CN111606825B - 一种1, 1-二氰基腙类化合物及其应用 - Google Patents
一种1, 1-二氰基腙类化合物及其应用 Download PDFInfo
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- CN111606825B CN111606825B CN202010101206.9A CN202010101206A CN111606825B CN 111606825 B CN111606825 B CN 111606825B CN 202010101206 A CN202010101206 A CN 202010101206A CN 111606825 B CN111606825 B CN 111606825B
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- hydrogen
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- butyl
- methyl
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 75
- 208000035143 Bacterial infection Diseases 0.000 claims abstract description 10
- -1 cyano, hydroxy, carboxyl Chemical group 0.000 claims description 150
- 229910052739 hydrogen Inorganic materials 0.000 claims description 97
- 239000001257 hydrogen Substances 0.000 claims description 97
- 150000002431 hydrogen Chemical class 0.000 claims description 67
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 claims description 46
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 46
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 40
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 38
- 239000000460 chlorine Substances 0.000 claims description 38
- 229910052801 chlorine Inorganic materials 0.000 claims description 38
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 34
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 32
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 32
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 claims description 31
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 30
- 230000001580 bacterial effect Effects 0.000 claims description 25
- 125000006255 cyclopropyl carbonyl group Chemical group [H]C1([H])C([H])([H])C1([H])C(*)=O 0.000 claims description 21
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 19
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- 125000003545 alkoxy group Chemical group 0.000 claims description 15
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- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 229910052736 halogen Inorganic materials 0.000 claims description 13
- 150000002367 halogens Chemical class 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 125000005929 isobutyloxycarbonyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])OC(*)=O 0.000 claims description 12
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 9
- 125000005843 halogen group Chemical group 0.000 claims description 9
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 8
- 241000196324 Embryophyta Species 0.000 claims description 8
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 8
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 8
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 8
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 8
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 8
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 8
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 8
- 235000010149 Brassica rapa subsp chinensis Nutrition 0.000 claims description 6
- 235000000536 Brassica rapa subsp pekinensis Nutrition 0.000 claims description 6
- 241000499436 Brassica rapa subsp. pekinensis Species 0.000 claims description 6
- 235000013399 edible fruits Nutrition 0.000 claims description 6
- FKTXDTWDCPTPHK-UHFFFAOYSA-N 1,1,1,2,3,3,3-heptafluoropropane Chemical group FC(F)(F)[C](F)C(F)(F)F FKTXDTWDCPTPHK-UHFFFAOYSA-N 0.000 claims description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 5
- 240000007594 Oryza sativa Species 0.000 claims description 5
- 235000007164 Oryza sativa Nutrition 0.000 claims description 5
- 125000004772 dichloromethyl group Chemical group [H]C(Cl)(Cl)* 0.000 claims description 5
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- 235000009566 rice Nutrition 0.000 claims description 5
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 claims description 5
- 125000004916 (C1-C6) alkylcarbonyl group Chemical group 0.000 claims description 4
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 4
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 4
- 235000007688 Lycopersicon esculentum Nutrition 0.000 claims description 4
- 240000003768 Solanum lycopersicum Species 0.000 claims description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 4
- 235000011054 acetic acid Nutrition 0.000 claims description 4
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 239000001530 fumaric acid Substances 0.000 claims description 4
- 235000011087 fumaric acid Nutrition 0.000 claims description 4
- 239000004310 lactic acid Substances 0.000 claims description 4
- 235000014655 lactic acid Nutrition 0.000 claims description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 4
- 239000011976 maleic acid Substances 0.000 claims description 4
- 239000001630 malic acid Substances 0.000 claims description 4
- 235000011090 malic acid Nutrition 0.000 claims description 4
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 4
- 235000011007 phosphoric acid Nutrition 0.000 claims description 4
- 235000019260 propionic acid Nutrition 0.000 claims description 4
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 4
- 229960004889 salicylic acid Drugs 0.000 claims description 4
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- 235000002906 tartaric acid Nutrition 0.000 claims description 4
- 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 4
- 229940005605 valeric acid Drugs 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- 241000219112 Cucumis Species 0.000 claims description 3
- 235000015510 Cucumis melo subsp melo Nutrition 0.000 claims description 3
- 240000008067 Cucumis sativus Species 0.000 claims description 3
- 235000010799 Cucumis sativus var sativus Nutrition 0.000 claims description 3
- FJJCIZWZNKZHII-UHFFFAOYSA-N [4,6-bis(cyanoamino)-1,3,5-triazin-2-yl]cyanamide Chemical compound N#CNC1=NC(NC#N)=NC(NC#N)=N1 FJJCIZWZNKZHII-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 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
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- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 125000005928 isopropyloxycarbonyl group Chemical group [H]C([H])([H])C([H])(OC(*)=O)C([H])([H])[H] 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 125000001424 substituent group Chemical group 0.000 abstract description 6
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 22
- 239000000243 solution Substances 0.000 description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 10
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- 238000004440 column chromatography Methods 0.000 description 6
- 230000006837 decompression Effects 0.000 description 6
- 239000003480 eluent Substances 0.000 description 6
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 description 6
- 238000012544 monitoring process Methods 0.000 description 6
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- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 5
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- 238000012360 testing method Methods 0.000 description 5
- GTVGGHQLKNCAMB-UHFFFAOYSA-N 2-[(3,4-dichlorophenyl)hydrazinylidene]propanedinitrile Chemical compound ClC1=CC=C(NN=C(C#N)C#N)C=C1Cl GTVGGHQLKNCAMB-UHFFFAOYSA-N 0.000 description 4
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
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- XZDJDCVLKLFOLK-UHFFFAOYSA-N 2-(naphthalen-1-ylhydrazinylidene)propanedinitrile Chemical compound C1=CC=C2C(NN=C(C#N)C#N)=CC=CC2=C1 XZDJDCVLKLFOLK-UHFFFAOYSA-N 0.000 description 2
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
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- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 2
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- 125000004890 (C1-C6) alkylamino group Chemical group 0.000 description 1
- 125000006700 (C1-C6) alkylthio group Chemical group 0.000 description 1
- 125000006619 (C1-C6) dialkylamino group Chemical group 0.000 description 1
- LEASIZFYTLXFRQ-UHFFFAOYSA-N 2-(2h-naphthalen-1-ylidene)propanedinitrile Chemical compound C1=CC=C2C(=C(C#N)C#N)CC=CC2=C1 LEASIZFYTLXFRQ-UHFFFAOYSA-N 0.000 description 1
- QTMAZYGAVHCKKX-UHFFFAOYSA-N 2-[(4-amino-5-bromopyrrolo[2,3-d]pyrimidin-7-yl)methoxy]propane-1,3-diol Chemical compound NC1=NC=NC2=C1C(Br)=CN2COC(CO)CO QTMAZYGAVHCKKX-UHFFFAOYSA-N 0.000 description 1
- SDYWXFYBZPNOFX-UHFFFAOYSA-N 3,4-dichloroaniline Chemical compound NC1=CC=C(Cl)C(Cl)=C1 SDYWXFYBZPNOFX-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 235000009434 Actinidia chinensis Nutrition 0.000 description 1
- 244000298697 Actinidia deliciosa Species 0.000 description 1
- 235000009436 Actinidia deliciosa Nutrition 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- JGLMVXWAHNTPRF-CMDGGOBGSA-N CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O Chemical compound CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O JGLMVXWAHNTPRF-CMDGGOBGSA-N 0.000 description 1
- 241000207199 Citrus Species 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 208000031888 Mycoses Diseases 0.000 description 1
- 241000353135 Psenopsis anomala Species 0.000 description 1
- 206010039509 Scab Diseases 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000004448 alkyl carbonyl group Chemical group 0.000 description 1
- 230000003698 anagen phase Effects 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 244000000007 bacterial human pathogen Species 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 235000020971 citrus fruits Nutrition 0.000 description 1
- 229940126543 compound 14 Drugs 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000006254 cycloalkyl carbonyl group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- JPMJNRPHIMXRAP-UHFFFAOYSA-N cyclopropyl carbonochloridate Chemical compound ClC(=O)OC1CC1 JPMJNRPHIMXRAP-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- RIFGWPKJUGCATF-UHFFFAOYSA-N ethyl chloroformate Chemical compound CCOC(Cl)=O RIFGWPKJUGCATF-UHFFFAOYSA-N 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 230000035784 germination Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000004438 haloalkoxy group Chemical group 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 125000004995 haloalkylthio group Chemical group 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- XMJHPCRAQCTCFT-UHFFFAOYSA-N methyl chloroformate Chemical compound COC(Cl)=O XMJHPCRAQCTCFT-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000009331 sowing Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000003419 tautomerization reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C07C255/66—Carboxylic acid nitriles containing cyano groups and nitrogen atoms further bound to other hetero atoms, other than oxygen atoms of nitro or nitroso groups, bound to the same carbon skeleton with the nitrogen atoms further bound to nitrogen atoms having cyano groups and nitrogen atoms being part of hydrazine or hydrazone groups bound to the same carbon skeleton
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- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
- A01N37/50—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids the nitrogen atom being doubly bound to the carbon skeleton
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
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- 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
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof
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- A—HUMAN NECESSITIES
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- A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
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Abstract
本发明公开了一种结构新颖的1,1‑二氰基腙类化合物,结构如通式I所示,式中各取代基的定义见说明书。
Description
技术领域
本发明属农用杀细菌剂领域。具体地涉及一种1, 1-二氰基腙类化合物及其应用。
背景技术
细菌性病害已成为我国农业生产中仅次于真菌性病害的第二大常发性病害,据不完全统计,我国细菌性病害目前发生面积在1.2亿亩次,细菌性病害防治市场容量超过20亿元。目前农业生产中,防治细菌性病害药剂主要包括用量较大的铜制剂(包括有机或无机铜制剂)和抗生素类产品;其中,铜制剂的防效较低并且大量的重金属喷施到环境中,对土壤、水体和食品形成污染,引发环境及食品的安全担忧;而另一方面,抗生素的大量使用,可能引起人体病原菌对医用抗生素产生抗药性。其它能用于农业细菌治疗的仅有少量品种,实际生产中受到抗性及防效的双重限制,推广面积较小。因此,研发新型、高效、低毒、环境友好型细菌性病害防治药剂是非常必要而迫切的。
现有技术中,如本发明所示的1, 1-二氰基腙类化合物及其杀细菌活性未见报道。
发明内容
本发明的目的是提供一种1, 1-二氰基腙类化合物及其在农业、林业或卫生领域中作为杀细菌剂的应用。
本发明的技术方案如下:
一种1, 1-二氰基腙类化合物,其特征在于,化合物如通式I所示:
式中:
W选自W1,G选自氢,X1、X2、X4、X5选自氢,X3选自C2-C6烷基;
或者,W选自W1,G选自氢,X1、X5选自氢,X2、X3、X4选自氯;
或者,W选自W1、W2或W3,且,
G选自C1-C6烷基、卤代C1-C6烷基、C1-C6烷基羰基、C3-C6环烷基羰基或C1-C6烷氧基羰基,
X1、X2、X3、X4、X5各自独立地选自氢、卤素、氰基、硝基、羟基、巯基、氨基、羧基、C1-C6烷基、卤代C1-C6烷基、C1-C6烷氧基、卤代C1-C6烷氧基、C1-C6烷硫基、卤代C1-C6烷硫基、C1-C6烷基氨基、C1-C6二烷基氨基、C1-C6烷基羰基或C1-C6烷氧基羰基,
X6、X7、X8、X9、X10、X11、X12、X13、X14、X15、X16、X17、X18、X19各自独立地选自氢、卤素、氰基、硝基、羟基、巯基、氨基、羧基、C1-C6烷基、卤代C1-C6烷基、C1-C6烷氧基或卤代C1-C6烷氧基;
但,当W选自W1时,不选自以下化合物:
X1、X2、X3、X4、X5选自氢,G选自甲基、乙基或正丙氧基羰基;或者,G选自甲基,X1、X2、X4、X5选自氢,X3选自硝基、羧基、氯、溴、甲基、三氟甲基或甲氧基;或者,G选自甲基,X1、X3、X4、X5选自氢,X2选自硝基、氯、甲基或三氟甲基;或者,X2、X4选自三氟甲基,X1、X3、X5选自氢,G选自乙基、乙酰基、正丙酰基、正丁酰基、甲氧基羰基、乙氧基羰基、异丁氧基羰基、正戊氧基羰基或正己氧基羰基;或者,X2、X4选自氯,X1、X3、X5选自氢,G选自甲基、甲氧基羰基或乙氧基羰基;或者,X2、X3、X4选自氯,X1、X5选自氢,G选自乙酰基、正丙酰基、甲氧基羰基、乙氧基羰基、正丙氧基羰基、正丁氧基羰基或异丁氧基羰基;或者,X1、X3、X4选自氯,X2、X5选自氢,G选自乙酰基、正丙酰基、甲氧基羰基、乙氧基羰基、正丙氧基羰基、异丙氧基羰基、异丁氧基羰基、正戊氧基羰基或正己氧基羰基;或者,G选自乙基,X1、X2、X4、X5选自氢,X3选自氯;或者,G选自甲基,X1、X4、X5选自氢,X2、X3选自氯;或者,G选自甲基,X2、X4选自氢,X1、X3、X5选自氯;或者,G选自乙酰基,X1、X3、X4、X5选自氢,X2选自氯或三氟甲基;或者,G选自乙氧基羰基,X1、X2、X4、X5选自氢,X3选自氟;或者,G选自乙酰基或乙氧基羰基,X2、X4选自氢,X1、X5选自溴,X3选自氯;或者,G选自正丙酰基,X1、X3、X4、X5选自氢,X2选自三氟甲基;或者,G选自异丁氧基羰基,X1、X2、X4、X5选自氢,X3选自氟;或者,G选自乙氧基羰基,X1、X3、X4、X5选自氢,X2选自三氟甲基;或者,G选自正丙酰基、乙氧基羰基或异丁氧基羰基,X1选自氯,X4选自三氟甲基,X2、X3、X5选自氢;或者,G选自乙氧基羰基或异丁氧基羰基,X1选自甲氧基,X3选自硝基,X4选自甲基,X2、X5选自氢;或者,G选自乙氧基羰基,X1、X4选自甲氧基,X3选自氯,X2、X5选自氢;或者,G选自乙氧基羰基,X1选自甲氧基,X3选自氯,X4选自甲基,X2、X5选自氢;
或通式I化合物的互变异构体;
或通式I化合物的盐。
本发明中较优选的化合物为:通式I中,
W选自W1,G选自氢,X1、X2、X4、X5选自氢,X3选自C2-C4烷基;
或者,W选自W1,G选自氢,X1、X5选自氢,X2、X3、X4选自氯;
或者,W选自W1、W2或W3,且,
G选自C1-C4烷基、卤代C1-C4烷基、C1-C4烷基羰基、C3-C6环烷基羰基或C1-C4烷氧基羰基,
X1、X2、X3、X4、X5各自独立地选自氢、卤素、氰基、硝基、羟基、巯基、氨基、羧基、C1-C4烷基、卤代C1-C4烷基、C1-C4烷氧基、卤代C1-C4烷氧基、C1-C4烷硫基、卤代C1-C4烷硫基、C1-C4烷基氨基、C1-C4二烷基氨基、C1-C4烷基羰基或C1-C4烷氧基羰基,
X6、X7、X8、X9、X10、X11、X12、X13、X14、X15、X16、X17、X18、X19各自独立地选自氢、卤素、氰基、硝基、羟基、巯基、氨基、羧基、C1-C4烷基、卤代C1-C4烷基、C1-C4烷氧基或卤代C1-C4烷氧基;
或通式I化合物的互变异构体;
或通式I化合物的盐。
本发明中进一步优选的化合物为:通式I中,
W选自W1,G选自氢,X1、X2、X4、X5选自氢,X3选自乙基、正丙基、异丙基、正丁基、异丁基、仲丁基或叔丁基;
或者,W选自W1,G选自氢,X1、X5选自氢,X2、X3、X4选自氯;
或者,W选自W1、W2或W3,且,
G选自甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、一氯甲基、二氯甲基、三氯甲基、一溴甲基、二溴甲基、三溴甲基、一氟甲基、二氟甲基、三氟甲基、2, 2,2-三氟乙基、七氟异丙基、乙酰基、正丙酰基、环丙基甲酰基、甲氧基羰基、乙氧基羰基、正丙氧基羰基或正丁氧基羰基,
X1、X2、X3、X4、X5各自独立地选自氢、氟、氯、溴、氰基、硝基、羟基、巯基、氨基、羧基、甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、一氯甲基、二氯甲基、三氯甲基、一溴甲基、二溴甲基、三溴甲基、一氟甲基、二氟甲基、三氟甲基、2, 2, 2-三氟乙基、七氟异丙基、甲氧基、乙氧基、正丙氧基、异丙氧基、二氟甲氧基、三氟甲氧基、甲硫基、乙硫基、三氟甲硫基、2, 2, 2-三氟乙硫基、甲氨基、乙氨基、N, N-二甲基氨基、甲氧基羰基或乙氧基羰基,
X6、X7、X8、X9、X10、X11、X12、X13、X14、X15、X16、X17、X18、X19选自氢;
或通式I化合物的互变异构体;
或通式I化合物与盐酸、氢溴酸、硫酸、磷酸、甲酸、乙酸、丙酸、丁酸、戊酸、三氟乙酸、草酸、丙二酸、甲磺酸、4-甲苯磺酸、苹果酸、富马酸、乳酸、马来酸、水杨酸、酒石酸或柠檬酸形成的盐。
本发明中更进一步优选的化合物为:通式I中,
W选自W1,G选自氢,X1、X2、X4、X5选自氢,X3选自乙基、正丙基、异丙基、正丁基、异丁基、仲丁基或叔丁基;
或者,W选自W1,G选自氢、甲基、乙基、正丙基、异丙基或正丁基,X1、X5选自氢,X2、X3、X4选自氯;
或者,W选自W1,G选自甲基、乙基、正丙基、异丙基、正丁基、乙酰基、正丙酰基、环丙基甲酰基、甲氧基羰基、乙氧基羰基、正丙氧基羰基或正丁氧基羰基,X1选自甲基、乙基、正丙基、异丙基、正丁基或叔丁基,X2、X3、X4、X5选自氢;
或者,W选自W1,G选自甲基、乙基、正丙基、异丙基、正丁基、乙酰基、正丙酰基、环丙基甲酰基、甲氧基羰基、乙氧基羰基、正丙氧基羰基或正丁氧基羰基,X1、X5各自独立地选自甲基、乙基、正丙基、异丙基、正丁基或叔丁基,X2、X3、X4选自氢;
或者,W选自W1,G选自甲基、乙基、正丙基、异丙基、正丁基、乙酰基、正丙酰基、环丙基甲酰基、甲氧基羰基、乙氧基羰基、正丙氧基羰基或正丁氧基羰基,X2、X4选自甲基,X1、X3、X5选自氢;
或者,W选自W1,G选自甲基,X2、X4选自三氟甲基,X1、X3、X5选自氢;
或者,W选自W1,G选自甲基、乙基、正丙基、异丙基、正丁基、乙酰基、正丙酰基、环丙基甲酰基、甲氧基羰基、乙氧基羰基、正丙氧基羰基或正丁氧基羰基,X1、X2选自氯,X3、X4、X5选自氢;
或者,W选自W1,G选自甲基、乙基、正丙基、异丙基、正丁基、乙酰基、正丙酰基、环丙基甲酰基、甲氧基羰基、乙氧基羰基、正丙氧基羰基或正丁氧基羰基,X1、X3选自氯,X2、X4、X5选自氢;
或者,W选自W1,G选自甲基、乙基、正丙基、异丙基、正丁基、乙酰基、正丙酰基、环丙基甲酰基、甲氧基羰基、乙氧基羰基、正丙氧基羰基或正丁氧基羰基,X1、X4选自氯,X2、X3、X5选自氢;
或者,W选自W1,G选自甲基、乙基、正丙基、异丙基、正丁基、乙酰基、正丙酰基、环丙基甲酰基、甲氧基羰基、乙氧基羰基、正丙氧基羰基或正丁氧基羰基,X1、X5选自氯,X2、X3、X4选自氢;
或者,W选自W1,G选自甲基、乙基、正丙基、异丙基、正丁基、乙酰基、正丙酰基、环丙基甲酰基、甲氧基羰基、乙氧基羰基、正丙氧基羰基或正丁氧基羰基,X2、X3选自氯,X1、X4、X5选自氢;
或者,W选自W2,G选自甲基、乙基、正丙基、异丙基、正丁基、乙酰基、正丙酰基、环丙基甲酰基、甲氧基羰基、乙氧基羰基、正丙氧基羰基或正丁氧基羰基,X6、X7、X8、X9、X10、X11、X12选自氢;
或者,W选自W3,G选自甲基、乙基、正丙基、异丙基、正丁基、乙酰基、正丙酰基、环丙基甲酰基、甲氧基羰基、乙氧基羰基、正丙氧基羰基或正丁氧基羰基,X13、X14、X15、X16、X17、X18、X19选自氢;
或通式I化合物的互变异构体;
或通式I化合物与盐酸、氢溴酸、硫酸、磷酸、甲酸、乙酸、丙酸、丁酸、戊酸、三氟乙酸、草酸、丙二酸、甲磺酸、4-甲苯磺酸、苹果酸、富马酸、乳酸、马来酸、水杨酸、酒石酸或柠檬酸形成的盐。
上面给出的通式化合物的定义中,汇集所用术语一般代表如下取代基:
卤素:指氟、氯、溴或碘。
烷基:直链或支链烷基,例如甲基、乙基、正丙基、异丙基或不同的丁基、戊基或己基异构体等。
卤代烷基:直链或支链烷基,在这些烷基上的氢原子可部分或全部被卤素所取代,例如一氯甲基、二氯甲基、三氯甲基、一溴甲基、二溴甲基、三溴甲基、一氟甲基、二氟甲基、三氟甲基、2, 2, 2-三氟乙基、七氟异丙基等。
烷氧基:直链或支链烷基,经氧原子键连接到结构上,例如甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、叔丁氧基等。
卤代烷氧基:直链或支链烷氧基,在这些烷氧基上的氢原子可部分或全部被卤素所取代,例如氯甲氧基、二氯甲氧基、三氯甲氧基、氟甲氧基、二氟甲氧基、三氟甲氧基、氯氟甲氧基、2, 2, 2-三氟乙氧基等。
烷硫基:直链或支链烷基,经硫原子键连接到结构上,例如甲硫基、乙硫基等。
卤代烷硫基:直链或支链烷硫基,在这些烷硫基上的氢原子可部分或全部被卤素所取代,例如二氟甲硫基、三氟甲硫基、2, 2, 2-三氟乙硫基等。
烷基氨基:直链或支链烷基,经氮原子键连接到结构上,例如甲氨基、乙氨基、正丙基氨基、异丙基氨基或同分异构的丁基胺。
二烷基氨基:两个相同或不同的直链或支链烷基,经氮原子键连接到结构上,例如N, N-二甲基氨基、N-甲基-N-乙基氨基等。
烷基羰基:烷基经羰基连接到结构上,例如乙酰基(CH3CO-),正丙酰基(CH3CH2CO-)等。
环烷基羰基:环烷基经羰基连接到结构上,例如环丙基甲酰基。
烷氧基羰基:烷基-O-CO-,例如甲氧基羰基(CH3OCO-)、乙氧基羰基(CH3CH2OCO-)、正丙氧基羰基(CH3CH2CH2OCO-)、正丁氧基羰基(CH3CH2CH2CH2OCO-)等。
本发明所示的通式I中,当G为氢原子时,通式I化合物存在如下互变异构,通式I化合物还包括,在这种情况下所有的互变异构体。
本发明部分通式I化合物如表1~表3所示,但本发明绝非仅限于这些化合物。
通式I中,当W=W1时,通式I可以通式I-W1表示;取代基X1、X2、X3、X4、X5、G见表1。
表1
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通式I中,当W=W2且X6=X7=X8=X9=X10=X11=X12=H时,通式I可以通式I-W2表示;取代基G见表2。
表2
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通式I中,当W=W3且X13=X14=X15=X16=X17=X18=X19=H时,通式I可以通式I-W3表示;取代基G见表3。
表1~表3所列举的部分化合物的物化性质及其核磁数据、质谱数据如表4所示:
表4
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本发明的通式I化合物可按照以下方法制备(式中各基团除另有说明外定义同前):
通式I化合物中G为H时化合物由通式I-1所示,G为其他取代基时化合物由通式I-2所示:
通式II化合物通过常规重氮化反应即可制得相应的重氮盐产物,即通式III化合物。
通式III化合物与丙二腈在适宜的碱存在下,在适宜的溶剂中,在温度从-10°C到溶剂沸点下反应0.5-48小时可制得通式I-1化合物。适宜的碱可为醋酸钠、醋酸钾、氢氧化钾、氢氧化钠、碳酸钠、碳酸钾、碳酸氢钠、三乙胺、吡啶、甲醇钠、乙醇钠、氢化钠、叔丁醇钾或叔丁醇钠等。适宜的溶剂可为水、二氯甲烷、氯仿、四氯化碳、己烷、苯、甲苯、甲醇、乙醇、乙酸乙酯、乙腈、二氧六环、THF、DMF、DMSO或上述溶剂的混合溶剂。
通式I-1化合物与通式G-LG化合物在适宜的溶剂中,在无碱或有碱的环境中,在温度从-10°C到溶剂沸点下反应0.5-48小时可制得通式I-2化合物。适宜的碱可为醋酸钠、醋酸钾、氢氧化钾、氢氧化钠、碳酸钠、碳酸钾、碳酸氢钠、三乙胺、吡啶、甲醇钠、乙醇钠、氢化钠、叔丁醇钾或叔丁醇钠等。适宜的溶剂可为水、二氯甲烷、氯仿、四氯化碳、己烷、苯、甲苯、甲醇、乙醇、乙酸乙酯、乙腈、二氧六环、THF、DMF、DMSO或上述溶剂的混合溶剂。通式G-LG化合物中,LG表示离去基团,合适的离去基团可为卤素或其它常规的离核基团,例如C1-C4烷氧基或C1-C4烷硫基,具体如甲氧基、乙氧基、甲硫基或乙硫基等。
通式II化合物、通式G-LG化合物及其它原料和试剂通常有市售,也可按常规方法自制。
本发明化合物亦可按照US3755598A、US3660462A、US3202698、US3157569、US3062635、JP07206800A、WO9735863A1、US4115104A、JP48087020A、JP48087019A、US3213124、US3135736或European Journal of Biochemistry, 33(2), 247-52; 1973等公开的方法制备,或者参照其它已知的方法制备。
本发明通式I所示的化合物用于控制植物细菌性病害的用途,可用于防治多种植物细菌性病害,例如果斑病(如甜瓜果斑病等)、叶斑病(如番茄细菌性叶斑病等)、青枯病(如番茄青枯病、马铃薯青枯病等)、细菌性疫病、溃疡病(如柑橘溃疡病、猕猴桃溃疡病等)、软腐病(如大白菜软腐病等)、细菌性角斑病(如黄瓜细菌性角斑病等)、细菌性条斑病(如水稻细菌性条斑病等)、叶枯病、白叶枯病(如水稻白叶枯病等)、野火病和细菌性疮痂病等。
具体实施方式
以下具体实施例用来进一步说明本发明,但本发明绝非限于这些例子。(除另有注明外,所用原料均有市售)
合成实施例
按照上述记载的合成路线,采用不同的原料化合物,即可分别制备获得本发明通式I所示化合物,进一步具体描述如下:
实施例1:化合物14的制备
称取邻甲苯胺1.00克(9.35 mmol)溶解于35 ml H2O与9 ml 浓盐酸的混合溶液中,降温至0-5°C;向此溶液中缓慢滴加0.67克(9.71 mmol)亚硝酸钠的10毫升冰水溶液,在此过程中维持反应温度0-5°C;滴加完毕后,冰浴下继续搅拌反应10分钟。重氮盐溶液制备完成。
称取醋酸钠22.15克(270.12 mmol),加入100 ml水,降温至0-5°C;加入丙二腈0.92克(13.94 mmol);向此溶液中缓慢滴加上述制备好的重氮盐溶液,在此过程中维持反应温度0-5°C;滴加完毕后,冰浴下继续搅拌反应30分钟;过滤、烘干后得到中间体(邻甲苯基亚肼基)丙二腈,黄色固体1.22克。
称取中间体(邻甲苯基亚肼基)丙二腈0.35克(1.90 mmol)、氢化钠0.11克(4.58mmol)、碘甲烷0.54克(3.80 mmol),加入15 ml四氢呋喃,室温搅拌反应;TLC监测反应完毕后,用适量的水淬灭氢化钠,加入水和乙酸乙酯萃取、无水硫酸镁干燥、过滤、减压脱溶,残余物柱层析(洗脱剂为乙酸乙酯与石油醚,体积比为1:10~1:4)纯化,得目标化合物,灰色固体0.23克。
实施例2:化合物176的制备
称取3, 4-二氯苯胺0.50克(3.11 mmol)溶解于20 ml H2O与3 ml 浓盐酸的混合溶液中,降温至0-5°C;向此溶液中缓慢滴加0.22克(3.19 mmol)亚硝酸钠的3毫升冰水溶液,在此过程中维持反应温度0-5°C;滴加完毕后,冰浴下继续搅拌反应10分钟。重氮盐溶液制备完成。
称取醋酸钠7.80克(95.12 mmol),加入35 ml水,降温至0-5°C;加入丙二腈0.31克(4.70 mmol);向此溶液中缓慢滴加上述制备好的重氮盐溶液,在此过程中维持反应温度0-5°C;滴加完毕后,冰浴下继续搅拌反应30分钟;过滤、烘干后得到中间体(3, 4-二氯苯基亚肼基)丙二腈,黄色固体0.72克。
称取中间体(3, 4-二氯苯基亚肼基)丙二腈0.50克(2.10 mmol)、吡啶0.33克(4.18 mmol)、乙酰氯0.20克(2.56 mmol),加入20 ml二氯甲烷,室温下搅拌反应3小时;TLC监测反应完毕后,减压脱溶,残余物柱层析(洗脱剂为乙酸乙酯与石油醚,体积比为1:10~1:4)纯化,得目标化合物,白色固体0.52克。
实施例3:化合物178的制备
称取中间体(3, 4-二氯苯基亚肼基)丙二腈0.35克(1.47 mmol)、吡啶0.23克(2.91 mmol)、环丙基甲酰氯0.18克(1.73 mmol),加入20 ml二氯甲烷,室温下搅拌反应;TLC监测反应完毕后,减压脱溶,残余物柱层析(洗脱剂为乙酸乙酯与石油醚,体积比为1:10~1:4)纯化,得目标化合物,白色固体0.32克。
实施例4:化合物180的制备
称取中间体(3, 4-二氯苯基亚肼基)丙二腈0.50克(2.10 mmol)、氢化钠0.10克(4.17 mmol)、氯甲酸乙酯0.27克(2.50 mmol),加入20 ml四氢呋喃;将反应温度升至50°C,搅拌反应3小时;TLC监测反应完毕后,用适量的水淬灭氢化钠,加入水和乙酸乙酯萃取、无水硫酸镁干燥、过滤、减压脱溶,残余物柱层析(洗脱剂为乙酸乙酯与石油醚,体积比为1:10~1:4)纯化,得目标化合物,灰色固体0.55克。
实施例5:化合物183的制备
称取1-萘胺0.80克(5.59 mmol)溶解于35 ml H2O与6 ml 浓盐酸的混合溶液中,降温至0-5°C;向此溶液中缓慢滴加0.41克(5.94 mmol)亚硝酸钠的8毫升冰水溶液,在此过程中维持反应温度0-5°C;滴加完毕后,冰浴下继续搅拌反应10分钟。重氮盐溶液制备完成。
称取醋酸钠13.76克(167.80 mmol),加入60 ml水,降温至0-5°C;加入丙二腈0.55克(8.33 mmol);向此溶液中缓慢滴加上述制备好的重氮盐溶液,在此过程中维持反应温度0-5°C;滴加完毕后,冰浴下继续搅拌反应30分钟;过滤、烘干后得到中间体(萘-1-基亚肼基)丙二腈,红色固体0.78克。
称取中间体(萘-1-基亚肼基)丙二腈0.42克(1.91 mmol)、氢化钠0.12克(5.00mmol)、碘甲烷0.55克(3.87 mmol),加入20 ml四氢呋喃,室温搅拌反应;TLC监测反应完毕后,用适量的水淬灭氢化钠,加入水和乙酸乙酯萃取、无水硫酸镁干燥、过滤、减压脱溶,残余物柱层析(洗脱剂为乙酸乙酯与石油醚,体积比为1:10~1:4)纯化,得目标化合物,白色固体0.25克。
实施例6:化合物191的制备
称取中间体(萘-1-基亚肼基)丙二腈0.32克(1.45 mmol)、氢化钠0.15克(6.25mmol)、氯甲酸甲酯0.16克(1.70 mmol),加入15 ml四氢呋喃;将反应温度升至50°C,搅拌反应5小时;TLC监测反应完毕后,用适量的水淬灭氢化钠,加入水和乙酸乙酯萃取、无水硫酸镁干燥、过滤、减压脱溶,残余物柱层析(洗脱剂为乙酸乙酯与石油醚,体积比为1:10~1:4)纯化,得目标化合物,棕色固体0.21克。
参照以上实施例可以制备本发明通式I中其它化合物。
生物活性测定
实施例7:对植物细菌病害防治效果的测定
用本发明的化合物对多种植物细菌性病害进行了防效测定,针对不同的细菌性病害,试验程序如下:
甜瓜果斑病,将待测化合物用少量N,N二甲基甲酰胺溶解,用水稀释至所需要的浓度。将培养至稳定生长期的病原细菌与定量化合物溶液混合均匀,将经过催芽的甜瓜种子放入菌液与化合物的混合液中浸泡半小时,再将种子播种于蚯蚓土培养杯中,放入温室中保湿培养,一般培养两周时间,待对照充分发病后进行防效调查。
大白菜软腐病,切取2厘米见方的白菜叶片,放入垫有双层滤纸的玻璃培养皿中。将用N,N二甲基甲酰胺溶解,并用水稀释至所需浓度的化合物喷雾于白菜叶片表面,于通风橱内晾干白菜叶片表面药液后,使用接种针在白菜叶片表面针刺造成伤口,将培养至稳定生长期的大白菜软腐病菌取5微升加入伤口内,进行接种。最后将试材放入培养箱中避光培养48小时,待对照充分发病后进行防效调查。
黄瓜细菌性角斑病、番茄细菌性叶斑病、水稻细菌性条斑病、水稻白叶枯病,将待测化合物用少量N,N二甲基甲酰胺溶解,用水稀释至所需要的浓度。将化合物其喷雾于植物试材表面,于阴凉处风干表面药液后,将培养至稳定生长期的病原细菌菌液喷雾接种于植物试材表面,然后将植物试材放入温室中保湿培养。通常培养十天左右,待对照充分发病后,进行防效调查。
测试结果如下:
600 mg/L时,化合物1、7、8、14、110、122、132、143、144、176、178、180、183、191、192对甜瓜果斑病的防效为100%。
400 mg/L时,化合物1、7、8、14、110、122、132、143、144、176、178、180、183、191、192对黄瓜细菌性角斑病、水稻细菌性条斑病、水稻白叶枯病的防效均为100%。
400 mg/L时,化合物1、7、8、14、110、122、132、143、144、176、178、180、183、191、192对大白菜软腐病或番茄细菌性叶斑病的防效均为100%。
Claims (12)
1.一种1,1-二氰基腙类化合物,其特征在于,化合物如通式I所示:
式中:
W选自W1,G选自氢,X1、X2、X4、X5选自氢,X3选自C2-C6烷基;
或者,W选自W1或W2,且,
G选自C1-C6烷基、卤代C1-C6烷基、C1-C6烷基羰基、C3-C6环烷基羰基或C1-C6烷氧基羰基,
X1、X2、X3、X4、X5各自独立地选自氢、卤素、氰基、羟基、羧基、C1-C6烷基、卤代C1-C6烷基、C1-C6烷氧基、卤代C1-C6烷氧基、C1-C6烷基羰基或C1-C6烷氧基羰基,
X6、X7、X8、X9、X10、X11、X12各自独立地选自氢、卤素、氰基、羟基、羧基、C1-C6烷基、卤代C1-C6烷基、C1-C6烷氧基或卤代C1-C6烷氧基;
但,当W选自W1时,不选自以下化合物:
X1、X2、X3、X4、X5选自氢,G选自甲基、乙基或正丙氧基羰基;或者,G选自甲基,X1、X2、X4、X5选自氢,X3选自硝基、羧基、氯、溴、甲基、三氟甲基或甲氧基;或者,G选自甲基,X1、X3、X4、X5选自氢,X2选自硝基、氯、甲基或三氟甲基;或者,X2、X4选自三氟甲基,X1、X3、X5选自氢,G选自乙基、乙酰基、正丙酰基、正丁酰基、甲氧基羰基、乙氧基羰基、异丁氧基羰基、正戊氧基羰基或正己氧基羰基;或者,X2、X4选自氯,X1、X3、X5选自氢,G选自甲基、甲氧基羰基或乙氧基羰基;或者,X2、X3、X4选自氯,X1、X5选自氢,G选自乙酰基、正丙酰基、甲氧基羰基、乙氧基羰基、正丙氧基羰基、正丁氧基羰基或异丁氧基羰基;或者,X1、X3、X4选自氯,X2、X5选自氢,G选自乙酰基、正丙酰基、甲氧基羰基、乙氧基羰基、正丙氧基羰基、异丙氧基羰基、异丁氧基羰基、正戊氧基羰基或正己氧基羰基;或者,G选自乙基,X1、X2、X4、X5选自氢,X3选自氯;或者,G选自甲基,X1、X4、X5选自氢,X2、X3选自氯;或者,G选自甲基,X2、X4选自氢,X1、X3、X5选自氯;或者,G选自乙酰基,X1、X3、X4、X5选自氢,X2选自氯或三氟甲基;或者,G选自乙氧基羰基,X1、X2、X4、X5选自氢,X3选自氟;或者,G选自乙酰基或乙氧基羰基,X2、X4选自氢,X1、X5选自溴,X3选自氯;或者,G选自正丙酰基,X1、X3、X4、X5选自氢,X2选自三氟甲基;或者,G选自异丁氧基羰基,X1、X2、X4、X5选自氢,X3选自氟;或者,G选自乙氧基羰基,X1、X3、X4、X5选自氢,X2选自三氟甲基;或者,G选自正丙酰基、乙氧基羰基或异丁氧基羰基,X1选自氯,X4选自三氟甲基,X2、X3、X5选自氢;或者,G选自乙氧基羰基或异丁氧基羰基,X1选自甲氧基,X3选自硝基,X4选自甲基,X2、X5选自氢;或者,G选自乙氧基羰基,X1、X4选自甲氧基,X3选自氯,X2、X5选自氢;或者,G选自乙氧基羰基,X1选自甲氧基,X3选自氯,X4选自甲基,X2、X5选自氢;
或通式I化合物的盐;
条件是,所述通式I化合物不为 N-异丙基-N-(3,5-二(三氟甲基)苯基)偶氮丙二腈,N-甲基-N-(3,5-二(三氟甲基)苯基)偶氮丙二腈,N-正丙基-N-(3,5-二(三氟甲基)苯基)偶氮丙二腈,N-正丁基-N-(3,5-二(三氟甲基)苯基)偶氮丙二腈以及N-异丁基-N-(3,5-二(三氟甲基)苯基)偶氮丙二腈。
2.根据权利要求1所述的化合物,其特征在于,通式I中,
W选自W1,G选自氢,X1、X2、X4、X5选自氢,X3选自C2-C4烷基;
或者,W选自W1或W2,且,
G选自C1-C4烷基、卤代C1-C4烷基、C1-C4烷基羰基、C3-C6环烷基羰基或C1-C4烷氧基羰基,
X1、X2、X3、X4、X5各自独立地选自氢、卤素、氰基、羟基、羧基、C1-C4烷基、卤代C1-C4烷基、C1-C4烷氧基、卤代C1-C4烷氧基、C1-C4烷基羰基或C1-C4烷氧基羰基,
X6、X7、X8、X9、X10、X11、X12各自独立地选自氢、卤素、氰基、羟基、羧基、C1-C4烷基、卤代C1-C4烷基、C1-C4烷氧基或卤代C1-C4烷氧基;
或通式I化合物的盐。
3.根据权利要求2所述的化合物,其特征在于,通式I中,
W选自W1,G选自氢,X1、X2、X4、X5选自氢,X3选自乙基、正丙基、异丙基、正丁基、异丁基、仲丁基或叔丁基;
或者,W选自W1或W2,且,
G选自甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、一氯甲基、二氯甲基、三氯甲基、一溴甲基、二溴甲基、三溴甲基、一氟甲基、二氟甲基、三氟甲基、2,2,2-三氟乙基、七氟异丙基、乙酰基、正丙酰基、环丙基甲酰基、甲氧基羰基、乙氧基羰基、正丙氧基羰基或正丁氧基羰基,
X1、X2、X3、X4、X5各自独立地选自氢、氟、氯、溴、氰基、羟基、羧基、甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、一氯甲基、二氯甲基、三氯甲基、一溴甲基、二溴甲基、三溴甲基、一氟甲基、二氟甲基、三氟甲基、2,2,2-三氟乙基、七氟异丙基、甲氧基、乙氧基、正丙氧基、异丙氧基、二氟甲氧基、三氟甲氧基、甲氧基羰基或乙氧基羰基,
X6、X7、X8、X9、X10、X11、X12选自氢;
或通式I化合物与盐酸、氢溴酸、硫酸、磷酸、甲酸、乙酸、丙酸、丁酸、戊酸、三氟乙酸、草酸、丙二酸、甲磺酸、4-甲苯磺酸、苹果酸、富马酸、乳酸、马来酸、水杨酸、酒石酸或柠檬酸形成的盐。
4.根据权利要求1-3中任一项所述的化合物,其特征在于,通式I中,
W选自W1,G选自氢,X1、X2、X4、X5选自氢,X3选自乙基、正丙基、异丙基、正丁基、异丁基、仲丁基或叔丁基;
或者,W选自W1,G选自甲基、乙基、正丙基、异丙基或正丁基,X1、X5选自氢,X2、X3、X4选自氯;
或者,W选自W1,G选自甲基、乙基、正丙基、异丙基、正丁基、乙酰基、正丙酰基、环丙基甲酰基、甲氧基羰基、乙氧基羰基、正丙氧基羰基或正丁氧基羰基,X1选自甲基、乙基、正丙基、异丙基、正丁基或叔丁基,X2、X3、X4、X5选自氢;
或者,W选自W1,G选自甲基、乙基、正丙基、异丙基、正丁基、乙酰基、正丙酰基、环丙基甲酰基、甲氧基羰基、乙氧基羰基、正丙氧基羰基或正丁氧基羰基,X1、X5各自独立地选自甲基、乙基、正丙基、异丙基、正丁基或叔丁基,X2、X3、X4选自氢;
或者,W选自W1,G选自甲基、乙基、正丙基、异丙基、正丁基、乙酰基、正丙酰基、环丙基甲酰基、甲氧基羰基、乙氧基羰基、正丙氧基羰基或正丁氧基羰基,X2、X4选自甲基,X1、X3、X5选自氢;
或者,W选自W1,G选自甲基、乙基、正丙基、异丙基、正丁基、乙酰基、正丙酰基、环丙基甲酰基、甲氧基羰基、乙氧基羰基、正丙氧基羰基或正丁氧基羰基,X1、X2选自氯,X3、X4、X5选自氢;
或者,W选自W1,G选自甲基、乙基、正丙基、异丙基、正丁基、乙酰基、正丙酰基、环丙基甲酰基、甲氧基羰基、乙氧基羰基、正丙氧基羰基或正丁氧基羰基,X1、X3选自氯,X2、X4、X5选自氢;
或者,W选自W1,G选自甲基、乙基、正丙基、异丙基、正丁基、乙酰基、正丙酰基、环丙基甲酰基、甲氧基羰基、乙氧基羰基、正丙氧基羰基或正丁氧基羰基,X1、X4选自氯,X2、X3、X5选自氢;
或者,W选自W1,G选自甲基、乙基、正丙基、异丙基、正丁基、乙酰基、正丙酰基、环丙基甲酰基、甲氧基羰基、乙氧基羰基、正丙氧基羰基或正丁氧基羰基,X1、X5选自氯,X2、X3、X4选自氢;
或者,W选自W1,G选自乙基、正丙基、异丙基、正丁基、乙酰基、正丙酰基、环丙基甲酰基、甲氧基羰基、乙氧基羰基、正丙氧基羰基或正丁氧基羰基,X2、X3选自氯,X1、X4、X5选自氢;
或者,W选自W2,G选自甲基、乙基、正丙基、异丙基、正丁基、乙酰基、正丙酰基、环丙基甲酰基、甲氧基羰基、乙氧基羰基、正丙氧基羰基或正丁氧基羰基,X6、X7、X8、X9、X10、X11、X12选自氢;
或通式I化合物与盐酸、氢溴酸、硫酸、磷酸、甲酸、乙酸、丙酸、丁酸、戊酸、三氟乙酸、草酸、丙二酸、甲磺酸、4-甲苯磺酸、苹果酸、富马酸、乳酸、马来酸、水杨酸、酒石酸或柠檬酸形成的盐。
5.根据权利要求1所述的化合物,其特征在于,所述化合物通式I化合物选自如下化合物:
6.一种按照权利要求1所述的通式I化合物在用于控制植物细菌性病害中的用途;
其特征在于,所述植物细菌病害选自果斑病、软腐病、角斑病、叶斑病、条斑病和白叶枯病。
7.根据权利要求6所述的用途,其特征在于,所述果斑病为甜瓜果斑病。
8.根据权利要求6所述的用途,其特征在于,所述软腐病为大白菜软腐病。
9.根据权利要求6所述的用途,其特征在于,所述角斑病为黄瓜细菌性角斑病。
10.根据权利要求6所述的用途,其特征在于,所述叶斑病为番茄细菌性叶斑病。
11.根据权利要求6所述的用途,其特征在于,所述条斑病为水细菌性条斑病。
12.根据权利要求6所述的用途,其特征在于,所述白叶枯病为水稻白叶枯病。
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