CN107266381A - Application containing acylhydrazone structure triazone derivatives and preparation method thereof and in terms of desinsection, sterilization - Google Patents
Application containing acylhydrazone structure triazone derivatives and preparation method thereof and in terms of desinsection, sterilization Download PDFInfo
- Publication number
- CN107266381A CN107266381A CN201610219375.6A CN201610219375A CN107266381A CN 107266381 A CN107266381 A CN 107266381A CN 201610219375 A CN201610219375 A CN 201610219375A CN 107266381 A CN107266381 A CN 107266381A
- Authority
- CN
- China
- Prior art keywords
- nmr
- dmso
- ketone
- methyl
- triazines
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 230000001954 sterilising effect Effects 0.000 title claims abstract description 6
- 238000004659 sterilization and disinfection Methods 0.000 title claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- -1 substituted-phenyl Chemical group 0.000 claims description 43
- 229910052799 carbon Inorganic materials 0.000 claims description 31
- 150000001875 compounds Chemical class 0.000 claims description 31
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- QMNWYGTWTXOQTP-UHFFFAOYSA-N 1h-triazin-6-one Chemical compound O=C1C=CN=NN1 QMNWYGTWTXOQTP-UHFFFAOYSA-N 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 125000001424 substituent group Chemical group 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 14
- 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
- 241000255967 Helicoverpa zea Species 0.000 claims description 11
- 241000409991 Mythimna separata Species 0.000 claims description 10
- 241000346285 Ostrinia furnacalis Species 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 8
- 241001124076 Aphididae Species 0.000 claims description 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 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
- 125000004185 ester group Chemical group 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 6
- 150000003349 semicarbazides Chemical class 0.000 claims description 6
- 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 6
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 claims description 6
- 241000256113 Culicidae Species 0.000 claims description 5
- 240000007594 Oryza sativa Species 0.000 claims description 5
- 235000007164 Oryza sativa Nutrition 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
- 238000000034 method Methods 0.000 claims description 5
- 235000009566 rice Nutrition 0.000 claims description 5
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 4
- 240000008067 Cucumis sativus Species 0.000 claims description 4
- 235000010799 Cucumis sativus var sativus Nutrition 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 4
- 235000007688 Lycopersicon esculentum 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
- 240000003768 Solanum lycopersicum Species 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000002837 carbocyclic group Chemical group 0.000 claims description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N diethylenediamine Natural products C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 244000052769 pathogen Species 0.000 claims description 4
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 241000238631 Hexapoda Species 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 201000010099 disease Diseases 0.000 claims description 3
- 208000037265 diseases, disorders, signs and symptoms Diseases 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
- 241001530056 Athelia rolfsii Species 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
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 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
- 241001558929 Sclerotium <basidiomycota> Species 0.000 claims description 2
- 235000021307 Triticum Nutrition 0.000 claims description 2
- 244000098338 Triticum aestivum 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
- 150000001299 aldehydes Chemical class 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 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
- 125000005708 carbonyloxy group Chemical group [*:2]OC([*:1])=O 0.000 claims description 2
- 235000005822 corn Nutrition 0.000 claims description 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 2
- 239000012362 glacial acetic acid Substances 0.000 claims description 2
- 230000036571 hydration Effects 0.000 claims description 2
- 238000006703 hydration reaction Methods 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- ZRNSSRODJSSVEJ-UHFFFAOYSA-N 2-methylpentacosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC(C)C ZRNSSRODJSSVEJ-UHFFFAOYSA-N 0.000 claims 1
- 235000017060 Arachis glabrata Nutrition 0.000 claims 1
- 244000105624 Arachis hypogaea Species 0.000 claims 1
- 235000010777 Arachis hypogaea Nutrition 0.000 claims 1
- 235000018262 Arachis monticola Nutrition 0.000 claims 1
- 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
- 239000007810 chemical reaction solvent Substances 0.000 claims 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N monofluoromethane Natural products FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims 1
- 230000001717 pathogenic effect Effects 0.000 claims 1
- 235000020232 peanut Nutrition 0.000 claims 1
- RDRCCJPEJDWSRJ-UHFFFAOYSA-N pyridine;1h-pyrrole Chemical compound C=1C=CNC=1.C1=CC=NC=C1 RDRCCJPEJDWSRJ-UHFFFAOYSA-N 0.000 claims 1
- 230000000749 insecticidal effect Effects 0.000 abstract description 9
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 5
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 386
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 159
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 112
- 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
- DUIOPKIIICUYRZ-UHFFFAOYSA-N semicarbazide Chemical compound NNC(N)=O DUIOPKIIICUYRZ-UHFFFAOYSA-N 0.000 description 97
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 40
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 24
- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 description 22
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 21
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 16
- 230000000694 effects Effects 0.000 description 15
- 238000012360 testing method Methods 0.000 description 13
- 239000005925 Pymetrozine Substances 0.000 description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical class C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- 229910021529 ammonia Inorganic materials 0.000 description 12
- QHMTXANCGGJZRX-WUXMJOGZSA-N pymetrozine Chemical compound C1C(C)=NNC(=O)N1\N=C\C1=CC=CN=C1 QHMTXANCGGJZRX-WUXMJOGZSA-N 0.000 description 12
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 10
- XZBIXDPGRMLSTC-UHFFFAOYSA-N formohydrazide Chemical compound NNC=O XZBIXDPGRMLSTC-UHFFFAOYSA-N 0.000 description 10
- 239000003814 drug Substances 0.000 description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 241000894006 Bacteria Species 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 5
- YFNXJADPSPDMAV-UHFFFAOYSA-N N1=NNC(C=C1)=O.NC(=O)N Chemical compound N1=NNC(C=C1)=O.NC(=O)N YFNXJADPSPDMAV-UHFFFAOYSA-N 0.000 description 5
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 5
- 238000007689 inspection Methods 0.000 description 5
- 238000012544 monitoring process Methods 0.000 description 5
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
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- 239000002917 insecticide Substances 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- FYADHXFMURLYQI-UHFFFAOYSA-N 1,2,4-triazine Chemical compound C1=CN=NC=N1 FYADHXFMURLYQI-UHFFFAOYSA-N 0.000 description 3
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 3
- 0 CC(C*1*C(**=C)=O)=**C1=O Chemical compound CC(C*1*C(**=C)=O)=**C1=O 0.000 description 3
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- 230000003385 bacteriostatic effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- CTAWBMDQTAZKIE-UHFFFAOYSA-N n,n-diaminoformamide Chemical compound NN(N)C=O CTAWBMDQTAZKIE-UHFFFAOYSA-N 0.000 description 3
- 125000001639 phenylmethylene group Chemical group [H]C(=*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LUZDYPLAQQGJEA-UHFFFAOYSA-N 2-Methoxynaphthalene Chemical compound C1=CC=CC2=CC(OC)=CC=C21 LUZDYPLAQQGJEA-UHFFFAOYSA-N 0.000 description 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 2
- ZMYFQNLVBIXLAR-UHFFFAOYSA-N CC(CN1NC(NN)=O)=NNC1=O Chemical compound CC(CN1NC(NN)=O)=NNC1=O ZMYFQNLVBIXLAR-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
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- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 description 2
- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
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- 239000007788 liquid Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
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- 238000000967 suction filtration Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
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- 230000009466 transformation Effects 0.000 description 2
- 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 description 1
- ZYMCBJWUWHHVRX-UHFFFAOYSA-N (4-nitrophenyl)-phenylmethanone Chemical class C1=CC([N+](=O)[O-])=CC=C1C(=O)C1=CC=CC=C1 ZYMCBJWUWHHVRX-UHFFFAOYSA-N 0.000 description 1
- MTXSIJUGVMTTMU-JTQLQIEISA-N (S)-anabasine Chemical compound N1CCCC[C@H]1C1=CC=CN=C1 MTXSIJUGVMTTMU-JTQLQIEISA-N 0.000 description 1
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- 150000002397 1-phenylpyrazoles Chemical class 0.000 description 1
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- OBTZDIRUQWFRFZ-UHFFFAOYSA-N 2-(5-methylfuran-2-yl)-n-(4-methylphenyl)quinoline-4-carboxamide Chemical compound O1C(C)=CC=C1C1=CC(C(=O)NC=2C=CC(C)=CC=2)=C(C=CC=C2)C2=N1 OBTZDIRUQWFRFZ-UHFFFAOYSA-N 0.000 description 1
- 125000004204 2-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C(OC([H])([H])[H])C([H])=C1[H] 0.000 description 1
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- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 1
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000006306 4-iodophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1I 0.000 description 1
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- 125000006519 CCH3 Chemical group 0.000 description 1
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- 229930182555 Penicillin Natural products 0.000 description 1
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 description 1
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- 229920001213 Polysorbate 20 Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 241000534944 Thia Species 0.000 description 1
- 241001512566 Valsa mali Species 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- WRLRISOTNFYPMU-UHFFFAOYSA-N [S].CC1=CC=CC=C1 Chemical compound [S].CC1=CC=CC=C1 WRLRISOTNFYPMU-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229930014345 anabasine Natural products 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 229950011260 betanaphthol Drugs 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000001390 capsicum minimum Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- LVWZTYCIRDMTEY-UHFFFAOYSA-N metamizole Chemical compound O=C1C(N(CS(O)(=O)=O)C)=C(C)N(C)N1C1=CC=CC=C1 LVWZTYCIRDMTEY-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000002231 mosquitocidal effect Effects 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 231100001160 nonlethal Toxicity 0.000 description 1
- 229940049954 penicillin Drugs 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000002728 pyrethroid Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 238000005556 structure-activity relationship Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 208000011580 syndromic disease Diseases 0.000 description 1
- 231100000583 toxicological profile Toxicity 0.000 description 1
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
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
Abstract
The present invention relates to the application containing acylhydrazone structure triazone derivatives (I) and preparation method thereof and in terms of desinsection, sterilization, the meaning of each group is shown in specification in formula.This patent contains acylhydrazone structure triazone derivatives and shows good insecticidal activity, while also having bactericidal activity.
Description
Technical field
The present invention relates to answering containing acylhydrazone structure triazone derivatives and preparation method thereof and in terms of desinsection, sterilization
With category technical field of pesticide.
Background technology
Novartis Co., Ltd of Switzerland 1988 is found that a kind of non-lethal insecticide pymetrozine, and it belongs to triazinone compounds,
With the brand-new mode of action, there is excellent prevention effect to a variety of suckings pest.In addition, pymetrozine with it is traditional
Organochlorine, organochlorine, carbamate, pyrethroid, 1- phenyl pyrazoles, anabasine insecticide no interactions resistance, because
This, pymetrozine can apply to the preventing and treating of multiple resistance strain insect.The toxicological profile of pymetrozine is unique, and environmental compatible, right
Insect has the selectivity of interaction, the implementation for being conducive to comprehensive preventive health measures and resistance syndrome to administer in agricultural production, simultaneously
Pymetrozine can also mitigate the generation of crops virus harm, and above advantage determines that pymetrozine has wide answer in agricultural production
Use prospect.Summarize it has been reported that structure-activity relationship, it is found that modification is mainly concentrated in research work of the forefathers to pymetrozine insecticides
With transformation triazinone ring and pyridine loop section, it is and less to the transformation report of intermediate link arm.Beriger reports Asia within 1994
Amine transform the compound structure of acid amides as, but does not report its activity data (Beriger, E.；Kristinsson, H.US
5324842.1994-06-28.).Uehara in 1996 reports the compound knot that N atoms after imine reduction contain substituent
Structure, and part of compounds is reported under 500ppm concentration, 100% insecticidal activity is shown to black peach aphid and the brown aleyrodid of rice
(Uehara, M.；Shimizu.T.；Fujioka.S.et al.EP 0987255A2.1996-03-28.).Ou Yanggui in 2013
Flat group reports the compound structure that imines is replaced by acid amides, while have studied such compound to fusarium graminearum, capsicum
Bacteriostatic activity (Zhang Yonglu, Ou Yangguiping, He Baoan the moderns .2013.12 (2) of wilt, Valsa mali
.10-13.).With being widely used for pymetrozine, the resistance problem of pymetrozine equally can be protruded increasingly, and therefore, exploitation is provided
The insecticide having with pymetrozine similar effect mode is the important topic that researcher faces.
The content of the invention
It is an object of the invention to provide containing acylhydrazone structure triazone derivatives and preparation method thereof and in desinsection, sterilization side
The application in face.This patent containing acylhydrazone structure triazone derivatives shows good insecticidal activity, also with bactericidal activity.
The present invention is the compound with structure shown in below formula (I) containing acylhydrazone structure triazone derivatives：
Of the present invention is with following three kinds of formula (I containing acylhydrazone structure triazone derivatives (I)a, Ib.Ic) institute
Show the compound of structure：
The present invention contains acylhydrazone structure triazone derivatives Ia-1--1a- 57 can be prepared as follows (route one)：It is first
First amino triazine ketone (II) and phenyl chloroformate reaction generation compound III, compound III and hydration hydrazine reaction generation intermediate
Semicarbazides triazinone IV, then compound IV and various aldehyde VaReact the generation triazineon compounds of structure containing acylhydrazone Ia；
Route one：
The solvent of first step reaction can be methanol, dichloromethane, chloroform, 1,2- dichloroethanes, acetonitrile；Acid binding agent can be with
It is pyridine, sodium carbonate, triethylamine, potassium carbonate, cesium carbonate；Reaction temperature is in 60 DEG C to 80 DEG C progress；The solvent of second step reaction
Can be methanol, dichloromethane, ethanol, 1,2- dichloroethanes, acetonitrile；Reaction temperature is in 80 DEG C to 100 DEG C progress；3rd step is anti-
The solvent answered can be methanol, ethanol, acetonitrile, DMF；Catalyst can be trifluoroacetic acid, to methylbenzene sulphur
Acid, glacial acetic acid；Reaction temperature is in 70 to 100 DEG C of progress.
The present invention contains acylhydrazone structure triazone derivatives Ib-1--1b- 28 can be prepared as follows (route two)：Ammonia
Base urea triazinone (IV) contains acylhydrazone structure triazineon compounds I with the generation of various reactive ketonesb；
Route two：
Solvent can be methanol, ethanol, 1,2- dichloroethanes, chloroform, acetonitrile；Catalyst can be trifluoroacetic acid, to first
Base benzene sulfonic acid；Reaction temperature is in 80 DEG C to 120 DEG C progress.
The present invention contains acylhydrazone structure triazone derivatives Ic-1--1c- 15 can be prepared as follows (route three)：Ammonia
The picolyl ketone V that base urea triazinone (II) replaces with various phenoxy groupscThe generation that reacts contains acylhydrazone structure triazine assimilation
Compound Ic；
Route three：
Solvent can be methanol, ethanol, chloroform, 1,2- dichloroethanes, acetonitrile；Catalyst can be trifluoroacetic acid, to first
Base benzene sulfonic acid；Reaction temperature is in 80 DEG C to 120 DEG C progress.
Above in each formula,
R12-10 carbon alkyl, 3-6 carbocyclic rings alkyl are represented respectively, benzyl, naphthyl, (wherein substituent can be with for the phenyl of substitution
It is hydrogen, hydroxyl, halogen atom, cyano group, nitro, ester group, dimethylamino, trifluoromethyl, trifluoromethoxy, 1-5 carbon alkyl, 1-6
Carbon alkoxy and simultaneously containing 2-3 above-mentioned substituents), 1-10 carbon nitrogen heterocyclic ring, 1-10 carbon oxygen heterocycle, 1-10 carbon contains
Thia ring；
R2Represent respectively 1-10 carbon alkyl, phenyl, substituted-phenyl (wherein substituent can be hydrogen, hydroxyl, halogen atom,
Cyano group, nitro, ester group, fluorine, trifluoromethyl, trifluoromethoxy, 1-5 carbon alkyl, 1-6 carbon alkoxy and contain 2-3 simultaneously
Above-mentioned substituent), and R2And R3The 3-6 carbocyclic ring alkyl collectively constituted；
R3Represent respectively substituted phenyl (wherein substituent can be hydrogen, hydroxyl, halogen atom, cyano group, nitro, ester group,
Fluorine, trifluoromethyl, trifluoromethoxy, 1-5 carbon alkyl, 1-6 carbon alkoxy and simultaneously containing 2-3 above-mentioned substituents)；
R4Hydrogen, hydroxyl, 1-6 carbon alkoxy 1-10 carbon alkylamino radical, halogen atom, cyano group, aldehyde radical, 1-6 carbon alkane are represented respectively
Carbonyl, 1-10 carbon alkoxy carbonyl group, 1-10 carbon alkanamines carbonyl, 1-6 carbon alkyl oxy carbonyl oxygen, 1-6 carbon alkanamine carbonyloxy groups；And contain simultaneously
There is 2-3 R4Representative substituent.
It is of the present invention to be preferably as follows compound containing acylhydrazone triazone derivatives (I)：
(E) -2- (2,2- dimethylpropylidene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl)
Carbamyl hydrazine (Ia-3)；
(E) -2- (cyclohexylmethylene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) amino
Formylhydrazine (Ia-4)；
(E) -2- (2,3- dimethoxy benzene methylene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4
(5H)-yl) carbamyl hydrazine (Ia-13)；
(E) -2- (2,4- dimethoxy benzene methylene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4
(5H)-yl) carbamyl hydrazine (Ia-14)；
(E) -2- (3,5- dimethoxy benzene methylene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4
(5H)-yl) carbamyl hydrazine (Ia-15)；
(E)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) -2- (2,3,4- trimethoxy-benzenes
Methylene) carbamyl hydrazine (Ia-16)；
(E) -2- (3- cyano-phenyls methylene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl)
Carbamyl hydrazine (Ia-35)；
(E)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) -2- (3- nitrobenzophenones methylene)
Carbamyl hydrazine (Ia-38)；
(E) -2- (4- (dimethylamino) phenylmethylene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4
(5H)-yl) carbamyl hydrazine (Ia-44)；
(E) -2- ((6- methoxynaphthalene -2- bases) phenylmethylene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- tri-
Piperazine -4 (5H)-yl) carbamyl hydrazine (Ia-47)；
(E) -2- ((1H- indol-3-yls) phenylmethylene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4
(5H)-yl) carbamyl hydrazine (Ia-50)；
(E)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) -2- (pyridine -2- base phenyl methylidenes
Base) carbamyl hydrazine (Ia-51)；
(E)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) -2- (pyridin-3-yl phenyl methylidenes
Base) carbamyl hydrazine (Ia-52)；
(E) -2- (furans -2- bases phenylmethylene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H) -
Base) carbamyl hydrazine (Ia-54)；
(E)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) -2- (thiophene -2- base phenyl methylidenes
Base) carbamyl hydrazine (Ia-55)；
2- cyclopentylenes-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) carbamyl hydrazine (Ib-
3)；
(E)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) -2- (1- phenylethylenes) amino first
Hydrazides (Ib-6)；
(E) -2- (1- (4- methoxyphenyls) ethylidene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4
(5H)-yl) -2- (1- phenylethylenes) carbamyl hydrazines (Ib-11)；
(E)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) -2- (1- (3,4,5- trimethoxies
Phenyl) ethylidene) carbamyl hydrazine (Ib-13)；
(E) -2- (1- (4- chlorphenyls) ethylidene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H) -
Base) -2- (1- phenylethylenes) carbamyl hydrazines (Ib-16)；
(E)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) -2- (1- p-methylphenyls Asia second
Base) carbamyl hydrazine (Ib-22)；
(E) -2- (1- (4- hydroxy phenyls) ethylidene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4
(5H)-yl) -2- (1- phenylethylenes) carbamyl hydrazines (Ib-25)；
(E) -2- (1- (6- (2- ethoxy phenoxies) pyridin-3-yl) ethylidene)-N- (6- methyl -3- ketone -2,3- bis-
Hydrogen -1,2,4- triazines -4 (5H)-yl) -2- (1- phenylethylenes) carbamyl hydrazines (Ic-2)；
(E) -2- (1- (6- (4- ethyls phenoxy group) pyridin-3-yl) ethylidene)-N- (6- methyl -3- ketone -2,3- dihydro -
(the 5H)-yl of 1,2,4- triazine -4) -2- (1- phenylethylenes) carbamyl hydrazines (Ic-5)；
(E) -2- (1- (6- (4- cumenes epoxide) pyridin-3-yl) ethylidene)-N- (6- methyl -3- ketone -2,3- bis-
Hydrogen -1,2,4- triazines -4 (5H)-yl) -2- (1- phenylethylenes) carbamyl hydrazines (Ic-6)；
(E) -2- (1- (6- (4- tert-butyl benzenes epoxide) pyridin-3-yl) ethylidene)-N- (6- methyl -3- ketone -2,3- bis-
Hydrogen -1,2,4- triazines -4 (5H)-yl) -2- (1- phenylethylenes) carbamyl hydrazines (Ic-7)；
(E) -2- (1- (6- (4- bromobenzenes epoxide) pyridin-3-yl) ethylidene)-N- (6- methyl -3- ketone -2,3- dihydro -1,
(the 5H)-yl of 2,4- triazine -4) -2- (1- phenylethylenes) carbamyl hydrazines (Ic-8)；
(E) -2- (1- (6- (4- iodobenzenes epoxide) pyridin-3-yl) ethylidene)-N- (6- methyl -3- ketone -2,3- dihydro -1,
(the 5H)-yl of 2,4- triazine -4) -2- (1- phenylethylenes) carbamyl hydrazines (Ic-9)；
(E) -2- (1- (6- (4- isopropyl -3- methylphenoxies) pyridin-3-yl) ethylidene)-N- (6- methyl -3- ketone -
2,3- dihydros -1,2,4- triazines -4 (5H)-yl) -2- (1- phenylethylenes) carbamyl hydrazines (Ic-12)。
The compound of the logical formula (I) of the present invention shows good killing aphids activity, wherein, 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 show the activity suitable with pymetrozine under 5mg/kg concentration.Part of compounds is shown very well to mosquito larvae simultaneously
Activity, especially compound Ia- 47 show 40% insecticidal activity under 0.01mg/kg concentration to mosquito larvae.In addition, institute
There is compound to show insecticidal activity to bollworm, corn borer and mythimna separata.Wherein compound Ib- 44 in 100mg/kg, right
Bollworm, corn borer and mythimna separata show 30%, 20% and 60% insecticidal activity respectively.
The compound of the logical formula (I) of the present invention shows bactericidal activity to following 14 kinds of pathogens, and 14 kinds of pathogens are respectively：
Tomato early epidemic, gibberella saubinetii, potato late blight, Phytophthora capsici, rape sclerotium, cucumber grey mold, rice banded sclerotial blight, cucumber are withered, flower
Raw foxiness, apple wheel line, withered wheat line, corn stigma, watermelon anthrax and rice bakanae disease, 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 Ic- 14 under 50mg/kg concentration to a variety of cause of diseases
Bacterium shows good bacteriostatic activity.
Embodiment
Following embodiments and raw test result can be used to further illustrate the present invention, but be not intended to limit this hair
It is bright.
Embodiment 1：The synthesis of N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) carbamyl hydrazine
The synthesis of phenyl (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) carbamate (III)
In 100mL single port bottles, dichloromethane (50mL), amino triazine ketone (II) (2.56g, 20mmol), carbonic acid are added
Potassium (2.76g, 20mmol), is sufficiently stirred for, and phenyl chloroformate (3.13g, 20mmol) is slowly added dropwise at room temperature, about 1h is dripped
Finish, 6h is heated to reflux afterwards, TLC monitoring reactions are finished.Room temperature is cooled to, is filtered, solution decompression precipitation, with petroleum ether/acetic acid
Ethyl ester (1: 1) carries out normal pressure column chromatography and obtains compound III4.5g, white solid, yield 91%, 181-182 DEG C of fusing point.1H NMR
(300MHz, DMSO-d6) δ 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) δ 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
The synthesis of N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) carbamyl hydrazine (IV)
In 250mL single port bottles, addition methanol (120mL), compound III (2.7g, 11mmol), hydrazine hydrate (10mL),
It is sufficiently stirred for, 8h is heated to reflux afterwards, TLC monitoring reactions is finished.Room temperature is cooled to, IV1.56g is filtrated to get, white solid,
Yield 77%, 229-231 DEG C of fusing point.1H NMR (300MHz, DMSO-d6) δ 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)δ
159.1,151.7,144.7,52.4,19.9.ESI-HRMS (m/z)：Calcd.for C5H11N6O2[M+H]+187.0938；
found 187.0939.
Embodiment 2：(E)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) -2- propylidene amino
Formylhydrazine (Ia- 1) synthesis
In 250mL single port bottles, add semicarbazides triazinone (0.74g, 4mmol), p-methyl benzenesulfonic acid (0.14g,
8mmol), positive propionic aldehyde (0.23g, 4mmol), methanol (120mL) stirring and dissolving, are then heated to reflux 6h, and TLC monitorings have been reacted
Finish.Solid will be separated out after reaction solution removed under reduced pressure solvent, normal pressure suction filtration is washed with methanol and obtains target compound 0.48g, white
Solid, yield 53%, 148 DEG C of fusing point.1H NMR (400MHz, CDCl3) δ 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) δ 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 pass through the completion that repeats the above steps.
(E) -2- butylidenes-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) carbamyl hydrazine
(Ia-2)
White solid, yield 57%, 173-175 DEG C of fusing point.1H NMR (400MHz, CDCl3) δ 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) δ 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- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl)
Carbamyl hydrazine (Ia-3)
White solid, yield 67%, 230-231 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) amino
Formylhydrazine (Ia-4)；
White solid, yield 75%, 213-214 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 154.6,151.6,149.0,144.8,52.2,29.8,25.6,25.1,19.9.ESI-HRMS (m/z)：Calcd.for
C12H21N6O2[M+H]+281.1721；found 281.1725.
(E)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) -2- (2- phenyl-ethylenes) amino
Formylhydrazine (Ia-5)
White solid, yield 48%, 125-126 DEG C of fusing point.1H NMR (400MHz, CDCl3) δ 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) δ 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- phenylmethylenes-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) carbamyl
Hydrazine (Ia-6)；
White solid, yield 69%, 219-220 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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.for
C12H15N6O2[M+H]+275.1251；found 275.1246.
(E)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) -2- (2- aminomethyl phenyls methylene)
Carbamyl hydrazine (Ia-7)；
White solid, yield 72%, 229-230 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) -2- (3- aminomethyl phenyls methylene)
Carbamyl hydrazine (Ia-8)；
White solid, yield 62%, 215-216 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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.for
C13H17N6O2[M+H]+289.1408；found 289.1410.
(E)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) -2- (4- aminomethyl phenyls methylene)
Carbamyl hydrazine (Ia-9)；
White solid, yield 78%, 264-265 DEG C of fusing point.1H NMR (400MHz, DMSO-d6)：δ 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) δ 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- methoxybenzenes methylene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H) -
Base) carbamyl hydrazine (Ia-10)；
Yellow solid, yield 67%, 232-233 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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- methoxybenzenes methylene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H) -
Base) carbamyl hydrazine (Ia-11)；
White solid, yield 67%, 226-227 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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.for
C13H17N6O3[M+H]+305.1357；found 305.1359.
(E) -2- (4- methoxybenzenes methylene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H) -
Base) carbamyl hydrazine (Ia-12)；
White solid, yield 82%, 230-231 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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- dimethoxy benzene methylene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4
(5H)-yl) carbamyl hydrazine (Ia-13)；
White solid, yield 80%, 226-227 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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- dimethoxy benzene methylene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4
(5H)-yl) carbamyl hydrazine (Ia-14)；
White solid, yield 76%, 210-211 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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.for
C14H19N6O4[M+H]+335.1462；found 335.1463.
(E) -2- (3,5- dimethoxy benzene methylene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4
(5H)-yl) carbamyl hydrazine (Ia-15)；
White solid, yield 87%, 245 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) -2- (2,3,4- trimethoxy-benzenes
Methylene) carbamyl hydrazine (Ia-16)；
White solid, yield 78%, 244-245 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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.for
C15H21N6O5[M+H]+365.1568；found 365.1569.
(E)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) -2- (3,4,5- trimethoxy-benzenes
Methylene) carbamyl hydrazine (Ia-17)；
White solid, yield 71%, 233-234 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) -2- (2- (trifluoromethyl) phenyl
Methylene) carbamyl hydrazine (Ia-18)；
White solid, yield 79%, 262-263 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) -2- (3- (trifluoromethyl) phenyl
Methylene) carbamyl hydrazine (Ia-19)；
White solid, yield 86%, 278-279 DEG C of fusing point.1H NMR (300MHz, DMSO-d6) δ 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) δ 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- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) -2- (4- (trifluoromethyl) phenyl
Methylene) carbamyl hydrazine (Ia-20)；
White solid, yield 76%, 239-241 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) -2- (3- (trifluoromethoxy) benzene
Methylene) carbamyl hydrazine (Ia-21)；
White solid, yield 78%, 264-265 DEG C of fusing point.1H NMR (300MHz, DMSO-d6) δ 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) δ 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.for
C13H14F3N6O3[M+H]+359.1074；found 359.1077.
(E)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) -2- (4- (trifluoromethoxy) benzene
Methylene) carbamyl hydrazine (Ia-22)；
White solid, yield 87%, 266-267 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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- fluorobenzene methylene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) ammonia
Base formylhydrazine (Ia-23)；
White solid, yield 78%, 233-234 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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.for
C12H14FN6O2[M+H]+293.1157；found 293.1157.
(E) -2- (3- fluorobenzene methylene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) ammonia
Base formylhydrazine (Ia-24)；
White solid, yield 87%, 213-215 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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- fluorobenzene methylene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) ammonia
Base formylhydrazine (Ia-25)；
White solid, yield 75%, 240 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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；
found 293.1159.
(E) -2- (2- chlorobenzenes methylene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) ammonia
Base formylhydrazine (Ia-26)；
White solid, yield 89%, 248-249 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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- chlorobenzenes methylene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) ammonia
Base formylhydrazine (Ia-27)；
White solid, yield 88%, 242-243 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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- chlorobenzenes methylene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) ammonia
Base formylhydrazine (Ia-28)；
White solid, yield 85%, 275-276 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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.for
C12H14ClN6O2[M+H]+309.0861；found 309.0861.
(E) -2- (2,4- dichlorophenyl methylene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H) -
Base) carbamyl hydrazine (Ia-29)；
White solid, yield 93%, 285-286 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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- dichlorophenyl methylene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H) -
Base) carbamyl hydrazine (Ia-30)；
White solid, yield 88%, 265-266 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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- bromobenzenes methylene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) ammonia
Base formylhydrazine (Ia-31)；
White solid, yield 89%, 265 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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)；13C
NMR (100MHz, DMS0-d6) δ 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- bromobenzenes methylene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) ammonia
Base formylhydrazine (Ia-32)；
White solid, yield 85%, 253-254 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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- bromobenzenes methylene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) ammonia
Base formylhydrazine (Ia-33)；
White solid, yield 82%, 271-272 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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.for
C12H14BrN6O2[M+H]+353.0356；found 353.0354.
(E) -2- (2- cyano-phenyls methylene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl)
Carbamyl hydrazine (Ia-34)；
White solid, yield 84%, 274-275 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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- cyano-phenyls methylene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl)
Carbamyl hydrazine (Ia-35)；
White solid, yield 65%, 249-250 DEG C of fusing point.1H NMR (300MHz, DMSO-d6) δ 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) δ 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- cyano-phenyls methylene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl)
Carbamyl hydrazine (Ia-36)；
White solid, yield 78%, 293-294 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) -2- (2- nitrobenzophenones methylene)
Carbamyl hydrazine (Ia-37)；
Yellow solid, yield 89%, 232-233 DEG C of fusing point.1H NMR (300MHz, DMSO-d6) δ 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) δ 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- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) -2- (3- nitrobenzophenones methylene)
Carbamyl hydrazine (Ia-38)；
White solid, yield 79%, 277-278 DEG C of fusing point.1H NMR (300MHz, DMSO-d6) δ 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) δ 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- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) -2- (4- nitrobenzophenones methylene)
Carbamyl hydrazine (Ia-39)；
White solid, yield 82%, 294-295 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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.for
C12H14N7O4[M+H]+320.1102；found 320.1103.
(E) -2- (3- hydroxy phenyls methylene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl)
Carbamyl hydrazine (Ia-40)；
White solid, yield 95%, 264-265 DEG C of fusing point.1H NMR (300MHz, DMSO-d6) δ 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) δ 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- hydroxy phenyls methylene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl)
Carbamyl hydrazine (Ia-41)；
White solid, yield 74%, 237-238 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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- dihydroxy benzenes methylene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4
(5H)-yl) carbamyl hydrazine (Ia-42)；
White solid, yield 68%, 251-252 DEG C of fusing point.1H NMR (300MHz, DMSO-d6) δ 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) δ 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-butyl benzenes methylene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H) -
Base) carbamyl hydrazine (Ia-43)；
White solid, yield 69%, 211-212 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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- ketone -2,3- dihydros -1,2,4- triazines -4
(5H)-yl) carbamyl hydrazine (Ia-44)；
Pink solid, yield 69%, 229-230 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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 hydroxy naphthalene -1- bases) methylene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4
(5H)-yl) carbamyl hydrazine (Ia-45)；
Yellow solid, yield 98%, 258 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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-HRMS (m/z)：Calcd.for C16H17N6O3[M+H]+341.1357；found
341.1360.
(E) -2- ((6- hydroxyl naphthalene -2- bases) methylene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4
(5H)-yl) carbamyl hydrazine (Ia-46)；
Yellow solid, yield 92%, 265-267 DEG C of fusing point.1H NMR (300MHz, DMSO-d6) δ 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) δ 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；found
341.1359.
(E) -2- ((6- methoxynaphthalene -2- bases) methylene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4
(5H)-yl) carbamyl hydrazine (Ia-47)；
Yellow solid, yield 79%, 232-233 DEG C of fusing point.1H NMR (300MHz, DMSO-d6) δ 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) δ 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；found
355.1516.
(E) -2- (benzo [d] [1,3] dioxy -5- methylene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -
4 (5H)-yls) carbamyl hydrazine (Ia-48)；
White solid, yield 96%, 266-267 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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- dihydrobenzos [b] [Isosorbide-5-Nitrae] dioxin -6- bases) methylene)-N- (6- methyl -3- ketone -2,3- bis-
Hydrogen -1,2,4- triazines -4 (5H)-yl) carbamyl hydrazine (Ia-49)；
White solid, yield 86%, 264-265 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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-yls) methylene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4
(5H)-yl) carbamyl hydrazine (Ia-50)；
White solid, yield 97%, 255-257 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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)δ
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- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) -2- (pyridine -2- methylenes)
Carbamyl hydrazine (Ia-51)；
White solid, yield 55%, 230-231 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) -2- (pyridin-3-yl methylene)
Carbamyl hydrazine (Ia-52)；
White solid, yield 89%, 227-228 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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；found
276.1205.
(E)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) -2- (pyridin-4-yl methylene)
Carbamyl hydrazine (Ia-53)；
White solid, yield 80%, 289-290 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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- (furans -2- methylenes)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl)
Carbamyl hydrazine (Ia-54)；
Brown solid, yield 65%, 186-187 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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.for
C10H13N6O3[M+H]+265.1044；found 265.1047.
(E)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) -2- (thiophene -2- methylenes)
Carbamyl hydrazine (Ia-55)；
Yellow solid, yield 68%, 226-227 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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)；13C
NMR (100MHz, DMSO-d6) δ 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- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) -2- (thiene-3-yl methylene)
Carbamyl hydrazine (Ia-56)；
Yellow solid, yield 87%, 244-245 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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- imidazoles -2-yl) methylene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4
(5H)-yl) carbamyl hydrazine (Ia-57)；
White solid, yield 59%, 215-216 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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)
δ 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.
Embodiment 3：N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) -2- (propane -2- ketone) ammonia
Base formylhydrazine (Ib- 1) synthesis
In 250mL single port bottles, add semicarbazides triazinone (IV) (0.93g, 4mmol), p-methyl benzenesulfonic acid (0.14g,
0.8mmol), acetone (0.23g, 4mmol), methanol (120mL) stirring and dissolving, are then heated to reflux 5h, and TLC monitorings have been reacted
Finish.Solid will be separated out after reaction solution removed under reduced pressure solvent, normal pressure suction filtration is washed with methanol and obtains compound Ib- 10.79g, white
Solid, yield 88%, 224-226 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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 pass through the completion that repeats the above steps.
(E) -2- (butane -2- ketone)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) amino first
Hydrazides (Ib-2)
White solid, yield 65%, 225-226 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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)δ
155.3,152.5,151.6,144.8,52.2,31.4,19.9,15.5,10.8.ESI-HRMS (m/z)：Calcd.for
C9H17N6O2[M+H]+241.1408；found 241.1410.
2- cyclopenta ketone-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) carbamyl hydrazine (Ib-
3)
White solid, yield 68%, 227-229 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 160.7,155.2,151.6,144.7,52.2,32.8,28.0,24.5,19.9.ESI-HRMS (m/z)：Calcd.for
C10H17N6O2[M+H]+253.1408；found 253.1413.
2- cyclohexyl ketones-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) carbamyl hydrazine (Ib-
4)
White solid, yield 56%, 233 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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.for
C11H19N6O2[M+H]+267.1564；found 267.1567.
2- suberyl ketone-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) carbamyl hydrazine (Ib-
5)
White solid, yield 55%, 224-226 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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)δ
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- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) -2- (1- phenylethylketones) amino first
Hydrazides (Ib-6)
White solid, yield 66%, 249-250 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) -2- (1- phenylpropyls ketone) amino first
Hydrazides (Ib-7)
White solid, yield 68%, 232-233 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) -2- (1- benzene butyl ketone) amino first
Hydrazides (Ib-8)
White solid, yield 60%, 221-222 DEG C of fusing point.1H NMR (300MHz, DMSO-d6) δ 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) δ 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- methoxyphenyls) ethylidene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4
(5H)-yl) carbamyl hydrazine (Ib-9)
White solid, yield 66%, 188-189 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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；found
319.1519.
(E) -2- (1- (3- methoxyphenyls) ethylidene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4
(5H)-yl) carbamyl hydrazine (Ib-10)
White solid, yield 86%, 228-229 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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- methoxyphenyls) ethylidene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4
(5H)-yl) carbamyl hydrazine (Ib-11)
White solid, yield 77%, 249 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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) ethylidene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- tri-
Piperazine -4 (5H)-yl) carbamyl hydrazine (Ib-12)
White solid, yield 86%, 226-227 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) -2- (1- (3,4,5- trimethoxies
Phenyl) ethylidene) carbamyl hydrazine (Ib-13)
White solid, yield 85%, 260 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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- chlorphenyls) ethylidene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H) -
Base) carbamyl hydrazine (Ib-14)
White solid, yield 50%, 218-219 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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- chlorphenyls) ethylidene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H) -
Base) carbamyl hydrazine (Ib-15)
White solid, yield 86%, 274-275 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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)δ
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- chlorphenyls) ethylidene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H) -
Base) carbamyl hydrazine (Ib-16)
White solid, yield 89%, 268-269 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 155.1,
151.7,144.8,136.7,133.5,128.1,52.1,19.9,13.2.ESI-HRMS (m/z)：Calcd.for
C13H16ClN6O2[M+H]+323.1018；found 323.1022.
(E) -2- (1- (2,4- dichlorophenyl) ethylidene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4
(5H)-yl) carbamyl hydrazine (Ib-17)
White solid, yield 80%, 252-253 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) -2- (1- (2,3,4- trichloro-benzenes
Base) ethylidene) carbamyl hydrazine (Ib-18)
White solid, yield 97%, 258 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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- fluorophenyls) ethylidene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H) -
Base) carbamyl hydrazine (Ib-19)
White solid, yield 88%, 272-274 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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)δ162.6
(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- bromophenyls) ethylidene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H) -
Base) carbamyl hydrazine (Ib-20)
White solid, yield 90%, 265-266 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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- iodophenyls) ethylidene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H) -
Base) carbamyl hydrazine (Ib-21)
Yellow solid, yield 79%, 279-280 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) -2- (1- p-methylphenyls Asia second
Base) carbamyl hydrazine (Ib-22)
White solid, yield 87%, 271-273 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) -2- (1- (4- (trifluoromethyl) benzene
Base) ethylidene) carbamyl hydrazine (Ib-23)
White solid, yield 89%, 280-281 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) -2- (1- (4- (trifluoromethoxy)
Phenyl) ethylidene) carbamyl hydrazine (Ib-24)
White solid, yield 86%, 280-281 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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- hydroxyls) ethylidene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl)
Carbamyl hydrazine (Ib-25)
White solid, yield 75%, 237-238 DEG C of fusing point.1H NMR (300MHz, DMSO-d6) δ 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) δ 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) (1- (4- nitrobenzophenones) is sub- by-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) -2-
Ethyl) carbamyl hydrazine (Ib-26)
Yellow solid, yield 89%, 229-230 DEG C of fusing point.1H NMR (300MHz, DMSO-d6) δ 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) δ 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- aminophenyls) ethylidene)-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4
(5H)-yl) carbamyl hydrazine (Ib-27)
Yellow solid, yield 54%, 298-300 DEG C of fusing point.1H NMR (300MHz, DMSO-d6) δ 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) δ 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- ketone -2,3- dihydros -1,2,4- triazines -4 (5H) -2- (1- (pyridin-3-yl) ethylidene)
Carbamyl hydrazine (Ib-28)
White solid, yield 97.7%, 228-229 DEG C of fusing point.1H NMR (400MHz, CDCl3) δ 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) δ 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.
Embodiment 4：(E) ((6- is (adjacent by 1- by-N- (6- methyl -3- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) -2-
Methylphenoxy) pyridin-3-yl) ethylidene) carbamyl hydrazine (Ic- 1) synthesis
In 250mL single port bottles, add amino triazine ketone (0.74g, 4mmol), p-methyl benzenesulfonic acid (0.14g,
0.8mmol) pyridone (0.91g, 4mmol), methanol (120mL) stirring and dissolving, are then heated to reflux 6h, and TLC monitorings have been reacted
Finish.Reaction solution is depressurized after precipitation, silica gel column chromatography is carried out with petrol ether/ethyl acetate (30: 1--10: 1) and obtains yellow solid
0.85g, yield 54%, 218 DEG C of fusing point.1H NMR (400MHz, DMSO-d6)：δ 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) δ 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 pass through the completion that repeats the above steps.
(E) -2- (1- (6- (2- ethoxy phenoxies) pyridin-3-yl) ethylidene)-N- (6- methyl -3- ketone -2,3- bis-
Hydrogen -1,2,4- triazines -4 (5H)-yl) carbamyl hydrazine (Ic-2)
White solid, yield 61%, 217-218 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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- ketone -2,3- dihydros -1,2,4- triazines -4 (5H)-yl) -2- (1- (6- (2- ethoxybenzenes
Epoxide) pyridin-3-yl) ethylidene) carbamyl hydrazine (Ic-3)
Yellow solid, yield 81%, 261-262 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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- amino-benzene oxygens) pyridin-3-yl) ethylidene)-N- (6- methyl -3- ketone -2,3- dihydro -
(the 5H)-yl of 1,2,4- triazine -4) carbamyl hydrazine (Ic-4)
Yellow solid, yield 80%, 233-234 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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- ethyls phenoxy group) pyridin-3-yl) ethylidene)-N- (6- methyl -3- ketone -2,3- dihydro -
(the 5H)-yl of 1,2,4- triazine -4) carbamyl hydrazine (Ic-5)
Yellow solid, yield 85%, 214-216 DEG C of fusing point.1H NMR (400MHz, DMSO-d6)：δ 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) δ 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- cumenes epoxide) pyridin-3-yl) ethylidene)-N- (6- methyl -3- ketone -2,3- bis-
Hydrogen -1,2,4- triazines -4 (5H)-yl) carbamyl hydrazine (Ic-6)
Yellow solid, yield 87%, 222-223 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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-butyl benzenes epoxide) pyridin-3-yl) ethylidene)-N- (6- methyl -3- ketone -2,3- bis-
Hydrogen -1,2,4- triazines -4 (5H)-yl) carbamyl hydrazine (Ic-7)
White solid, yield 88%, 208 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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)δ
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- bromobenzenes epoxide) pyridin-3-yl) ethylidene)-N- (6- methyl -3- ketone -2,3- dihydro -1,
(the 5H)-yl of 2,4- triazine -4) carbamyl hydrazine (Ic-8)
Yellow solid, yield 75%, 238-239 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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- iodobenzenes epoxide) pyridin-3-yl) ethylidene)-N- (6- methyl -3- ketone -2,3- dihydro -1,
(the 5H)-yl of 2,4- triazine -4) carbamyl hydrazine (Ic-9)
White solid, yield 72%, 244-245 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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 group) pyridin-3-yl) ethylidene)-N- (6- methyl -3- ketone -2,3- bis-
Hydrogen -1,2,4- triazines -4 (5H)-yl) carbamyl hydrazine (Ic-10)
Yellow solid yield 32%, 212-213 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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- benzophenones epoxide) pyridin-3-yl) ethylidene)-N- (6- methyl -3- ketone -2,3- bis-
Hydrogen -1,2,4- triazines -4 (5H)-yl) carbamyl hydrazine (Ic-11)
White solid, yield 22%, 234-235 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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- methylphenoxies) pyridin-3-yl) ethylidene)-N- (6- methyl -3- ketone -
2,3- dihydros -1,2,4- triazines -4 (5H)-yl) carbamyl hydrazine (Ic-12)
White solid, yield 78%, 224-225 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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- methylphenoxies) pyridin-3-yl) ethylidene)-N- (6- methyl -3- ketone -
2,3- dihydros -1,2,4- triazines -4 (5H)-yl) carbamyl hydrazine (Ic-13)
White solid, yield 25%, 236-237 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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；
found 438.2246.
(E) -2- (1- (6- (4- pi-allyl -2- methoxyphenoxies) pyridin-3-yl) ethylidene)-N- (6- methyl -3-
Ketone -2,3- dihydro -1,2,4- triazines -4 (5H)-yl) carbamyl hydrazine (Ic-14)
White solid, yield 61%, 241-242 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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- methoxyphenoxies) pyridin-3-yl) ethylidene)-N- (6- methyl -3-
Ketone -2,3- dihydro -1,2,4- triazines -4 (5H)-yl) carbamyl hydrazine (Ic-15)
White solid, yield 49%, 210-211 DEG C of fusing point.1H NMR (400MHz, DMSO-d6) δ 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) δ 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.
Embodiment 5：The measure of killing aphids, mensuration program is as follows：
The active testing of aphid
Killing aphids determination of activity step is as follows：Test worm is bean aphid (Aphis laburni Kaltenbach), laboratory silkworm
The normal population that beans leaf is raised.Medicine, plus 1mL DMF dissolvings are weighed, plus two and drips Tween-20 emulsifying agent, a certain amount of steam is added
Distilled water, stirs, the decoction of concentration needed for being made into.It will be taken out with 5 seconds in aphid (about 60) Broad Bean Leaves immersion medicament
Gently dry, unnecessary medicament is blotted with filter paper, then enter broad bean stem cutting in water-absorbing sponge, and branch is covered with cloche, use
Gauze is sealed, and 96 hours inspection results, each compound is repeated 3 times.Control only adds emulsifying agent and solvent into distilled water, stirs
Mix uniform.
Table 1 contains the killing aphids active testing result of acylhydrazone structure triazone derivatives (I)：
a- is not surveyed
It can be seen in table 1 that in 100mg/kg concentration, big portion contains acylhydrazone structure triazone derivatives and shown well
Killing aphids activity.In 5mg/kg concentration, 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 show the activity suitable with pymetrozine.
Embodiment 6：The measure of mosquito-larvicidal activity, mensuration program is as follows：
The active testing of mosquito larvae
The experimental method of mosquitocidal larva：Culex pipiens pallens, the normal population of indoor feeding.Weigh test compound
About 5mg is in penicillin medicine bottle, plus 5mL acetone (or suitable solvent), vibration dissolving, as 1000ppm mother liquors.Pipette
0.5mL mother liquors, add in the 100mL beakers for filling 89.9mL water, larvae at the beginning of 10 first 4 ages are chosen, together with 10mL feeding liquids
Pour into the lump in beaker, the concentration of its decoction is 5ppm.It is put into standard process chamber, 24h inspection results.To contain 0.5mL
The aqueous solution of test solvent is blank control.
Table 2 contains the mosquito-larvicidal activity test result of acylhydrazone structure triazone derivatives (I)：
aThe death rate under 0.25mg/kg,bThe death rate under 0.1mg/kg,c- is not surveyed
From table 2 and table 4, it is most of mosquito larvae is shown containing acylhydrazone structure triazone derivatives it is good
Activity.Especially compound Ia-35、Ia-47、Ia-53、Ib-11、Ib-16、Ib- 22 and Ib-25.In 0.25mg/kg to mosquito children
Worm shows higher activity, wherein compound Ia- 47 show 40% insecticidal activity in 0.01mg/kg.
Embodiment 7：Bollworm, corn borer, the measure of mythimna separata activity are killed, mensuration program is as follows：
The active testing of bollworm
The experimental method of bollworm：Feed mixes medicine method, and the firm configuration that 3mL adds about 27g is pipetted from the solution configured
In good feed, so as to obtain the required concentration of ten times of dilution.Medicament is equably poured into 24 clean orifice plates after mixing, and dries in the air cool
24 first three ages bollworms are accessed afterwards, inspection result after observing 3-4 days.
The active testing of corn borer
The test method of corn borer：Leaf dipping method, after concentration needed for postponing, the blade for being about 5-6cm diameter immerses medicine
5-6 seconds in liquid, take out, be placed on blotting paper and dry, be placed in the culture dish specified, access 10 first 3 instar larvaes, be put into 27 ± 1
DEG C insectary in observation 3-4 days after inspection result.
The active testing of mythimna separata
The experimental method of mythimna separata：Leaf dipping method, after concentration needed for postponing, the blade for being about 5-6cm diameter immerses decoction
It is middle 5-6 seconds, take out, be placed on blotting paper and dry, be placed in the culture dish specified, access 10 first 3 instar larvaes, be put into 27 ± 1 DEG C
Insectary in observation 3-4 days after inspection result.
Table 3 kills bollworm, corn borer, mythimna separata active testing result containing acylhydrazone structure triazone derivatives (I)
aThe death rate under 200mg/kg,bThe death rate under 100mg/kg
As seen from Table 3, it is most of that bollworm, corn borer and mythimna separata are showed containing acylhydrazone structure triazone derivatives
Go out insecticidal activity.Especially compound Ia- 35 and Ia- 44 bollworm, corn borer and mythimna separata are shown in 100mg/kg it is higher
Activity, wherein compound Ib- 44 in 100mg/kg, shows 30%, 20% and respectively to bollworm, corn borer and mythimna separata
60% insecticidal activity.
Embodiment 8：The measure of Fungicidally active, mensuration program is as follows：
By taking tomato early blight bacterium as an example, other bacterium can be changed into
In vitro method of testing：Tomato early blight bacterium is connected in PDA culture medium and cultivated 7 days, with card punch in colony edge
The bacterium dish for producing diameter 4cm is inoculated into culture 4 days in the PDA culture medium containing 50ug/ml and without medicament, measures bacterium colony straight
Footpath, the suppression percentage of medicament is calculated with comparing.
Table 4 spreads out the bactericidal activity test result of derivative (I) containing acylhydrazone structure triazinone：
It is as seen from Table 4, most of that bactericidal activity is shown to 14 kinds of fungies containing the acylhydrazone structure triazinone derivative that spreads out,
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 Ic- 14
Under 50mg/kg concentration a variety of pathogens are shown with good bacteriostatic activity.
Claims (8)
1. structure shown in below formula (I) contain acylhydrazone structure triazone derivatives
Of the present invention is with following three kinds of formula (I containing acylhydrazone structure triazone derivatives (I)a, Ib, Ic) shown knot
The compound of structure：
Wherein,
R1Represent respectively 2-10 carbon alkyl, 3-6 carbocyclic rings alkyl, benzyl, naphthyl, substitution phenyl (wherein substituent can be hydrogen,
Hydroxyl, halogen atom, cyano group, nitro, ester group, dimethylamino, trifluoromethyl, trifluoromethoxy, 1-5 carbon alkyl, 1-6 carbon alcoxyls
Base and simultaneously containing 2-3 above-mentioned substituents), 1-10 carbon nitrogen heterocyclic ring, 1-10 carbon oxygen heterocycle, 1-10 carbon sulfur heterocyclic rings；
R2Represent respectively 1-10 carbon alkyl, phenyl, substituted-phenyl (wherein substituent can be hydrogen, hydroxyl, halogen atom, cyano group,
Nitro, ester group, fluorine, trifluoromethyl, trifluoromethoxy, 1-5 carbon alkyl, 1-6 carbon alkoxy and simultaneously above-mentioned containing 2-3
Substituent), and R2And R3The 3-6 carbocyclic ring alkyl collectively constituted；
R3Representing substituted phenyl respectively, (wherein substituent can be hydrogen, hydroxyl, halogen atom, cyano group, nitro, ester group, fluorine, three
Methyl fluoride, trifluoromethoxy, 1-5 carbon alkyl, 1-6 carbon alkoxy and simultaneously containing 2-3 above-mentioned substituents)；
R4Represent respectively hydrogen, hydroxyl, 1-6 carbon alkoxy 1-10 carbon alkylamino radical, halogen atom, cyano group, aldehyde radical, 1-6 carbon alkyl carbonyl,
1-10 carbon alkoxy carbonyl group, 1-10 carbon alkanamines carbonyl, 1-6 carbon alkyl oxy carbonyl oxygen, 1-6 carbon alkanamine carbonyloxy groups；And contain 2-3 simultaneously
Individual R4Representative substituent.
2. a kind of succinct preparation contains acylhydrazone structure triazone derivatives Ia-1--1a- 57 method (route one)：Amino first
Triazinone (II) and phenyl chloroformate reaction generation compound III, compound III and hydration hydrazine reaction generation intermediate semicarbazides
Triazinone IV, then compound IV and various aldehyde VaReact the generation triazineon compounds of structure containing acylhydrazone Ia；
Route one：
The solvent of first step reaction can be methanol, dichloromethane, chloroform, 1,2- dichloroethanes, acetonitrile；Acid binding agent can be pyrrole
Pyridine, sodium carbonate, triethylamine, potassium carbonate, cesium carbonate；Reaction temperature is in 60 DEG C to 80 DEG C progress；The solvent of second step reaction can be with
It is methanol, dichloromethane, ethanol, 1,2- dichloroethanes, acetonitrile；Reaction temperature is in 80 DEG C to 100 DEG C progress；Three-step reaction
Solvent can be methanol, ethanol, acetonitrile, DMF；Catalyst can be trifluoroacetic acid, p-methyl benzenesulfonic acid,
Glacial acetic acid；Reaction temperature is in 70 to 100 DEG C of progress.
3. a kind of succinct preparation contains acylhydrazone structure triazone derivatives Ib-1--1b- 28 method (route two)：Semicarbazides three
Piperazine ketone (IV) contains acylhydrazone structure triazineon compounds I with the generation of various reactive ketonesb；
Route two：
Solvent can be methanol, ethanol, 1,2- dichloroethanes, chloroform, acetonitrile；Catalyst can be trifluoroacetic acid, to methylbenzene
Sulfonic acid；Reaction temperature is in 80 DEG C to 120 DEG C progress.
4. a kind of succinct preparation contains acylhydrazone structure triazone derivatives Ic-1--1c- 15 method (route three)：Semicarbazides three
The picolyl ketone V that piperazine ketone (II) replaces with various phenoxy groupscThe generation that reacts contains acylhydrazone structure triazineon compounds Ic；
Route three：
Solvent can be methanol, ethanol, chloroform, 1,2- dichloroethanes, acetonitrile；Catalyst can be trifluoroacetic acid, to methylbenzene
Sulfonic acid；Reaction temperature is in 80 DEG C to 120 DEG C progress.
5. according to described in claim 1 containing acylhydrazone structure triazone derivatives desinsection in terms of application.
6. application according to claim 5, wherein insect are aphid, mosquito larvae, bollworm, corn borer and mythimna separata.
7. according to described in claim 1 containing acylhydrazone structure triazone derivatives sterilization in terms of application.
8. application according to claim 7, wherein pathogen be tomato early epidemic, gibberella saubinetii, potato late blight, Phytophthora capsici,
Rape sclerotium, cucumber grey mold, rice banded sclerotial blight, cucumber are withered, peanut foxiness, apple wheel line, withered wheat line, corn stigma, watermelon
Anthrax and rice bakanae disease.
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| CN110759911A (en) * | 2018-07-26 | 2020-02-07 | 南开大学 | Carboline derivative, preparation method thereof and application thereof in preventing and treating plant viruses, killing bacteria and killing insects |
| CN110759911B (en) * | 2018-07-26 | 2022-05-24 | 南开大学 | Carboline derivative, preparation method thereof and application thereof in preventing and treating plant viruses, killing bacteria and killing insects |
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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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