CN1268206C - 用作杀真菌剂的噻唑并[4,5-b]吡啶 - Google Patents
用作杀真菌剂的噻唑并[4,5-b]吡啶 Download PDFInfo
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- CN1268206C CN1268206C CNB028177592A CN02817759A CN1268206C CN 1268206 C CN1268206 C CN 1268206C CN B028177592 A CNB028177592 A CN B028177592A CN 02817759 A CN02817759 A CN 02817759A CN 1268206 C CN1268206 C CN 1268206C
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- Prior art keywords
- alkyl
- phenyl
- group
- halogen
- independently
- Prior art date
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- BBAWTPDTGRXPDG-UHFFFAOYSA-N [1,3]thiazolo[4,5-b]pyridine Chemical class C1=CC=C2SC=NC2=N1 BBAWTPDTGRXPDG-UHFFFAOYSA-N 0.000 title abstract 2
- 239000000417 fungicide Substances 0.000 title description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 58
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 56
- 150000002367 halogens Chemical class 0.000 claims abstract description 56
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 36
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 29
- 239000001257 hydrogen Substances 0.000 claims abstract description 29
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 16
- 125000004765 (C1-C4) haloalkyl group Chemical group 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- 241000233866 Fungi Species 0.000 claims abstract description 10
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 9
- 125000001424 substituent group Chemical group 0.000 claims abstract description 7
- 239000002689 soil Substances 0.000 claims abstract description 6
- -1 Phenyl Chemical group 0.000 claims description 175
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 121
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 62
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 47
- 125000000623 heterocyclic group Chemical group 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 31
- 229910052760 oxygen Inorganic materials 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 15
- 229910052717 sulfur Inorganic materials 0.000 claims description 15
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 12
- 125000003342 alkenyl group Chemical group 0.000 claims description 11
- 229920006395 saturated elastomer Polymers 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 10
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims description 10
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 claims description 9
- 206010017533 Fungal infection Diseases 0.000 claims description 8
- 208000031888 Mycoses Diseases 0.000 claims description 8
- 125000005842 heteroatom Chemical group 0.000 claims description 8
- 150000002431 hydrogen Chemical group 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- 125000006656 (C2-C4) alkenyl group Chemical group 0.000 claims description 6
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 239000000839 emulsion Substances 0.000 claims description 6
- 239000004533 oil dispersion Substances 0.000 claims description 6
- 125000002813 thiocarbonyl group Chemical group *C(*)=S 0.000 claims description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- 125000002541 furyl group Chemical group 0.000 claims description 5
- 238000009331 sowing Methods 0.000 claims description 5
- 125000000232 haloalkynyl group Chemical group 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- 125000001544 thienyl group Chemical group 0.000 claims description 4
- 125000006650 (C2-C4) alkynyl group Chemical group 0.000 claims description 3
- 235000001674 Agaricus brunnescens Nutrition 0.000 claims description 3
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 3
- 125000006371 dihalo methyl group Chemical group 0.000 claims description 3
- 125000004953 trihalomethyl group Chemical group 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 abstract description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract description 4
- 241001465754 Metazoa Species 0.000 abstract description 3
- 241000607479 Yersinia pestis Species 0.000 abstract description 2
- 125000004786 difluoromethoxy group Chemical group [H]C(F)(F)O* 0.000 abstract description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 abstract 1
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 abstract 1
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- 239000002585 base Substances 0.000 description 131
- 239000000460 chlorine Substances 0.000 description 86
- 150000001875 compounds Chemical class 0.000 description 41
- 241000196324 Embryophyta Species 0.000 description 32
- 125000001309 chloro group Chemical group Cl* 0.000 description 32
- 229920000728 polyester Polymers 0.000 description 32
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 25
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 22
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 18
- 229910052731 fluorine Inorganic materials 0.000 description 18
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 17
- 229910052794 bromium Inorganic materials 0.000 description 17
- 229910052801 chlorine Inorganic materials 0.000 description 17
- 239000011737 fluorine Substances 0.000 description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 16
- 230000000855 fungicidal effect Effects 0.000 description 15
- 239000002904 solvent Substances 0.000 description 15
- 125000006230 (methoxyethoxy)ethanyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 13
- 239000007900 aqueous suspension Substances 0.000 description 13
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 229930192474 thiophene Natural products 0.000 description 12
- 241000894006 Bacteria Species 0.000 description 11
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 10
- 239000003995 emulsifying agent Substances 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 240000003768 Solanum lycopersicum Species 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 8
- 125000005843 halogen group Chemical group 0.000 description 8
- 229910052740 iodine Inorganic materials 0.000 description 8
- LJXPWUAAAAXJBX-UHFFFAOYSA-N 2-methylallyl radical Chemical compound [CH2]C(C)=C LJXPWUAAAAXJBX-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 7
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 240000006365 Vitis vinifera Species 0.000 description 7
- 235000014787 Vitis vinifera Nutrition 0.000 description 7
- 150000001721 carbon Chemical group 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000004128 high performance liquid chromatography Methods 0.000 description 7
- 239000011630 iodine Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 7
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 6
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical compound NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 6
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- 241000233622 Phytophthora infestans Species 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 241000209140 Triticum Species 0.000 description 6
- 235000013339 cereals Nutrition 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- ZRNSSRODJSSVEJ-UHFFFAOYSA-N 2-methylpentacosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC(C)C ZRNSSRODJSSVEJ-UHFFFAOYSA-N 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
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- 239000002253 acid Substances 0.000 description 5
- 230000000843 anti-fungal effect Effects 0.000 description 5
- 229940121375 antifungal agent Drugs 0.000 description 5
- 239000004009 herbicide Substances 0.000 description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 5
- 238000011081 inoculation Methods 0.000 description 5
- 229920005610 lignin Polymers 0.000 description 5
- LULAYUGMBFYYEX-UHFFFAOYSA-N metachloroperbenzoic acid Natural products OC(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-N 0.000 description 5
- NBVXSUQYWXRMNV-UHFFFAOYSA-N monofluoromethane Natural products FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 5
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- 238000012360 testing method Methods 0.000 description 5
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- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 4
- 241000123650 Botrytis cinerea Species 0.000 description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
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- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
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- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 4
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- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 4
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
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- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- ZLIBICFPKPWGIZ-UHFFFAOYSA-N pyrimethanil Chemical compound CC1=CC(C)=NC(NC=2C=CC=CC=2)=N1 ZLIBICFPKPWGIZ-UHFFFAOYSA-N 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
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- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
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- WJCNZQLZVWNLKY-UHFFFAOYSA-N thiabendazole Chemical compound S1C=NC(C=2NC3=CC=CC=C3N=2)=C1 WJCNZQLZVWNLKY-UHFFFAOYSA-N 0.000 description 1
- 125000001113 thiadiazolyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000004149 thio group Chemical group *S* 0.000 description 1
- 125000005323 thioketone group Chemical group 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 125000003774 valeryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
- C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
- C07D513/04—Ortho-condensed systems
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
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- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
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- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
- Plural Heterocyclic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
本发明涉及一种防治有害真菌的方法,包括用有效量的至少一种式(I)的噻唑并[4,5-b]吡啶处理真菌或需要防止真菌和/或动物害虫侵染的材料、植物、土壤或种子,在式(I)中,n为0、1或2,取代基R1、R2、R3相互独立地为氢、卤素、C1-C4烷基、C1-C4烷氧基、C1-C4卤代烷基、C1-C4烷氧基-C1-C4烷基或可以未被取代或带有1、2、3或4个相互独立地选自卤素、硝基、氰基、烷基、烷氧基、OCHF2或CF3的取代基的苯基,且其中A和R如权利要求1所定义。
Description
本发明涉及新的噻唑并[4,5-b]吡啶以及防治有害真菌的方法。
其中噻唑环与6元芳环稠合的噻唑化合物作为药物活性化合物多次描述于文献中。例如,EP-A 405967公开了稠合的唑并吡啶,它们在五元杂环上带有有机硫代基团或有机亚磺酰基。WO 93/24480公开了几种唑并苯和唑并吡啶,它们带有2-吡啶基甲硫基或2-吡啶基甲基亚磺酰基且对幽门日光属杆菌(Heliobacter pylori)具有抗菌作用。由JP 62-207271已知类似化合物可以用作抗溃疡药。
WO 97/28128公开了6-溴-2-甲硫基噻唑并[4,5-b]吡啶和6-溴-2-甲基磺酰基噻唑并[4,5-b]吡啶在制备用于氧化角鲨烯环化酶的新型抑制剂中用作中间体。
EP-A 1000946描述了几种2-(取代硫基)噻唑并[4,5-b]吡啶的杀虫和杀寄生虫用途。
迄今为止尚未描述过可以用作杀真菌剂的噻唑并[4,5-b]吡啶。
原则上讲,人们总是需要开发新型杀真菌剂以拓宽活性谱并避免对已知杀真菌剂的抗药性的可能形成。
本发明的目的是提供一种防治有害真菌的新方法以及可用于防治有害真菌的新化合物。
我们发现该目的令人惊奇地由下面所定义的式I的噻唑并[4,5-b]吡啶实现。
因此,本发明涉及一种防治有害真菌的方法,包括用有效量的至少一种式I的噻唑并[4,5-b]吡啶和/或至少一种其可农用盐处理真菌或需要防止真菌和/或动物害虫侵袭的材料、植物、土壤或种子:
其中取代基R1、R2、R3、A和符号n具有如下含义:
R1、R2、R3相互独立地为氢,卤素,C1-C4烷基,C1-C4烷氧基,C1-C4卤代烷基,C1-C4卤代烷氧基,C1-C4烷氧基-C1-C4烷基或可以未被取代或带有1、2、3或4个相互独立地选自卤素、硝基、氰基、C1-C4烷基、C1-C4烷氧基、OCHF2、CHF2、OCF3或CF3的取代基的苯基;
n为0、1或2;
R为氢,氰基,卤素,C1-C6烷基,C1-C4卤代烷基,C1-C4烷氧基,C2-C4链烯基,C2-C4卤代链烯基,C2-C4炔基,C2-C4卤代炔基,氰基-C1-C4烷基,C1-C4烷氧基-C1-C4烷基,C1-C4烷氧基-C1-C4烷氧基,C3-C8环烷基,其可以带有1、2、3或4个相互独立地选自卤素和C1-C4烷基的取代基,
三(C1-C4烷基)甲硅烷基,三(C1-C4烷基)甲硅烷氧基,COR4,COOR5,CONR6R7,S(O)kR8,苯基,苯氧基,带有1、2或3个选自O、S和N的杂原子且可以为饱和、不饱和或芳族的5或6元杂环,其中苯基、苯氧基和杂环相互独立地可以带有1、2、3或4个相互独立地选自如下的取代基:卤素、硝基、氰基、C1-C4烷基、C1-C4烷氧基、甲基磺酰基、OCHF2、CHF2、OCF3或CF3;或可以带有1、2或3个选自卤素、C1-C4烷基、甲基磺酰基、OCHF2、CHF2、OCF3或CF3的基团的苯基;其中
k为0、1或2;
R4为氢,C1-C6烷基,苯基和苯基-C1-C4烷基,其中苯基和苯基-C1-C4烷基可以在苯基环上带有1、2、3或4个相互独立地选自卤素、硝基、氰基、C1-C4烷基、C1-C4烷氧基、OCHF2或CF3的取代基;
R5为C1-C6烷基,C1-C4烷氧基-C1-C4烷基,苯基和苯基-C1-C4烷基,其中苯基和苯基-C1-C4烷基可以在苯基环上带有1、2、3或4个相互独立地选自卤素、硝基、氰基、C1-C4烷基、C1-C4烷氧基、甲基磺酰基、OCHF2、CHF2、OCF3或CF3的取代基;
R6、R7相互独立地为氢,C1-C6烷基,C1-C4烷氧基-C1-C4烷基,苯基和苯基-C1-C4烷基,其中苯基和苯基-C1-C4烷基可以在苯基环上带有1、2、3或4个相互独立地选自卤素、硝基、氰基、C1-C4烷基、C1-C4烷氧基、甲基磺酰基、OCHF2、CHF2、OCF3或CF3的取代基;或可以一起形成5或6元杂环,该杂环除氮原子外还可以额外带有1或2个选自N、O或S的其他杂原子;
R8为C1-C6烷基,C1-C4卤代烷基,苯基和苯基-C1-C4烷基,其中苯基和苯基-C1-C4烷基可以在苯基环上带有1、2、3或4个相互独立地选自卤素、硝基、氰基、C1-C4烷基、C1-C4烷氧基、甲基磺酰基、OCHF2、CHF2、OCF3或CF3的取代基;
A为C1-C4亚烷基;或
A-R可以一起为二卤代甲基,三卤代甲基,C2-C4链烯基,C2-C4卤代链烯基,C3-C8环烷基,可以带有1、2、3或4个相互独立地选自卤素和C1-C4烷基的取代基的C5-C8环烯基,或可以带有1、2或3个选自O、S和N的杂原子的5或6元杂环,该杂环可以是饱和、不饱和或芳族的且可以带有1、2、3或4个相互独立地选自卤素、硝基、氰基、C1-C4烷基、C1-C4烷氧基、甲基磺酰基、OCHF2、CF3或苯基的取代基,其中该苯基可以带有1、2或3个选自卤素、C1-C4烷基、甲基磺酰基、OCHF2或CF3的基团,其中环烷基和环烯基可以独立地带有1、2、3或4个相互独立地选自卤素和C1-C4烷基的取代基和/或可以含有羰基或硫羰基作为环成员。
本发明还涉及如上所定义的式I的噻唑并[4,5-b]吡啶化合物,但如下化合物除外:
—2-甲基磺酰基噻唑并[4,5-b]吡啶,
—2-甲基磺酰基-6-溴噻唑并[4,5-b]吡啶,
—2-甲硫基-6-溴噻唑并[4,5-b]吡啶,
—2-[(甲氧羰基)甲基亚磺酰基]噻唑并[4,5-b]吡啶,
—2-[(甲氧羰基)甲基亚磺酰基]-6-三氟甲基噻唑并[4,5-b]吡啶,
—2-[(甲氧羰基)甲硫基]-6-三氟甲基噻唑并[4,5-b]吡啶,
—2-[(甲氧羰基)甲硫基]噻唑并[4,5-b]吡啶,
—2-[(乙氧羰基)甲基亚磺酰基]噻唑并[4,5-b]吡啶,
—2-[(乙氧羰基)甲基亚磺酰基]-6-三氟甲基噻唑并[4,5-b]吡啶,
—2-[(乙氧羰基)甲硫基]-6-三氟甲基噻唑并[4,5-b]吡啶,
—2-[(乙氧羰基)甲硫基]噻唑并[4,5-b]吡啶,
—2-[(4,4,3-三氟-3-丁烯基)硫基]噻唑并[4,5-b]吡啶,
—2-[(2-丙烯-1-基)硫基]噻唑并[4,5-b]吡啶,
—2-[(环丙基甲基)硫基]噻唑并[4,5-b]吡啶,
—2-[1-(乙氧羰基)乙硫基]噻唑并[4,5-b]吡啶,
—2-[(一溴二氟甲基)硫基]噻唑并[4,5-b]吡啶,
—2-[(二氟甲基)硫基]噻唑并[4,5-b]吡啶,和
—2-[(2,2,2-三氟乙基)硫基]噻唑并[4,5-b]吡啶。
本发明还涉及农业配制剂,其优选呈粉末、悬浮液、分散体、乳液、乳油、油分散体、糊、粉剂、直接可喷溶液、撒播用材料或粒剂形式,其包含至少一种式I的噻唑并[4,5-b]吡啶化合物和/或至少一种其可农用盐和至少一种可以为液体或固体的可农用载体。
在取代基中,式I的噻唑并[4,5-b]吡啶可以具有一个或多个手性中心,此时它们以对映体或非对映体的混合物存在。本发明提供了纯净的对映体或非对映体及其混合物。
合适的可农用盐尤其是那些其抗衡离子不会对噻唑并[4,5-b]吡啶I的除草作用具有不利影响的盐。优选的可农用盐选自噻唑并[4,5-b]吡啶I的酸加成盐。
有用酸加成盐的优选阴离子主要是氯离子、溴离子、氟离子、硫酸氢根、硫酸根、磷酸二氢根、磷酸氢根、磷酸根、硝酸根、碳酸氢根、碳酸根、六氟硅酸根、六氟磷酸根、苯甲酸根,以及C1-C4链烷酸的阴离子,优选甲酸根、乙酸根、丙酸根和丁酸根。它们可以通过使噻唑并[4,5-b]吡啶I与对应阴离子的酸,优选盐酸、氢溴酸、硫酸、磷酸或硝酸反应而形成。
在基团A、R、R1-R8的定义中或作为环烷(烯)基、苯基或杂环上的基团提到的有机部分与术语“卤素”一样是各所列组员的集合性术语。所有碳链,即所有烷基、卤代烷基、烷氧基、卤代烷氧基、烷基亚磺酰基、卤代烷基亚磺酰基、烷基磺酰基、卤代烷基磺酰基、链烯基、卤代链烯基、炔基和卤代炔基,以及较大基团如烷氧羰基、烷氧羰基烷基等中的对应部分都可以是直链或支化的,其中前缀Cn-Cm在每种情况下表示该基团中的可能碳原子数。卤代取代基优选带有1、2、3、4或5个相同或不同的卤原子。术语卤素在每种情况下表示氟、氯、溴或碘。其他含义的实例如下:
—C1-C4烷基和C1-C4烷氧基、C1-C4烷硫基、C1-C4烷基氨基、二-C1-C4烷基氨基或C1-C4烷基羰基氧基的烷基部分:具有1-4个碳原子的饱和直链或支化烃基,具体如甲基、乙基、丙基、1-甲基乙基、丁基、1-甲基丙基、2-甲基丙基、1,1-二甲基乙基;
—C1-C6烷基:具有1-6个碳原子的饱和直链或支化烃基,例如上述C1-C4烷基或戊基、1-甲基丁基、2-甲基丁基、3-甲基丁基、2,2-二甲基丙基、1-乙基丙基、己基、1,1-二甲基丙基、1,2-二甲基丙基、1-甲基戊基、2-甲基戊基、3-甲基戊基、4-甲基戊基、1,1-二甲基丁基、1,2-二甲基丁基、1,3-二甲基丁基、2,2-二甲基丁基、2,3-二甲基丁基、3,3-二甲基丁基、1-乙基丁基、2-乙基丁基、1,1,2-三甲基丙基、1,2,2-三甲基丙基、1-乙基-1-甲基丙基和1-乙基-2-甲基丙基;
—C1-C4亚烷基:亚甲基、1,1-亚乙基、1,2-亚乙基、1,1-亚丙基、1,2-亚丙基、2,2-亚丙基、1,3-亚丙基、2-甲基-1,2-亚丙基、2-甲基-1,3-亚丙基、1,1-亚丁基、1,2-亚丁基、1,3-亚丁基、1,4-亚丁基、2,2-亚丁基或2,3-亚丁基;
—二卤代甲基:带有2个卤原子的甲基,如二氯甲基、二氟甲基、一氯一氟甲基;
—三卤代甲基:带有3个卤原子的甲基,如三氯甲基、三氟甲基、二氯一氟甲基、一氯二氟甲基、一溴二氟甲基;
—C1-C4卤代烷基和C1-C4卤代烷氧基的卤代烷基部分:具有1-4个碳原子的直链或支化烷基(如上所述),其中这些基团中的氢原子可以被上述卤素原子部分或全部替代,尤其是C1-C2卤代烷基,如氯甲基、溴甲基、二氯甲基、三氯甲基、氟甲基、二氟甲基、三氟甲基、一氯一氟甲基、二氯一氟甲基、一氯二氟甲基、1-氯乙基、1-溴乙基、1-氟乙基、2-氟乙基、2,2-二氟乙基、2,2,2-三氟乙基、2-氯-2-氟乙基、2-氯-2,2-二氟乙基、2,2-二氯-2-氟乙基、2,2,2-三氯乙基和五氟乙基;
—C1-C4烷氧基:OCH3、OC2H5、正丙氧基、OCH(CH3)2、正丁氧基、OCH(CH3)-C2H5、OCH2-CH(CH3)2或OC(CH3)3,优选OCH3、OC2H5或OCH(CH3)2;
—C1-C4卤代烷氧基:被氟、氯、溴和/或碘部分或全部取代的上述C1-C4烷氧基,例如OCH2F、OCHF2、OCF3、OCH2Cl、OCH(Cl)2、OC(Cl)3、一氯一氟甲氧基、二氯一氟甲氧基、一氯二氟甲氧基、2-氟乙氧基、2-氯乙氧基、2-溴乙氧基、2-碘乙氧基、2,2-二氟乙氧基、2,2,2-三氟乙氧基、2-氯-2-氟乙氧基、2-氯-2,2-二氟乙氧基、2,2-二氯-2-氟乙氧基、2,2,2-三氯乙氧基、OC2F5、2-氟丙氧基、3-氟丙氧基、2,2-二氟丙氧基、2,3-二氟丙氧基、2-氯丙氧基、3-氯丙氧基、2,3-二氯丙氧基、2-溴丙氧基、3-溴丙氧基、3,3,3-三氟丙氧基、3,3,3-氯丙氧基、2,2,3,3,3-五氟丙氧基、OCF2-C2F5、1-(CH2F)-2-氟乙氧基、1-(CH2Cl)-2-氯乙氧基、1-(CH2Br)-2-溴乙氧基、4-氟丁氧基、4-氯丁氧基、4-溴丁氧基或九氟丁氧基,优选OCHF2、OCF3、二氯一氟甲氧基、一氯二氟甲氧基或2,2,2-三氟乙氧基;
—C1-C4烷氧基-C1-C4烷基:被上述C1-C4烷氧基取代的C1-C4烷基,即例如CH2-OCH3、CH2-OC2H5、正丙氧基甲基、CH2-OCH(CH3)2、正丁氧基甲基、(1-甲基丙氧基)甲基、(2-甲基丙氧基)甲基、CH2-OC(CH3)3、2-(甲氧基)乙基、2-(乙氧基)乙基、2-(正丙氧基)乙基、2-(1-甲基乙氧基)乙基、2-(正丁氧基)乙基、2-(1-甲基丙氧基)乙基、2-(2-甲基丙氧基)乙基、2-(1,1-二甲基乙氧基)乙基、2-(甲氧基)丙基、2-(乙氧基)丙基、2-(正丙氧基)丙基、2-(1-甲基乙氧基)丙基、2-(正丁氧基)丙基、2-(1-甲基丙氧基)丙基、2-(2-甲基丙氧基)丙基、2-(1,1-二甲基乙氧基)丙基、3-(甲氧基)丙基、3-(乙氧基)丙基、3-(正丙氧基)丙基、3-(1-甲基乙氧基)丙基、3-(正丁氧基)丙基、3-(1-甲基丙氧基)丙基、3-(2-甲基丙氧基)丙基、3-(1,1-二甲基乙氧基)丙基、2-(甲氧基)丁基、2-(乙氧基)丁基、2-(正丙氧基)丁基、2-(1-甲基乙氧基)丁基、2-(正丁氧基)丁基、2-(1-甲基丙氧基)丁基、2-(2-甲基丙氧基)丁基、2-(1,1-二甲基乙氧基)丁基、3-(甲氧基)丁基、3-(乙氧基)丁基、3-(正丙氧基)丁基、3-(1-甲基乙氧基)丁基、3-(正丁氧基)丁基、3-(1-甲基丙氧基)丁基、3-(2-甲基丙氧基)丁基、3-(1,1-二甲基乙氧基)丁基、4-(甲氧基)丁基、4-(乙氧基)丁基、4-(正丙氧基)丁基、4-(1-甲基乙氧基)丁基、4-(正丁氧基)丁基、4-(1-甲基丙氧基)丁基、4-(2-甲基丙氧基)丁基或4-(1,1-二甲基乙氧基)丁基,优选CH2-OCH3、CH2-OC2H5、2-甲氧基乙基或2-乙氧基乙基;
—C3-C4链烯基:具有3-4个碳原子且在任何位置,优选在1位上具有双键的不饱和直链或支化烃基,例如1-丙烯基、2-丙烯基、1-甲基乙烯基、1-丁烯基、2-丁烯基、3-丁烯基、1-甲基-1-丙烯基、2-甲基-1-丙烯基、1-甲基-2-丙烯基和2-甲基-2-丙烯基;
—C2-C4链烯基和C2-C4链烯氧基的链烯基部分:乙烯基或C3-C4链烯基(如上所述);
—C2-C4卤代链烯基和C2-C4卤代链烯氧基的卤代链烯基部分:具有2-4个碳原子且在任何位置上具有双键的不饱和直链或支化烃基(如上所述),其中这些基团中的氢原子可以被如上所述的卤原子,尤其是氟、氯和溴部分或全部替代;
—C3-C4炔基:具有3-4个碳原子且在任何位置,优选在1位上具有叁键的直链或支化烃基,例如乙炔基、1-丙炔基、2-丙炔基、1-丁炔基、2-丁炔基、3-丁炔基和1-甲基-2-丙炔基;
—C2-C4炔基和C2-C4炔氧基的炔基部分:乙炔基或C3-C4炔基(如上所述);
—C2-C4卤代炔基和C2-C4卤代炔氧基的卤代炔基部分:具有2-4个碳原子且在任何位置上具有叁键的不饱和直链或支化烃基(如上所述),其中这些基团中的氢原子可以被如上所述的卤原子,尤其是氟、氯和溴部分或全部替代;
—C3-C8环烷基:环丙基、环丁基、环戊基、环己基、环庚基或环辛基;
—含有羰基或硫羰基环成员的C3-C8环烷基:例如环丁酮-2-基、环丁酮-3-基、环戊酮-2-基、环戊酮-3-基、环己酮-2-基、环己酮-4-基、环庚酮-2-基、环辛酮-2-基、环丁硫酮-2-基、环丁硫酮-3-基、环戊硫酮-2-基、环戊硫酮-3-基、环己硫酮-2-基、环己硫酮-4-基、环庚硫酮-2-基或环辛硫酮-2-基,优选环戊酮-2-基或环己酮-2-基;
—C5-C8环烯基:环戊烯-2-基、环己烯-2-基、环庚烯-2-基、环辛烯-2-基、环戊烯-1-基、环己烯-3-基、环庚烯-3-基、环辛烯-3-基或环辛烯-4-基;
—氰基-C1-C4烷基:氰基甲基、1-氰基乙基、2-氰基乙基、1-氰基丙-1-基、2-氰基丙-1-基、3-氰基丙-1-基、1-氰基丁-1-基、2-氰基丁-1-基、3-氰基丁-1-基、4-氰基丁-1-基、1-氰基丁-2-基、2-氰基丁-2-基、3-氰基丁-2-基、4-氰基丁-2-基、1-氰基甲基乙-1-基、1-氰基甲基-1-甲基乙-1-基或1-氰基甲基丙-1-基,优选氰基甲基或2-氰基乙基;
—三(C1-C4烷基)甲硅烷基和三(C1-C4烷基)甲硅烷氧基中的三(C1-C4烷基)甲硅烷基残基:式Ra 3Si的基团,其中Ra为C1-C4烷基且可以相同或不同,例如三甲基甲硅烷基、三乙基甲硅烷基、二甲基乙基甲硅烷基、二甲基异丙基甲硅烷基、二甲基正丁基甲硅烷基或二甲基叔丁基甲硅烷基;
—带有1、2或3个选自O、S和N的杂原子且可以是饱和的、部分或完全不饱和的或芳族的5或6元杂环。饱和的5或6元杂环还可以含有羰基、硫羰基或磺酰基作为环成员。
可以含有羰基、硫羰基或磺酰基环成员的饱和杂环的实例是:四氢呋喃-2-基、四氢呋喃-3-基、四氢噻吩-2-基、四氢噻吩-3-基、吡咯烷-1-基、吡咯烷-2-基、吡咯烷-3-基、1,3-二氧戊环-2-基、1,3-二氧戊环-4-基、1,3-氧硫杂戊环-2-基、1,3-氧硫杂戊环-4-基、1,3-氧硫杂戊环-5-基、1,3-噁唑烷-2-基、1,3-噁唑烷-3-基、1,3-噁唑烷-4-基、1,3-噁唑烷-5-基、1,2-噁唑烷-2-基、1,2-噁唑烷-3-基、1,2-噁唑烷-4-基、1,2-噁唑烷-5-基、1,3-二硫杂戊环-2-基、1,3-二硫杂戊环-4-基、吡咯烷-1-基、吡咯烷-2-基、吡咯烷-5-基、四氢吡唑-1-基、四氢吡唑-3-基、四氢吡唑-4-基、四氢吡喃-2-基、四氢吡喃-3-基、四氢吡喃-4-基(=噁烷-4-基)、四氢噻喃-2-基(=噻烷-4-基)、四氢噻喃-3-基(=噻烷-3-基)、四氢吡喃-3-基(=噁烷-3-基)、哌啶-1-基、哌啶-2-基、哌啶-3-基、哌啶-4-基、1,3-二噁烷-2-基、1,3-二噁烷-4-基、1,3-二噁烷-5-基、1,4-二噁烷-2-基、1,3-氧硫杂己环-2-基、1,3-氧硫杂己环-4-基、1,3-氧硫杂己环-5-基、1,3-氧硫杂己环-6-基、1,4-氧硫杂己环-2-基、1,4-氧硫杂己环-3-基、吗啉-2-基、吗啉-3-基、吗啉-4-基、六氢哒嗪-1-基、六氢哒嗪-3-基、六氢哒嗪-4-基、六氢嘧啶-1-基、六氢嘧啶-2-基、六氢嘧啶-4-基、六氢嘧啶-5-基、哌嗪-1-基、哌嗪-2-基、哌嗪-3-基、六氢-1,3,5-三嗪-1-基、六氢-1,3,5-三嗪-2-基。
部分不饱和杂环的实例是:二氢呋喃-2-基、1,2-噁唑啉-3-基、1,2-噁唑啉-5-基、1,3-噁唑啉-2-基。
芳族杂环的实例是呋喃基,如2-呋喃基和3-呋喃基;噻吩基,如2-噻吩基和3-噻吩基;吡咯基,如2-吡咯基和3-吡咯基;异噁唑基,如3-异噁唑基、4-异噁唑基和5-异噁唑基;异噻唑基,如3-异噻唑基、4-异噻唑基和5-异噻唑基;吡唑基,如3-吡唑基、4-吡唑基和5-吡唑基;噁唑基,如2-噁唑基、4-噁唑基和5-噁唑基;噻唑基,如2-噻唑基、4-噻唑基和5-噻唑基;咪唑基,如2-咪唑基和4-咪唑基;噁二唑基,如1,2,4-噁二唑-3-基、1,2,4-噁二唑-5-基和1,3,4-噁二唑-2-基;噻二唑基,如1,2,4-噻二唑-3-基、1,2,4-噻二唑-5-基和1,3,4-噻二唑-2-基;三唑基,如1,2,4-三唑-3-基、1,2,4-三唑-3-基和1,2,4-三唑-4-基;吡啶基,如2-吡啶基、3-吡啶基和4-吡啶基;哒嗪基,如3-哒嗪基和4-哒嗪基;嘧啶基,如2-嘧啶基、4-嘧啶基和5-嘧啶基;以及2-吡嗪基、1,3,5-三嗪基和1,2,4-三嗪基,尤其是吡啶基、嘧啶基、呋喃基和噻吩基。
在本发明的优选实施方案中,变量R、R1、R2、R3和n具有下列含义:
R1、R2、R3相互独立地为氢,卤素,C1-C4烷基,C1-C4烷氧基,C1-C4卤代烷基,C1-C4烷氧基-C1-C4烷基或可以未被取代或带有1、2、3或4个相互独立地选自卤素、硝基、氰基、烷基、烷氧基、OCHF2或CF3的取代基的苯基;
n为0、1或2;
R为氢,氰基,卤素,C1-C6烷基,C1-C4卤代烷基,C1-C4烷氧基,C2-C4链烯基,C2-C4卤代链烯基,C2-C4炔基,C2-C4卤代炔基,氰基-C1-C4烷基,C1-C4烷氧基-C1-C4烷基,C3-C8环烷基,三(C1-C4烷基)甲硅烷基,三(C1-C4烷基)甲硅烷氧基,COR4,COOR5,CONR6R7,S(O)kR8,苯基,苯氧基,带有1、2或3个选自O、S和N的杂原子且可以为饱和、不饱和或芳族的5或6元杂环,其中苯基、苯氧基和杂环相互独立地可以带有1、2、3或4个相互独立地选自如下的取代基:卤素、硝基、氰基、C1-C4烷基、C1-C4烷氧基、甲基磺酰基、OCHF2、CF3或可以带有1、2或3个相互独立地选自卤素、C1-C4烷基、甲基磺酰基、OCHF2或CF3的基团的苯基;
k为0、1或2;
R4为氢,C1-C6烷基,苯基和苯基-C1-C4烷基,其中苯基和苯基-C1-C4烷基可以在苯基环上带有1、2、3或4个相互独立地选自卤素、硝基、氰基、C1-C4烷基、C1-C4烷氧基、OCHF2或CF3的取代基;
R5为C1-C6烷基,C1-C4烷氧基-C1-C4烷基,苯基和苯基-C1-C4烷基,其中苯基和苯基-C1-C4烷基可以在苯基环上带有1、2、3或4个相互独立地选自卤素、硝基、氰基、C1-C4烷基、C1-C4烷氧基、OCHF2或CF3的取代基;
R6、R7相互独立地为氢,C1-C6烷基,C1-C4烷氧基-C1-C4烷基,苯基和苯基-C1-C4烷基,其中苯基和苯基-C1-C4烷基可以在苯基环上带有1、2、3或4个相互独立地选自卤素、硝基、氰基、C1-C4烷基、C1-C4烷氧基、OCHF2或CF3的取代基;或可以一起形成5或6元杂环,该杂环除氮原子外还可以额外带有1或2个选自N、O或S的其他杂原子;
R8为C1-C6烷基,C1-C4卤代烷基,苯基和苯基-C1-C4烷基,其中苯基和苯基-C1-C4烷基可以在苯基环上带有1、2、3或4个相互独立地选自卤素、硝基、氰基、C1-C4烷基、C1-C4烷氧基、OCHF2或CF3的取代基;
A为C1-C4亚烷基;或
A-R可以一起为二卤代甲基,三卤代甲基,C3-C8环烷基,C2-C4链烯基,C2-C4卤代链烯基,C5-C8环烯基,或带有1、2或3个选自O、S和N的杂原子的5或6元杂环,该杂环可以是饱和、不饱和或芳族的且可以带有1、2、3或4个相互独立地选自卤素、硝基、氰基、C1-C4烷基、C1-C4烷氧基、甲基磺酰基、OCHF2、CF3或苯基的取代基,其中该苯基可以带有1、2或3个选自卤素、C1-C4烷基、甲基磺酰基、OCHF2或CF3的基团,其中环烷基和环烯基可以独立地带有1、2、3或4个相互独立地选自卤素和C1-C4烷基的取代基和/或可以含有羰基或硫羰基作为环成员。
对于它们作为杀真菌剂的意欲用途,优选其中基团R1-R3中至少一个且特别优选R2不为氢的式I噻唑并[4,5-b]吡啶。优选其中R2选自卤素、C1-C4烷基和C1-C4卤代烷基,尤其是氯、溴、甲基和三氟甲基的那些式I化合物。
特别优选其中基团R1-R3如下所定义的那些式I的噻唑并[4,5-b]吡啶,其中在每种情况下无论是单独还是组合均有效:
R1为氢或C1-C4烷基,尤其是氢、卤素、甲基或乙基;
R2为氢、卤素、C1-C4烷基、C1-C4卤代烷基,尤其是氯、溴、甲基或三氟甲基;
R3为氢。
在本发明的优选实施方案中,式I中的变量A选自亚甲基、1,2-亚乙基、1,1-亚乙基或1,3-亚丙基。
在本发明的特别优选实施方案中,式I中的R为环状基团,例如苯基、苯氧基、具有1、2或3个,优选1或2个选自O、S和N的杂原子且可以是饱和、不饱和或芳族的5或6元杂环。苯基、苯氧基和杂环相互独立地可以如上所定义未被取代或被取代。苯基、苯氧基和杂环上的优选取代基为:F、Cl、甲基、二氟甲基、三氟甲基、甲氧基、二氟甲氧基、三氟甲氧基或如上所定义未被取代或被取代的苯基。在该实施方案中,优选如下的噻唑并[4,5-b]吡啶I,其中R为苯基、苯氧基、呋喃基、噻吩基或吡啶基,它们各自可以如上所定义未被取代或被取代。还优选四氢吡喃基(=噁烷基)、四氢噻喃基(=噻烷基)和四氢噻喃基-S,S-二氧化物(=1,1-二氧代噻烷基)。在该特别优选的实施方案中,R还可以为C3-C8环烷基,其可以是未取代的或如上所述被取代。环烷基上的优选取代基选自氯和甲基。
在本发明的另一优选实施方案中,R选自氰基、C1-C4烷氧基、C1-C4烷基、C3-C4链烯基、C1-C4烷氧基-C1-C4烷氧基、氰基-C1-C4烷基、C1-C4烷氧基-C1-C4烷基、三(C1-C4烷基)甲硅烷基、三(C1-C4烷基)甲硅烷氧基、COR4、COOR5、CONR6R7或S(O)kR8,其中基团R4-R8和整数k如上所定义。整数k优选为2。在该实施方案中,优选C1-C4烷氧基、C1-C4烷基、C3-C4链烯基、C1-C4烷氧基-C1-C4烷氧基、C1-C4烷氧基-C1-C4烷基、三(C1-C4烷基)甲硅烷基和三(C1-C4烷基)甲硅烷氧基。
优选R4-R8具有下列含义:
R4为C1-C4烷基和可以在苯基环上带有1、2、3或4个相互独立地选自卤素和C1-C4烷基的取代基的苯基;
R5为C1-C6烷基、C1-C4烷氧基-C1-C4烷基、苯基和苯基-C1-C4烷基,其中苯基和苯基-C1-C4烷基可以在苯基环上带有1或2个相互独立地选自卤素、硝基、氰基、C1-C4烷基、C1-C4烷氧基、OCHF2和CF3的取代基;
R6、R7相互独立地为氢、C1-C6烷基,或者可以与氮原子一起形成吗啉基、哌啶基、哌嗪基或吡咯烷基;
R8为苯基,其可以带有或2个相互独立地选自卤素、C1-C4烷基和CF3的取代基。
优选其中变量n为1或2的式I的噻唑并[4,5-b]吡啶。
式I的噻唑并[4,5-b]吡啶的代表性实例列于表1中。
表1:
实施例 | n | R1 | R2 | R3 | A-R | 计算质量[D] | [M+H]+m/z |
1 | 0 | CH3 | Br | H | CH2CH2OCH2CH2OCH3 | 363,30 | 364,05 |
2 | 0 | CH3 | Br | H | CH2CH=CH2 | 301,23 | 302,95 |
3 | 0 | CH3 | Br | H | CH2CH2CH2CH3 | 317,28 | 319,00 |
4 | 0 | CH3 | Br | H | CH2(4-(CF3)C6H4) | 419,29 | 420,95 |
5 | 0 | CH3 | Br | H | CH2CF3 | 343,19 | 344,95 |
6 | 0 | CH3 | Br | H | CH2(4-(CF3O)C6H4) | 435,29 | 436,95 |
7 | 0 | CH3 | Br | H | CH2CH2O(4-(CH3)C6H4) | 395,35 | 396,05 |
8 | 0 | CH3 | Br | H | CH2(5-(NO2)呋喃-2基) | 386,25 | 387,05 |
9 | 0 | CH3 | Br | H | CH2(3,5-(CH3O)2C6H3) | 411,34 | 413,05 |
10 | 0 | CH3 | Br | H | CH2-c-C6H11 | 357,34 | 358,10 |
11 | 0 | CH3 | Br | H | CH2CH2CH=CH2 | 315,26 | 317,05 |
12 | 0 | CH3 | Br | H | CH2C(CH3)3 | 331,30 | 333,05 |
13 | 0 | CH3 | Br | H | CH2-c-C3H5 | 315,26 | 316,05 |
14 | 0 | CH3 | Br | H | CH3 | 275,19 | 276,00 |
15 | 0 | H | Br | H | CH2CH2CH3 | 289,22 | 290,95 |
16 | 0 | H | Br | H | CH2CH2CH=CH2 | 301,23 | 300,95 |
17 | 0 | H | Br | H | CH2(2-FC6H4) | 355,26 | 356,95 |
18 | 0 | H | Br | H | CH2(2,6-F2C6H3) | 373,25 | 374,85 |
19 | 0 | H | Br | H | CH2(4-FC6H4) | 355,26 | 355,90 |
20 | 0 | H | Br | H | CH2-c-C3H5 | 301,23 | 302,95 |
21 | 0 | H | Br | H | CH3 | 261,17 | 262,85 |
22 | 0 | H | Br | H | c-C5H9 | 315,26 | 316,95 |
23 | 0 | H | Br | H | CH2-c-C6H11 | 343,31 | 344,95 |
24 | 0 | H | Br | H | CH2(2-(CF3)C6H4) | 405,26 | 406,95 |
25 | 0 | H | Br | H | CH2(3,4-C12C6H3) | 406,16 | 406,85 |
26 | 0 | H | Br | H | CH2CHF2 | 311,17 | 312,85 |
27 | 0 | H | Br | H | CH2(2-(C6H5)C6H4) | 413,36 | 412,95 |
28 | 0 | H | Br | H | CH2(噁烷-3-基) | 345,29 | 346,95 |
29 | 0 | H | Br | H | CH2(2,2-Cl2-(3-CH3)-c-C3H2) | 384,15 | 384,85 |
30 | 0 | H | Br | H | CH2-C6H5 | 337,27 | 336,95 |
31 | 0 | H | Br | H | CH2CH(CH3)2 | 303,25 | 304,95 |
32 | 0 | H | Br | H | CH2CH2OC6H5 | 367,29 | 366,95 |
33 | 0 | H | Br | H | CH2CH2OCH2CH2OCH3 | 349,27 | 350,95 |
34 | 0 | H | Br | H | CH2CH=CH2 | 287,21 | 288,85 |
35 | 0 | H | Br | H | CH2CH2CH2CH3 | 303,25 | 302,95 |
36 | 0 | H | Br | H | CH2(4-(CF3)C6H4) | 405,26 | 406,85 |
37 | 0 | H | Br | H | CH2CF3 | 329,16 | 330,85 |
38 | 0 | H | Br | H | CH2(3-ClC6H4) | 371,71 | 372,85 |
39 | 0 | H | Br | H | CH2(3-(CF3O)C6H4) | 421,26 | 422,85 |
40 | 0 | H | Br | H | CH2C(CH3)=CH2 | 301,23 | 300,95 |
41 | 0 | H | Br | H | CH2(3,5-(CH3O)2C6H3) | 397,32 | 398,95 |
42 | 0 | C2H5 | Br | H | CH2C(CH3)3 | 345,33 | 347,15 |
43 | 0 | C2H5 | Br | H | CH2CH2CH3 | 317,28 | 319,15 |
44 | 0 | C2H5 | Br | H | CH2CH2CH=CH2 | 329,29 | 331,15 |
45 | 0 | C2H5 | Br | H | CH2(2-FC6H4) | 383,31 | 385,15 |
46 | 0 | C2H5 | Br | H | CH2(2,6-F2C6H3) | 401,30 | 403,15 |
47 | 0 | C2H5 | Br | H | CH2(4-FC6H4) | 383,31 | 385,15 |
48 | 0 | C2H5 | Br | H | CH3 | 289,22 | 291,15 |
49 | 0 | C2H5 | Br | H | C2H5 | 303,25 | 305,15 |
实施例 | n | R1 | R2 | R3 | A-R | 计算质量[D] | [M+H]+m/z |
50 | 0 | C2H5 | Br | H | CH2-c-C6H11 | 371,37 | 373,25 |
51 | 0 | C2H5 | Br | H | CH2-C6H5 | 365,32 | 367,15 |
52 | 0 | C2H5 | Br | H | CH2CH(CH3)2 | 331,30 | 333,15 |
53 | 0 | C2H5 | Br | H | CH2CH=CH2 | 315,26 | 317,15 |
54 | 0 | C2H5 | Br | H | CH2CH2CH2CH3 | 331,30 | 333,15 |
55 | 0 | C2H5 | Br | H | CH2(4-(CF3)C6H4) | 433,32 | 435,15 |
56 | 0 | C2H5 | Br | H | CH2CH2O(4-(CH3)C6H4) | 409,37 | 411,25 |
57 | 0 | C2H5 | Br | H | CH2(3,4-Cl2C6H3) | 434,21 | 435,15 |
58 | 0 | C2H5 | Br | H | CH2(2,5-Cl2C6H3) | 434,21 | 435,15 |
59 | 0 | C2H5 | Br | H | CH2-c-C3H5 | 329,29 | 331,15 |
60 | 0 | C2H5 | Br | H | C-C5H9 | 343,31 | 345,15 |
61 | 0 | C2H5 | Br | H | CH2(2-(CF3)C6H4) | 433,32 | 435,15 |
62 | 0 | C2H5 | Br | H | CH2CHF2 | 339,23 | 341,15 |
63 | 0 | C2H5 | Br | H | CH2(2-(C6H5)C6H4) | 441,42 | 443,25 |
64 | 0 | C2H5 | Br | H | CH2(噁烷-3-基) | 373,34 | 375,15 |
65 | 0 | C2H5 | Br | H | CH2(2,2-Cl2-(3-CH3)-c-C3H2) | 412,20 | 413,15 |
66 | 0 | C2H5 | Br | H | CH2CH2OC6H5 | 395,35 | 397,15 |
67 | 0 | C2H5 | Br | H | CH2CH2OCH2CH2OCH3 | 377,33 | 379,15 |
68 | 0 | C2H5 | Br | H | CH2(3-ClC6H4) | 399,76 | 400,90 |
69 | 0 | C2H5 | Br | H | CH2(3-(CF3O)C6H4) | 449,32 | 450,90 |
70 | 0 | C2H5 | Br | H | CH2C(CH3)=CH2 | 329,29 | 330,90 |
71 | 0 | C2H5 | Br | H | CH2(3,5-(CH3O)2C6H3) | 425,37 | 426,90 |
72 | 0 | H | CF3 | H | CH2(3,5-(CH3O)2C6H3) | 386,41 | 387,05 |
73 | 0 | H | CF3 | H | CH2C(CH3)=CH2 | 290,33 | 290,95 |
74 | 0 | H | CF3 | H | CH2CH2O(4-(CH3)C6H4) | 370,41 | 371,05 |
75 | 0 | H | CF3 | H | CH2(3-(CF3O)C6H4) | 410,36 | 410,95 |
76 | 0 | H | CF3 | H | CH2CH2(4-(NO2)C6H4) | 385,39 | 385,95 |
77 | 0 | H | CF3 | H | CH2(3-ClC6H4) | 360,81 | 360,95 |
78 | 0 | H | CF3 | H | CH2CF3 | 318,26 | 318,95 |
79 | 0 | H | CF3 | H | CH2(4-(CF3)C6H4) | 394,36 | 394,95 |
80 | 0 | H | CF3 | H | CH2CH2CH2CH3 | 292,34 | 293,05 |
81 | 0 | H | CF3 | H | CH2CH=CH2 | 276,30 | 276,95 |
82 | 0 | H | CF3 | H | CH2CH2OCH2CH2OCH3 | 338,37 | 339,05 |
83 | 0 | H | CF3 | H | CH2CH2OC6H5 | 356,39 | 356,95 |
84 | 0 | H | CF3 | H | CH2CH(CH3)2 | 292,34 | 293,05 |
85 | 0 | H | CF3 | H | CH2-C6H5 | 326,36 | 326,95 |
86 | 0 | H | CF3 | H | CH2(2,2-Cl2-(3-CH3)-c-C3H2) | 373,25 | 372,95 |
87 | 0 | H | CF3 | H | CH2(噻烷-3-基) | 350,45 | 350,95 |
88 | 0 | H | CF3 | H | CH2(噁烷-3-基) | 334,38 | 335,05 |
89 | 0 | H | CF3 | H | CH2(2,5-Cl2C6H3) | 395,25 | 395,85 |
90 | 0 | H | CF3 | H | CH2(2-(C6H5)C6H4) | 402,46 | 403,05 |
91 | 0 | H | CF3 | H | CH2CHF2 | 300,27 | 300,95 |
92 | 0 | H | CF3 | H | CH2(3,4-Cl2C6H3) | 395,25 | 395,85 |
93 | 0 | H | CF3 | H | CH2(2-(CF3)C6H4) | 394,36 | 394,95 |
94 | 0 | H | CF3 | H | CH=C(CH3)2 | 290,33 | 290,95 |
95 | 0 | H | CF3 | H | CH2-c-C6H11 | 332,41 | 330,05 |
96 | 0 | H | CF3 | H | c-C5H9 | 304,36 | 305,05 |
97 | 0 | H | CF3 | H | CH3 | 250,26 | 250,95 |
98 | 0 | H | CF3 | H | CH2-c-C3H5 | 290,33 | 290,95 |
实施例 | n | R1 | R2 | R3 | A-R | 计算质量[D] | [M+H]+m/z |
99 | 0 | H | CH3 | H | CH2-C6H5 | 272,39 | 273,05 |
100 | 0 | H | CH3 | H | CH2CH(CH3)2 | 238,37 | 239,05 |
101 | 0 | H | CH3 | H | CH2CH2OC6H5 | 302,42 | |
102 | 0 | H | CH3 | H | CH2CH2CH2CH3 | 238,37 | 239,15 |
103 | 0 | H | CH3 | H | CH2(4-(CF3)C6H4) | 340,39 | 341,05 |
104 | 0 | H | CH3 | H | CH2CF3 | 264,29 | 265,05 |
105 | 0 | H | CH3 | H | CH2(4-ClC6H4) | 306,84 | 307,05 |
106 | 0 | H | CH3 | H | CH2CH2(4-(NO2)C6H4) | 331,42 | 332,05 |
107 | 0 | H | CH3 | H | CH2C(CH3)=CH2 | 236,36 | 237,10 |
108 | 0 | H | CH3 | H | CH2(5-(NO2)呋喃-2基) | 307,35 | 308,05 |
109 | 0 | H | CH3 | H | c-C5H9 | 250,39 | 251,15 |
110 | 0 | H | CH3 | H | CH2-c-C6H11 | 278,44 | 279,15 |
111 | 0 | H | CH3 | H | CH2C(CH3)3 | 252,40 | 253,15 |
112 | 0 | H | CH3 | H | c-C4H7 | 236,36 | 237,10 |
113 | 0 | H | CH3 | H | CH2CHF2 | 246,30 | 247,05 |
114 | 0 | H | CH3 | H | CH2(噁烷-3-基) | 280,41 | 281,15 |
115 | 0 | H | CH3 | H | CH2(2-(CF3)C6H4) | 340,39 | 341,05 |
116 | 0 | H | CH3 | H | CH2(4-FC6H4) | 290,38 | 291,00 |
117 | 0 | H | CH3 | H | CH3 | 196,29 | 197,00 |
118 | 0 | H | H | H | CH2-c-C3H5 | 222,33 | 223,00 |
119 | 0 | H | H | H | CH3 | 182,27 | 183,05 |
120 | 0 | H | H | H | CH2-C6H5 | 258,36 | 259,00 |
121 | 0 | H | H | H | CH2(2,5-Cl2C6H3) | 327,25 | 328,90 |
122 | 0 | H | H | H | CH2(3-ClC6H4) | 292,81 | 293,90 |
123 | 0 | H | H | H | CH2-c-C6H11 | 264,41 | 265,05 |
124 | 0 | H | H | H | CH2C(CH3)3 | 238,37 | 239,00 |
125 | 0 | H | H | H | CH2CH(CH3)2 | 224,35 | 223,00 |
126 | 0 | H | H | H | CH2CH2CH2CH3 | 224,35 | 225,00 |
127 | 0 | H | H | H | CH2CH3 | 196,29 | 197,00 |
128 | 0 | H | H | H | CH2OC6H5 | 274,36 | 275,90 |
129 | 0 | H | H | H | CH2(3-(CF3)C6H4) | 326,36 | 327,00 |
130 | 0 | H | H | H | CH2CF=CF2 | 262,27 | |
131 | 0 | H | H | H | CH2CHF2 | 232,27 | 232,90 |
132 | 0 | H | Cl | H | CH2CH2OC6H5 | 322,84 | 322,90 |
133 | 0 | H | Cl | H | CH2CH2CH2CH3 | 258,79 | 258,90 |
134 | 0 | H | Cl | H | CH2CH2OCH2CH2OCH3 | 304,82 | 304,90 |
135 | 0 | H | Cl | H | CH2C6H5 | 292,81 | 292,90 |
136 | 0 | H | F | H | CH3 | 200,26 | 200,90 |
137 | 0 | H | F | H | CH2CH3 | 214,28 | 214,90 |
138 | 1 | H | Br | H | CH2CH2CH3 | 305,22 | 304,90 |
139 | 1 | H | Br | H | CH2CH2CH=CH2 | 317,23 | 316,80 |
140 | 1 | H | Br | H | CH2(2-FC6H4) | 371,25 | 372,80 |
141 | 1 | H | Br | H | CH2(2,6-F2C6H3) | 389,24 | 390,80 |
142 | 1 | H | Br | H | CH2(4-FC6H4) | 371,25 | 372,80 |
143 | 1 | H | Br | H | CH2-c-C3H5 | 317,23 | 318,80 |
144 | 1 | H | Br | H | CH3 | 277,17 | 378,80 |
145 | 1 | H | Br | H | c-C5H9 | 331,26 | 330,90 |
146 | 1 | H | Br | H | CH2-c-C6H11 | 359,31 | 360,90 |
147 | 1 | H | Br | H | CH2(2-(CF3)C6H4) | 421,26 | 422,80 |
实施例 | n | R1 | R2 | R3 | A-R | 计算质量[D] | [M+H]+m/z |
148 | 1 | H | Br | H | CH2(3,4-Cl2C6H3) | 422,15 | 422,70 |
149 | 1 | H | Br | H | CH2(2-(C6H5)C6H4) | 429,36 | 430,80 |
150 | 1 | H | Br | H | CH2(噁烷-3-基) | 361,28 | 362,90 |
151 | 1 | H | Br | H | CH2(噻烷-3-基) | 377,35 | 378,15 |
152 | 1 | H | Br | H | CH2(2,2-Cl2-(3-CH3)-c-C3H2) | 400,15 | 400,70 |
153 | 1 | H | Br | H | CH2CH(CH3)2 | 319,25 | 320,80 |
154 | 1 | H | Br | H | CH2CH2OC6H5 | 383,29 | 384,80 |
155 | 1 | H | Br | H | CH2CH2OCH2CH2OCH3 | 365,27 | 366,80 |
156 | 1 | H | Br | H | CH2(4-(CF3)C6H4) | 421,26 | 422,80 |
157 | 1 | H | Br | H | CH2(3-ClC6H4) | 387,71 | 388,80 |
158 | 1 | H | Br | H | CH2(3-(OCF3)C6H4) | 437,26 | 438,80 |
159 | 1 | H | Br | H | CH2(3,5-(CH3O)2C6H3) | 413,32 | 414,80 |
160 | 1 | CH3 | Br | H | CH2CH2CH=CH2 | 331,26 | 332,95 |
161 | 1 | CH3 | Br | H | CH2-c-C3H5 | 331,26 | 332,95 |
162 | 1 | CH3 | Br | H | CH3 | 291,19 | 292,85 |
163 | 1 | CH3 | Br | H | CH2(2,6-F2C6H3) | 403,27 | 404,90 |
164 | 1 | CH3 | Br | H | CH2CHF2 | 341,20 | 342,80 |
165 | 1 | CH3 | Br | H | CH2(2-(C6H5)C6H4) | 443,39 | 442,90 |
166 | 1 | CH3 | Br | H | CH2(3,4-Cl2C6H3) | 436,18 | 436,80 |
167 | 1 | CH3 | Br | H | CH2CH2CH2CH3 | 333,27 | 335,05 |
168 | 1 | CH3 | Br | H | CH2(4-ClC6H4) | 401,74 | 402,95 |
169 | 1 | CH3 | Br | H | CH2CH2(4-(NO2)C6H4) | 426,32 | 425,95 |
170 | 1 | CH3 | Br | H | CH2(3,5-(CH3O)2C6H3) | 427,34 | 429,05 |
171 | 1 | CH3 | Br | H | c-C5H9 | 345,29 | 346,95 |
172 | 1 | CH3 | Br | H | CH2-c-C6H11 | 373,34 | 374,95 |
173 | 1 | CH3 | Br | H | CH2C(CH3)3 | 347,30 | 348,95 |
174 | 1 | CH3 | Br | CH3 | CH2C(CH3)3 | 361,33 | 363,00 |
175 | 1 | CH3 | Br | CH3 | CH2CH2CH=CH2 | 345,29 | 346,70 |
176 | 1 | CH3 | Br | CH3 | CH2(2,6-F2C6H3) | 417,30 | 418,70 |
177 | 1 | CH3 | Br | CH3 | CH2(4-FC6H4) | 399,31 | 400,70 |
178 | 1 | CH3 | Br | CH3 | CH2CH2CH2O(4-ClC6H4) | 459,82 | 460,60 |
179 | 1 | CH3 | Br | CH3 | c-C5H9 | 359,31 | 361,00 |
180 | 1 | CH3 | Br | CH3 | CH2(2-(CF3)C6H4) | 449,32 | 450,70 |
181 | 1 | CH3 | Br | CH3 | CH2(3,4-Cl2C6H3) | 450,21 | 450,90 |
182 | 1 | CH3 | Br | CH3 | CH2(2,5-Cl2C6H3) | 450,21 | 450,60 |
183 | 1 | CH3 | Br | CH3 | CH2(2,2-Cl2-(3-CH3)-c-C3H2) | 428,20 | 428,60 |
184 | 1 | CH3 | Br | CH3 | CH2CH2CH3 | 333,27 | 334,90 |
185 | 1 | CH3 | Br | CH3 | CH2-c-C3H5 | 345,29 | 346,90 |
186 | 1 | CH3 | Br | CH3 | CH2-c-C6H11 | 387,37 | 388,90 |
187 | 1 | CH3 | Br | CH3 | CH2C6H5 | 381,32 | 382,90 |
188 | 1 | CH3 | Br | CH3 | CH2CH(CH3)2 | 347,30 | 348,90 |
189 | 1 | CH3 | Br | CH3 | CH2CH2OC6H5 | 411,34 | 412,90 |
190 | 1 | CH3 | Br | CH3 | CH2(4-(CF3)C6H4) | 449,32 | 450,90 |
191 | 1 | CH3 | Br | CH3 | CH2(3-ClC6H4) | 415,76 | 416,80 |
192 | 1 | CH3 | Br | CH3 | CH2(3-(OCF3)C6H4) | 465,31 | 466,80 |
193 | 1 | CH3 | Br | CH3 | CH2CH2O(4-(CH3)C6H4) | 425,37 | 426,90 |
194 | 1 | CH3 | Br | CH3 | CH2(2-FC6H4) | 399,31 | 400,90 |
195 | 1 | CH3 | Br | CH3 | C2H5 | 319,25 | 320,90 |
196 | 1 | CH3 | Br | CH3 | CH2CHF2 | 355,23 | 356,80 |
实施例 | n | R1 | R2 | R3 | A-R | 计算质量[D] | [M+H]+m/2 |
197 | 1 | CH3 | Br | CH3 | CH2(2-(C6H5)C6H4) | 457,42 | 453,90 |
198 | 1 | CH3 | Br | CH3 | CH2(噁烷-3-基) | 389,34 | 390,90 |
199 | 1 | CH3 | Br | CH3 | CH2CH2CH2CH3 | 347,30 | 348,90 |
200 | 1 | CH3 | Br | CH3 | CH2(3,5-(CH3O)2C6H3) | 441,37 | 442,90 |
201 | 1 | H | Br | C2H5 | CH2(噻烷-3-基) | 405,40 | 407,00 |
202 | 1 | H | Br | C2H5 | CH2CH2CH3 | 333,27 | 334,90 |
203 | 1 | H | Br | C2H5 | CH2CH2CH=CH2 | 345,29 | 346,90 |
204 | 1 | H | Br | C2H5 | CH2(4-FC6H4) | 399,31 | 400,90 |
205 | 1 | H | Br | C2H5 | CH3 | 305,22 | 306,90 |
206 | 1 | H | Br | C2H5 | CH2-c-C3H5 | 345,29 | 346,90 |
207 | 1 | H | Br | C2H5 | CH2(噁烷-3-基) | 389,34 | 390,90 |
208 | 1 | H | Br | C2H5 | CH2CH(CH3)2 | 347,30 | 348,90 |
209 | 1 | H | Br | C2H5 | CH2CH2CH2CH3 | 347,30 | 348,90 |
210 | 1 | H | Br | C2H5 | CH2CH2O(4-(CH3)C6H4) | 425,37 | 426,90 |
211 | 1 | C2H5 | Br | H | CH2C(CH3)3 | 361,33 | 362,90 |
212 | 1 | C2H5 | Br | H | CH2(2-FC6H4) | 399,31 | 400,90 |
213 | 1 | C2H5 | Br | H | CH2(2,6-F2C6H3) | 417,30 | 418,90 |
214 | 1 | C2H5 | Br | H | CH2-c-C6H11 | 387,37 | 388,90 |
215 | 1 | C2H5 | Br | H | CH2C6H5 | 381,32 | 382,90 |
216 | 1 | C2H5 | Br | H | CH2(4-(CF3)C6H4) | 449,32 | 450,90 |
217 | 1 | C2H5 | Br | H | CH2CH2O(4-(CH3)C6H4) | 425,37 | 426,90 |
218 | 1 | C2H5 | Br | H | CH2(2,5-Cl2C6H3) | 450,21 | 450,80 |
219 | 1 | C2H5 | Br | H | CH2-c-C3H5 | 345,29 | 346,90 |
220 | 1 | C2H5 | Br | H | c-C5H9 | 359,31 | 360,90 |
221 | 1 | C2H5 | Br | H | CH2(2-(CF3)C6H4) | 449,32 | 450,90 |
222 | 1 | C2H5 | Br | H | CH2CHF2 | 355,23 | 356,90 |
223 | 1 | C2H5 | Br | H | CH2(2-(C6H5)C6H4) | 457,42 | 459,00 |
224 | 1 | C2H5 | Br | H | CH2(噁烷-3-基) | 389,34 | 391,00 |
225 | 1 | C2H5 | Br | H | CH2(2,2-Cl2-(3-CH3)-c-C3H2) | 428,20 | 428,90 |
226 | 1 | C2H5 | Br | H | CH2CH2OC6H5 | 411,34 | 412,90 |
227 | 1 | C2H5 | Br | H | CH2CH2OCH2CH2OCH3 | 393,33 | 395,00 |
228 | 1 | C2H5 | Br | H | CH2(3-ClC6H4) | 415,76 | 416,90 |
229 | 1 | C2H5 | Br | H | CH2(3-(OCF3)C6H4) | 465,31 | 466,90 |
230 | 1 | C2H5 | Br | H | CH2(3,5-(CH3O)2C6H3) | 441,37 | 442,90 |
231 | 1 | H | CF3 | H | CH2(3,5-(CH3O)2C6H3) | 402,41 | 402,90 |
232 | 1 | H | CF3 | H | CH2(3-ClC6H4) | 376,81 | 376,80 |
233 | 1 | H | CF3 | H | CH2(4-(CF3)C6H4) | 410,36 | 410,80 |
234 | 1 | H | CF3 | H | CH2CH2OC6H5 | 372,39 | 372,90 |
235 | 1 | H | CF3 | H | CH2(2,2-Cl2-(3-CH3)-c-C3H2) | 389,24 | 388,90 |
236 | 1 | H | CF3 | H | CH2(噻烷-3-基) | 366,45 | 367,90 |
237 | 1 | H | CF3 | H | CH2(2,5-Cl2C6H3) | 411,25 | 410,80 |
238 | 1 | H | CF3 | H | CH2(2-(C6H5)C6H4) | 418,46 | 418,90 |
239 | 1 | H | CF3 | H | CH2CHF2 | 316,27 | 316,80 |
240 | 1 | H | CF3 | H | CH2(3,4-Cl2C6H3) | 411,25 | 410,80 |
241 | 1 | H | CF3 | H | CH2(2-(CF3)C6H4) | 410,36 | 410,90 |
242 | 1 | H | CF3 | H | CH2CH2O(4-(CH3)C6H4) | 386,41 | 387,00 |
243 | 1 | H | CF3 | H | CH2(3-(OCF3)C6H4) | 426,36 | 426,90 |
244 | 1 | H | CF3 | H | CH2CH2CH2CH3 | 308,34 | 308,90 |
245 | 1 | H | CF3 | H | CH2CH2OCH2CH2OCH3 | 354,37 | 354,90 |
实施例 | n | R1 | R2 | R3 | A-R | 计算质量[D] | [M+H]+m/z |
246 | 1 | H | CF3 | H | CH2CH(CH3)2 | 308,34 | 308,90 |
247 | 1 | H | CF3 | H | CH2C6H5 | 342,36 | 342,90 |
248 | 1 | H | CF3 | H | CH2(噁烷-3-基) | 350,38 | 350,90 |
249 | 1 | H | CH3 | H | CH2(2-(CF3)C6H4) | 356,39 | 356,95 |
250 | 1 | H | CH3 | H | CH2(4-FC6H4) | 306,38 | 306,95 |
251 | 1 | H | CH3 | H | CH2C(CH3)3 | 268,40 | 269,00 |
252 | 1 | H | CH3 | H | CH2(2,6-Cl2C6H3) | 357,28 | 356,90 |
253 | 1 | H | CH3 | H | CH2(4-(NO2)C6H4) | 333,39 | 334,00 |
254 | 1 | H | CH3 | H | CH2CH2CH=CH2 | 252,36 | 253,00 |
255 | 1 | H | CH3 | H | CH2(3,4-Cl2C6H3) | 357,28 | 356,90 |
256 | 1 | H | CH3 | H | CH2(噁烷-3-基) | 296,41 | 297,00 |
257 | 1 | H | CH3 | H | CH2(4-(NO2)C6H4) | 333,39 | 333,90 |
258 | 1 | H | CH3 | H | CH2(2-(C6H5)C6H4) | 364,49 | 365,00 |
259 | 1 | H | CH3 | H | CH2(2,5-Cl2C6H3) | 357,28 | 356,90 |
260 | 1 | H | CH3 | H | CH2(2-FC6H4) | 306,38 | 307,00 |
261 | 1 | H | CH3 | H | c-C5H9 | 266,38 | 267,00 |
262 | 1 | H | CH3 | H | CH2-c-C6H11 | 294,44 | 295,00 |
263 | 1 | H | CH3 | H | CH2CH2CH3 | 240,35 | 241,00 |
264 | 1 | H | CH3 | H | CH2C(CH3)3 | 268,40 | 269,00 |
265 | 1 | H | CH3 | H | c-C4H7 | 252,36 | 252,90 |
266 | 1 | H | CH3 | H | CH2CHF2 | 262,30 | 262,90 |
267 | 1 | H | CH3 | H | CH2(噁烷-3-基) | 296,41 | 296,90 |
268 | 1 | H | Cl | H | CH2CH2CH2CH3 | 274,79 | 275,15 |
269 | 1 | H | Cl | H | CH2CH2OC6H5 | 338,83 | 339,15 |
270 | 1 | H | Cl | H | CH2CH2CH2CH3 | 274,79 | 275,15 |
271 | 1 | H | Cl | H | CH2CH2OCH2CH2OCH3 | 320,82 | 321,15 |
272 | 1 | H | Cl | H | CH2C6H5 | 308,81 | 309,15 |
273 | 2 | H | Br | H | CH2(2-FC6H4) | 387,25 | 388,8 |
274 | 2 | H | Br | H | CH2(2,6-F2C6H3) | 405,24 | 406,85 |
275 | 2 | H | Br | H | CH2(4-FC6H4) | 387,25 | 388,85 |
276 | 2 | H | Br | H | CH2-c-C3H5 | 333,23 | 334,95 |
277 | 2 | H | Br | H | CH3 | 293,17 | 294,85 |
278 | 2 | H | Br | H | c-C5H9 | 347,26 | 348,95 |
279 | 2 | H | Br | H | CH2-c-C6H11 | 375,31 | 376,95 |
280 | 2 | H | Br | H | CH2(2-(CF3)C6H4) | 437,26 | 438,85 |
281 | 2 | H | Br | H | CH2(3,4-Cl2C6H3) | 438,15 | 438,85 |
282 | 2 | H | Br | H | CH2CHF2 | 343,17 | 344,85 |
283 | 2 | H | Br | H | CH2(噁烷-3-基) | 377,28 | 376,95 |
284 | 2 | H | Br | H | CH2(噻烷-3-基) | 393,35 | 394,05 |
285 | 2 | H | Br | H | CH2(2,2-Cl2-(3-CH3)-c-C3H2) | 416,15 | 416,85 |
286 | 2 | H | Br | H | CH2C6H5 | 369,26 | 370,95 |
287 | 2 | H | Br | H | CH2CH(CH3)2 | 335,25 | 336,95 |
288 | 2 | H | Br | H | CH2CH2OCH2CH2OCH3 | 381,27 | 382,95 |
289 | 2 | H | Br | H | CH2CH2CH2CH3 | 335,25 | 336,95 |
290 | 2 | H | Br | H | CH2CF3 | 361,16 | 362,85 |
291 | 2 | H | Br | H | CH2(3-ClC6H4) | 403,71 | 404,8 |
292 | 2 | H | Br | H | CH2(3,5-(CH3O)2C6H3) | 429,32 | 430,95 |
293 | 2 | CH3 | Br | H | CH2(噻烷-3-基) | 407,38 | 408,05 |
294 | 2 | CH3 | Br | H | CH2CH2CH3 | 335,25 | 336,8 |
实施例 | n | R1 | R2 | R3 | A-R | 计算质量[D] | [M+H]+m/z |
295 | 2 | CH3 | Br | H | c-C4H7 | 347,26 | 348,9 |
296 | 2 | CH3 | Br | H | CH2(2,6-F2C6H3) | 419,27 | 420,8 |
297 | 2 | CH3 | Br | H | CH2(2,2-Cl2-(3-CH3)-c-C3H2) | 430,17 | 430,8 |
298 | 2 | CH3 | Br | H | CH2(2-FC6H4) | 401,28 | 402,8 |
299 | 2 | CH3 | Br | H | CH2C6H5 | 383,29 | 384,9 |
300 | 2 | CH3 | Br | H | CH2CH2OC6H5 | 413,32 | 414,9 |
301 | 2 | CH3 | Br | H | CH2CH2OCH2CH2OCH3 | 395,30 | 396,9 |
302 | 2 | CH3 | Br | H | CH2(4-(CF3)C6H4) | 451,29 | 452,8 |
303 | 2 | CH3 | Br | H | CH2(4-(OCF3)C6H4) | 467,29 | 468,9 |
304 | 2 | CH3 | Br | H | CH2CH(CH3)2 | 349,27 | 350,8 |
305 | 2 | CH3 | Br | H | CH2CH2CH2CH3 | 349,27 | 350,9 |
306 | 2 | CH3 | Br | H | CH2CH2(4-(NO2)C6H4) | 442,31 | 441,9 |
307 | 2 | CH3 | Br | H | CH2(4-(OCF3)C6H4) | 467,29 | 468,9 |
308 | 2 | CH3 | Br | H | CH2CF3 | 375,19 | 374,8 |
309 | 2 | CH3 | Br | CH3 | CH2C(CH3)3 | 377,33 | 379 |
310 | 2 | CH3 | Br | CH3 | CH2CH2CH3 | 349,27 | 350,9 |
311 | 2 | CH3 | Br | CH3 | CH2(2,6-F2C6H3) | 433,30 | 434,9 |
312 | 2 | CH3 | Br | CH3 | CH2-c-C3H5 | 361,28 | 362,9 |
313 | 2 | CH3 | Br | CH3 | CH2CH3 | 335,25 | 336,9 |
314 | 2 | CH3 | Br | CH3 | c-C5H9 | 375,31 | 377 |
315 | 2 | CH3 | Br | CH3 | CH2-c-C6H11 | 403,37 | 405 |
316 | 2 | CH3 | Br | CH3 | CH2(2-(CF3)C6H4) | 465,31 | 466,9 |
317 | 2 | CH3 | Br | CH3 | CH2CHF2 | 371,23 | 372,9 |
318 | 2 | CH3 | Br | CH3 | CH2(1,1-二氧代噻烷-3-基) | 453,40 | 454,9 |
319 | 2 | CH3 | Br | CH3 | CH2(2,2-Cl2-(3-CH3)-c-C3H2) | 444,20 | 444,9 |
320 | 2 | CH3 | Br | CH3 | CH2C6H5 | 397,32 | 398,9 |
321 | 2 | CH3 | Br | CH3 | CH2CH(CH3)2 | 363,30 | 365 |
322 | 2 | CH3 | Br | CH3 | CH2CH2OC6H5 | 427,34 | 429 |
323 | 2 | CH3 | Br | CH3 | CH2CH2CH2CH3 | 363,30 | 356 |
324 | 2 | CH3 | Br | CH3 | CH2CF3 | 389,22 | 390,9 |
325 | 2 | CH3 | Br | CH3 | CH2CH2O(4-(CH3)C6H4) | 441,37 | 443 |
326 | 2 | CH3 | Br | CH3 | CH2(噻烷-3-基) | 421,40 | 422,9 |
327 | 2 | CH3 | Br | CH3 | CH2(2-FC6H4) | 415,31 | 416,9 |
328 | 2 | CH3 | Br | CH3 | CH2(4-FC6H4) | 415,31 | 416,9 |
329 | 2 | CH3 | Br | CH3 | CH2CH2CH2O(4-ClC6H4) | 475,82 | 476,9 |
330 | 2 | CH3 | Br | CH3 | CH2(2-(C6H5)C6H4) | 473,42 | 474,8 |
331 | 2 | CH3 | Br | CH3 | CH2(4-(CF3)C6H4) | 465,31 | 466,8 |
332 | 2 | CH3 | Br | CH3 | CH2(3-ClC6H4) | 431,76 | 432,8 |
333 | 2 | CH3 | Br | CH3 | CH2CH2(4-(NO2)C6H4) | 456,34 | 457,9 |
334 | 2 | CH3 | Br | CH3 | CH2(3-(OCF3)C6H4) | 481,31 | 482,8 |
335 | 2 | CH3 | Br | CH3 | CH2(3,5-(CH3O)2C6H3) | 457,37 | 458,9 |
336 | 2 | H | Br | C2H5 | CH2(2,2-Cl2-(3-CH3)-c-C3H2) | 444,20 | 444,9 |
337 | 2 | C2H5 | Br | H | CH2C(CH3)3 | 377,33 | 378,9 |
338 | 2 | C2H5 | Br | H | CH2CH2CH3 | 349,27 | 350,9 |
339 | 2 | C2H5 | Br | H | CH2(2-FC6H4) | 415,31 | 416,9 |
340 | 2 | C2H5 | Br | H | CH2(4-FC6H4) | 415,31 | 416,9 |
341 | 2 | C2H5 | Br | H | CH2CH3 | 335,25 | 336,9 |
342 | 2 | C2H5 | Br | H | CH2-c-C6H11 | 403,37 | 405 |
343 | 2 | C2H5 | Br | H | CH2CH(CH3)2 | 363,30 | 364,9 |
实施例 | n | R1 | R2 | R3 | A-R | 计算质量[D] | [M+H]+m/z |
344 | 2 | C2H5 | Br | H | CH2CH2CH2CH3 | 363,30 | 364,9 |
345 | 2 | C2H5 | Br | H | CH2(4-(CF3)C6H4) | 465,31 | 466,9 |
346 | 2 | C2H5 | Br | H | CH2CH2O(4-(CH3)C6H4) | 441,37 | 442,9 |
347 | 2 | C2H5 | Br | H | CH2(2,5-Cl2C6H3) | 466,21 | 466,8 |
348 | 2 | C2H5 | Br | H | c-C5H9 | 375,31 | 367,9 |
349 | 2 | C2H5 | Br | H | CH2(2-(CF3)C6H4) | 465,31 | 466,9 |
350 | 2 | C2H5 | Br | H | CH2(2-(C6H5)C6H4) | 473,42 | 474,9 |
351 | 2 | C2H5 | Br | H | CH2(2,2-Cl2-(3-CH3)-c-C3H2) | 444,20 | 444.8 |
352 | 2 | C2H5 | Br | H | CH2CH2OC6H5 | 427,34 | 428,9 |
353 | 2 | C2H5 | Br | H | CH2(3-ClC6H4) | 431,76 | 432,9 |
354 | 2 | C2H5 | Br | H | CH2(3-(OCF3)C6H4) | 481,31 | 482,9 |
355 | 2 | C2H5 | Br | H | CH2(3,5-(CH3O)2C6H3) | 457,37 | 458,9 |
356 | 2 | C2H5 | Br | H | CH2-c-C3H5 | 361,28 | 362,9 |
357 | 2 | C2H5 | Br | H | CH2(噁烷-3-基) | 405,34 | 406,9 |
358 | 2 | H | CF3 | H | CH3 | 282,26 | 282,9 |
359 | 2 | H | CF3 | H | CH2-c-C3H5 | 322,33 | 323,9 |
360 | 2 | H | CF3 | H | CH2(2-(C6H5)C6H4) | 434,46 | 435,25 |
361 | 2 | H | CF3 | H | CH2C(CH3)=CH2 | 322,33 | 322,9 |
362 | 2 | H | CF3 | H | CH2CH=CH2 | 308,30 | 308,9 |
363 | 2 | H | CH3 | H | CH2C(CH3)3 | 284,40 | 285,05 |
364 | 2 | H | CH3 | H | CH2(噁烷-3-基) | 312,41 | 313 |
365 | 2 | H | CH3 | H | CH2(2-(CF3)C6H4) | 372,39 | 372,95 |
366 | 2 | H | CH3 | H | CH2(4-FC6H4) | 322,38 | 323,05 |
367 | 2 | H | CH3 | H | CH2(1,1-二氧代噻烷-3-基) | 360,47 | 360,9 |
368 | 2 | H | CH3 | H | CH2-c-C3H5 | 268,36 | 269 |
369 | 2 | H | CH3 | H | CH2(2-(C6H5)C6H4) | 380,49 | 380,9 |
370 | 2 | H | CH3 | H | CH2(3,4-Cl2C6H3) | 373,28 | 372,8 |
371 | 2 | H | CH3 | H | CH2(2,5-Cl2C6H3) | 373,28 | 372,9 |
372 | 2 | H | CH3 | H | CH2(2-FC6H4) | 322,38 | 322,9 |
373 | 2 | H | CH3 | H | CH2C6H5 | 304,39 | 305 |
374 | 2 | H | CH3 | H | CH2CH2CH2CH3 | 270,37 | 271 |
375 | 2 | H | CH3 | H | CH2CF3 | 296,29 | 297 |
376 | 2 | H | CH3 | H | CH2(4-ClC6H4) | 338,83 | 338,9 |
377 | 2 | H | CH3 | H | CH2CH(CH3)2 | 270,37 | 271 |
378 | 2 | H | CH3 | H | CH2CH2OCH2CH2OCH3 | 316,40 | 317 |
379 | 2 | H | CH3 | H | CH2CH2(4-(NO2)C6H4) | 363,41 | 364,05 |
380 | 2 | H | CH3 | H | CH2CH2O(4-(CH3)C6H4) | 348,44 | 448,95 |
381 | 2 | H | CH3 | H | c-C5H9 | 282,38 | 283,05 |
382 | 2 | H | CH3 | H | CH2-c-C6H11 | 310,44 | 311,05 |
383 | 2 | H | CH3 | H | CH2CH2CH3 | 256,35 | 257,05 |
384 | 2 | H | Cl | H | CH3 | 248,71 | 248,9 |
385 | 2 | H | Cl | H | CH2CH2CH2CH3 | 290,79 | 291,15 |
386 | 2 | H | Cl | H | CH2CH2OC6H5 | 354,83 | 355,15 |
387 | 2 | H | Cl | H | CH2CH2OCH2CH2OCH3 | 336,82 | 337,15 |
388 | 2 | H | Cl | H | CH2C6H5 | 324,81 | 325,15 |
[M+H]+由质谱测定
其中R3为氢的式I的噻唑并[4,5-b]吡啶的其他代表性实例列于表2中。
表2:噻唑并[4,5-b]吡啶389-621
序号 | R1 | R2 | n | A-R | HPLC[t,s] | MS1)[m/z] | MM2)[D] |
389 | H | Cl | 0 | (CH2)2CH=CH2 | |||
400 | H | Cl | 0 | (CH2)2Ph | |||
401 | H | Cl | 0 | (CH2)2(4-ClPh) | |||
402 | H | Cl | 0 | i-C3H7 | |||
403 | H | Cl | 0 | CH2OCH3 | |||
404 | H | Cl | 0 | n-C3H7 | |||
405 | H | Cl | 0 | CH2(c-C3H5) | |||
406 | H | Cl | 0 | c-C4H8 | |||
407 | H | Cl | 0 | c-C5H9 | |||
408 | H | Cl | 0 | C2H5 | |||
409 | H | Cl | 0 | CH2CH=CH2 | |||
410 | H | Cl | 0 | (CH2)3COOC2H5 | |||
411 | H | Cl | 0 | CH2(4-ClPh) | |||
412 | H | Cl | 0 | CH2(4-(CF3)Ph) | |||
413 | H | Cl | 0 | CH2COOCH3 | |||
414 | H | Cl | 0 | CH2CONH2 | |||
415 | H | Cl | 0 | n-C7H15 | |||
416 | H | Cl | 0 | (CH2)5CN | |||
417 | H | Cl | 0 | (CH2)3Cl | |||
418 | H | Br | 0 | C2H5 | |||
419 | H | Br | 0 | CH2CH2-t-C4H9 | |||
420 | H | Br | 0 | CH2CH2-i-C3H7 | |||
421 | H | Br | 0 | i-C3H7 | |||
422 | H | Br | 0 | CH2-c-C4H7 | |||
423 | H | Br | 0 | c-C6H11 | |||
424 | H | Br | 0 | c-C7H13 | |||
425 | H | Br | 0 | c-C8H15 | |||
426 | H | Br | 0 | 2-环己烯基 | |||
427 | H | Br | 0 | CH2C≡CH | |||
428 | H | Br | 0 | CH2Si(CH3)3 | |||
429 | H | Br | 0 | CH2O-n-C8H17 | |||
430 | H | Br | 0 | CH2SCH3 | |||
431 | H | Br | 0 | CH2O(4-ClPh) | |||
432 | H | Br | 0 | CH2SO2Ph |
序号 | R1 | R2 | n | A-R | HPLC[t,s] | MS1)[m/z] | MM2)[D] |
433 | H | Br | 0 | CH2CH2CN | |||
434 | H | Br | 0 | (CH2)3COOC2H5 | |||
435 | H | Br | 0 | CH2COPh | |||
436 | H | Br | 0 | CH2CONH2 | |||
437 | H | Br | 0 | (CH2)3-(4-吡啶基) | |||
438 | H | CH3 | 0 | CH2CH2-t-C4H9 | |||
439 | H | CH3 | 0 | CH2CH2-i-C3H7 | |||
440 | H | CH3 | 0 | i-C3H7 | |||
441 | H | CH3 | 0 | CH2Si(CH3)2(t-C4H9) | |||
442 | H | CH3 | 0 | CH2-c-C3H5 | |||
443 | H | CH3 | 0 | c-C6H12 | |||
444 | H | CH3 | 0 | CH(CH3)Ph | |||
445 | H | CH3 | 0 | (CH2)3-(4-吡啶基) | |||
446 | H | CH3 | 0 | CH2O(4-ClPh) | |||
447 | H | CH3 | 0 | CH2COCH3 | |||
448 | H | CH3 | 0 | CH2CO-t-C4H9 | |||
449 | H | CH3 | 0 | CH(CH3)CONH2 | |||
450 | H | CH3 | 0 | CH2SO2Ph | |||
451 | H | H | 0 | CH2Ph | 3.115 | 259 | 258.37 |
452 | H | H | 0 | CH2CH2OPh | 3.139 | 289.05 | 288.39 |
453 | H | H | 0 | 2-(CH3O-CH2CH2O)C2H4 | 2.169 | 271.05 | 270.37 |
454 | H | H | 0 | CH=CH2 | 2.785 | 209 | 208.31 |
455 | H | H | 0 | CH2[3-(CF3)Ph] | 3.224 | 327 | 326.36 |
456 | H | H | 0 | CH2CF3 | 2.788 | 251.95 | 250.27 |
457 | H | H | 0 | CH2CH2[4-(NO2)Ph] | 2.929 | 318 | 317.39 |
458 | H | H | 0 | CH2[3-(OCF3)Ph] | 3.287 | 344 | 342.36 |
459 | H | H | 0 | CH2[4-(OCF3)Ph] | 3.322 | 344 | 342.36 |
460 | H | H | 0 | CH2C(CH3)=CH2 | 2.983 | 223 | 222.33 |
461 | H | H | 0 | CH2[3,5-(OCH3)2Ph] | 2.914 | 319.05 | 318.42 |
462 | CH3 | Br | 0 | CH2Ph | 3.435 | 352 | 351.29 |
463 | CH3 | Br | 0 | CH2-i-C3H7 | 3.503 | 318.05 | 317.27 |
464 | CH3 | Br | 0 | CH=CH2 | 3.175 | 302.95 | 301.23 |
465 | CH3 | Br | 0 | CH2[3-(CF3)Ph] | 3.546 | 420.05 | 419.29 |
466 | CH3 | Br | 0 | CH2(3-ClPh) | 3.583 | 386.95 | 385.73 |
467 | CH3 | Br | 0 | CH2CH2[4-(NO2)Ph] | 3.289 | 410.95 | 410.31 |
468 | CH3 | Br | 0 | CH2[3-(OCF3)Ph] | 3.597 | 436.95 | 435.29 |
469 | CH3 | Br | 0 | CH2[4-(OCF3)Ph] | 3.646 | 436.95 | 435.29 |
470 | CH3 | Br | 0 | CH2C(CH3)=CH2 | 3.338 | 316.95 | 315.26 |
序号 | R1 | R2 | n | A-R | HPLC[t,s] | MS1)[m/z] | MM2)[D] |
471 | CH3 | Br | 0 | c-C5H9 | 3.55 | 330.05 | 329.28 |
472 | CH3 | Br | 0 | 2-噻吩基 | 3.086 | 344.05 | 343.29 |
473 | CH3 | Br | 0 | CH=C(CH3)2 | 3.186 | 316.05 | 315.26 |
474 | CH3 | Br | 0 | CH2-四氢吡喃-3-基 | 3.495 | 376.05 | 375.37 |
475 | CH3 | Br | 0 | n-C3H7 | 3.359 | 304.05 | 303.24 |
476 | CH3 | Br | 0 | C(CH3)=CH2 | 3.208 | 302.95 | 301.23 |
477 | CH3 | Br | 0 | c-C4H7 | 3.376 | 316.05 | 315.26 |
478 | CH3 | Br | 0 | CH2[2,6-(F)2Ph] | 3.420 | 388.95 | 387.27 |
479 | CH3 | Br | 0 | 3-噻吩基 | 3.038 | 344.5 | 343.29 |
480 | CH3 | Br | 0 | CH2CHF2 | 3.113 | 326.8 | 325.2 |
481 | CH3 | Br | 0 | CH2[2-(Ph)Ph] | 3.812 | 428.05 | 427.39 |
482 | CH3 | Br | 0 | CH2[3,4-(Cl)2Ph] | 3.870 | 421.05 | 420.18 |
483 | CH3 | Br | 0 | CH2-[3-CH3-1,1-(Cl)2-环丙-2-基] | 3.076 | 360.05 | 359.31 |
484 | CH3 | Br | 0 | CH2-四氢噻喃-3-基 | 3.673 | 399.95 | 398.17 |
485 | CH3 | Br | 0 | CH2[2,5-(Cl)2Ph] | 3.839 | 420.95 | 420.18 |
486 | CH3 | Br | 0 | CH2(2-FPh) | 3.476 | 370 | 369.28 |
487 | CH3 | Br | 0 | CH2(4-FPh) | 3.464 | 370.05 | 369.28 |
488 | CH3 | Br | 0 | CH2[4-(NO2)Ph] | 3.215 | 397 | 396.29 |
489 | H | CH3 | 0 | 2-(CH3O-CH2CH2O)C2H4 | 1.877 | 285.05 | 284.4 |
490 | H | CH3 | 0 | CH=CH2 | 2.427 | 223.05 | 222.33 |
491 | H | CH3 | 0 | n-C4H9 | 2.934 | 239.15 | 238.38 |
492 | H | CH3 | 0 | CH2[3-(CF3)Ph] | 3.095 | 341.05 | 340.39 |
493 | H | CH3 | 0 | CH2(3-ClPh) | 3.103 | 307.05 | 306.84 |
494 | H | CH3 | 0 | CH2[3-(OCF3)Ph] | 3.157 | 357.05 | 356.39 |
495 | H | CH3 | 0 | CH2[4-(OCF3)Ph] | 3.151 | 357.05 | 356.39 |
496 | H | CH3 | 0 | CH2C(CH3)=CH2 | 2.711 | 237.1 | 236.36 |
497 | H | CH3 | 0 | CH2-[5-(NO2)呋喃-2基] | 2.373 | 308.05 | 307.35 |
498 | H | CH3 | 0 | CH2[3,5-(OCH3)2Ph] | 2.719 | 333.1 | 332.45 |
499 | H | CH3 | 0 | 4-CH3-c-C6H10 | 3.365 | 279.15 | 278 |
500 | H | CH3 | 0 | CH=C(CH3)2 | 2.736 | 237.05 | 236.36 |
501 | H | CH3 | 0 | CH2CH2CH=CH2 | 2.759 | 237.05 | 236.36 |
502 | H | CH3 | 0 | n-C3H7 | 2.66 | 225.05 | 224.35 |
503 | H | CH3 | 0 | C(CH3)=CH2 | 2.443 | 223.05 | 222.33 |
504 | H | CH3 | 0 | CH2[2,6-(F)2Ph] | 2.905 | 309.05 | 308.37 |
505 | H | CH3 | 0 | CH2-c-C3H5 | 2.707 | 237.1 | 236.36 |
506 | H | CH3 | 0 | CH2[2-(Ph)Ph] | 3.347 | 349.15 | 348.49 |
序号 | R1 | R2 | n | A-R | HPLC[t,s] | MS1)[m/z] | MM2)[D] |
507 | H | CH3 | 0 | CH2[3,4-(Cl)2Ph] | 3.276 | 342.05 | 341.28 |
508 | H | CH3 | 0 | CH2-[3-CH3-1,1-(Cl)2-环丙-2-基] | 2.36 | 281.15 | 280.41 |
509 | H | CH3 | 0 | CH2-四氢噻喃-3-基 | 3.205 | 320.05 | 319.28 |
510 | H | CH3 | 0 | CH2[2,5-(Cl)2Ph] | 3.363 | 342.05 | 341.28 |
511 | H | CH3 | 0 | CH2(2-FPh) | 2.956 | 291.05 | 290.38 |
512 | H | CH3 | 0 | CH2(4-(NO2)Ph) | 2.699 | 318.1 | 317.39 |
513 | H | Cl | 1 | (CH2)2CH=CH2 | |||
514 | H | Cl | 1 | (CH2)2Ph | |||
515 | H | Cl | 1 | (CH2)2(4-ClPh) | |||
516 | H | Cl | 1 | c-C5H9 | |||
517 | H | Cl | 1 | n-C3H7 | |||
518 | H | Cl | 1 | CH2CH=CH2 | |||
519 | H | Cl | 1 | C2H5 | |||
520 | H | Cl | 1 | CH2-c-C3H7 | |||
521 | H | Cl | 1 | (CH2)3COOC2H5 | |||
522 | H | Cl | 1 | CH2O(4-ClPh) | |||
523 | H | Br | 1 | C2H5 | |||
524 | H | Br | 1 | nC4H9 | |||
525 | H | Br | 1 | CH2CH2-t-Bu | |||
526 | H | Br | 1 | CH2CH2-CH(CH3)2 | |||
527 | H | Br | 1 | i-C3H7 | |||
528 | H | Br | 1 | CH2-c-C3H5 | |||
529 | H | Br | 1 | CH2-c-C4-H7 | |||
530 | H | Br | 1 | CH2-c-C6H11 | |||
531 | H | Br | 1 | CH2Ph | |||
532 | H | Br | 1 | CH2C=CH2(CH3) | |||
533 | H | Br | 1 | CH2CH=(CH3)2 | |||
534 | H | Br | 1 | CH2Si(CH3)3 | |||
535 | H | Br | 1 | CH2OC8H17 | |||
536 | H | Br | 1 | CH2CH2CN | |||
537 | H | Br | 1 | (CH2)3COOC2H5 | |||
H | Br | 1 | CH2CH2OPh | ||||
538 | H | Br | 1 | (CH2)3-4-吡啶基 | |||
539 | H | Br | 1 | n-C4H9 | |||
540 | H | Br | 1 | CH2CH2-t-Bu | |||
541 | H | Br | 1 | CH2CH2-i-C3H7 | |||
H | Br | 1 | CH2-c-C6H11 |
序号 | R1 | R2 | n | A-R | HPLC[t,s] | MS1)[m/z] | MM2)[D] |
542 | H | Br | 1 | CH2Ph | |||
543 | H | H | 1 | CH2Ph | 2.24 | 275 | 274.37 |
544 | H | H | 1 | CH2-i-C3H7 | 2.105 | 241.05 | 240.35 |
545 | H | H | 1 | C2H4OPh | 2.289 | 305.05 | 304.39 |
546 | H | H | 1 | 2-(CH3O-CH2CH2O)C2H4 | 1.477 | 287.15 | 286.37 |
547 | H | H | 1 | n-C4H9 | 2.134 | 241.05 | 240.35 |
548 | H | H | 1 | CH2[3-(CF3)Ph] | 2.522 | 343 | 342.36 |
549 | H | H | 1 | CH2CF3 | 1.89 | 268 | 266.27 |
550 | H | H | 1 | CH2(3-ClPh) | 2.522 | 309.85 | 308.81 |
551 | H | H | 1 | CH2CH2[4-(NO2)Ph] | 2.174 | 334 | 333.39 |
552 | H | H | 1 | CH2[3-(OCF3)Ph] | 2.596 | 359 | 358.36 |
553 | H | H | 1 | CH2[4-(OCF3)Ph] | 2.526 | 359 | 358.36 |
554 | H | H | 1 | CH2[3,5-(OCH3)2Ph] | 2.102 | 335.05 | 334.42 |
555 | H | CH3 | 1 | 4-CH3-c-C6H10 | 3.894 | ||
556 | H | CH3 | 1 | CH=C(CH3)2 | 3.186 | ||
557 | H | CH3 | 1 | C(CH3)=CH2 | 3.208 | ||
558 | H | CH3 | 1 | CH2[2,6-(F)2-Ph] | 3.463 | ||
559 | H | CH3 | 1 | CH2-c-C3H5 | 3.338 | ||
560 | H | CH3 | 1 | CH3 | 2.863 | ||
561 | H | Cl | 2 | (CH2)2CH=CH2 | |||
562 | H | Cl | 2 | (CH2)2(4-ClPh) | |||
563 | H | Cl | 2 | (CH2)2Ph | |||
564 | H | Cl | 2 | i-C3H7 | |||
565 | H | Cl | 2 | c-C5H10 | |||
566 | H | Cl | 2 | n-C3H7 | |||
567 | H | Cl | 2 | C2H5 | |||
568 | H | Cl | 2 | CH2CH=CH2 | |||
569 | H | Cl | 2 | CH2[4-(CF3)Ph] | |||
570 | H | Br | 2 | C2H5 | |||
571 | H | Br | 2 | n-C3H7 | |||
572 | H | Br | 2 | CH2CH2-t-C4H9 | |||
573 | H | Br | 2 | CH2CH2-i-C3H7 | |||
574 | H | Br | 2 | i-C3H7 | |||
575 | H | Br | 2 | CH2-c-C4H7 | |||
576 | H | Br | 2 | CH2[4-(CF3)Ph] | |||
577 | H | Br | 2 | c-C6H11 | |||
578 | H | Br | 2 | c-C7H13 | |||
579 | H | Br | 2 | c-C8H15 |
序号 | R1 | R2 | n | A-R | HPLC[t,s] | MS1)[m/z] | MM2)[D] |
580 | H | Br | 2 | CH2CH=CH2 | |||
581 | H | Br | 2 | CH2C=CH(CH3) | |||
582 | H | Br | 2 | CH2SCH3 | |||
583 | H | Br | 2 | (CH2)3COOC2H5 | |||
584 | H | Br | 2 | CH2CH2OPh | |||
585 | H | CF3 | 2 | CH2CH2OSi(CH3)2t-C4H9 | |||
586 | H | Br | 2 | CH2Si(CH3)2t-C4H9 | |||
587 | H | Br | 2 | CH2-c-C4H7 | |||
588 | H | CH3 | 2 | n-C3H7 | |||
589 | H | CH3 | 2 | CH(CH3)-n-C3H7 | |||
590 | H | CH3 | 2 | CH(CH3)-n-C6H13 | |||
591 | H | CH3 | 2 | c-C6H11 | |||
592 | H | CH3 | 2 | c-C7H13 | |||
593 | H | CH3 | 2 | c-C8H15 | |||
594 | H | CH3 | 2 | CH(CH3)CONH2 | |||
595 | H | CH3 | 2 | CH2SO2Ph | |||
596 | H | CH3 | 2 | C2H5 | |||
597 | H | CH3 | 2 | CH2CH2-i-C3H7 | |||
598 | H | CH3 | 2 | CH2CH2OPh | |||
599 | H | CH3 | 2 | (CH2)3-4-吡啶基 | |||
600 | H | H | 2 | CH2Ph | 2.225 | 291 | 290.36 |
601 | H | H | 2 | CH2-i-C3H7 | 2.242 | 257.05 | 256.35 |
602 | H | H | 2 | 2-(C2H5O)Ph | 2.388 | 321.05 | 320.39 |
603 | H | H | 2 | 2-(CH3O-CH2CH2O)C2H4 | 1.571 | 303.05 | 302.37 |
604 | H | H | 2 | n-C4H9 | 2.253 | 257.05 | 256.35 |
605 | H | H | 2 | CH2[3-(CF3)Ph] | 2.629 | 359.05 | 358.36 |
606 | H | H | 2 | CH2CF3 | 2.109 | 283 | 282.26 |
607 | H | H | 2 | CH2[3-ClPh] | 2.522 | 325.95 | 324.81 |
608 | H | H | 2 | CH2CH2[4-(NO2)Ph] | 2.235 | 350.05 | 349.39 |
609 | H | H | 2 | CH2[3-(OCF3)Ph] | 2.708 | 375.05 | 374.36 |
610 | H | H | 2 | CH2[4-(OCF3)Ph] | 2.532 | 375.05 | 374.36 |
611 | H | H | 2 | CH2[3,5-(OCH3)2Ph] | 2.213 | 351.05 | 350.42 |
612 | CH3 | Br | 2 | 2-(C2H5O)Ph | 2.797 | 414.9 | 413.31 |
612 | CH3 | Br | 2 | CH2[3-(CF3)Ph] | 3.001 | 452.9 | 451.29 |
614 | CH3 | Br | 2 | CH2[3-(Cl)Ph] | 2.951 | 418.8 | 417.73 |
615 | CH3 | Br | 2 | CH2[3,5-(OCH3)2Ph] | 2.770 | 444.9 | 443.34 |
616 | H | CH3 | 2 | 2-(C2H5O)Ph | 2.382 | 335 | 334.42 |
617 | H | CH3 | 2 | 2-(CH3O-CH2CH2O)C2H4 | 1.711 | 317 | 316.4 |
序号 | R1 | R2 | n | A-R | HPLC[t,s] | MS1)[m/z] | MM2)[D] |
618 | H | CH3 | 2 | CH2[3-(CF3)Ph] | 2.798 | 373 | 372.39 |
619 | H | CH3 | 2 | CH2CF3 | 2.166 | 296.9 | 296.29 |
620 | H | CH3 | 2 | CH2[3-(Cl)Ph] | 2.581 | 339.5 | 338.84 |
621 | H | CH3 | 2 | CH2[4-(OCF3)Ph] | 2.574 | 349.9 | 348.39 |
1)MS=质谱
2)MM=摩尔质量(计算值)
n-CmH2m+1:正烷基;
c-CmH2m-1:环烷基;
i-C3H7:异丙基;
t-C4H9:叔丁基;
Ph:C6H5;
2-FPh=2-FC6H4:2-氟苯基;
4-FPh=4-FC6H4:4-氟苯基;
3-ClPh=2-ClC6H4:3-氯苯基;
4-ClPh=4-ClC6H4:4-氯苯基;
2-(CF3)Ph=2-(CF3)C6H4:2-(三氟甲基)苯基;
3-(CF3)Ph=3-(CF3)C6H4:3-(三氟甲基)苯基;
4-(CF3)Ph=4-(CF3)C6H4:4-(三氟甲基)苯基;
4-(CH3)Ph=4-(CH3)C6H4:4-(甲基)苯基;
3-(OCF3)Ph=3-(OCF3)C6H4:3-(三氟甲氧基)苯基;
4-(OCF3)Ph=4-(OCF3)C6H4:4-(三氟甲氧基)苯基;
4-(NO2)Ph=4-(NO2)C6H4:4-(硝基)苯基;
2-(Ph)Ph=2-(C6H5)C6H4:邻联苯基;
3,5-(OCH3)2Ph=3,5-(OCH3)2C6H3:3,5-二(甲氧基)苯基;
2,6-(F)2Ph=2,6-(F)2C6H3:2,6-二氟苯基;
3,4-(Cl)2Ph=3,4-(Cl)2C6H3:3,4-二氯苯基;
2,5-(Cl)2Ph=2,5-(Cl)2C6H3:2,5-二氯苯基;
2-CH3-5-(NO2)呋喃基=2-甲基-5-硝基呋喃基;
CH2(1,1-二氧代噻烷-3-基):
CH2(2,2-Cl2-(3-CH3)-c-C3H2):
式I化合物可以根据下列方案1所示的反应顺序得到:
方案1:
在式I、II、III和IV中,变量A、R、R1、R2、R3具有上面所定义的含义。Hal表示溴或碘。卤化物表示氯化物、溴化物或碘化物。
在步骤a)中,首先将式II的2-氨基吡啶卤化,得到式III的3-卤代-2-氨基吡啶。通常使用溴进行溴化[参见:A.Fuss,V.Koch,Synthesis(合成)1990,681-685;M.Tonga,J.Bupp,T.Tochimoto,J.Heterocycl.Chem.(杂环化学杂志)1994,31,1641-1644]或使用N-溴代琥珀酰亚胺(NBS)进行溴化[参见:J.Mouton,M.Schmitt,V.Collort,J.Bourguignon,Heterocycles(杂环)1997,45,897-910;R.Beugelmans,M.Chban,Bull.Soc.Chim.France(法国化学会公报)1995,132,290-305]。碘化可以通过用碘或ICl处理式II的2-氨基吡啶而完成[参见:M.V.Jovanovic,Heterocycles 1994,22,1195-1210]。特别优选使用溴进行溴化。
有利的是使用至少1摩尔当量的卤素,优选1.05-1.5摩尔当量的卤素进行卤化。该反应通常在惰性有机溶剂中进行。合适的溶剂是羧酸,优选C2-C5羧酸,如乙酸、丙酸、丁酸和戊酸,以及环状或无环烃类,如正戊烷、正己烷、正庚烷、正辛烷、石油醚、环己烷或卤代溶剂,如二氯甲烷、三氯甲烷。还可以使用这些溶剂的混合物。
卤化通常在0℃至溶剂的沸点的温度下进行,优选在10-70℃下进行。
以常规方式对反应混合物进行后处理。化合物III可能因形成区域异构体或二次溴化而伴有副产物。这些副产物可以通过柱层析或结晶而除去。
另外,如方案2所示,还可以根据L.Estel,F.Marsais,G.Queguiner,J.Org.Chem.(有机化学杂志)1988,53,2740-2744所述的程序制备化合物III。
方案2:
首先例如通过酰化保护氨基。新戊酰基是有用的氨基保护基团且可以例如通过L.Estel,F.Marsais,G.Queguiner,J.Org.Chem.(有机化学杂志)1988,53,2740-2744所述的方法引入II中。然后通过加入有机锂化合物如正丁基锂或叔丁基锂、苯基锂或优选在仲胺如二异丙基胺、2,2,6,6-四甲基哌啶或二环己基胺存在下或通过加入相应的氨基锂如二异丙基氨基锂、2,2,6,6-四甲基哌啶锂、二环己基氨基锂或六甲基二硅氮烷制备相应的3-锂代吡啶。金属化通常需要不止1摩尔当量的有机锂化合物,优选1.1-5摩尔当量,基于化合物II。通过随后加入碘并裂解保护基团将所得有机锂化合物转化成化合物III。通常使用稍微摩尔过量的碘。例如通过使III’与酸或碱如盐酸(Heterocycles,1994,39,S.271)或氢氧化锂(TetrahedronLetters(四面体通讯)1997,38,4037)反应而脱除保护基团。
金属化和碘化通常在-100℃至50℃,优选-80℃至20℃下在惰性有机溶剂中进行。合适的溶剂是醚类,如乙醚、甲基叔丁基醚、二异丙基醚、四氢呋喃、二噁烷、1,2-二甲氧基乙烷;烷烃类,如正戊烷、正己烷、正庚烷、正辛烷、石油醚和环己烷或其混合物。
制备化合物I所需的原料,即式II的2-氨基吡啶由文献已知,或可以通过已知方法制备[参见:Pozharskii,Simonov,Doron’kin,Russ.Chem.Rev.(俄罗斯化学综述)1978,47,1042-1060]。
在步骤b)中,用黄原酸酯的钾盐,优选黄原酸乙酯的钾盐处理式III化合物,得到式IV的对应2-硫基噻唑并[4,5-b]吡啶。可以类似于由邻卤代苯胺制备苯并噻唑而进行环化,如N.C.Chaudhuri,Synth.Commun.(合成通报)1996,26,3783-3790;N.Suzuki,Y.Tanaka,R.Dohmari,Chem.Pharm.Bull.(化学药物公报),1079,27,1-11所述。优选使用1.5-5摩尔当量的所述钾盐处理化合物III。该反应通常在极性溶剂如水和/或醇,和/或无质子极性溶剂如酰胺(如N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮)或亚砜(如二甲亚砜)或其混合物中进行。优选该反应在N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮或其混合物中进行。使用无质子极性溶剂和额外的水作为助溶剂是可能的(参见EP-A 35219)。此时水的量基于有机溶剂量为约10-200重量%。该反应通常在25-250℃,优选60-210℃,尤其是180℃以上进行。
在步骤c)中,引入基团R,得到式I的噻唑并[4,5-b]吡啶,其中n为0。为了得到化合物I,可以使化合物IV与式R-A-卤化物的有机卤化物在碱存在下反应。卤化物是指氯化物、溴化物或碘化物。可以使用的碱对本领域熟练技术人员来说是众所周知的且例如为碱金属碳酸盐,如碳酸锂、碳酸钠、碳酸钾,碳酸氢盐,如碳酸氢镁、碳酸镁,碱金属醇盐,如甲醇钠、乙醇钠、甲醇钾、乙醇钾、叔丁醇钾。特别优选碳酸钠、碳酸钾、甲醇钠、甲醇钾、乙醇钠和乙醇钾。通常使用稍微过量,优选1.1-2摩尔当量的有机卤化物。该反应通常在无质子极性溶剂,如N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮,醚类如四氢呋喃、乙醚、甲基叔丁基醚,亚砜如二甲亚砜或其混合物中进行,优选在四氢呋喃、乙醚、甲基叔丁基醚、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮或二甲亚砜中进行。该反应通常在约0-200℃,优选约20-150℃的温度下进行。
另外,其中基团-A-R代表烯属不饱和基团的化合物I可以通过使化合物IV与带有α-氢的脂族或环状醛在路易斯酸存在下例如根据Mukaiama和Saigo,Chem.Lett.(化学通讯)479(1973)或Akiyania,Bull.Chem.Soc.Jpn.(日本化学会通报)50,936(1977)反应而制备。
在式I中,n还可以为1或2。其中n为0的硫化物I可以通过大约等摩尔量的过氧化氢或通过用其他氧化剂如氢过氧化叔丁基或过酸如间氯过苯甲酸、过乙酸处理而转化成其中n=1的亚砜化合物I(步骤d))。该亚砜化合物可以通过另一摩尔的氧化剂进一步氧化成其中n=2的砜化合物I。硫化物I(n=0)可以在不分离亚砜的情况下直接转化成砜化合物I(n=2)(步骤e)。步骤d)和e)的合适溶剂是卤代烷烃,如二氯甲烷、氯仿、四氯甲烷或氯苯,醇类,如甲醇、乙醇、正丙醇、异丙醇、正丁醇,酰胺类,如二甲基甲酰胺、二甲基乙酰胺,环状或无环烷烃,如环己烷、己烷、戊烷、庚烷、石油醚。优选的溶剂是二氯甲烷和氯仿。氧化通常在约-80℃至100℃,优选约-20℃至50℃下进行。
化合物I适于作为杀真菌剂。它们对宽范围的植物病原性真菌具有显著的活性,所述真菌尤其选自子囊菌纲(Ascomycetes)、半知菌纲(Deuteromycetes)、藻菌纲(Phycomycetes)和担子菌纲(Basidiomycetes)真菌。它们中的一些起内吸作用并可以作为叶面和土壤作用杀真菌剂用于作物保护中。
它们对在各种作物如小麦、黑麦、大麦、燕麦、稻、玉米、禾草、香蕉、棉花、大豆、咖啡、甘蔗、葡萄藤、水果品种、观赏植物和蔬菜如黄瓜、豆类、西红柿、土豆和葫芦科植物以及这些植物的种子中防治大量真菌尤其重要。
具体而言,它们适于防治下列植物病害:
蔬菜和水果上的链格孢(Alternaria)属,
草莓、蔬菜、观赏植物和葡萄藤上的Botrytis cinerea(灰霉病),
花生上的落花生尾孢(Cercospora arachidicola),
葫芦科植物上的二孢白粉菌(Erysiphe cichoracearum)和单丝壳(Sphaerotheca fuliginea),
禾谷类上的Erysiphe graminis(白粉病),
各种植物上的链孢霉(Fusarium)和轮枝孢(Verticillium)属,
禾谷类上的长蠕孢(Helminthosporium)属,
香蕉和花生上的球腔菌(Mycosphaerella)属,
土豆和西红柿上的致病疫霉(Phytophthora infestans),
葡萄藤上的葡萄生单轴霉(Plasmopara viticola),
苹果上的苹果白粉病菌(Podosphaera leucotricha),
小麦和大麦上的眼斑病菌(Pseudocercosporella herpotrichoides),
啤酒花和黄瓜上的假霜霉(Pseudoperonospora)属,
禾谷类上的柄锈菌(Puccinia)属,
稻上的稻瘟病菌(Pyricularia oryzae),
棉花、稻和草坪上的丝核菌(Rhizoctonia)属,
小麦上的颖枯壳针孢(Septoria nodorum),
葡萄藤上的葡萄钩丝壳(Uncinula necator),
禾谷类和甘蔗上的黑粉菌(Ustilago)属,以及
苹果和梨上的Venturia属(黑星病)。
此外,化合物I还适于防治有害真菌如拟青霉(Paecilomyces variotii)以保护材料(如木材、纸张、漆分散体、纤维和织物)和保护储藏的产品。
化合物I通过用杀真菌有效量的活性成分处理真菌或需要防止真菌侵染的植物、种子、材料或土壤而施用。施用可以在材料、植物或种子被真菌侵染之前或之后进行。
通常而言,杀真菌组合物包含0.1-95重量%,优选0.5-90重量%的活性成分。
当用于作物保护时,施用率取决于所需效果的性质为0.01-2.0kg活性成分/公顷。
在处理种子时,每kg种子通常需要的活性成分量为0.001-0.1g,优选0.01-0.05g。
当用于保护材料或储藏产品时,活性成分的施用率取决于施用场地的性质和所需效果。在保护材料中通常使用的施用率例如为0.001g至2kg,优选0.005g至1kg活性成分/m3处理材料。
可以将化合物I转化成常规配制剂,例如溶液、乳液、悬浮液、粉剂、粉末、糊和粒剂。使用形式取决于具体的目的;在每种情况下都应确保本发明化合物精细和均匀地分布。
配制剂以已知方式制备,例如通过将活性成分与溶剂和/或载体混合来制备,需要的话使用乳化剂和分散剂,若使用水作为稀释剂,则还可以使用其它有机溶剂作为辅助溶剂。适合的助剂主要是溶剂如芳族化合物(如二甲苯),氯代芳族化合物(如氯苯),链烷烃(如矿物油馏分),醇(如甲醇、丁醇),酮(如环己酮),胺(如乙醇胺、二甲基甲酰胺)和水;载体如磨碎的天然矿物(如高岭土、粘土、滑石、白垩)和磨碎的合成矿物(如高度分散的硅石、硅酸盐);乳化剂如非离子和阴离子乳化剂(如聚氧乙烯脂肪醇醚、烷基磺酸盐和芳基磺酸盐)以及分散剂如木素亚硫酸盐废液和甲基纤维素。
合适的表面活性剂是木质素磺酸、萘磺酸、苯酚磺酸、二丁基萘磺酸的碱金属盐、碱土金属盐和铵盐,烷基芳基磺酸盐,烷基硫酸盐,烷基磺酸盐,脂肪醇硫酸盐以及脂肪酸及其碱金属和碱土金属盐,硫酸化脂肪醇乙二醇醚的盐,磺化萘和萘衍生物与甲醛的缩合物,萘或萘磺酸与苯酚或甲醛的缩合物,聚氧乙烯辛基苯基醚,乙氧基化的异辛基酚、辛基酚、壬基酚,烷基酚聚乙二醇醚,三丁基苯基聚乙二醇醚,烷基芳基聚醚醇,异十三烷醇,脂肪醇/氧化乙烯缩合物,乙氧基化蓖麻油,聚氧乙烯烷基醚,乙氧基化聚氧丙烯,月桂醇聚乙二醇醚缩醛,山梨醇酯,木素亚硫酸盐废液和甲基纤维素。
适于制备直接可喷雾溶液、乳液、糊或油分散体的物质是中沸点到高沸点的矿物油馏分,如煤油或柴油,此外还有煤焦油和植物或动物来源的油,脂族、环状和芳族烃,例如苯、甲苯、二甲苯、链烷烃、四氢化萘、烷基化萘或其衍生物、甲醇、乙醇、丙醇、丁醇、氯仿、四氯化碳、环己醇、环己酮、氯苯、异佛尔酮,强极性溶剂,例如二甲基甲酰胺、二甲亚砜、N-甲基吡咯烷酮和水。
粉末、撒播用材料和粉剂可以通过将活性物质与固体载体混合或同时研磨而制备。
粒剂如包膜粒剂、浸渍粒剂和均相粒剂可以通过将活性成分与固体载体粘附而制备。固体载体的实例是矿土如硅石、硅胶、硅酸盐、滑石、高岭土、Attaclay、石灰石、石灰、白垩、红玄武土、黄土、粘土、白云石、硅藻土、硫酸钙、硫酸镁、氧化镁;磨碎的合成材料;肥料如硫酸铵、磷酸铵、硝酸铵、尿素;植物来源的产品如谷粉、树皮粉、木粉和坚果壳粉;纤维素粉和其它固体载体。
通常而言,配制剂包含0.01-95重量%,优选0.1-90重量%的活性成分。活性成分以90-100%,优选95-100%的纯度(根据NMR光谱)使用。
下列为配制剂的实例:
I.将5重量份本发明化合物与95重量份细碎高岭土均匀混合。这得到包含5重量%活性成分的粉剂。
II.将30重量份本发明化合物与92重量份粉状硅胶和8重量份喷雾于该硅胶表面上的石蜡油的混合物均匀混合。这得到具有良好粘附性能的活性成分配制剂(包含23重量%活性成分)。
III.将10重量份本发明化合物溶于由90重量份二甲苯、6重量份的8-10mol氧化乙烯与1mol油酸N-单乙醇酰胺的加合物、2重量份十二烷基苯磺酸钙和2重量份的40mol氧化乙烯与1mol蓖麻油的加合物组成的混合物中(包含9重量%活性成分)。
IV.将20重量份本发明化合物溶于由60重量份环己酮、30重量份异丁醇、5重量份的7mol氧化乙烯与1mol异辛基苯酚的加合物和5重量份的40mol氧化乙烯与1mol蓖麻油的加合物组成的混合物中(包含16重量%活性成分)。
V.将80重量份本发明化合物与3重量份二异丁基萘-α-磺酸钠、10重量份来自亚硫酸盐废液的木质素磺酸的钠盐和7重量份粉状硅胶彻底混合,并将该混合物(包含80重量%活性成分)在锤磨机中研磨。
VI.将90重量份本发明化合物与10重量份N-甲基-α-吡咯烷酮混合,得到适于以微滴形式使用的溶液(包含90重量%活性成分)。
VII.将20重量份本发明化合物溶于由40重量份环己酮、30重量份异丁醇、20重量份的7mol氧化乙烯与1mol异辛基苯酚的加合物以及10重量份的40mol氧化乙烯与1mol蓖麻油的加合物组成的混合物中。将该溶液倾入100,000重量份水中并使其在其中精细分布,得到包含0.02重量%活性成分的水分散体。
VIII.将20重量份本发明化合物与3重量份二异丁基萘-α-磺酸钠、17重量份来自亚硫酸盐废液的木质素磺酸的钠盐和60重量份粉状硅胶彻底混合,并将该混合物在锤磨机中研磨。将该混合物精细地分布在20,000重量份水中,得到包含0.1重量%活性成分的喷雾混合物。
活性成分可以通过喷雾、雾化、撒粉、撒播或浇灌直接使用,以其配制剂形式或由其制备的使用形式使用,例如以直接可喷溶液、粉末、悬浮液或分散体、乳液、油分散体、糊、粉剂、撒播用材料或粒剂形式使用。使用形式完全取决于意欲的目的;在各种情况下都应确保本发明的活性成分尽可能精细地分布。
含水使用形式可以通过添加水由乳油、糊或可湿性粉剂(可喷雾粉末、油分散体)制备。为了制备乳液、糊或油分散体,可以通过湿润剂、增稠剂、分散剂或乳化剂将物质直接或溶于油或溶剂之后在水中均化。作为选择,可以制备由活性物质、湿润剂、增稠剂、分散剂或乳化剂以及合适的话,溶剂或油组成的浓缩物且该类浓缩物适于用水稀释。
活性成分在即用产品中的浓度可以在较宽范围内变化。它们通常为0.0001-10重量%,优选0.01-1重量%,基于组合物总量。
活性成分还可成功地以超低容量方法(ULV)使用,其中可以施用包含超过95重量%活性成分的配制剂或甚至可以在没有添加剂的情况下施用活性成分。
可以将各种类型的油、除草剂、杀真菌剂、其它杀虫剂或杀菌剂加入活性成分中,合适的话在紧临使用之前(桶混合)加入。这些试剂通常可以与本发明试剂以1∶50至50∶1,优选1∶10至10∶1的重量比混合。
在作为杀真菌剂的使用形式中,本发明组合物还可与其它活性成分一起存在,例如与除草剂、杀虫剂、生长调节剂、杀真菌剂或肥料一起存在。将化合物I或包含它们的组合物以作为杀真菌剂的使用形式与其它杀真菌剂混合通常产生更宽的杀真菌作用谱。
下列本发明化合物可以与其一起使用的杀真菌剂用来阐述可能的组合,而不施以任何限制:
硫,二硫代氨基甲酸盐及其衍生物,例如二甲基二硫代氨基甲酸铁(III)、二甲基二硫代氨基甲酸锌、亚乙基双-二硫代氨基甲酸锌、亚乙基双-二硫代氨基甲酸锰、乙二胺双-二硫代氨基甲酸锰锌、二硫化四甲基秋兰姆、(N,N-亚乙基双-二硫代氨基甲酸)锌的氨配合物、(N,N’-亚丙基双-二硫代氨基甲酸)锌的氨配合物、(N,N’-亚丙基双-二硫代氨基甲酸)锌、N,N’-聚亚丙基双(硫代氨基甲酰基)二硫化物;
硝基衍生物,例如巴豆酸二硝基(1-甲基庚基)苯基酯、3,3-二甲基丙烯酸2-仲丁基-4,6-二硝基苯基酯、碳酸2-仲丁基-4,6-二硝基苯基异丙基酯、5-硝基-间苯二甲酸二异丙基酯;
杂环物质,例如乙酸2-十七烷基-2-咪唑啉酯、2,4-二氯-6-(邻氯苯胺基)-s-三嗪、邻苯二甲酰亚胺基硫代膦酸O,O-二乙基酯、5-氨基-1-[双(二甲基氨基)氧膦基]-3-苯基-1,2,4-三唑、2,3-二氰基-1,4-二硫代蒽醌、2-硫代-1,3-二硫杂环戊二烯并[4,5-b]-喹喔啉、1-(丁基氨基甲酰基)-2-苯并咪唑氨基甲酸甲酯、2-甲氧基羰基氨基苯并咪唑、2-(2-呋喃基)-苯并咪唑、2-(4-噻唑基)苯并咪唑、N-(1,1,2,2-四氯乙硫基)四氢邻苯二甲酰亚胺、N-三氯甲硫基四氢邻苯二甲酰亚胺、N-三氯甲硫基邻苯二甲酰亚胺;
N-二氯一氟甲硫基-N’,N’-二甲基-N-苯基磺基二酰胺、5-乙氧基-3-三氯甲基-1,2,3-噻二唑、2-硫氰酸基甲硫基苯并噻唑、1,4-二氯-2,5-二甲氧基苯、4-(2-氯苯基亚肼基)-3-甲基-5-异噁唑酮、吡啶-2-硫醇1-氧化物、8-羟基喹啉或其铜盐、2,3-二氢-5-甲酰苯胺基-6-甲基-1,4-氧硫杂环己二烯、2,3-二氢-5-甲酰苯胺基-6-甲基-1,4-氧硫杂环己二烯4,4-二氧化物、2-甲基-5,6-二氢-4H-吡喃-3-甲酰苯胺、2-甲基呋喃-3-甲酰苯胺、2,5-二甲基呋喃-3-甲酰苯胺、2,4,5-三甲基呋喃-3-甲酰苯胺、N-环己基-2,5-二甲基呋喃-3-甲酰胺、N-环己基-N-甲氧基-2,5-二甲基呋喃-3-甲酰胺、2-甲基苯甲酰苯胺、2-碘代苯甲酰苯胺、N-甲酰基-N-吗啉-2,2,2-三氯乙基缩醛、哌嗪-1,4-二基双-1-(2,2,2-三氯乙基)甲酰胺、1-(3,4-二氯苯胺基)-1-甲酰基氨基-2,2,2-三氯乙烷、2,6-二甲基-N-十三烷基吗啉或其盐、2,6-二甲基-N-环十二烷基吗啉或其盐、N-[3-(对叔丁基苯基)-2-甲基丙基]-顺式-2,6-二甲基吗啉、N-[3-(对叔丁基苯基)-2-甲基丙基]哌啶、1-[2-(2,4-二氯苯基)-4-乙基-1,3-二氧戊环-2-基-乙基]-1H-1,2,4-三唑、1-[2-(2,4-二氯苯基)-4-正丙基-1,3-二氧戊环-2-基-乙基]-1H-1,2,4-三唑、N-(正丙基)-N-(2,4,6-三氯苯氧基乙基)-N’-咪唑基脲、1-(4-氯苯氧基)-3,3-二甲基-1-(1H-1,2,4-三唑-1-基)-2-丁酮、1-(4-氯苯氧基)-3,3-二甲基-1-(1H-1,2,4-三唑-1-基)-2-丁醇、(2RS,3RS)-1-[3-(2-氯苯基)-2-(4-氟苯基)-氧化乙烯-2-基甲基]-1H-1,2,4-三唑、α-(2-氯苯基)-α-(4-氯苯基)-5-嘧啶甲醇、5-丁基-2-二甲基氨基-4-羟基-6-甲基嘧啶、双(对氯苯基)-3-吡啶甲醇、1,2-双(3-乙氧基羰基-2-硫脲基)苯、1,2-双(3-甲氧基羰基-2-硫脲基)苯;
嗜球果伞素,例如E-甲氧亚氨基-[α-(邻甲苯氧基)-邻甲苯基]乙酸甲酯、E-2-{2-[6-(2-氰基苯氧基)嘧啶-4-基氧基]苯基}-3-甲氧基丙烯酸甲酯、甲基-E-甲氧亚氨基-[α-(2-苯氧基苯基)]乙酰胺、甲基-E-甲氧亚氨基-[α-(2,5-二甲基苯氧基)-邻甲苯基]乙酰胺;
苯胺基嘧啶,例如N-(4,6-二甲基嘧啶-2-基)苯胺、N-[4-甲基-6-(1-丙炔基)嘧啶-2-基]苯胺、N-[4-甲基-6-环丙基嘧啶-2-基]苯胺;
苯基吡咯,例如4-(2,2-二氟-1,3-苯并二氧杂环戊烯-4-基)吡咯-3-甲腈;
肉桂酰胺,例如3-(4-氯苯基)-3-(3,4-二甲氧基苯基)丙烯酰基吗啉;和
各种杀真菌剂,例如乙酸十二烷基胍、3-[3-(3,5-二甲基-2-氧基环己基)-2-羟乙基]戊二酰亚胺、六氯苯、N-(2,6-二甲基苯基)-N-(2-呋喃甲酰基)-DL-丙氨酸甲酯、DL-N-(2,6-二甲基苯基)-N-(2’-甲氧基乙酰基)-丙氨酸甲酯、N-(2,6-二甲基苯基)-N-氯乙酰基-D,L-2-氨基-丁内酯、DL-N-(2,6-二甲基苯基)-N-(苯基乙酰基)-丙氨酸甲酯、5-甲基-5-乙烯基-3-(3,5-二氯苯基)-2,4-二氧代-1,3-噁唑烷、3-[3,5-二氯苯基(5-甲基-5-甲氧基甲基)-1,3-噁唑烷-2,4-二酮、3-(3,5-二氯苯基)-1-异丙基氨基甲酰基乙内酰脲、N-(3,5-二氯苯基)-1,2-二甲基环丙烷-1,2-二甲酰亚胺、2-氰基-[N-(乙基氨基羰基)-2-甲氧亚氨基]乙酰胺、1-[2-(2,4-二氯苯基)戊基]-1H-1,2,4-三唑、2,4-二氟-α-(1H-1,2,4-三唑基-1-甲基)二苯甲醇、N-(3-氯-2,6-二硝基-4-三氟甲基苯基)-5-三氟甲基-3-氯-2-氨基吡啶、1-((双(4-氟苯基)甲基甲硅烷基)甲基)-1H-1,2,4-三唑。
I.合成实施例
实施例1:6-氯-2-[(3-烯丙基)硫基]噻唑并[4,5-b]吡啶
1.1 2-氨基-3-溴-5-氯吡啶
在1小时内将257g(1.61mol)溴在380ml乙酸中的溶液滴加入187g(1.45mol)2-氨基-5-氯吡啶在1.5升乙酸中的溶液中。将该反应混合物回流3小时,然后冷却至室温。加入1.9升软化水并真空浓缩该混合物。将残余物分配在4升乙酸乙酯和1.8升水之间。将该混合物用3升10重量%氢氧化钠水溶液碱化。分离有机层并用盐水洗涤(2×1.5升),用硫酸镁干燥,过滤并真空浓缩。过滤残余物,用己烷洗涤(2×100ml)并真空干燥,得到192g 2-氨基-3-溴-5-氯吡啶。真空浓缩母液,过滤,用己烷洗涤并干燥,得到另外75g相同产物。
1.2 6-氯-2-巯基噻唑并[4,5-b]吡啶
将133g(0.64mol)来自实施例1.1的2-氨基-3-溴-5-氯吡啶在1.02升N-甲基吡咯烷酮中的溶液与205g(1.28mol)黄原酸O-乙酯钾盐混合。将该反应混合物回流6小时,然后冷却至室温。加入2.7升软化水,然后加入乙酸将该反应混合物调至pH 4.5。过滤所得沉淀,用软化水洗涤(2×600ml)。将固体依次用软化水(2×4.2升)和乙醇(1.5升)研制,过滤,用乙醇(2×300ml)洗涤,然后用己烷(2×400ml)洗涤,并在45℃下真空干燥,得到127g(产率:98%)6-氯-2-巯基噻唑并[4,5-b]吡啶,其无需进一步提纯就可使用。
1.3 6-氯-2-[(3-烯丙基)硫基]噻唑并[4,5-b]吡啶
向0.3g(1.7mmol)来自实施例1.2的硫醇在1ml二甲基甲酰胺中的搅拌溶液中加入0.3g(2.52mmol)烯丙基溴在1ml二甲基甲酰胺和0.3g(1.8mmol)碳酸钾中的溶液。将该反应混合物在90℃下搅拌12小时,然后冷却至室温。加入2ml软化水,然后用二氯甲烷萃取混合物。有机层用水(2×5ml)洗涤,用硫酸钠干燥,过滤,然后真空浓缩,得到0.4g标题产物。
实施例2:6-氯-2-[(3-烯丙基)亚磺酰基]噻唑并[4,5-b]吡啶
向0.03g(0.1mmol)来自实施例1.3的6-氯-2-[(3-烯丙基)硫基]噻唑并[4,5-b]吡啶在2ml二氯甲烷和乙酸的2∶1混合物中的溶液中加入13ml(0.4mmol)30重量%过氧化氢水溶液。将该溶液在室温下搅拌12小时。将反应溶液用3ml水稀释,然后用4ml二氯甲烷萃取。有机层用3mlNa2S2O4水溶液洗涤,用硫酸钠干燥,然后真空浓缩,得到0.04g标题化合物。
实施例3:6-氯-2-(甲硫基)噻唑并[4,5-b]吡啶
在5℃下将328g(2.31mol)甲基碘滴加入363g(2.62mol)碳酸钾和354g(1.75mol)来自实施例1.2的6-氯-2-巯基噻唑并[4,5-b]吡啶在2.28升二甲基甲酰胺中的搅拌悬浮液中。将该反应混合物在室温下搅拌68小时,然后倾入4.5升软化水中。过滤沉淀,用水漂洗(2×500ml),然后在45℃下真空干燥,得到308.9g(产率:81%)6-氯-2-(甲硫基)噻唑并[4,5-b]吡啶。
实施例4:6-氯-2-(甲基磺酰基)噻唑并[4,5-b]吡啶
在20分钟内向333g(1.45mol)过3-氯苯甲酸(75%分析值)在2升二氯甲烷中的溶液中分批加入120g(0.55mol)来自实施例3.1的6-氯-2-(甲硫基)噻唑并[4,5-b]吡啶在700ml二氯甲烷中的浆液。将该溶液回流6小时,然后加入额外部分的50g过3-氯苯甲酸在500ml二氯甲烷中的溶液。然后将该反应混合物再回流2小时。将该反应混合物冷却至室温,用二氯甲烷(1升)稀释,然后用6升5重量%碳酸钠水溶液洗涤。将碳酸钠水层用2升二氯甲烷萃取。合并各有机相,并用3升饱和碳酸氢钠水溶液洗涤,然后用3升盐水洗涤,用硫酸钠干燥,过滤,然后真空浓缩,得到稠浆液。将残余物溶于100ml己烷中,过滤,先后用150ml乙酸乙酯(20体积%)在己烷中的溶液和300ml己烷洗涤,然后在45℃下真空干燥,得到117g(产率:85%)标题化合物(熔点为201-202℃)。
以类似方式制备列于表1和2中的化合物。
II.杀真菌活性实施例
表3-7中活性成分(化合物)的编号指表1和2中所给的编号。
杀真菌活性实施例1:对葡萄霜霉病(Plasmopara viticola)的防治
将栽培品种为“Riesling”的葡萄苗盆栽生长至4-5叶阶段。将这些植物用含水悬浮液喷雾至滴流,该悬浮液含有200ppm下表3所提到的活性化合物且由含有5%活性成分、94%环己酮和1%乳化剂(Tween 20)的储备溶液制备。将植物风干(3-5小时)。然后通过喷雾叶子下侧而将处理过的植物用葡萄霜霉病菌的含水悬浮液接种。然后将试验植物立即转移到潮湿室中。在22-24℃和接近100%的相对湿度下放置1天后,在20-23℃和约60-80%的相对湿度下将植物在玻璃室中培育12天。为了刺激病害症状的爆发,再次将植物转移到潮湿室中达24小时(22-24℃和接近100%的相对湿度)。以患病叶面积%肉眼评价叶子上的真菌侵染程度。
表3:对葡萄霜霉病(Plasmopara viticola)的防治
活性化合物编号 | 用含有200ppm活性化合物的含水悬浮液处理后的患病叶面积% |
131 | 3 |
513 | 3 |
514 | 0 |
518 | 0 |
519 | 0 |
520 | 0 |
521 | 0 |
132 | 0 |
522 | 0 |
135 | 3 |
153 | 3 |
525 | 7 |
526 | 0 |
534 | 7 |
154 | 7 |
384 | 3 |
385 | 7 |
567 | 0 |
568 | 0 |
578 | 7 |
581 | 0 |
277 | 3 |
588 | 7 |
589 | 3 |
592 | 3 |
596 | 3 |
597 | 7 |
368 | 0 |
373 | 7 |
598 | 0 |
599 | 7 |
563 | 3 |
585 | 3 |
386 | 0 |
569 | 3 |
385 | 0 |
来处理 | 85 |
杀真菌活性实施例2:对由颖枯小球腔菌(Leptosphaeria nodorum)引起的小麦叶黑斑病(blotch)的杀真菌防治(保护性)
将栽培品种为“Hereward”的盆栽小麦苗的叶子用含水悬浮液喷雾至滴流,该悬浮液含有250ppm下表4所提到的活性化合物且由含有5%活性成分、94%环己酮和1%乳化剂(Tween 20)的储备溶液制备。将植物风干(3-5小时)。然后将处理过的植物用颖枯小球腔菌的含水悬浮液(含有0.5×106个孢子/ml)接种。然后将试验植物立即转移到潮湿室中。在20-23℃和接近100%的相对湿度下放置2天后,将植物转移到玻璃室中并培育5-7天,然后以患病叶面积%肉眼评价叶子上的真菌侵染程度。
表4:对由颖枯小球腔菌引起的小麦叶黑斑病的杀真菌防治
活性化合物编号 | 用含有250ppm活性化合物的含水悬浮液处理后的患病叶面积% |
131 | 15 |
517 | 15 |
519 | 15 |
520 | 7 |
269 | 15 |
135 | 15 |
526 | 15 |
534 | 15 |
154 | 7 |
384 | 7 |
385 | 7 |
567 | 7 |
568 | 15 |
386 | 3 |
569 | 15 |
388 | 7 |
289 | 15 |
572 | 7 |
276 | 7 |
575 | 7 |
279 | 3 |
576 | 15 |
578 | 15 |
580 | 3 |
581 | 3 |
277 | 7 |
598 | 15 |
563 | 15 |
561 | 7 |
565 | 15 |
566 | 15 |
未处理 | 80 |
杀真菌活性实施例3:对西红柿上的早疫病菌(Alternaria solani)的杀真菌防治
将栽培品种为“Groβe Fleischtomate St.Pierre”的西红柿植物幼苗在盆中生长至2-4叶阶段。将这些植物用含水悬浮液喷雾至滴流,该悬浮液含有250ppm下表5所提到的活性化合物且由含有10%活性化合物、85%环己酮和5%乳化剂的储备溶液制备。第二天将处理过的植物用早疫病菌的含水悬浮液(含有0.2×106个孢子/ml)接种。然后将试验植物立即转移到潮湿室中。在20-23℃和接近100%的相对湿度下放置6天后,以患病叶面积%肉眼评价叶子上的真菌侵染程度。
表5:对西红柿上的早疫病菌的杀真菌防治
活性化合物编号 | 用含有250ppm活性化合物的含水悬浮液处理后的患病叶面积% |
14 | 15 |
30 | 15 |
34 | 15 |
35 | 15 |
86 | 15 |
118 | 0 |
119 | 15 |
136 | 3 |
139 | 15 |
141 | 10 |
144 | 5 |
145 | 15 |
146 | 3 |
150 | 7 |
154 | 15 |
163 | 3 |
166 | 15 |
168 | 5 |
169 | 5 |
172 | 7 |
173 | 1 |
188 | 15 |
214 | 5 |
232 | 15 |
233 | 10 |
234 | 7 |
235 | 15 |
238 | 7 |
240 | 5 |
241 | 7 |
244 | 0 |
246 | 0 |
252 | 3 |
255 | 15 |
257 | 15 |
273 | 1 |
275 | 1 |
276 | 3 |
277 | 3 |
278 | 7 |
279 | 15 |
283 | 3 |
285 | 10 |
286 | 3 |
287 | 3 |
289 | 3 |
291 | 5 |
292 | 10 |
294 | 1 |
297 | 15 |
299 | 7 |
300 | 1 |
302 | 1 |
303 | 5 |
304 | 4 |
305 | 3 |
338 | 7 |
341 | 5 |
342 | 3 |
343 | 3 |
344 | 3 |
363 | 10 |
365 | 15 |
366 | 5 |
370 | 1 |
371 | 3 |
384 | 1 |
385 | 0 |
未处理 | 90 |
杀真菌活性实施例4:对青椒叶上的灰葡萄孢(Botrytis cinerea)的保护性防治(温室)
将栽培品种为“Neusiedler Ideal Elite”的青椒幼苗在盆中生长至4-5叶阶段。将这些植物用含水悬浮液喷雾至滴流,该悬浮液含有250ppm下表6所提到的活性成分且由含有10%活性成分、85%环己酮和5%乳化剂的储备溶液制备。第二天将处理过的植物用在2%生物麦芽水溶液中的灰葡萄孢的孢子悬浮液(含有1.7×106个孢子/ml)接种。然后立即将试验植物转移到潮湿室中。在22-24℃和接近100%的相对湿度下放置5天后,以患病叶面积%肉眼评价叶子上的真菌侵染程度。
表6:对青椒叶上的灰霉病菌的保护性防治(温室)
活性化合物编号 | 用含有250ppm活性化合物的含水悬浮液处理后的患病叶面积% |
80 | 15 |
96 | 10 |
137 | 9 |
138 | 5 |
139 | 5 |
140 | 7 |
143 | 3 |
144 | 5 |
145 | 5 |
146 | 3 |
147 | 10 |
150 | 7 |
153 | 1 |
155 | 3 |
156 | 15 |
160 | 0 |
161 | 0 |
165 | 15 |
166 | 7 |
167 | 0 |
168 | 10 |
169 | 0 |
171 | 3 |
172 | 3 |
194 | 15 |
211 | 1 |
212 | 1 |
213 | 1 |
214 | 1 |
215 | 1 |
216 | 1 |
217 | 3 |
219 | 0 |
224 | 5 |
225 | 7 |
227 | 5 |
232 | 5 |
233 | 0 |
234 | 0 |
235 | 0 |
237 | 7 |
238 | 5 |
240 | 15 |
241 | 15 |
242 | 1 |
243 | 5 |
244 | 0 |
246 | 1 |
247 | 1 |
248 | 10 |
251 | 15 |
252 | 15 |
256 | 15 |
259 | 15 |
260 | 15 |
264 | 0 |
268 | 15 |
269 | 0 |
270 | 3 |
273 | 1 |
274 | 3 |
275 | 15 |
276 | 0 |
277 | 3 |
278 | 15 |
283 | 1 |
285 | 0 |
287 | 0 |
289 | 0 |
290 | 7 |
294 | 1 |
295 | 1 |
297 | 0 |
298 | 1 |
299 | 0 |
300 | 10 |
302 | 5 |
304 | 0 |
305 | 0 |
307 | 0 |
337 | 10 |
338 | 10 |
339 | 1 |
340 | 1 |
341 | 0 |
342 | 0 |
343 | 1 |
344 | 0 |
345 | 15 |
346 | 0 |
347 | 0 |
365 | 15 |
384 | 1 |
385 | 0 |
388 | 0 |
未处理 | 100 |
杀真菌活性实施例5:对由致病疫霉菌(Phytophthora infestans)引起的西红柿晚疫病的防治
将栽培品种为“Groβe Fleischtomate St.Pierre”的西红柿植物幼苗在盆中生长至2-4叶阶段。将这些植物用含水悬浮液喷雾至滴流,该悬浮液含有下表7所示浓度的活性成分且由含有10%活性化合物、85%环己酮和5%乳化剂的储备溶液制备。第二天将处理过的植物用致病疫霉菌的含水游动孢子悬浮液(含有0.2×106个孢子/ml)接种。在接种之后将试验植物立即转移到潮湿室中。在18-20℃和接近100%的相对湿度下放置6天后,以患病叶面积%肉眼评价叶子上的真菌侵染程度。
表7:对由致病疫霉引起的西红柿晚疫病的防治
活性化合物编号 | 用含有250ppm活性化合物的含水悬浮液处理后的患病叶面积% |
3 | 0 |
6 | 0 |
14 | 15 |
21 | 15 |
60 | 15 |
143 | 15 |
150 | 3 |
152 | 15 |
161 | 15 |
167 | 10 |
232 | 15 |
233 | 15 |
234 | 3 |
236 | 15 |
238 | 15 |
240 | 10 |
241 | 10 |
242 | 15 |
276 | 1 |
277 | 1 |
278 | 15 |
283 | 3 |
284 | 3 |
287 | 0 |
289 | 7 |
290 | 5 |
294 | 1 |
295 | 15 |
296 | 15 |
299 | 1 |
300 | 1 |
301 | 15 |
304 | 3 |
305 | 0 |
341 | 10 |
344 | 5 |
367 | 1 |
370 | 15 |
371 | 10 |
384 | 1 |
385 | 15 |
未处理 | 90 |
Claims (13)
1.一种防治有害真菌的方法,包括用有效量的式I的噻唑并[4,5-b]吡啶和/或其可农用盐处理真菌或需要防止真菌侵染的材料、植物、土壤或种子:
其中基团R1、R2、R3、A和符号n具有如下含义:
R1、R2、R3相互独立地为氢,卤素,C1-C4烷基,C1-C4烷氧基,C1-C4卤代烷基,C1-C4卤代烷氧基,C1-C4烷氧基-C1-C4烷基或可以未被取代或带有1、2、3或4个相互独立地选自卤素、硝基、氰基、C1-C4烷基、C1-C4烷氧基、OCHF2、CHF2、OCF3或CF3的取代基的苯基;
n为0、1或2;
R为氢,氰基,卤素,C1-C6烷基,C1-C4卤代烷基,C1-C4烷氧基,C2-C4链烯基,C2-C4卤代链烯基,C2-C4炔基,C2-C4卤代炔基,氰基-C1-C4烷基,C1-C4烷氧基-C1-C4烷基,C1-C4烷氧基-C1-C4烷氧基,C3-C8环烷基,其可以带有1、2、3或4个相互独立地选自卤素和C1-C4烷基的取代基,
三(C1-C4烷基)甲硅烷基,三(C1-C4烷基)甲硅烷氧基,COR4,COOR5,CONR6R7,S(O)kR8,苯基,苯氧基,带有1、2或3个选自O、S和N的杂原子且可以为饱和、不饱和或芳族的5或6元杂环,其中苯基、苯氧基和杂环相互独立地可以带有1、2、3或4个相互独立地选自如下的取代基:卤素、硝基、氰基、C1-C4烷基、C1-C4烷氧基、甲基磺酰基、OCHF2、CHF2、OCF3或CF3;或可以带有1、2或3个选自卤素、C1-C4烷基、甲基磺酰基、OCHF2、CHF2、OCF3或CF3的基团的苯基;其中
k为0、1或2;
R4为氢,C1-C6烷基,苯基和苯基-C1-C4烷基,其中苯基和苯基-C1-C4烷基可以在苯基环上带有1、2、3或4个相互独立地选自卤素、硝基、氰基、C1-C4烷基、C1-C4烷氧基、OCHF2或CF3的取代基;
R5为C1-C6烷基,C1-C4烷氧基-C1-C4烷基,苯基和苯基-C1-C4烷基,其中苯基和苯基-C1-C4烷基可以在苯基环上带有1、2、3或4个相互独立地选自卤素、硝基、氰基、C1-C4烷基、C1-C4烷氧基、甲基磺酰基、OCHF2、CHF2、OCF3或CF3的取代基;
R6、R7相互独立地为氢,C1-C6烷基,C1-C4烷氧基-C1-C4烷基,苯基和苯基-C1-C4烷基,其中苯基和苯基-C1-C4烷基可以在苯基环上带有1、2、3或4个相互独立地选自卤素、硝基、氰基、C1-C4烷基、C1-C4烷氧基、甲基磺酰基、OCHF2、CHF2、OCF3或CF3的取代基;或可以一起形成5或6元杂环,该杂环除氮原子外还可以额外带有1或2个选自N、O或S的其他杂原子;
R8为C1-C6烷基,C1-C4卤代烷基,苯基和苯基-C1-C4烷基,其中苯基和苯基-C1-C4烷基可以在苯基环上带有1、2、3或4个相互独立地选自卤素、硝基、氰基、C1-C4烷基、C1-C4烷氧基、甲基磺酰基、OCHF2、CHF2、OCF3或CF3的取代基;
A为C1-C4亚烷基;或
A-R可以一起为二卤代甲基,三卤代甲基,C2-C4链烯基,C2-C4卤代链烯基,C3-C8环烷基,可以带有1、2、3或4个相互独立地选自卤素和C1-C4烷基的取代基的C5-C8环烯基,或可以带有1、2或3个选自O、S和N的杂原子的5或6元杂环,该杂环可以是饱和、不饱和或芳族的且可以带有1、2、3或4个相互独立地选自卤素、硝基、氰基、C1-C4烷基、C1-C4烷氧基、甲基磺酰基、OCHF2、CF3或苯基的取代基,其中该苯基可以带有1、2或3个选自卤素、C1-C4烷基、甲基磺酰基、OCHF2或CF3的基团,其中环烷基和环烯基可以独立地带有1、2、3或4个相互独立地选自卤素和C1-C4烷基的取代基和/或可以含有羰基或硫羰基作为环成员。
2.如权利要求1所要求的方法,其中式I中的基团R2不为氢。
3.如权利要求1所要求的方法,其中式I中的基团R1-R3如下所定义:
R1为氢或C1-C4烷基;
R2为氢、卤素、C1-C4烷基、C1-C4卤代烷基;
R3为氢。
4.如权利要求1所要求的方法,其中式I中的A为亚甲基、1,2-亚乙基、1,1-亚乙基或1,3-亚丙基且R为苯基,苯氧基,C3-C8环烷基,具有1、2或3个选自O、S和N的杂原子的5或6元杂环,其中苯基、苯氧基、C3-C8环烷基和杂环相互独立地可以如权利要求1所定义未被取代或被取代。
5.如权利要求1所要求的方法,其中式I中的A为亚甲基、1,2-亚乙基、1,1-亚乙基或1,3-亚丙基且R选自氰基、C1-C4烷氧基、C1-C4烷基、C3-C4链烯基、C1-C4烷氧基-C1-C4烷氧基、氰基-C1-C4烷基、C1-C4烷氧基-C1-C4烷基、三(C1-C4烷基)甲硅烷基、三(C1-C4烷基)甲硅烷氧基、COR4、COOR5、CONR6R7或S(O)kR8,其中基团R4-R8和整数k如权利要求1所定义。
6.如权利要求5所要求的方法,其中R选自C1-C4烷氧基、C1-C4烷基、C3-C4链烯基、C1-C4烷氧基-C1-C4烷氧基、C1-C4烷氧基-C1-C4烷基、三(C1-C4烷基)甲硅烷基和三(C1-C4烷基)甲硅烷氧基。
7.式I的噻唑并[4,5-b]吡啶及其可农用盐:
其中基团R1、R2、R3和符号n如权利要求1所定义,
A为亚甲基、1,2-亚乙基、1,1-亚乙基或1,3-亚丙基以及
R为苯基,苯氧基,具有1、2或3个选自O、S和N的杂原子的5或6元芳族杂环,其中苯基、苯氧基和杂环相互独立地可以如权利要求1所定义未被取代或被取代,或者
氰基、C1-C4烷氧基-C1-C4烷氧基、氰基-C1-C4烷基、C1-C4烷氧基-C1-C4烷基、三(C1-C4烷基)甲硅烷基、三(C1-C4烷基)甲硅烷氧基、COR4或S(O)kR8,其中基团R4和R8以及整数k如权利要求1所定义,或者A-R一起为带有1、2或3个选自O、S和N的杂原子的5或6元杂环,该杂环可以是饱和、不饱和或芳族的且可以带有1、2、3或4个相互独立地选自卤素、硝基、氰基、C1-C4烷基、C1-C4烷氧基、甲基磺酰基、OCHF2、CF3或苯基的取代基,其中该苯基可以带有1、2或3个选自卤素、C1-C4烷基、甲基磺酰基、OCHF2或CF3的基团。
8.如权利要求7所要求的噻唑并[4,5-b]吡啶,其中式I中的基团R2不为氢。
9.如权利要求7所要求的噻唑并[4,5-b]吡啶,其中式I中的基团R1-R3如下所定义:
R1为氢或C1-C4烷基;
R2为氢、卤素、C1-C4烷基、C1-C4卤代烷基;
R3为氢。
10.如权利要求7所要求的噻唑并[4,5-b]吡啶,其中式I中的n为1或2。
11.如权利要求7所要求的噻唑并[4,5-b]吡啶,其中式I中的A为亚甲基、1,2-亚乙基、1,1-亚乙基或1,3-亚丙基且R为苯基,苯氧基,呋喃基或噻吩基,它们各自相互独立地可以如权利要求1所定义未被取代或被取代。
12.如权利要求7所要求的噻唑并[4,5-b]吡啶,其中R选自C1-C4烷氧基-C1-C4烷氧基、三(C1-C4烷基)甲硅烷基和三(C1-C4烷基)甲硅烷氧基。
13.一种呈直接可喷溶液、粉末、悬浮液、分散体、乳液、乳油、油分散体、糊、粉剂、撒播用材料或粒剂形式的农业配制剂,包含至少一种如权利要求1所定义的式I的噻唑并[4,5-b]吡啶和/或至少一种其可农用盐和至少一种可以为液体或固体的可农用载体。
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US09/902,783 US6914068B2 (en) | 2001-07-12 | 2001-07-12 | Thiazolo[4,5-b]pyridines as fungicides |
US09/902,783 | 2001-07-12 |
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PL1824482T3 (pl) * | 2004-12-17 | 2014-07-31 | Anadys Pharmaceuticals Inc | 3,5-Dipodstawione oraz 3,5,7-tripodstawione związki 3H-oksazolo- oraz 3H-tiazolo[4,5-d]pirymidyn-2-onowe i ich proleki |
CN115698021A (zh) | 2020-04-07 | 2023-02-03 | 拜耳公司 | 经取代的噻唑并吡啶、其盐及其作为除草活性物质的用途 |
TW202328151A (zh) | 2021-09-07 | 2023-07-16 | 德商拜耳廠股份有限公司 | 經取代之2,3-二氫[1,3]噻唑并[4,5-b]吡啶、其鹽及其作為除草活性物質之用途 |
TW202328150A (zh) | 2021-09-07 | 2023-07-16 | 德商拜耳廠股份有限公司 | 經取代之噻唑并吡啶、其鹽及其作為除草活性物質之用途 |
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2001
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