CN107266381B - Acylhydrazone structure-containing triazinone derivative, preparation method thereof and application thereof in insecticidal and bactericidal aspects - Google Patents
Acylhydrazone structure-containing triazinone derivative, preparation method thereof and application thereof in insecticidal and bactericidal aspects Download PDFInfo
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- CN107266381B CN107266381B CN201610219375.6A CN201610219375A CN107266381B CN 107266381 B CN107266381 B CN 107266381B CN 201610219375 A CN201610219375 A CN 201610219375A CN 107266381 B CN107266381 B CN 107266381B
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- nmr
- carbon
- dmso
- methyl
- dihydro
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- QMNWYGTWTXOQTP-UHFFFAOYSA-N 1h-triazin-6-one Chemical class O=C1C=CN=NN1 QMNWYGTWTXOQTP-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 230000000749 insecticidal effect Effects 0.000 title abstract description 11
- 230000000844 anti-bacterial effect Effects 0.000 title abstract description 6
- DUIOPKIIICUYRZ-UHFFFAOYSA-N semicarbazide Chemical compound NNC(N)=O DUIOPKIIICUYRZ-UHFFFAOYSA-N 0.000 claims description 94
- -1 cyano, nitro, dimethylamino Chemical group 0.000 claims description 70
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- 229910052799 carbon Inorganic materials 0.000 claims description 35
- 150000001875 compounds Chemical class 0.000 claims description 35
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 24
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 18
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 125000000623 heterocyclic group Chemical group 0.000 claims description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- 125000001424 substituent group Chemical group 0.000 claims description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 12
- 125000005843 halogen group Chemical group 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- 241000255967 Helicoverpa zea Species 0.000 claims description 10
- 241001477931 Mythimna unipuncta Species 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- VKJMPYGLTDMUPZ-UHFFFAOYSA-N 5-amino-1h-triazin-6-one Chemical compound NC1=CN=NNC1=O VKJMPYGLTDMUPZ-UHFFFAOYSA-N 0.000 claims description 9
- 241000256113 Culicidae Species 0.000 claims description 9
- 241000346285 Ostrinia furnacalis Species 0.000 claims description 9
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 9
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 9
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 8
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 8
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 8
- 241001124076 Aphididae Species 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 5
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims description 5
- 244000052616 bacterial pathogen Species 0.000 claims description 5
- 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 claims description 5
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 claims description 5
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 claims description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 4
- 240000007594 Oryza sativa Species 0.000 claims description 4
- 235000007164 Oryza sativa Nutrition 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 235000021307 Triticum Nutrition 0.000 claims description 4
- 235000009566 rice Nutrition 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- 240000008067 Cucumis sativus Species 0.000 claims description 3
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- 240000003768 Solanum lycopersicum Species 0.000 claims description 3
- 241000607479 Yersinia pestis Species 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 125000001624 naphthyl group Chemical group 0.000 claims description 3
- 239000000575 pesticide Substances 0.000 claims description 3
- AHWALFGBDFAJAI-UHFFFAOYSA-N phenyl carbonochloridate Chemical compound ClC(=O)OC1=CC=CC=C1 AHWALFGBDFAJAI-UHFFFAOYSA-N 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 235000017060 Arachis glabrata Nutrition 0.000 claims description 2
- 244000105624 Arachis hypogaea Species 0.000 claims description 2
- 235000010777 Arachis hypogaea Nutrition 0.000 claims description 2
- 235000018262 Arachis monticola Nutrition 0.000 claims description 2
- 241000193738 Bacillus anthracis Species 0.000 claims description 2
- 244000241235 Citrullus lanatus Species 0.000 claims description 2
- 235000012828 Citrullus lanatus var citroides Nutrition 0.000 claims description 2
- 241000223218 Fusarium Species 0.000 claims description 2
- 241000233616 Phytophthora capsici Species 0.000 claims description 2
- 241000233622 Phytophthora infestans Species 0.000 claims description 2
- 240000008042 Zea mays Species 0.000 claims description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 2
- 229960000583 acetic acid Drugs 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000001299 aldehydes Chemical class 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- 235000005822 corn Nutrition 0.000 claims description 2
- 239000012362 glacial acetic acid Substances 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 235000020232 peanut Nutrition 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 4
- 241000209140 Triticum Species 0.000 claims 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 2
- FKLJPTJMIBLJAV-UHFFFAOYSA-N Compound IV Chemical compound O1N=C(C)C=C1CCCCCCCOC1=CC=C(C=2OCCN=2)C=C1 FKLJPTJMIBLJAV-UHFFFAOYSA-N 0.000 claims 1
- 101100117236 Drosophila melanogaster speck gene Proteins 0.000 claims 1
- 241000576755 Sclerotia Species 0.000 claims 1
- 239000000417 fungicide Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000001954 sterilising effect Effects 0.000 abstract description 3
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 3
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 392
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 106
- 239000007787 solid Substances 0.000 description 104
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 102
- 238000005160 1H NMR spectroscopy Methods 0.000 description 102
- 238000002844 melting Methods 0.000 description 59
- 230000008018 melting Effects 0.000 description 59
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 21
- 230000000694 effects Effects 0.000 description 18
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 16
- 239000005925 Pymetrozine Substances 0.000 description 11
- QHMTXANCGGJZRX-WUXMJOGZSA-N pymetrozine Chemical compound C1C(C)=NNC(=O)N1\N=C\C1=CC=CN=C1 QHMTXANCGGJZRX-WUXMJOGZSA-N 0.000 description 11
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- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical group COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 2
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
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- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 2
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- NJXYTXADXSRFTJ-UHFFFAOYSA-N 1,2-Dimethoxy-4-vinylbenzene Chemical group COC1=CC=C(C=C)C=C1OC NJXYTXADXSRFTJ-UHFFFAOYSA-N 0.000 description 1
- WGGLDBIZIQMEGH-UHFFFAOYSA-N 1-bromo-4-ethenylbenzene Chemical group BrC1=CC=C(C=C)C=C1 WGGLDBIZIQMEGH-UHFFFAOYSA-N 0.000 description 1
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- PECUPOXPPBBFLU-UHFFFAOYSA-N 1-ethenyl-3-methoxybenzene Chemical group COC1=CC=CC(C=C)=C1 PECUPOXPPBBFLU-UHFFFAOYSA-N 0.000 description 1
- JWVTWJNGILGLAT-UHFFFAOYSA-N 1-ethenyl-4-fluorobenzene Chemical group FC1=CC=C(C=C)C=C1 JWVTWJNGILGLAT-UHFFFAOYSA-N 0.000 description 1
- KWHSBYQFELZKKS-UHFFFAOYSA-N 1-ethenyl-4-iodobenzene Chemical group IC1=CC=C(C=C)C=C1 KWHSBYQFELZKKS-UHFFFAOYSA-N 0.000 description 1
- WITMXBRCQWOZPX-UHFFFAOYSA-N 1-phenylpyrazole Chemical compound C1=CC=NN1C1=CC=CC=C1 WITMXBRCQWOZPX-UHFFFAOYSA-N 0.000 description 1
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- OWDHNYUHCPSQFR-UHFFFAOYSA-N 2,4-diphenylpentan-3-one Chemical compound C=1C=CC=CC=1C(C)C(=O)C(C)C1=CC=CC=C1 OWDHNYUHCPSQFR-UHFFFAOYSA-N 0.000 description 1
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- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D253/00—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00
- C07D253/02—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00 not condensed with other rings
- C07D253/06—1,2,4-Triazines
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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Abstract
The invention relates to an acylhydrazone structure-containing triazinone derivative (I), a preparation method thereof and application thereof in the aspects of disinsection and sterilization, wherein the meanings of all groups in the formula are shown in the specification. The acylhydrazone-structure-containing triazinone derivative has good insecticidal activity and bactericidal activity.
Description
Technical Field
The invention relates to acylhydrazone structure-containing triazinone derivatives, a preparation method thereof and application thereof in the aspects of insect disinfestation and sterilization, and belongs to the technical field of pesticides.
Background
Nowa company 1988, Switzerland, discovered a non-lethal insecticide, pymetrozine, which belongs to triazinone compounds, has a completely new mode of action, and has excellent control effects on a variety of sucking mouthparts pests. In addition, the pymetrozine has no cross resistance with traditional organochlorine, carbamate, pyrethroid, 1-phenylpyrazole and neonicotinoid insecticides, so the pymetrozine can be applied to the control of pests of various resistant strains. The pymetrozine has unique toxicological characteristics, is compatible with the environment, has interactive selectivity to insects, is beneficial to the implementation of comprehensive control measures and comprehensive resistance treatment in agricultural production, and can reduce the occurrence of virus hazard of crops, so that the advantages determine that the pymetrozine has wide application prospect in agricultural production. In conclusion of the reported structure-activity relationship, the research work of the predecessor on the pymetrozine insecticide is mainly focused on modifying and modifying the parts of the triazine ketone ring and the pyridine ring, and the modification of the intermediate connecting arm is less reported. The structure of compounds with imine-to-amide modifications was reported in Beriger 1994, but no activity data was reported (Beriger, E.; Kristinsson, H.US 5324842.1994-06-28.). In 1996 Uehara reported the structure of compounds in which the N atom contained substituents after imine reduction, and reported that some of the compounds exhibited 100% insecticidal activity against Myzus persicae and Sorbodes oryzae at a concentration of 500ppm (Uehara, M.; Shimizu. T.; Fujioka. S. et al. EP 0987255A 2.1996-03-28.). The compound structure with imine replaced by amide is reported in the Europe Guiping group in 2013, and the bacteriostatic activity of the compound on wheat scab pathogen, pepper fusarium wilt pathogen and apple rot pathogen is researched (Zhang Yonglu, Europe Guiping, Hebao An. modern pesticide 2013.12(2) 10-13.). With the wide application of pymetrozine, the problem of pymetrozine resistance is also more and more prominent, and therefore, the development of an insecticide with a similar action mode to that of pymetrozine is an important subject faced by researchers.
Disclosure of Invention
The invention aims to provide acylhydrazone structure-containing triazinone derivatives, a preparation method thereof and application thereof in the aspects of disinsection and sterilization. The acylhydrazone structure-containing triazinone derivative has good insecticidal activity and bactericidal activity.
The acylhydrazone structure-containing triazinone derivative is a compound having a structure shown in the following general formula (I):
the acylhydrazone structure-containing triazone derivative (I) provided by the invention has the following three general formulasa，Ib，Ic) A compound of the structure:
the invention relates to acylhydrazone structure-containing triazinone derivative Ia-1--1a-57 can be prepared as follows (scheme one): firstly, the aminotriazinone (II) reacts with phenyl chloroformate to generate a compound III, the compound III reacts with hydrazine hydrate to generate an intermediate semicarbazide triazone IV, and thenCompounds IV and aldehydes VaReacting to generate acylhydrazone structure-containing triazinone compound Ia；
Route one:
the solvent for the first step reaction can be methanol, dichloromethane, chloroform, 1, 2-dichloroethane, acetonitrile; the acid-binding agent can be pyridine, sodium carbonate, triethylamine, potassium carbonate, and cesium carbonate; the reaction temperature is between 60 ℃ and 80 ℃; the solvent for the second step reaction can be methanol, dichloromethane, ethanol, 1, 2-dichloroethane, acetonitrile; the reaction temperature is between 80 ℃ and 100 ℃; the solvent for the third step reaction can be methanol, ethanol, acetonitrile, N-dimethylformamide; the catalyst can be trifluoroacetic acid, p-toluenesulfonic acid and glacial acetic acid; the reaction temperature is 70 to 100 ℃.
The invention relates to acylhydrazone structure-containing triazinone derivative Ib-1--1b-28 can be prepared as follows (scheme two): reacting semicarbazide triazone (IV) with various ketones to generate triazone compound I containing acylhydrazone structureb；
And a second route:
the solvent can be methanol, ethanol, 1, 2-dichloroethane, chloroform, acetonitrile; the catalyst can be trifluoroacetic acid, p-toluenesulfonic acid; the reaction temperature is between 80 ℃ and 120 ℃.
The invention relates to acylhydrazone structure-containing triazinone derivative Ic-1--1c-15 can be prepared as follows (scheme three): semicarbazide triazinones (II) with various phenoxy-substituted pyridylmethyl ketones VcReacting to generate a compound I containing acylhydrazone structure triazonec；
And a third route:
the solvent can be methanol, ethanol, chloroform, 1, 2-dichloroethane, acetonitrile; the catalyst can be trifluoroacetic acid, p-toluenesulfonic acid; the reaction temperature is between 80 ℃ and 120 ℃.
In the above general formula, the compound represented by the formula,
R1respectively represent 2-10 carbon alkyl, 3-6 carbon cycloalkyl, benzyl, naphthyl, substituted phenyl (wherein the substituent can be hydrogen, hydroxyl, halogen atom, cyano, nitro, ester group, dimethylamino, trifluoromethyl, trifluoromethoxy, 1-5 carbon alkyl, 1-6 carbon alkoxy, and simultaneously contains 2-3 of the above substituents), 1-10 carbon nitrogen-containing heterocycle, 1-10 carbon oxygen-containing heterocycle and 1-10 carbon sulfur-containing heterocycle;
R2respectively represent 1-10 carbon hydrocarbyl, phenyl, substituted phenyl (wherein the substituent can be hydrogen, hydroxyl, halogen atom, cyano, nitro, ester group, fluorine, trifluoromethyl, trifluoromethoxy, 1-5 carbon hydrocarbyl, 1-6 carbon alkoxy and simultaneously contain 2-3 substituents), and R2And R3A 3-6 carbon cycloalkyl group;
R3respectively represent substituted phenyl (wherein the substituent can be hydrogen, hydroxyl, halogen atom, cyano, nitro, ester group, fluorine, trifluoromethyl, trifluoromethoxy, 1-5 carbon hydrocarbyl, 1-6 carbon alkoxy and simultaneously contains 2-3 substituents);
R4respectively represent hydrogen, hydroxyl, 1-6 carbon alkoxy, 1-10 carbon alkylamino, halogen atom, cyano, aldehyde group, 1-6 carbon alkylcarbonyl, 1-10 carbon alkoxycarbonyl, 1-10 carbon alkylaminocarbonyl, 1-6 carbon alkoxycarbonyloxy and 1-6 carbon alkylaminocarbonyloxy; and simultaneously contains 2 to 3R4The substituents are as represented.
The acylhydrazone-containing triazinone derivative (I) of the present invention is preferably a compound of:
(E) -2- (2, 2-dimethylpropylidene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoyl hydrazine (I)a-3)；
(E) -2- (cyclohexylmethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoylhydrazine (I)a-4)；
(E) -2- (2, 3-dimethoxyphenylmethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoylhydrazine (I)a-13)；
(E) -2- (2, 4-dimethoxyphenylmethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoylhydrazine (I)a-14)；
(E) -2- (3, 5-Dimethoxyphenylmethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoylhydrazine (I)a-15)；
(E) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) -2- (2, 3, 4-trimethoxyphenylmethylene) carbamoyl hydrazine (I)a-16)；
(E) -2- (3-cyanophenylmethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoylhydrazine (I)a-35)；
(E) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) -2- (3-nitrophenylmethylene) carbamoyl hydrazine (I)a-38)；
(E) -2- (4- (dimethylamino) phenylmethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoylhydrazine (I)a-44)；
(E) -2- ((6-methoxynaphthalen-2-yl) phenylmethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoyl hydrazine (I)a-47)；
(E) -2- ((1H-indol-3-yl) phenylmethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoyl hydrazine (I)a-50)；
(E) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) -2- (pyridin-2-ylphenylmethylene) carbamoylhydrazine (I)a-51)；
(E) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) -2- (pyridin-3-ylphenylmethylene) carbamoylhydrazine (I)a-52)；
(E) -2- (furan-2-ylphenylmethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoylhydrazine (I)a-54)；
(E) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) -2- (thien-2-ylphenylmethylene) carbamoylhydrazine (I)a-55)；
2-cyclopentylidene-N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoylhydrazine (I)b-3)；
(E) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) -2- (1-phenylethylene) carbamoyl hydrazine (I)b-6)；
(E) -2- (1- (4-methoxyphenyl) ethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) -2- (1-phenylethylene) carbamoyl hydrazine (I)b-11)；
(E) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) -2- (1- (3, 4, 5-trimethoxyphenyl) ethylene) carbamoyl hydrazine (I)b-13)；
(E) -2- (1- (4-chlorophenyl) ethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) -2- (1-phenylethylene) carbamoylhydrazine (I)b-16)；
(E) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) -2- (1-p-methylphenylethylene) carbamoylhydrazine (I)b-22)；
(E) -2- (1- (4-hydroxyphenyl) ethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) -2- (1-phenylethylene) carbamoylhydrazine (I)b-25)；
(E) -2- (1- (6- (2-ethoxyphenoxy) pyridin-3-yl) ethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) -2- (1-phenylethylene) carbamoyl hydrazine (I)c-2)；
(E) -2- (1- (6- (4-ethylphenoxy) pyridin-3-yl) ethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) -2- (1-phenylethylene) carbamoyl hydrazine (I)c-5)；
(E) -2- (1- (6- (4-isopropylphenoxy) pyridin-3-yl) ethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) -2- (1-phenylethylene) carbamoyl hydrazine (I)c-6)；
(E) -2- (1- (6- (4-tert-butylphenoxy) pyridine-3-yl) ethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) -2- (1-phenylethylene) carbamoylhydrazine (I)c-7)；
(E) -2- (1- (6- (4-bromophenoxy) pyridin-3-yl) ethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) -2- (1-phenylethylene) carbamoyl hydrazine (I)c-8)；
(E) -2- (1- (6- (4-iodophenoxy) pyridin-3-yl) ethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) -2- (1-phenylethylene) carbamoyl hydrazine (I)c-9)；
(E) -2- (1- (6- (4-isopropyl-3-methylphenoxy) pyridin-3-yl) ethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) -2- (1-phenylethylene) carbamoyl hydrazine (I)c-12)。
The compounds of the general formula (I) show good aphid killing activity, wherein the compound Ia-13、Ia-14、Ia-15、Ia-16、Ia-44、Ia-50、Ia-51、Ia-52、Ia-54、Ia-55、Ib-13、Ic-2、Ic-5、Ic-6、Ic-7、Ic-8、Ic-9、Ic-12 showed an activity comparable to pymetrozine at a concentration of 5 mg/kg. Meanwhile, part of compounds show good activity to mosquito larvae, in particular to compound Ia-47 shows 40% insecticidal activity against mosquito larvae at a concentration of 0.01 mg/kg. In addition, all compounds showed insecticidal activity against cotton bollworm, corn borer and armyworm. Wherein the compound Ib44 at 100mg/kg, the insecticidal activity on cotton bollworm, corn borer and armyworm is 30%, 20% and 60%, respectively.
The compound of the general formula (I) shows bactericidal activity to the following 14 pathogenic bacteria, wherein the 14 pathogenic bacteria are respectively: early blight of tomato, gibberella zeae, late blight of potato, phytophthora capsici, sclerotium of colza, botrytis cinerea, rice sheath blight, cucumber wilt, peanut brown spot, apple ring streak, wheat sheath blight, corn small spot, watermelon anthrax and rice bakanae, especially compound Ia-18、Ia-26、Ia-38、Ia-53、Ib-4、Ib-6、Ib-11、Ic-2、Ic-7、Ic-9、Ic-14 and Ic14 shows good bacteriostatic activity on various pathogenic bacteria at the concentration of 50 mg/kg.
Detailed Description
The following examples and biological test results are provided to further illustrate the invention and are not meant to limit the invention.
Example 1: synthesis of N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoylhydrazine
Synthesis of phenyl (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamate (III)
In a 100mL single-neck flask, dichloromethane (50mL), aminotriazinone (II) (2.56g, 20mmol) and potassium carbonate (2.76g, 20mmol) were added, followed by stirring thoroughly, phenyl chloroformate (3.13g, 20mmol) was slowly dropped at room temperature over about 1h, followed by heating and refluxing for 6h, and the completion of the reaction was monitored by TLC. Cooling to room temperature, filtering, desolventizing the solution under reduced pressure, and performing normal pressure column chromatography with petroleum ether/ethyl acetate (1: 1) to obtain a compound III4.5g, a white solid, a yield of 91 percent and a melting point of 181-182 ℃.1H NMR(300MHz，DMSO-d6)10.08(s，1H，NH)，9.92(s，1H，NH)，7.42(t，J＝14.7，7.8Hz，2H，Ph-H)，7.25(t，J＝14.7，7.2Hz，1H，Ph-H)，7.14(d，J＝7.8Hz，2H，Ph-H)，4.15(s，2H，CH2)，1.88(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)154.0，151.2，150.5，145.2，129.5，125.6，121.5，51.5，19.9；ESI-HRMS(m/z)：Calcd.for C11H13N4O3[M+H]+249.0982，found 249.0988
Synthesis of N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoylhydrazine (IV)
In a 250mL single-neck flask, methanol (120mL), compound III (2.7g, 11 mmol) was added) Hydrazine hydrate (10mL) was stirred well, then heated to reflux for 8h and the reaction was monitored by TLC for completion. The temperature was reduced to room temperature and the mixture was filtered to obtain IV1.56g of a white solid in a yield of 77% and a melting point of 229-.1H NMR(300MHz，DMSO-d6)9.65(s，1H，NH)，8.25(s，1H，NH)，7.60(s，1H，NH)，4.11(s，2H，NH2)，4.02(s，2H，CH2)，1.83(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)159.1，151.7，144.7，52.4，19.9.ESI-HRMS(m/z)：Calcd.for C5H11N6O2[M+H]+187.0938；found 187.0939.
Example 2: (E) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) -2-propylenecarbamoylhydrazine (I)aSynthesis of (1)
In a 250mL single-neck flask, semicarbazide triazone (0.74g, 4mmol), p-toluenesulfonic acid (0.14g, 8mmol), n-propionaldehyde (0.23g, 4mmol) and methanol (120mL) were added, stirred and dissolved, then heated under reflux for 6h, and the reaction was monitored by TLC for completion. And (3) removing the solvent from the reaction solution under reduced pressure to precipitate a solid, performing suction filtration at normal pressure, and washing with methanol to obtain 0.48g of a target compound, namely a white solid, wherein the yield is 53 percent, and the melting point is 148 ℃.1H NMR(400MHz，CDCl3)9.10(s，1H，NH)，7.99(s，2H，NH)，7.14(t，J＝4.0Hz，1H，＝CH)，4.23(s，2H，CH2)，2.24(q，2H，CH2CH3)，1.94(s，3H，CH3)，1.07(t，J＝6.8Hz，3H，CH2CH3)；13C NMR(100MHz，CDCl3)155.6，152.2，148.6，145.7，53.0，25.7，20.4，10.6.ESI-HRMS(m/z)：Calcd.for C8H14N6O2[M+H]+227.1251；found 227.1253.
Compound Ia-2-Ia-57 is done by repeating the above steps.
(E) -2-butylidene-N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoyl hydrazine(Ia-2)
White solid, yield 57%, melting point 173-.1H NMR(400MHz，CDCl3)8.63(s，1H，NH)，7.90(s，1H，NH)，7.66(s，1H，NH)，7.08(t，J＝5.2Hz，1H，＝CH)，4.25(s，2H，CH2)，2.21(m，2H，CH2CH2CH3)，1.95(s，3H，CH3)，1.54(m，2H，CH2CH2CH3)，0.95(t，J＝7.6Hz，3H，CH2CH2CH3)；13C NMR(100MHz，CDCl3)155.4，152.0，147.3，145.6，53.0，34.3，20.4，19.8，13.9.ESI-HRMS(m/z)：Calcd.for C9H16N6O2[M+H]+241.1408；found 241.1407.
(E) -2- (2, 2-dimethylpropylidene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoyl hydrazine (I)a-3)
White solid, yield 67%, m.p. 230-.1H NMR(400MHz，DMSO-d6)10.25(s，1H，NH)，9.73(s，1H，NH)，8.60(s，1H，NH)，7.12(s，1H，＝CH)，4.06(s，2H，CH2)，1.84(s，3H，CH3)，1.05(s，9H，C(CH3)3)；13C NMR(100MHz，DMSO-d6)154.6，152.5，151.7，144.8，52.2，34.2，27.4，19.8.ESI-HRMS(m/z)：Calcd.for C10H19N6O2[M+H]+255.1564；found 255.1567.
(E) -2- (cyclohexylmethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoylhydrazine (I)a-4)；
White solid, yield 75%, melting point 213-.1H NMR(400MHz，DMSO-d6)10.26(s，1H，NH)，9.72(s，1H，NH)，8.64(s，1H，NH)，7.09(d，J＝5.2Hz，1H，＝CH)，4.05(s，2H，CH2)，1.84(s，3H，CH3)，1.68-76(m，CH2)，1.61-1.64(m，1H)，1.14-1.27(m，6H，CH2)；13C NMR(100MHz，DMSO-d6)154.6，151.6，149.0，144.8，52.2，29.8，25.6，25.1，19.9.ESI-HRMS(m/z)：Calcd.forC12H21N6O2[M+H]+281.1721；found 281.1725.
(E) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) -2- (2-phenylethylidene) carbamoyl hydrazine (I)a-5)
White solid, 48% yield, melting point 125-.1H NMR(400MHz，CDCl3)9.10(s，1H，NH)，8.03(s，1H，NH)，7.81(s，1H，NH)，7.33(d，J＝7.2Hz，2H，Ar-H)，7.28(t，J＝6.0Hz，1H，＝CH)，7.22(d，J＝7.2Hz，2H，Ar-H)，7.19(t，J＝5.6Hz，1H，Ar-H)，4.24(s，2H，CH2)，3.46(d，J＝5.6Hz，2H，＝CHCH2)，1.95(s，3H，CH3)；13C NMR(100MHz，CDCl3)155.3，152.0，148.5，145.7，130.4，129.1，129.0，127.3，53.0，38.9，20.4.ESI-HRMS(m/z)：Calcd.for C13H16N6O2[M+H]+289.1408；found 289.1404.
(E) -2-phenylmethylene-N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoyl hydrazine (I)a-6)；
White solid, yield 69%, melting point 219-.1H NMR(400MHz，DMSO-d6)10.77(s，1H，NH)，9.78(s，1H，NH)，9.25(s，1H，NH)，7.87(s，1H，＝CH)，7.78(d，J＝6.8Hz，2H，Ar-H)，7.37-7.43(m，3H，Ar-H)，4.12(s，2H，CH2)，1.87(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)154.7，151.7，144.9，141.1，134.4，129.5，128.6，126.9，52.2，19.9.ESI-HRMS(m/z)：Calcd.forC12H15N6O2[M+H]+275.1251；found 275.1246.
(E) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) -2- (2-methylphenylmethylene) carbamoylhydrazine (I)a-7)；
White solid, yield 72%, melting point 229-.1H NMR(400MHz，DMSO-d6)10.69(s，1H，NH)，9.77(s，1H，NH)，9.16(s，1H，NH)，8.18(s，1H，＝CH)，8.04(d，J＝6.4Hz，1H，Ar-H)，7.22-7.26(m，3H，Ar-H)，4.11(s，2H，CH2)，2.38(s，3H，CH3)，1.87(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)154.6，151.7，144.8，139.6，136.2，132.3，130.7，129.2，126.0，125.7，52.2，19.9，18.8.ESI-HRMS(m/z)：Calcd.for C13H17N6O2[M+H]+289.1408；found 289.1412.
(E) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) -2- (3-methylphenylmethylene) carbamoylhydrazine (I)a-8)；
White solid, 62% yield, melting point 215-.1H NMR(400MHz，DMSO-d6)10.73(s，1H，NH)，9.77(s，1H，NH)，9.22(s，1H，NH)，7.83(s，1H，＝CH)，7.65(s，1H，Ar-H)，7.52(d，J＝7.6Hz，1H，Ar-H)，7.29(t，J＝7.6Hz，1H，Ar-H)，7.19(d，J＝7.6Hz，1H，Ar-H)，4.12(s，2H，CH2)，2.33(s，3H，CH3)，1.87(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)154.8，151.8，145.0，141.3，137.9，134.4，130.2，128.6，127.2，124.5，52.3，21.0，19.9.ESI-HRMS(m/z)：Calcd.forC13H17N6O2[M+H]+289.1408；found 289.1410.
(E) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) -2- (4-methylphenylmethylene) carbamoylhydrazine (I)a-9)；
White solid, yield 78%, melting point 264-.1H NMR(400MHz，DMSO-d6)：10.69(s，1H，NH)，9.76(s，1H，NH)，9.20(s，1H，NH)，7.83(s，1H，＝CH)，7.67(d，J＝7.2Hz，2H，Ar-H)，7.22(d，J＝7.2Hz，2H，Ar-H)，4.11(s，2H，CH2)，2.32(s，3H，CH3)，1.87(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)154.7，151.8，144.9，141.2，139.2，131.8，129.3，126.9，52.2，21.0，19.9.ESI-HRMS(m/z)：Calcd.for C13H17N6O2[M+H]+289.1408；found 289.1413.
(E) -2- (2-methoxyphenylmethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoylhydrazine (I)a-10)；
Yellow solid, yield 67%, m.p. 232-.1H NMR(400MHz，DMSO-d6)10.73(s，1H，NH)，9.76(s，1H，NH)，9.21(s，1H，NH)，8.22(s，1H，＝CH)，8.08(d，J＝7.6Hz，1H，Ar-H)，7.36(t，J＝8.0Hz，1H，Ar-H)，7.07(d，J＝8.0Hz，1H，Ar-H)，6.97(t，J＝7.6Hz，1H，Ar-H)，4.11(s，2H，CH2)，3.83(s，3H，OCH3)，1.87(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)157.3，154.6，151.7，144.8，136.4，130.9，125.8，122.3，120.5，111.6，55.6，52.2，19.9.ESI-HRMS(m/z)：Calcd.for C13H17N6O3[M+H]+305.1357；found 305.1359.
(E) -2- (3-methoxyphenylmethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoylhydrazine (I)a-11)；
White solid, yield 67%, m.p. 226-.1H NMR(400MHz，DMSO-d6)10.78(s，1H，NH)，9.78(s，1H，NH)，9.29(s，1H，NH)，7.83(s，1H，＝CH)，7.43(s，1H，Ar-H)，7.31(t，J＝7.6Hz，1H，Ar-H)，7.25(d，J＝7.2Hz，1H，Ar-H)，6.94(d，J＝7.2Hz，1H，Ar-H)，4.12(s，2H，CH2)，3.80(s，3H，OCH3)，1.87(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)159.6，154.6，151.8，144.9，141.0，135.8，129.7，120.2，115.8，110.8，55.3，52.2，19.9.ESI-HRMS(m/z)：Calcd.forC13H17N6O3[M+H]+305.1357；found 305.1359.
(E) -2- (4-Methoxyphenylmethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoylhydrazine (I)a-12)；
White solid, yield 82%, m.p. 230-.1H NMR(400MHz，DMSO-d6)10.62(s，1H，NH)，9.76(s，1H，NH)，9.17(s，1H，NH)，7.80(s，1H，＝CH)，7.72(d，J＝8.0Hz，2H，Ar-H)，6.96(d，J＝8.0Hz，2H，Ar-H)，4.11(s，2H，CH2)，3.79(s，3H，OCH3)，1.87(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)160.4，154.7，151.7，144.8，141.0，128.5，127.1，114.1，55.3，52.2，19.9.ESI-HRMS(m/z)：Calcd.for C13H17N6O3[M+H]+305.1357；found 305.1359.
(E) -2- (2, 3-dimethoxyphenylmethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoylhydrazine (I)a-13)；
White solid, yield 80%, melting point 226-.1H NMR(400MHz，DMSO-d6)10.75(s，1H，NH)，9.77(s，1H，NH)，9.21(s，1H，NH)，8.16(s，1H，＝CH)，7.68(d，J＝6.8Hz，2H，Ar-H)，7.04-7.10(m，2H，Ar-H)，4.10(s，2H，CH2)，3.82(s，3H，OCH3)，3.74(s，3H，OCH3)，1.86(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)154.6，152.6，151.7，147.5，144.8，136.7，127.8，124.1，117.4，113.6，61.2，55.7，52.2，19.9.ESI-HRMS(m/z)：Calcd.for C14H19N6O4[M+H]+335.1462；found 335.1469.
(E) -2- (2, 4-dimethoxyphenylmethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoylhydrazine (I)a-14)；
White solid, yield 76%, m.p. 210-.1H NMR(400MHz，DMSO-d6)10.57(s，1H，NH)，9.75(s，1H，NH)，9.13(s，1H，NH)，8.11(s，1H，＝CH)，7.99(d，J＝8.4Hz，1H，Ar-H)，6.59(s，1H，Ar-H)，6.56(d，J＝8.4Hz，1H，Ar-H)，4.10(s，2H，CH2)，3.82(s，3H，OCH3)，3.80(s，3H，OCH3)，1.86(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)161.9，158.6，154.7，151.7，144.8，136.6，127.0，115.2，106.2，98.0，55.7，55.4，52.2，19.9.ESI-HRMS(m/z)：Calcd.forC14H19N6O4[M+H]+335.1462；found 335.1463.
(E) -2- (3, 5-Dimethoxyphenylmethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoylhydrazine (I)a-15)；
White solid, yield 87%, m.p. 245 ℃.1H NMR(400MHz，DMSO-d6)10.81(s，1H，NH)，9.80(s，1H，NH)，9.33(s，1H，NH)，7.77(s，1H，＝CH)，6.95(brs，2H，Ar-H)，6.49(s，1H，Ar-H)，4.13(s，2H，CH2)，3.77(s，6H，OCH3)，1.87(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)160.6，154.6，151.8，144.9，141.0，136.4，104.7，101.8，55.4，52.2，19.9.ESI-HRMS(m/z)：Calcd.for C14H19N6O4[M+H]+335.1462；found 335.1460.
(E) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) -2- (2, 3, 4-trimethoxyphenylmethylene) carbamoyl hydrazine (I)a-16)；
White solid, yield 78%, melting point 244-.1H NMR(400MHz，DMSO-d6)10.64(s，1H，NH)，9.77(s，1H，NH)，9.17(s，1H，NH)，8.06(s，1H，＝CH)，7.81(d，J＝8.4Hz，1H，Ar-H)，6.87(d，J＝8.4Hz，1H，Ar-H)，4.10(s，2H，CH2)，3.84(s，3H，OCH3)，3.79(s，3H，OCH3)，3.75(s，3H，OCH3)，1.86(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)154.6，152.2，151.8，144.8，141.5，136.7，120.8，120.5，108.5，61.8，60.5，56.0，52.2，19.9.ESI-HRMS(m/z)：Calcd.forC15H21N6O5[M+H]+365.1568；found 365.1569.
(E) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazine-4 (5H)-yl) -2- (3, 4, 5-trimethoxyphenylmethylene) carbamoyl hydrazine (I)a-17)；
White solid, yield 71%, m.p. 233-.1H NMR(400MHz，DMSO-d6)10.80(s，1H，NH)，9.81(s，1H，NH)，9.32(s，1H，NH)，7.78(s，1H，＝CH)，7.09(s，2H，Ar-H)，4.16(s，2H，CH2)，3.84(s，6H，OCH3)，3.69(s，3H，OCH3)，1.88(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)154.7，153.2，151.9，145.0，141.1，138.6，129.9，104.2，60.1，56.1，52.2，19.9.ESI-HRMS(m/z)：Calcd.for C15H21N6O5[M+H]+365.1568；found 365.1569.
(E) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) -2- (2- (trifluoromethyl) phenylmethylene) carbamoylhydrazine (I)a-18)；
White solid, yield 79%, melting point 262-.1H NMR(400MHz，DMSO-d6)11.07(s，1H，NH)，9.80(s，1H，NH)，9.41(s，1H，NH)，8.48(d，J＝7.2Hz，1H，Ar-H)，8.23(s，1H，＝CH)，7.70-7.77(m，2H，Ar-H)，7.58(t，J＝7.2Hz，1H，Ar-H)，4.12(s，2H，CH2)，1.87(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)154.4，151.7，144.9，136.2，132.5，132.2，129.5，127.1，126.3(q，J＝268.5Hz)，125.7(q，J＝8.4Hz)，122.9，52.1，19.9.ESI-HRMS(m/z)：Calcd.for C13H14F3N6O2[M+H]+343.1125；found 343.1130.
(E) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) -2- (3- (trifluoromethyl) phenylmethylene) carbamoylhydrazine (I)a-19)；
White solid, yield 86%, melting point 278-.1H NMR(300MHz，DMSO-d6)10.95(s，1H，NH)，9.79(s，1H，NH)，9.46(s，1H，NH)，8.28(s，1H，＝CH)，8.00(d，J＝7.5Hz，1H，Ar-H)，7.95(s，1H，Ar-H)，7.71(d，J＝6.0Hz，1H，Ar-H)，7.63(t，J＝7.5Hz，1H，Ar-H)，4.14(s，2H，CH2)，1.88(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)154.6，151.8，144.9，139.5，135.6，131.3，129.7，129.7(q，J＝253.2Hz)，129.6(q，J＝31.8Hz)，125.6，122.8，52.2，19.9.ESI-HRMS(m/z)：Calcd.for C13H14F3N6O2[M+H]+343.1125；found 343.1128.
(E) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) -2- (4- (trifluoromethyl) phenylmethylene) carbamoylhydrazine (I)a-20)；
White solid, yield 76%, melting point 239-.1H NMR(400MHz，DMSO-d6)10.99(s，1H，NH)，9.79(s，1H，NH)，9.40(s，1H，NH)，8.02(d，J＝8.0Hz，2H，Ar-H)，7.94(s，1H，＝CH)，7.76(d，J＝8.0Hz，2H，Ar-H)，4.13(s，2H，CH2)，1.88(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)154.5，151.7，144.9，139.4，138.4，129.1(q，J＝254.4Hz)，127.4，125.4(q，J＝10.0Hz)，122.9，52.2，19.9.ESI-HRMS(m/z)：Calcd.for C13H14F3N6O2[M+H]+343.1125；found 343.1130.
(E) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) -2- (3- (trifluoromethoxy) phenylmethylene) carbamoylhydrazine (I)a-21)；
White solid, yield 78%, melting point 264-.1H NMR(300MHz，DMSO-d6)10.94(s，1H，NH)，9.80(s，1H，NH)，9.44(s，1H，NH)，7.97(s，1H，＝CH)，7.89(s，1H，Ar-H)，7.71(d，J＝8.0Hz，1H，Ar-H)，7.53(t，J＝8.0Hz，1H，Ar-H)，7.36(d，J＝8.0Hz，1H，Ar-H)，4.13(s，2H，CH2)，1.87(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)154.6，151.8，148.9，144.9，139.4，137.0，130.6，126.7，121.6，120.1(q，J＝254.5Hz)，118.6，52.2，19.8.ESI-HRMS(m/z)：Calcd.forC13H14F3N6O3[M+H]+359.1074；found 359.1077.
(E) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) -2- (4- (trifluoromethoxy) phenylmethylene) carbamoylhydrazine (I)a-22)；
White solid, yield 87%, melting point 266-.1H NMR(400MHz，DMSO-d6)10.86(s，1H，NH)，9.78(s，1H，NH)，9.32(s，1H，NH)，7.93(d，J＝8.4Hz，2H，Ar-H)，7.89(s，1H，＝CH)，7.40(d，J＝8.4Hz，2H，Ar-H)，4.12(s，2H，CH2)，1.87(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)154.7，151.8，148.9，144.9，139.5，133.9，128.8，121.2，120.1(q，J＝254.8Hz)，52.2，19.9.ESI-HRMS(m/z)：Calcd.for C13H14F3N6O3[M+H]+359.1074；found 359.1081.
(E) -2- (2-fluorophenylmethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoyl hydrazine (I)a-23)；
White solid, yield 78%, melting point 233-.1H NMR(400MHz，DMSO-d6)10.92(s，1H，NH)，9.79(s，1H，NH)，9.33(s，1H，NH)，8.17-7.22(m，1H，Ar-H)，8.09(s，1H，＝CH)，7.41-7.46(m，1H，Ar-H)，7.23-7.28(m，2H，Ar-H)，4.12(s，2H，CH2)，1.87(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)160.5(d，J＝248.1Hz)，154.5，151.7，144.9，133.5，131.3(d，J＝6.8Hz)，126.6，124.6，121.9(d，J＝9.3Hz)，115.8(d，J＝20.5Hz)，52.2，19.9.ESI-HRMS(m/z)：Calcd.forC12H14FN6O2[M+H]+293.1157；found 293.1157.
(E) -2- (3-fluorophenylmethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoyl hydrazine (I)a-24)；
White solid, yield 87%, melting point 213-.1H NMR(400MHz，DMSO-d6)10.88(s，1H，NH)，9.78(s，1H，NH)，9.38(s，1H，NH)，7.86(s，1H，＝CH)，7.82(d，J＝10.4Hz，1H，Ar-H)，7.51(d，J＝7.6Hz，1H，Ar-H)，7.41-7.47(m，2H，Ar-H)，7.20(t，J＝8.0Hz，1H，Ar-H)，4.12(s，2H，CH2)，1.87(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)162.6(d，J＝241.4Hz)，154.6，151.7，144.9，139.6，137.1(d，J＝8.1Hz)，130.6(d，J＝8.3Hz)，123.9，116.2(d，J＝21.1Hz)，112.4(d，J＝22.7Hz)，52.2，19.9.ESI-HRMS(m/z)：Calcd.for C12H14FN6O2[M+H]+293.1157；found 293.1160.
(E) -2- (4-fluorophenylmethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoyl hydrazine (I)a-25)；
White solid, 75% yield, m.p. 240 ℃.1H NMR(400MHz，DMSO-d6)10.77(s，1H，NH)，9.77(s，1H，NH)，9.27(s，1H，NH)，7.87(s，1H，＝CH)，7.85(d，J＝8.0Hz，2H，Ar-H)，7.25(t，J＝8.0Hz，2H，Ar-H)，4.11(s，2H，CH2)，1.87(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)162.8(d，J＝245.4Hz)，154.7，151.7，144.8，139.9，131.7(d，J＝2.4Hz)，129.0(d，J＝8.2Hz)，115.6(d，J＝21.6Hz)，52.2，19.8.ESI-HRMS(m/z)：Calcd.for C12H14FN6O2[M+H]+293.1157；found293.1159.
(E) -2- (2-chlorophenylmethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoylhydrazine (I)a-26)；
White solid in 89% yield, mp 248-249 ℃.1H NMR(400MHz，DMSO-d6)10.99(s，1H，NH)，9.78(s，1H，NH)，9.35(s，1H，NH)，8.28(brs，2H，＝CH，Ar-H)，7.47-7.50(m，1H，Ar-H)，7.36-7.42(m，2H，Ar-H)，4.12(s，2H，CH2)，1.87(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)154.5，151.7，144.9，137.0，132.6，131.6，130.9，129.9，127.3，129.2，52.2，19.9.ESI-HRMS(m/z)：Calcd.for C12H14ClN6O2[M+H]+309.0861；found 309.0865.
(E) -2- (3-chlorophenylmethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoylhydrazine (I)a-27)；
White solid, 88% yield, melting point 242-.1H NMR(400MHz，DMSO-d6)10.89(s，1H，NH)，9.79(s，1H，NH)，9.41(s，1H，NH)，8.05(s，1H，Ar-H)，7.84(s，1H，＝CH)，7.61(d，J＝3.2Hz，1H，Ar-H)，7.41-7.44(m，2H，Ar-H)，4.12(s，2H，CH2)，1.87(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)154.6，151.8，144.9，139.5，136.7，133.8，130.5，129.1，126.3，125.6，52.2，19.9.ESI-HRMS(m/z)：Calcd.for C12H14ClN6O2[M+H]+309.0861；found 309.0867.
(E) -2- (4-chlorophenylmethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoyl hydrazine (I)a-28)；
White solid, yield 85%, melting point 275-.1H NMR(400MHz，DMSO-d6)10.86(s，1H，NH)，9.79(s，1H，NH)，9.33(s，1H，NH)，7.85(s，1H，＝CH)，7.83(d，J＝8.0Hz，2H，Ar-H)，7.47(d，J＝8.0Hz，2H，Ar-H)，4.11(s，2H，CH2)，1.87(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)154.6，151.7，144.9，139.7，133.8，133.4，128.9，128.6，52.2，19.9.ESI-HRMS(m/z)：Calcd.forC12H14ClN6O2[M+H]+309.0861；found 309.0861.
(E) -2- (2, 4-dichlorophenylmethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoyl hydrazine (I)a-29)；
White solid, 93% yield, melting point 285-.1H NMR(400MHz，DMSO-d6)11.05(s，1H，NH)，9.80(s，1H，NH)，9.43(s，1H，NH)，8.31(d，J＝8.8Hz，1H，Ar-H)，8.21(s，1H，＝CH)，7.68(s，1H，Ar-H)，7.49(d，J＝8.8Hz，1H，Ar-H)，4.11(s，2H，CH2)，1.87(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)154.4，151.7，144.9，135.8，134.4，133.2，130.7，129.2，128.4，127.7，52.1，19.9.ESI-HRMS(m/z)：Calcd.for C12H13Cl2N6O2[M+H]+343.0472；found 343.0470.
(E) -2- (3, 4-dichlorophenylmethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoyl hydrazine (I)a-30)；
White solid, 88% yield, melting point 265-.1H NMR(400MHz，DMSO-d6)10.97(s，1H，NH)，9.80(s，1H，NH)，9.47(s，1H，NH)，8.24(s，1H，Ar-H)，7.83(s，1H，＝CH)，7.71(d，J＝8.0Hz，1H，Ar-H)，7.67(d，J＝8.0Hz，1H，Ar-H)，4.12(s，2H，CH2)，1.87(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)154.5，151.7，144.8，138.4，135.3，131.7，131.5，130.8，127.8，127.5，52.1，19.9.ESI-HRMS(m/z)：Calcd.for C12H13Cl2N6O2[M+H]+343.0472；found 343.0466.
(E) -2- (2-bromophenylmethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoyl hydrazine (I)a-31)；
White solid, 89% yield, melting point 265 ℃.1H NMR(400MHz，DMSO-d6)11.00(s，1H，NH)，9.78(s，1H，NH)，9.34(s，1H，NH)，8.24(s，2H，＝CH，Ar-H)，7.65(d，J＝7.6Hz，1H，Ar-H)，7.41(t，J＝7.6Hz，1H，Ar-H)，7.31(t，J＝7.6Hz，1H，Ar-H)，4.11(s，2H，CH2)，1.87(s，3H，CH3)；13CNMR(100MHz，DMSO-d6)154.5，151.7，144.9，139.4，133.0，131.2，127.8，127.6，123.0，52.2，19.9.ESI-HRMS(m/z)：Calcd.for C12H14BrN6O2[M+H]+353.0356；found 353.0356.
(E) -2- (3-bromophenylmethylene)Yl) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoylhydrazine (I)a-32)；
White solid, yield 85%, melting point 253-.1H NMR(400MHz，DMSO-d6)10.87(s，1H，NH)，9.78(s，1H，NH)，9.40(s，1H，NH)，8.18(s，1H，Ar-H)，7.83(s，1H，＝CH)，7.66(d，J＝8.0Hz，1H，Ar-H)，7.54(d，J＝8.0Hz，1H，Ar-H)，7.35(t，J＝8.0Hz，1H，Ar-H)，4.12(s，2H，CH2)，1.87(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)154.6，151.8，144.9，139.4，136.9，132.0，130.8，128.5，126.8，122.4，52.2，19.9.ESI-HRMS(m/z)：Calcd.for C12H14BrN6O2[M+H]+353.0356；found 353.0355.
(E) -2- (4-bromophenylmethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoyl hydrazine (I)a-33)；
White solid, yield 82%, melting point 271-272 ℃.1H NMR(400MHz，DMSO-d6)10.86(s，1H，NH)，9.79(s，1H，NH)，9.33(s，1H，NH)，7.84(s，1H，＝CH)，7.76(d，J＝8.0Hz，2H，Ar-H)，7.61(d，J＝8.0Hz，2H，Ar-H)，4.11(s，2H，CH2)，1.87(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)154.6，151.7，144.9，139.8，133.8，131.6，128.9，122.6，52.2，19.9.ESI-HRMS(m/z)：Calcd.forC12H14BrN6O2[M+H]+353.0356；found 353.0354.
(E) -2- (2-cyanophenylmethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoylhydrazine (I)a-34)；
White solid, 84% yield, melting point 274-.1H NMR(400MHz，DMSO-d6)11.15(s，1H，NH)，9.81(s，1H，NH)，9.33(s，1H，NH)，8.36(d，J＝6.8Hz，1H，Ar-H)，8.22(s，1H，＝CH)，7.87(d，J＝7.6Hz，1H，Ar-H)，7.74(t，J＝7.6Hz，1H，Ar-H)，7.56(t，J＝7.6Hz，1H，Ar-H)，4.13(s，2H，CH2)，1.87(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)154.3，151.6，144.9，137.0，136.5，133.2，129.8，126.2，117.4，110.0，52.1，19.9.ESI-HRMS(m/z)：Calcd.for C13H14N7O2[M+H]+300.1203；found 300.1202.
(E) -2- (3-cyanophenylmethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoylhydrazine (I)a-35)；
White solid, yield 65%, melting point 249-.1H NMR(300MHz，DMSO-d6)10.99(s，1H，NH)，9.79(s，1H，NH)，9.46(s，1H，NH)，8.46(s，1H，Ar-H)，8.02(d，J＝7.8Hz，1H，Ar-H)，7.88(s，1H，＝CH)，7.81(d，J＝7.8Hz，1H，Ar-H)，7.61(t，J＝7.8Hz，1H，Ar-H)，4.13(s，2H，CH2)，1.88(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)154.5，151.7，144.9，138.6，135.8，132.3，131.9，129.8，129.7，118.7，111.9，52.1，19.9.ESI-HRMS(m/z)：Calcd.for C13H14N7O2[M+H]+300.1203；found 300.1210.
(E) -2- (4-cyanophenylmethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoylhydrazine (I)a-36)；
White solid, yield 78%, melting point 293-294 ℃.1H NMR(400MHz，DMSO-d6)11.06(s，1H，NH)，9.80(s，1H，NH)，9.44(s，1H，NH)，8.00(d，J＝7.2Hz，2H，Ar-H)，7.90(s，1H，＝CH)，7.88(d，J＝7.2Hz，2H，Ar-H)，4.12(s，2H，CH2)，1.87(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)154.5，151.6，144.8，139.1，139.0，132.5，127.5，118.8，111.2，52.1，19.9.ESI-HRMS(m/z)：Calcd.for C13H14N7O2[M+H]+300.1203；found 300.1206.
(E) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) -2- (2-nitrophenylmethylene) carbamoyl hydrazine (I)a-37)；
Yellow solid, 89% yield, mp 232-.1H NMR(300MHz，DMSO-d6)11.11(s，1H，NH)，9.80(s，1H，NH)，9.38(s，1H，NH)，8.43(d，J＝7.5Hz，1H，Ar-H)，8.31(s，1H，＝CH)，8.03(d，J＝7.5Hz，1H，Ar-H)，7.76(t，J＝7.5Hz，1H，Ar-H)，7.62(t，J＝7.5Hz，1H，Ar-H)，4.12(s，2H，CH2)，1.87(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)154.4，151.7，148.0，144.9，136.2，133.3，130.1，128.6，128.0，124.6，52.1，19.9.ESI-HRMS(m/z)：Calcd.for C12H14N7O4[M+H]+320.1102；found 320.1103.
(E) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) -2- (3-nitrophenylmethylene) carbamoyl hydrazine (I)a-38)；
White solid, yield 79%, melting point 277-.1H NMR(300MHz，DMSO-d6)11.02(s，1H，NH)，9.80(s，1H，NH)，9.53(s，1H，NH)，8.69(s，1H，Ar-H)，8.20(d，J＝7.2Hz，2H，Ar-H)，7.99(s，1H，＝CH)，7.69(t，J＝8.0Hz，1H，Ar-H)，4.13(s，2H，CH2)，1.88(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)154.5，151.7，148.4，144.9，139.0，136.4，133.4，130.1，123.6，120.8，52.2，19.9.ESI-HRMS(m/z)：Calcd.for C12H14N7O4[M+H]+320.1102；found 320.1102.
(E) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) -2- (4-nitrophenylmethylene) carbamoyl hydrazine (I)a-39)；
White solid, yield 82%, melting point 294-.1H NMR(400MHz，DMSO-d6)11.13(s，1H，NH)，9.81(s，1H，NH)，9.49(s，1H，NH)，8.24(d，J＝7.2Hz，2H，Ar-H)，8.08(d，J＝7.2Hz，2H，Ar-H)，7.97(s，1H，＝CH)，4.13(s，2H，CH2)，1.87(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)154.5，151.7，147.4，144.9，140.9，138.7，127.8，123.9，52.1，19.9.ESI-HRMS(m/z)：Calcd.forC12H14N7O4[M+H]+320.1102；found 320.1103.
(E) -2- (3-hydroxyphenylmethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoyl hydrazine (I)a-40)；
White solid, yield 95%, melting point 264-.1H NMR(300MHz，DMSO-d6)10.69(s，1H，NH)，9.76(s，1H，NH)，9.52(s，1H，NH)，9.17(s，1H，OH)，7.78(s，1H，＝CH)，7.16-7.23(m，3H，Ar-H)，6.80(s，1H，Ar-H)，4.10(s，2H，CH2)，1.87(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)157.6，154.7，151.7，144.9，141.4，135.8，129.6，118.1，116.6，113.3，52.2，19.9.ESI-HRMS(m/z)：Calcd.for C12H15N6O3[M+H]+291.1200；found 291.1205.
(E) -2- (4-hydroxyphenylmethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoyl hydrazine (I)a-41)；
White solid, 74% yield, mp 237-.1H NMR(400MHz，DMSO-d6)10.54(s，1H，NH)，9.81(s，1H，NH)，9.75(s，1H，NH)，9.10(s，1H，OH)，7.76(s，1H，＝CH)，7.59(d，J＝8.0Hz，2H，Ar-H)，6.77(d，J＝8.0Hz，2H，Ar-H)，4.10(s，2H，CH2)，1.86(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)158.9，154.8，151.8，144.8，141.4，128.6，125.5，115.5，52.2，19.9.ESI-HRMS(m/z)：Calcd.for C12H15N6O3[M+H]+291.1200；found 291.1200.
(E) -2- (2, 4-dihydroxyphenylmethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoylhydrazine (I)a-42)；
White solid, 68% yield, melting point 251-.1H NMR(300MHz，DMSO-d6)10.48(s，1H，NH)，9.74(s，1H，NH)，9.42(s，1H，NH)，9.02(s，1H，OH)，8.94(s，1H，OH)，7.69(s，1H，＝CH)，7.19(s，1H，Ar-H)，6.98(d，J＝7.8Hz，1H，Ar-H)，6.74(d，J＝7.8Hz，1H，Ar-H)，4.10(s，2H，CH2)，1.86(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)154.8，151.8，147.3，145.6，144.9，141.9，126.0，119.7，115.4，113.6，52.3，19.9.ESI-HRMS(m/z)：Calcd.for C12H15N6O4[M+H]+307.1149；found 307.1153.
(E) -2- (4-tert-butylphenylmethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoyl hydrazine (I)a-43)；
White solid, yield 69%, melting point 211-.1H NMR(400MHz，DMSO-d6)10.71(s，1H，NH)，9.77(s，1H，NH)，9.19(s，1H，NH)，7.84(s，1H，＝CH)，7.69(d.J＝7.2Hz，2H，Ar-H)，7.42(d，J＝7.2Hz，2H，Ar-H)，4.12(s，2H，CH2)，1.87(s，3H，CH3)，1.29(s，9H，C(CH3)3)；13C NMR(100MHz，DMSO-d6)154.7，152.2，151.7，144.8，141.1，131.7，126.7，125.4，52.2，34.6，31.0，19.9.ESI-HRMS(m/z)：Calcd.for C16H23N6O2[M+H]+331.1877；found 331.1882.
(E) -2- (4- (dimethylamino) phenylmethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoylhydrazine (I)a-44)；
Pink solid, 69% yield, melting point 229-.1H NMR(400MHz，DMSO-d6)10.46(s，1H，NH)，9.75(s，1H，NH)，9.06(s，1H，NH)，7.73(s，1H，＝CH)，7.57(d，J＝8.4Hz，2H，Ar-H)，6.70(d，J＝8.4Hz，2H，Ar-H)，4.11(s，2H，CH2)，2.95(s，6H，N(CH3)2)，1.86(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)154.7，151.7，151.1，144.8，141.9，128.1，121.9，111.7，52.2，39.8，19.8.ESI-HRMS(m/z)：Calcd.for C14H20N7O2[M+H]+318.1673；found 318.1677.
(E) -2- ((2-hydroxynaphthalen-1-yl) methylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoyl hydrazine (I)a-45)；
Yellow solid, 98% yield, mp 258 ℃.1H NMR(400MHz，DMSO-d6)10.77(s，1H，NH)，9.85(s，1H，NH)，9.00(s，2H，NH，OH)，8.37(s，1H，＝CH)，7.87(d，J＝4.4Hz，1H，Ar-H)，7.85(d，J＝3.6Hz，1H，Ar-H)，7.56(t，J＝7.2Hz，1H，Ar-H)，7.38(t，J＝7.2Hz，1H，Ar-H)，7.20(d，J＝8.8Hz，1H，Ar-H)，4.13(s，2H，CH2)，1.89(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)156.6，154.2，151.8，145.0，142.4，132.0，131.4，128.8，128.0，127.7，123.5，122.1，118.6，109.5，52.3，19.9.ESI-HIMS(m/z)：Calcd.for C16H17N6O3[M+H]+341.1357；found341.1360.
(E) -2- ((6-hydroxynaphthalen-2-yl) methylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoyl hydrazine (I)a-46)；
Yellow solid, 92% yield, melting point 265-.1H NMR(300MHz，DMSO-d6)10.74(s，1H，NH)，9.92(s，1H，NH)，9.77(s，1H，NH)，9.25(s，1H，OH)，8.03(d，J＝8.4Hz，1H，Ar-H)，7.96(s，1H，＝CH)，7.93(s，1H，Ar-H)，7.78(d，J＝8.7Hz，1H，Ar-H)，7.69(d，J＝8.7Hz，1H，Ar-H)，7.09-7.14(m，2H，Ar-H)，4.14(s，2H，CH2)，1.88(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)156.3，154.7，151.8，144.9，141.6，135.3，129.9，129.2，128.1，127.4，126.5，123.3，119.1，109.1，52.2，19.9.ESI-HRMS(m/z)：Calcd.for C16H17N6O3[M+H]+341.1357；found341.1359.
(E) -2- ((6-methoxynaphthalen-2-yl) methylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-trisOxazin-4 (5H) -yl) carbamoylhydrazines (I)a-47)；
Yellow solid, yield 79%, m.p. 232-.1H NMR(300MHz，DMSO-d6)10.79(s，1H，NH)，9.79(s，1H，NH)，9.29(s，1H，NH)，8.11(d，J＝8.4Hz，1H，Ar-H)，8.02(s，1H，Ar-H)，7.99(s，1H，＝CH)，7.84(t，J＝8.0Hz，2H，Ar-H)，7.36(s，1H，Ar-H)，7.20(d，J＝8.4Hz，1H，Ar-H)，4.14(s，2H，CH2)，3.89(s，3H，OCH3)，1.88(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)158.0，154.7，151.7，144.8，141.3，135.0，130.0，129.7，128.2，127.8，127.1，123.6，119.0，106.4，55.3，52.2，19.8.ESI-HRMS(m/z)：Calcd.for C17H19N6O3[M+H]+355.1513；found355.1516.
(E) -2- (benzo [ d ]][1，3]Dioxo-5-methylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoylhydrazine (I)a-48)；
White solid in 96% yield, melting point 266-.1H NMR(400MHz，DMSO-d6)10.64(s，1H，NH)，9.76(s，1H，NH)，9.27(s，1H，NH)，7.76(s，1H，＝CH)，7.62(s，1H，Ar-H)，7.07(d，J＝8.0Hz，1H，Ar-H)，6.93(d，J＝8.0Hz，1H，Ar-H)，6.06(s，2H，OCH2)，4.11(s，2H，CH2)，1.87(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)154.7，151.7，148.5，148.0，144.8，140.7，129.1，123.1，108.1，105.1，101.4，52.2，19.9.ESI-HRMS(m/z)：Calcd.for C13H15N6O4[M+H]+319.1149；found 319.1155.
(E) -2- ((2, 3-dihydrobenzo [ b)][1，4]Dioxin-6-yl) methylene-N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoyl hydrazine (I)a-49)；
White solid, yield 86%, melting point 264-.1H NMR(400MHz，DMSO-d6)10.63(s，1H，NH)，9.76(s，1H，NH)，9.22(s，1H，NH)，7.73(s，1H，＝CH)，7.41(s，1H，Ar-H)，7.18(d，J＝8.0Hz，1H，Ar-H)，6.87(d，J＝8.0Hz，1H，Ar-H)，4.26(s，4H，-OCH2)，4.10(s，2H，CH2)，1.86(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)154.7，151.7，144.8，144.7，143.6，140.7，127.9，120.8，117.1，114.9，64.3，64.0，52.2，19.9.ESI-HRMS(m/z)：Calcd.for C14H17N6O4[M+H]+333.1306；found 333.1309.
(E) -2- ((1H-indol-3-yl) methylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoyl hydrazine (I)a-50)；
White solid, yield 97%, melting point 255-.1H NMR(400MHz，DMSO-d6)11.51(s，1H，NH)，10.36(s，1H，NH)，9.76(s，1H，NH)，8.69(s，1H，NH)，8.31(d，J＝8.0Hz，1H，Ar-H)，8.08(s，1H，N＝CH)，7.74(s，1H，C＝CH)，7.40(d，J＝7.6Hz，1H，Ar-H)，7.18(t，J＝7.6Hz，1H，Ar-H)，7.10(d，J＝7.2Hz，1H，Ar-H)，4.15(s，2H，CH2)，1.88(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)154.7，151.8，144.9，139.4，137.0，129.9，124.0，122.6，122.5，120.3，111.6，111.4，52.3，19.9.ESI-HRMS(m/z)：Calcd.for C14H16N7O2[M+H]+314.1360；found 314.1359.
(E) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) -2- (pyridin-2-ylmethylene) carbamoylhydrazine (I)a-51)；
White solid, yield 55%, m.p. 230-.1H NMR(400MHz，DMSO-d6)11.02(s，1H，NH)，9.80(s，1H，NH)，9.40(s，1H，NH)，8.55(d，J＝4.4Hz，1H，Py-H)，8.22(d，J＝3.6Hz，1H，Py-H)，7.91(s，1H，＝CH)，7.84(t，J＝7.6Hz，1H，Py-H)，7.36(t，J＝6.8Hz，1H，Py-H)，4.12(s，2H，CH2)，1.87(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)154.5，153.4，151.7，149.3，144.9，141.6，136.6，123.9，119.9，52.2，19.9.ESI-HRMS(m/z)：Calcd.for C11H14N7O2[M+H]+276.1203；found 276.1206.
(E) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) -2- (pyridin-3-ylmethylene) carbamoylhydrazine (I)a-52)；
White solid, 89% yield, mp 227-.1H NMR(400MHz，DMSO-d6)10.96(s，1H，NH)，9.73(s，1H，NH)，9.37(s，1H，NH)，8.93(s，1H，Py-H)，8.55(d，J＝4.0Hz，1H，Py-H)，8.24(d，J＝4.0Hz，1H，Py-H)，7.90(s，1H，＝CH)，7.42-7.45(m，1H，Py-H)，4.12(s，2H，CH2)，1.87(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)154.5，151.8，150.0，148.4，145.0，138.2，133.7，130.4，123.8，52.2，19.9.ESI-HRMS(m/z)：Calcd.for C11H14N7O2[M+H]+276.1203；found276.1205.
(E) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) -2- (pyridin-4-ylmethylene) carbamoylhydrazine (I)a-53)；
White solid in 80% yield, melting point 289-.1H NMR(400MHz，DMSO-d6)11.10(s，1H，NH)，9.81(s，1H，NH)，9.44(s，1H，NH)，8.59(brs，2H，Py-H)，7.84(s，1H，＝CH)，7.76(brs，2H，Py-H)，4.12(s，2H，CH2)，1.87(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)154.4，151.7，150.0，144.9，141.6，138.5，120.9，52.1，19.9.ESI-HRMS(m/z)：Calcd.for C11H14N7O2[M+H]+276.1203；found 276.1205.
(E) -2- (furan-2-ylmethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoylhydrazine (I)a-54)；
Brown solid in 65% yield, mp 186-.1H NMR(400MHz，DMSO-d6)10.74(s，1H，NH)，9.76(s，1H，NH)，8.91(s，1H，NH)，7.79(brs，2H，＝CH，Het-H)，6.88(brs，1H，Het-H)，6.62(brs，1H，Het-H)，4.09(s，2H，CH2)，1.86(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)154.4，151.6，149.6，144.8，144.4，131.7，112.1，111.7，52.1，19.9.ESI-HRMS(m/z)：Calcd.forC10H13N6O3[M+H]+265.1044；found 265.1047.
(E) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) -2- (thien-2-ylmethylene) carbamoyl hydrazine (I)a-55)；
Yellow solid in 68% yield, mp 226-.1H NMR(400MHz，DMSO-d6)10.73(s，1H，NH)，9.76(s，1H，NH)，8.89(s，1H，NH)，8.09(s，1H，＝CH)，7.62(d，J＝4.8Hz，1H，Het-H)，7.39(d，J＝3.2Hz，1H，Het-H)，7.10(t，J＝4.8Hz，1H，Het-H)，4.10(s，2H，CH2)，1.86(s，3H，CH3)；13CNMR(100MHz，DMSO-d6)154.3，151.7，144.9，138.9，136.8，129.7，128.2，127.8，52.1，19.9.ESI-HRMS(m/z)：Calcd.for C10H13N6O2S[M+H]+281.0815；found 281.0815.
(E) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) -2- (thien-3-ylmethylene) carbamoyl hydrazine (I)a-56)；
Yellow solid, yield 87%, m.p. 244-.1H NMR(400MHz，DMSO-d6)10.67(s，1H，NH)，9.78(s，1H，NH)，9.17(s，1H，NH)，7.90(s，1H，＝CH)，7.83(s，1H，Het-H)，7.69(d，J＝4.8Hz，1H，Het-H)，7.60(d，J＝4.8Hz，1H，Het-H)，4.11(s，2H，CH2)，1.86(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)154.7，151.8，144.9，137.8，136.8，127.1，126.7，125.3，52.2，19.9.ESI-HRMS(m/z)：Calcd.for C10H13N6O2S[M+H]+281.0815；found 281.0819.
(E) -2- ((1H-imidazol-2-yl) methylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoyl hydrazine (I)a-57)；
White solid, 59% yield, melting point 215-.1H NMR(400MHz，DMSO-d6)12.37(s，1H，Het-H)，10.92(s，1H，NH)，9.85(s，1H，NH)，9.25(s，1H，NH)，7.70(s，1H，＝CH)，7.32(brs，1H，Het-H)，7.01(brs，1H，Het-H)，4.16(s，2H，CH2)，1.88(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)154.7，151.8，145.1，143.5，131.5，52.2，19.9.ESI-HRMS(m/z)：Calcd.for C9H13N8O2[M+H]+265.1156；found 265.1157.
Example 3: n- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) -2- (propan-2-one) carbamoylhydrazine (I)bSynthesis of (1)
In a 250mL single-neck flask, semicarbazide triazone (IV) (0.93g, 4mmol), p-toluenesulfonic acid (0.14g, 0.8mmol), acetone (0.23g, 4mmol), and methanol (120mL) were added, stirred to dissolve, then heated under reflux for 5h, and the reaction was monitored by TLC for completion. Removing solvent from the reaction solution under reduced pressure, separating out solid, vacuum filtering at normal pressure, and washing with methanol to obtain compound Ib10.79g of a white solid, yield 88%, m.p. 224-.1H NMR(400MHz，DMSO-d6)9.70(s，1H，NH)，9.42(s，1H，NH)，8.69(s，1H，NH)，4.07(s，2H，CH2)，1.90(s，3H，CH3)，1.85(s，3H，CH3)，1.80(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)155.3，151.6，148.6，144.7，52.2，24.9，19.9，16.9.ESI-HRMS(m/z)：Calcd.for C8H15N6O2[M+H]+227.1251；found 227.1256.
Compound Ib-2--Ib-28 is completed by repeating the above steps.
(E) -2- (butan-2-one) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-trisOxazin-4 (5H) -yl) carbamoylhydrazines (I)b-2)
White solid, yield 65%, melting point 225-.1H NMR(400MHz，DMSO-d6)9.70(s，1H，NH)，9.41(s，1H，NH)，8.62(s，1H，NH)，4.07(s，2H，CH2)，2.20(q，J＝7.6Hz，2H，CH2CH3)，1.85(s，3H，CH3)，1.79(s，3H，CH3)，1.03(t，J＝7.6Hz，3H，CH2CH3)；13C NMR(100MHz，DMSO-d6)155.3，152.5，151.6，144.8，52.2，31.4，19.9，15.5，10.8.ESI-HRMS(m/z)：Calcd.forC9H17N6O2[M+H]+241.1408；found 241.1410.
2-Cyclopentylketone-N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoyl hydrazine (I)b-3)
White solid, 68% yield, melting point 227-.1H NMR(400MHz，DMSO-d6)9.70(s，1H，NH)，9.33(s，1H，NH)，8.66(s，1H，NH)，4.05(s，2H，CH2)，2.29(t，J＝7.2Hz，2H)，2.22(t，J＝7.6Hz，2H)，1.84(s，3H，CH3)，1.72-1.77(m，2H)，1.64-1.69(m，2H)；13C NMR(100MHz，DMSO-d6)160.7，155.2，151.6，144.7，52.2，32.8，28.0，24.5，19.9.ESI-HRMS(m/z)：Calcd.forC10H17N6O2[M+H]+253.1408；found 253.1413.
2-Cyclohexylketone-N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoylhydrazine (I)b-4)
White solid, 56% yield, mp 233 ℃.1H NMR(400MHz，DMSO-d6)9.69(s，1H，NH)，9.60(s，1H，NH)，8.69(s，1H，NH)，4.07(s，2H，CH2)，2.31(t，J＝6.4Hz，2H)，2.21(t，J＝6.4Hz，2H)，1.84(s，3H，CH3)，1.61(brs，2H)，1.54(brs，4H)；13C NMR(100MHz，DMSO-d6)155.5，153.8，151.6，144.7，52.2，34.8，26.8，26.3，25.6，25.2，19.9.ESI-HRMS(m/z)：Calcd.forC11H19N6O2[M+H]+267.1564；found 267.1567.
2-cycloheptylketone-N- (6-methyl-3-ketone-2, 3-dihydro-1, 2, 4-triazine-4 (5H) -yl) carbamyl hydrazine (I)b-5)
White solid, 55% yield, m.p. 224-.1H NMR(400MHz，DMSO-d6)9.72(s，1H，NH)，9.33(s，1H，NH)，8.75(s，1H，NH)，4.07(s，2H，CH2)，2.39(d，J＝5.6Hz，2H)，2.32(t，J＝5.6Hz，2H)，1.85(s，3H，CH3)，1.62(brs，2H)，1.53(brs，6H)；13C NMR(100MHz，DMSO-d6)156.5，155.2，151.6，144.7，52.2，36.4，30.1，29.9，29.8，27.3，24.0，19.8.ESI-HRMS(m/z)：Calcd.for C12H21N6O2[M+H]+281.1721；found 281.1723.
(E) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) -2- (1-phenylethyl ketone) carbamoyl hydrazine (I)b-6)
White solid, 66% yield, melting point 249-.1H NMR(400MHz，DMSO-d6)9.89(s，1H，NH)，9.76(s，1H，NH)，9.13(s，1H，NH)，7.91(d，J＝7.6Hz，2H，Ar-H)，7.38(d，J＝5.6Hz，3H，Ar-H)，4.13(s，2H，CH2)，2.21(s，3H，CH3)，1.87(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)155.2，151.7，146.0，144.8，137.8，128.8，128.2，126.3，52.2，19.9，13.3.ESI-HRMS(m/z)：Calcd.for C13H17N6O2[M+H]+289.1408；found 289.1407.
(E) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) -2- (1-phenylpropyl ketone) carbamoyl hydrazine (I)b-7)
White solid, 68% yield, mp 232-.1H NMR(400MHz，DMSO-d6)10.03(s，1H，NH)，9.76(s，1H，NH)，9.11(s，1H，NH)，7.91(d，J＝7.2Hz，2H，Ar-H)，7.38(d，J＝6.8Hz，3H，Ar-H)，4.13(s，2H，CH2)，2.76(q，J＝7.2Hz，2H，CH2CH3)，1.87(s，3H，CH3)，1.01(t，J＝7.2Hz，3H，CH2CH3)；13C NMR(100MHz，DMSO-d6)155.2，151.7，145.0，144.8，136.6，128.8，128.3，126.3，52.2，19.9，18.7，10.7.ESI-HRMS(m/z)：Calcd.for C14H19N6O2[M+H]+303.1564；found 303.1565.
(E) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) -2- (1-phenylbutylketone) carbamoylhydrazine (I)b-8)
White solid, yield 60%, melting point 221-.1H NMR(300MHz，DMSO-d6)10.07(s，1H，NH)，9.76(s，1H，NH)，9.10(s，1H，NH)，7.90(d，J＝5.1Hz，2H，Ar-H)，7.38(d，J＝5.4Hz，，3H，Ar-H)，4.13(s，2H，CH2)，2.73(t，J＝7.5Hz，2H，CH2CH2CH3)，1.87(s，3H，CH3)，1.43(q，J＝7.2Hz，2H，CH2CH2CH3)，0.94(t，J＝6.9Hz，3H，CH3CH2CH3)；13C NMR(100MHz，DMSO-d6)155.3，151.7，149.9，144.8，136.9，128.8，128.3，126.4，52.2，27.1，19.9，19.4，13.8.ESI-HRMS(m/z)：Calcd.for C15H21N6O2[M+H]+317.1721；found 317.1724.
(E) -2- (1- (2-methoxyphenyl) ethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoylhydrazine (I)b-9)
White solid, 66% yield, mp 188-.1H NMR(400MHz，DMSO-d6)9.78(s，1H，NH)，9.71(s，1H，NH)，8.82(s，1H，NH)，7.37(brs，2H，Ar-H)，7.05(brs，1H，Ar-H)，6.95(brs，1H，Ar-H)，4.08(s，2H，CH2)，3.80(s，3H，OCH3)，2.12(s，3H，CH3)，1.85(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)157.2，155.3，151.6，148.5，144.8，130.0，129.6，129.0，120.3，111.6，55.6，52.2，19.9，17.7.ESI-HRMS(m/z)：Calcd.for C14H19N6O3[M+H]+319.1513；found319.1519.
(E) -2- (1- (3-methoxyphenyl) ethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoylhydrazine (I)b-10)
White solid, yield 86%, melting point 228-.1H NMR(400MHz，DMSO-d6)9.85(s，1H，NH)，9.75(s，1H，NH)，9.13(s，1H，NH)，7.43-7.47(m，2H，Ar-H)，7.30(t，J＝8.0Hz，1H，Ar-H)，6.94(d，J＝8.0Hz，，1H，Ar-H)，4.12(s，2H，CH2)，3.80(s，3H，OCH3)，2.19(s，3H，CH3)，1.87(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)159.3，155.2，151.7，146.1，144.9，139.4，129.3，118.9，114.3，111.9，55.3，52.2，19.9，13.6.ESI-HRMS(m/z)：Calcd.for C14H19N6O3[M+H]+319.1513；found 319.1517.
(E) -2- (1- (4-methoxyphenyl) ethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoylhydrazine (I)b-11)
White solid, 77% yield, m.p. 249 ℃.1H NMR(400MHz，DMSO-d6)9.76(s，2H，NH)，9.09(s，1H，NH)，7.86(d，J＝8.4Hz，2H，Ar-H)，6.92(d，J＝8.4Hz，2H，Ar-H)，4.12(s，2H，CH2)，3.78(s，3H，OCH3)，2.17(s，3H，CH3)，1.87(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)159.9，155.3，151.7，145.9，144.8，130.4，127.8，113.5，55.2，52.2，19.9，13.2.ESI-HRMS(m/z)：Calcd.for C14H19N6O3[M+H]+319.1513；found 319.1518.
(E) -2- (1- (3, 4-dimethoxyphenyl) ethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoylhydrazine (I)b-12)
White solid, yield 86%, m.p. 226-.1H NMR(400MHz，DMSO-d6)9.76(s，1H，NH)，9.73(s，1H，NH)，9.12(s，1H，NH)，7.51(s，1H，Ar-H)，7.33(d，J＝8.0Hz，2H，Ar-H)，6.93(d，J＝8.0Hz，2H，Ar-H)，4.14(s，2H，CH2)，3.83(s，3H，OCH3)，3.78(s，3H，OCH3)，2.18(s，3H，CH3)，1.87(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)155.3，151.8，149.9，148.6，146.3，144.8，130.6，119.6，110.9，109.7，55.9，55.5，52.2，19.9，13.5.ESI-HRMS(m/z)：Calcd.for C15H21N6O4[M+H]+349.1619；found 349.1622.
(E) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) -2- (1- (3, 4, 5-trimethoxyphenyl) ethylene) carbamoyl hydrazine (I)b-13)
White solid, 85% yield, mp 260 ℃.1H NMR(400MHz，DMSO-d6)9.79(s，1H，NH)，9.77(s，1H，NH)，9.15(s，1H，NH)，7.10(s，2H，Ar-H)，4.14(s，2H，CH2)，3.84(s，6H，OCH3)，3.67(s，3H，OCH3)，2.21(s，3H，CH3)，1.87(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)155.2，152.7，151.8，146.4，144.8，138.5，133.6，104.2，60.1，56.2，52.2，19.9，13.8.ESI-HRMS(m/z)：Calcd.for C16H23N6O5[M+H]+379.1724；found 379.1724.
(E) -2- (1- (2-chlorophenyl) ethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoyl hydrazine (I)b-14)
White solid, 50% yield, melting point 218-.1H NMR(400MHz，DMSO-d6)9.97(s，1H，NH)，9.73(s，1H，NH)，8.87(s，1H，NH)，7.45-7.50(m，2H，Ar-H)，7.36-7.42(m，2H，Ar-H)，4.07(s，2H，CH2)，2.18(s，3H，CH3)，1.84(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)155.0，151.5，147.2，144.7，138.9，131.2，130.7，130.0，129.6，127.2，52.1，19.8，18.0.ESI-HRMS(m/z)：Calcd.for C13H16ClN6O2[M+H]+323.1018；found 323.1022.
(E) -2- (1- (3-chlorophenyl) ethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoyl hydrazine (I)b-15)
White solid, yield 86%, melting point 274-.1H NMR(400MHz，DMSO-d6)9.96(s，1H，NH)，9.76(s，1H，NH)，9.29(s，1H，NH)，8.07(s，1H，Ar-H)，7.76-7.85(m，1H，Ar-H)，7.34-7.46(m，2H，Ar-H)，4.13(s，2H，CH2)，2.20(s，3H，CH3)，1.87(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)155.1，151.7，144.8，144.7，139.9，133.5，130.0，128.6，125.8，125.0，52.1，19.9，13.3.ESI-HRMS(m/z)：Calcd.for C13H16ClN6O2[M+H]+323.1018；found 323.1020.
(E) -2- (1- (4-chlorophenyl) ethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoyl hydrazine (I)b-16)
White solid in 89% yield, mp 268-.1H NMR(400MHz，DMSO-d6)9.96(s，1H，NH)，9.77(s，1H，NH)，9.21(s，1H，NH)，7.96(d，J＝8.0Hz，2H，Ar-H)，7.43(d，J＝8.0Hz，2H，Ar-H)，4.12(s，2H，CH2)，2.19(s，3H，CH3)，1.87(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)155.1，151.7，144.8，136.7，133.5，128.1，52.1，19.9，13.2.ESI-HRMS(m/z)：Calcd.forC13H16ClN6O2[M+H]+323.1018；found 323.1022.
(E) -2- (1- (2, 4-dichlorophenyl) ethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoyl hydrazine (I)b-17)
White solid, yield 80%, melting point 252-.1H NMR(400MHz，DMSO-d6)10.02(s，1H，NH)，9.74(s，1H，NH)，8.92(s，1H，NH)，7.68(s，1H，Ar-H)，7.46-7.52(m，2H，Ar-H)，4.07(s，2H，CH2)，2.17(s，3H，CH3)，1.84(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)155.0，151.5，146.1，144.8，137.8，133.8，132.4，132.1，129.1，127.4，52.1，19.9，17.9.ESI-HRMS(m/z)：Calcd.for C13H15Cl2N6O2[M+H]+357.0628；found 357.0630.
(E) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) -2- (1- (2, 3, 4-trichlorophenyl) ethylidene) carbamoyl hydrazine (I)b-18)
White solid, 97% yield, mp 258 ℃.1H NMR(400MHz，DMSO-d6)10.05(s，1H，NH)，9.71(s，1H，NH)，8.90(s，1H，NH)，7.70(d，J＝8.4Hz，1H，Ar-H)，7.47(d，J＝8.4Hz，1H，Ar-H)，4.07(s，2H，CH2)，2.18(s，3H，CH3)，1.84(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)154.9，151.5，145.9，144.7，140.0，132.8，131.5，130.5，129.6，128.9，52.1，19.9，17.8.ESI-HRMS(m/z)：Calcd.for C13H14Cl3N6O2[M+H]+391.0238；found 391.0236.
(E) -2- (1- (4-fluorophenyl) ethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoyl hydrazine (I)b-19)
White solid, 88% yield, m.p. 272-274 ℃.1H NMR(400MHz，DMSO-d6)9.90(s，1H，NH)，9.77(s，1H，NH)，9.18(s，1H，NH)，7.98(d，J＝8.0Hz，2H，Ar-H)，7.20(t，J＝8.0Hz，2H，Ar-H)，4.12(s，2H，CH2)，2.20(s，3H，CH3)，1.87(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)162.6(d，J＝244.7Hz)，155.2，151.7，145.1，144.8，134.3(d，J＝2.5Hz)，128.5(d，J＝8.0Hz)，115.0(d，J＝21.2Hz)，52.2，19.9，13.3.ESI-HRMS(m/z)：Calcd.for C13H16FN6O2[M+H]+307.1313；found 307.1316.
(E) -2- (1- (4-bromophenyl) ethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoyl hydrazine (I)b-20)
White solid, yield 90%, melting point 265-.1H NMR(400MHz，DMSO-d6)9.96(s，1H，NH)，9.77(s，1H，NH)，9.21(s，1H，NH)，7.89(d，J＝7.2Hz，2H，Ar-H)，7.56(d，J＝7.2Hz，2H，Ar-H)，4.12(s，2H，CH2)，2.19(s，3H，CH3)，1.87(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)155.1.151.6，144.9，144.8，137.0，131.0，128.4，122.2，52.1，19.9，13.1.ESI-HRMS(m/z)：Calcd.for C13H16BrN6O2[M+H]+367.0513；found 367.0516.
(E) -2- (1- (4-iodophenyl) ethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoylhydrazine (I)b-21)
Yellow solid, yield 79%, m.p. 279-280 ℃.1H NMR(400MHz，DMSO-d6)9.93(s，1H，NH)，9.76(s，1H，NH)，9.17(s，1H，NH)，7.73(brs，4H，Ar-H)，4.12(s，2H，CH2)，2.17(s，3H，CH3)，1.87(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)155.1，151.6，144.1，144.8，137.4，136.9，128.4，95.2，52.1，19.9，13.0.ESI-HRMS(m/z)：Calcd.for C13H16IN6O2[M+H]+415.0374；found 415.0372.
(E) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) -2- (1-p-methylphenylethylene) carbamoylhydrazine (I)b-22)
White solid, yield 87%, melting point 271-273 ℃.1H NMR(400MHz，DMSO-d6)9.83(s，1H，NH)，9.76(s，1H，NH)，9.10(s，1H，NH)，7.81(d，J＝7.6Hz，2H，Ar-H)，7.19(d，J＝7.6Hz，2H，Ar-H)，4.12(s，2H，CH2)，2.32(s，3H，CH3)，2.18(s，3H，CH3)，1.87(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)155.3，151.7，146.0，144.8，138.3，135.1，128.8，126.2，52.2，20.9，19.9，13.2.ESI-HRMS(m/z)：Calcd.for C14H19N6O2[M+H]+303.1564；found 303.1561.
(E) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) -2- (1- (4- (trifluoromethyl) phenyl) ethylidene) carbamoyl hydrazine (I)b-23)
White solid, 89% yield, melting point 280-.1H NMR(400MHz，DMSO-d6)10.08(s，1H，NH)，9.79(s，1H，NH)，9.27(s，1H，NH)，8.14(d，J＝7.6Hz，2H，Ar-H)，7.72(d，J＝7.6Hz，2H，Ar-H)，4.13(s，2H，CH2)，2.25(s，3H，CH3)，1.88(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)155.1，151.7，144.8，144.5，141.7，128.7(q，J＝31.3Hz)，127.0，125.0(d，J＝3.4Hz)，124.3(q，J＝270.1Hz)，52.1，19.9，13.3.ESI-HRMS(m/z)：Calcd.for C14H16F3N6O2[M+H]+357.1281；found 357.1282.
(E) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) -2- (1- (4- (trifluoromethoxy) phenyl) ethylidene) carbamoyl hydrazine (I)b-24)
White solid, yield 86%, melting point 280-.1H NMR(400MHz，DMSO-d6)9.99(s，1H，NH)，9.78(s，1H，NH)，9.22(s，1H，NH)，8.04(brs，2H，Ar-H)，7.35(brs，2H，Ar-H)，4.13(s，2H，CH2)，2.22(s，3H，CH3)，1.88(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)155.2，151.7，148.6，144.8，144.7，137.1，128.3，120.6，120.1(q，J＝244.8Hz)，52.1，19.9，13.3.ESI-HRMS(m/z)：Calcd.for C14H16F3N6O3[M+H]+373.1230；found 357.1234.
(E) -2- (1- (4-hydroxy) ethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) ammoniaCarbamoyl hydrazines (I)b-25)
White solid, yield 75%, m.p. 237-.1H NMR(300MHz，DMSO-d6)9.74(s，1H，NH)，9.70(s，1H，NH)，9.66(s，1H，OH)，9.02(s，1H，NH)，7.75(d，J＝8.7Hz，2H，Ar-H)，6.75(d，J＝8.7Hz，2H，Ar-H)，4.12(s，2H，CH2)，2.14(s，3H，CH3)，1.87(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)158.4，155.4，151，8，146.4，144.9，128.9，127.9，115.0，52.3，19.9，13.2.ESI-HRMS(m/z)：Calcd.for C13H17N6O3[M+H]+305.1357；found 305.1357.
(E) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) -2- (1- (4-nitrophenyl) ethylene) carbamoyl hydrazine (I)b-26)
Yellow solid, 89% yield, mp 229-.1H NMR(300MHz，DMSO-d6)10.2(s，1H，NH)，9.80(s，1H，NH)，9.35(s，1H，NH)，8.21(brs，4H，Ar-H)，4.14(s，2H，CH2)，2.26(s，3H，CH3)，1.88(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)154.9，151.6，147.2，144.8，144.0，143.9，127.4，123.3，52.1，19.9，13.2.ESI-HRMS(m/z)：Calcd.for C13H16N7O4[M+H]+334.1258；found 334.1258.
(E) -2- (1- (4-aminophenyl) ethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoylhydrazine (I)b-27)
Yellow solid, 54% yield, mp 298-.1H NMR(300MHz，DMSO-d6)9.73(s，1H，NH)，9.58(s，1H，NH)，8.95(s，1H，NH)，7.61(d，J＝6.3Hz，2H，Ar-H)，6.55(d，J＝6.3Hz，2H，Ar-H)，5.55(s，2H，NH2)，4.11(s，2H，CH2)，2.09(s，3H，CH3)，1.87(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)155.3，151.7，149.7，146.8，144.7，127.4，125.2，113.1，52.2，19.8，12.9.ESI-HRMS(m/z)：Calcd.for C13H18N7O2[M+H]+304.1516；found 304.1521.
(E) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazine-4 (5H) -2- (1- (pyridin-3-yl) ethylidene) carbamoyl hydrazine (I)b-28)
White solid, 97.7% yield, mp 228-.1H NMR(400MHz，CDCl3)10.10(s，1H，NH)，9.78(s，1H，NH)，9.32(s，1H，NH)，9.07(s，1H，Py-H)，8.61(d，J＝4.4Hz，1H，Py-H)，8.43(d，J＝8.0Hz，1H，Py-H)，7.53(q，J＝4.8Hz，1H，Py-H)，4.12(s，2H，CH2)，2.24(s，3H，＝CCH3)，1.87(s，3H，CH3)；13C NMR(100MHz，CDCl3)155.0，151.6，148.0，146.3，144.8，143.4，135.0，133.9，123.8，52.1，19.9，13.0.ESI-HRMS(m/z)：Calcd.for C12H15N7O2[M+H]+290.1360；found 290.1357.
Example 4: (E) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) -2- (1- (6- (o-methylphenoxy) pyridin-3-yl) ethylene) carbamoylhydrazine (I)cSynthesis of (1)
In a 250mL single-neck flask, aminotriazinone (0.74g, 4mmol), p-toluenesulfonic acid (0.14g, 0.8mmol), pyridone (0.91g, 4mmol), and methanol (120mL) were added, stirred and dissolved, then heated under reflux for 6h, and the reaction was monitored by TLC for completion. After the reaction solution was desolventized under reduced pressure, silica gel column chromatography was carried out using petroleum ether/ethyl acetate (30: 1- -10: 1) to obtain 0.85g of a yellow solid, 54% yield and 218 ℃ melting point.1H NMR(400MHz，DMSO-d6)：9.96(s，1H，NH)，9.77(s，1H，NH)，9.22(s，1H，NH)，8.56(s，1H，Py-H)，8.45(d，J＝8.0Hz，1H，Py-H)，7.31(d，J＝7.2Hz，1H，Ar-H)，7.24(t，J＝7.2Hz，1H，Ar-H)，7.14(t，J＝7.2Hz，1H，Ar-H)，7.06(d，J＝8.0Hz，1H，Py-H)，7.02(d，J＝8.8Hz，1H，Ar-H)，4.10(s，2H，CH2)，2.18(s，3H，CH3)，2.08(s，3H，CH3)，1.86(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)163.2，155.1，151.9，151.6，145.6，144.7，143.5，137.9，131.2，130.2，128.7，127.2，125.1，122.0，110.0，52.1，19.8，16.0，13.0.ESI-HRMS(m/z)：Calcd.for C19H22N7O3[M+H]+396.1779；found 396.1779.
Compound Ic-2--Ic-15 is completed by repeating the above steps.
(E) -2- (1- (6- (2-ethoxyphenoxy) pyridin-3-yl) ethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoylhydrazine (I)c-2)
White solid, 61% yield, m.p. 217-218 ℃.1H NMR(400MHz，DMSO-d6)9.94(s，1H，NH)，9.77(s，1H，NH)，9.22(s，1H，NH)，8.54(s，1H，Py-H)，8.43(d，J＝8.4Hz，1H，Py-H)，7.19(t，J＝8.0Hz，1H，Ar-H)，7.12(t，J＝8.0Hz，2H，Ar-H)，6.97(t，J＝8.4Hz，2H，Ar-H，Py-H)，4.10(s，2H，CH2)，3.94(q，J＝6.8Hz，14.0Hz，2H，CH2CH3)，2.18(s，3H，CH3)，1.87(s，3H，CH3)，1.05(t，J＝6.8Hz，3H，CH2CH3)；13C NMR(100MHz，DMSO-d6)163.5，155.1，151.7，150.7，145.3，144.8，143.6，142.4，137.5，128.5，126.0，123.0，120.8，114.2，109.7，63.7，52.1，19.9，14.5，13.0.ESI-HRMS(m/z)：Calcd.for C20H24N7O4[M+H]+426.1884；found 426.1887.
(E) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) -2- (1- (6- (2-ethoxyphenoxy) pyridin-3-yl) ethylene) carbamoyl hydrazine (I)c-3)
Yellow solid, yield 81%, melting point 261-.1H NMR(400MHz，DMSO-d6)10.00(s，1H，NH)，9.77(s，1H，NH)，9.27(s，1H，NH)，8.65(s，1H，Py-H)，8.54(d，J＝6.8Hz，1H，Py-H)，8.10(d，J＝7.2Hz，1H，Ar-H)，8.03(s，1H，Ar-H)，7.67(m，2H，Ar-H)，7.19(d，J＝8.4Hz，1H，Py-H)，4.11(s，2H，CH2)，2.21(s，3H，CH3)，1.87(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)162.2，155.0，154.0，151.6，148.4，145.4，144.7，143.2，138.3，130.9，129.8，128.2，119.5，116.2，111.2，52.1，19.8，12.9.ESI-HRMS(m/z)：Calcd.for C18H19N8O5[M+H]+427.1473；found 427.1474.
(E) -2- (1- (6- (3-aminophenoxy) pyridin-3-yl) ethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoylhydrazine (I)c-4)
Yellow solid, yield 80%, m.p. 233-.1H NMR(400MHz，DMSO-d6)9.95(s，1H，NH)，9.76(s，1H，NH)，9.22(s，1H，NH)，8.63(s，1H，Py-H)，8.42(d，J＝8.4Hz，1H，Py-H)，7.02(t，J＝8.0Hz，1H，Ar-H)，6.93(d，J＝8.4Hz，1H，Py-H)，6.39(d，J＝8.0Hz，1H，Ar-H)，6.27(s，1H，Ar-H)，6.22(d，J＝8.0Hz，1H，Ar-H)，5.24(s，2H，NH2)，4.11(s，2H，CH2)，2.20(s，3H，CH3)，1.87(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)163.4，155.1，155.0，151.6，150.3，145.8，144.8，143.5，137.7，129.8，128.9，110.6，110.4，107.8，106.0，52.1，19.9，13.0.ESI-HRMS(m/z)：Calcd.for C18H21N8O3[M+H]+397.1731；found 397.1739.
(E) -2- (1- (6- (4-ethylphenoxy) pyridin-3-yl) ethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoyl hydrazine (I)c-5)
Yellow solid, 85% yield, mp 214-.1H NMR(400MHz，DMSO-d6)：9.95(s，1H，NH)，9.76(s，1H，NH)，9.22(s，1H，NH)，8.59(s，1H，Py-H)，8.45(d，J＝8.4Hz，1H，Py-H)，7.25(d，J＝8.4Hz，2H，Ar-H)，7.05(d，J＝8.4Hz，2H，Ar-H)，7.00(d，J＝8.4Hz，1H，Py-H)，4.11(s，2H，CH2)，2.62(q，J＝7.2，14.8Hz，2H，CH2CH3)，2.19(s，3H，CH3)，1.87(s，3H，CH3)，1.20(t，J＝7.6Hz，3H，CH2CH3)；13C NMR(100MHz，DMSO-d6)163.4，155.1，151.2，145.6，144.8，143.5，140.1，137.8，128.9，121.2，110.6，52.1，27.6，19.9，15.8，13.0.ESI-HRMS(m/z)：Calcd.for C20H24N7O3[M+H]+410.1935；found 410.1941.
(E) -2- (1- (6- (4-isopropylphenoxy) pyridin-3-yl) ethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoyl hydrazine (I)c-6)
Yellow solid, yield 87%, m.p. 222-.1H NMR(400MHz，DMSO-d6)9.96(s，1H，NH)，9.77(s，1H，NH)，9.23(s，1H，NH)，8.59(s，1H，Py-H)，8.45(d，J＝8.4Hz，1H，Py-H)，7.28(d，J＝7.6Hz，2H，Ar-H)，7.05(d，J＝8.0Hz，2H，Ar-H)，7.01(d，J＝8.4Hz，1H，Py-H)，4.11(s，2H，CH2)，2.91(m，1H，CH(CH3)2)，2.19(s，3H，CH3)，1.87(s，3H，CH3)，1.22(d，J＝6.4Hz，6H，CH(CH3)2)；13C NMR(100MHz，DMSO-d6)155.1，151.6，145.6，144.7，143.4，137.8，128.9，127.4，121.1，110.6，52.1，32.9，24.0，19.9，13.0.ESI-HRMS(m/z)：Calcd.for C21H26N7O3[M+H]+424.2092；found 424.2096.
(E) -2- (1- (6- (4-tert-butylphenoxy) pyridin-3-yl) ethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoyl hydrazine (I)c-7)
White solid, 88% yield, m.p. 208 ℃.1H NMR(400MHz，DMSO-d6)9.95(s，1H，NH)，9.76(s，1H，NH)，9.22(s，1H，NH)，8.59(s，1H，Py-H)，8.46(d，J＝8.8Hz，1H，Py-H)，7.43(d，J＝8.4Hz，2H，Ar-H)，7.06(d，J＝8.4Hz，2H，Ar-H)，7.02(d，J＝8.8Hz，1H，Py-H)，4.11(s，2H，CH2)，2.19(s，3H，CH3)，1.87(s，3H，CH3)，1.30(s，9H，C(CH3)3)；13C NMR(100MHz，DMSO-d6)163.4，155.1，151.6，151.3，147.0，145.6，144.7，143.4，137.8，128.9，126.3，120.8，110.6，52.1，34.2，31.3，19.9，13.0.ESI-HRMS(m/z)：Calcd.for C22H28N7O3[M+H]+438.2248；found 438.2253.
(E) -2- (1- (6- (4-bromophenoxy) pyridin-3-yl) ethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoyl hydrazine (I)c-8)
Yellow solid, yield 75%, mp 238-.1H NMR(400MHz，DMSO-d6)9.97(s，1H，NH)，9.77(s，1H，NH)，9.24(s，1H，NH)，8.61(s，1H，Py-H)，8.49(d，J＝8.8Hz，1H，Py-H)，7.60(d，J＝8.4Hz，2H，Ar-H)，7.14(d，J＝8.4Hz，2H，Ar-H)，7.08(d，J＝8.8Hz，1H，Py-H)，4.11(s，2H，CH2)，2.20(s，3H，CH3)，1.87(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)162.7，155.1，153.0，151.6，145.5，144.7，143.3，138.1，132.4，129.4，123.6，116.6，111.0，52.1，19.8，13.0.ESI-HRMS(m/z)：Calcd.for C18H19BrN7O3[M+H]+460.0727；found 460.0722.
(E) -2- (1- (6- (4-iodophenoxy) pyridin-3-yl) ethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoyl hydrazine (I)c-9)
White solid, yield 72%, melting point 244-.1H NMR(400MHz，DMSO-d6)9.97(s，1H，NH)，9.77(s，1H，NH)，9.24(s，1H，NH)，8.61(s，1H，Py-H)，8.48(d，J＝8.8Hz，1H，Py-H)，7.75(d，J＝8.4Hz，2H，Ar-H)，7.08(d，J＝8.8Hz，1H，Py-H)，6.99(d，J＝8.4Hz，2H，Ar-H)，4.11(s，2H，CH2)，2.19(s，3H，CH3)，1.87(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)162.7，155.1，153.7，151.6，145.5，144.8，143.3，138.3，138.1，129.4，123.8，111.0，88.8，52.1，19.9，13.0.ESI-HRMS(m/z)：Calcd.for C18H19IN7O3[M+H]+508.0589；found 508.0590.
(E) -2- (1- (6- (4- (benzyloxy) phenoxy) pyridin-3-yl) ethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoyl hydrazine (I)c-10)
Yield of yellow solid 32%, melting point 212-.1H NMR(400MHz，DMSO-d6)9.95(s，1H，NH)，9.77(s，1H，NH)，9.22(s，1H，NH)，8.58(s，1H，Py-H)，8.44(d，J＝8.4Hz，1H，Py-H)，7.47(d，J＝7.2Hz，2H，Ar-H)，7.41(t，J＝7.2Hz，2H，Ar-H)，7.35(d，J＝6.4Hz，1H，Ar-H)，7.06(q，J＝7.2，16.0Hz，4H，Ar-H)，6.98(d，J＝8.4Hz，1H，Py-H)，5.12(s，2H，OCH2)，4.11(s，2H，CH2)，2.19(s，3H，CH3)，1.87(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)163.6，155.3，155.1，151.6，147.1，145.5，144.8，143.5，137.8，137.1，128.8，128.5，127.9，127.7，122.5，115.6，110.3，69.6，52.1，19.9，13.0.ESI-HRMS(m/z)：Calcd.for C25H26N7O4[M+H]+488.2041；found 488.2049.
(E) -2- (1- (6- (4-benzoylphenoxy) pyridin-3-yl) ethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoyl hydrazine (I)c-11)
White solid, 22% yield, mp 234-.1H NMR(400MHz，DMSO-d6)10.00(s，1H，NH)，9.77(s，1H，NH)，9.27(s，1H，NH)，8.69(s，1H，Py-H)，8.53(d，J＝8.4Hz，1H，Py-H)，7.82(d，J＝8.0Hz，2H，Ar-H)，7.75(d，J＝7.2Hz，2H，Ar-H)，7.69(t，J＝6.0Hz，1H，Ar-H)，7.58(t，J＝7.2Hz，2H，Ar-H)，7.32(d，J＝8.4Hz，2H，Ar-H)，7.18(d，J＝8.4Hz，1H，Py-H)，4.11(s，2H，CH2)，2.22(s，3H，CH3)，1.87(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)194.7，162.3，157.6，155.1，151.6，145.7，144.8，143.3，138.3，137.2，133.0，132.6，131.8，129.9，129.5，128.6，120.7，111.6，52.1，19.9，13.0.ESI-HRMS(m/z)：Calcd.for C25H24N7O4[M+H]+486.1884；found 486.1891.
(E) -2- (1- (6- (4-isopropyl-3-methylphenoxy) pyridin-3-yl) ethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoylhydrazine (I)c-12)
White solid, yield 78%, melting point 224-.1H NMR(400MHz，DMSO-d6)9.95(s，1H，NH)，9.76(s，1H，NH)，9.22(s，1H，NH)，8.60(s，1H，Py-H)，8.44(d，J＝8.4Hz，1H，Py-H)，7.26(d，J＝7.6Hz，1H，Ar-H)，6.99(d，J＝8.4Hz，1H，Py-H)，6.92(d，J＝7.6Hz，2H，Ar-H)，4.11(s，2H，CH2)，3.10(m，1H，CH(CH3)2)，2.29(s，3H，CH3)，2.19(s，3H，CH3)，1.87(s，3H，CH3)，1.19(d，J＝6.4Hz，6H，CH(CH3)2)；13C NMR(100MHz，DMSO-d6)163.5，155.1，151.6，151.2，145.6，144.7，143.5，142.7，137.8，136.2，128.8，125.7，122.6，118.8，110.5，52.1，28.3，23.2，19.8，18.9，13.0.ESI-HRMS(m/z)：Calcd.for C22H28N7O3[M+H]+438.2248；found 438.2254.
(E) -2- (1- (6- (2-isopropyl-5-methylphenoxy) pyridin-3-yl) ethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoylhydrazine (I)c-13)
White solid, 25% yield, mp 236-.1H NMR(400MHz，DMSO-d6)9.94(s，1H，NH)，9.76(s，1H，NH)，9.21(s，1H，NH)，8.58(s，1H，Py-H)，8.43(d，J＝8.8Hz，1H，Py-H)，7.26(d，J＝8.0Hz，1H，Ar-H)，7.03(d，J＝8.0Hz，1H，Ar-H)，6.99(d，J＝8.8Hz，1H，Py-H)，6.83(s，1H，Ar-H)，4.11(s，2H，CH2)，2.97(m，1H，CH(CH3)2)，2.26(s，3H，CH3)，2.19(s，3H，CH3)，1.87(s，3H，CH3)，1.10(d，J＝7.2Hz，6H，CH(CH3)2)；13C NMR(100MHz，DMSO-d6)163.8，155.1，151.6，150.6，145.7，144.8，143.5，137.9，137.1，136.3，128.7，126.6，126.1，122.6，110.0，52.1，26.5，23.0，20.4，19.9，13.0.ESI-HRMS(m/z)：Calcd.for C22H28N7O3[M+H]+438.2248；found438.2246.
(E) -2- (1- (6- (4-allyl-2-methoxyphenoxy) pyridin-3-yl) ethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoylhydrazine (I)c-14)
White solid, yield 61%, melting point 241-242 ℃.1H NMR(400MHz，DMSO-d6)9.93(s，1H，NH)，9.76(s，1H，NH)，9.20(s，1H，NH)，8.52(s，1H，Py-H)，8.40(d，J＝8.8Hz，1H，Py-H)，7.05(d，J＝7.6Hz，1H，Ar-H)，6.95(d，J＝6.8Hz，2H，Ar-H，Py-H)，6.79(d，J＝7.6Hz，1H，Ar-H)，6.00(m，1H，＝CH)，5.10(m，1H，＝CH2)，4.10(s，2H，CH2)，3.66(s，3H，CH3)，3.39(d，J＝5.6Hz，2H，CH2)，2.17(s，3H，CH3)，1.87(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)163.4，155.1，151.6，151.3，145.4，144.8，143.6，140.0，138.0，137.6，128.5，122.9，120.5，116.0，113.1，109.6，55.5，52.1，19.9，13.0.ESI-HRMS(m/z)：Calcd.for C22H26N7O4[M+H]+452.2041；found 452.2044.
(E) -2- (1- (6- (2-benzoyl-4-methoxyphenoxy) pyridin-3-yl) ethylene) -N- (6-methyl-3-one-2, 3-dihydro-1, 2, 4-triazin-4 (5H) -yl) carbamoyl hydrazine (I)c-15)
White solid, 49% yield, mp 210-.1H NMR(400MHz，DMSO-d6)9.92(s，1H，NH)，9.75(s，1H，NH)，9.19(s，1H，NH)，8.47(s，1H，Py-H)，8.29(d，J＝8.4Hz，1H，Py-H)，7.55(t，J＝8.8Hz，4H，Ar-H)，7.39(t，J＝7.6Hz，2H，Ar-H)，6.98(d，J＝8.4Hz，1H，Py-H)，6.87(s，1H，Ar-H)，6.57(d，J＝8.8Hz，1H，Ar-H)，4.10(s，2H，CH2)，3.85(s，3H，CH3)，2.14(s，3H，CH3)，1.87(s，3H，CH3)；13C NMR(100MHz，DMSO-d6)193.6，162.8，162.6，155.1，153.0，151.6，145.0，144.8，143.3，137.8，137.7，132.7，132.0，129.0，128.9，128.2，124.2，110.9，110.2，108.6，55.8，52.1，19.9，12.9.ESI-HRMS(m/z)：Calcd.for C26H26N7O5[M+H]+516.1990；found 516.1986.
Example 5: aphid killing assay, the assay procedure was as follows:
activity assay of aphids
The aphid killing activity determination steps are as follows: the test insects are normal colony of Aphis fabae (Aphis laburni Kaltenbach) bred by broad bean leaves in a laboratory. Weighing the medicines, adding 1mL of DMF for dissolving, adding two drops of Tween-20 emulsifier, adding a certain amount of distilled water, and stirring uniformly to prepare the liquid medicine with the required concentration. Soaking the leaves of broad beans with aphids (about 60) in the medicament for 5 seconds, taking out and lightly drying, sucking the redundant medicament with filter paper, then inserting the branches of the broad beans into water-absorbing sponge, covering the branches with glass covers, sealing with gauze, checking the result for 96 hours, and repeating the steps for 3 times for each compound. The control was prepared by adding the emulsifier and solvent to distilled water and stirring the mixture uniformly.
Table 1 results of aphid-killing activity test of acylhydrazone structure-containing triazinone derivative (I):
a-not tested.
As can be seen from Table 1, most of the acylhydrazone structure-containing triazinone derivatives exhibited very good aphid-killing activity at a concentration of 100 mg/kg. At a concentration of 5mg/kg, Ia-13、Ia-14、Ia-15、Ia-16、Ia-44、Ia-50、Ia-51、Ia-52、Ia-54、Ia-55、Ib-13、Ic-2、Ic-5、Ic-6、Ic-7、Ic-8、Ic-9、Ic-12 shows an activity comparable to that of pymetrozine.
Example 6: the activity of killing mosquito larvae is determined by the following procedure:
activity assay for mosquito larvae
Experimental method for killing mosquito larvae: culex pipiens light subspecies, normal population raised indoors. Weighing about 5mg of test compound into a penicillin drug bottle, adding 5mL of acetone (or a suitable solvent), and shaking to dissolve to obtain 1000ppm of mother liquor. 0.5mL of mother liquor is transferred and added into a 100mL beaker filled with 89.9mL of water, 10 heads of young mosquito larvae of 4 years old are selected and poured into the beaker together with 10mL of feeding liquid, and the concentration of the liquid medicine is 5 ppm. The sample is placed in a standard processing chamber, and the result is checked for 24 h. An aqueous solution containing 0.5mL of test solvent was used as a blank.
Table 2 mosquito larva killing activity test results of acylhydrazone structure-containing triazinone derivative (I):
athe death rate is lower than 0.25mg/kg,bthe mortality rate is 0.1mg/kg,c-not tested.
As can be seen from tables 2 and 4, most of the acylhydrazone structure-containing triazinone derivatives showed good activity against mosquito larvae. Especially compounds Ia-35、Ia-47、Ia-53、Ib-11、Ib-16、Ib-22 and Ib-25. Shows higher activity on mosquito larvae at 0.25mg/kg, wherein the compound Ia-47 shows 40% insecticidal activity at 0.01 mg/kg.
Example 7: the activity of killing bollworm, corn borer and armyworm is measured by the following procedure:
activity test of bollworm
The experimental method of the cotton bollworm comprises the following steps: the feed mixing method is a method in which 3mL of the solution is transferred from the prepared solution and added to about 27g of the freshly prepared feed to obtain a desired concentration of ten times the dilution. The preparation is uniformly mixed and poured into a clean 24-hole plate, then is inoculated into 24-head three-year-old cotton bollworms after being cooled, and the inspection result is observed after 3 to 4 days.
Activity test of corn borer
Test method of corn borer: the leaf soaking method comprises soaking leaf with diameter of 5-6cm in the medicinal liquid for 5-6 s after the required concentration is set, taking out, air drying on absorbent paper, placing in a designated culture dish, inoculating 10-head 3-year larva, placing in insect-raising room at 27 + -1 deg.C, observing for 3-4 days, and inspecting the result.
Activity test of armyworm
The experimental method of the armyworm comprises the following steps: the leaf soaking method comprises soaking leaf with diameter of 5-6cm in the medicinal liquid for 5-6 s after the required concentration is set, taking out, air drying on absorbent paper, placing in a designated culture dish, inoculating 10-head 3-year larva, placing in insect-raising room at 27 + -1 deg.C, observing for 3-4 days, and inspecting the result.
TABLE 3 Activity test results of acylhydrazone structure-containing triazinone derivative (I) for killing bollworm, corn borer and armyworm
aThe death rate is reduced under the condition of 200mg/kg,bmortality rate at 100mg/kg
As can be seen from Table 3, most of the triazinone derivatives containing acylhydrazone structures exhibit insecticidal activity against Helicoverpa armigera, Diatraea zeae and armyworm. Especially compounds Ia-35 and Ia44 shows higher activity to bollworm, corn borer and armyworm at 100mg/kg, wherein the compound Ib44 at 100mg/kg, the insecticidal activity on cotton bollworm, corn borer and armyworm is 30%, 20% and 60%, respectively.
Example 8: the fungicidal activity was determined by the following procedure:
taking tomato early blight as an example, other bacteria can be replaced
In vitro test method: inoculating the tomato early blight bacteria to PDA culture medium, culturing for 7 days, preparing bacterial dish with diameter of 4cm at colony edge with puncher, inoculating to PDA culture medium containing 50ug/ml and no medicine, culturing for 4 days, measuring colony diameter, and comparing with control to calculate the inhibition percentage of the medicine.
Table 4 bactericidal activity test results of acylhydrazone structure-containing triazinone derivative (I):
as can be seen from Table 4, most of the acylhydrazone structure-containing triazinone derivative compounds exhibit fungicidal activity against 14 kinds of fungi, especially compound Ia-18、Ia-26、Ia-38、Ia-53、Ib-4、Ib-6、Ib-11、Ic-2、Ic-7、Ic-9、Ic-14 and Ic14 shows good bacteriostatic activity on various pathogenic bacteria at the concentration of 50 mg/kg.
Claims (8)
1. Acylhydrazone structure-containing triazinone derivative represented by the following general formula (I)
The acylhydrazone structure-containing triazone derivative (I) provided by the invention has the following three general formulasa，Ib，Ic) A compound of the structure:
wherein,
R1respectively represent ethyl, n-propyl, tert-butyl, 3-6 carbon cycloalkyl, benzyl, naphthyl, substituted phenyl, 1-10 carbon nitrogen-containing heterocycle, 1-10 carbon oxygen-containing heterocycle and 1-10 carbon sulfur-containing heterocycle, wherein the substituent on the phenyl group contains 2-3 following groups: hydrogen, hydroxyl, halogen atom, cyano, nitro, dimethylamino, trifluoromethyl, trifluoromethoxy, methyl, 1-6 carbon alkoxy;
R2respectively represent methyl, ethyl, n-propyl, 3-6 carbon cycloalkyl, substituted phenyl, 1-10 carbon nitrogen-containing heterocycle, 1-10 carbon oxygen-containing heterocycle and 1-10 carbon sulfur-containing heterocycle, wherein the substituent on the phenyl group contains 2-3 groups: hydrogen, hydroxyl, halogen atom, cyano, nitro, trifluoromethyl, trifluoromethoxy and 1-6 carbon alkoxy; and R2And R3A 3-6 carbon cycloalkyl group;
R3each represents a substituted phenyl group, wherein the substituents on the phenyl group are groups containing 2 to 3 of the following groups: hydrogen, hydroxyl, halogen atom, cyano, nitro, trifluoromethyl, trifluoromethoxy and 1-6 carbon alkoxy;
R4respectively represent hydrogen, hydroxyl, methyl, ethyl, isopropyl, tertiary butyl, 1-6 carbon alkoxy, 1-10 carbon alkylamino, halogen atom, cyano, 1-6 carbon alkylcarbonyl and 1-10 carbon alkoxycarbonyl; and simultaneously contains 2 to 3R4The substituents are as represented.
2. A process for preparing acylhydrazone structure-containing triazinone derivatives (scheme one): firstly, the aminotriazinone (II) reacts with phenyl chloroformate to generate a compound III, the compound III reacts with hydrazine hydrate to generate an intermediate semicarbazide triazone IV, and then the compound IV reacts with various aldehydes VaReacting to generate acylhydrazone structure-containing triazinone compound Ia；
Wherein R is1Respectively represent ethyl, n-propyl, tert-butyl, 3-6 carbon cycloalkyl, benzyl, naphthyl, substituted phenyl, 1-10 carbon nitrogen-containing heterocycle, 1-10 carbon oxygen-containing heterocycle and 1-10 carbon sulfur-containing heterocycle, wherein the substituent on the phenyl group contains 2-3 following groups: hydrogen, hydroxyl, halogen atom, cyano, nitro, dimethylamino, trifluoromethyl, trifluoromethoxy, methyl, 1-6 carbon alkoxy;
route one:
the solvent of the first step reaction is one of methanol, dichloromethane, chloroform, 1, 2-dichloroethane and acetonitrile; the acid-binding agent is one of pyridine, sodium carbonate, triethylamine, potassium carbonate and cesium carbonate; the reaction temperature is between 60 ℃ and 80 ℃; the solvent of the second step reaction is one of methanol, dichloromethane, ethanol, 1, 2-dichloroethane and acetonitrile; the reaction temperature is between 80 ℃ and 100 ℃; the solvent of the third step reaction is one of methanol, ethanol, acetonitrile and N, N-dimethylformamide; the catalyst is one of trifluoroacetic acid, p-toluenesulfonic acid and glacial acetic acid; the reaction temperature is 70 to 100 ℃.
3. A process for the preparation of acylhydrazone structure-containing triazinone derivatives (scheme II): reacting semicarbazide triazone (IV) with various ketones to generate triazone compound I containing acylhydrazone structureb；
Wherein, methyl, ethyl, n-propyl, 3-6 carbon cycloalkyl, substituted phenyl, 1-10 carbon nitrogen-containing heterocycle, 1-10 carbon oxygen-containing heterocycle and 1-10 carbon sulfur-containing heterocycle, wherein the substituent on the phenyl contains 2-3 following groups: hydrogen, hydroxyl, halogen atom, cyano, nitro, trifluoromethyl, trifluoromethoxy and 1-6 carbon alkoxy;
and a second route:
the solvent is selected from methanol, ethanol, 1, 2-dichloroethane, chloroform, and acetonitrile; the catalyst is selected from trifluoroacetic acid and p-toluenesulfonic acid; the reaction temperature is between 80 ℃ and 120 ℃.
4. A process for the preparation of acylhydrazone structure-containing triazinone derivatives (scheme three): semicarbazide triazinones (II) with various phenoxy-substituted pyridylmethyl ketones VcReacting to generate a compound I containing acylhydrazone structure triazonec；
Wherein R is4Respectively represent hydrogen, hydroxyl, methyl, ethyl, isopropyl, tertiary butyl, 1-6 carbon alkoxy, 1-10 carbon alkylamino, halogen atom, cyano, 1-6 carbon alkylcarbonyl and 1-10 carbon alkoxycarbonyl; and simultaneously contains 2 to 3R4A substituent represented by;
and a third route:
the solvent is one of methanol, ethanol, chloroform, 1, 2-dichloroethane and acetonitrile; the catalyst is one of trifluoroacetic acid and p-toluenesulfonic acid; the reaction temperature is between 80 ℃ and 120 ℃.
5. Use of the triazinone derivatives according to claim 1 for the preparation of pesticides.
6. Use according to claim 5, wherein the pests are aphids, mosquito larvae, cotton bollworms, corn borers and armyworms.
7. Use of the triazinone derivative according to claim 1 for the preparation of fungicides.
8. Use according to claim 7, wherein the pathogenic bacteria are tomato early blight, wheat gibberella, potato late blight, phytophthora capsici, sclerotia napellus, cucumber gray mold, rice sheath blight, cucumber wilt, peanut brown spot, apple ring rot, wheat sheath blight, corn speck, watermelon anthrax and rice bakanae.
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Application publication date: 20171020 Assignee: HEBEI LINGANG CHEMICAL Co.,Ltd. Assignor: NANKAI University Contract record no.: X2024980000456 Denomination of invention: Triazine ketone derivatives containing acylhydrazone structures and their preparation methods, as well as their applications in insecticidal and bactericidal applications Granted publication date: 20201020 License type: Exclusive License Record date: 20240111 |
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