA-N 1,1'-biphenyl;methanamine Chemical compound NC.C1=CC=CC=C1C1=CC=CC=C1 WHJMGMTWMIGGQF-UHFFFAOYSA-N 0.000 description 1
- 241000238876 Acari Species 0.000 description 1
- 241001124076 Aphididae Species 0.000 description 1
- 244000003416 Asparagus officinalis Species 0.000 description 1
- 235000005340 Asparagus officinalis Nutrition 0.000 description 1
- 241001481710 Cerambycidae Species 0.000 description 1
- 241000426497 Chilo suppressalis Species 0.000 description 1
- 241001414720 Cicadellidae Species 0.000 description 1
- 241001498622 Cixius wagneri Species 0.000 description 1
- 241000008892 Cnaphalocrocis patnalis Species 0.000 description 1
- 241001465977 Coccoidea Species 0.000 description 1
- 241000254173 Coleoptera Species 0.000 description 1
- 241000254171 Curculionidae Species 0.000 description 1
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 1
- 241000255925 Diptera Species 0.000 description 1
- 241001517923 Douglasiidae Species 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000255967 Helicoverpa zea Species 0.000 description 1
- 241000255777 Lepidoptera Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 241000257226 Muscidae Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 241000320508 Pentatomidae Species 0.000 description 1
- 241001325166 Phacelia congesta Species 0.000 description 1
- 241000255969 Pieris brassicae Species 0.000 description 1
- 241000500441 Plutellidae Species 0.000 description 1
- 241001414857 Psyllidae Species 0.000 description 1
- 239000005869 Pyraclostrobin Substances 0.000 description 1
- 241000254062 Scarabaeidae Species 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000005658 Tebufenpyrad Substances 0.000 description 1
- 230000000895 acaricidal effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229940125890 compound Ia Drugs 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- HZRSNVGNWUDEFX-UHFFFAOYSA-N pyraclostrobin Chemical compound COC(=O)N(OC)C1=CC=CC=C1COC1=NN(C=2C=CC(Cl)=CC=2)C=C1 HZRSNVGNWUDEFX-UHFFFAOYSA-N 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000005556 structure-activity relationship Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000004546 suspension concentrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- ZZYSLNWGKKDOML-UHFFFAOYSA-N tebufenpyrad Chemical compound CCC1=NN(C)C(C(=O)NCC=2C=CC(=CC=2)C(C)(C)C)=C1Cl ZZYSLNWGKKDOML-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- WPALTCMYPARVNV-UHFFFAOYSA-N tolfenpyrad Chemical compound CCC1=NN(C)C(C(=O)NCC=2C=CC(OC=3C=CC(C)=CC=3)=CC=2)=C1Cl WPALTCMYPARVNV-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- 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
- A01N43/713—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with four or more nitrogen atoms as the only ring hetero atoms
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- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Dentistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
本发明涉及一种含四氮唑联苯基结构的吡唑酰胺类化合物(I)及其制备方法和应用。通过取代基吡唑甲酰基氯(II)与四氮唑联苯基甲基胺(III)缩合得到。所述含四氮唑联苯基结构的吡唑酰胺类化合物对有害昆虫具有效的防治效果，该化合物可用于制备农业、园艺等领域的杀虫剂。 The invention relates to a pyrazole amide compound (I) containing a tetrazolium biphenyl structure and a preparation method and application thereof. Obtained by the condensation of substituted pyrazolecarbonyl chloride (II) with tetrazolium biphenylmethylamine (III). The pyrazole amide compound containing a tetrazolium biphenyl structure has an effective control effect on harmful insects, and the compound can be used for preparing pesticides in the fields of agriculture, horticulture and the like.
Description
Technical Field
The invention relates to the field of chemical pesticides, and particularly relates to a pyrazole amide compound containing a tetrazole biphenyl structure, and a preparation method and application thereof.
Background
The prevention and control of pests are always the core field of pesticide science research, and the wide use of pesticides enables most pests to be effectively treated. However, with the continuous expansion of the application scale of the pesticide, the problem of drug resistance of the traditional pesticide varieties becomes more and more prominent, and the continuous research and development of new pesticides become necessary choices due to the continuous emergence of new plant diseases and insect pests.
Pyrazole rings are widely applied in agricultural production, pyrazole compounds have excellent insecticidal and acaricidal activities, and pyrazole heterocycles are widely introduced into pesticide compound molecules, such as pyraclostrobin, tebufenpyrad and tolfenpyrad, and have excellent killing activities on mites, aphids and the like (Biochim. Biophys. acta 1998,1364, 236-244).
Tetrazole is also an important nitrogen-containing heterocycle, and plays an important role in the aspect of insect killing in the field of pesticides. Some researches in recent years report that tetrazole derivatives have good insecticidal effect.
Therefore, in order to further search for a compound with excellent biological activity from the pyrazole amide compounds, the pyrazole amide group and the tetrazole skeleton are reasonably connected together by adopting an active group splicing method, and the invention discloses a pyrazole amide compound containing a tetrazole phenyl structure and having an agricultural insecticidal application value.
Disclosure of Invention
The invention aims to provide a pyrazole amide compound containing a tetrazole biphenyl structure, which has an excellent control effect on various pests, is efficient, safe and environment-friendly, and meets the requirement of crop protection on efficient pesticides.
It is a further object of the present invention to provide the use of the above compounds in the preparation of insecticides.
Another object of the present invention is to provide a process for the preparation of the above compounds.
In order to solve the technical problems, the invention provides a pyrazole amide compound containing a tetrazole biphenyl structure, which has a structure shown in a general formula I,
wherein R is 4-OCH3C6H4,4-FC6H4,2,4-F2C6H3,CH3,C2H5。
Preferably, the pyrazole amide compound containing the tetrazole biphenyl structure has the following structure:
the second aspect of the invention provides a preparation method of the pyrazole amide compound containing the tetrazole biphenyl structure, which comprises the following steps:
dissolving a compound III in an organic solvent, adding an acid-binding agent, adding an intermediate II, reacting for a period of time, carrying out suction filtration on a reaction solution, carrying out reduced pressure concentration on a mother solution, separating and purifying an obtained residue to obtain a target compound,
wherein R is 4-OCH3C6H4,4-FC6H4,2,4-F2C6H3,CH3,C2H5
Preferably, the acid scavenger is selected from DIPEA, pyridine, triethylamine and sodium carbonate, and the solvent is selected from acetonitrile, DMF, dichloromethane and 1, 2-dichloroethane. The heating reaction temperature is 0-82 ℃, and the reaction time is 8-13 hours.
Preferably, the preparation method of the pyrazole amide compound containing the tetrazole biphenyl structure comprises the following steps:
wherein, the intermediate III of tetrazole biphenyl methylamine can be synthesized by the method of reference literature (J.Med.chem.1998,41,2390); the intermediates IIa to IIe can be synthesized by the method described in the literature (J.Agric.food chem.2013,61, 8730-8736).
The compound of the general formula I has excellent control activity on insects, so that the compound can be used for preparing pesticides to protect plants in agriculture, horticulture and the like. The insects comprise lepidoptera pests such as cotton bollworms, asparagus caterpillars, diamond back moths, cabbage caterpillars, rice leaf rollers, chilo suppressalis and the like; homoptera pests such as leafhopper, plant hopper, vermin, whitefly, coccid of psyllidae, etc.; dipteran pests such as houseflies, leaf miner, mosquitoes, etc.; locusts of the order orthoptera, pests of the order Coleoptera, longicorn beetles, scarab beetles, weevils, and the like; stinkbugs of the order hemiptera, and the like. Of course, the pests which the compounds of the invention can control are not limited to the above exemplified ranges.
When the compound of the invention represented by the general formula I is used as an insecticide in the fields of agriculture, horticulture and the like, the compound can be used alone or in the form of an insecticidal composition, for example, the compound is prepared into an aqueous emulsion, a suspending agent, a water dispersible granule, an emulsion and the like by taking the formula I as an active ingredient and adding pesticide auxiliaries commonly used in the field.
Commonly used pesticide adjuvants include liquid carriers such as water; organic solvents such as toluene, xylene, cyclohexanol, methanol, butanol, ethylene glycol, acetone, dimethylformamide, acetic acid, dimethyl sulfoxide, animal and vegetable oils and fatty acids; common surfactants such as emulsifiers and dispersants, including anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants; other adjuvants, such as wetting agents, thickeners, and the like.
When the compound of the present invention represented by the general formula I is used as an active ingredient in an insecticide, the content in the insecticide is selected in the range of 0.1% to 99.5%, and an appropriate content of the active ingredient may be determined according to the formulation form and the application method. In general, the aqueous emulsion contains 5% to 50% (by weight, the same applies hereinafter) of the active ingredient, preferably 10% to 40%; the suspension concentrate contains 5% to 50% of active ingredient, preferably 5% to 40%.
For the use of the insecticide of the present invention, a commonly used application method such as stem and leaf spraying, water surface application, soil treatment, seed treatment, and the like can be selected. For example, when spray application from stems and leaves is employed, the compounds represented by the general formula I as active ingredients can be used in the form of aqueous emulsions, suspensions, water-dispersible granules, emulsifiable concentrates in the concentration range of 1 to 1000. mu.g/mL, preferably in the concentration range of 1 to 500. mu.g/mL.
The pyrazole amide compound containing the tetrazole biphenyl structure disclosed by the invention has an excellent control effect on harmful insects, and therefore, can be used for preparing pesticides used in the fields of agriculture, horticulture and the like.
Detailed Description
The above-described scheme is further illustrated below with reference to specific examples. It should be understood that these examples are for illustrative purposes and are not intended to limit the scope of the present invention. The conditions used in the examples may be further adjusted according to the conditions of the particular manufacturer, and the conditions not specified are generally the conditions in routine experiments.
Example 1:
5mmol of compound III are dissolved in 30mL of DMF, followed by addition of 15mmol of DIPEA (N, N-diisopropylethylamine). 6mmol of intermediate IIa was added thereto at room temperature, and after the addition was completed, the mixture was stirred at room temperature for 11 hours. And stopping the reaction, pouring the reaction solution into a beaker filled with 100mL of water, extracting with ethyl acetate, drying with anhydrous sodium sulfate, carrying out reduced pressure rotary evaporation to dryness, and carrying out column chromatography separation and purification on the obtained residue to obtain the target compound Ia.1H NMR(400MHz,CDCl3):δ8.66(s,1H,Tetrazole-H),8.16(d,J＝8.8Hz,2H,Ar-H),7.86(d,J＝2.0Hz,1H,Ar-H),6.99～7.73(m,6H,Ar-H and NH),4.77(d,J＝6.0Hz,2H,CH2),4.24(s,3H,N-CH3),3.95(s,3H,OCH3).
Example 2:
4mmol of Compound III are dissolved in 20mL of dichloromethane and subsequently20mmol of pyridine was added thereto, and 6mmol of intermediate IIb was added thereto at room temperature. After the addition, the mixture was refluxed for 10 hours. Stopping the reaction, carrying out rotary evaporation on the reaction liquid under reduced pressure until the reaction liquid is dried, and carrying out column chromatography separation and purification on the obtained residue to obtain the target compound Ib.1H NMR(400MHz,CDCl3):δ8.66(s,1H,Tetrazole-H),8.16(d,J＝8.4Hz,2H,Ar-H),7.78～7.82(m,2H,Ar-H),7.58(d,J＝8.8Hz,2H,Ar-H),7.12～7.24(m,3H,Ar-H and NH),4.78(d,J＝6.0Hz,2H,CH2),4.25(s,3H,N-CH3).
Example 3:
6mmol of compound III are dissolved in 20mL of acetonitrile, followed by the addition of 30mmol of pyridine. The intermediate IIc 9mmol was added thereto under ice-bath conditions, and after the addition, the mixture was heated under reflux for 13 hours. Stopping the reaction, carrying out rotary evaporation on the reaction liquid under reduced pressure until the reaction liquid is dried, and carrying out column chromatography separation and purification on the obtained residue to obtain the target compound Ic.1H NMR(400MHz,CDCl3):δ8.66(s,1H,Tetrazole-H),8.16(d,J＝8.4Hz,2H,Ar-H),7.58(d,J＝8.8Hz,2H,Ar-H),6.91～7.51(m,4H,Ar-H and NH),4.77(d,J＝6.0Hz,2H,CH2),4.27(s,3H,N-CH3).
Example 4:
10mmol of compound III are dissolved in 25mL of dichloromethane, followed by addition of 30mmol of triethylamine. And adding 13mmol of intermediate Id under ice bath condition, and continuing stirring for 8 hours in ice bath after the addition is finished. Stopping the reaction, carrying out rotary evaporation on the reaction liquid under reduced pressure until the reaction liquid is dried, and carrying out column chromatography separation and purification on the obtained residue to obtain the target compound Id.1H NMR(400MHz,CDCl3):δ8.66(s,1H,Tetrazole-H),8.15(d,J＝8.8Hz,2H,Ar-H),7.56(d,J＝8.4Hz,2H,Ar-H),7.17(brs,1H,NH),4.73(d,J＝6.0Hz,2H,CH2),4.15(s,3H,N-CH3),2.25(s,3H,CH3).
Example 5:
20mmol of compound III are dissolved in 30mL of 1, 2-dichloroethane, followed by addition of 38mmol of sodium carbonate. To this was added 18mmol of intermediate IIe under ice-bath conditions, and stirring was continued at room temperature for 12 hours. Stopping the reaction, carrying out rotary evaporation on the reaction liquid under reduced pressure until the reaction liquid is dried, and carrying out column chromatography separation and purification on the obtained residue to obtain the target compound Ie.1H NMR(400MHz,CDCl3):δ8.66(s,1H,Tetrazole-H),8.15(d,J＝8.8Hz,2H,Ar-H),7.56(d,J＝8.4Hz,2H,Ar-H),7.18(brs,1H,NH),4.73(d,J＝6.0Hz,2H,CH2),4.15(s,3H,N-CH3),2.66(q,J＝7.6Hz,2H,CH2),1.25(t,J＝7.6Hz,3H,CH3).
Example 6:
insecticidal activity screening of samples against armyworm
The leaf soaking method proposed by the International Resistance Action Committee (IRAC) was adopted: the target for testing is armyworm, namely, a proper amount of corn leaves are fully soaked in prepared liquid medicine and then naturally dried in the shade, the corn leaves are placed into a culture dish filled with filter paper, 10 heads/dish of armyworm larvae in the 3-instar middle stage are connected, the corn leaves are placed into an observation room for culture at 24-27 ℃, and the result is investigated after 48 hours. If the body of the insect is touched by a brush pen, no response is regarded as dead insect. The test concentration is 500. mu.g/mL (other concentrations of the drug solution can be obtained by diluting 500. mu.g/mL of the drug solution).
The result of the insecticidal activity test shows that all the compounds show the armyworm killing activity. At the tested concentration of 500. mu.g/mL (Table 1), the insecticidal activity of compounds Ia-Ie against armyworm was better, with the kill rates being 100%, 100%, 100%, 100% and 100%, respectively.
TABLE 1 Primary insecticidal Activity data for Ia-Ie
The experimental data show that the new compound obtained by reasonably combining the tetrazole biphenyl structure and the pyrazole amide active unit has good biological activity, and the compound can be selected as a disinsection lead to be used for further research on structure derivation and structure-activity relationship. The experimental data also provide important theoretical basis for continuing molecular design, synthesis and biological activity research of the novel pyrazole amide compounds in the future.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited by the foregoing examples, which are provided to illustrate the principles of the invention, and that various changes and modifications may be made without departing from the spirit and scope of the invention, which is also intended to be covered by the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (4)
1. A pyrazole amide compound I containing a tetrazole biphenyl structure is characterized by having a structure as follows:
2. the preparation method of the pyrazole amide compound I containing the tetrazole biphenyl structure as claimed in claim 1 is characterized by comprising the following steps:
3. the application of the pyrazole amide compound I containing the tetrazole biphenyl structure as claimed in claim 1 in preparing pesticide medicaments, wherein the insect is selected from armyworm, and is characterized in that: the compound is used alone; or in the form of an insecticidal composition, namely the compound I is used as an active ingredient and is added with pesticide auxiliaries commonly used in the field to be processed into an aqueous emulsion, a suspending agent, a water dispersible granule and an emulsifiable concentrate.
4. The application of the pyrazole amide compound I containing the tetrazole biphenyl structure as claimed in claim 3 in preparing pesticide medicaments is characterized in that: when compound I is used as an active ingredient in an insecticide, the content in the insecticide is selected in the range of 0.1% to 99.5%.
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| CN1028713C (en) * | 1987-04-24 | 1995-06-07 | 三菱化成株式会社 | insecticidal or acaricidal composition containing pyrazole derivatives |
| CN103081916A (en) * | 2011-11-02 | 2013-05-08 | 中国中化股份有限公司 | Application of pyrazole amide compound as agricultural bactericide |
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| CN1028713C (en) * | 1987-04-24 | 1995-06-07 | 三菱化成株式会社 | insecticidal or acaricidal composition containing pyrazole derivatives |
| CN103081916A (en) * | 2011-11-02 | 2013-05-08 | 中国中化股份有限公司 | Application of pyrazole amide compound as agricultural bactericide |
| CN103781357A (en) * | 2011-11-02 | 2014-05-07 | 中国中化股份有限公司 | Use of compound of pyrazole amides as agricultural fungicide |
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