WO2022228402A1 - 含突烯片段的三唑磺酰胺类衍生物及其制备方法和应用和一种杀菌剂及其应用 - Google Patents
含突烯片段的三唑磺酰胺类衍生物及其制备方法和应用和一种杀菌剂及其应用 Download PDFInfo
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- WO2022228402A1 WO2022228402A1 PCT/CN2022/089090 CN2022089090W WO2022228402A1 WO 2022228402 A1 WO2022228402 A1 WO 2022228402A1 CN 2022089090 W CN2022089090 W CN 2022089090W WO 2022228402 A1 WO2022228402 A1 WO 2022228402A1
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- methoxy
- methyl
- cyclopropyl
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- 239000012634 fragment Substances 0.000 title claims abstract description 18
- 125000003342 alkenyl group Chemical group 0.000 title claims abstract description 17
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 15
- 239000003899 bactericide agent Substances 0.000 title claims abstract description 13
- HFFXLYHRNRKAPM-UHFFFAOYSA-N 2,4,5-trichloro-n-(5-methyl-1,2-oxazol-3-yl)benzenesulfonamide Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C(=CC(Cl)=C(Cl)C=2)Cl)=N1 HFFXLYHRNRKAPM-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 150000003852 triazoles Chemical class 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 241000233679 Peronosporaceae Species 0.000 claims abstract description 26
- 241000196324 Embryophyta Species 0.000 claims abstract description 13
- 240000008067 Cucumis sativus Species 0.000 claims abstract description 12
- 235000010799 Cucumis sativus var sativus Nutrition 0.000 claims abstract description 12
- 235000000832 Ayote Nutrition 0.000 claims abstract description 6
- 241000207199 Citrus Species 0.000 claims abstract description 6
- 240000004244 Cucurbita moschata Species 0.000 claims abstract description 6
- 235000009854 Cucurbita moschata Nutrition 0.000 claims abstract description 6
- 235000009804 Cucurbita pepo subsp pepo Nutrition 0.000 claims abstract description 6
- 244000068988 Glycine max Species 0.000 claims abstract description 6
- 235000010469 Glycine max Nutrition 0.000 claims abstract description 6
- 235000007688 Lycopersicon esculentum Nutrition 0.000 claims abstract description 6
- 240000003768 Solanum lycopersicum Species 0.000 claims abstract description 6
- 244000061458 Solanum melongena Species 0.000 claims abstract description 6
- 235000002597 Solanum melongena Nutrition 0.000 claims abstract description 6
- 235000009754 Vitis X bourquina Nutrition 0.000 claims abstract description 6
- 235000012333 Vitis X labruscana Nutrition 0.000 claims abstract description 6
- 240000006365 Vitis vinifera Species 0.000 claims abstract description 6
- 235000014787 Vitis vinifera Nutrition 0.000 claims abstract description 6
- 235000020971 citrus fruits Nutrition 0.000 claims abstract description 6
- 235000015136 pumpkin Nutrition 0.000 claims abstract description 6
- 241000233622 Phytophthora infestans Species 0.000 claims abstract description 5
- 208000010801 foot rot Diseases 0.000 claims abstract description 5
- 241000233614 Phytophthora Species 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 626
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 332
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 330
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 288
- 239000000843 powder Substances 0.000 claims description 176
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 34
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 33
- 125000000217 alkyl group Chemical group 0.000 claims description 26
- 125000003545 alkoxy group Chemical group 0.000 claims description 24
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 24
- 229910052736 halogen Inorganic materials 0.000 claims description 21
- 150000002367 halogens Chemical class 0.000 claims description 21
- -1 triazole sulfonamide Chemical class 0.000 claims description 20
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- 229940124530 sulfonamide Drugs 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 208000031888 Mycoses Diseases 0.000 claims description 13
- 229910052801 chlorine Inorganic materials 0.000 claims description 13
- 239000004480 active ingredient Substances 0.000 claims description 10
- 239000000417 fungicide Substances 0.000 claims description 9
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 8
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 7
- 102000018832 Cytochromes Human genes 0.000 claims description 7
- 108010052832 Cytochromes Proteins 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 230000000855 fungicidal effect Effects 0.000 claims description 4
- 239000003112 inhibitor Substances 0.000 claims description 4
- 125000001188 haloalkyl group Chemical group 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- DQXKOHDUMJLXKH-PHEQNACWSA-N (e)-n-[2-[2-[[(e)-oct-2-enoyl]amino]ethyldisulfanyl]ethyl]oct-2-enamide Chemical compound CCCCC\C=C\C(=O)NCCSSCCNC(=O)\C=C\CCCCC DQXKOHDUMJLXKH-PHEQNACWSA-N 0.000 claims description 2
- YQXNCQIIKGZOMK-UHFFFAOYSA-N 6-[4-[7-tert-butyl-5-(4-chloro-3-fluorophenyl)furo[3,2-b]pyridine-2-carbonyl]-3,3-dimethylpiperazin-1-yl]-2,4-dimethylpyridine-3-carboxylic acid Chemical compound C(C)(C)(C)C1=C2C(=NC(=C1)C1=CC(=C(C=C1)Cl)F)C=C(O2)C(=O)N1C(CN(CC1)C1=CC(=C(C(=N1)C)C(=O)O)C)(C)C YQXNCQIIKGZOMK-UHFFFAOYSA-N 0.000 claims description 2
- 239000002552 dosage form Substances 0.000 claims description 2
- 239000004495 emulsifiable concentrate Substances 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 claims description 2
- 150000001336 alkenes Chemical group 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000004497 emulsifiable granule Substances 0.000 claims 1
- 230000036571 hydration Effects 0.000 claims 1
- 238000006703 hydration reaction Methods 0.000 claims 1
- 201000010099 disease Diseases 0.000 abstract description 13
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 11
- 241000233654 Oomycetes Species 0.000 abstract description 4
- 239000000460 chlorine Substances 0.000 description 283
- 238000005481 NMR spectroscopy Methods 0.000 description 195
- 238000000816 matrix-assisted laser desorption--ionisation Methods 0.000 description 194
- 239000011734 sodium Substances 0.000 description 54
- 238000012360 testing method Methods 0.000 description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 239000007787 solid Substances 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000000543 intermediate Substances 0.000 description 7
- 238000011282 treatment Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 229940079593 drug Drugs 0.000 description 6
- 239000003814 drug Substances 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 5
- 230000003902 lesion Effects 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 4
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000012544 monitoring process Methods 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 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 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000005754 Cyazofamid Substances 0.000 description 3
- HTJDQJBWANPRPF-UHFFFAOYSA-N Cyclopropylamine Chemical compound NC1CC1 HTJDQJBWANPRPF-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 102000015782 Electron Transport Complex III Human genes 0.000 description 3
- 108010024882 Electron Transport Complex III Proteins 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- YXKMMRDKEKCERS-UHFFFAOYSA-N cyazofamid Chemical compound CN(C)S(=O)(=O)N1C(C#N)=NC(Cl)=C1C1=CC=C(C)C=C1 YXKMMRDKEKCERS-UHFFFAOYSA-N 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 238000011835 investigation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000575 pesticide Substances 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 2
- VXQNNTLJMJDESO-UHFFFAOYSA-N 2-(2-methyl-5-nitroimidazol-1-yl)ethyl n-[2,2,2-trichloro-1-(2-methylanilino)ethyl]carbamate Chemical compound CC1=NC=C([N+]([O-])=O)N1CCOC(=O)NC(C(Cl)(Cl)Cl)NC1=CC=CC=C1C VXQNNTLJMJDESO-UHFFFAOYSA-N 0.000 description 2
- GDTROMIWQVPIEM-UHFFFAOYSA-N 2-(2-methyl-5-nitroimidazol-1-yl)ethyl n-[2,2,2-trichloro-1-[(2-chlorophenyl)methylamino]ethyl]carbamate Chemical compound CC1=NC=C([N+]([O-])=O)N1CCOC(=O)NC(C(Cl)(Cl)Cl)NCC1=CC=CC=C1Cl GDTROMIWQVPIEM-UHFFFAOYSA-N 0.000 description 2
- 229910014265 BrCl Inorganic materials 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 244000052616 bacterial pathogen Species 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 230000002438 mitochondrial effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 2
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- BAXOFTOLAUCFNW-UHFFFAOYSA-N 1H-indazole Chemical compound C1=CC=C2C=NNC2=C1 BAXOFTOLAUCFNW-UHFFFAOYSA-N 0.000 description 1
- 239000005727 Amisulbrom Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- YKOFCSHVCPZACH-UHFFFAOYSA-N ClC(Cl)=C(C1=CC=CC=C1)NC1CC1 Chemical compound ClC(Cl)=C(C1=CC=CC=C1)NC1CC1 YKOFCSHVCPZACH-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 231100000674 Phytotoxicity Toxicity 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 244000098338 Triticum aestivum Species 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- BREATYVWRHIPIY-UHFFFAOYSA-N amisulbrom Chemical compound CN(C)S(=O)(=O)N1C=NC(S(=O)(=O)N2C3=CC(F)=CC=C3C(Br)=C2C)=N1 BREATYVWRHIPIY-UHFFFAOYSA-N 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000004166 bioassay Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- ACTIUHUUMQJHFO-UPTCCGCDSA-N coenzyme Q10 Chemical compound COC1=C(OC)C(=O)C(C\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CCC=C(C)C)=C(C)C1=O ACTIUHUUMQJHFO-UPTCCGCDSA-N 0.000 description 1
- 235000017471 coenzyme Q10 Nutrition 0.000 description 1
- 229940125507 complex inhibitor Drugs 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- QGTOTYJSCYHYFK-RBODFLQRSA-N fenpicoxamid Chemical compound COC1=CC=NC(C(=O)N[C@@H]2C(O[C@@H](C)[C@H](OC(=O)C(C)C)[C@@H](CC=3C=CC=CC=3)C(=O)OC2)=O)=C1OCOC(=O)C(C)C QGTOTYJSCYHYFK-RBODFLQRSA-N 0.000 description 1
- 230000035558 fertility Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000004677 hydrates Chemical group 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000004898 mitochondrial function Effects 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 125000006413 ring segment Chemical group 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000004016 soil organic matter Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
- C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D249/12—Oxygen or sulfur atoms
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- 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
- A01N51/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds having the sequences of atoms O—N—S, X—O—S, N—N—S, O—N—N or O-halogen, regardless of the number of bonds each atom has and with no atom of these sequences forming part of a heterocyclic ring
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P3/00—Fungicides
Definitions
- the present invention relates to the field of pesticides, in particular, to a triazole sulfonamide derivative containing a butene fragment and a preparation method thereof, and a triazole sulfonamide derivative containing a butene fragment as a cytochrome bc 1 complex Qi site inhibitor and its use against plant fungal diseases, a fungicide and its use against plant fungal diseases.
- Complex III (also called cytochrome bc 1 complex) is one of the most promising targets for agricultural fungicides. Its role is to catalyze the electron transfer process from coenzyme Q to cytochrome C, while pumping protons from the mitochondrial matrix. to the membrane gap. Cytochrome bc 1 complex inhibitor acts on the complex III on the mitochondrial respiratory electron transport chain of pathogenic bacteria, interferes with the respiratory electron transport chain to inhibit mitochondrial function, prevents it from producing energy, inhibits the growth of pathogenic bacteria, and eventually leads to its death. achieve the purpose of disease control. According to the function of complex III, the target can be divided into Q o site and Qi site. There are as many as 21 kinds of commercial Q o site fungicides based on this target.
- the present invention optimizes the substituents of the amine moiety to design triazole sulfonamide derivatives with novel structures.
- the raw materials are cheap and easy to obtain, the reaction steps and post-processing are simple, and the compound has the advantages of high safety and good sustainability, and this new type of compound still has good bactericidal activity at low concentrations.
- the purpose of the present invention is to provide a new triazole sulfonamide derivative, with the expectation that the triazole sulfonamide derivative can achieve significantly higher antifungal disease control effect at low concentration.
- the first aspect of the present invention provides a triazole sulfonamide derivative containing a butene fragment, and the derivative has the structure shown in formula (I):
- R 1 is selected from C 1-6 alkyl, C 1-6 alkoxy, C 3-6 cycloalkyl;
- R 2 is selected from H, C 1-6 alkyl
- R 3 , R 4 , R 5 , R 6 , R 7 are selected from H, halogen, C 1-6 alkyl, C 1-6 alkoxy, cyano, C 1-6 substituted with at least one halogen Alkyl, C 1-6 alkoxy substituted by at least one halogen;
- R 8 is both H or Cl.
- the second aspect of the present invention provides a method for preparing the triazole sulfonamide derivatives containing alkenyl fragments described in the first aspect, the method comprising combining the compound represented by the formula (II) with the compound represented by the formula (III) The compound undergoes a contact reaction;
- R 9 and R 10 are halogen, the other is -NHR 1 ,
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are the same as those described in the first aspect.
- the third aspect of the present invention provides the use of the aforementioned triazole sulfonamide derivatives containing a tetramethylene fragment as an inhibitor of the Qi site of the cytochrome bc 1 complex.
- the fourth aspect of the present invention provides the use of the aforementioned triazole sulfonamide derivatives containing alkenyl fragments in anti-plant fungal diseases.
- a fifth aspect of the present invention provides a bactericide, the active ingredient of which is at least one of the aforementioned triazole sulfonamide derivatives containing alkenyl fragments, and based on the total weight of the bactericide, the The content of active ingredient is 0.1-100% by weight.
- the sixth aspect of the present invention provides an application of the fungicide described in the fifth aspect in resisting plant fungal diseases.
- the compounds provided by the present invention have obviously better effects than the prior art against downy mildew, downy mildew, blight, late blight and other oomycete plant diseases at relatively low concentrations, such as cucumber downy mildew, soybean Mildew, tomato late blight, potato late blight, eggplant downy mildew, citrus foot rot, pumpkin blight, grape downy mildew, etc., have potential commercial value.
- C 1-6 alkyl group means an alkyl group with a total number of carbon atoms of 1-6, including straight-chain alkyl groups and branched-chain alkyl groups, for example, can be 1, 2, 3, 4, 5 or 6 carbon atoms in total
- the straight-chain alkyl group and branched-chain alkyl group can be, for example, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, etc.; the definition of "C 1-3 alkyl group” is the same as
- the definitions of " C1-6 alkyl” are similar, except that the total number of carbon atoms is different.
- C 1-6 alkoxy is similar to that of “C 1-6 alkyl”, except that “C 1-6 alkoxy” is directly attached to the parent nucleus through an O atom; "C The definition of “alkoxy of 1-3” is similar to that of “alkoxy of C 1-6 ", except that the total number of carbon atoms is different.
- C 1-6 alkyl substituted by at least one halogen is similar to the definition of “C 1-6 alkyl ", except that in “C 1-6 alkyl substituted by at least one halogen” At least one H on the alkyl group is substituted by at least one halogen atom selected from fluorine, chlorine, bromine, iodine, and the total number of carbon atoms of the "C 1-6 alkyl substituted by at least one halogen" is 1- 6.
- C 1-6 alkoxy substituted by at least one halogen is similar to the definition of “C 1-6 alkoxy ", except that "C 1-6 alkoxy substituted by at least one halogen”"base" is represented as “C 1-6 alkoxy” where at least one H is substituted by at least one halogen atom selected from fluorine, chlorine, bromine, iodine, and the "C 1-6 substituted by at least one halogen”
- the total number of carbon atoms in "alkoxy” is 1-6.
- C 3-6 cycloalkyl refers to an alkyl group with a total number of 3-6 carbon atoms, and the ring atoms are all C atoms, and any of the "C 3-6 cycloalkyl” can be substituted Positions can be substituted or unsubstituted by substituents, and when substituted, the total number of carbon atoms in the overall group including the substituents is 3-6.
- the first aspect of the present invention provides a triazole sulfonamide derivative containing a butene fragment, and the derivative has the structure shown in formula (I):
- R 1 is selected from C 1-6 alkyl, C 1-6 alkoxy, C 3-6 cycloalkyl;
- R 2 is selected from H, C 1-6 alkane base;
- R 3 , R 4 , R 5 , R 6 , R 7 are selected from H, halogen, C 1-6 alkyl, C 1-6 alkoxy, cyano, C 1-6 substituted with at least one halogen Alkyl, C 1-6 alkoxy substituted by at least one halogen;
- R 8 is both H or Cl.
- R 1 is selected from C 1-3 alkoxy, C 3-6 cycloalkyl
- R 2 is selected from H, C 1-3 alkyl
- R 3 , R 4 , R 5 , R 6 , R 7 are selected from H, halogen, C 1-6 alkyl, C 1-3 alkoxy, cyano, C 1-3 substituted with at least one halogen The alkyl group, the C 1-3 alkoxy group substituted by at least one halogen;
- R 8 is both H or Cl.
- R 1 is selected from methoxy, cyclopropyl
- R 2 is selected from H, methyl
- R 3 , R 4 , R 5 are selected from H, F, Cl, methyl, ethyl, isopropyl, tert-butyl, methoxy, -CF 3 , -OCF 3 , cyano;
- R 6 is selected from H, F, Cl;
- R 7 is H
- R 8 is both H or Cl.
- the triazole sulfonamide derivatives containing alkenyl fragments are any one of the following compounds:
- R 1 is cyclopropyl, and R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are all H;
- R 1 is cyclopropyl
- R 2 is H
- R 3 is F
- R 4 , R 5 , R 6 , R 7 , and R 8 are all H
- R 1 is cyclopropyl
- R 2 is H
- R 3 is -CF 3
- R 4 , R 5 , R 6 , R 7 and R 8 are all H
- R 1 is cyclopropyl
- R 2 is H
- R 4 is ethyl
- R 3 , R 5 , R 6 , R 7 , and R 8 are all H
- R 1 is cyclopropyl
- R 2 is H
- R 4 is tert-butyl
- R 3 , R 5 , R 6 , R 7 , and R 8 are all H
- R 1 is cyclopropyl
- R 2 is H
- R 4 is -CF 3
- R 3 , R 5 , R 6 , R 7 , and R 8 are all H
- R 1 is cyclopropyl
- R 2 is H
- R 4 is -OCF 3
- R 3 , R 5 , R 6 , R 7 and R 8 are all H
- R 1 is cyclopropyl
- R 2 is H
- R 5 is F
- R 3 , R 4 , R 6 , R 7 and R 8 are all H
- R 1 is cyclopropyl
- R 2 is H
- R 5 is Cl
- R 3 , R 4 , R 6 , R 7 and R 8 are all H
- R 1 is cyclopropyl
- R 2 is H
- R 5 is methyl
- R 3 , R 4 , R 6 , R 7 and R 8 are all H
- R 1 is cyclopropyl
- R 2 is H
- R 5 is tert-butyl
- R 3 , R 4 , R 6 , R 7 , and R 8 are all H
- R 1 is cyclopropyl
- R 2 is H
- R 5 is -CF 3
- R 3 , R 4 , R 6 , R 7 and R 8 are all H
- R 1 is cyclopropyl
- R 2 is H
- R 5 is -OCF 3
- R 3 , R 4 , R 6 , R 7 and R 8 are all H
- R 1 is cyclopropyl
- R 2 is H
- R 3 and R 4 are all methyl groups
- R 5 , R 6 , R 7 , and R 8 are all H
- R 1 is cyclopropyl
- R 2 is H
- R 3 and R 4 are both F
- R 5 , R 6 , R 7 , and R 8 are all H
- R 1 is cyclopropyl
- R 2 is H
- R 3 is Cl
- R 4 is F
- R 5 , R 6 , R 7 , and R 8 are all H
- R 1 is cyclopropyl
- R 2 is H
- R 3 and R 5 are all methyl groups
- R 4 , R 6 , R 7 , and R 8 are all H
- R 1 is cyclopropyl
- R 2 is H
- R 3 and R 5 are both F
- R 4 , R 6 , R 7 , and R 8 are all H
- R 1 is cyclopropyl
- R 2 is H
- R 3 and R 5 are both -CF 3
- R 4 , R 6 , R 7 , and R 8 are all H
- R 1 is cyclopropyl
- R 2 is H
- R 4 and R 5 are all methyl
- R 3 , R 6 , R 7 , and R 8 are all H
- R 1 is cyclopropyl
- R 2 is H
- R 4 and R 5 are both F
- R 3 , R 6 , R 7 , and R 8 are all H
- R 1 is cyclopropyl
- R 2 is H
- R 4 and R 5 are both -CF 3
- R 3 , R 6 , R 7 , and R 8 are all H
- R 1 is cyclopropyl
- R 2 is H
- R 4 and R 6 are both methyl
- R 3 , R 5 , R 7 , and R 8 are all H
- R 1 is cyclopropyl
- R 2 and R 3 are all methyl groups
- R 4 , R 5 , R 6 , R 7 , and R 8 are all H
- R 1 is cyclopropyl
- R 2 and R 4 are all methyl groups
- R 3 , R 5 , R 6 , R 7 , and R 8 are all H;
- R 1 is cyclopropyl
- R 2 is methyl
- R 4 is tert-butyl
- R 3 , R 5 , R 6 , R 7 and R 8 are all H
- R 1 is cyclopropyl
- R 2 and R 5 are methyl groups
- R 3 , R 4 , R 6 , R 7 , and R 8 are all H
- R 1 is cyclopropyl
- R 2 is methyl
- R 5 is -CF 3
- R 3 , R 4 , R 6 , R 7 , and R 8 are all H;
- R 1 is cyclopropyl
- R 2 , R 3 and R 4 are all methyl groups
- R 5 , R 6 , R 7 , and R 8 are all H
- R 1 is cyclopropyl
- R 2 , R 3 and R 5 are all methyl groups
- R 4 , R 6 , R 7 , and R 8 are all H
- R 1 is cyclopropyl
- R 2 is methyl
- R 3 and R 5 are both F
- R 4 , R 6 , R 7 , and R 8 are all H
- R 1 is cyclopropyl
- R 2 is methyl
- R 3 and R 5 are both -CF 3
- R 4 , R 6 , R 7 and R 8 are all H ;
- R 1 is cyclopropyl
- R 2 , R 4 , and R 5 are all methyl groups
- R 3 , R 6 , R 7 , and R 8 are all H
- R 1 is cyclopropyl
- R 2 is methyl
- R 4 and R 5 are both F
- R 3 , R 6 , R 7 , and R 8 are all H
- R 1 is cyclopropyl
- R 2 , R 4 and R 6 are all methyl groups
- R 3 , R 5 , R 7 , and R 8 are all H
- R 1 is methoxy
- R 2 , R 3 and R 4 are all methyl groups
- R 5 , R 6 , R 7 , and R 8 are all H
- R 1 is methoxy
- R 2 is methyl
- R 3 and R 5 are both -CF 3
- R 4 , R 6 , R 7 , and R 8 are all H ;
- R 1 is cyclopropyl
- R 2 , R 3 , R 4 , R 5 , R 6 , R 7 are all H
- R 8 is all Cl
- R 1 is cyclopropyl
- R 2 is H
- R 3 is F
- R 4 , R 5 , R 6 , R 7 are all H
- R 8 are all Cl
- R 1 is cyclopropyl
- R 2 is H
- R 4 is methyl
- R 3 , R 5 , R 6 , R 7 are all H
- R 8 are all Cl ;
- R 1 is cyclopropyl
- R 2 is H
- R 4 is ethyl
- R 3 , R 5 , R 6 , R 7 are all H
- R 8 are all Cl ;
- R 1 is cyclopropyl
- R 2 is H
- R 4 is -CF 3
- R 3 , R 5 , R 6 , R 7 are all H
- R 8 are all Cl
- R 1 is cyclopropyl
- R 2 is H
- R 5 is F
- R 3 , R 4 , R 6 , R 7 are all H
- R 8 are all Cl
- R 1 is cyclopropyl
- R 2 is H
- R 5 is methyl
- R 3 , R 4 , R 6 , R 7 are all H
- R 8 are all Cl ;
- R 1 is cyclopropyl
- R 2 is H
- R 5 is ethyl
- R 3 , R 4 , R 6 , R 7 are all H
- R 8 are all Cl ;
- R 1 is cyclopropyl
- R 2 is H
- R 5 is isopropyl
- R 3 , R 4 , R 6 , R 7 are all H
- R 8 are all Cl
- R 1 is cyclopropyl
- R 2 is H
- R 5 is tert-butyl
- R 3 , R 4 , R 6 , R 7 are all H
- R 8 are all Cl
- R 1 is cyclopropyl
- R 2 is H
- R 5 is -CF 3
- R 3 , R 4 , R 6 , R 7 are all H
- R 8 are all Cl
- R 1 is cyclopropyl
- R 2 is H
- R 5 is -OCF 3
- R 3 , R 4 , R 6 , R 7 are all H
- R 8 are all Cl
- R 1 is cyclopropyl
- R 2 is H
- R 4 and R 5 are all methyl groups
- R 3 , R 6 , R 7 are all H
- R 8 are all Cl
- R 1 is cyclopropyl
- R 2 is H
- R 4 and R 5 are all F
- R 3 , R 6 , R 7 are all H
- R 8 are all Cl ;
- R 1 is cyclopropyl
- R 2 is H
- R 4 is Cl
- R 5 is F
- R 3 , R 6 , R 7 are all H
- R 8 are all Cl
- R 1 is cyclopropyl
- R 2 is H
- R 4 and R 5 are all Cl
- R 3 , R 6 , R 7 are all H
- R 8 are all Cl ;
- R 1 is cyclopropyl
- R 2 is H
- R 4 and R 5 are both -CF 3
- R 3 , R 6 , R 7 are all H
- R 8 are all is Cl
- R 1 is cyclopropyl
- R 2 is H
- R 4 and R 6 are all methyl groups
- R 3 , R 5 , R 7 are all H
- R 8 are all Cl
- R 1 is cyclopropyl
- R 2 is H
- R 4 and R 6 are all Cl
- R 3 , R 5 , R 7 are all H
- R 8 are all Cl ;
- R 1 is cyclopropyl
- R 2 is H
- R 4 , R 5 and R 6 are all F
- R 3 and R 7 are all H
- R 8 are all Cl ;
- R 1 is methoxy
- R 2 is H
- R 4 and R 6 are all methyl groups
- R 3 , R 5 , R 7 are all H
- R 8 are all Cl
- R 1 is methoxy
- R 2 is H
- R 4 , R 5 and R 6 are all F
- R 3 and R 7 are all H
- R 8 are all Cl ;
- R 1 is cyclopropyl
- R 2 is methyl
- R 4 is methoxy
- R 3 , R 5 , R 6 , R 7 are all H
- R 8 are all H is Cl
- R 1 is cyclopropyl
- R 2 is methyl
- R 5 is methoxy
- R 3 , R 4 , R 6 , R 7 are all H
- R 8 are all H is Cl
- R 1 is cyclopropyl
- R 2 is methyl
- R 5 is -OCF 3
- R 3 , R 4 , R 6 and R 7 are all H
- R 8 are all is Cl
- R 1 is cyclopropyl
- R 2 , R 4 , R 5 are all methyl groups
- R 3 , R 6 , R 7 are all H
- R 8 are all Cl
- R 1 is cyclopropyl
- R 2 is methyl
- R 4 and R 5 are all F
- R 3 , R 6 , R 7 are all H
- R 8 are all Cl
- R 1 is cyclopropyl
- R 2 , R 4 , R 6 are all methyl groups
- R 3 , R 5 , R 7 are all H
- R 8 are all Cl
- R 1 is a methoxy group
- R 2 is a methyl group
- R 3 , R 4 , R 5 , R 6 , R 7 are all H
- R 8 are all Cl
- R 1 is methoxy
- R 2 is methyl
- R 5 is F
- R 3 , R 4 , R 6 , R 7 are all H
- R 8 is all Cl ;
- R 1 is a methoxy group
- R 2 is a methyl group
- R 5 is a cyano group
- R 3 , R 4 , R 6 , R 7 are all H
- R 8 are all Cl
- the stereostructure of the compound represented by the formula (I) is not particularly limited in the present invention, and the compound represented by the formula (I) may be in different stereoisomers, optical isomers or tautomers Existing forms, the present invention includes all stereoisomers or optical isomers or tautomers and mixtures thereof in various ratios.
- Any asymmetric atom (eg, carbon, etc.) of the compounds disclosed herein may exist in a racemic or enantiomerically enriched form, eg, in a (R)-, (S)- or (R,S)-configurational form exist.
- the present invention has no particular limitations on the method for preparing the triazole sulfonamide derivatives containing alkenyl fragments, and those skilled in the art can prepare them by combining the features of the structural formula with known methods in the field of organic synthesis.
- the present invention provides the method as described in the second aspect below to prepare the triazole sulfonamide derivative containing a butene fragment.
- the second aspect of the present invention provides a method for preparing the triazole sulfonamide derivatives containing alkenyl fragments described in the first aspect, the method comprising formula (II) The compound is contacted with the compound shown in formula (III);
- R 9 and R 10 are halogen, the other is -NHR 1 ,
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are the same as those described in the first aspect.
- the contact conditions at least satisfy: the temperature is 5-45° C. and the time is 20-60 min.
- the molar ratio of the compound represented by the formula (II) to the compound represented by the formula (III) is (0.5-3):1.
- the third aspect of the present invention provides the use of the aforementioned triazole sulfonamide derivatives containing alkenyl fragments as inhibitors of Qi site of cytochrome bc 1 complex.
- the fourth aspect of the present invention provides the use of the aforementioned triazole sulfonamide derivatives containing alkenyl fragments in anti-plant fungal diseases.
- the plants include, but are not limited to, cucumber, soybean, wheat, tomato, potato, eggplant, corn, rice, pumpkin, citrus, grape.
- the plant fungal diseases include but are not limited to downy mildew, downy mildew, blight, late blight.
- the plant fungal diseases include but are not limited to cucumber downy mildew, soybean phytophthora, tomato late blight, potato late blight, eggplant downy mildew, citrus foot rot, pumpkin blight, grape downy mildew.
- the fifth aspect of the present invention provides a bactericide
- the active ingredient of the bactericide is at least one of the triazole sulfonamide derivatives containing alkenyl fragments
- the bactericide is The content of the active ingredient is 0.1-100% by weight based on the total weight.
- the content of the active ingredient is 1-98% by weight.
- the content of the active ingredient is 5-90% by weight.
- the dosage form of the bactericide is selected from hydrates, powders, emulsions, suspensions, emulsifiable concentrates and granules.
- the sixth aspect of the present invention provides the use of the fungicides described in the fifth aspect in fighting fungal diseases of plants.
- room temperature or normal temperature described below refers to 25 ⁇ 1°C.
- Step a The compound represented by formula 1-3 (10 mmol) was added to the ultra-dry THF (10 mL) solution in which the compound represented by formula 1-2 (10 mmol) was dissolved under an ice bath, and the ice was removed after the addition was completed.
- Step b preheat the temperature to 100 °C in advance, then add NBS (6 mmol) to a solution of the compound represented by formula 1-4 (5 mmol) in THF (10 mL), and then add p-toluenesulfonic acid (1.2 mmol). ), refluxed for 25 min, after monitoring the completion of the reaction by TLC, adding water to quench, then extracting with ethyl acetate, drying over anhydrous Na 2 SO 4 , and spinning off the solvent to obtain the compound represented by formula 1-5.
- Step c Under ice bath, cyclopropylamine (11 mmol) was added to the acetonitrile solution (10 mL) in which the compound represented by formula 1-5 (5 mmol) was dissolved, then potassium carbonate (15 mmol) was added, and the reaction was carried out at room temperature for 10 min, monitored by TLC. After the reaction is complete, the sample is directly mixed, subjected to column chromatography, and then the eluent is spun out to obtain the compound represented by formula (II-1).
- Step a Dissolve 5.05 g of the compound represented by formula 2-1 in 25.0 mL of re-distilled CH 2 Cl 2 , continue to add 3.95 g of re-distilled pyridine, and dropwise add 4.4 g of re-distilled benzene under ice bath conditions Sulfonyl chloride, after 1 hour of dropwise addition, remove the ice bath, react at room temperature for 16 hours, then evaporate CH 2 Cl 2 , then add 25 mL of ethanol, react for 1 hour, filter to obtain a solid, and then use 10 mL of water and Wash with 10 mL of ethanol, and dry in vacuum (65° C.) to obtain the compound represented by formula 2-2.
- Step b Dissolve 4.68 g of the compound represented by formula 2-2 in 50 mL of re-distilled DMF, mix with 7.8 g of anhydrous potassium carbonate solution and stir for 1 hour, add 7.0 g of N,N-dimethylformaldehyde under ice bath sulfonyl chloride, after the reaction is complete, add water and CH 2 Cl 2 in order to extract and de-dry to obtain a colorless oily substance. Add a small amount of methanol to precipitate a large amount of white solid, which is filtered and dried to obtain the formula shown in formula 2-3. compound.
- Step c Dissolve 829 mg of the compound of formula 2-3 in 10 mL of 1,2-dichloroethane, add 20 mL of water, add 10 mL of acetic acid under ice bath, and then continuously pass chlorine gas for 20 min, TLC detects the reaction After completion, extract with CH 2 Cl 2 , dry with anhydrous sodium sulfate, and spin out the solvent to obtain the compound represented by formula (III-1).
- Step a add raw material 1 (30mmol) into 250mL eggplant-shaped flask, under room temperature, add 80mL ultra-dry dichloromethane solvent and Ph 3 P (90mmol) successively, after 15min of reaction, add CCl 3 Br (48mmol) , and reacted at room temperature for 2 hours. After the reaction was detected by TCL, column chromatography was performed, and the solvent was removed under reduced pressure to obtain intermediate 2.
- Step b preheat the temperature to 100 ° C in advance, then add NBS (24 mmol) to a solution of intermediate 2 (20 mmol) in THF (40 mL), then add p-toluenesulfonic acid (4.8 mmol), reflux for 25 min, After monitoring the completion of the reaction by TLC, add water to quench, then extract with ethyl acetate, dry over anhydrous Na 2 SO 4 , and spin out the solvent to obtain the intermediate represented by formula (IV-1).
- intermediate formula (IV-1) Add 1.2 mmol of intermediate formula (IV-1) to a 50 mL pear-shaped bottle, add 10 mL of acetonitrile to dissolve, add potassium carbonate (1.5 mmol), and finally add intermediate formula (V-1) (1 mmol), react at room temperature for 30 min, and monitor the reaction by TLC After completion, the solvent is spun out under reduced pressure, and the target compound represented by formula (VI-1) can be obtained by column chromatography.
- This test example conducts activity test on the following compounds shown in Table 1, and the results are shown in Table 3.
- the specific test method is:
- the experiment was carried out by the seedling pot method.
- Grade 1 The lesion area accounts for less than 5% of the entire leaf area
- Grade 3 The lesion area accounts for 6% to 10% of the entire leaf area
- Grade 5 The lesion area accounts for 11% to 25% of the entire leaf area
- Grade 7 The lesion area accounts for 26% to 50% of the entire leaf area
- Grade 9 The lesion area accounts for more than 50% of the entire leaf area.
- disease index of CK 0 blank control area before application disease index of CK 1 blank control area after application
- disease index of PT 0 drug treatment area before application disease index of PT 1 drug treatment area after application.
- test and investigation methods of this test example are the same as those of Test Example 1, except that the tested compounds are the compounds shown in Table 4, and the test concentrations are listed in Table 4.
- the trial was arranged in Xingping City, Shaanxi province (from May 2021 to June 2021, the drug was applied once every 10 days, for a total of 2 times).
- the experimental plot (clay loam, pH 5.8, high fertility level and soil organic matter content) was cultivated in a greenhouse for cucumber, and the soil type, cultivation conditions and water and fertilizer management of each experimental plot were uniform. Use a sprayer to evenly spray the prepared medicinal solution of each participating drug on the stems and leaves of the cucumber.
- test chemicals The treatment of the test chemicals was carried out according to the method required by the Ministry of Agriculture for the field efficacy test of pesticides. -2000) grading standard grading records, the disease index is used to calculate the prevention and treatment effect, and the specific test results of this test example are shown in Table 5.
- the compounds provided by the present invention have the efficacies against the fungal diseases of Oomycetes such as cucumber downy mildew, soybean phytophthora, tomato late blight, potato late blight, eggplant downy mildew, citrus foot rot, pumpkin blight, grape downy mildew, etc. Significantly better results than the prior art.
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Abstract
式(I)所示的含突烯片段的三唑磺酰胺类衍生物，其制备方法和应用，以及包含该衍生物的杀菌剂及其应用。所述衍生物在相对较低浓度下针对霜霉病、霜疫霉病、疫病、晚疫病等卵菌纲植物病害具有明显比现有技术更好的效果，如黄瓜霜霉病、大豆疫霉病、番茄晚疫病、马铃薯晚疫病、茄子霜霉病、柑桔脚腐病、南瓜疫病、葡萄霜霉病等。
Description
相关申请的交叉引用
本申请要求2021年04月25日提交的中国专利申请202110448842.3的权益，该申请的内容通过引用被合并于本文。
本发明涉及农药领域，具体地，涉及一种含突烯片段的三唑磺酰胺类衍生物及其制备方法，一种含突烯片段的三唑磺酰胺类衍生物作为细胞色素bc
1复合物Q
i位点抑制剂以及在抗植物真菌病中的应用，一种杀菌剂及其在抗植物真菌病中的应用。
复合物Ⅲ(也叫细胞色素bc
1复合物)作为当前最具发展前景的农用杀菌剂靶标之一，其作用是催化从辅酶Q到细胞色素C的电子传递过程，同时将质子由线粒体基质泵至膜间隙。而细胞色素bc
1复合物抑制剂是通过作用于病原菌线粒体呼吸电子传递链上的复合体Ⅲ，干扰呼吸电子传递链来抑制线粒体功能，阻止其产生能量，抑制病原菌生长，最终导致其死亡，以达到防治病害的目的。根据复合物Ⅲ的功能该靶标可分为Q
o位点和Q
i位点，基于该靶标的商品化Q
o位点杀菌剂数量多达21种，但随着使用时间的延长，这些杀菌剂的抗性问题越来越严重。目前商品化的3个Q
i位点杀菌剂(cyazofamid、amisulbrom、fenpicoxamid)，很少有抗性问题的报道，其中，氰霜唑和吲唑磺菌胺对卵菌纲病害有着很好的防效。但由于氰霜唑和吲唑磺菌胺合成复杂，成本高昂。
基于此，本发明将胺部分进行取代基优化，设计出具有新颖结构的三唑磺酰胺类衍生物。同时，对于本发明中的中间体酸和重要中间体N-(2-苯基烯丙基)环丙胺、N-(2,2-二氯-1-苯基乙烯基)环丙胺等的合成，原料廉价易得，反应步骤和后处理简单，并且化合物具有安全性高，持续性好的优点，且这类新型化合物在低浓度下仍具有良好的杀菌活性。
发明内容
本发明的目的是为了提供一种新的三唑磺酰胺类衍生物，以期该类三唑磺酰胺类衍生物能够在低浓度下实现明显更高的抗真菌病防效。
为了实现上述目的，本发明第一方面提供一种含突烯片段的三唑磺酰胺类衍生物，该衍生物具有式(I)所示的结构：
其中，式(I)中，R
1选自C
1-6的烷基、C
1-6的烷氧基、C
3-6的环烷基；
R
2选自H、C
1-6的烷基；
R
3、R
4、R
5、R
6、R
7选自H、卤素、C
1-6的烷基、C
1-6的烷氧基、氰基、由至少一个卤素取代的C
1-6的烷基、由至少一个卤素取代的C
1-6的烷氧基；
R
8均为H或Cl。
本发明第二方面提供一种制备第一方面所述的含突烯片段的三唑磺酰胺类衍生物的方法，该方法包括将式(II)所示的化合物与式(III)所示的化合物进行接触反应；
其中，R
9和R
10中一者为卤素，另一者为-NHR
1，
R
1、R
2、R
3、R
4、R
5、R
6、R
7、R
8的定义与第一方面所述的定义对应相同。
本发明的第三方面提供前述含突烯片段的三唑磺酰胺类衍生物作为细胞色素bc
1复合物Q
i位点抑制剂的应用。
本发明的第四方面提供前述含突烯片段的三唑磺酰胺类衍生物在抗植物真菌病中的应用。
本发明的第五方面提供一种杀菌剂，该杀菌剂的活性成分为前述含突烯片段的三唑磺酰胺类衍生物中的至少一种，以所述杀菌剂的总重量计，所述活性成分的含量为0.1-100重量％。
本发明的第六方面提供一种第五方面所述的杀菌剂在抗植物真菌病中的应用。
本发明提供的化合物在相对较低浓度下针对霜霉病、霜疫霉病、疫病、晚疫病等卵菌纲植物病害具有明显比现有技术更好的效果，如黄瓜霜霉病、大豆疫霉病、番茄晚疫病、马铃薯晚疫病、茄子霜霉病、柑桔脚腐病、南瓜疫病、葡萄霜霉病等，具有潜在的商业化价值。
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
以下针对本发明的部分基团提供一些示例性的解释，在没有特别说明的情况下，未列举的部分参照如下示例性的解释进行解释。
“C
1-6的烷基”表示碳原子总数为1-6的烷基，包括直链烷基、支链烷基，例如可以为碳原子总数为1、2、3、4、5或6的直链烷基、支链烷基，例如可以为正丁基、异丁基、叔丁基、正戊基、异戊基、正己基等；“C
1-3的烷基”的定义与“C
1-6烷基”的定义相似，不同的是，碳原子总数不同。
“C
1-6的烷氧基”的定义与“C
1-6烷基”的定义相似，不同的是，“C
1-6的烷氧基”通过O原子直接与母核连接；“C
1-3的烷氧基”的定义与“C
1-6的烷氧基”的定义相似，不同的是，碳原子总数不同。
“由至少一个卤素取代的C
1-6的烷基”的定义与“C
1-6烷基”的定义相似，不同的是，“由至少一个卤素取代的C
1-6的烷基”中的烷基上的至少一个H由选自氟、氯、溴、碘的至少一种卤素原子取代，且该“由至少一个卤素取代的C
1-6的烷基”的碳原子总数为1-6。
“由至少一个卤素取代的C
1-6的烷氧基”的定义与“C
1-6烷氧基”的定义相似，不同的是，“由至少一个卤素取代的C
1-6的烷氧基”表示为“C
1-6烷氧基”上的至少一个H由选自氟、氯、溴、碘的至少一种卤素原子取代，且该“由至少一个卤素取代的C
1-6的烷氧基”的碳原子总数为1-6。
“C
3-6的环烷基”表示碳原子总数为3-6的烷基，且成环原子均为C原子，且所述“C
3-6的环烷基”上任意能够被取代的位置能够被取代基取代或未取代，当被取代时，包含取代基在内的整体基团的碳原子总数为3-6。
如前所述，本发明的第一方面提供了一种含突烯片段的三唑磺酰胺类衍生物，该衍生物具有式(I)所示的结构：
其中，式(I)中，R
1选自C
1-6的烷基、C
1-6的烷氧基、C
3-6的环烷基；R
2选自H、C
1-6的烷基；
R
3、R
4、R
5、R
6、R
7选自H、卤素、C
1-6的烷基、C
1-6的烷氧基、氰基、由至少一个卤素取代的C
1-6的烷基、由至少一个卤素取代的C
1-6的烷氧基；
R
8均为H或Cl。
优选地，在式(I)中，
R
1选自C
1-3的烷氧基、C
3-6的环烷基；
R
2选自H、C
1-3的烷基；
R
3、R
4、R
5、R
6、R
7选自H、卤素、C
1-6的烷基、C
1-3的烷氧基、氰基、由至少一个卤素取代的C
1-3的烷基、由至少一个卤素取代的C
1-3的烷氧基；
R
8均为H或Cl。
特别优选地，在式(I)中，
R
1选自甲氧基、环丙基；
R
2选自H、甲基；
R
3、R
4、R
5选自H、F、Cl、甲基、乙基、异丙基、叔丁基、甲氧基、-CF
3、-OCF
3、氰基；
R
6选自H、F、Cl；
R
7为H；
R
8均为H或Cl。
根据一种特别优选的具体实施方式，所述含突烯片段的三唑磺酰胺类衍生物为以下化合物中的任意一种：
化合物I-1：在式(I)中，R
1为环丙基，R
2、R
3、R
4、R
5、R
6、R
7、R
8均为H；
化合物I-2：在式(I)中，R
1为环丙基，R
2为H，R
3为F，R
4、R
5、R
6、R
7、R
8均为H；
化合物I-3：在式(I)中，R
1为环丙基，R
2为H，R
3为Cl，R
4、R
5、R
6、R
7、R
8均为H；
化合物I-4：在式(I)中，R
1为环丙基，R
2为H，R
3为甲基，R
4、R
5、R
6、R
7、R
8均为H；
化合物I-5：在式(I)中，R
1为环丙基，R
2为H，R
3为乙基，R
4、R
5、R
6、R
7、R
8均为H；
化合物I-6：在式(I)中，R
1为环丙基，R
2为H，R
3为甲氧基，R
4、R
5、R
6、R
7、R
8均为H；
化合物I-7：在式(I)中，R
1为环丙基，R
2为H，R
3为-CF
3，R
4、R
5、R
6、R
7、R
8均为H；
化合物I-8：在式(I)中，R
1为环丙基，R
2为H，R
3为氰基，R
4、R
5、R
6、R
7、R
8均为H；
化合物I-9：在式(I)中，R
1为环丙基，R
2为H，R
4为F，R
3、R
5、R
6、R
7、R
8均为H；
化合物I-10：在式(I)中，R
1为环丙基，R
2为H，R
4为Cl，R
3、R
5、R
6、R
7、R
8均为H；
化合物I-11：在式(I)中，R
1为环丙基，R
2为H，R
4为甲基，R
3、R
5、R
6、R
7、R
8均为H；
化合物I-12：在式(I)中，R
1为环丙基，R
2为H，R
4为乙基，R
3、R
5、R
6、R
7、R
8均为H；
化合物I-13：在式(I)中，R
1为环丙基，R
2为H，R
4为甲氧基，R
3、R
5、R
6、R
7、R
8均为H；
化合物I-14：在式(I)中，R
1为环丙基，R
2为H，R
4为异丙基，R
3、R
5、R
6、R
7、R
8均为H；
化合物I-15：在式(I)中，R
1为环丙基，R
2为H，R
4为叔丁基，R
3、R
5、R
6、R
7、R
8均为H；
化合物I-16：在式(I)中，R
1为环丙基，R
2为H，R
4为-CF
3，R
3、R
5、R
6、R
7、R
8均为H；
化合物I-17：在式(I)中，R
1为环丙基，R
2为H，R
4为-OCF
3，R
3、R
5、R
6、R
7、R
8均为H；
化合物I-18：在式(I)中，R
1为环丙基，R
2为H，R
5为F，R
3、R
4、R
6、R
7、R
8均 为H；
化合物I-19：在式(I)中，R
1为环丙基，R
2为H，R
5为Cl，R
3、R
4、R
6、R
7、R
8均为H；
化合物I-20：在式(I)中，R
1为环丙基，R
2为H，R
5为甲基，R
3、R
4、R
6、R
7、R
8均为H；
化合物I-21：在式(I)中，R
1为环丙基，R
2为H，R
5为氰基，R
3、R
4、R
6、R
7、R
8均为H；
化合物I-22：在式(I)中，R
1为环丙基，R
2为H，R
5为甲氧基，R
3、R
4、R
6、R
7、R
8均为H；
化合物I-23：在式(I)中，R
1为环丙基，R
2为H，R
5为异丙基，R
3、R
4、R
6、R
7、R
8均为H；
化合物I-24：在式(I)中，R
1为环丙基，R
2为H，R
5为叔丁基，R
3、R
4、R
6、R
7、R
8均为H；
化合物I-25：在式(I)中，R
1为环丙基，R
2为H，R
5为-CF
3，R
3、R
4、R
6、R
7、R
8均为H；
化合物I-26：在式(I)中，R
1为环丙基，R
2为H，R
5为-OCF
3，R
3、R
4、R
6、R
7、R
8均为H；
化合物I-27：在式(I)中，R
1为环丙基，R
2为H，R
3和R
4均为甲基，R
5、R
6、R
7、R
8均为H；
化合物I-28：在式(I)中，R
1为环丙基，R
2为H，R
3和R
4均为F，R
5、R
6、R
7、R
8均为H；
化合物I-29：在式(I)中，R
1为环丙基，R
2为H，R
3为F，R
4为Cl，R
5、R
6、R
7、R
8均为H；
化合物I-30：在式(I)中，R
1为环丙基，R
2为H，R
3为Cl，R
4为F，R
5、R
6、R
7、R
8均为H；
化合物I-31：在式(I)中，R
1为环丙基，R
2为H，R
3和R
4均为Cl，R
5、R
6、R
7、R
8均为H；
化合物I-32：在式(I)中，R
1为环丙基，R
2为H，R
3和R
5均为甲基，R
4、R
6、R
7、R
8均为H；
化合物I-33：在式(I)中，R
1为环丙基，R
2为H，R
3和R
5均为F，R
4、R
6、R
7、R
8均为H；
化合物I-34：在式(I)中，R
1为环丙基，R
2为H，R
3为F，R
5为Cl，R
4、R
6、R
7、R
8均为H；
化合物I-35：在式(I)中，R
1为环丙基，R
2为H，R
3为Cl，R
5为F，R
4、R
6、R
7、R
8均为H；
化合物I-36：在式(I)中，R
1为环丙基，R
2为H，R
3和R
5均为Cl，R
4、R
6、R
7、R
8均为H；
化合物I-37：在式(I)中，R
1为环丙基，R
2为H，R
3和R
5均为-CF
3，R
4、R
6、R
7、R
8均为H；
化合物I-38：在式(I)中，R
1为环丙基，R
2为H，R
4和R
5均为甲基，R
3、R
6、R
7、R
8均为H；
化合物I-39：在式(I)中，R
1为环丙基，R
2为H，R
4和R
5均为F，R
3、R
6、R
7、R
8均为H；
化合物I-40：在式(I)中，R
1为环丙基，R
2为H，R
4为F，R
5为Cl、R
3、R
6、R
7、R
8均为H；
化合物I-41：在式(I)中，R
1为环丙基，R
2为H，R
4为Cl，R
5为F、R
3、R
6、R
7、R
8均为H；
化合物I-42：在式(I)中，R
1为环丙基，R
2为H，R
4和R
5均为Cl，R
3、R
6、R
7、R
8均为H；
化合物I-43：在式(I)中，R
1为环丙基，R
2为H，R
4和R
5均为-CF
3，R
3、R
6、R
7、R
8均为H；
化合物I-44：在式(I)中，R
1为环丙基，R
2为H，R
4和R
6均为甲基，R
3、R
5、R
7、R
8均为H；
化合物I-45：在式(I)中，R
1为环丙基，R
2为H，R
4为F，R
6为Cl，R
3、R
5、R
7、R
8均为H；
化合物I-46：在式(I)中，R
1为环丙基，R
2为H，R
4和R
6均为Cl，R
3、R
5、R
7、R
8均为H；
化合物I-47：在式(I)中，R
1为环丙基，R
2为H，R
4、R
5和R
6均为F，R
3、R
7、R
8均为H；
化合物I-48：在式(I)中，R
1为环丙基，R
2为H，R
4、R
5和R
6均为Cl，R
3、R
7、R
8均为H；
化合物I-49：在式(I)中，R
1为甲氧基，R
2、R
3、R
4、R
5、R
6、R
7、R
8均为H；
化合物I-50：在式(I)中，R
1为甲氧基，R
2为H，R
3为F，R
4、R
5、R
6、R
7、R
8均为H；
化合物I-51：在式(I)中，R
1为甲氧基，R
2为H，R
3为Cl，R
4、R
5、R
6、R
7、R
8均为H；
化合物I-52：在式(I)中，R
1为甲氧基，R
2为H，R
3为甲基，R
4、R
5、R
6、R
7、R
8均为H；
化合物I-53：在式(I)中，R
1为甲氧基，R
2为H，R
3为乙基，R
4、R
5、R
6、R
7、R
8均为H；
化合物I-54：在式(I)中，R
1为甲氧基，R
2为H，R
3为甲氧基，R
4、R
5、R
6、R
7、R
8均为H；
化合物I-55：在式(I)中，R
1为甲氧基，R
2为H，R
3为-CF
3，R
4、R
5、R
6、R
7、R
8均为H；
化合物I-56：在式(I)中，R
1为甲氧基，R
2为H，R
3为-OCF
3，R
4、R
5、R
6、R
7、R
8均为H；
化合物I-57：在式(I)中，R
1为甲氧基，R
2为H，R
4为F，R
3、R
5、R
6、R
7、R
8均为H；
化合物I-58：在式(I)中，R
1为甲氧基，R
2为H，R
4为Cl，R
3、R
5、R
6、R
7、R
8均为H；
化合物I-59：在式(I)中，R
1为甲氧基，R
2为H，R
4为甲基，R
3、R
5、R
6、R
7、R
8均为H；
化合物I-60：在式(I)中，R
1为甲氧基，R
2为H，R
4为乙基，R
3、R
5、R
6、R
7、R
8均为H；
化合物I-61：在式(I)中，R
1为甲氧基，R
2为H，R
4为甲氧基，R
3、R
5、R
6、R
7、R
8均为H；
化合物I-62：在式(I)中，R
1为甲氧基，R
2为H，R
4为异丙基，R
3、R
5、R
6、R
7、R
8均为H；
化合物I-63：在式(I)中，R
1为甲氧基，R
2为H，R
4为叔丁基，R
3、R
5、R
6、R
7、R
8均为H；
化合物I-64：在式(I)中，R
1为甲氧基，R
2为H，R
4为-CF
3，R
3、R
5、R
6、R
7、R
8均为H；
化合物I-65：在式(I)中，R
1为甲氧基，R
2为H，R
4为-OCF
3，R
3、R
5、R
6、R
7、R
8均为H；
化合物I-66：在式(I)中，R
1为甲氧基，R
2为H，R
5为F，R
3、R
4、R
6、R
7、R
8均为H；
化合物I-67：在式(I)中，R
1为甲氧基，R
2为H，R
5为Cl，R
3、R
4、R
6、R
7、R
8均为H；
化合物I-68：在式(I)中，R
1为甲氧基，R
2为H，R
5为甲基，R
3、R
4、R
6、R
7、R
8均为H；
化合物I-69：在式(I)中，R
1为甲氧基，R
2为H，R
5为乙基，R
3、R
4、R
6、R
7、R
8均为H；
化合物I-70：在式(I)中，R
1为甲氧基，R
2为H，R
5为甲氧基，R
3、R
4、R
6、R
7、R
8均为H；
化合物I-71：在式(I)中，R
1为甲氧基，R
2为H，R
5为异丙基，R
3、R
4、R
6、R
7、R
8均为H；
化合物I-72：在式(I)中，R
1为甲氧基，R
2为H，R
5为-CF
3，R
3、R
4、R
6、R
7、R
8均为H；
化合物I-73：在式(I)中，R
1为甲氧基，R
2为H，R
5为-OCF
3，R
3、R
4、R
6、R
7、R
8均为H；
化合物I-74：在式(I)中，R
1为甲氧基，R
2为H，R
3和R
4均为甲基，R
5、R
6、R
7、 R
8均为H；
化合物I-75：在式(I)中，R
1为甲氧基，R
2为H，R
3和R
4均为F，R
5、R
6、R
7、R
8均为H；
化合物I-76：在式(I)中，R
1为甲氧基，R
2为H，R
3为F，R
4为Cl，R
5、R
6、R
7、R
8均为H；
化合物I-77：在式(I)中，R
1为甲氧基，R
2为H，R
3为Cl，R
4为F，R
5、R
6、R
7、R
8均为H；
化合物I-78：在式(I)中，R
1为甲氧基，R
2为H，R
3和R
4均为Cl，R
5、R
6、R
7、R
8均为H；
化合物I-79：在式(I)中，R
1为甲氧基，R
2为H，R
3和R
5均为甲基，R
4、R
6、R
7、R
8均为H；
化合物I-80：在式(I)中，R
1为甲氧基，R
2为H，R
3和R
5均为F，R
4、R
6、R
7、R
8均为H；
化合物I-81：在式(I)中，R
1为甲氧基，R
2为H，R
3为F，R
5为Cl，R
4、R
6、R
7、R
8均为H；
化合物I-82：在式(I)中，R
1为甲氧基，R
2为H，R
3为Cl，R
5为F，R
4、R
6、R
7、R
8均为H；
化合物I-83：在式(I)中，R
1为甲氧基，R
2为H，R
3和R
5均为Cl，R
4、R
6、R
7、R
8均为H；
化合物I-84：在式(I)中，R
1为甲氧基，R
2为H，R
3和R
5均为-CF
3，R
4、R
6、R
7、R
8均为H；
化合物I-85：在式(I)中，R
1为甲氧基，R
2为H，R
4和R
5均为甲基，R
3、R
6、R
7、R
8均为H；
化合物I-86：在式(I)中，R
1为甲氧基，R
2为H，R
4和R
5均为F，R
3、R
6、R
7、R
8均为H；
化合物I-87：在式(I)中，R
1为甲氧基，R
2为H，R
4为F，R
5为Cl，R
3、R
6、R
7、R
8均为H；
化合物I-88：在式(I)中，R
1为甲氧基，R
2为H，R
4为Cl，R
5为F，R
3、R
6、R
7、R
8均为H；
化合物I-89：在式(I)中，R
1为甲氧基，R
2为H，R
4和R
5均为Cl，R
3、R
6、R
7、R
8均为H；
化合物I-90：在式(I)中，R
1为甲氧基，R
2为H，R
4和R
5均为-CF
3，R
3、R
6、R
7、R
8均为H；
化合物I-91：在式(I)中，R
1为甲氧基，R
2为H，R
4和R
6均为甲基，R
3、R
5、R
7、R
8均为H；
化合物I-92：在式(I)中，R
1为甲氧基，R
2为H，R
4为F，R
6为Cl，R
3、R
5、R
7、R
8均为H；
化合物I-93：在式(I)中，R
1为甲氧基，R
2为H，R
4和R
6均为Cl，R
3、R
5、R
7、R
8均为H；
化合物I-94：在式(I)中，R
1为甲氧基，R
2为H，R
4、R
5和R
6均为F，R
3、R
7、R
8均为H；
化合物I-95：在式(I)中，R
1为甲氧基，R
2为H，R
4、R
5和R
6均为Cl，R
3、R
7、R
8均为H；
化合物I-96：在式(I)中，R
1为环丙基，R
2为甲基，R
3、R
4、R
5、R
6、R
7、R
8均为H；
化合物I-97：在式(I)中，R
1为环丙基，R
2为甲基，R
3为F，R
4、R
5、R
6、R
7、R
8均为H；
化合物I-98：在式(I)中，R
1为环丙基，R
2为甲基，R
3为Cl，R
4、R
5、R
6、R
7、R
8均为H；
化合物I-99：在式(I)中，R
1为环丙基，R
2、R
3均为甲基，R
4、R
5、R
6、R
7、R
8均为H；
化合物I-100：在式(I)中，R
1为环丙基，R
2为甲基，R
3为甲氧基，R
4、R
5、R
6、R
7、R
8均为H；
化合物I-101：在式(I)中，R
1为环丙基，R
2为甲基，R
4为F，R
3、R
5、R
6、R
7、R
8均为H；
化合物I-102：在式(I)中，R
1为环丙基，R
2为甲基，R
4为Cl，R
3、R
5、R
6、R
7、R
8均为H；
化合物I-103：在式(I)中，R
1为环丙基，R
2、R
4均为甲基，R
3、R
5、R
6、R
7、R
8均为H；
化合物I-104：在式(I)中，R
1为环丙基，R
2为甲基，R
4为乙基，R
3、R
5、R
6、R
7、R
8均为H；
化合物I-105：在式(I)中，R
1为环丙基，R
2为甲基，R
4为甲氧基，R
3、R
5、R
6、R
7、R
8均为H；
化合物I-106：在式(I)中，R
1为环丙基，R
2为甲基，R
4为异丙基，R
3、R
5、R
6、R
7、R
8均为H；
化合物I-107：在式(I)中，R
1为环丙基，R
2为甲基，R
4为叔丁基，R
3、R
5、R
6、R
7、R
8均为H；
化合物I-108：在式(I)中，R
1为环丙基，R
2为甲基，R
4为-CF
3，R
3、R
5、R
6、R
7、R
8均为H；
化合物I-109：在式(I)中，R
1为环丙基，R
2为甲基，R
4为-OCF
3，R
3、R
5、R
6、R
7、R
8均为H；
化合物I-110：在式(I)中，R
1为环丙基，R
2为甲基，R
5为F，R
3、R
4、R
6、R
7、R
8均为H；
化合物I-111：在式(I)中，R
1为环丙基，R
2为甲基，R
5为Cl，R
3、R
4、R
6、R
7、 R
8均为H；
化合物I-112：在式(I)中，R
1为环丙基，R
2、R
5均为甲基，R
3、R
4、R
6、R
7、R
8均为H；
化合物I-113：在式(I)中，R
1为环丙基，R
2为甲基，R
5为甲氧基，R
3、R
4、R
6、R
7、R
8均为H；
化合物I-114：在式(I)中，R
1为环丙基，R
2为甲基，R
5为异丙基，R
3、R
4、R
6、R
7、R
8均为H；
化合物I-115：在式(I)中，R
1为环丙基，R
2为甲基，R
5为叔丁基，R
3、R
4、R
6、R
7、R
8均为H；
化合物I-116：在式(I)中，R
1为环丙基，R
2为甲基，R
5为-CF
3，R
3，R
4、R
6、R
7、R
8均为H；
化合物I-117：在式(I)中，R
1为环丙基，R
2为甲基，R
5为-OCF
3，R
3、R
4、R
6、R
7、R
8均为H；
化合物I-118：在式(I)中，R
1为环丙基，R
2、R
3、R
4均为甲基，R
5、R
6、R
7、R
8均为H；
化合物I-119：在式(I)中，R
1为环丙基，R
2为甲基，R
3和R
4均为F，R
5、R
6、R
7、R
8均为H；
化合物I-120：在式(I)中，R
1为环丙基，R
2为甲基，R
3和R
4均为Cl，R
5、R
6、R
7、R
8均为H；
化合物I-121：在式(I)中，R
1为环丙基，R
2、R
3、R
5均为甲基，R
4、R
6、R
7、R
8均为H；
化合物I-122：在式(I)中，R
1为环丙基，R
2为甲基，R
3和R
5均为F，R
4、R
6、R
7、R
8均为H；
化合物I-123：在式(I)中，R
1为环丙基，R
2为甲基，R
3和R
5均为Cl，R
4、R
6、R
7、R
8均为H；
化合物I-124：在式(I)中，R
1为环丙基，R
2为甲基，R
3和R
5均为-CF
3，R
4、R
6、R
7、R
8均为H；
化合物I-125：在式(I)中，R
1为环丙基，R
2、R
4、R
5均为甲基，R
3、R
6、R
7、R
8均为H；
化合物I-126：在式(I)中，R
1为环丙基，R
2为甲基，R
4和R
5均为F，R
3、R
6、R
7、R
8均为H；
化合物I-127：在式(I)中，R
1为环丙基，R
2为甲基，R
4和R
5均为Cl，R
3、R
6、R
7、R
8均为H；
化合物I-128：在式(I)中，R
1为环丙基，R
2、R
4、R
6均为甲基，R
3、R
5、R
7、R
8均为H；
化合物I-129：在式(I)中，R
1为环丙基，R
2为甲基，R
4为F，R
6为Cl，R
3、R
5、R
7、R
8均为H；
化合物I-130：在式(I)中，R
1为环丙基，R
2为甲基，R
4为Cl，R
6为F，R
3、R
5、R
7、R
8均为H；
化合物I-131：在式(I)中，R
1为环丙基，R
2为甲基，R
4和R
6均为Cl，R
3、R
5、R
7、R
8均为H；
化合物I-132：在式(I)中，R
1为环丙基，R
2为甲基，R
4、R
5和R
6均为F，R
3、R
7、R
8均为H；
化合物I-133：在式(I)中，R
1为环丙基，R
2为甲基，R
4、R
5和R
6均为Cl，R
3、R
7、R
8均为H；
化合物I-134：在式(I)中，R
1为甲氧基，R
2为甲基，R
3、R
4、R
5、R
6、R
7、R
8均为H；
化合物I-135：在式(I)中，R
1为甲氧基，R
2为甲基，R
3为F，R
4、R
5、R
6、R
7、R
8均为H；
化合物I-136：在式(I)中，R
1为甲氧基，R
2为甲基，R
3为Cl，R
4、R
5、R
6、R
7、R
8均为H；
化合物I-137：在式(I)中，R
1为甲氧基，R
2为甲基，R
3为甲基，R
4、R
5、R
6、R
7、R
8均为H；
化合物I-138：在式(I)中，R
1为甲氧基，R
2为甲基，R
3为甲氧基，R
4、R
5、R
6、R
7、R
8均为H；
化合物I-139：在式(I)中，R
1为甲氧基，R
2为甲基，R
4为F、R
3、R
5、R
6、R
7、R
8均为H；
化合物I-140：在式(I)中，R
1为甲氧基，R
2为甲基，R
4为Cl，R
3、R
5、R
6、R
7、R
8均为H；
化合物I-141：在式(I)中，R
1为甲氧基，R
2为甲基，R
4为甲基，R
3、R
5、R
6、R
7、R
8均为H；
化合物I-142：在式(I)中，R
1为甲氧基，R
2为甲基，R
4为乙基，R
3、R
5、R
6、R
7、R
8均为H；
化合物I-143：在式(I)中，R
1为甲氧基，R
2为甲基，R
4为甲氧基，R
3、R
5、R
6、R
7、R
8均为H；
化合物I-144：在式(I)中，R
1为甲氧基，R
2为甲基，R
4为异丙基，R
3、R
5、R
6、R
7、R
8均为H；
化合物I-145：在式(I)中，R
1为甲氧基，R
2为甲基，R
4为叔丁基，R
3、R
5、R
6、R
7、R
8均为H；
化合物I-146：在式(I)中，R
1为甲氧基，R
2为甲基，R
4为-CF
3，R
3、R
5、R
6、R
7、R
8均为H；
化合物I-147：在式(I)中，R
1为甲氧基，R
2为甲基，R
4为-OCF
3，R
3、R
5、R
6、R
7、R
8均为H；
化合物I-148：在式(I)中，R
1为甲氧基，R
2为甲基，R
5为F，R
3、R
4、R
6、R
7、R
8 均为H；
化合物I-149：在式(I)中，R
1为甲氧基，R
2为甲基，R
5为Cl，R
3、R
4、R
6、R
7、R
8均为H；
化合物I-150：在式(I)中，R
1为甲氧基，R
2为甲基，R
5为甲基，R
3、R
4、R
6、R
7、R
8均为H；
化合物I-151：在式(I)中，R
1为甲氧基，R
2为甲基，R
5为甲氧基，R
3、R
4、R
6、R
7、R
8均为H；
化合物I-152：在式(I)中，R
1为甲氧基，R
2为甲基，R
5为异丙基，R
3、R
4、R
6、R
7、R
8均为H；
化合物I-153：在式(I)中，R
1为甲氧基，R
2为甲基，R
5为叔丁基，R
3、R
4、R
6、R
7、R
8均为H；
化合物I-154：在式(I)中，R
1为甲氧基，R
2为甲基，R
5为-CF
3，R
3、R
4、R
6、R
7、R
8均为H；
化合物I-155：在式(I)中，R
1为甲氧基，R
2为甲基，R
5为-OCF
3，R
3、R
4、R
6、R
7、R
8均为H；
化合物I-156：在式(I)中，R
1为甲氧基，R
2、R
3、R
4均为甲基，R
5、R
6、R
7、R
8均为H；
化合物I-157：在式(I)中，R
1为甲氧基，R
2为甲基，R
3和R
4均为F，R
5、R
6、R
7、R
8均为H；
化合物I-158：在式(I)中，R
1为甲氧基，R
2为甲基，R
3和R
4均为Cl，R
5、R
6、R
7、R
8均为H；
化合物I-159：在式(I)中，R
1为甲氧基，R
2、R
3、R
5均为甲基，R
4、R
6、R
7、R
8均为H；
化合物I-160：在式(I)中，R
1为甲氧基，R
2为甲基，R
3和R
5均为F，R
4、R
6、R
7、R
8均为H；
化合物I-161：在式(I)中，R
1为甲氧基，R
2为甲基，R
3和R
5均为Cl，R
4、R
6、R
7、R
8均为H；
化合物I-162：在式(I)中，R
1为甲氧基，R
2为甲基，R
3和R
5均为-CF
3，R
4、R
6、R
7、R
8均为H；
化合物I-163：在式(I)中，R
1为甲氧基，R
2、R
4、R
5均为甲基，R
3、R
6、R
7、R
8均为H；
化合物I-164：在式(I)中，R
1为甲氧基，R
2为甲基，R
4和R
5均为F，R
3、R
6、R
7、R
8均为H；
化合物I-165：在式(I)中，R
1为甲氧基，R
2为甲基，R
4和R
5均为Cl，R
3、R
6、R
7、R
8均为H；
化合物I-166：在式(I)中，R
1为甲氧基，R
2为甲基，R
4和R
6均为甲基，R
3、R
5、R
7、R
8均为H；
化合物I-167：在式(I)中，R
1为甲氧基，R
2为甲基，R
4为F，R
6为Cl，R
3、R
5、R
7、R
8均为H；
化合物I-168：在式(I)中，R
1为甲氧基，R
2为甲基，R
4为Cl，R
6为F，R
3、R
5、R
7、R
8均为H；
化合物I-169：在式(I)中，R
1为甲氧基，R
2为甲基，R
4和R
6均为Cl，R
3、R
5、R
7、R
8均为H；
化合物I-170：在式(I)中，R
1为甲氧基，R
2为甲基，R
4、R
5和R
6均为F、R
3、R
7、R
8均为H；
化合物I-171：在式(I)中，R
1为甲氧基，R
2为甲基，R
4、R
5和R
6均为Cl，R
3、R
7、R
8均为H；
化合物II-1：在式(I)中，R
1为环丙基，R
2、R
3、R
4、R
5、R
6、R
7均为H，R
8均为Cl；
化合物II-2：在式(I)中，R
1为环丙基，R
2为H，R
3为F，R
4、R
5、R
6、R
7均为H，R
8均为Cl；
化合物II-3：在式(I)中，R
1为环丙基，R
2为H，R
4为F，R
3、R
5、R
6、R
7均为H，R
8均为Cl；
化合物II-4：在式(I)中，R
1为环丙基，R
2为H，R
4为Cl，R
3、R
5、R
6、R
7均为H，R
8均为Cl；
化合物II-5：在式(I)中，R
1为环丙基，R
2为H，R
4为甲基，R
3、R
5、R
6、R
7均为H，R
8均为Cl；
化合物II-6：在式(I)中，R
1为环丙基，R
2为H，R
4为乙基，R
3、R
5、R
6、R
7均为H，R
8均为Cl；
化合物II-7：在式(I)中，R
1为环丙基，R
2为H，R
4为甲氧基，R
3、R
5、R
6、R
7均为H，R
8均为Cl；
化合物II-8：在式(I)中，R
1为环丙基，R
2为H，R
4为异丙基，R
3、R
5、R
6、R
7均为H，R
8均为Cl；
化合物II-9：在式(I)中，R
1为环丙基，R
2为H，R
4为叔丁基，R
3、R
5、R
6、R
7均为H，R
8均为Cl；
化合物II-10：在式(II)中，R
1为环丙基，R
2为H，R
4为-CF
3，R
3、R
5、R
6、R
7均为H，R
8均为Cl；
化合物II-11：在式(I)中，R
1为环丙基，R
2为H，R
4为-OCF
3，R
3、R
5、R
6、R
7均为H，R
8均为Cl；
化合物II-12：在式(I)中，R
1为环丙基，R
2为H，R
5为F，R
3、R
4、R
6、R
7均为H，R
8均为Cl；
化合物II-13：在式(I)中，R
1为环丙基，R
2为H，R
5为Cl，R
3、R
4、R
6、R
7均为H，R
8均为Cl；
化合物II-14：在式(I)中，R
1为环丙基，R
2为H，R
5为甲基，R
3、R
4、R
6、R
7均为 H，R
8均为Cl；
化合物II-15：在式(I)中，R
1为环丙基，R
2为H，R
5为乙基，R
3、R
4、R
6、R
7均为H，R
8均为Cl；
化合物II-16：在式(I)中，R
1为环丙基，R
2为H，R
5为甲氧基，R
3、R
4、R
6、R
7均为H，R
8均为Cl；
化合物II-17：在式(I)中，R
1为环丙基，R
2为H，R
5为异丙基，R
3、R
4、R
6、R
7均为H，R
8均为Cl；
化合物II-18：在式(I)中，R
1为环丙基，R
2为H，R
5为叔丁基，R
3、R
4、R
6、R
7均为H，R
8均为Cl；
化合物II-19：在式(I)中，R
1为环丙基，R
2为H，R
5为-CF
3，R
3、R
4、R
6、R
7均为H，R
8均为Cl；
化合物II-20：在式(I)中，R
1为环丙基，R
2为H，R
5为-OCF
3，R
3、R
4、R
6、R
7均为H，R
8均为Cl；
化合物II-21：在式(I)中，R
1为环丙基，R
2为H，R
4和R
5均为甲基，R
3、R
6、R
7均为H，R
8均为Cl；
化合物II-22：在式(I)中，R
1为环丙基，R
2为H，R
4和R
5均为F，R
3、R
6、R
7均为H，R
8均为Cl；
化合物II-23：在式(I)中，R
1为环丙基，R
2为H，R
4为F，R
5为Cl，R
3、R
6、R
7均为H，R
8均为Cl；
化合物II-24：在式(I)中，R
1为环丙基，R
2为H，R
4为Cl，R
5为F，R
3、R
6、R
7均为H，R
8均为Cl；
化合物II-25：在式(I)中，R
1为环丙基，R
2为H，R
4和R
5均为Cl，R
3、R
6、R
7均为H，R
8均为Cl；
化合物II-26：在式(I)中，R
1为环丙基，R
2为H，R
4和R
5均为-CF
3，R
3、R
6、R
7均为H，R
8均为Cl；
化合物II-27：在式(I)中，R
1为环丙基，R
2为H，R
4和R
6均为甲基，R
3、R
5、R
7均为H，R
8均为Cl；
化合物II-28：在式(I)中，R
1为环丙基，R
2为H，R
4为F，R
6为Cl，R
3、R
5、R
7均为H，R
8均为Cl；
化合物II-29：在式(I)中，R
1为环丙基，R
2为H，R
4和R
6均为Cl，R
3、R
5、R
7均为H，R
8均为Cl；
化合物II-30：在式(I)中，R
1为环丙基，R
2为H，R
4、R
5和R
6均为F，R
3、R
7均为H，R
8均为Cl；
化合物II-31：在式(I)中，R
1为环丙基，R
2为H，R
4、R
5和R
6均为Cl，R
3、R
7均为H，R
8均为Cl；
化合物II-32：在式(I)中，R
1为甲氧基，R
2为H，R
3、R
4、R
5、R
6、R
7均为H，R
8均为Cl；
化合物II-33：在式(I)中，R
1为甲氧基，R
2为H，R
4为F，R
3、R
5、R
6、R
7均为H，R
8均为Cl；
化合物II-34：在式(I)中，R
1为甲氧基，R
2为H，R
4为Cl，R
3、R
5、R
6、R
7均为H，R
8均为Cl；
化合物II-35：在式(I)中，R
1为甲氧基，R
2为H，R
4为甲基，R
3、R
5、R
6、R
7均为H，R
8均为Cl；
化合物II-36：在式(I)中，R
1为甲氧基，R
2为H，R
4为氰基，R
3、R
5、R
6、R
7均为H，R
8均为Cl；
化合物II-37：在式(I)中，R
1为甲氧基，R
2为H，R
4为甲氧基，R
3、R
5、R
6、R
7均为H，R
8均为Cl；
化合物II-38：在式(I)中，R
1为甲氧基，R
2为H，R
4为异丙基，R
3、R
5、R
6、R
7均为H，R
8均为Cl；
化合物II-39：在式(I)中，R
1为甲氧基，R
2为H，R
4为叔丁基，R
3、R
5、R
6、R
7均为H，R
8均为Cl；
化合物II-40：在式(I)中，R
1为甲氧基，R
2为H，R
4为-CF
3，R
3、R
5、R
6、R
7均为H，R
8均为Cl；
化合物II-41：在式(I)中，R
1为甲氧基，R
2为H，R
4为-OCF
3，R
3、R
5、R
6、R
7均为H，R
8均为Cl；
化合物II-42：在式(I)中，R
1为甲氧基，R
2为H，R
5为F，R
3、R
4、R
6、R
7均为H，R
8均为Cl；
化合物II-43：在式(I)中，R
1为甲氧基，R
2为H，R
5为Cl，R
3、R
4、R
6、R
7均为H，R
8均为Cl；
化合物II-44：在式(I)中，R
1为甲氧基，R
2为H，R
5为甲基，R
3、R
4、R
6、R
7均为H，R
8均为Cl；
化合物II-45：在式(I)中，R
1为甲氧基，R
2为H，R
5为乙基，R
3、R
4、R
6、R
7均为H，R
8均为Cl；
化合物II-46：在式(I)中，R
1为甲氧基，R
2为H，R
5为甲氧基，R
3、R
4、R
6、R
7均为H，R
8均为Cl；
化合物II-47：在式(I)中，R
1为甲氧基，R
2为H，R
5为异丙基，R
3、R
4、R
6、R
7均为H，R
8均为Cl；
化合物II-48：在式(I)中，R
1为甲氧基，R
2为H，R
5为叔丁基，R
3、R
4、R
6、R
7均为H，R
8均为Cl；
化合物II-49：在式(I)中，R
1为甲氧基，R
2为H，R
5为-CF
3，R
3、R
4、R
6、R
7均为H，R
8均为Cl；
化合物II-50：在式(I)中，R
1为甲氧基，R
2为H，R
5为-OCF
3，R
3、R
4、R
6、R
7均为H，R
8均为Cl；
化合物II-51：在式(I)中，R
1为甲氧基，R
2为H，R
4和R
5均为甲基，R
3、R
6、R
7 均为H，R
8均为Cl；
化合物II-52：在式(I)中，R
1为甲氧基，R
2为H，R
4和R
5均为F，R
3、R
6、R
7均为H，R
8均为Cl；
化合物II-53：在式(I)中，R
1为甲氧基，R
2为H，R
4为F，R
5为Cl，R
3、R
6、R
7均为H，R
8均为Cl；
化合物II-54：在式(I)中，R
1为甲氧基，R
2为H，R
4为Cl，R
5为F，R
3、R
6、R
7均为H，R
8均为Cl；
化合物II-55：在式(I)中，R
1为甲氧基，R
2为H，R
4和R
5均为Cl，R
3、R
6、R
7均为H，R
8均为Cl；
化合物II-56：在式(I)中，R
1为甲氧基，R
2为H，R
4和R
5均为-CF
3，R
3、R
6、R
7均为H，R
8均为Cl；
化合物II-57：在式(I)中，R
1为甲氧基，R
2为H，R
4和R
6均为甲基，R
3、R
5、R
7均为H，R
8均为Cl；
化合物II-58：在式(I)中，R
1为甲氧基，R
2为H，R
4为F，R
6为Cl，R
5、R
3、R
7均为H，R
8均为Cl；
化合物II-59：在式(I)中，R
1为甲氧基，R
2为H，R
4为Cl，R
6为F，R
5、R
3、R
7均为H，R
8为Cl；
化合物II-60：在式(I)中，R
1为甲氧基，R
2为H，R
4和R
6均为Cl，R
5、R
3、R
7均为H，R
8均为Cl；
化合物II-61：在式(I)中，R
1为甲氧基，R
2为H，R
4、R
5和R
6均为F，R
3、R
7均为H，R
8均为Cl；
化合物II-62：在式(I)中，R
1为环丙基，R
2为甲基，R
3、R
4、R
5、R
6、R
7均为H，R
8均为Cl；
化合物II-63：在式(I)中，R
1为环丙基，R
2为甲基，R
4为F，R
3、R
5、R
6、R
7均为H，R
8均为Cl；
化合物II-64：在式(I)中，R
1为环丙基，R
2为甲基，R
4为Cl，R
3、R
5、R
6、R
7均为H，R
8均为Cl；
化合物II-65：在式(II)中，R
1为环丙基，R
2为甲基，R
4为甲基，R
3、R
5、R
6、R
7均为H，R
8均为Cl；
化合物II-66：在式(I)中，R
1为环丙基，R
2为甲基，R
4为氰基，R
3、R
5、R
6、R
7均为H，R
8均为Cl；
化合物II-67：在式(I)中，R
1为环丙基，R
2为甲基，R
4为甲氧基，R
3、R
5、R
6、R
7均为H，R
8均为Cl；
化合物II-68：在式(I)中，R
1为环丙基，R
2为甲基，R
4为异丙基，R
3、R
5、R
6、R
7均为H，R
8均为Cl；
化合物II-69：在式(I)中，R
1为环丙基，R
2为甲基，R
4为叔丁基，R
3、R
5、R
6、R
7均为H，R
8均为Cl；
化合物II-70：在式(I)中，R
1为环丙基，R
2为甲基，R
4为-CF
3，R
3、R
5、R
6、R
7均为H，R
8均为Cl；
化合物II-71：在式(I)中，R
1为环丙基，R
2为甲基，R
4为-OCF
3，R
3、R
5、R
6、R
7均为H，R
8均为Cl；
化合物II-72：在式(I)中，R
1为环丙基，R
2为甲基，R
5为F，R
3、R
4、R
6、R
7均为H，R
8均为Cl；
化合物II-73：在式(I)中，R
1为环丙基，R
2为甲基，R
5为Cl，R
3、R
4、R
6、R
7均为H，R
8均为Cl；
化合物II-74：在式(I)中，R
1为环丙基，R
2为甲基，R
5为甲基，R
3、R
4、R
6、R
7均为H，R
8均为Cl；
化合物II-75：在式(I)中，R
1为环丙基，R
2为甲基，R
5为甲氧基，R
3、R
4、R
6、R
7均为H，R
8均为Cl；
化合物II-76：在式(I)中，R
1为环丙基，R
2为甲基，R
5为异丙基，R
3、R
4、R
6、R
7均为H，R
8均为Cl；
化合物II-77：在式(I)中，R
1为环丙基，R
2为甲基，R
5为叔丁基，R
3、R
4、R
6、R
7均为H，R
8均为Cl；
化合物II-78：在式(I)中，R
1为环丙基，R
2为甲基，R
5为-CF
3，R
3、R
4、R
6、R
7均为H，R
8均为Cl；
化合物II-79：在式(I)中，R
1为环丙基，R
2为甲基，R
5为-OCF
3，R
3、R
4、R
6、R
7均为H，R
8均为Cl；
化合物II-80：在式(I)中，R
1为环丙基，R
2、R
4、R
5均为甲基、R
3、R
6、R
7均为H，R
8均为Cl；
化合物II-81：在式(I)中，R
1为环丙基，R
2为甲基，R
4和R
5均为F，R
3、R
6、R
7均为H，R
8均为Cl；
化合物II-82：在式(I)中，R
1为环丙基，R
2为甲基，R
4和R
5均为Cl，R
3、R
6、R
7均为H，R
8均为Cl；
化合物II-83：在式(I)中，R
1为环丙基，R
2、R
4、R
6均为甲基，R
3、R
5、R
7均为H，R
8均为Cl；
化合物II-84：在式(I)中，R
1为环丙基，R
2为甲基，R
4为F，R
6为Cl，R
3、R
5、R
7均为H，R
8均为Cl；
化合物II-85：在式(I)中，R
1为环丙基，R
2为甲基，R
4为Cl，R
6为F，R
3、R
5、R
7均为H，R
8均为Cl；
化合物II-86：在式(I)中，R
1为环丙基，R
2为甲基，R
4和R
6均为Cl，R
3、R
5、R
7均为H，R
8均为Cl；
化合物II-87：在式(I)中，R
1为环丙基，R
2为甲基，R
4、R
5和R
6均为F，R
3、R
7均为H，R
8均为Cl；
化合物II-88：在式(I)中，R
1为环丙基，R
2为甲基，R
4、R
5和R
6均为Cl，R
3、R
7 均为H，R
8均为Cl；
化合物II-89：在式(I)中，R
1为甲氧基，R
2为甲基，R
3、R
4、R
5、R
6、R
7均为H，R
8均为Cl；
化合物II-90：在式(I)中，R
1为甲氧基，R
2为甲基，R
4为F，R
3、R
5、R
6、R
7均为H，R
8均为Cl；
化合物II-91：在式(I)中，R
1为甲氧基，R
2为甲基，R
4为Cl，R
3、R
5、R
6、R
7均为H，R
8均为Cl；
化合物II-92：在式(I)中，R
1为甲氧基，R
2为甲基，R
4为甲基，R
3、R
5、R
6、R
7均为H，R
8均为Cl；
化合物II-93：在式(I)中，R
1为甲氧基，R
2为甲基，R
4为乙基，R
3、R
5、R
6、R
7均为H，R
8均为Cl；
化合物II-94：在式(I)中，R
1为甲氧基，R
2为甲基，R
4为氰基，R
3、R
5、R
6、R
7均为H，R
8均为Cl；
化合物II-95：在式(I)中，R
1为甲氧基，R
2为甲基，R
4为甲氧基，R
3、R
5、R
6、R
7均为H，R
8均为Cl；
化合物II-96：在式(I)中，R
1为甲氧基，R
2为甲基，R
4为异丙基，R
3、R
5、R
6、R
7均为H，R
8均为Cl；
化合物II-97：在式(I)中，R
1为甲氧基，R
2为甲基，R
4为叔丁基，R
3、R
5、R
6、R
7均为H，R
8均为Cl；
化合物II-98：在式(I)中，R
1为甲氧基，R
2为甲基，R
4为-CF
3，R
3、R
5、R
6、R
7均为H，R
8均为Cl；
化合物II-99：在式(I)中，R
1为甲氧基，R
2为甲基，R
4为-OCF
3，R
3、R
5、R
6、R
7均为H，R
8均为Cl；
化合物II-100：在式(I)中，R
1为甲氧基，R
2为甲基，R
5为F、R
3、R
4、R
6、R
7均为H，R
8均为Cl；
化合物II-101：在式(I)中，R
1为甲氧基，R
2为甲基，R
5为Cl，R
3、R
4、R
6、R
7均为H，R
8均为Cl；
化合物II-102：在式(I)中，R
1为甲氧基，R
2为甲基，R
5为甲基，R
3、R
4、R
6、R
7均为H，R
8均为Cl；
化合物II-103：在式(I)中，R
1为甲氧基，R
2为甲基，R
5为氰基，R
3、R
4、R
6、R
7均为H，R
8均为Cl；
化合物II-104：在式(I)中，R
1为甲氧基，R
2为甲基，R
5为甲氧基，R
3、R
4、R
6、R
7均为H，R
8均为Cl；
化合物II-105：在式(I)中，R
1为甲氧基，R
2为甲基，R
5为异丙基，R
3、R
4、R
6、R
7均为H，R
8均为Cl；
化合物II-106：在式(I)中，R
1为甲氧基，R
2为甲基，R
5为叔丁基，R
3、R
4、R
6、R
7均为H，R
8均为Cl；
化合物II-107：在式(I)中，R
1为甲氧基，R
2为甲基，R
5为-CF
3，R
3、R
4、R
6、R
7均为H，R
8均为Cl；
化合物II-108：在式(I)中，R
1为甲氧基，R
2为甲基，R
5为-OCF
3，R
3、R
4、R
6、R
7均为H，R
8均为Cl；
化合物II-109：在式(I)中，R
1为甲氧基，R
2为甲基，R
4和R
5均为甲基，R
3、R
6、R
7均为H，R
8均为Cl；
化合物II-110：在式(I)中，R
1为甲氧基，R
2为甲基，R
4和R
5均为F，R
3、R
6、R
7均为H，R
8均为Cl；
化合物II-111：在式(I)中，R
1为甲氧基，R
2为甲基，R
4和R
5均为Cl，R
3、R
6、R
7均为H，R
8均为Cl；
化合物II-112：在式(I)中，R
1为甲氧基，R
2为甲基，R
4和R
6均为甲基，R
3、R
5、R
7均为H，R
8均为Cl；
化合物II-113：在式(I)中，R
1为甲氧基，R
2为甲基，R
4为F，R
6为Cl，R
3、R
5、R
7均为H，R
8均为Cl；
化合物II-114：在式(I)中，R
1为甲氧基，R
2为甲基，R
4为Cl，R
6为F，R
3、R
5、R
7均为H，R
8均为Cl；
化合物II-115：在式(I)中，R
1为甲氧基，R
2为甲基，R
4和R
6均为Cl，R
3、R
5、R
7均为H，R
8均为Cl；
化合物II-116：在式(I)中，R
1为甲氧基，R
2为甲基，R
4、R
5和R
6均为F，R
3、R
7均为H，R
8均为Cl；
化合物II-117：在式(I)中，R
1为甲氧基，R
2为甲基，R
4、R
5和R
6均为Cl，R
3、R
7均为H，R
8均为Cl。
本发明中对所述式(I)所示的化合物的立体结构没有特别限制，所述式(I)所示的化合物可以以不同的立体异构体或光学异构体或互变异构的形式存在，本发明包含所有立体异构体或光学异构体或互变异构及其各种比例的混合物。
本发明公开化合物的任何不对称原子(例如，碳等)均可以以外消旋或对映体富集的形式存在，例如(R)-、(S)-或(R,S)-构型形式存在。
本发明对制备所述含突烯片段的三唑磺酰胺类衍生物的方法没有特别的限制，本领域技术人员可以通过结构式的特征，结合有机合成领域内的已知方法制备获得，但是，为了更高收率地获得本发明所述的含突烯片段的三唑磺酰胺类衍生物，本发明提供如下第二方面所述的方法制备含突烯片段的三唑磺酰胺类衍生物。
具体地，如前所述，本发明的第二方面提供了一种制备第一方面所述的含突烯片段的三唑磺酰胺类衍生物的方法，该方法包括将式(II)所示的化合物与式(III)所示的化合物进行接触反应；
其中，R
9和R
10中一者为卤素，另一者为-NHR
1，
R
1、R
2、R
3、R
4、R
5、R
6、R
7、R
8的定义与第一方面所述的定义对应相同。
优选地，所述接触的条件至少满足：温度为5-45℃，时间为20-60min。
优选地，所述式(II)所示的化合物与式(III)所示的化合物的用量摩尔比为(0.5-3)：1。
如前所述，本发明的第三方面提供了前述含突烯片段的三唑磺酰胺类衍生物作为细胞色素bc
1复合物Q
i位点抑制剂的应用。
如前所述，本发明的第四方面提供了前述含突烯片段的三唑磺酰胺类衍生物在抗植物真菌病中的应用。
优选地，所述植物包括但不限于黄瓜、大豆、小麦、番茄、马铃薯、茄子、玉米、水稻、南瓜、柑桔、葡萄。
特别优选地，所述植物真菌病包括但不限于霜霉病、霜疫霉病、疫病、晚疫病。
优选地，所述植物真菌病包括但不限于黄瓜霜霉病、大豆疫霉病、番茄晚疫病、马铃薯晚疫病、茄子霜霉病、柑桔脚腐病、南瓜疫病、葡萄霜霉病。
如前所述，本发明的第五方面提供了一种杀菌剂，该杀菌剂的活性成分为前述含突烯片段的三唑磺酰胺类衍生物中的至少一种，以所述杀菌剂的总重量计，所述活性成分的含量为0.1-100重量％。
优选情况下，所述活性成分的含量为1-98重量％。
更优选地，所述活性成分的含量为5-90重量％。
优选地，所述杀菌剂的剂型选自水合剂、粉剂、乳剂、悬浮剂、乳油剂和粒剂。
如前所述，本发明的第六方面提供了第五方面所述的杀菌剂在抗植物真菌病中的应用。
以下将通过实例对本发明进行详细描述。以下实例中，在没有特别说明的情况下，使用的各种原料均为市售品。
在没有特别说明的情况下，以下所述的室温或常温均表示25±1℃。
制备例1：
该制备例用来说明式(II-1)所示的化合物的合成：
步骤a：在冰浴下将式1-3所示的化合物(10mmol)，加入到溶有式1-2所示的化合物(10mmol)的超干THF(10mL)溶液中，加完后撤冰浴，于室温下反应5min，再继续在冰浴下加入式1-1所示的化合物(5mmol)，加完后撤冰浴，于室温下反应10min，TLC监测反应完全后，加水猝灭，乙酸乙酯萃取，拌样(45℃以下)，柱层析(纯石油醚为洗脱剂)，旋出洗脱剂(45℃以下)，即得式1-4所示的化合物。
步骤b：提前将温度预热到100℃，然后将NBS(6mmol)加入到溶有式1-4所示的化合物(5mmol)的THF(10mL)溶液中，接着加入对甲苯磺酸(1.2mmol)，回流25min，TLC监测反应完全后，加水猝灭，然后用乙酸乙酯萃取，无水Na
2SO
4干燥，旋出溶剂，即得式1-5所示的化合物。
步骤c：冰浴下将环丙胺(11mmol)加入到溶有式1-5所示的化合物(5mmol)的乙腈溶液(10mL)中，再加入碳酸钾(15mmol)，室温下反应10min，TLC监测反应完全后直接拌样，柱层析，然后旋出洗脱剂，即得式(II-1)所示的化合物。
制备例2：
该制备例用来说明式(III-1)所示的化合物的合成：
步骤a：将5.05g式2-1所示的化合物溶于25.0mL重蒸的CH
2Cl
2中，继续加入3.95g重蒸的吡啶，在冰浴的条件下滴加4.4g重蒸的苯磺酰氯，1小时滴加完毕后，移去冰浴，在常温条件下反应16小时，然后蒸去CH
2Cl
2，接着加入25mL乙醇，反应1小时，过滤得固体，然后依次用10mL水和10mL乙醇清洗，真空干燥(65℃)，即得式2-2所示的化合物。
步骤b：将4.68g式2-2所示的化合物溶于50mL重蒸的DMF，与7.8g无水碳酸钾的溶液混合搅拌1小时后，冰浴下加入7.0g的N,N-二甲基磺酰氯，反应完全后，依次加入水、CH
2Cl
2萃取，脱干，得到无色油状物，加入少量甲醇，即析出大量白色固体，抽滤干燥，即得到式2-3所示的化合物。
步骤c：将829mg的式2-3所示结构的化合物溶于10mL的1,2-二氯乙烷中，加入20mL水，冰浴下加入10mL乙酸，然后连续通入氯气20min，TLC检测反应完全后，用CH
2Cl
2萃取，无水硫酸钠干燥，旋出溶剂，即得式(III-1)所示的化合物。
制备例3：
该制备例用来说明式(I-1)所示的化合物的合成：
向50mL梨形瓶中加入1.1mmol式(II-1)所示的化合物，然后加入10mL超干四氢呋喃溶解，接着加入三乙胺(0.2mL，1.5mmol)，最后加入式(III-1)所示的化合物(1mmol)，室温反应30min，TLC监测反应完全后，减压旋出溶剂，柱色谱层析即得式(I-1)所示的化合物。
采用制备例3所述的方法制备表1中所述的化合物，仅仅是原料取代基进行替换。
表1
以下列举前述获得的部分具体化合物的核磁数据：
白色粉末,mp＝87.6-88.2℃.
1H NMR(600MHz,DMSO-d
6)δ9.45(s,1H),7.47(d,J＝ 7.5Hz,2H),7.37(t,J＝7.4Hz,2H),7.33(d,J＝7.2Hz,1H),5.54(s,1H),5.34(s,1H),4.39(s,2H),2.99(s,6H),2.49–2.46(m,1H),0.73(s,2H),0.65(d,J＝6.7Hz,2H).HRMS(MALDI)理论值C
16H
21N
5O
4S
2(M+Na)
+:434.0927,实测值434.0933.
白色粉末,mp＝67.2-68.0℃.
1H NMR(600MHz,DMSO-d
6)δ9.42(s,1H),7.36(dt,J＝15.9,6.1Hz,2H),7.26–7.11(m,2H),5.53(s,1H),5.38(s,1H),4.31(s,2H),2.98(s,6H),2.09(s,1H),0.84–0.56(m,4H).HRMS(MALDI)理论值C
16H
20FN
5O
4S
2(M+H)
+:430.10135,实测值430.10100.
白色粉末,mp＝76.2-77.0℃.
1H NMR(600MHz,DMSO-d
6)δ9.41(s,1H),7.52–7.43(m,1H),7.41–7.30(m,2H),7.26(d,J＝6.5Hz,1H),5.53(s,1H),5.21(s,1H),4.26(s,2H),2.97(s,6H),2.64–2.55(m,1H),0.77(s,2H),0.68(d,J＝6.3Hz,2H).HRMS(MALDI)理论值C
16H
20ClN
5O
4S
2(M+Na)
+:468.05374,实测值468.05359.
白色粉末,mp＝85.4-86.2℃.
1H NMR(600MHz,DMSO-d
6)δ9.41(s,1H),7.29–7.13(m,3H),7.08(d,J＝7.3Hz,1H),5.41(s,1H),5.05(s,1H),4.12(s,2H),2.96(s,6H),2.66–2.58(m,1H),2.27(s,3H),0.85–0.63(m,4H).HRMS(MALDI)理论值C
17H
23N
5O
4S
2(M+H)
+:426.12642,实测值426.12626.
白色粉末,mp＝80.4-81.2℃.
1H NMR(600MHz,DMSO-d
6)δ9.38(s,1H),7.29(t,J＝8.0Hz,1H),7.08(d,J＝7.2Hz,1H),6.98(d,J＝8.3Hz,1H),6.92(q,J＝8.4,7.5Hz,1H),5.34(s, 1H),5.15(s,1H),4.29(s,2H),3.76(s,3H),2.96(d,J＝2.7Hz,6H),2.08(s,1H),0.74(d,J＝3.5Hz,2H),0.64(d,J＝7.0Hz,2H).HRMS(MALDI)理论值C
17H
23N
5O
5S
2(M+H)
+:442.12134,实测值442.12122.
黄色粉末,mp＝99.0-99.9℃.
1H NMR(600MHz,DMSO-d
6)δ9.43(s,1H),7.77(d,J＝7.9Hz,1H),7.69(t,J＝7.6Hz,1H),7.57(t,J＝7.8Hz,1H),7.34(d,J＝7.6Hz,1H),5.49(s,1H),5.13(s,1H),4.14(s,2H),2.96(s,6H),2.76–2.62(m,1H),0.85–0.66(m,4H).HRMS(MALDI)理论值C
17H
20F
3N
5O
4S
2(M+Na)
+:502.08010,实测值502.08085.
白色粉末,mp＝78.4-79.3℃.
1H NMR(600MHz,DMSO-d
6)δ9.42(s,1H),7.48(t,J＝7.6Hz,1H),7.45–7.33(m,3H),5.54(s,1H),5.29(s,1H),4.24(s,2H),2.97(s,6H),2.58(td,J＝7.0,3.6Hz,1H),0.77(p,J＝4.7Hz,2H),0.71–0.64(m,2H).HRMS(MALDI)理论值C
17H
20F
3N
5O
5S
2(M+Na)
+:518.07502,实测值518.07548.
黄色粉末,mp＝95.8-96.5℃.
1H NMR(600MHz,DMSO-d
6)δ9.46(s,1H),7.41(d,J＝7.4Hz,1H),7.32(d,J＝9.2Hz,2H)7.16(t,J＝8.5Hz,1H),5.63(s,1H),5.41(s,1H),4.38(s,2H),2.99(s,6H),2.47(dt,J＝6.6,3.2Hz,1H),0.75–0.61(m,4H).HRMS(MALDI)理论值C16H20FN5O4S2(M+H)+:430.1014,实测值430.1028.
黄色粉末,mp＝111.2-112.0℃.
1H NMR(600MHz,DMSO-d
6)δ9.46(s,1H),7.54(s,1H),7.42(dd,J＝27.0,5.5Hz,3H),5.62(s,1H),5.41(s,1H),4.38(s,2H),2.99(s,6H),2.47(s,1H),0.82–0.59(m,4H).HRMS(MALDI)理论值C
16H
20ClN
5O
4S
2(M+H)
+:446.0718,实测值446.07135.
白色粉末,mp＝94.0-94.3℃.
1H NMR(600MHz,DMSO-d
6)δ9.46(s,1H),7.26(d,J＝19.4Hz,3H),7.14(s,1H),5.51(s,1H),5.31(s,1H),4.36(s,2H),2.99(s,6H),2.31(s,3H),2.09(s,1H),0.73(d,J＝3.2Hz,2H),0.65(d,J＝5.2Hz,2H).HRMS(MALDI)理论值C
17H
23N
5O
4S
2(M+H)
+:426.1264,实测值426.1272.
白色粉末,mp＝102.5-103.0℃.
1H NMR(600MHz,DMSO-d
6)δ9.46(s,1H),7.28(t,J＝7.8Hz,1H),7.09–6.98(m,2H),6.90(d,J＝7.9Hz,1H),5.56(s,1H),5.34(s,1H),4.38(s,2H),3.77(s,3H),2.99(d,J＝3.2Hz,6H),2.47(q,J＝3.7Hz,1H),0.80–0.57(m,4H).HRMS(MALDI)理论值C
17H
23N
5O
5S
2(M+H)
+:442.12134,实测值442.12114.
黄色粉末,mp＝131.3-131.8℃.
1H NMR(600MHz,DMSO-d
6)δ9.46(s,1H),7.83–7.78(m,2H),7.70(d,J＝7.8Hz,1H),7.62(t,J＝7.8Hz,1H),5.68(s,1H),5.47(s,1H),4.45(s,2H),2.99(s,6H),2.48–2.44(m,1H),0.71(s,2H),0.66(d,J＝6.8Hz,2H).HRMS(MALDI)理论值C
17H
20F
3N
5O
4S
2(M+H)
+:480.0982,实测值480.1008.
白色粉末,mp＝85.9-86.5℃.
1H NMR(600MHz,DMSO-d
6)δ9.47(s,1H),7.52(d,J＝6.3Hz,2H),7.47(s,1H),7.34(d,J＝6.6Hz,1H),5.66(s,1H),5.45(s,1H),4.41(s,2H),2.99(s,6H),2.47(s,1H),0.76–0.61(m,4H).HRMS(MALDI)理论值C
17H
20F
3N
5O
5S
2(M+Na)
+:518.07502,实测值518.07522.
白色粉末,mp＝101.1-101.9℃.
1H NMR(600MHz,DMSO-d
6)δ9.45(s,1H),7.59–7.46(m,2H),7.20(t,J＝8.6Hz,2H),5.52(s,1H),5.34(s,1H),4.37(s,2H),2.99(s,6H),2.50–2.42(m,1H),0.72(s,2H),0.65(d,J＝5.7Hz,2H).HRMS(MALDI)理论值C
16H
20FN
5O
4S
2(M+H)
+:430.10135,实测值430.10136.
白色粉末,mp＝128.1-128.7℃.
1H NMR(600MHz,DMSO-d
6)δ9.46(s,1H),7.50(d,J＝8.1Hz,2H),7.43(d,J＝8.2Hz,2H),5.57(s,1H),5.38(s,1H),4.38(s,2H),2.99(s,6H),2.46(s,1H),0.71(s,2H),0.65(d,J＝6.1Hz,2H).HRMS(MALDI)理论值C
16H
20ClN
5O
4S
2(M+H)
+:446.0718,实测值446.0733.
白色粉末,mp＝106.8-107.5℃.1H NMR(600MHz,DMSO-d6)δ9.44(s,1H),7.35(d,J＝7.9Hz,2H),7.16(d,J＝7.8Hz,2H),5.48(s,1H),5.28(s,1H),4.36(s,2H),2.98(s,6H),2.46(tt,J＝7.1,3.7Hz,1H),2.30(s,3H),0.72(q,J＝3.9Hz,2H),0.64(dd,J＝7.6,5.3Hz,2H).HRMS(MALDI)理论值C
17H
23N
5O
4S
2(M+H)
+:426.12642,实测值426.12641.
白色粉末,mp＝139.5-140.1℃.
1H NMR(600MHz,DMSO-d
6)δ9.45(s,1H),7.84(d,J＝8.0Hz,2H),7.67(d,J＝8.0Hz,2H),5.71(s,1H),5.52(s,1H),4.43(s,2H),2.98(s,6H),2.45(tt,J＝7.1,3.7Hz,1H),0.70(d,J＝3.8Hz,2H),0.65(d,J＝6.7Hz,2H).HRMS(MALDI)理论值C
17H
20N
6O
4S
2(M+H)
+:437.10602,实测值437.10527.
黄色粉末,mp＝118.5-119.4℃.
1H NMR(600MHz,DMSO-d
6)δ9.45(s,1H),7.41(d,J＝7.6Hz,2H),6.92(d,J＝7.3Hz,2H),5.44(s,1H),5.23(s,1H),4.35(s,2H),3.77(s,3H),2.99(s,6H),2.46(s,1H),0.77–0.57(m,4H).HRMS(MALDI)理论值C
17H
23N
5O
5S
2(M+H)
+:442.12134,实测值442.12111.
白色粉末,mp＝123.7-124.3℃.
1H NMR(600MHz,DMSO-d
6)δ9.45(s,1H),7.39(d,J＝8.0Hz,2H),7.23(d,J＝8.0Hz,2H),5.50(s,1H),5.29(s,1H),4.36(s,2H),2.99(s,6H),2.89(p,J＝6.7Hz,1H),2.50–2.45(m,1H),1.20(d,J＝6.9Hz,6H),0.77–0.70(m,2H),0.68–0.61(m,2H).HRMS(MALDI)理论值C
19H
27N
5O
4S
2(M+Na)
+:476.13967,实测值476.13960.
白色粉末,mp＝155.7-156.3℃.
1H NMR(600MHz,DMSO-d
6)δ9.45(s,1H),7.39(q,J＝8.2Hz,4H),5.51(s,1H),5.29(s,1H),4.37(s,2H),2.99(s,6H),2.48(s,1H),1.28(s,9H),0.73(s,2H),0.65(q,J＝6.6Hz,2H).HRMS(MALDI)理论值C
20H
29N
5O
4S
2(M+H)
+:468.17337,实测值468.17282.
黄色粉末,mp＝111.5-112.0℃.
1H NMR(600MHz,DMSO-d
6)δ9.46(s,1H),7.76–7.67(m,4H),5.68(s,1H),5.49(s,1H),4.44(s,2H),2.99(s,6H),2.49–2.44(m,1H),0.74–0.64(m,4H).HRMS(MALDI)理论值C
17H
20F
3N
5O
4S
2(M+H)
+:480.0972,实测值480.0975.
黄色粉末,mp＝106.7-107℃.
1H NMR(600MHz,DMSO-d
6)δ9.46(s,1H),7.60(d,J＝8.3Hz,2H),7.37(d,J＝8.3Hz,2H),5.59(s,1H),5.40(s,1H),4.39(s,2H),2.99(s,6H),2.48(s,1H),0.72(s,2H),0.66(d,J＝6.8Hz,2H).HRMS(MALDI)理论值C
17H
20F
3N
5O
5S
2(M+Na)
+:518.075,实测值518.0762.
白色粉末,mp＝91.8-92.7℃.
1H NMR(600MHz,DMSO-d
6)δ9.42(s,1H),7.15–7.02(m,2H),6.90(d,J＝7.5Hz,1H),5.39(s,1H),5.00(s,1H),4.08(s,2H),2.96(s,6H),2.71–2.58(m,1H),2.24(s,3H),2.16(s,3H),0.78(s,2H),0.75–0.64(m,2H).HRMS(MALDI)理论值C
18H
25N
5O
4S
2(M+Na)
+:462.12402,实测值462.12404.
白色粉末,mp＝76.8-77.6℃.
1H NMR(600MHz,DMSO-d
6)δ9.43(s,1H),7.40(q,J＝9.4,9.0Hz,1H),7.25–7.14(m,2H),5.61(s,1H),5.45(s,1H),4.32(s,2H),2.98(s,6H),2.48(s,1H),0.76(s,2H),0.68(d,J＝6.8Hz,2H).HRMS(MALDI)理论值C
16H
19F
2N
5O
4S
2(M+Na)
+:470.07387,实测值470.07381.
白色粉末,mp＝100.9-101.7℃.
1H NMR(600MHz,DMSO-d
6)δ9.41(s,1H),7.62(d,J＝8.0Hz,1H),7.38(t,J＝7.7Hz,1H),7.25(d,J＝7.5Hz,1H),5.57(s,1H),5.25(s,1H),4.26(s,2H),2.98(s,6H),2.61(s,1H),0.74(d,J＝45.1Hz,4H).HRMS(MALDI)理论值C
16H
19Cl
2N
5O
4S
2(M+H)
+:480.03283,实测值480.03282.
白色粉末,mp＝106.7-107.0℃.
1H NMR(600MHz,DMSO-d
6)δ9.38(s,1H),7.00(s,1H),6.94(s,2H),5.38(s,1H),4.99(s,1H),4.09(s,2H),2.94(s,6H),2.62–2.56(m,1H),2.23(d,J＝17.4Hz,6H),0.76(s,2H),0.70–0.65(m,2H).HRMS(MALDI)理论值C
18H
25N
5O
4S
2(M+H)
+:440.1421,实测值440.1410.
白色粉末,mp＝96.7-97.6℃.
1H NMR(600MHz,DMSO-d
6)δ9.43(s,1H),7.40(q,J＝8.2Hz,1H),7.26(t,J＝10.8Hz,1H),7.10(t,J＝7.4Hz,1H),5.55(s,1H),5.37(s,1H),4.29(s,2H),2.98(s,6H),2.48(s,1H)0.81–0.62(m,4H).HRMS(MALDI)理论值C
16H
19F
2N
5O
4S
2(M+Na)
+:470.07387,实测值470.07338.
白色粉末,mp＝112.4-113.2℃.
1H NMR(600MHz,DMSO-d
6)δ9.41(s,1H),7.48–7.33(m,2H),7.30(d,J＝8.3Hz,1H),5.56(s,1H),5.40(s,1H),4.29(s,2H),2.97(s,6H),2.50(s, 1H),0.73(s,2H),0.66(s,2H).HRMS(MALDI)理论值C
16H
19ClFN
5O
4S
2(M+H)
+:464.06238,实测值464.06258.
白色粉末,mp＝107.1-108.2℃.
1H NMR(400MHz,DMSO-d
6)δ9.40(s,1H),7.64(d,J＝2.1Hz,1H),7.45–7.42(m,1H),7.29(d,J＝8.3Hz,1H),5.57(s,1H),5.24(s,1H),4.24(s,2H),2.97(s,6H),2.59–2.55(m,1H),0.76(d,J＝2.9Hz,2H),0.68(d,J＝6.2Hz,2H).HRMS(MALDI)理论值C
16H
19Cl
2N
5O
4S
2(M+Na)
+:502.0148,实测值502.0154.
白色粉末,mp＝80.0-80.7℃.
1H NMR(600MHz,DMSO-d
6)δ9.42(s,1H),7.09(d,J＝7.7Hz,1H),7.01(d,J＝7.8Hz,1H),6.88(s,1H),5.39(s,1H),5.02(s,1H),4.10(s,2H),2.96(s,6H),2.63(s,1H),2.23(d,J＝21.3Hz,6H),0.84–0.66(m,4H).HRMS(MALDI)理论值C
18H
25N
5O
4S
2(M+Na)
+:462.12402,实测值462.12472.
白色粉末,mp＝108.7-109.3℃.
1H NMR(600MHz,DMSO-d
6)δ9.43(s,1H),7.25(d,J＝29.1Hz,3H),5.59(s,1H),5.46(s,1H),4.31(s,2H),2.98(s,6H),2.50(s,1H),0.75(s,2H),0.68(s,2H).HRMS(MALDI)理论值C
16H
19F
2N
5O
4S
2(M+H)
+:448.09193,实测值448.09135.
黄色粉末,mp＝160.1-160.7℃.
1H NMR(600MHz,DMSO-d
6)δ9.42(s,1H),7.52(d,J＝8.6Hz,1H),7.44(d,J＝8.5Hz,1H),7.36–7.30(m,1H),5.58(s,1H),5.28(s,1H),4.26(s,2H), 2.97(s,6H),2.59(dt,J＝7.0,3.3Hz,1H),0.82–0.66(m,4H).HRMS(MALDI)理论值C
16H
19Cl
2N
5O
4S
2(M+H)
+:480.03283,实测值480.03226.
白色粉末,mp＝85.2-86.1℃.
1H NMR(600MHz,DMSO-d
6)δ9.40(s,1H),7.43(q,J＝7.0,6.5Hz,1H),7.12(t,J＝7.9Hz,2H),5.74(s,1H),5.37(s,1H),4.21(s,2H),2.97(s,6H),2.63–2.54(m,1H),0.80(s,2H),0.69(t,J＝6.1Hz,2H).HRMS(MALDI)理论值C
16H
19F
2N
5O
4S
2(M+H)
+:448.09193,实测值448.09150.
白色粉末,mp＝90.3-91.0℃.
1H NMR(600MHz,DMSO-d
6)δ9.41(s,1H),7.45–7.33(m,1H),7.26(t,J＝8.4Hz,2H),5.77–5.67(m,2H),4.17(s,2H),2.97(s,6H),2.66(dt,J＝6.9,3.5Hz,1H),0.82(s,2H),0.70(d,J＝5.7Hz,2H).HRMS(MALDI)理论值C
16H
19ClFN
5O
4S
2(M+Na)
+:486.04432,实测值486.04418.
黄色粉末,mp＝110.5-111.2℃.
1H NMR(600MHz,DMSO-d
6)δ9.45(s,1H),7.24(s,1H),7.17(d,J＝7.8Hz,1H),7.11(d,J＝7.8Hz,1H),5.47(s,1H),5.26(s,1H),4.35(s,2H),2.98(s,6H),2.50–2.45(m,1H),2.22(d,J＝7.2Hz,6H),0.73(s,2H),0.65(d,J＝6.7Hz,2H).HRMS(MALDI)理论值C
18H
25N
5O
4S
2(M+Na)
+:462.12402,实测值462.12431.
白色粉末,mp＝113.5-114.0℃.
1H NMR(600MHz,DMSO-d
6)δ9.46(s,1H),7.57(t,J＝10.2Hz,1H),7.43(q,J＝9.1Hz,1H),7.33(s,1H),5.61(s,1H),5.40(s,1H),4.37(s,2H),2.98 (s,6H),2.48–2.44(m,1H),0.71(d,J＝3.5Hz,2H),0.65(d,J＝6.9Hz,2H).HRMS(MALDI)理论值C
16H
19F
2N
5O
4S
2(M+H)
+:448.09193,实测值448.09166.
白色粉末,mp＝131.9-132.4℃.
1H NMR(600MHz,DMSO-d
6)δ9.47(s,1H),7.70(t,J＝7.8Hz,1H),7.51(d,J＝9.9Hz,1H),7.29(d,J＝8.2Hz,1H),5.69(s,1H),5.45(s,1H),4.38(s,2H),2.98(s,6H),2.46(s,1H),0.76–0.58(m,4H).HRMS(MALDI)理论值C
16H
19BrFN
5O
4S
2(M+Na)
+:529.99381,实测值529.99360.
黄色粉末,mp＝137.7-138.3℃.
1H NMR(600MHz,DMSO-d
6)δ9.47(s,1H),7.37(d,J＝13.0Hz,1H),7.27(d,J＝8.4Hz,1H),7.15(t,J＝8.8Hz,1H),5.54(s,1H),5.30(s,1H),4.35(s,2H),3.85(s,3H),2.99(s,6H),2.46(tt,J＝7.0,3.6Hz,1H),0.71(d,J＝3.7Hz,2H),0.65(q,J＝6.9,6.5Hz,2H).HRMS(MALDI)理论值C
14H
17Br
2N
5O
5S
2(M+Na)
+:482.09386,实测值482.09341.
白色粉末,mp＝119.6-120.5℃.
1H NMR(600MHz,DMSO-d
6)δ9.47(s,1H),7.75(s,1H),7.64(d,J＝8.4Hz,1H),7.48(d,J＝8.1Hz,1H),5.67(s,1H),5.45(s,1H),4.39(s,2H),2.99(s,6H),2.48–2.44(m,1H),0.71(s,2H),0.65(d,J＝6.9Hz,2H).HRMS(MALDI)理论值C
16H
19Cl
2N
5O
4S
2(M+H)
+:480.0328,实测值480.0343.
白色粉末,mp＝130.1-130.6℃.
1H NMR(600MHz,DMSO-d
6)δ9.46(s,1H),7.06(s,2H),6.95(s,1H),5.48(s,1H),5.28(s,1H),4.34(s,2H),2.48(s,1H),2.99(s,6H),2.27(s,6H),0.74(s,2H),0.66(d,J＝6.2Hz,2H).HRMS(MALDI)理论值C
18H
25N
5O
4S
2(M+Na)
+:462.12402,实测值462.12390.
黄色粉末,mp＝130.1-130.6℃.
1H NMR(600MHz,DMSO-d
6)δ9.47(s,1H),7.22(dd,J＝21.5,8.7Hz,3H),5.73(s,1H),5.47(s,1H),4.38(s,2H),2.99(s,6H),2.47(d,J＝2.9Hz,1H),0.76–0.63(m,4H).HRMS(MALDI)理论值C
16H
19F
2N
5O
4S
2(M+Na)
+:470.07387,实测值470.07366.
白色固体,mp＝137.8-138.1℃.
1H NMR(600MHz,DMSO-d
6)δ9.47(s,1H),7.58–7.56(m,1H),7.54(t,J＝1.9Hz,2H),5.72(s,1H),5.47(s,1H),2.99(s,6H),2.46(s,1H),0.71(d,J＝3.8Hz,2H),0.68–0.60(m,2H).HRMS(MALDI)理论值C
16H
19Cl
2N
5O
4S
2(M+H)
+:480.08283,实测值480.03326.
黄色固体,mp＝148.2-149.0℃.
1H NMR(600MHz,DMSO-d
6)δ9.46(s,1H),8.16(s,2H),8.07(s,1H),5.87(s,1H),5.60(s,1H),4.51(s,2H),2.99(s,6H),2.48–2.43(m,1H),0.75–0.62(m,4H).HRMS(MALDI)理论值C
18H
19F
6N
5O
4S
2(M+H)
+:548.08554,实测值548.08530.
黄色固体,mp＝153.9-154.5℃.
1H NMR(600MHz,DMSO-d
6)δ9.48(s,1H),7.81(s,1H),7.71(s,2H),5.70(s,1H),5.46(s,1H),4.37(s,2H),2.99(s,6H),2.46(s,1H),0.78–0.58(m,4H).HRMS(MALDI)理论值C
16H
19Br
2N
5O
4S
2(M+H)
+:567.93180,实测值567.93110.
白色固体,mp＝90.9-91.6℃.
1H NMR(600MHz,DMSO-d
6)δ9.41(s,1H),7.72–7.64(m,1H),7.21–7.10(m,2H),5.56(s,1H),5.25(s,1H),4.26(s,2H),2.97(s,6H),2.66–2.57(m,1H),0.77(d,J＝3.8Hz,2H),0.70(d,J＝6.7Hz,2H).HRMS(MALDI)理论值C
16H
19BrFN
5O
4S
2(M+Na)
+:529.99381,实测值529.99400.
白色固体,mp＝100.4-101.2℃.
1H NMR(600MHz,DMSO-d
6)δ9.43(s,1H),7.58(t,J＝7.3Hz,1H),7.43–7.34(m,2H),5.52(s,1H),5.15(s,1H),4.13(s,2H),2.96(s,6H),2.72–2.62(m,1H),0.77(q,J＝4.1Hz,2H),0.71(q,J＝7.3,6.2Hz,2H).HRMS(MALDI)理论值C
17H
19F
4N
5O
4S
2(M+Na)
+:529.99381,实测值520.07070.
白色固体,mp＝132.9-133.6℃.
1H NMR(600MHz,DMSO-d
6)δ9.46(s,1H),7.91(s,1H),7.81(d,J＝8.1Hz,1H),7.74(d,J＝8.4Hz,1H),5.73(s,1H),5.51(s,1H),4.45(s,2H),2.99(s,6H),2.48–2.40(m,1H),0.74–0.62(m,4H).HRMS(MALDI)理论值C
17H
19ClF
3N
5O
4S
2(M+Na)
+:536.04113,实测值536.04125.
黄色固体,mp＝83.8-84.5℃.
1H NMR(600MHz,DMSO-d
6)δ9.41(s,1H),7.23(t,J＝8.7Hz,2H),5.75(s,1H),5.38(s,1H),4.19(s,2H),2.97(s,6H),2.59–2.53(m,1H),0.78(s,2H),0.74–0.61(m,2H).HRMS(MALDI)理论值C
16H
18F
3N
5O
4S
2(M+H)
+:466.08251,实测值466.08281.
白色固体,mp＝118.6-119.4℃.
1H NMR(600MHz,DMSO-d
6)δ9.42(s,1H),7.84(d,J＝6.4Hz,1H),7.42(d,J＝9.6Hz,1H),5.63(s,1H),5.32(s,1H),4.27(s,2H),2.97(s,6H),2.66–2.57(m,1H),0.79(t,J＝3.7Hz,2H),0.70(d,J＝6.4Hz,2H).HRMS(MALDI)理论值C
16H
18Cl
2FN
5O
4S
2(M+Na)
+:520.00535,实测值520.00575.
黄色固体,mp＝114.5-115.3℃.
1H NMR(600MHz,DMSO-d
6)δ9.47(s,1H),7.56–7.40(m,2H),5.70(s,1H),5.46(s,1H),4.36(s,2H),2.98(s,6H),2.48(s,1H),0.77–0.60(m,4H).HRMS(MALDI)理论值C
16H
18F
3N
5O
4S
2(M+H)
+:466.08251,实测值466.08226.
白色粉末,mp＝88.4-89.0℃.
1H NMR(600MHz,DMSO-d
6)δ9.57(s,1H),7.58(d,J＝7.4Hz,2H),7.43(t,J＝7.4Hz,2H),7.36(t,J＝7.4Hz,1H),5.69(s,1H),5.40(s,1H),4.39(s,2H),3.51(s,3H),3.01(s,6H).HRMS(MALDI)理论值C
14H
19N
5O
5S
2(M+H)
+:402.09,实测值402.0909.
白色粉末,mp＝75.2-76.1℃.
1H NMR(600MHz,DMSO-d
6)δ9.56(s,1H),7.54–7.36(m,2H),7.27(t,J＝9.6Hz,2H),5.61(s,1H),5.54(s,1H),4.36(s,2H),3.54(s,3H),3.00(s,6H).HRMS(MALDI)理论值C
14H
18FN
5O
5S
2(M+Na)
+:442.06256,实测值442.06213.
白色粉末,mp＝92.0-92.8℃.
1H NMR(600MHz,DMSO-d
6)δ9.54(s,1H),7.52(d,J＝7.1Hz,1H),7.42(d,J＝13.7Hz,3H),5.66(s,1H),5.39(s,1H),4.36(s,2H),3.66(s,3H),2.99(s,6H).HRMS(MALDI)理论值C
14H
18ClN
5O
5S
2(M+H)
+:436.05106,实测值436.05103.
黄色粉末,mp＝92.9-93.7℃.
1H NMR(600MHz,DMSO-d
6)δ9.53(s,1H),7.31–7.17(m,4H),5.58(s,1H),5.22(s,1H),4.25(s,2H),3.61(s,3H),2.98(s,6H),2.31(s,3H).HRMS(MALDI)理论值C
15H
21N
5O
5S
2(M+H)
+:416.10569,实测值416.10556.
白色粉末,mp＝71.8-72.6℃.
1H NMR(600MHz,DMSO-d
6)δ9.51(s,1H),7.79(d,J＝7.9Hz,1H),7.71(d,J＝7.7Hz,1H),7.60(d,J＝7.8Hz,1H),7.49(d,J＝7.8Hz,1H),5.69(s,1H),5.28(s,1H),4.19(s,2H),3.76(s,3H),2.97(s,6H).HRMS(MALDI)理论值C
15H
18F
3N
5O
5S
2(M+Na)
+:492.05937,实测值492.05913.
油,
1H NMR(600MHz,DMSO-d
6)δ9.55(s,1H),7.53(d,J＝7.9Hz,2H),7.45(q,J＝9.1,8.0Hz,2H),5.65(s,1H),5.46(s,1H),4.33(s,2H),3.58(s,3H),2.99(s,6H).HRMS(MALDI)理论值C
15H
18F
3N
5O
6S
2(M+H)
+:486.07234,实测值486.07262.
黄色粉末,mp＝67.4-68.2℃.
1H NMR(600MHz,DMSO-d
6)δ9.58(s,1H),7.48(q,J＝7.9Hz,1H),7.42(d,J＝13.4Hz,2H),7.21(t,J＝8.2Hz,1H),5.79(s,1H),5.48(s,1H),4.39(s,2H),3.52(s,3H),3.01(s,6H).HRMS(MALDI)理论值C
14H
18FN
5O
5S
2(M+H)
+:420.0806,实测值420.0800.
黄色粉末,mp＝63.8-64.6℃.
1H NMR(600MHz,DMSO-d
6)δ9.57(s,1H),7.64(s,1H),7.55(d,J＝7.7Hz,1H),7.50–7.41(m,2H),5.78(s,1H),5.47(s,1H),4.39(s,2H),3.52(s,3H),3.01(s,6H).HRMS(MALDI)理论值C
14H
18ClN
5O
5S
2(M+H)
+:436.05106,实测值436.05136.
黄色粉末,mp＝57.8-58.6℃.
1H NMR(600MHz,DMSO-d
6)δ9.56(s,1H),7.40–7.29(m,3H),7.17(d,J＝7.4Hz,1H),5.66(s,1H),5.37(s,1H),4.37(s,2H),3.52(s,3H),3.00(s,6H),2.34(s,3H).HRMS(MALDI)理论值C
15H
21N
5O
5S
2(M+H)
+:416.10569,实测值416.10573.
黄色粉末,mp＝82.9-83.6℃.
1H NMR(600MHz,DMSO-d
6)δ9.57(d,J＝3.1Hz,1H),7.34(t,J＝7.6Hz,1H),7.22–7.08(m,2H),6.94(d,J＝8.3Hz,1H),5.71(s,1H),5.40(s,1H),4.38(s,2H),3.79(s,3H),3.53(s,3H),3.01(s,6H).HRMS(MALDI)理论值C
15H
21N
5O
6S
2(M+H)
+:432.10060,实测值432.10032.
黄色粉末,mp＝75.1-75.7℃.
1H NMR(600MHz,DMSO-d
6)δ8.72(d,J＝2.2Hz,1H),7.82–7.74(m,2H),7.60(d,J＝7.9Hz,1H),7.53(t,J＝7.8Hz,1H),5.72(s,1H),5.48(s,1H),4.46(s,2H),3.10(s,6H).HRMS(MALDI)理论值C
15H
18F
3N
5O
5S
2(M+H)
+:470.0774,实测值470.0781.
油,
1H NMR(600MHz,DMSO-d
6)δ9.57(s,1H),7.68–7.52(m,3H),7.37(d,J＝8.2Hz,1H),5.81(s,1H),5.51(s,1H),4.41(s,2H),3.50(s,3H),3.01(s,6H).HRMS(MALDI)理论值C
15H
18F
3N
5O
6S
2(M+H)
+:486.07234,实测值486.07225.
白色粉末,mp＝125.2-125.7℃.
1H NMR(600MHz,DMSO-d
6)δ9.57(s,1H),7.60(d,J＝8.5Hz,2H),7.50(d,J＝8.5Hz,2H),5.73(s,1H),5.44(s,1H),4.39(s,2H),3.50(s,3H),3.01(s,6H).HRMS(MALDI)理论值C
14H
18ClN
5O
5S
2(M+H)
+:436.0511,实测值436.0521.
白色粉末,mp＝120.2-120.7℃.
1H NMR(600MHz,DMSO-d
6)δ9.56(s,1H),7.46(d,J＝7.8Hz,2H),7.23(d,J＝7.9Hz,2H),5.64(s,1H),5.33(s,1H),4.36(s,2H),3.50(s,3H),3.00(s,6H),2.32(s,3H).HRMS(MALDI)理论值C
15H
21N
5O
5S
2(M+H)
+:416.10569,实测值416.10601.
黄色粉末,mp＝87.1-88.0℃.
1H NMR(600MHz,DMSO-d
6)δ9.56(s,1H),7.52(d,J＝8.4Hz,2H),6.99(d,J＝8.4Hz,2H),5.59(s,1H),5.28(s,1H),4.35(s,2H),3.79(s,3H),3.50(s,3H),3.01(s,6H)HRMS(MALDI)理论值C
15H
21N
5O
6S
2(M+H)
+:432.10060,实测值432.10020.
黄色粉末,mp＝99.4-100.3℃.
1H NMR(600MHz,DMSO-d
6)δ9.57(s,1H),7.50(d,J＝6.8Hz,2H),7.30(d,J＝5.9Hz,2H),5.65(s,1H),5.35(s,1H),4.37(s,2H),3.52(s,3H),3.01(s,6H),1.22(d,J＝6.8Hz,7H).HRMS(MALDI)理论值C
17H
25N
5O
5S
2(M+H)
+:444.13699,实测值444.13633.
白色粉末,mp＝86.2-86.9℃.
1H NMR(600MHz,DMSO-d
6)δ9.56(s,1H),7.54–7.48(m,2H),7.44(d,J＝8.0Hz,2H),5.65(s,1H),5.35(s,1H),4.37(s,2H),3.53(s,3H),3.01(s,6H),1.30(s,9H).HRMS(MALDI)理论值C
18H
27N
5O
5S
2(M+H)
+:458.15264,实测值458.15205.
白色粉末,mp＝108.6-109.7℃.
1H NMR(600MHz,DMSO-d
6)δ9.58(s,1H),7.80(s,4H),5.84(s,1H),5.56(s,1H),4.45(s,2H),3.50(s,3H),3.01(s,6H).HRMS(MALDI)理论值C
15H
18F
3N
5O
5S
2(M+H)
+:470.0774,实测值470.0784.
白色粉末,mp＝60.9-61.6℃.
1H NMR(600MHz,DMSO-d
6)δ9.57(s,1H),7.71(d,J＝ 9.2Hz,2H),7.43(d,J＝8.5Hz,2H),5.74(s,1H),5.47(s,1H),4.41(s,2H),3.51(s,3H),3.01(s,6H).HRMS(MALDI)理论值C
15H
18F
3N
5O
6S
2(M+H)
+:486.0723,实测值486.0717.
白色粉末,mp＝145.8-146.9℃.
1H NMR(600MHz,DMSO-d
6)δ9.58(s,1H),7.91(d,J＝7.9Hz,2H),7.78(d,J＝7.9Hz,2H),5.87(s,1H),5.59(s,1H),4.43(s,2H),3.49(d,J＝2.0Hz,3H),3.00(d,J＝2.0Hz,6H).HRMS(MALDI)理论值C
15H
18N
6O
5S
2(M+H)
+:427.08529,实测值427.08452.
白色粉末,mp＝104.1-104.9℃.
1H NMR(600MHz,DMSO-d
6)δ9.56(s,1H),7.50–7.40(m,1H),7.38–7.25(m,2H),5.70(s,1H),5.61(s,1H),4.36(s,2H),3.55(s,3H),3.00(s,6H).HRMS(MALDI)理论值C
14H
17F
2N
5O
5S
2(M+Na)
+:460.05314,实测值460.05319.
白色粉末,mp＝74.8-75.6℃.
1H NMR(600MHz,DMSO-d
6)δ9.54(s,1H),7.67(d,J＝4.8Hz,1H),7.43(s,2H),5.70(s,1H),5.42(s,1H),4.35(s,2H),3.68(s,3H),2.99(s,6H).HRMS(MALDI)理论值C
14H
17Cl
2N
5O
5S
2(M+H)
+:470.01209,实测值470.01195.
白色粉末,mp＝80.3-81.0℃.
1H NMR(600MHz,DMSO-d
6)δ9.55(s,1H),7.60–7.49(m,2H),7.38(d,J＝8.4Hz,1H),5.65(s,1H),5.56(s,1H),4.35(s,2H),3.54(s,3H),3.00(s,6H).HRMS(MALDI)理论值C
14H
17ClFN
5O
5S
2(M+H)
+:454.04164,实测值454.04186.
黄色粉末,mp＝57.6-58.3℃.
1H NMR(600MHz,DMSO-d
6)δ9.53(s,1H),7.13(d,J＝7.6Hz,1H),7.05(d,J＝10.2Hz,2H),5.56(s,1H),5.19(s,1H),4.23(s,2H),3.62(s,3H),2.98(s,6H),2.26(d,J＝17.0Hz,6H).HRMS(MALDI)理论值C
16H
23N
5O
5S
2(M+Na)
+:452.10328,实测值452.10342.
白色粉末,84.2％,mp＝68.2-69.0℃.
1H NMR(600MHz,DMSO-d
6)δ9.56(s,1H),7.43–7.26(m,3H),5.67(s,1H),5.61(s,1H),4.36(s,2H),3.56(s,3H),3.00(s,6H).HRMS(MALDI)理论值C
14H
17F
2N
5O
5S
2(M+Na)
+:460.05314,实测值460.05324.
白色粉末,mp＝140.8-141.4℃.
1H NMR(600MHz,DMSO-d
6)δ9.55(s,1H),7.67–7.52(m,2H),7.52–7.42(m,1H),5.72(s,1H),5.46(s,1H),4.36(s,2H),3.67(s,3H),2.99(s,6H).HRMS(MALDI)理论值C
14H
17Cl
2N
5O
5S
2(M+H)
+:470.01209,实测值470.01228.
黄色粉末,mp＝97.7-98.5℃.
1H NMR(600MHz,DMSO-d
6)δ9.54(s,1H),7.55–7.41(m,1H),7.28–7.13(m,2H),5.83(s,1H),5.51(s,1H),4.27(s,2H),3.63(s,3H),2.99(s,6H).HRMS(MALDI)理论值C
14H
17F
2N
5O
5S
2(M+H)
+:438.07119,实测值438.07098.
白色粉末,mp＝116.6-117.4℃.
1H NMR(600MHz,DMSO-d
6)δ9.54(s,1H),7.50–7.39(m,2H),7.33(t,J＝8.6Hz,1H),5.87(s,1H),5.45(s,1H),4.27(s,2H),3.71(s,3H),2.98(s, 6H).HRMS(MALDI)理论值C
14H
17ClFN
5O
5S
2(M+H)
+:454.04164,实测值454.04121.
黄色粉末,mp＝112.2-112.8℃.
1H NMR(600MHz,DMSO-d
6)δ9.55(s,1H),7.74(t,J＝7.1Hz,1H),7.34(d,J＝9.2Hz,1H),7.22(t,J＝8.7Hz,1H),5.71(s,1H),5.42(s,1H),4.35(s,2H),3.70(s,3H),2.99(s,6H).HRMS(MALDI)理论值C
14H
17BrFN
5O
5S
2(M+Na)
+:519.97307,实测值519.97313.
白色粉末,mp＝119.1-110.2℃.
1H NMR(600MHz,DMSO-d
6)δ9.57(s,1H),7.67(dd,J＝12.1,8.4Hz,1H),7.51(q,J＝9.2Hz,1H),7.43(s,1H),5.75(s,1H),5.46(s,1H),4.38(s,2H),3.51(s,3H),3.00(s,6H).HRMS(MALDI)理论值C
14H
17F
2N
5O
5S
2(M+H)
+:438.07199,实测值438.07073.
白色粉末,mp＝111.4-112.2℃.
1H NMR(600MHz,DMSO-d
6)δ9.58(s,1H),8.02(s,1H),7.92(d,J＝8.2Hz,2H),7.81(d,J＝8.4Hz,1H),5.89(s,1H),5.57(s,1H),4.45(s,2H),3.51(s,3H),3.01(s,6H).HRMS(MALDI)理论值C
15H
17ClF
3N
5O
5S
2(M+H)
+:504.03845,实测值504.03888.
黄色粉末,mp＝138.6-139.4℃.
1H NMR(600MHz,DMSO-d
6)δ9.57(s,1H),7.46(d,J＝13.0Hz,1H),7.37(d,J＝7.9Hz,1H),7.22(t,J＝8.5Hz,1H),5.68(s,1H),5.34(s,1H),4.35(s,2H),3.87(s,3H),3.51(s,3H),3.01(s,6H).HRMS(MALDI)理论值C
15H
20FN
5O
6S
2(M+Na)
+: 472.07312,实测值472.07328.
黄色粉末,mp＝103.7-104.5℃.
1H NMR(600MHz,DMSO-d
6)δ9.58(s,1H),7.78(t,J＝8.0Hz,1H),7.61(dd,J＝10.6,2.1Hz,1H),7.43–7.36(m,1H),5.83(s,1H),5.51(s,1H),4.39(s,2H),3.51(s,3H),3.00(s,6H).HRMS(MALDI)理论值C
14H
17BrFN
5O
5S
2(M+H)
+:497.99113,实测值497.991
黄色粉末,mp＝95.0-96.1℃.
1H NMR(600MHz,DMSO-d
6)δ9.58(s,1H),7.85(s,1H),7.71(d,J＝8.3Hz,1H),7.58(d,J＝8.5Hz,1H),5.83(s,1H),5.51(s,1H),4.40(s,2H),3.52(s,3H),3.01(s,6H).HRMS(MALDI)理论值C
14H
17Cl
2N
5O
5S
2(M+H)
+:470.0721,实测值470.0721.
白色粉末,mp＝102.5-103.3℃.
1H NMR(600MHz,DMSO-d
6)δ9.58(s,1H),7.38–7.22(m,3H),5.87(s,1H),5.54(s,1H),4.39(s,2H),3.53(s,3H),3.01(s,6H).HRMS(MALDI)理论值C
14H
17F
2N
5O
5S
2(M+H)
+:438.07119,实测值438.07113.
黄色粉末,mp＝104.7-105.6℃.
1H NMR(600MHz,DMSO-d
6)δ9.55(s,1H),7.17(s,2H),6.99(s,1H),5.63(s,1H),5.35(s,1H),4.34(s,2H),3.53(s,3H),3.00(s,6H),2.29(s,6H).HRMS(MALDI)理论值C
16H
23N
5O
5S
2(M+H)
+:430.12134,实测值430.12183.
白色粉末,mp＝114.9-115.5℃.
1H NMR(600MHz,DMSO-d
6)δ9.58(s,1H),7.65(d,J＝2.0Hz,2H),7.61(s,1H),5.88(s,1H),5.54(s,1H),4.39(s,2H),3.53(s,3H),3.00(s,1H).HRMS(MALDI)理论值C
14H
17Cl
2N
5O
5S
2(M+H)
+:470.01209,实测值470.01055.
黄色粉末,mp＝118.1-118.9℃.
1H NMR(600MHz,DMSO-d
6)δ9.58(s,1H),7.84(s,1H),7.81(d,J＝1.7Hz,2H),5.86(s,1H),5.53(s,1H),4.38(s,2H),3.53(s,3H),3.01(s,6H).HRMS(MALDI)理论值C
14H
17Br
2N
5O
5S
2(M+H)
+:557.91106,实测值557.911
白色粉末,mp＝76.1-76.9℃.
1H NMR(600MHz,DMSO-d
6)δ9.55(s,1H),7.32(t,J＝8.9Hz,2H),5.84(s,1H),5.52(s,1H),4.24(s,2H),3.63(s,3H),2.99(s,6H).HRMS(MALDI)理论值C
14H
16F
3N
5O
5S
2(M+H)
+:456.06177,实测值456.06179.
白色粉末,mp＝102.9-103.7℃.
1H NMR(600MHz,DMSO-d
6)δ9.55(s,1H),7.91(d,J＝6.7Hz,1H),7.63(d,J＝9.7Hz,1H),5.76(s,1H),5.49(s,1H),4.37(s,2H),3.68(s,3H),3.00(s,6H).HRMS(MALDI)理论值C
14H
16Cl
2FN
5O
5S
2(M+H)
+:488.00267,实测值488.00365.
白色粉末,mp＝110.7-111.6℃.
1H NMR(600MHz,DMSO-d
6)δ9.58(s,1H),7.56(t,J＝ 8.2Hz,2H),5.83(s,1H),5.53(s,1H),4.39(s,2H),3.53(s,3H),3.01(s,6H).HRMS(MALDI)理论值C
14H
16F
3N
5O
5S
2(M+H)
+:456.06177,实测值456.06199.
白色粉末,mp＝121.5-122.0℃.
1H NMR(600MHz,DMSO-d
6)δ9.36(s,1H),7.27(p,J＝6.6Hz,1H),7.16(t,J＝7.3Hz,1H),7.12–7.07(m,2H),5.74(q,J＝7.0Hz,1H),4.38(s,2H),2.95(s,6H),2.25(tt,J＝7.2,3.5Hz,1H),1.85(d,J＝6.7Hz,4H),0.70–0.65(m,3H),0.56(d,J＝6.9Hz,3H).HRMS(MALDI)理论值C17H22FN5O4S2(M+H)
+:444.117,实测值444.11710.
白色粉末,mp＝92.3-93.1℃.
1H NMR(600MHz,DMSO-d
6)δ9.45(s,1H),7.35(q,J＝7.5Hz,1H),7.19(t,J＝9.1Hz,2H),7.09–7.05(m,1H),6.05(q,J＝7.0Hz,1H),4.48(s,2H),2.99(s,6H),2.22(dt,J＝7.0,3.5Hz,1H),1.87(d,J＝7.0Hz,3H),0.65(d,J＝3.5Hz,2H),0.60–0.55(m,2H).HRMS(MALDI)理论值C
17H
22FN
5O
4S
2(M+H)
+:444.1170,实测值444.11728.
白色粉末,mp＝96.4-97.2℃.
1H NMR(600MHz,DMSO-d
6)δ9.44(s,1H),7.41(s,1H),7.31(d,J＝10.1Hz,3H),6.01(q,J＝7.4,3.4Hz,1H),4.47(s,2H),2.99(s,6H),2.27–2.16(m,1H),1.87(d,J＝3.5Hz,3H),0.66(s,2H),0.58(s,2H).HRMS(MALDI)理论值C
17H
22ClN
5O
4S
2(M+H)
+:460.08745,实测值460.08739.
白色粉末,mp＝94.2-95.0℃.
1H NMR(600MHz,DMSO-d
6)δ9.43(s,1H),7.22–7.09(m, 3H),7.05(d,J＝7.1Hz,1H),5.92(q,J＝6.2,5.3Hz,1H),4.47(s,2H),2.99(s,6H),2.29(s,3H),2.24–2.16(m,1H),1.86(d,J＝4.9Hz,3H),0.67(s,2H),0.57(d,J＝6.8Hz,2H).HRMS(MALDI)理论值C
18H
25N
5O
4S
2(M+H)
+:440.14207,实测值440.14138.
白色粉末,mp＝58.4-59.3℃.
1H NMR(600MHz,DMSO-d
6)δ9.44(s,1H),6.92(t,J＝5.2Hz,2H),6.81(dd,J＝8.3,2.5Hz,1H),6.76–6.70(m,1H),5.99(q,J＝7.0Hz,1H),4.48(s,2H),3.75(s,3H),2.99(s,6H),2.21(dq,J＝6.9,3.5Hz,1H),1.86(d,J＝7.0Hz,3H),0.66(p,J＝5.3,4.4Hz,2H),0.57(dt,J＝6.9,3.5Hz,2H).HRMS(MALDI)理论值C
18H
25N
5O
5S
2(M+Na)
+:478.11893,实测值478.11893.
白色粉末,mp＝68.0-68.7℃.
1H NMR(600MHz,DMSO-d
6)δ9.43(s,1H),7.77–7.58(m,4H),6.06(q,J＝7.1Hz,1H),4.53(s,2H),2.99(s,6H),2.28–2.15(m,1H),1.89(d,J＝7.7Hz,3H),0.65(s,2H),0.58(s,2H).HRMS(MALDI)理论值C
18H
22F
3N
5O
4S
2(M+H)
+:494.11381,实测值494.11405.
白色粉末,mp＝109.0-109.5℃.
1H NMR(600MHz,DMSO-d
6)δ9.42(s,1H),7.42–7.32(m,2H),7.12(t,J＝8.9Hz,2H),5.91(q,J＝6.9Hz,1H),4.47(s,2H),2.99(s,6H),2.25–2.18(m,1H),1.86(d,J＝7.0Hz,3H),0.65(q,J＝4.3,3.8Hz,2H),0.57(q,J＝6.3,5.7Hz,2H).HRMS(MALDI)理论值C
17H
22FN
5O
4S
2(M+H)
+:444.11700,实测值444.11739.
白色粉末,mp＝109.2-109.9℃.
1H NMR(600MHz,DMSO-d
6)δ9.43(s,1H),7.36(s,4H),5.97(q,J＝9.3,8.0Hz,1H),4.47(s,2H),2.99(s,6H),2.26–2.15(m,1H),1.95–1.79(m,3H),0.65(s,2H),0.57(s,2H).HRMS(MALDI)理论值C
17H
22ClN
5O
4S
2(M+Na)
+:482.06939,实测值482.07012.
白色粉末,mp＝129.8-130.6℃.
1H NMR(600MHz,DMSO-d
6)δ9.41(s,1H),7.22(d,J＝4.0Hz,2H),7.10(d,J＝4.1Hz,2H),5.91(dd,J＝7.2,3.6Hz,1H),4.47(s,2H),2.98(s,6H),2.23(s,3H),1.86(d,J＝10.5Hz,3H),0.66(s,2H),0.62–0.48(m,3H).HRMS(MALDI)理论值C
18H
25N
5O
4S
2(M+H)
+:440.14207,实测值440.14201.
白色粉末,mp＝145.6-146.1℃.
1H NMR(600MHz,DMSO-d
6)δ9.43(s,1H),7.27(d,J＝8.4Hz,2H),6.86(d,J＝8.1Hz,2H),5.87(q,J＝7.1Hz,1H),4.45(s,2H),3.74(s,3H),2.99(s,6H),2.23–2.16(m,1H),1.84(d,J＝7.1Hz,3H),0.66(s,2H),0.56(d,J＝6.8Hz,2H).HRMS(MALDI)理论值C
18H
25N
5O
5S
2(M+H)
+:456.13699,实测值456.13682.
白色粉末,mp＝115.2-115.8℃.
1H NMR(600MHz,DMSO-d
6)δ9.38(s,1H),7.23(d,J＝8.0Hz,2H),7.10(d,J＝7.9Hz,2H),5.90(q,J＝7.0Hz,1H),4.45(s,2H),2.96(s,6H),2.56(q,J＝7.7Hz,2H),2.18(tt,J＝7.2,3.7Hz,1H),1.83(d,J＝7.0Hz,3H),1.15(t,J＝7.6Hz,3H),0.64(q,J＝4.4,3.9Hz,2H),0.54(t,J＝6.7Hz,2H).HRMS(MALDI)理论值C
19H
27N
5O
4S
2(M+H)
+:454.15772,实测值454.15753.
白色粉末,mp＝87.8-88.4℃.
1H NMR(600MHz,DMSO-d
6)δ9.42(s,1H),7.66(d,J＝8.2Hz,2H),7.57(d,J＝8.0Hz,2H),6.08(q,J＝7.0Hz,1H),4.53(s,2H),2.99(s,6H),2.27–2.18(m,1H),1.90(d,J＝7.0Hz,2H),0.67–0.63(m,2H),0.59(t,J＝5.9Hz,2H).HRMS(MALDI)理论值C
18H
22F
3N
5O
4S
2(M+Na)
+:516.09575,实测值516.09533.
白色粉末,mp<50℃.
1H NMR(600MHz,DMSO-d
6)δ9.39(s,1H),7.24(p,J＝8.8,7.6Hz,3H),5.97(q,J＝6.9Hz,1H),4.37(s,2H),2.98(s,6H),2.36–2.28(m,1H),1.87(d,J＝7.1Hz,3H),0.77–0.67(m,4H).HRMS(MALDI)理论值C
17H
21F
2N
5O
4S
2(M+H)
+:462.10758,实测值462.10731.
白色粉末,mp＝74.1-74.9℃.
1H NMR(600MHz,DMSO-d
6)δ9.45(d,J＝2.1Hz,1H),7.40(s,1H),7.35(t,J＝8.9Hz,1H),7.19(t,J＝6.0Hz,1H),6.00(q,J＝7.1Hz,1H),4.46(s,2H),2.99(s,6H),2.24(dp,J＝7.6,3.6Hz,1H),1.86(d,J＝7.1Hz,3H),0.67–0.64(m,2H),0.58(d,J＝6.8Hz,2H).HRMS(MALDI)理论值C
17H
21F
2N
5O
4S
2(M+H)
+:462.10758,实测值462.10725.
白色粉末,mp＝96.1-96.9℃.
1H NMR(600MHz,DMSO-d
6)δ9.44(s,1H),7.63–7.59(m,1H),7.56(d,J＝8.4Hz,1H),7.39–7.32(m,1H),6.05(q,J＝7.0Hz,1H),4.47(s,2H),3.33(s,3H),2.99(s,7H),2.28–2.19(m,1H),1.87(d,J＝7.1Hz,3H),0.66(s,2H),0.59(d,J＝6.6Hz, 2H).HRMS(MALDI)理论值C
17H
21Cl
2N
5O
4S
2(M+H)
+:494.04848,实测值494.04800.
白色粉末,mp＝87.7-88.3℃.
1H NMR(600MHz,DMSO-d
6)δ9.44(s,1H),8.04(s,6H),7.97(s,3H),6.21(q,J＝6.9Hz,3H),4.58(s,6H),2.99(s,8H),2.24(tt,J＝7.0,3.7Hz,3H),1.92(d,J＝7.0Hz,8H),0.65(d,J＝3.8Hz,5H),0.62–0.55(m,5H).HRMS(MALDI)理论值C
19H
21F
6N
5O
4S
2(M+Na)
+:584.08314,实测值584.08315.
白色粉末,mp＝95.0-96.1℃.
1H NMR(600MHz,DMSO-d
6)δ9.52(s,1H),7.37(t,J＝7.8Hz,1H),7.32(t,J＝6.8Hz,1H),7.19(dd,J＝9.3,5.0Hz,2H),5.99(q,J＝7.1Hz,1H),4.38(s,2H),3.51(s,3H),2.96(s,6H),1.79(d,J＝7.0Hz,3H).HRMS(MALDI)理论值C
15H
20FN
5O
5S
2(M+Na)
+:456.07821,实测值456.07845.
白色粉末,mp＝136.7-137.2℃.
1H NMR(600MHz,DMSO-d
6)δ9.48(s,1H),7.79(d,J＝7.9Hz,1H),7.73(t,J＝7.6Hz,2H),7.57(t,J＝7.7Hz,1H),7.36(d,J＝7.6Hz,1H),6.02(q,J＝6.8Hz,1H),4.38(s,2H),3.50(s,3H),2.94(s,6H),1.36(d,J＝6.7Hz,3H).HRMS(MALDI)理论值C
16H
20F
3N
5O
5S
2(M+Na)+:506.07502,实测值506.07499.
白色粉末,mp＝63.0-63.8℃.
1H NMR(600MHz,DMSO-d
6)δ9.57(s,1H),7.41(q,J＝7.4Hz,2H),7.32(t,J＝9.9Hz,1H),7.12(t,J＝8.7Hz,1H),6.31(q,J＝6.9Hz,1H),4.46(s,2H),3.51(s,3H),3.00(s,6H),1.81(d,J＝7.0Hz,3H).HRMS(MALDI)理论值 C
15H
20FN
5O
5S
2(M+H)
+:434.0963,实测值434.09621.
油状产物,
1H NMR(600MHz,DMSO-d
6)δ9.57(s,1H),7.53(s,1H),7.48–7.37(m,2H),7.35(d,J＝8.0Hz,1H),6.29(q,J＝7.9,7.4Hz,1H),4.46(s,2H),3.52(s,3H),3.00(s,6H),1.81(d,J＝6.7Hz,3H).HRMS(MALDI)理论值C
15H
20ClN
5O
5S
2(M+H)
+:450.06671,实测值450.06888.
白色粉末,mp＝95.0-96.1℃.
1H NMR(600MHz,DMSO-d
6)δ9.55(s,1H),7.27(t,J＝8.0Hz,1H),7.04(d,J＝7.8Hz,1H),7.01(s,1H),6.85(d,J＝8.8Hz,1H),6.23(q,J＝7.0Hz,1H),4.43(s,2H),3.75(s,3H),2.99(s,6H),2.07(s,3H),1.79(d,J＝6.9Hz,3H).HRMS(MALDI)理论值C
16H
23N
5O
6S
2(M+Na)
+:468.0982,实测值468.09775.
白色粉末,mp＝63.8-64.4℃.
1H NMR(600MHz,DMSO-d
6)δ9.57(s,1H),7.80(d,J＝8.2Hz,2H),7.64(s,2H),6.35(q,J＝6.2,5.7Hz,1H),4.51(s,2H),3.51(s,3H),3.01(s,6H),1.84(d,J＝6.2Hz,3H).HRMS(MALDI)理论值C
16H
20F
3N
5O
5S
2(M+H)
+:484.09307,实测值484.09298.
白色粉末,mp＝65.5-66.3℃.
1H NMR(600MHz,DMSO-d
6)δ9.56(s,1H),7.55–7.45(m,2H),7.23–7.15(m,2H),6.17(q,J＝6.8Hz,1H),4.45(s,2H),3.51(s,3H),3.00(s,6H),1.80(d,J＝6.9Hz,3H).HRMS(MALDI)理论值C
15H
20FN
5O
5S
2(M+H)
+:434.09626,实测值434.09586.
白色粉末,mp＝72.3-72.8℃.
1H NMR(600MHz,DMSO-d
6)δ9.56(s,1H),7.49(s,2H),7.43(d,J＝5.0Hz,2H),6.24(q,J＝6.4Hz,1H),4.46(s,2H),3.50(s,3H),3.00(s,6H),1.81(d,J＝6.4Hz,3H).HRMS(MALDI)理论值C
15H
20ClN
5O
5S
2(M+H)+:450.06671,实测值450.06901.
白色粉末,mp＝100.6-101.4℃.
1H NMR(600MHz,DMSO-d
6)δ9.56(s,1H),7.36(d,J＝7.9Hz,2H),7.17(d,J＝7.8Hz,2H),6.16(q,J＝6.9Hz,1H),4.44(s,2H),3.50(s,3H),3.00(s,6H),2.30(s,3H),1.79(d,J＝7.0Hz,6H).HRMS(MALDI)理论值C
16H
23N
5O5S
2(M+Na)
+:452.10328,实测值452.10312.
白色粉末,mp＝95.0-96.1℃.
1H NMR(600MHz,DMSO-d
6)δ9.56(s,1H),7.40(d,J＝8.2Hz,2H),6.93(d,J＝8.2Hz,2H),6.11(q,J＝7.0Hz,1H),4.43(s,2H),3.76(s,3H),3.50(s,3H),3.00(s,6H),1.78(d,J＝6.9Hz,3H).HRMS(MALDI)理论值C
16H
23N
5O
6S
2(M+H)
+:446.11625,实测值446.11593.
白色粉末,mp＝127.0-127.6℃.
1H NMR(600MHz,DMSO-d
6)δ9.56(d,J＝1.9Hz,1H),7.43–7.32(m,2H),7.20(d,J＝7.8Hz,2H),6.17(q,J＝7.0Hz,1H),4.44(s,2H),3.51(d,J＝1.7Hz,3H),3.00(d,J＝1.7Hz,6H),2.61(dq,J＝15.4,7.7Hz,2H),1.79(d,J＝7.1Hz,3H),1.28–1.11(m,3H).HRMS(MALDI)理论值C
17H
25N
5O
5S
2(M+H)
+:444.13699,实测值444.13628.
白色粉末,mp＝104.3-104.9℃.
1H NMR(600MHz,DMSO-d
6)δ9.57(s,1H),7.74(d,J＝8.2Hz,2H),7.70(d,J＝8.1Hz,2H),6.36(q,J＝7.0Hz,1H),4.51(s,2H),3.51(s,3H),3.00(s,6H),1.85(d,J＝7.0Hz,3H).HRMS(MALDI)理论值C
16H
20F
3N
5O
5S
2(M+H)
+:484.09307,实测值484.09307.
黄色粉末,mp＝59.6-60.3℃.
1H NMR(600MHz,DMSO-d
6)δ9.54(s,1H),7.55–7.39(m,2H),7.37–7.29(m,1H),6.01(t,J＝8.1Hz,1H),4.38(s,2H),3.61(s,3H),2.99(s,6H),1.81(d,J＝6.9Hz,3H).HRMS(MALDI)理论值C
15H
19F
2N
5O
5S
2(M+H)
+:452.08684,实测值452.08717.
黄色粉末,mp＝90.1-91.0℃.
1H NMR(600MHz,DMSO-d
6)δ9.57(s,1H),7.59–7.52(m,1H),7.44(q,J＝9.3Hz,1H),7.32(d,J＝8.7Hz,1H),6.26(q,J＝7.0Hz,1H),4.45(s,2H),3.51(s,3H),3.00(s,6H),1.80(d,J＝7.0Hz,3H).HRMS(MALDI)理论值C
15H
19F
2N
5O
5S
2(M+H)
+:452.0868,实测值452.08678.
白色粉末,mp＝95.6-96.3℃.
1H NMR(600MHz,DMSO-d
6)δ9.56(s,1H),7.76–7.72(m,1H),7.63(d,J＝8.4Hz,1H),7.51–7.45(m,1H),6.33(q,J＝6.9Hz,1H),4.46(s,2H),3.52(s,3H),3.00(s,6H),1.82(d,J＝7.0Hz,3H).HRMS(MALDI)理论值C
15H
19Cl
2N
5O
5S
2(M+H)
+:484.02774,实测值484.02804.
白色粉末,mp＝145.3-146.0℃.
1H NMR(600MHz,DMSO-d
6)δ9.54(s,1H),8.13(s,1H),8.04(s,1H),7.98(s,1H),6.50(q,J＝6.9Hz,1H),4.54(s,2H),3.48(s,3H),2.98(s,6H),1.84(d,J＝7.0Hz,3H).HRMS(MALDI)理论值C
17H
19F
6N
5O
5S
2(M+H)
+:552.08046,实测值552.08021
制备例4
该制备例用来说明式(IV-1)所示的化合物的合成：
步骤a:将原料1(30mmol)加入到250mL茄形瓶中，室温条件下，依次加入80mL超干二氯甲烷溶剂和Ph
3P(90mmol),反应15min后，再加入CCl
3Br(48mmol)，室温条件下反应2小时，TCL检测反应完成后，进行柱层析，减压脱去溶剂，得中间体2。
步骤b：提前将温度预热到100℃，然后将NBS(24mmol)加入到溶有中间体2(20mmol)的THF(40mL)溶液中，接着加入对甲苯磺酸(4.8mmol)，回流25min，TLC监测反应完全后，加水猝灭，然后用乙酸乙酯萃取，无水Na
2SO
4干燥，旋出溶剂，即得式(IV-1)所示的中间体。
制备例5
该制备例用来说明式(V-1)所示的化合物的合成：
将式(III-1)(20mmol)所示结构溶于超干THF(30mL)中，然后在冰浴下滴加环丙胺(30mmol)，室温条件下反应2小时，TCL检测反应完成后，用乙酸乙酯萃取，无水Na
2SO
4干燥，旋出溶剂，即得式(V-1)所示化合物。
制备例6
该制备例用来说明如下所示的化合物的合成：
向50mL梨形瓶中加入1.2mmol中间体式(IV-1)，加入10mL乙腈溶解，加入碳酸钾(1.5mmol)，最后加入中间体式(V-1)(1mmol)，室温反应30min，TLC监测反应完全后，减压旋出溶剂，柱层析即可得式(VI-1)所示目标化合物。
采用制备例6所示的方法制备表2中所示的具体化合物，仅仅是原料取代基进行替换。
表2
以下列举前述获得的部分具体化合物的核磁数据：
白色粉末,mp＝90.4-91.5℃.
1H NMR(600MHz,DMSO-d
6)δ9.44(s,1H),7.44–7.34(m,3H),7.31(d,J＝7.6Hz,2H),4.57(s,2H),2.98(s,6H),2.38-2.35(m,1H),0.55(d,J＝42.5Hz,4H).HRMS(MALDI)理论值C
16H
19Cl
2N
5O
4S
2(M+H)
+:480.0328,实测值480.0310.
白色粉末,mp＝133.5-134.1℃.
1H NMR(600MHz,DMSO-d
6)δ9.42(s,1H),7.46(p,J＝6.5,5.6Hz,1H),7.36(td,J＝7.6,1.7Hz,1H),7.27(q,J＝8.3,7.1Hz,2H),4.53(s,2H),2.98(s,6H),2.40-2.38(m,1H),0.71–0.57(m,4H).HRMS(MALDI)理论值C
16H
18Cl
2FN
5O
4S
2(M+H)
+:498.02341,实测值498.02237.
黄色粉末,mp＝98.0-98.8℃.
1H NMR(600MHz,DMSO-d
6)δ9.43(s,1H),7.50–7.40(m,1H),7.26–7.08(m,3H),4.55(s,2H),2.96(s,6H),2.34–2.28(m,1H),0.61(d,J＝5.4Hz,2H),0.53(s,2H).HRMS(MALDI)理论值C
16H
18Cl
2FN
5O
4S
2(M+Na)
+:520.0054,实测值520.0060.
白色粉末,mp＝117.8-118.2℃.
1H NMR(600MHz,DMSO-d
6)δ9.45(s,1H),7.44(d,J＝17.4Hz,3H),7.29(s,1H),4.57(s,2H),2.98(d,J＝2.3Hz,6H),2.33(s,1H),0.58(d,J＝48.2Hz,4H).HRMS(MALDI)理论值C
16H
18Cl
3N
5O
4S
2(M+H)
+:513.99386,实测值513.99298.
白色粉末,mp＝101.0-101.8℃.
1H NMR(600MHz,DMSO-d
6)δ9.46(s,1H),7.43–7.25(m,2H),7.18(d,J＝7.5Hz,1H),7.16–7.06(m,1H),4.56(s,2H),2.98(s,6H),2.34(d,J＝23.5Hz,3H),2.29–2.24(m,1H),0.56(dd,J＝38.6,5.2Hz,4H).HRMS(MALDI)理论值C
17H
21Cl
2N
5O
4S
2(M+Na)
+:516.0304,实测值516.0305.
黄色粉末,mp＝110.1-110.6℃.
1H NMR(600MHz,DMSO-d
6)δ9.46(s,1H),7.79–7.73(m,2H),7.71–7.63(m,2H),4.62(s,2H),2.99(s,6H),2.32(dt,J＝7.0,3.4Hz,1H),0.61(d,J＝5.8Hz,2H),0.50(s,2H).HRMS(MALDI)理论值C
17H
18Cl
2F
3N
5O
4S
2(M+H)
+:548.0202,实测值548.0199.
白色粉末,mp＝119.1-119.6℃.
1H NMR(600MHz,DMSO-d
6)δ9.45(s,1H),7.41–7.34(m,2H),7.27(t,J＝8.7Hz,2H),4.57(s,2H),2.98(s,6H),2.32(dt,J＝6.9,3.4Hz,1H),0.62(d,J＝5.6Hz,2H),0.55(s,2H).HRMS(MALDI)理论值C
16H
18Cl
2FN
5O
4S
2(M+H)
+:498.0234,实测值498.0265.
白色粉末，mp＝112.8-113.5℃.
1H NMR(600MHz,DMSO-d
6)δ9.44(s,1H),7.50(d,J＝7.3Hz,2H),7.36(d,J＝7.4Hz,2H),4.57(s,2H),2.98(s,6H),2.37–2.29(m,1H),0.64(d,J＝6.3Hz,2H),0.56(s,2H).HRMS(MALDI)理论值C
16H
18Cl
3N
5O
4S
2(M+Na)
+:535.9758,实测值535.9758.
黄色粉末,mp＝116.3-117.1℃.
1H NMR(600MHz,DMSO-d
6)δ9.42(s,1H),7.21(d,J＝8.1Hz,2H),7.18(d,J＝8.1Hz,1H),4.56(s,2H),2.98(s,6H),2.32(s,3H),2.30–2.25(m,1H),0.67–0.53(m,4H).HRMS(MALDI)理论值C
17H
21Cl
2N
5O
4S
2(M+H)
+:494.04848,实测值494.04800.
白色粉末,mp＝125.7-126.1℃.
1H NMR(600MHz,DMSO-d
6)δ9.72–9.11(m,1H),7.53–7.10(m,2H),6.96(d,J＝8.2Hz,2H),4.56(s,2H),3.78(d,J＝2.4Hz,3H),2.98(d,J＝2.3Hz,6H),2.28(s,1H),0.70–0.50(m,4H).HRMS(MALDI)理论值C
17H
21Cl
2N
5O
5S
2(M+H)
+:510.04339,实测值510.04409.
白色粉末,mp＝137.3-137.8℃.
1H NMR(600MHz,DMSO-d
6)δ9.43(s,1H),7.43(d,J＝ 8.2Hz,2H),7.24(d,J＝8.1Hz,2H),4.56(s,2H),2.98(s,6H),2.25(dd,J＝7.5,2.9Hz,1H),1.40(s,9H),0.58(d,J＝6.9Hz,2H),0.52(d,J＝3.8Hz,2H).HRMS(MALDI)理论值C
20H
27Cl
2N
5O
4S
2(M+H)
+:536.09543,实测值536.09518.
黄色粉末，mp＝112.8-113.5℃.
1H NMR(600MHz,DMSO-d
6)δ9.44(s,1H),7.81(d,J＝8.0Hz,2H),7.58(d,J＝7.9Hz,2H),4.60(s,2H),2.98(s,6H),2.36–2.31(m,1H),0.66–0.53(m,4H).HRMS(MALDI)理论值C
17H
18Cl
2F
3N
5O
4S
2(M+H)
+:548.0202,实测值548.0176.
黄色粉末,mp＝114.4-115.1℃.
1H NMR(600MHz,DMSO-d
6)δ9.45(s,1H),7.47(d,J＝8.7Hz,2H),7.43(d,J＝8.4Hz,2H),4.57(s,2H),2.98(s,6H),2.36–2.28(m,1H),0.64–0.50(m,4H).HRMS(MALDI)理论值C
17H
18Cl
2F
3N
5O
5S
2(M+H)
+:564.0151,实测值564.0126.
白色粉末,mp＝88.4-89.3℃.
1H NMR(600MHz,DMSO-d
6)δ9.45(s,1H),7.51(d,J＝10.0Hz,2H),7.20(d,J＝8.2Hz,1H),4.56(s,2H),2.98(s,6H),2.38(dt,J＝6.9,3.4Hz,1H),0.69–0.58(m,4H).HRMS(MALDI)理论值C
16H
17Cl
2F
2N
5O
4S
2(M+H)
+:516.0140,实测值516.0148.
黄色粉末,mp＝86.5-87.3℃.
1H NMR(600MHz,DMSO-d
6)δ9.43(s,1H),7.65(t,J＝7.5Hz,1H),7.38(t,J＝7.0Hz,1H),7.31(t,J＝7.9Hz,1H),4.52(d,J＝41.0Hz,2H),2.97(s,6H),2.45–2.40(m,1H),0.71–0.60(m,4H).HRMS(MALDI)理论值C
16H
17Cl
3FN
5O4S
2(M+Na)
+: 553.96638,实测值553.96931.
黄色粉末，mp＝73.9-74.5℃.
1H NMR(600MHz,DMSO-d
6)δ9.42(s,1H),7.45(q,J＝8.0Hz,1H),7.35(t,J＝9.5Hz,1H),7.18(dd,J＝9.3,6.6Hz,1H),4.51(s,2H),2.97(s,6H),2.41(s,1H),0.65(d,J＝9.9Hz,4H).HRMS(MALDI)理论值C
16H
17Cl
2F
2N
5O
4S
2(M+H)
+:516.01398,实测值516.01386.
白色粉末,mp＝100.3-100.9℃.
1H NMR(600MHz,DMSO-d
6)δ9.42(s,1H),7.55(dd,J＝9.9,2.1Hz,1H),7.44(t,J＝8.0Hz,1H),7.38(dd,J＝8.4,2.1Hz,1H),4.52(s,2H),2.97(d,J＝2.0Hz,6H),2.42(d,J＝7.0Hz,1H),0.71–0.58(m,4H).HRMS(MALDI)理论值C
16H
17Cl
3FN
5O
4S
2(M+H)
+:531.98443,实测值531.98510.
白色粉末,mp＝123.7-124.1℃.
1H NMR(600MHz,DMSO-d
6)δ9.43(s,1H),7.25–7.17(m,2H),7.10(d,J＝8.2Hz,1H),4.55(s,2H),3.87(s,3H),2.98(s,6H),2.40(s,1H),0.64(d,J＝6.9Hz,2H),0.59(s,2H).HRMS(MALDI)理论值C
17H
20Cl
2FN
5O
5S
2(M+Na)
+:550.01591,实测值550.01606.
黄色粉末,mp＝81.0-81.6℃.
1H NMR(600MHz,DMSO-d
6)δ9.43(t,J＝3.3Hz,1H),7.33(s,3H),4.53(s,2H),2.97(s,6H),2.50(s,1H),0.81–0.51(m,4H).HRMS(MALDI)理论值C
16H
17Cl
2F
2N
5O
4S
2(M+H)
+:516.01398,实测值516.01355.
白色粉末,mp＝81.9-82.8℃.
1H NMR(600MHz,DMSO-d
6)δ9.48(s,1H),7.34(d,J＝7.9Hz,1H),7.19–7.09(m,2H),4.52(s,2H),3.00(s,6H),2.30(s,1H),2.17(s,6H),0.62(d,J＝6.0Hz,4H).HRMS(MALDI)理论值C
18H
23Cl
2N
5O
4S
2(M+H)
+:508.06413,实测值508.06399.
白色粉末,mp＝88.4-89.3℃.
1H NMR(600MHz,DMSO-d
6)δ9.45(s,1H),7.51(d,J＝10.0Hz,2H),7.20(d,J＝8.2Hz,1H),4.56(s,2H),2.98(s,6H),2.38(dt,J＝6.9,3.4Hz,1H),0.69–0.58(m,4H).HRMS(MALDI)理论值C
16H
17Cl
2F
2N
5O
4S
2(M+H)
+:516.01398,实测值516.01380.
白色粉末,mp＝120.8-121.4℃.
1H NMR(600MHz,DMSO-d
6)δ9.43(s,1H),7.26–7.16(m,2H),7.10(d,J＝8.4Hz,1H),4.55(s,2H),3.87(s,3H),2.98(s,6H),2.32(td,J＝7.3,6.9,3.8Hz,1H),0.64(d,J＝7.0Hz,2H),0.61–0.57(m,2H).HRMS(MALDI)理论值C
17H
20Cl
2FN
5O
5S
2(M+Na)
+:550.01591,实测值550.01554.
白色粉末,mp＝109.9-110.8℃.
1H NMR(600MHz,DMSO-d
6)δ9.44(d,J＝1.6Hz,1H),7.61(dd,J＝7.0,2.2Hz,1H),7.49(t,J＝8.8Hz,1H),7.39–7.33(m,1H),4.56(s,2H),2.98(d,J＝1.7Hz,6H),2.37(td,J＝6.9,3.6Hz,1H),0.71–0.51(m,4H).HRMS(MALDI)理论值C
16H17Cl
3FN
5O
4S
2(M+H)
+:531.98443,实测值531.98363.
黄色粉末,mp＝127.3-128.1℃.
1H NMR(600MHz,DMSO-d
6)δ9.45(s,1H),7.74–7.65(m,2H),7.35(d,J＝8.2Hz,1H),4.57(s,2H),2.98(s,6H),2.38(td,J＝7.5,7.0,3.7Hz,1H),0.66(d,J＝5.4Hz,2H),0.60(s,2H).HRMS(MALDI)理论值C
16H
17Cl
4N
5O
4S
2(M+H)
+:547.9538,实测值547.9531.
白色粉末,mp＝73.8-74.6℃.
1H NMR(600MHz,DMSO-d6)δ9.45(s,1H),7.88(s,1H),7.83(s,1H),7.69(s,1H),4.61(s,2H),2.98(s,6H),2.09(s,1H),0.62(d,J＝53.9Hz,4H).HRMS(MALDI)理论值C
17H
17Cl
3F
3N
5O
4S
2(M+H)
+:581.98124,实测值581.98055.
白色粉末,mp＝106.1-106.7℃.
1H NMR(600MHz,DMSO-d
6)δ9.44(s,1H),6.98(s,1H),6.88(s,2H),4.54(s,2H),2.98(d,J＝3.6Hz,6H),2.30(s,1H),2.28(d,J＝3.7Hz,6H),0.56(d,J＝33.8Hz,4H).HRMS(MALDI)理论值C
18H
23Cl
2N
5O
4S
2(M+H)
+:508.06413,实测值508.06446.
白色粉末,mp＝112.2-112.7℃.
1H NMR(600MHz,DMSO-d
6)δ9.42(s,1H),7.27(t,J＝9.4Hz,1H),7.10(d,J＝7.2Hz,2H),4.53(s,2H),2.95(s,6H),2.38(s,1H),0.77–0.46(m,4H).HRMS(MALDI)理论值C
16H
17Cl
2F
2N
5O
4S
2(M+Na)
+:537.99593,实测值537.99751.
白色粉末,mp＝126.5-127.1℃.
1H NMR(600MHz,DMSO-d
6)δ9.45(s,1H),7.49(d,J＝8.6Hz,1H),7.31(s,1H),7.26(d,J＝9.2Hz,1H),4.56(s,2H),2.98(s,6H),2.40(td,J＝7.2,3.6Hz,1H),0.66(d,J＝6.7Hz,2H),0.60(d,J＝3.8Hz,2H).HRMS(MALDI)理论值C
16H
17Cl
3FN
5O
4S
2(M+H)
+:531.98443,实测值531.98366.
白色粉末,mp＝109.8-110.4℃.
1H NMR(600MHz,DMSO-d
6)δ9.45(s,1H),7.65(d,J＝2.0Hz,1H),7.44(d,J＝2.0Hz,2H),4.56(s,2H),2.98(s,6H),2.40(dd,J＝7.3,4.0Hz,1H),0.73–0.48(m,4H).HRMS(MALDI)理论值C
16H
17Cl
4N
5O
4S
2(M+H)
+:547.95488,实测值547.95584.
黄色粉末,mp＝58.9-59.2℃.
1H NMR(400MHz,DMSO-d
6)δ9.44(s,1H),8.18(s,1H),8.11(s,2H),4.65(s,2H),2.97(s,6H),2.40(s,1H),0.59(d,J＝44.3Hz,4H).HRMS(MALDI)理论值C
18H
17Cl
2F
6N
5O
4S
2(M+H)
+:616.0076,实测值616.00948.
白色粉末,mp＝78.7-79.4℃.
1H NMR(600MHz,DMSO-d
6)δ9.56(s,1H),7.44(d,J＝39.3Hz,5H),4.61(s,2H),3.58(s,3H),2.98(s,6H).HRMS(MALDI)理论值C
14H
17Cl
2N
5O
5S
2(M+Na)
+:491.994,实测值491.9915.
黄色粉末,mp＝101.3-102.1℃.
1H NMR(600MHz,DMSO-d
6)δ9.56(s,1H),7.56(s,1H),7.54(s,1H),7.50(dd,J＝13.4,6.2Hz,1H),7.37–7.29(m,1H),4.57(s,2H),3.60(s,3H),2.99(s,6H).HRMS(MALDI)理论值C
14H
16Cl
2FN
5O
5S
2(M+H)
+:488.00267,实测值488.00258.
油状物.
1H NMR(600MHz,DMSO-d
6)δ9.57(s,1H),7.53(d,J＝6.9Hz,1H),7.40(d,J＝9.9Hz,1H),7.34(d,J＝7.3Hz,1H),7.27(t,J＝8.1Hz,1H),4.62(s,2H),3.61(s,3H),2.99(s,6H).HRMS(MALDI)理论值C
14H
16Cl
2FN
5O
5S
2(M+H)
+:488.0037,实测值488.0051.
白色粉末,mp＝81.4-82.0℃.
1H NMR(600MHz,DMSO-d
6)δ9.56(s,1H),7.60(s,1H),7.49(q,J＝7.4Hz,2H),7.46(d,J＝7.2Hz,1H),4.61(s,2H),3.61(s,3H),2.99(s,6H).HRMS(MALDI)理论值C
14H
16Cl
3N
5O
5S
2(M+H)
+:503.97312,实测值503.97415.
油,
1H NMR(600MHz,DMSO-d
6)δ9.56(s,1H),7.35(t,J＝7.6Hz,1H),7.30–7.19(m,3H),4.58(s,2H),3.60(s,3H),2.99(s,6H),2.35(s,3H).HRMS(MALDI)理论值C
15H
19Cl
2N
5O
5S
2(M+Na)
+:506.0097,实测值506.0092.
黄色粉末,mp＝84.5-85.4℃.
1H NMR(600MHz,DMSO-d
6)δ9.57(s,1H),7.58–7.51(m,2H),7.32(t,J＝8.5Hz,2H),4.61(s,2H),3.60(s,3H),2.99(s,6H).HRMS(MALDI)理论值C
14H
16Cl
2FN
5O
5S
2(M+Na)
+:509.9846,实测值509.9848.
黄色粉末,mp＝105.5-106.6℃.
1H NMR(600MHz,DMSO-d
6)δ9.56(s,1H),7.59–7.48(m,4H),4.61(s,2H),3.61(s,3H),2.99(s,6H).HRMS(MALDI)理论值C
14H
16Cl
3N
5O
5S
2(M+H)
+:503.9731,实测值503.9744.
油.
1H NMR(600MHz,DMSO-d
6)δ9.55(s,1H),7.35(d,J＝7.7Hz,2H),7.27(d,J＝7.4Hz,2H),4.58(s,2H),3.59(s,3H),2.98(d,J＝3.4Hz,6H),2.33(s,3H).HRMS(MALDI)理论值C
15H
19Cl
2N
5O
5S
2(M+H)
+:484.02774,实测值484.02784.
油.
1H NMR(600MHz,DMSO-d
6)δ9.55(s,1H),7.40(d,J＝8.1Hz,2H),7.01(d,J＝8.4Hz,2H),4.59(s,2H),3.80(s,3H),3.58(s,3H),2.99(d,J＝4.0Hz,6H).HRMS(MALDI)理论值C
15H
19Cl
2N
5O
6S
2(M+H)
+:500.02266,实测值500.02386.
油.
1H NMR(600MHz,DMSO-d
6)δ9.55(s,1H),7.50–7.45(m,2H),7.40(dd,J＝8.4,1.8Hz,2H),4.58(s,2H),3.59(d,J＝1.7Hz,3H),2.98(d,J＝1.8Hz,6H),1.30(s,9H).HRMS(MALDI)理论值C
18H
25Cl
2N
5O
5S
2(M+H)
+:526.07469,实测值526.07504.
油.
1H NMR(600MHz,DMSO-d
6)δ9.57(s,1H),7.86(d,J＝8.1Hz,2H),7.74(d,J＝8.0Hz,2H),4.65(s,2H),3.62(s,3H),2.99(s,6H).HRMS(MALDI)理论值C
15H
16Cl
2F
3N
5O
5S
2(M+H)
+:537.9995,实测值538.0002.
油.
1H NMR(400MHz,DMSO-d
6)δ9.59(s,1H),7.58(q,J＝9.0Hz,1H),7.48–7.30(m,2H),4.62(s,2H),3.66(s,3H),2.97(s,6H).HRMS(MALDI)理论值C
14H
15Cl
2F
2N
5O
5S
2(M+Na)
+:527.97519,实测值527.97599.
白色粉末,mp＝93.2-94.3℃.
1H NMR(600MHz,DMSO-d
6)δ9.55(s,1H),7.65(q,J＝8.3Hz,1H),7.43(t,J＝9.9Hz,1H),7.25(t,J＝8.4Hz,1H),4.56(s,2H),3.61(s,3H),2.99(s,6H).HRMS(MALDI)理论值C
14H
15Cl
2F
2N
5O
5S
2(M+H)
+:505.99325,实测值505.99382.
白色粉末,mp＝97.7-98.2℃.
1H NMR(600MHz,DMSO-d
6)δ9.57(s,1H),δ7.62(dt,J＝9.8,3.2Hz,2H),7.45(d,J＝8.0Hz,1H),4.56(s,2H),3.72–3.48(m,3H),2.95(s,6H).HRMS(MALDI)理论值C
14H
15Cl
3FN
5O
5S
2(M+H)
+:521.9637,实测值521.96469.
黄色粉末,mp＝100.5-101.3℃.
1H NMR(600MHz,DMSO-d
6)δ9.55(s,J＝2.3Hz,1H), 7.41(d,J＝12.3Hz,1H),7.32–7.23(m,2H),4.59(s,2H),3.88(s,3H),3.61(s,3H),2.99(s,6H).HRMS(MALDI)理论值C
15H
18Cl
2FN
5O
6S
2(M+Na)
+:539.99518,实测值539.99702.
白色粉末,mp＝72.4-72.8℃.
1H NMR(600MHz,DMSO-d
6)δ9.56(s,1H),7.57–7.52(m,1H),7.42(td,J＝9.1,4.4Hz,1H),7.39–7.35(m,1H),4.57(s,2H),3.63(s,3H),2.99(s,6H).HRMS(MALDI)理论值C
14H
15Cl
2F
2N
5O
5S
2(M+H)
+:505.99325,实测值505.99304.
白色粉末,mp＝202.6-203.1℃.
1H NMR(600MHz,DMSO-d
6)δ9.58(s,1H),7.30(d,J＝7.8Hz,1H),7.22(d,J＝6.7Hz,1H),7.15(d,J＝7.9Hz,1H),4.48(s,2H),3.32(s,3H),3.01(s,6H),2.40(d,J＝3.1Hz,6H).HRMS(MALDI)理论值C
16H
21Cl
2N
5O
5S
2(M+H)
+:498.04339,实测值498.04323.
油.
1H NMR(600MHz,DMSO-d
6)δ9.57(s,1H),7.68(t,J＝9.3Hz,1H),7.56(q,J＝9.2Hz,1H),7.38(d,J＝8.1Hz,1H),4.61(s,2H),3.63(s,3H),2.99(s,6H).HRMS(MALDI)理论值C
14H
15Cl
2F
2N
5O
5S
2(M+Na)
+:527.9752,实测值527.9754.
白色粉末,mp＝101.9-102.4℃.
1H NMR(600MHz,DMSO-d
6)δ9.55(s,1H),7.41(d,J＝12.3Hz,1H),7.25(dd,J＝15.0,6.9Hz,2H),4.59(s,2H),3.88(s,3H),3.69–3.57(m,3H),2.99(s,6H).HRMS(MALDI)理论值C
15H
18Cl
2FN
5O
6S
2(M+H)
+:518.01323,实测值518.01318.
白色粉末,mp＝88.8-89.5℃.
1H NMR(600MHz,DMSO-d
6)δ9.56(s,1H),7.79(d,J＝6.9Hz,1H),7.53(d,J＝6.9Hz,2H),4.60(s,2H),3.62(s,3H),2.99(s,6H).HRMS(MALDI)理论值C
14H
15Cl
3FN
5O
5S
2(M+H)
+:521.9637,实测值521.96381.
黄色粉末,mp＝131.9-132.8℃.
1H NMR(600MHz,DMSO-d
6)δ9.57(s,1H),7.85(s,1H),7.76(d,J＝8.2Hz,1H),7.52(d,J＝8.3Hz,1H),4.61(s,2H),3.63(s,3H),2.99(s,6H).HRMS(MALDI)理论值C
14H
15Cl
4N
5O
5S
2(M+H)
+:537.9341,实测值537.9349.
白色粉末,mp＝85.6-86.8℃.
1H NMR(600MHz,DMSO-d
6)δ9.56(s,1H),8.02(s,1H),7.85(d,J＝5.9Hz,2H),4.65(s,2H),3.62(d,J＝4.2Hz,3H),2.98(d,J＝4.3Hz,6H).HRMS(MALDI)理论值C
15H
15Cl
3F
3N
5O
5S
2(M+H)
+:571.9605,实测值571.96096.
白色粉末,mp＝92.1-93.2℃.
1H NMR(600MHz,DMSO-d
6)δ9.52(s,1H),7.02(s,2H),7.00(s,1H),4.53(s,2H),3.58(s,3H),2.96(s,6H),2.27(s,6H).HRMS(MALDI)理论值C
16H
21Cl
2N
5O
5S
2(M+H)
+:498.04339,实测值498.04326.
白色粉末,mp＝76.9-77.3℃.
1H NMR(600MHz,DMSO-d
6)δ9.44(d,J＝3.8Hz,1H),7.29(t,J＝9.5Hz,2H),7.02(s,1H),4.56(d,J＝4.4Hz,2H),3.58(s,3H),2.97(s,6H).HRMS (MALDI)理论值C
14H
15Cl
2F
2N
5O
5S
2(M+H)
+:505.99325,实测值505.99286.
黄色粉末,mp＝104.5-105.6℃.
1H NMR(600MHz,DMSO-d
6)δ9.56(s,1H),7.53(d,J＝8.9Hz,1H),7.49(s,1H),7.44(d,J＝9.3Hz,1H),4.61(s,2H),3.64(s,3H),2.99(s,6H).HRMS(MALDI)理论值C
14H
15Cl
3FN
5O
5S2(M+H)
+:521.9637,实测值521.96642.
白色粉末,mp＝92.1-93.2℃.
1H NMR(600MHz,DMSO-d
6)δ9.52(s,1H),7.02(s,2H),7.00(s,1H),4.53(s,2H),3.58(s,3H),2.96(s,6H),2.27(s,6H).HRMS(MALDI)理论值C
16H
21Cl
2N
5O
5S
2(M+H)
+:498.04339,实测值498.04326.
黄色粉末,mp＝84.4-85.3℃.
1H NMR(600MHz,DMSO-d
6)δ9.02(s,1H),7.60(t,J＝7.6Hz,2H),4.60(s,2H),2.91(s,6H),2.08(s,3H).HRMS(MALDI)理论值C
14H
14Cl
2F
3N
5O
5S
2(M+H)
+:523.9838,实测值523.9815.
白色粉末,mp＝150.6-151.3℃.
1H NMR(600MHz,DMSO-d
6)δ9.50(s,1H),7.55(q,J＝7.5Hz,1H),7.32(td,J＝8.8,2.6Hz,1H),7.03(s,2H),5.45(q,J＝7.4Hz,1H),2.99(s,6H),2.09–1.99(m,1H),1.43(d,J＝7.4Hz,3H),0.59(q,J＝7.8Hz,2H),0.28(dq,J＝13.5,7.5Hz,1H),-0.97(d,J＝9.5Hz,1H).HRMS(MALDI)理论值C
17H
20Cl
2FN
5O
4S
2(M+Na)
+:534.021,实测值534.02263.
白色粉末,mp＝161.1-162.0℃.
1H NMR(600MHz,DMSO-d
6)δ9.49(s,1H),7.53(d,J＝6.2Hz,2H),7.21(s,1H),7.15(s,1H),5.44(q,J＝7.2Hz,1H),2.98(s,6H),2.07(td,J＝7.0,3.6Hz,1H),1.45(d,J＝7.4Hz,3H),0.58(p,J＝7.3,6.4Hz,2H),0.27(q,J＝7.4Hz,1H),-1.01(s,1H).HRMS(MALDI)理论值C
17H
20Cl
3N
5O
4S
2(M+H)
+:547.0079,实测值547.00724.
白色粉末,mp＝141.3-142.1℃.
1H NMR(600MHz,DMSO-d
6)δ9.48(s,1H),7.65(d,J＝8.1Hz,1H),7.44(t,J＝7.9Hz,1H),7.33(s,1H),7.18(s,1H),5.41(q,J＝7.4Hz,1H),2.96(s,6H),1.42(d,J＝7.3Hz,3H),0.57(s,2H),0.25(s,1H),-1.05(s,1H).(MALDI)理论值C
17H
20BrCl
2N
5O
4S
2(M+H)
+:547.959,实测值571.95923.
白色粉末,mp＝120.1-120.8℃.
1H NMR(600MHz,DMSO-d
6)δ9.50(s,1H),7.85(d,J＝7.8Hz,1H),7.76(s,1H),7.52(s,2H),5.48(d,J＝9.3Hz,1H),2.98(s,6H),2.08(s,1H),1.47(d,J＝7.4Hz,3H),0.55(d,J＝26.2Hz,2H),0.24(s,1H),-1.18(s,1H).(MALDI)理论值C
18H
20Cl
2F
3N
5O
4S
2(M+H)
+:562.0359,实测值562.03576.
白色粉末,mp＝161.1-162.0℃.
1H NMR(600MHz,DMSO-d
6)δ9.49(s,1H),7.34(t,J＝8.7Hz,2H),7.20(s,2H),5.44(d,J＝7.4Hz,1H),2.98(s,6H),2.05(s,1H),1.44(d,J＝7.3Hz,3H),0.58(q,J＝7.3,6.2Hz,2H),0.26(t,J＝7.2Hz,1H),-1.00(s,1H).(MALDI)理论值C
17H
20Cl
2FN
5O
4S
2(M+H)
+:512.0391,实测值512.03932.
白色粉末,mp＝185.1-185.9℃.
1H NMR(600MHz,DMSO-d
6)δ9.50(s,1H),7.58(d,J＝8.2Hz,2H),7.20(d,J＝7.9Hz,2H),5.45(q,J＝7.4Hz,1H),2.99(s,6H),2.07(s,1H),1.45(d,J＝7.4Hz,3H),0.60(q,J＝8.3Hz,2H),0.29(d,J＝7.7Hz,1H),-0.94(s,1H).(MALDI)理论值C
17H
20Cl
3N
5O
4S
2(M+H)
+:528.0089,实测值528.00854.
白色粉末，mp＝171.0-171.8℃.
1H NMR(600MHz,DMSO-d
6)δ9.49(s,1H),7.06(d,J＝8.8Hz,2H),7.03(d,J＝8.0Hz,2H),5.47–5.37(m,1H),3.78(s,3H),2.98(s,6H),2.04(s,1H),1.44(d,J＝7.3Hz,3H),0.56(d,J＝9.4Hz,2H),0.22(d,J＝8.5Hz,1H),-0.93(s,1H).(MALDI)理论值C
18H
23Cl
2N
5O
5S
2(M+H)
+:524.059,实测值524.05879.
白色粉末,mp＝122.6-123.2℃.
1H NMR(600MHz,DMSO-d
6)δ9.50(s,1H),7.89(d,J＝8.0Hz,2H),7.43(s,2H),5.49(q,J＝7.4Hz,1H),2.99(s,6H),2.07(s,1H),1.48(d,J＝7.4Hz,3H),0.58(d,J＝8.8Hz,2H),0.27(s,1H),-1.07(s,1H).(MALDI)理论值C
18H
20Cl
2F
3N
5O
4S
2(M+H)
+:562.0359,实测值562.03489.
白色粉末,mp＝161.5-162.3℃.
1H NMR(600MHz,DMSO-d
6)δ9.49(s,1H),7.72(d,J＝7.7Hz,2H),7.13(s,2H),5.44(d,J＝7.4Hz,1H),2.98(s,6H),2.07(s,1H),1.46(d,J＝7.8Hz,3H),0.60(s,2H),0.29(s,1H),-0.93(s,1H).(MALDI)理论值C
17H
20BrCl
2N
5O
4S
2(M+H)
+:571.959,实测值571.95879.
白色粉末,mp＝102.7-103.4℃.
1H NMR(600MHz,DMSO-d
6)δ9.48(s,1H),7.79(dd,J＝8.4,2.9Hz,1H),7.44(s,1H),7.18(s,1H),5.40(d,J＝7.5Hz,1H),2.96(s,6H),2.10(s,1H),1.43(d,J＝7.4Hz,3H),0.60(d,J＝8.9Hz,2H),0.35(s,1H),-0.89(s,1H).HRMS(MALDI)理论值C
17H
19Cl
2F
2N
5O
4S
2(M+H)
+:530.02963,实测值530.02951.
白色粉末,mp＝175.4-176.1℃.
1H NMR(600MHz,DMSO-d
6)δ9.50(s,1H),7.60(t,J＝9.5Hz,1H),7.31(s,1H),7.04(s,1H),5.43(q,J＝7.3Hz,1H),2.99(s,6H),2.09(d,J＝10.3Hz,1H),1.46(d,J＝7.3Hz,3H),0.62(d,J＝9.2Hz,2H),0.37(s,1H),-0.85(s,1H).HRMS(MALDI)理论值C
17H
19Cl
2F
2N
5O
4S
2(M+H)
+:530.02963,实测值530.02941.
白色粉末,mp＝148.2-148.9℃.
1H NMR(600MHz,DMSO-d
6)δ9.48(s,1H),7.79(dd,J＝8.4,2.9Hz,1H),7.44(s,1H),7.18(s,1H),5.40(d,J＝7.5Hz,1H),2.96(s,6H),2.10(s,1H),1.43(d,J＝7.3Hz,3H),0.60(d,J＝8.9Hz,2H),0.35(s,1H),-0.89(s,1H).HRMS(MALDI)理论值C
17H
19Cl
4N
5O
4S
2(M+H)
+:561.9705,实测值561.9702.
白色粉末,mp＝124.7-125.3℃.
1H NMR(400MHz,DMSO-d
6)δ9.50(s,1H),7.51–7.35(m,1H),6.96(s,2H),5.43(q,J＝7.3Hz,1H),2.99(s,6H),2.13(dt,J＝6.9,3.3Hz,1H),1.48(d,J＝7.3Hz,3H),0.72–0.54(m,2H),0.41(dq,J＝14.3,6.7Hz,1H),-0.76(d,J＝9.0Hz,1H).HRMS(MALDI)理论值C
17H
19Cl
2F
2N
5O
4S
2(M+H)
+:530.02963,实测值530.02961.
白色粉末,mp＝155.6-156.4℃.
1H NMR(600MHz,DMSO-d
6)δ9.49(s,1H),8.28(s,1H),7.95(d,J＝47.3Hz,2H),5.44(d,J＝7.5Hz,1H),2.97(s,6H),2.13(d,J＝7.6Hz,1H),1.45(d,J＝7.2Hz,3H),0.59(s,1H),0.49(s,1H),0.32(s,1H),-1.17(s,1H).HRMS(MALDI)理论值C
19H
19Cl
2F
6N
5O
4S
2(M+H)
+:630.0232,实测值630.0212.
测试例1
本测试例针对表1中所示的如下化合物进行活性测试，结果见表3。
具体测试方法为：
试验采取幼苗盆栽法。
幼苗盆栽试验的处理，实验化合物剂量见表3。另设不施药剂的空白对照。每个处理重复3次。选用2片真叶平展的黄瓜盆栽幼苗，剪去生长点，用喉头喷雾器进行人工手动喷雾。处理后的试验材料均在药液晾干后，第二天接种黄瓜霜霉病孢子悬浮液，然后放置人工气候室中培养。培养温度：昼25℃。夜间20℃；相对湿度：90％～100％。保湿培养7天后调查防治效果。调查方法按农业部药检所《农药室内生物测定试验准则》-杀菌剂防治黄瓜霜霉病试验盆栽法(NY/T 1156.7-2006)的分级标准分级记载，以病情指数计算防治效果。
0级：无病；
1级：病斑面积占整片叶面积的5％以下；
3级：病斑面积占整片叶面积的6％～10％；
5级：病斑面积占整片叶面积的11％～25％；
7级：病斑面积占整片叶面积的26％～50％；
9级：病斑面积占整片叶面积的50％以上。
病情指数及防治效果计算方法如下：
式中：CK
0空白对照区施药前病情指数，CK
1空白对照区施药后病情指数，PT
0药剂处理区施药前病情指数，PT
1药剂处理区施药后病情指数。
防效评级列于表3中。
表3
80％≦A≦100％；70％≦B<80％，50％≦C<70％，D<50％
测试例2
本测试例的测试和调查方法同测试例1，不同之处在于，被测试化合物为表4中所示的化合物，测试浓度列于表4中。
防效评级列于表4中。
表4
80％≦A≦100％；70％≦B<80％，50％≦C<70％，D<50％
测试例3
田间活性测试。
以黄瓜霜霉病为试验对象、作物和品种。
试验安排在陕西省兴平市进行(2021年5月至2021年6月，每间隔10天施药一次，共施药2次)。试验地(粘壤土，pH值为5.8，肥力水平及土壤有机质含量较高)黄瓜大棚栽培，各试验小区的土壤类型、栽培条件及水肥管理等均匀一致。采用喷雾器将配制好的各参试药剂的药液均匀喷施到黄瓜茎叶上。
其余调查和评价方法同测试例1。
本试验期间各药剂处理区内，试验作物均生长正常，未发生药害及其它不良影响。
采用农业部针对农药田间药效试验要求的方法进行试验药剂的处理，调查方法按农业部农药检定所《农药田间药效试验准则(一)》-杀菌剂防治黄瓜霜霉病(GB/T 17980.26-2000)的分级标准分级记载，以病情指数计算防治效果，本测试例的具体测试结果见表5。
表5
80％≦A≦100％；70％≦B<80％，50％≦C<70％，D<50％
本发明提供的化合物针对黄瓜霜霉病、大豆疫霉病、番茄晚疫病、马铃薯晚疫病、茄子霜霉病、柑桔脚腐病、南瓜疫病、葡萄霜霉病等卵菌纲植物真菌病具有明显比现有技术更好的效果。
以上详细描述了本发明的优选实施方式，但是，本发明并不限于此。在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。
Claims (14)
- 一种含突烯片段的三唑磺酰胺类衍生物，其特征在于，该衍生物具有式(I)所示的结构：
其中，在式(I)中，R 1选自C 1-6的烷基、C 1-6的烷氧基、C 3-6的环烷基；R 2选自H、C 1-6的烷基；R 3、R 4、R 5、R 6、R 7选自H、卤素、C 1-6的烷基、C 1-6的烷氧基、氰基、由至少一个卤素取代的C 1-6的烷基、由至少一个卤素取代的C 1-6的烷氧基；R 8均为H或Cl。 - 根据权利要求1所述的含突烯片段的三唑磺酰胺类衍生物，其中，在式(I)中，R 1选自C 1-3的烷氧基、C 3-6的环烷基；R 2选自H、C 1-3的烷基；R 3、R 4、R 5、R 6、R 7选自H、卤素、C 1-6的烷基、C 1-3的烷氧基、氰基、由至少一个卤素取代的C 1-3的烷基、由至少一个卤素取代的C 1-3的烷氧基；R 8均为H或Cl。
- 根据权利要求1或2所述的含突烯片段的三唑磺酰胺类衍生物，其中，在式(I)中，R 1选自甲氧基、环丙基；R 2选自H、甲基；R 3、R 4、R 5选自H、F、Cl、甲基、乙基、异丙基、叔丁基、甲氧基、-CF 3、-OCF 3、氰基；R 6选自H、F、Cl；R 7为H；R 8均为H或Cl。
- 根据权利要求1-3中任意一项所述的含突烯片段的三唑磺酰胺类衍生物，其中，所述含突烯片段的三唑磺酰胺类衍生物为以下化合物中的任意一种：化合物I-1：在式(I)中，R 1为环丙基，R 2、R 3、R 4、R 5、R 6、R 7、R 8均为H；化合物I-2：在式(I)中，R 1为环丙基，R 2为H，R 3为F，R 4、R 5、R 6、R 7、R 8均为H；化合物I-3：在式(I)中，R 1为环丙基，R 2为H，R 3为Cl，R 4、R 5、R 6、R 7、R 8均为H；化合物I-4：在式(I)中，R 1为环丙基，R 2为H，R 3为甲基，R 4、R 5、R 6、R 7、R 8均为H；化合物I-5：在式(I)中，R 1为环丙基，R 2为H，R 3为乙基，R 4、R 5、R 6、R 7、R 8均为H；化合物I-6：在式(I)中，R 1为环丙基，R 2为H，R 3为甲氧基，R 4、R 5、R 6、R 7、R 8均为H；化合物I-7：在式(I)中，R 1为环丙基，R 2为H，R 3为-CF 3，R 4、R 5、R 6、R 7、R 8均为H；化合物I-8：在式(I)中，R 1为环丙基，R 2为H，R 3为氰基，R 4、R 5、R 6、R 7、R 8均为H；化合物I-9：在式(I)中，R 1为环丙基，R 2为H，R 4为F，R 3、R 5、R 6、R 7、R 8均为H；化合物I-10：在式(I)中，R 1为环丙基，R 2为H，R 4为Cl，R 3、R 5、R 6、R 7、R 8均为H；化合物I-11：在式(I)中，R 1为环丙基，R 2为H，R 4为甲基，R 3、R 5、R 6、R 7、R 8均为H；化合物I-12：在式(I)中，R 1为环丙基，R 2为H，R 4为乙基，R 3、R 5、R 6、R 7、R 8均为H；化合物I-13：在式(I)中，R 1为环丙基，R 2为H，R 4为甲氧基，R 3、R 5、R 6、R 7、R 8均为H；化合物I-14：在式(I)中，R 1为环丙基，R 2为H，R 4为异丙基，R 3、R 5、R 6、R 7、R 8均为H；化合物I-15：在式(I)中，R 1为环丙基，R 2为H，R 4为叔丁基，R 3、R 5、R 6、R 7、R 8均为H；化合物I-16：在式(I)中，R 1为环丙基，R 2为H，R 4为-CF 3，R 3、R 5、R 6、R 7、R 8均为H；化合物I-17：在式(I)中，R 1为环丙基，R 2为H，R 4为-OCF 3，R 3、R 5、R 6、R 7、R 8均为H；化合物I-18：在式(I)中，R 1为环丙基，R 2为H，R 5为F，R 3、R 4、R 6、R 7、R 8均为H；化合物I-19：在式(I)中，R 1为环丙基，R 2为H，R 5为Cl，R 3、R 4、R 6、R 7、R 8均为H；化合物I-20：在式(I)中，R 1为环丙基，R 2为H，R 5为甲基，R 3、R 4、R 6、R 7、R 8均为H；化合物I-21：在式(I)中，R 1为环丙基，R 2为H，R 5为氰基，R 3、R 4、R 6、R 7、R 8均为H；化合物I-22：在式(I)中，R 1为环丙基，R 2为H，R 5为甲氧基，R 3、R 4、R 6、R 7、R 8均为H；化合物I-23：在式(I)中，R 1为环丙基，R 2为H，R 5为异丙基，R 3、R 4、R 6、R 7、R 8均为H；化合物I-24：在式(I)中，R 1为环丙基，R 2为H，R 5为叔丁基，R 3、R 4、R 6、R 7、R 8均为H；化合物I-25：在式(I)中，R 1为环丙基，R 2为H，R 5为-CF 3，R 3、R 4、R 6、R 7、R 8均为H；化合物I-26：在式(I)中，R 1为环丙基，R 2为H，R 5为-OCF 3，R 3、R 4、R 6、R 7、R 8均为H；化合物I-27：在式(I)中，R 1为环丙基，R 2为H，R 3和R 4均为甲基，R 5、R 6、R 7、R 8均为H；化合物I-28：在式(I)中，R 1为环丙基，R 2为H，R 3和R 4均为F，R 5、R 6、R 7、R 8均为H；化合物I-29：在式(I)中，R 1为环丙基，R 2为H，R 3为F，R 4为Cl，R 5、R 6、R 7、R 8均为H；化合物I-30：在式(I)中，R 1为环丙基，R 2为H，R 3为Cl，R 4为F，R 5、R 6、R 7、R 8均为H；化合物I-31：在式(I)中，R 1为环丙基，R 2为H，R 3和R 4均为Cl，R 5、R 6、R 7、R 8均为H；化合物I-32：在式(I)中，R 1为环丙基，R 2为H，R 3和R 5均为甲基，R 4、R 6、R 7、R 8均为H；化合物I-33：在式(I)中，R 1为环丙基，R 2为H，R 3和R 5均为F，R 4、R 6、R 7、R 8均为H；化合物I-34：在式(I)中，R 1为环丙基，R 2为H，R 3为F，R 5为Cl，R 4、R 6、R 7、R 8均为H；化合物I-35：在式(I)中，R 1为环丙基，R 2为H，R 3为Cl，R 5为F，R 4、R 6、R 7、R 8均为H；化合物I-36：在式(I)中，R 1为环丙基，R 2为H，R 3和R 5均为Cl，R 4、R 6、R 7、R 8均为H；化合物I-37：在式(I)中，R 1为环丙基，R 2为H，R 3和R 5均为-CF 3，R 4、R 6、R 7、R 8均为H；化合物I-38：在式(I)中，R 1为环丙基，R 2为H，R 4和R 5均为甲基，R 3、R 6、R 7、R 8均为H；化合物I-39：在式(I)中，R 1为环丙基，R 2为H，R 4和R 5均为F，R 3、R 6、R 7、R 8均为H；化合物I-40：在式(I)中，R 1为环丙基，R 2为H，R 4为F，R 5为Cl、R 3、R 6、R 7、 R 8均为H；化合物I-41：在式(I)中，R 1为环丙基，R 2为H，R 4为Cl，R 5为F、R 3、R 6、R 7、R 8均为H；化合物I-42：在式(I)中，R 1为环丙基，R 2为H，R 4和R 5均为Cl，R 3、R 6、R 7、R 8均为H；化合物I-43：在式(I)中，R 1为环丙基，R 2为H，R 4和R 5均为-CF 3，R 3、R 6、R 7、R 8均为H；化合物I-44：在式(I)中，R 1为环丙基，R 2为H，R 4和R 6均为甲基，R 3、R 5、R 7、R 8均为H；化合物I-45：在式(I)中，R 1为环丙基，R 2为H，R 4为F，R 6为Cl，R 3、R 5、R 7、R 8均为H；化合物I-46：在式(I)中，R 1为环丙基，R 2为H，R 4和R 6均为Cl，R 3、R 5、R 7、R 8均为H；化合物I-47：在式(I)中，R 1为环丙基，R 2为H，R 4、R 5和R 6均为F，R 3、R 7、R 8均为H；化合物I-48：在式(I)中，R 1为环丙基，R 2为H，R 4、R 5和R 6均为Cl，R 3、R 7、R 8均为H；化合物I-49：在式(I)中，R 1为甲氧基，R 2、R 3、R 4、R 5、R 6、R 7、R 8均为H；化合物I-50：在式(I)中，R 1为甲氧基，R 2为H，R 3为F，R 4、R 5、R 6、R 7、R 8均为H；化合物I-51：在式(I)中，R 1为甲氧基，R 2为H，R 3为Cl，R 4、R 5、R 6、R 7、R 8均为H；化合物I-52：在式(I)中，R 1为甲氧基，R 2为H，R 3为甲基，R 4、R 5、R 6、R 7、R 8均为H；化合物I-53：在式(I)中，R 1为甲氧基，R 2为H，R 3为乙基，R 4、R 5、R 6、R 7、R 8均为H；化合物I-54：在式(I)中，R 1为甲氧基，R 2为H，R 3为甲氧基，R 4、R 5、R 6、R 7、R 8均为H；化合物I-55：在式(I)中，R 1为甲氧基，R 2为H，R 3为-CF 3，R 4、R 5、R 6、R 7、R 8均为H；化合物I-56：在式(I)中，R 1为甲氧基，R 2为H，R 3为-OCF 3，R 4、R 5、R 6、R 7、R 8均为H；化合物I-57：在式(I)中，R 1为甲氧基，R 2为H，R 4为F，R 3、R 5、R 6、R 7、R 8均为H；化合物I-58：在式(I)中，R 1为甲氧基，R 2为H，R 4为Cl，R 3、R 5、R 6、R 7、R 8均为H；化合物I-59：在式(I)中，R 1为甲氧基，R 2为H，R 4为甲基，R 3、R 5、R 6、R 7、R 8 均为H；化合物I-60：在式(I)中，R 1为甲氧基，R 2为H，R 4为乙基，R 3、R 5、R 6、R 7、R 8均为H；化合物I-61：在式(I)中，R 1为甲氧基，R 2为H，R 4为甲氧基，R 3、R 5、R 6、R 7、R 8均为H；化合物I-62：在式(I)中，R 1为甲氧基，R 2为H，R 4为异丙基，R 3、R 5、R 6、R 7、R 8均为H；化合物I-63：在式(I)中，R 1为甲氧基，R 2为H，R 4为叔丁基，R 3、R 5、R 6、R 7、R 8均为H；化合物I-64：在式(I)中，R 1为甲氧基，R 2为H，R 4为-CF 3，R 3、R 5、R 6、R 7、R 8均为H；化合物I-65：在式(I)中，R 1为甲氧基，R 2为H，R 4为-OCF 3，R 3、R 5、R 6、R 7、R 8均为H；化合物I-66：在式(I)中，R 1为甲氧基，R 2为H，R 5为F，R 3、R 4、R 6、R 7、R 8均为H；化合物I-67：在式(I)中，R 1为甲氧基，R 2为H，R 5为Cl，R 3、R 4、R 6、R 7、R 8均为H；化合物I-68：在式(I)中，R 1为甲氧基，R 2为H，R 5为甲基，R 3、R 4、R 6、R 7、R 8均为H；化合物I-69：在式(I)中，R 1为甲氧基，R 2为H，R 5为乙基，R 3、R 4、R 6、R 7、R 8均为H；化合物I-70：在式(I)中，R 1为甲氧基，R 2为H，R 5为甲氧基，R 3、R 4、R 6、R 7、R 8均为H；化合物I-71：在式(I)中，R 1为甲氧基，R 2为H，R 5为异丙基，R 3、R 4、R 6、R 7、R 8均为H；化合物I-72：在式(I)中，R 1为甲氧基，R 2为H，R 5为-CF 3，R 3、R 4、R 6、R 7、R 8均为H；化合物I-73：在式(I)中，R 1为甲氧基，R 2为H，R 5为-OCF 3，R 3、R 4、R 6、R 7、R 8均为H；化合物I-74：在式(I)中，R 1为甲氧基，R 2为H，R 3和R 4均为甲基，R 5、R 6、R 7、R 8均为H；化合物I-75：在式(I)中，R 1为甲氧基，R 2为H，R 3和R 4均为F，R 5、R 6、R 7、R 8均为H；化合物I-76：在式(I)中，R 1为甲氧基，R 2为H，R 3为F，R 4为Cl，R 5、R 6、R 7、R 8均为H；化合物I-77：在式(I)中，R 1为甲氧基，R 2为H，R 3为Cl，R 4为F，R 5、R 6、R 7、R 8均为H；化合物I-78：在式(I)中，R 1为甲氧基，R 2为H，R 3和R 4均为Cl，R 5、R 6、R 7、R 8均为H；化合物I-79：在式(I)中，R 1为甲氧基，R 2为H，R 3和R 5均为甲基，R 4、R 6、R 7、R 8均为H；化合物I-80：在式(I)中，R 1为甲氧基，R 2为H，R 3和R 5均为F，R 4、R 6、R 7、R 8均为H；化合物I-81：在式(I)中，R 1为甲氧基，R 2为H，R 3为F，R 5为Cl，R 4、R 6、R 7、R 8均为H；化合物I-82：在式(I)中，R 1为甲氧基，R 2为H，R 3为Cl，R 5为F，R 4、R 6、R 7、R 8均为H；化合物I-83：在式(I)中，R 1为甲氧基，R 2为H，R 3和R 5均为Cl，R 4、R 6、R 7、R 8均为H；化合物I-84：在式(I)中，R 1为甲氧基，R 2为H，R 3和R 5均为-CF 3，R 4、R 6、R 7、R 8均为H；化合物I-85：在式(I)中，R 1为甲氧基，R 2为H，R 4和R 5均为甲基，R 3、R 6、R 7、R 8均为H；化合物I-86：在式(I)中，R 1为甲氧基，R 2为H，R 4和R 5均为F，R 3、R 6、R 7、R 8均为H；化合物I-87：在式(I)中，R 1为甲氧基，R 2为H，R 4为F，R 5为Cl，R 3、R 6、R 7、R 8均为H；化合物I-88：在式(I)中，R 1为甲氧基，R 2为H，R 4为Cl，R 5为F，R 3、R 6、R 7、R 8均为H；化合物I-89：在式(I)中，R 1为甲氧基，R 2为H，R 4和R 5均为Cl，R 3、R 6、R 7、R 8均为H；化合物I-90：在式(I)中，R 1为甲氧基，R 2为H，R 4和R 5均为-CF 3，R 3、R 6、R 7、R 8均为H；化合物I-91：在式(I)中，R 1为甲氧基，R 2为H，R 4和R 6均为甲基，R 3、R 5、R 7、R 8均为H；化合物I-92：在式(I)中，R 1为甲氧基，R 2为H，R 4为F，R 6为Cl，R 3、R 5、R 7、R 8均为H；化合物I-93：在式(I)中，R 1为甲氧基，R 2为H，R 4和R 6均为Cl，R 3、R 5、R 7、R 8均为H；化合物I-94：在式(I)中，R 1为甲氧基，R 2为H，R 4、R 5和R 6均为F，R 3、R 7、R 8均为H；化合物I-95：在式(I)中，R 1为甲氧基，R 2为H，R 4、R 5和R 6均为Cl，R 3、R 7、R 8均为H；化合物I-96：在式(I)中，R 1为环丙基，R 2为甲基，R 3、R 4、R 5、R 6、R 7、R 8均为H；化合物I-97：在式(I)中，R 1为环丙基，R 2为甲基，R 3为F，R 4、R 5、R 6、R 7、R 8均为H；化合物I-98：在式(I)中，R 1为环丙基，R 2为甲基，R 3为Cl，R 4、R 5、R 6、R 7、R 8均为H；化合物I-99：在式(I)中，R 1为环丙基，R 2、R 3均为甲基，R 4、R 5、R 6、R 7、R 8均为H；化合物I-100：在式(I)中，R 1为环丙基，R 2为甲基，R 3为甲氧基，R 4、R 5、R 6、R 7、R 8均为H；化合物I-101：在式(I)中，R 1为环丙基，R 2为甲基，R 4为F，R 3、R 5、R 6、R 7、R 8均为H；化合物I-102：在式(I)中，R 1为环丙基，R 2为甲基，R 4为Cl，R 3、R 5、R 6、R 7、R 8均为H；化合物I-103：在式(I)中，R 1为环丙基，R 2、R 4均为甲基，R 3、R 5、R 6、R 7、R 8均为H；化合物I-104：在式(I)中，R 1为环丙基，R 2为甲基，R 4为乙基，R 3、R 5、R 6、R 7、R 8均为H；化合物I-105：在式(I)中，R 1为环丙基，R 2为甲基，R 4为甲氧基，R 3、R 5、R 6、R 7、R 8均为H；化合物I-106：在式(I)中，R 1为环丙基，R 2为甲基，R 4为异丙基，R 3、R 5、R 6、R 7、R 8均为H；化合物I-107：在式(I)中，R 1为环丙基，R 2为甲基，R 4为叔丁基，R 3、R 5、R 6、R 7、R 8均为H；化合物I-108：在式(I)中，R 1为环丙基，R 2为甲基，R 4为-CF 3，R 3、R 5、R 6、R 7、R 8均为H；化合物I-109：在式(I)中，R 1为环丙基，R 2为甲基，R 4为-OCF 3，R 3、R 5、R 6、R 7、R 8均为H；化合物I-110：在式(I)中，R 1为环丙基，R 2为甲基，R 5为F，R 3、R 4、R 6、R 7、R 8均为H；化合物I-111：在式(I)中，R 1为环丙基，R 2为甲基，R 5为Cl，R 3、R 4、R 6、R 7、R 8均为H；化合物I-112：在式(I)中，R 1为环丙基，R 2、R 5均为甲基，R 3、R 4、R 6、R 7、R 8均为H；化合物I-113：在式(I)中，R 1为环丙基，R 2为甲基，R 5为甲氧基，R 3、R 4、R 6、R 7、R 8均为H；化合物I-114：在式(I)中，R 1为环丙基，R 2为甲基，R 5为异丙基，R 3、R 4、R 6、R 7、R 8均为H；化合物I-115：在式(I)中，R 1为环丙基，R 2为甲基，R 5为叔丁基，R 3、R 4、R 6、R 7、 R 8均为H；化合物I-116：在式(I)中，R 1为环丙基，R 2为甲基，R 5为-CF 3，R 3，R 4、R 6、R 7、R 8均为H；化合物I-117：在式(I)中，R 1为环丙基，R 2为甲基，R 5为-OCF 3，R 3、R 4、R 6、R 7、R 8均为H；化合物I-118：在式(I)中，R 1为环丙基，R 2、R 3、R 4均为甲基，R 5、R 6、R 7、R 8均为H；化合物I-119：在式(I)中，R 1为环丙基，R 2为甲基，R 3和R 4均为F，R 5、R 6、R 7、R 8均为H；化合物I-120：在式(I)中，R 1为环丙基，R 2为甲基，R 3和R 4均为Cl，R 5、R 6、R 7、R 8均为H；化合物I-121：在式(I)中，R 1为环丙基，R 2、R 3、R 5均为甲基，R 4、R 6、R 7、R 8均为H；化合物I-122：在式(I)中，R 1为环丙基，R 2为甲基，R 3和R 5均为F，R 4、R 6、R 7、R 8均为H；化合物I-123：在式(I)中，R 1为环丙基，R 2为甲基，R 3和R 5均为Cl，R 4、R 6、R 7、R 8均为H；化合物I-124：在式(I)中，R 1为环丙基，R 2为甲基，R 3和R 5均为-CF 3，R 4、R 6、R 7、R 8均为H；化合物I-125：在式(I)中，R 1为环丙基，R 2、R 4、R 5均为甲基，R 3、R 6、R 7、R 8均为H；化合物I-126：在式(I)中，R 1为环丙基，R 2为甲基，R 4和R 5均为F，R 3、R 6、R 7、R 8均为H；化合物I-127：在式(I)中，R 1为环丙基，R 2为甲基，R 4和R 5均为Cl，R 3、R 6、R 7、R 8均为H；化合物I-128：在式(I)中，R 1为环丙基，R 2、R 4、R 6均为甲基，R 3、R 5、R 7、R 8均为H；化合物I-129：在式(I)中，R 1为环丙基，R 2为甲基，R 4为F，R 6为Cl，R 3、R 5、R 7、R 8均为H；化合物I-130：在式(I)中，R 1为环丙基，R 2为甲基，R 4为Cl，R 6为F，R 3、R 5、R 7、R 8均为H；化合物I-131：在式(I)中，R 1为环丙基，R 2为甲基，R 4和R 6均为Cl，R 3、R 5、R 7、R 8均为H；化合物I-132：在式(I)中，R 1为环丙基，R 2为甲基，R 4、R 5和R 6均为F，R 3、R 7、R 8均为H；化合物I-133：在式(I)中，R 1为环丙基，R 2为甲基，R 4、R 5和R 6均为Cl，R 3、R 7、 R 8均为H；化合物I-134：在式(I)中，R 1为甲氧基，R 2为甲基，R 3、R 4、R 5、R 6、R 7、R 8均为H；化合物I-135：在式(I)中，R 1为甲氧基，R 2为甲基，R 3为F，R 4、R 5、R 6、R 7、R 8均为H；化合物I-136：在式(I)中，R 1为甲氧基，R 2为甲基，R 3为Cl，R 4、R 5、R 6、R 7、R 8均为H；化合物I-137：在式(I)中，R 1为甲氧基，R 2为甲基，R 3为甲基，R 4、R 5、R 6、R 7、R 8均为H；化合物I-138：在式(I)中，R 1为甲氧基，R 2为甲基，R 3为甲氧基，R 4、R 5、R 6、R 7、R 8均为H；化合物I-139：在式(I)中，R 1为甲氧基，R 2为甲基，R 4为F、R 3、R 5、R 6、R 7、R 8均为H；化合物I-140：在式(I)中，R 1为甲氧基，R 2为甲基，R 4为Cl，R 3、R 5、R 6、R 7、R 8均为H；化合物I-141：在式(I)中，R 1为甲氧基，R 2为甲基，R 4为甲基，R 3、R 5、R 6、R 7、R 8均为H；化合物I-142：在式(I)中，R 1为甲氧基，R 2为甲基，R 4为乙基，R 3、R 5、R 6、R 7、R 8均为H；化合物I-143：在式(I)中，R 1为甲氧基，R 2为甲基，R 4为甲氧基，R 3、R 5、R 6、R 7、R 8均为H；化合物I-144：在式(I)中，R 1为甲氧基，R 2为甲基，R 4为异丙基，R 3、R 5、R 6、R 7、R 8均为H；化合物I-145：在式(I)中，R 1为甲氧基，R 2为甲基，R 4为叔丁基，R 3、R 5、R 6、R 7、R 8均为H；化合物I-146：在式(I)中，R 1为甲氧基，R 2为甲基，R 4为-CF 3，R 3、R 5、R 6、R 7、R 8均为H；化合物I-147：在式(I)中，R 1为甲氧基，R 2为甲基，R 4为-OCF 3，R 3、R 5、R 6、R 7、R 8均为H；化合物I-148：在式(I)中，R 1为甲氧基，R 2为甲基，R 5为F，R 3、R 4、R 6、R 7、R 8均为H；化合物I-149：在式(I)中，R 1为甲氧基，R 2为甲基，R 5为Cl，R 3、R 4、R 6、R 7、R 8均为H；化合物I-150：在式(I)中，R 1为甲氧基，R 2为甲基，R 5为甲基，R 3、R 4、R 6、R 7、R 8均为H；化合物I-151：在式(I)中，R 1为甲氧基，R 2为甲基，R 5为甲氧基，R 3、R 4、R 6、R 7、R 8均为H；化合物I-152：在式(I)中，R 1为甲氧基，R 2为甲基，R 5为异丙基，R 3、R 4、R 6、R 7、R 8均为H；化合物I-153：在式(I)中，R 1为甲氧基，R 2为甲基，R 5为叔丁基，R 3、R 4、R 6、R 7、R 8均为H；化合物I-154：在式(I)中，R 1为甲氧基，R 2为甲基，R 5为-CF 3，R 3、R 4、R 6、R 7、R 8均为H；化合物I-155：在式(I)中，R 1为甲氧基，R 2为甲基，R 5为-OCF 3，R 3、R 4、R 6、R 7、R 8均为H；化合物I-156：在式(I)中，R 1为甲氧基，R 2、R 3、R 4均为甲基，R 5、R 6、R 7、R 8均为H；化合物I-157：在式(I)中，R 1为甲氧基，R 2为甲基，R 3和R 4均为F，R 5、R 6、R 7、R 8均为H；化合物I-158：在式(I)中，R 1为甲氧基，R 2为甲基，R 3和R 4均为Cl，R 5、R 6、R 7、R 8均为H；化合物I-159：在式(I)中，R 1为甲氧基，R 2、R 3、R 5均为甲基，R 4、R 6、R 7、R 8均为H；化合物I-160：在式(I)中，R 1为甲氧基，R 2为甲基，R 3和R 5均为F，R 4、R 6、R 7、R 8均为H；化合物I-161：在式(I)中，R 1为甲氧基，R 2为甲基，R 3和R 5均为Cl，R 4、R 6、R 7、R 8均为H；化合物I-162：在式(I)中，R 1为甲氧基，R 2为甲基，R 3和R 5均为-CF 3，R 4、R 6、R 7、R 8均为H；化合物I-163：在式(I)中，R 1为甲氧基，R 2、R 4、R 5均为甲基，R 3、R 6、R 7、R 8均为H；化合物I-164：在式(I)中，R 1为甲氧基，R 2为甲基，R 4和R 5均为F，R 3、R 6、R 7、R 8均为H；化合物I-165：在式(I)中，R 1为甲氧基，R 2为甲基，R 4和R 5均为Cl，R 3、R 6、R 7、R 8均为H；化合物I-166：在式(I)中，R 1为甲氧基，R 2为甲基，R 4和R 6均为甲基，R 3、R 5、R 7、R 8均为H；化合物I-167：在式(I)中，R 1为甲氧基，R 2为甲基，R 4为F，R 6为Cl，R 3、R 5、R 7、R 8均为H；化合物I-168：在式(I)中，R 1为甲氧基，R 2为甲基，R 4为Cl，R 6为F，R 3、R 5、R 7、R 8均为H；化合物I-169：在式(I)中，R 1为甲氧基，R 2为甲基，R 4和R 6均为Cl，R 3、R 5、R 7、R 8均为H；化合物I-170：在式(I)中，R 1为甲氧基，R 2为甲基，R 4、R 5和R 6均为F、R 3、R 7、 R 8均为H；化合物I-171：在式(I)中，R 1为甲氧基，R 2为甲基，R 4、R 5和R 6均为Cl，R 3、R 7、R 8均为H；化合物II-1：在式(I)中，R 1为环丙基，R 2、R 3、R 4、R 5、R 6、R 7均为H，R 8均为Cl；化合物II-2：在式(I)中，R 1为环丙基，R 2为H，R 3为F，R 4、R 5、R 6、R 7均为H，R 8均为Cl；化合物II-3：在式(I)中，R 1为环丙基，R 2为H，R 4为F，R 3、R 5、R 6、R 7均为H，R 8均为Cl；化合物II-4：在式(I)中，R 1为环丙基，R 2为H，R 4为Cl，R 3、R 5、R 6、R 7均为H，R 8均为Cl；化合物II-5：在式(I)中，R 1为环丙基，R 2为H，R 4为甲基，R 3、R 5、R 6、R 7均为H，R 8均为Cl；化合物II-6：在式(I)中，R 1为环丙基，R 2为H，R 4为乙基，R 3、R 5、R 6、R 7均为H，R 8均为Cl；化合物II-7：在式(I)中，R 1为环丙基，R 2为H，R 4为甲氧基，R 3、R 5、R 6、R 7均为H，R 8均为Cl；化合物II-8：在式(I)中，R 1为环丙基，R 2为H，R 4为异丙基，R 3、R 5、R 6、R 7均为H，R 8均为Cl；化合物II-9：在式(I)中，R 1为环丙基，R 2为H，R 4为叔丁基，R 3、R 5、R 6、R 7均为H，R 8均为Cl；化合物II-10：在式(II)中，R 1为环丙基，R 2为H，R 4为-CF 3，R 3、R 5、R 6、R 7均为H，R 8均为Cl；化合物II-11：在式(I)中，R 1为环丙基，R 2为H，R 4为-OCF 3，R 3、R 5、R 6、R 7均为H，R 8均为Cl；化合物II-12：在式(I)中，R 1为环丙基，R 2为H，R 5为F，R 3、R 4、R 6、R 7均为H，R 8均为Cl；化合物II-13：在式(I)中，R 1为环丙基，R 2为H，R 5为Cl，R 3、R 4、R 6、R 7均为H，R 8均为Cl；化合物II-14：在式(I)中，R 1为环丙基，R 2为H，R 5为甲基，R 3、R 4、R 6、R 7均为H，R 8均为Cl；化合物II-15：在式(I)中，R 1为环丙基，R 2为H，R 5为乙基，R 3、R 4、R 6、R 7均为H，R 8均为Cl；化合物II-16：在式(I)中，R 1为环丙基，R 2为H，R 5为甲氧基，R 3、R 4、R 6、R 7均为H，R 8均为Cl；化合物II-17：在式(I)中，R 1为环丙基，R 2为H，R 5为异丙基，R 3、R 4、R 6、R 7均为H，R 8均为Cl；化合物II-18：在式(I)中，R 1为环丙基，R 2为H，R 5为叔丁基，R 3、R 4、R 6、R 7均 为H，R 8均为Cl；化合物II-19：在式(I)中，R 1为环丙基，R 2为H，R 5为-CF 3，R 3、R 4、R 6、R 7均为H，R 8均为Cl；化合物II-20：在式(I)中，R 1为环丙基，R 2为H，R 5为-OCF 3，R 3、R 4、R 6、R 7均为H，R 8均为Cl；化合物II-21：在式(I)中，R 1为环丙基，R 2为H，R 4和R 5均为甲基，R 3、R 6、R 7均为H，R 8均为Cl；化合物II-22：在式(I)中，R 1为环丙基，R 2为H，R 4和R 5均为F，R 3、R 6、R 7均为H，R 8均为Cl；化合物II-23：在式(I)中，R 1为环丙基，R 2为H，R 4为F，R 5为Cl，R 3、R 6、R 7均为H，R 8均为Cl；化合物II-24：在式(I)中，R 1为环丙基，R 2为H，R 4为Cl，R 5为F，R 3、R 6、R 7均为H，R 8均为Cl；化合物II-25：在式(I)中，R 1为环丙基，R 2为H，R 4和R 5均为Cl，R 3、R 6、R 7均为H，R 8均为Cl；化合物II-26：在式(I)中，R 1为环丙基，R 2为H，R 4和R 5均为-CF 3，R 3、R 6、R 7均为H，R 8均为Cl；化合物II-27：在式(I)中，R 1为环丙基，R 2为H，R 4和R 6均为甲基，R 3、R 5、R 7均为H，R 8均为Cl；化合物II-28：在式(I)中，R 1为环丙基，R 2为H，R 4为F，R 6为Cl，R 3、R 5、R 7均为H，R 8均为Cl；化合物II-29：在式(I)中，R 1为环丙基，R 2为H，R 4和R 6均为Cl，R 3、R 5、R 7均为H，R 8均为Cl；化合物II-30：在式(I)中，R 1为环丙基，R 2为H，R 4、R 5和R 6均为F，R 3、R 7均为H，R 8均为Cl；化合物II-31：在式(I)中，R 1为环丙基，R 2为H，R 4、R 5和R 6均为Cl，R 3、R 7均为H，R 8均为Cl；化合物II-32：在式(I)中，R 1为甲氧基，R 2为H，R 3、R 4、R 5、R 6、R 7均为H，R 8均为Cl；化合物II-33：在式(I)中，R 1为甲氧基，R 2为H，R 4为F，R 3、R 5、R 6、R 7均为H，R 8均为Cl；化合物II-34：在式(I)中，R 1为甲氧基，R 2为H，R 4为Cl，R 3、R 5、R 6、R 7均为H，R 8均为Cl；化合物II-35：在式(I)中，R 1为甲氧基，R 2为H，R 4为甲基，R 3、R 5、R 6、R 7均为H，R 8均为Cl；化合物II-36：在式(I)中，R 1为甲氧基，R 2为H，R 4为氰基，R 3、R 5、R 6、R 7均为H，R 8均为Cl；化合物II-37：在式(I)中，R 1为甲氧基，R 2为H，R 4为甲氧基，R 3、R 5、R 6、R 7均为H，R 8均为Cl；化合物II-38：在式(I)中，R 1为甲氧基，R 2为H，R 4为异丙基，R 3、R 5、R 6、R 7均为H，R 8均为Cl；化合物II-39：在式(I)中，R 1为甲氧基，R 2为H，R 4为叔丁基，R 3、R 5、R 6、R 7均为H，R 8均为Cl；化合物II-40：在式(I)中，R 1为甲氧基，R 2为H，R 4为-CF 3，R 3、R 5、R 6、R 7均为H，R 8均为Cl；化合物II-41：在式(I)中，R 1为甲氧基，R 2为H，R 4为-OCF 3，R 3、R 5、R 6、R 7均为H，R 8均为Cl；化合物II-42：在式(I)中，R 1为甲氧基，R 2为H，R 5为F，R 3、R 4、R 6、R 7均为H，R 8均为Cl；化合物II-43：在式(I)中，R 1为甲氧基，R 2为H，R 5为Cl，R 3、R 4、R 6、R 7均为H，R 8均为Cl；化合物II-44：在式(I)中，R 1为甲氧基，R 2为H，R 5为甲基，R 3、R 4、R 6、R 7均为H，R 8均为Cl；化合物II-45：在式(I)中，R 1为甲氧基，R 2为H，R 5为乙基，R 3、R 4、R 6、R 7均为H，R 8均为Cl；化合物II-46：在式(I)中，R 1为甲氧基，R 2为H，R 5为甲氧基，R 3、R 4、R 6、R 7均为H，R 8均为Cl；化合物II-47：在式(I)中，R 1为甲氧基，R 2为H，R 5为异丙基，R 3、R 4、R 6、R 7均为H，R 8均为Cl；化合物II-48：在式(I)中，R 1为甲氧基，R 2为H，R 5为叔丁基，R 3、R 4、R 6、R 7均为H，R 8均为Cl；化合物II-49：在式(I)中，R 1为甲氧基，R 2为H，R 5为-CF 3，R 3、R 4、R 6、R 7均为H，R 8均为Cl；化合物II-50：在式(I)中，R 1为甲氧基，R 2为H，R 5为-OCF 3，R 3、R 4、R 6、R 7均为H，R 8均为Cl；化合物II-51：在式(I)中，R 1为甲氧基，R 2为H，R 4和R 5均为甲基，R 3、R 6、R 7均为H，R 8均为Cl；化合物II-52：在式(I)中，R 1为甲氧基，R 2为H，R 4和R 5均为F，R 3、R 6、R 7均为H，R 8均为Cl；化合物II-53：在式(I)中，R 1为甲氧基，R 2为H，R 4为F，R 5为Cl，R 3、R 6、R 7均为H，R 8均为Cl；化合物II-54：在式(I)中，R 1为甲氧基，R 2为H，R 4为Cl，R 5为F，R 3、R 6、R 7均为H，R 8均为Cl；化合物II-55：在式(I)中，R 1为甲氧基，R 2为H，R 4和R 5均为Cl，R 3、R 6、R 7均为 H，R 8均为Cl；化合物II-56：在式(I)中，R 1为甲氧基，R 2为H，R 4和R 5均为-CF 3，R 3、R 6、R 7均为H，R 8均为Cl；化合物II-57：在式(I)中，R 1为甲氧基，R 2为H，R 4和R 6均为甲基，R 3、R 5、R 7均为H，R 8均为Cl；化合物II-58：在式(I)中，R 1为甲氧基，R 2为H，R 4为F，R 6为Cl，R 5、R 3、R 7均为H，R 8均为Cl；化合物II-59：在式(I)中，R 1为甲氧基，R 2为H，R 4为Cl，R 6为F，R 5、R 3、R 7均为H，R 8为Cl；化合物II-60：在式(I)中，R 1为甲氧基，R 2为H，R 4和R 6均为Cl，R 5、R 3、R 7均为H，R 8均为Cl；化合物II-61：在式(I)中，R 1为甲氧基，R 2为H，R 4、R 5和R 6均为F，R 3、R 7均为H，R 8均为Cl；化合物II-62：在式(I)中，R 1为环丙基，R 2为甲基，R 3、R 4、R 5、R 6、R 7均为H，R 8均为Cl；化合物II-63：在式(I)中，R 1为环丙基，R 2为甲基，R 4为F，R 3、R 5、R 6、R 7均为H，R 8均为Cl；化合物II-64：在式(I)中，R 1为环丙基，R 2为甲基，R 4为Cl，R 3、R 5、R 6、R 7均为H，R 8均为Cl；化合物II-65：在式(II)中，R 1为环丙基，R 2为甲基，R 4为甲基，R 3、R 5、R 6、R 7均为H，R 8均为Cl；化合物II-66：在式(I)中，R 1为环丙基，R 2为甲基，R 4为氰基，R 3、R 5、R 6、R 7均为H，R 8均为Cl；化合物II-67：在式(I)中，R 1为环丙基，R 2为甲基，R 4为甲氧基，R 3、R 5、R 6、R 7均为H，R 8均为Cl；化合物II-68：在式(I)中，R 1为环丙基，R 2为甲基，R 4为异丙基，R 3、R 5、R 6、R 7均为H，R 8均为Cl；化合物II-69：在式(I)中，R 1为环丙基，R 2为甲基，R 4为叔丁基，R 3、R 5、R 6、R 7均为H，R 8均为Cl；化合物II-70：在式(I)中，R 1为环丙基，R 2为甲基，R 4为-CF 3，R 3、R 5、R 6、R 7均为H，R 8均为Cl；化合物II-71：在式(I)中，R 1为环丙基，R 2为甲基，R 4为-OCF 3，R 3、R 5、R 6、R 7均为H，R 8均为Cl；化合物II-72：在式(I)中，R 1为环丙基，R 2为甲基，R 5为F，R 3、R 4、R 6、R 7均为H，R 8均为Cl；化合物II-73：在式(I)中，R 1为环丙基，R 2为甲基，R 5为Cl，R 3、R 4、R 6、R 7均为H，R 8均为Cl；化合物II-74：在式(I)中，R 1为环丙基，R 2为甲基，R 5为甲基，R 3、R 4、R 6、R 7均为H，R 8均为Cl；化合物II-75：在式(I)中，R 1为环丙基，R 2为甲基，R 5为甲氧基，R 3、R 4、R 6、R 7均为H，R 8均为Cl；化合物II-76：在式(I)中，R 1为环丙基，R 2为甲基，R 5为异丙基，R 3、R 4、R 6、R 7均为H，R 8均为Cl；化合物II-77：在式(I)中，R 1为环丙基，R 2为甲基，R 5为叔丁基，R 3、R 4、R 6、R 7均为H，R 8均为Cl；化合物II-78：在式(I)中，R 1为环丙基，R 2为甲基，R 5为-CF 3，R 3、R 4、R 6、R 7均为H，R 8均为Cl；化合物II-79：在式(I)中，R 1为环丙基，R 2为甲基，R 5为-OCF 3，R 3、R 4、R 6、R 7均为H，R 8均为Cl；化合物II-80：在式(I)中，R 1为环丙基，R 2、R 4、R 5均为甲基、R 3、R 6、R 7均为H，R 8均为Cl；化合物II-81：在式(I)中，R 1为环丙基，R 2为甲基，R 4和R 5均为F，R 3、R 6、R 7均为H，R 8均为Cl；化合物II-82：在式(I)中，R 1为环丙基，R 2为甲基，R 4和R 5均为Cl，R 3、R 6、R 7均为H，R 8均为Cl；化合物II-83：在式(I)中，R 1为环丙基，R 2、R 4、R 6均为甲基，R 3、R 5、R 7均为H，R 8均为Cl；化合物II-84：在式(I)中，R 1为环丙基，R 2为甲基，R 4为F，R 6为Cl，R 3、R 5、R 7均为H，R 8均为Cl；化合物II-85：在式(I)中，R 1为环丙基，R 2为甲基，R 4为Cl，R 6为F，R 3、R 5、R 7均为H，R 8均为Cl；化合物II-86：在式(I)中，R 1为环丙基，R 2为甲基，R 4和R 6均为Cl，R 3、R 5、R 7均为H，R 8均为Cl；化合物II-87：在式(I)中，R 1为环丙基，R 2为甲基，R 4、R 5和R 6均为F，R 3、R 7均为H，R 8均为Cl；化合物II-88：在式(I)中，R 1为环丙基，R 2为甲基，R 4、R 5和R 6均为Cl，R 3、R 7均为H，R 8均为Cl；化合物II-89：在式(I)中，R 1为甲氧基，R 2为甲基，R 3、R 4、R 5、R 6、R 7均为H，R 8均为Cl；化合物II-90：在式(I)中，R 1为甲氧基，R 2为甲基，R 4为F，R 3、R 5、R 6、R 7均为H，R 8均为Cl；化合物II-91：在式(I)中，R 1为甲氧基，R 2为甲基，R 4为Cl，R 3、R 5、R 6、R 7均为H，R 8均为Cl；化合物II-92：在式(I)中，R 1为甲氧基，R 2为甲基，R 4为甲基，R 3、R 5、R 6、R 7均 为H，R 8均为Cl；化合物II-93：在式(I)中，R 1为甲氧基，R 2为甲基，R 4为乙基，R 3、R 5、R 6、R 7均为H，R 8均为Cl；化合物II-94：在式(I)中，R 1为甲氧基，R 2为甲基，R 4为氰基，R 3、R 5、R 6、R 7均为H，R 8均为Cl；化合物II-95：在式(I)中，R 1为甲氧基，R 2为甲基，R 4为甲氧基，R 3、R 5、R 6、R 7均为H，R 8均为Cl；化合物II-96：在式(I)中，R 1为甲氧基，R 2为甲基，R 4为异丙基，R 3、R 5、R 6、R 7均为H，R 8均为Cl；化合物II-97：在式(I)中，R 1为甲氧基，R 2为甲基，R 4为叔丁基，R 3、R 5、R 6、R 7均为H，R 8均为Cl；化合物II-98：在式(I)中，R 1为甲氧基，R 2为甲基，R 4为-CF 3，R 3、R 5、R 6、R 7均为H，R 8均为Cl；化合物II-99：在式(I)中，R 1为甲氧基，R 2为甲基，R 4为-OCF 3，R 3、R 5、R 6、R 7均为H，R 8均为Cl；化合物II-100：在式(I)中，R 1为甲氧基，R 2为甲基，R 5为F、R 3、R 4、R 6、R 7均为H，R 8均为Cl；化合物II-101：在式(I)中，R 1为甲氧基，R 2为甲基，R 5为Cl，R 3、R 4、R 6、R 7均为H，R 8均为Cl；化合物II-102：在式(I)中，R 1为甲氧基，R 2为甲基，R 5为甲基，R 3、R 4、R 6、R 7均为H，R 8均为Cl；化合物II-103：在式(I)中，R 1为甲氧基，R 2为甲基，R 5为氰基，R 3、R 4、R 6、R 7均为H，R 8均为Cl；化合物II-104：在式(I)中，R 1为甲氧基，R 2为甲基，R 5为甲氧基，R 3、R 4、R 6、R 7均为H，R 8均为Cl；化合物II-105：在式(I)中，R 1为甲氧基，R 2为甲基，R 5为异丙基，R 3、R 4、R 6、R 7均为H，R 8均为Cl；化合物II-106：在式(I)中，R 1为甲氧基，R 2为甲基，R 5为叔丁基，R 3、R 4、R 6、R 7均为H，R 8均为Cl；化合物II-107：在式(I)中，R 1为甲氧基，R 2为甲基，R 5为-CF 3，R 3、R 4、R 6、R 7均为H，R 8均为Cl；化合物II-108：在式(I)中，R 1为甲氧基，R 2为甲基，R 5为-OCF 3，R 3、R 4、R 6、R 7均为H，R 8均为Cl；化合物II-109：在式(I)中，R 1为甲氧基，R 2为甲基，R 4和R 5均为甲基，R 3、R 6、R 7均为H，R 8均为Cl；化合物II-110：在式(I)中，R 1为甲氧基，R 2为甲基，R 4和R 5均为F，R 3、R 6、R 7均为H，R 8均为Cl；化合物II-111：在式(I)中，R 1为甲氧基，R 2为甲基，R 4和R 5均为Cl，R 3、R 6、R 7均为H，R 8均为Cl；化合物II-112：在式(I)中，R 1为甲氧基，R 2为甲基，R 4和R 6均为甲基，R 3、R 5、R 7均为H，R 8均为Cl；化合物II-113：在式(I)中，R 1为甲氧基，R 2为甲基，R 4为F，R 6为Cl，R 3、R 5、R 7均为H，R 8均为Cl；化合物II-114：在式(I)中，R 1为甲氧基，R 2为甲基，R 4为Cl，R 6为F，R 3、R 5、R 7均为H，R 8均为Cl；化合物II-115：在式(I)中，R 1为甲氧基，R 2为甲基，R 4和R 6均为Cl，R 3、R 5、R 7均为H，R 8均为Cl；化合物II-116：在式(I)中，R 1为甲氧基，R 2为甲基，R 4、R 5和R 6均为F，R 3、R 7均为H，R 8均为Cl；化合物II-117：在式(I)中，R 1为甲氧基，R 2为甲基，R 4、R 5和R 6均为Cl，R 3、R 7均为H，R 8均为Cl。
- 一种制备权利要求1-4中任意一项所述的含突烯片段的三唑磺酰胺类衍生物的方法，其特征在于，该方法包括将式(II)所示的化合物与式(III)所示的化合物进行接触反应；
其中，在式(II)和式(III)中，R 9和R 10中一者为卤素，另一者为-NHR 1，R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8的定义与权利要求1-4中任意一项所述的定义对应相同。 - 根据权利要求5所述的方法，其中，所述接触反应至少满足以下条件：温度为5-45℃，时间为20-60min；优选地，所述式(II)所示的化合物与式(III)所示的化合物的用量摩尔比为(0.5-3)：1。
- 权利要求1-4中任意一项所述的含突烯片段的三唑磺酰胺类衍生物作为细胞色素bc 1复合物Q i位点抑制剂的应用。
- 权利要求1-4中任意一项所述的含突烯片段的三唑磺酰胺类衍生物在抗植物真菌病中的应用。
- 根据权利要求8所述的应用，其中，所述植物真菌病为霜霉病、霜疫霉病、疫病、晚疫病中的至少一种；优选地，所述植物真菌病为黄瓜霜霉病、大豆疫霉病、番茄晚疫病、马铃薯晚疫病、茄子霜霉病、柑桔脚腐病、南瓜疫病、葡萄霜霉病中的至少一种。
- 一种杀菌剂，其特征在于，该杀菌剂的活性成分为权利要求1-4中任意一项所述的含突烯片段的三唑磺酰胺类衍生物中的至少一种，以所述杀菌剂的总重量计，所述活性成分的含量为0.1-100重量％。
- 根据权利要求10所述的杀菌剂，其中，所述活性成分的含量为1-98重量％。
- 根据权利要求10或11所述的杀菌剂，其中，所述活性成分的含量为5-90重量％。
- 根据权利要求10-12中任意一项所述的杀菌剂，其中，所述杀菌剂的剂型选自水合剂、粉剂、乳剂、悬浮剂、乳油剂和粒剂中的至少一种。
- 权利要求10-13中任意一项所述的杀菌剂在抗植物真菌病中的应用。
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| CN115232081A (zh) | 2022-10-25 |
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