CN102007097A - 新型除草剂 - Google Patents
新型除草剂 Download PDFInfo
- Publication number
- CN102007097A CN102007097A CN2008800135336A CN200880013533A CN102007097A CN 102007097 A CN102007097 A CN 102007097A CN 2008800135336 A CN2008800135336 A CN 2008800135336A CN 200880013533 A CN200880013533 A CN 200880013533A CN 102007097 A CN102007097 A CN 102007097A
- Authority
- CN
- China
- Prior art keywords
- compound
- alkyl
- formula
- methyl
- ethyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 230000002363 herbicidal effect Effects 0.000 title claims description 5
- 239000004009 herbicide Substances 0.000 title abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 451
- -1 sec.-propyl Chemical group 0.000 claims description 223
- 239000000203 mixture Substances 0.000 claims description 90
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 72
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 71
- 229910052736 halogen Inorganic materials 0.000 claims description 64
- 150000002367 halogens Chemical class 0.000 claims description 62
- 239000001257 hydrogen Substances 0.000 claims description 57
- 229910052739 hydrogen Inorganic materials 0.000 claims description 57
- 238000002360 preparation method Methods 0.000 claims description 56
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 39
- 239000002904 solvent Substances 0.000 claims description 38
- 125000003545 alkoxy group Chemical group 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 37
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 35
- 125000001072 heteroaryl group Chemical group 0.000 claims description 34
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 34
- 239000003513 alkali Substances 0.000 claims description 32
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 32
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 26
- 241000196324 Embryophyta Species 0.000 claims description 25
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical group O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 25
- 125000000217 alkyl group Chemical group 0.000 claims description 24
- 125000004455 (C1-C3) alkylthio group Chemical group 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 20
- 229910052760 oxygen Inorganic materials 0.000 claims description 20
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 239000004327 boric acid Substances 0.000 claims description 13
- 229910052763 palladium Inorganic materials 0.000 claims description 13
- 125000006700 (C1-C6) alkylthio group Chemical group 0.000 claims description 10
- 239000002585 base Substances 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- 229920002554 vinyl polymer Polymers 0.000 claims description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 9
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- 244000038559 crop plants Species 0.000 claims description 8
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 8
- 238000009472 formulation Methods 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 150000003818 basic metals Chemical class 0.000 claims description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 6
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 6
- 229910052728 basic metal Inorganic materials 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 244000025254 Cannabis sativa Species 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- 125000004450 alkenylene group Chemical group 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 claims description 4
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 claims description 3
- 125000000171 (C1-C6) haloalkyl group Chemical group 0.000 claims description 2
- 125000006772 (C1-C6) haloalkylsulfonyloxy group Chemical group 0.000 claims description 2
- 125000006643 (C2-C6) haloalkenyl group Chemical group 0.000 claims description 2
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 2
- 125000005947 C1-C6 alkylsulfonyloxy group Chemical group 0.000 claims description 2
- 125000003601 C2-C6 alkynyl group Chemical group 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 12
- 125000002252 acyl group Chemical group 0.000 claims 2
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims 2
- 125000001475 halogen functional group Chemical group 0.000 claims 2
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical group [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 claims 2
- 230000003301 hydrolyzing effect Effects 0.000 claims 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims 1
- OILAIQUEIWYQPH-UHFFFAOYSA-N cyclohexane-1,2-dione Chemical class O=C1CCCCC1=O OILAIQUEIWYQPH-UHFFFAOYSA-N 0.000 abstract description 2
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 112
- 101150065749 Churc1 gene Proteins 0.000 description 112
- 102100038239 Protein Churchill Human genes 0.000 description 112
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 56
- 239000000243 solution Substances 0.000 description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 51
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 48
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 45
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 44
- 239000011541 reaction mixture Substances 0.000 description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 40
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 38
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 30
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 30
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 30
- 239000003921 oil Substances 0.000 description 30
- 0 C*(**)C(*)(*)C(*)(C(*)(CC(Cc1c(*)cc(*)c(*)c1*)=O)CC(O*)=O)I Chemical compound C*(**)C(*)(*)C(*)(C(*)(CC(Cc1c(*)cc(*)c(*)c1*)=O)CC(O*)=O)I 0.000 description 29
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 29
- 235000019198 oils Nutrition 0.000 description 29
- LJXPWUAAAAXJBX-UHFFFAOYSA-N 2-methylallyl radical Chemical compound [CH2]C(C)=C LJXPWUAAAAXJBX-UHFFFAOYSA-N 0.000 description 28
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 28
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 28
- 239000000706 filtrate Substances 0.000 description 27
- 239000007787 solid Substances 0.000 description 25
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 25
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 24
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 20
- 150000003839 salts Chemical class 0.000 description 19
- 239000000654 additive Substances 0.000 description 18
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 17
- 239000000741 silica gel Substances 0.000 description 17
- 229910002027 silica gel Inorganic materials 0.000 description 17
- 238000003756 stirring Methods 0.000 description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 15
- 238000004440 column chromatography Methods 0.000 description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 14
- 229910052938 sodium sulfate Inorganic materials 0.000 description 14
- 235000011152 sodium sulphate Nutrition 0.000 description 14
- 238000007738 vacuum evaporation Methods 0.000 description 14
- 230000000996 additive effect Effects 0.000 description 13
- 239000004094 surface-active agent Substances 0.000 description 13
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 12
- 150000003254 radicals Chemical class 0.000 description 12
- 239000003153 chemical reaction reagent Substances 0.000 description 11
- 238000003810 ethyl acetate extraction Methods 0.000 description 11
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 10
- 150000002148 esters Chemical class 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 10
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- 239000011630 iodine Substances 0.000 description 9
- 229910052740 iodine Inorganic materials 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- 238000010790 dilution Methods 0.000 description 8
- 239000012895 dilution Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 8
- 240000008042 Zea mays Species 0.000 description 7
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 7
- 238000000605 extraction Methods 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- 239000012044 organic layer Substances 0.000 description 7
- 235000017550 sodium carbonate Nutrition 0.000 description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 description 7
- 235000011121 sodium hydroxide Nutrition 0.000 description 7
- 229940083608 sodium hydroxide Drugs 0.000 description 7
- 239000007921 spray Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 229920000742 Cotton Polymers 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
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- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
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- 239000005864 Sulphur Substances 0.000 description 6
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 6
- 239000013543 active substance Substances 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 239000004305 biphenyl Substances 0.000 description 6
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 235000005822 corn Nutrition 0.000 description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 6
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 6
- 235000015110 jellies Nutrition 0.000 description 6
- 239000008274 jelly Substances 0.000 description 6
- 239000003094 microcapsule Substances 0.000 description 6
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical group [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 6
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 5
- 244000299507 Gossypium hirsutum Species 0.000 description 5
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 5
- 238000006114 decarboxylation reaction Methods 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
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- 125000005843 halogen group Chemical group 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
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- 230000003647 oxidation Effects 0.000 description 5
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 239000002689 soil Substances 0.000 description 5
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical group COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 5
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- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 description 4
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- 229910052799 carbon Inorganic materials 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-O oxonium Chemical compound [OH3+] XLYOFNOQVPJJNP-UHFFFAOYSA-O 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 4
- 239000000375 suspending agent Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000003053 toxin Substances 0.000 description 4
- 231100000765 toxin Toxicity 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- 239000004563 wettable powder Substances 0.000 description 4
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 3
- 244000075850 Avena orientalis Species 0.000 description 3
- KTOOMIYOUDGYCE-UHFFFAOYSA-N C1=CC=CC=C1.C(C)(=O)OIOC(C)=O Chemical compound C1=CC=CC=C1.C(C)(=O)OIOC(C)=O KTOOMIYOUDGYCE-UHFFFAOYSA-N 0.000 description 3
- 235000007516 Chrysanthemum Nutrition 0.000 description 3
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- 235000009566 rice Nutrition 0.000 description 1
- 239000010458 rotten stone Substances 0.000 description 1
- 210000000582 semen Anatomy 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- KZOJQMWTKJDSQJ-UHFFFAOYSA-M sodium;2,3-dibutylnaphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S([O-])(=O)=O)=C(CCCC)C(CCCC)=CC2=C1 KZOJQMWTKJDSQJ-UHFFFAOYSA-M 0.000 description 1
- 239000004550 soluble concentrate Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 235000020354 squash Nutrition 0.000 description 1
- KXCAEQNNTZANTK-UHFFFAOYSA-N stannane Chemical compound [SnH4] KXCAEQNNTZANTK-UHFFFAOYSA-N 0.000 description 1
- 229910000080 stannane Inorganic materials 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000003826 tablet Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- PZTAGFCBNDBBFZ-UHFFFAOYSA-N tert-butyl 2-(hydroxymethyl)piperidine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCCCC1CO PZTAGFCBNDBBFZ-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000005621 tetraalkylammonium salts Chemical class 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- 125000002769 thiazolinyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 238000003971 tillage Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 229940087291 tridecyl alcohol Drugs 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- RKBCYCFRFCNLTO-UHFFFAOYSA-N triisopropylamine Chemical compound CC(C)N(C(C)C)C(C)C RKBCYCFRFCNLTO-UHFFFAOYSA-N 0.000 description 1
- VSRBKQFNFZQRBM-UHFFFAOYSA-N tuaminoheptane Chemical compound CCCCCC(C)N VSRBKQFNFZQRBM-UHFFFAOYSA-N 0.000 description 1
- 229960003986 tuaminoheptane Drugs 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 241001478887 unidentified soil bacteria Species 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
- 239000004562 water dispersible granule Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
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- 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
- A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
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- A01N41/10—Sulfones; Sulfoxides
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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
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
- A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
-
- 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
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
- A01N43/18—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with sulfur as the ring hetero atom
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- C07C271/06—Esters of carbamic acids
- C07C271/32—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of rings other than six-membered aromatic rings
- C07C271/34—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of rings other than six-membered aromatic rings with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
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- C07C317/32—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C317/34—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring
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Abstract
环己二酮化合物及其衍生物,其在5位被取代,适宜用作除草剂。
Description
本发明涉及新型除草活性环二酮类及其衍生物,涉及它们的制备方法,涉及包括这些化合物的组合物,还涉及它们在防治杂草,特别是在有用植物作物中的杂草,或者抑制植物生长中的用途。
具有除草活性的环二酮类描述于,例如,WO 01/74770中。
目前已发现具有除草和生长抑制特性的新型环己烷二酮化合物及其衍生物。
因此,本发明涉及式(I)化合物
其中
R1是甲基、乙基、正丙基、异丙基、环丙基、卤代甲基、卤代乙基、卤素、乙烯基、乙炔基、甲氧基、乙氧基、卤代甲氧基或卤代乙氧基,
R2和R3彼此独立地是氢、卤素、C1-C6烷基、C1-C6卤代烷基、C1-C6烷氧基、C1-C6卤代烷氧基、C2-C6烯基、C2-C6卤代烯基、C2-C6炔基、C3-C6烯氧基、C3-C6卤代烯氧基、C3-C6炔氧基、C3-C6环烷基、C1-C6烷硫基、C1-C6烷基亚磺酰基、C1-C6烷基磺酰基、C1-C6烷基磺酰氧基、C1-C6卤代烷基磺酰氧基、氰基、硝基、苯基、苯基,被下述基团取代:C1-C4烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、氰基、硝基、卤素、C1-C3烷硫基、C1-C3烷基亚磺酰基或C1-C3烷基磺酰基、或杂芳基或杂芳基,被下述基团取代:C1-C4烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、氰基、硝基、卤素、C1-C3烷硫基、C1-C3烷基亚磺酰基或C1-C3烷基磺酰基,
R4是氢、甲基、乙基、正丙基、异丙基、卤代甲基、卤代乙基、卤素、乙烯基、乙炔基、甲氧基、乙氧基、卤代甲氧基或卤代乙氧基,
n是0、1、2或3,
X是O、S、S(O)或S(O)2,
R5是氢或甲基,
R6和R7彼此独立地是氢、甲基或乙基,其中,当n是2或3时,4个或6个取代基R6和R7的含义不必相同,
R8是C1-C18烷基、C1-C18卤代烷基、C3-C7环烷基、C3-C7环烷基,被下述基团取代:甲基或乙基、C1-C6烷氧基C1-C12烷基、C1-C6烷硫基C1-C12烷基、C3-C18烯基或C3-C18烯基,被下述基团取代:卤素、C3-C18炔基或C3-C18炔基,被下述基团取代:卤素,或者
R5,当n表示1或2时,与R8一起形成C2-C5亚烷基链,其是未经取代的或者被甲基或乙基取代,或C2-C5亚烯基链,其是未经取代的或者被甲基或乙基取代,其中,当n是2时,4个取代基R6和R7的含义不必相同,或
R6,当n表示1时,与R5、R7和R8之一一起形成C2-C5亚烷基链,其是未经取代的或者被甲基或乙基取代,或C2-C5亚烯基链,其是未经取代的或者被甲基或乙基取代,和
G是氢、碱金属、碱土金属、锍、铵或潜伏基团。
在式(I)化合物的取代基定义中,具有1-6个碳原子的烷基取代基和烷氧基、烷基氨基等的烷基部分优选是甲基、乙基、丙基、丁基、戊基和己基,及其直链和支化异构体。至多18个碳原子的更高级烷基优选包含辛基、壬基、癸基、十一烷基和十二烷基。具有2-6个碳原子以及至多18个碳原子的烯基和炔基残基可以是直链或支化的并且可以各自包含多于1个的双键或三键。实例是乙烯基、烯丙基、炔丙基、丁烯基、丁炔基、戊烯基和戊炔基。适宜的环烷基包含3-7个碳原子并且是例如环丙基、环丁基、环戊基、环己基和环庚基。优选环丙基、环丁基、环戊基和环己基。优选的杂芳基实例是噻吩基、呋喃基、吡咯基、噁唑基、噻唑基、吡唑基、咪唑基、三唑基、四唑基、吡啶基、嘧啶基、吡嗪基、三嗪基、苯并呋喃基、苯并噻吩基、苯并噻唑基、苯并噁唑基、吲哚基、喹啉基和喹喔啉基,以及合适时其N-氧化物和盐。基团G是氢或碱金属、碱土金属、锍(-S(C1-C6烷基3)+)、铵(-NH4 +或-N(C1-C6烷基)4 +)或潜伏基团。选择这种潜伏基团G从而在施用至经处理的区域或植物之前、期间或之后,可以通过生化、化学或物理方法中的一种或者组合将其除去以产生其中G是H的式I化合物。上述方法的实例包括酶解、化学水解和光解。带有潜伏基团G的化合物可以提供一些优势,比如经处理植物的改进的表皮穿透,作物增加的耐受性,包含其它除草剂、除草剂安全剂、植物生长调节剂、杀真菌剂或杀虫剂的制剂混合物中改进的相容性和稳定性,或者减少的土壤淋溶。本领域已知的大量潜伏基团可以用于新化合物中。
所述潜伏基团G优选选自:C1-C8烷基、C2-C8卤代烷基、苯基C1-C8烷基(其中所述苯基可以任选地被C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、C1-C3烷硫基、C1-C3烷基亚磺酰基、C1-C3烷基磺酰基、卤素、氰基取代或被硝基取代)、杂芳基C1-C8烷基(其中所述杂芳基可以任选地被C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、C1-C3烷硫基、C1-C3烷基亚磺酰基、C1-C3烷基磺酰基、卤素、氰基取代或被硝基取代)、C3-C8烯基、C3-C8卤代烯基、C3-C8炔基、C(Xa)-Ra、C(Xb)-Xc-Rb、C(Xd)-N(Rc)-Rd、-SO2-Re、-P(Xe)(Rf)-Rg或CH2-Xf-Rh,其中Xa、Xb、Xc、Xd、Xe和Xf彼此独立地是氧或硫;
Ra是氢,C1-C18烷基,C2-C18烯基,C2-C18炔基,C1-C10卤代烷基,C1-C10氰基烷基,C1-C10硝基烷基,C1-C10氨基烷基,C1-C5烷基氨基C1-C5烷基,C2-C8二烷基氨基C1-C5烷基,C3-C7环烷基C1-C5烷基,C1-C5烷氧基C1-C5烷基,C3-C5烯氧基C1-C5烷基,C3-C5炔氧基C1-C5烷基(oxyalkyl),C1-C5烷硫基C1-C5烷基,C1-C5烷基亚磺酰基C1-C5烷基,C1-C5烷基磺酰基C1-C5烷基,C2-C8亚烷基氨氧基C1-C5烷基,C1-C5烷基羰基C1-C5烷基,C1-C5烷氧基羰基C1-C5烷基,氨基羰基C1-C5烷基,C1-C5烷基氨基羰基C1-C5烷基,C2-C8二烷基氨基羰基C1-C5烷基,C1-C5烷基羰基氨基C1-C5烷基,N-C1-C5烷基羰基-N-C1-C5烷基氨基C1-C5烷基,C3-C6三烷基甲硅烷基C1-C5烷基,苯基C1-C5烷基(其中所述苯基可以任选地被C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、C1-C3烷硫基、C1-C3烷基亚磺酰基、C1-C3烷基磺酰基、卤素、氰基取代或被硝基取代),杂芳基C1-C5烷基,(其中所述杂芳基可以任选地被C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、C1-C3烷硫基、C1-C3烷基亚磺酰基、C1-C3烷基磺酰基、卤素、氰基取代或被硝基取代),C2-C5卤代烯基,C3-C8环烷基,苯基或被C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、卤素、氰基或硝基取代的苯基,杂芳基或被C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、卤素、氰基或硝基取代的杂芳基,
Rb是C1-C18烷基,C3-C18烯基,C3-C18炔基,C2-C10卤代烷基,C1-C10氰基烷基,C1-C10硝基烷基,C2-C10氨基烷基,C1-C5烷基氨基C1-C5烷基,C2-C8二烷基氨基C1-C5烷基,C3-C7环烷基C1-C5烷基,C1-C5烷氧基C1-C5烷基,C3-C5烯氧基C1-C5烷基,C3-C5炔氧基C1-C5烷基,C1-C5烷硫基C1-C5烷基,C1-C5烷基亚磺酰基C1-C5烷基,C1-C5烷基磺酰基C1-C5烷基,C2-C8亚烷基氨氧基C1-C5烷基,C1-C5烷基羰基C1-C5烷基,C1-C5烷氧基羰基C1-C5烷基,氨基羰基C1-C5烷基,C1-C5烷基氨基羰基C1-C5烷基,C2-C8二烷基氨基羰基C1-C5烷基,C1-C5烷基羰基氨基C1-C5烷基,N-C1-C5烷基羰基-N-C1-C5烷基氨基C1-C5烷基,C3-C6三烷基甲硅烷基C1-C5烷基,苯基C1-C5烷基(其中所述苯基可以任选地被C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、C1-C3烷硫基、C1-C3烷基亚磺酰基、C1-C3烷基磺酰基、卤素、氰基取代或被硝基取代),杂芳基C1-C5烷基,(其中所述杂芳基可以任选地被C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、C1-C3烷硫基、C1-C3烷基亚磺酰基、C1-C3烷基磺酰基、卤素、氰基取代或被硝基取代),C3-C5卤代烯基,C3-C8环烷基,苯基或被C1-C3烷基,C1-C3卤代烷基,C1-C3烷氧基,C1-C3卤代烷氧基,卤素,氰基或硝基取代的苯基,杂芳基或被C1-C3烷基,C1-C3卤代烷基,C1-C3烷氧基,C1-C3卤代烷氧基,卤素,氰基或硝基取代的杂芳基,
Rc和Rd各自彼此独立地是氢,C1-C10烷基,C3-C10烯基,C3-C10炔基,C2-C10卤代烷基,C1-C10氰基烷基,C1-C10硝基烷基,C1-C10氨基烷基,C1-C5烷基氨基C1-C5烷基,C2-C8二烷基氨基C1-C5烷基,C3-C7环烷基C1-C5烷基,C1-C5烷氧基C1-C5烷基,C3-C5烯氧基C1-C5烷基,C3-C5炔氧基C1-C5烷基,C1-C5烷硫基C1-C5烷基,C1-C5烷基亚磺酰基C1-C5烷基,C1-C5烷基磺酰基C1-C5烷基,C2-C8亚烷基氨氧基C1-C5烷基,C1-C5烷基羰基C1-C5烷基,C1-C5烷氧基羰基C1-C5烷基,氨基羰基C1-C5烷基,C1-C5烷基氨基羰基C1-C5烷基,C2-C8二烷基氨基羰基C1-C5烷基,C1-C5烷基羰基氨基C1-C5烷基,N-C1-C5烷基羰基-N-C2-C5烷基氨基烷基,C3-C6三烷基甲硅烷基C1-C5烷基,苯基C1-C5烷基(其中所述苯基可以任选地被C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、C1-C3烷硫基、C1-C3烷基亚磺酰基、C1-C3烷基磺酰基、卤素、氰基取代或被硝基取代),杂芳基C1-C5烷基,(其中所述杂芳基可以任选地被C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、C1-C3烷硫基、C1-C3烷基亚磺酰基、C1-C3烷基磺酰基、卤素、氰基取代或被硝基取代),C2-C5卤代烯基,C3-C8环烷基,苯基或被C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、卤素、氰基或硝基取代的苯基,杂芳基或被C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、卤素、氰基或硝基取代的杂芳基,杂芳基氨基或被C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、卤素、氰基或硝基取代的杂芳基氨基,二杂芳基氨基或被C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、卤素、氰基或硝基取代的二杂芳基氨基,苯基氨基或被C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、卤素、氰基取代或被硝基取代的苯基氨基,二苯基氨基或被C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、卤素、氰基取代或被硝基取代的二苯基氨基,或C3-C7环烷基氨基,二-C3-C7环烷基氨基或C3-C7环烷氧基或者Rc和Rd可以一起形成3-7元环,任选地包含选自O或S的一个杂原子,
Re是C1-C10烷基,C2-C10烯基,C2-C10炔基,C1-C10卤代烷基,C1-C10氰基烷基,C1-C10硝基烷基,C1-C10氨基烷基,C1-C5烷基氨基C1-C5烷基,C2-C8二烷基氨基C1-C5烷基,C3-C7环烷基C1-C5烷基,C1-C5烷氧基C1-C5烷基,C3-C5烯氧基C1-C5烷基,C3-C5炔氧基C1-C5烷基,C1-C5烷硫基C1-C5烷基,C1-C5烷基亚磺酰基C1-C5烷基,C1-C5烷基磺酰基C1-C5烷基,C2-C8亚烷基氨氧基C1-C5烷基,C1-C5烷基羰基C1-C5烷基,C1-C5烷氧基羰基C1-C5烷基,氨基羰基C1-C5烷基,C1-C5烷基氨基羰基C1-C5烷基,C2-C8二烷基氨基羰基C1-C5烷基,C1-C5烷基羰基氨基C1-C5烷基,N-C1-C5烷基羰基-N-C1-C5烷基氨基C1-C5烷基,C3-C6三烷基甲硅烷基C1-C5烷基,苯基C1-C5烷基(其中所述苯基可以任选地被C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、C1-C3烷硫基、C1-C3烷基亚磺酰基、C1-C3烷基磺酰基、卤素、氰基取代或被硝基取代),杂芳基C1-C5烷基(其中所述杂芳基可以任选地被C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、C1-C3烷硫基、C1-C3烷基亚磺酰基、C1-C3烷基磺酰基、卤素、氰基取代或被硝基取代),C2-C5卤代烯基,C3-C8环烷基,苯基或被C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、卤素、氰基或硝基取代的苯基,杂芳基或被C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、卤素、氰基取代或被硝基取代的杂芳基,杂芳基氨基或被C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、卤素、氰基取代或被硝基取代的杂芳基氨基,二杂芳基氨基或被C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、卤素、氰基或硝基取代的二杂芳基氨基,苯基氨基或被C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、卤素、氰基、硝基取代的苯基氨基,二苯基氨基或被C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、卤素、氰基或硝基取代的二苯基氨基,或C3-C7环烷基氨基,二C3-C7环烷基氨基或C3-C7环烷氧基,C1-C10烷氧基,C1-C10卤代烷氧基,C1-C5烷基氨基或C2-C8二烷基氨基,
Rf和Rg各自彼此独立地是C1-C10烷基,C2-C10烯基,C2-C10炔基,C1-C10烷氧基,C1-C10卤代烷基,C1-C10氰基烷基,C1-C10硝基烷基,C1-C10氨基烷基,C1-C5烷基氨基C1-C5烷基,C2-C8二烷基氨基C1-C5烷基,C3-C7环烷基C1-C5烷基,C1-C5烷氧基C1-C5烷基,C3-C5烯氧基C1-C5烷基,C3-C5炔氧基C1-C5烷基,C1-C5烷硫基C1-C5烷基,C1-C5烷基亚磺酰基C1-C5烷基,C1-C5烷基磺酰基C1-C5烷基,C2-C8亚烷基氨氧基C1-C5烷基,C1-C5烷基羰基C1-C5烷基,C1-C5烷氧基羰基C1-C5烷基,氨基羰基C1-C5烷基,C1-C5烷基氨基羰基C1-C5烷基,C2-C8二烷基氨基羰基C1-C5烷基,C1-C5烷基羰基氨基C1-C5烷基,N-C1-C5烷基羰基-N-C2-C5烷基氨基烷基,C3-C6三烷基甲硅烷基C1-C5烷基,苯基C1-C5烷基(其中所述苯基可以任选地被C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、C1-C3烷硫基、C1-C3烷基亚磺酰基、C1-C3烷基磺酰基、卤素、氰基取代或被硝基取代),杂芳基C1-C5烷基(其中所述杂芳基可以任选地被C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、C1-C3烷硫基、C1-C3烷基亚磺酰基、C1-C3烷基磺酰基、卤素、氰基取代或被硝基取代),C2-C5卤代烯基,C3-C8环烷基,苯基或被C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、卤素、氰基或硝基取代的苯基,杂芳基或被C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、卤素、氰基取代或被硝基取代的杂芳基,杂芳基氨基或被C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、卤素、氰基取代或被硝基取代的杂芳基氨基,二杂芳基氨基或被C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、卤素、氰基或硝基取代的二杂芳基氨基,苯基氨基或被C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、卤素、氰基或硝基取代的苯基氨基,二苯基氨基或被C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、卤素、氰基或硝基取代的二苯基氨基,或C3-C7环烷基氨基,二C3-C7环烷基氨基或C3-C7环烷氧基,C1-C10卤代烷氧基,C1-C5烷基氨基或C2-C8二烷基氨基,苄氧基或苯氧基,其中所述苄基和苯基可以又被C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、卤素、氰基或硝基取代,和
Rh是C1-C10烷基,C3-C10烯基,C3-C10炔基,C1-C10卤代烷基,C1-C10氰基烷基,C1-C10硝基烷基,C2-C10氨基烷基,C1-C5烷基氨基C1-C5烷基,C2-C8二烷基氨基C1-C5烷基,C3-C7环烷基C1-C5烷基,C1-C5烷氧基C1-C5烷基,C3-C5烯氧基C1-C5烷基,C3-C5炔氧基C1-C5烷基,C1-C5烷硫基C1-C5烷基,C1-C5烷基亚磺酰基C1-C5烷基,C1-C5烷基磺酰基C1-C5烷基,C2-C8亚烷基氨氧基C1-C5烷基,C1-C5烷基羰基C1-C5烷基,C1-C5烷氧基羰基C1-C5烷基,氨基羰基C1-C5烷基,C1-C5烷基氨基羰基C1-C5烷基,C2-C8二烷基氨基羰基C1-C5烷基,C1-C5烷基羰基氨基C1-C5烷基,N-C1-C5烷基羰基-N-C1-C5烷基氨基C1-C5烷基,C3-C6三烷基甲硅烷基C1-C5烷基,苯基C1-C5烷基(其中所述苯基可以任选地被C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、C1-C3烷硫基、C1-C3烷基亚磺酰基、C1-C3烷基磺酰基、卤素、氰基取代或被硝基取代),杂芳基C1-C5烷基(其中所述杂芳基可以任选地被C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、C1-C3烷硫基、C1-C3烷基亚磺酰基、C1-C3烷基磺酰基、卤素、氰基取代或被硝基取代),苯氧基C1-C5烷基(其中所述苯基可以任选地被C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、C1-C3烷硫基、C1-C3烷基亚磺酰基、C1-C3烷基磺酰基、卤素、氰基取代或被硝基取代),杂芳氧基C1-C5烷基(其中所述杂芳基可以任选地被C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、C1-C3烷硫基、C1-C3烷基亚磺酰基、C1-C3烷基磺酰基、卤素、氰基取代或被硝基取代),C3-C5卤代烯基,C3-C8环烷基,苯基或被C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、卤素取代或被硝基取代的苯基,或杂芳基或被C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、卤素、氰基取代或被硝基取代的杂芳基。
优选地,潜伏基团G是基团-C(Xa)-Ra或-C(Xb)-Xc-Rb,Xa、Ra、Xb、Xc和Rb的含义如前文所定义。
在式I化合物的优选组中,R1是甲基、乙基、乙烯基、乙炔基、甲氧基或卤素。更优选地,R1是甲基、乙基、甲氧基或卤素。最优选地,R1是甲基或乙基。
在式I化合物的优选组中,R2是氢、卤素、甲基、乙基、苯基或苯基,被下述基团取代:C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、氰基、硝基、卤素、C1-C3烷硫基、C1-C3烷基亚磺酰基或C1-C3烷基磺酰基。
优选地,R2是甲基。
在式I化合物的优选组中,R3是氢、卤素、甲基、乙基、苯基或苯基,被下述基团取代:C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、氰基、硝基、卤素、C1-C3烷硫基、C1-C3烷基亚磺酰基或C1-C3烷基磺酰基。
优选地,R2和R3独立地是氢、甲基、乙基、卤素、任选取代的苯基或任选取代的杂芳基。
优选地,R4是氢、甲基、乙基、乙烯基或乙炔基和,更优选地,R4是氢、甲基或乙基。
优选地,R5表示氢。
式(I)化合物的另-适宜组的特征在于R6和R7各自是氢。
优选地,R6和R7是甲基或乙基,或R6是氢和R7是甲基或乙基。
在式(I)化合物的优选组中,R8,当X表示S(O)或S(O)2时,是C1-C18烷基、C3-C7环烷基、被甲基或乙基取代的C3-C7环烷基、C1-C6烷氧基C1-C12烷基、C1-C6烷硫基C1-C12烷基、C3-C18烯基、C3-C18炔基或被卤素取代的C3-C18炔基。
更优选地,R8是C1-C6烷基或C3-C7环烷基,尤其是R8是甲基、乙基或丙基。
在式(I)化合物的另一优选组中,R8,当X表示O或S时,是甲基、乙基、丙基、丁基、戊基或己基、C7-C18烷基、C3-C7环烷基、被甲基或乙基取代的C3-C7环烷基、C1-C6烷氧基C1-C12烷基、C1-C6烷硫基C1-C12烷基、C3-C18烯基、C3-C18炔基或被卤素取代的C3-C18炔基。
尤其优选在式(I)化合物中,R8,当X表示O或S时,是甲基、乙基或丙基,特别是乙基或丙基。
在另一组优选式(I)化合物中,R8,当X表示S(O)或S(O)2,是C1-C18烷基、C3-C7环烷基、被甲基或乙基取代的C3-C7环烷基、C1-C6烷氧基C1-C12烷基、C1-C6烷硫基C1-C12烷基、C3-C18烯基、C3-C18炔基或被卤素取代的C3-C18炔基,以及R6和R7是甲基或乙基,或R6是氢和R7是甲基或乙基。
优选地,在式(I)化合物中,取代基R8-X-[CR6R7]1-不是CH3OCH2-和CH3SCH2-。
优选G是氢、碱金属或碱土金属,其中特别优选氢。
优选在式(I)化合物中,n是1或2。
在式(I)化合物中n表示2或3的情况下,4个或6个取代基R6和R7的含义不必相同。例如,部分结构[CR6R7]2也包含基团,比如CH(CH3)CH2、C(CH3)2CH2、CH2CH(CH3)和CH2C(CH3)2。
在式(I)化合物的另一优选组中,R5,当n表示1或2时,与R8一起形成C2-C5亚烷基链。
在式(I)化合物的另一优选组中,R5,当n表示1时,与R8一起形成亚丙基链以及R6和R7各自是氢。
优选地,R5,当n表示1或2且尤其是2时,与R8一起形成亚乙基链以及R6和R7各自是氢。R5的这些含义在当X是O或当X是S(O)或S(O)2尤其适用。
在式(I)化合物的另一优选组中,R1、R2和R4彼此独立地是甲基或乙基以及R3是氢。
在式(I)化合物的另一优选组中,R1是甲基或乙基,R2是氢,R3是苯基或苯基,被下述基团取代:C1-C4烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、氰基、硝基或卤素,或者杂芳基或杂芳基,被下述基团取代:C1-C4烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、氰基、硝基或卤素。
在式(I)化合物的另一优选组中,R1是甲基或乙基,R2是苯基或苯基,被下述基团取代:C1-C4烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、氰基、硝基或卤素,或者杂芳基或杂芳基,被下述基团取代:C1-C4烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、氰基、硝基或卤素、R3是氢以及R4是氢、甲基或乙基。
本发明还涉及式I化合物可与胺、碱金属和碱土金属碱或季铵碱形成的盐。在作为成盐物质的碱金属和碱土金属氢氧化物中,应特别提及锂、钠、钾、镁和钙的氢氧化物,更尤其是钠和钾的氢氧化物。根据本发明的式I化合物还包括可以在成盐期间形成的水合物。
适于形成铵盐的胺的实例包括氨以及伯、仲和叔C1-C18烷基胺、C1-C4羟基烷基胺和C2-C4烷氧基烷基胺,例如甲胺、乙胺、正丙胺、异丙胺、四种丁胺异构体、正戊胺、异戊胺、己胺、庚胺、辛胺、壬胺、葵胺、十五烷胺、十六烷胺、十七烷胺、十八烷胺、甲基乙胺、甲基异丙胺、甲基己胺、甲基壬胺、甲基十五烷胺、甲基十八烷胺、乙基丁胺、乙基庚胺、乙基辛胺、己基庚胺、己基辛胺、二甲胺、二乙胺、二正丙胺、二异丙胺、二正丁胺、二正戊胺、二异戊胺、二己胺、二庚胺、二辛胺、乙醇胺、正丙醇胺、异丙醇胺、N,N-二乙醇胺、N-乙基丙醇胺、N-丁基乙醇胺、烯丙胺、正丁-2-烯胺、正戊-2-烯胺、2,3-二甲基丁-2-烯胺、二丁-2-烯胺、正己-2-烯胺、丙二胺、三甲胺、三乙胺、三正丙胺、三异丙胺、三正丁胺、三异丁胺、三仲丁胺、三正戊胺、甲氧基乙胺和乙氧基乙胺;杂环胺,例如吡啶、喹啉、异喹啉、吗啉、哌啶、吡咯烷、二氢吲哚、奎宁环和氮杂卓;伯芳胺,例如苯胺、甲氧基苯胺、乙氧基苯胺、o-、m-和p-甲苯胺、苯二胺、联苯胺、萘胺和o-、m-和p-氯苯胺;但特别是三乙胺、异丙胺和二异丙胺。
优选适于成盐的季铵碱对应于,例如式[N(RaRbRcRd)]OH,其中Ra、Rb、Rc和Rd各自彼此独立地是C1-C4烷基。可以例如通过阴离子交换反应来获得其它的适宜四烷基铵与其它阴离子的碱。
根据取代基G、R2、R3、R6、R7和R8的含义,式(I)化合物可以以不同异构体形式存在。当G是氢时,例如,式(I)化合物可以以不同互变异构体形式存在。本发明涵盖全部比例的全部这些异构体和互变异构体及其混合物。另外,当取代基包含双键时,可以选择顺式和反式异构体。这些异构体,也在要求保护的式(I)化合物的范围内。
式I化合物,其中G是C1-C8烷基,C2-C8卤代烷基,苯基C1-C8烷基(其中所述苯基可以任选地被C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、C1-C3烷硫基、C1-C3烷基亚磺酰基、C1-C3烷基磺酰基、卤素、氰基取代或被硝基取代),杂芳基C1-C8烷基(其中所述杂芳基可以任选地被C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、C1-C3烷硫基、C1-C3烷基亚磺酰基、C1-C3烷基磺酰基、卤素、氰基取代或被硝基取代),C3-C8烯基,C3-C8卤代烯基,C3-C8炔基,C(Xa)-Ra,C(Xb)-Xc-Rb,C(Xd)-N(Rc)-Rd,-SO2-Re,-P(Xe)(Rf)-Rg或CH2-Xf-Rh,其中Xa、Xb、Xc、Xd、Xe、Xf、Ra、Rb、Rc、Rd、Re、Rf、Rg和Rh如前文所定义,可以通过将式(A)化合物,其中G是H的式(I)化合物,用试剂G-Z处理,其中G-Z是烷基化试剂比如卤代烷(卤代烷的定义包括简单卤代C1-C8烷如碘甲烷和碘乙烷,经取代的卤代烷如苯基C1-C8卤代烷、氯甲基烷基醚,Cl-CH2-Xf-Rh,其中Xf是氧,和氯甲基烷基硫醚,Cl-CH2-Xf-Rh,其中Xf是硫),磺酸C1-C8烷基酯,或硫酸二-C1-C8-烷基酯,或者用卤代C3-C8烯处理,或者用卤代C3-C8炔处理,或者用酰化试剂处理,比如羧酸,HO-C(Xa)Ra,其中Xa是氧,酰氯,Cl-C(Xa)Ra,其中Xa是氧,或酸酐,[RaC(Xa)]2O,其中Xa是氧,或异氰酸酯,RcN=C=O,或氨基甲酰氯,Cl-C(Xd)-N(Rc)-Rd(其中Xd是氧且条件是Rc或Rd都不是氢),或硫代氨基甲酰氯,Cl-(Xd)-N(Rc)-Rd(其中Xd是硫且条件是Rc或Rd都不是氢),或氯代甲酸酯,Cl-C(Xb)-Xc-Rb(其中Xb和Xc是氧),或氯代硫代甲酸酯,Cl-C(Xb)-Xc-Rb(其中Xb是氧且Xc是硫),或氯代二硫代甲酸酯,Cl-C(Xb)-Xc-Rb(其中Xb和Xc是硫),或异硫氰酸酯,RcN=C=S,或者通过顺序用二硫化碳和烷基化试剂处理,或者用磷酰化试剂处理,比如磷酰氯,Cl-P(Xe)(Rf)-Rg或者用磺酰化试剂处理,比如磺酰氯,Cl-SO2-Re,优选在至少1当量碱存在下来制备。
式(A) 式(I)
环1,3-二酮的O-烷基化是已知的;适宜方法由例如T.Wheeler,US4436666描述。另选方法报导于M.Pizzorno和S.Albonico,Chem.Ind.(London),(1972),425-426;H.Born等人,J.Chem.Soc.,(1953),1779-1782;M.G.Constantino等人,Synth.Commun.,(1992),22(19),2859-2864;Y.Tian等人,Synth.Commun.,(1997),27(9),1577-1582;S.Chandra Roy等人,Chem.Letters,(2006),35(1),16-17;P.K.Zubaidha等人,Tetrahedron Lett.,(2004),45,7187-7188。
环1,3-二酮的O-烷基化可以由与例如R.Haines,US4175135以及T.Wheeler,US4422870,US4659372和US4436666所描述的那些相类似的方法引起。式(A)二酮通常可以用酰化试剂处理,优选在至少1当量适宜碱存在下,并且任选地在适宜溶剂存在下。所述碱可以是无机碱,比如碱金属碳酸盐或氢氧化物,或金属氢化物,或者有机碱,比如叔胺或金属醇盐。适宜无机碱的实例包括碳酸钠、氢氧化钠或氢氧化钾、氢化钠,适宜的有机碱包括三烷基胺,比如三甲胺和三乙胺,吡啶或其它胺类碱比如1,4-二氮杂二环[2.2.2]-辛烷和1,8-二氮杂二环[5.4.0]十一-7-烯。优选的碱包括三乙胺和吡啶。选择对此反应适宜的溶剂从而与反应物相容并且包括醚类比如四氢呋喃和1,2-二甲氧基乙烷和卤化溶剂比如二氯甲烷和氯仿。某些碱,比如吡啶和三乙胺,可以成功地用作碱和溶剂。在酰化试剂是羧酸的情况下,优选在已知偶联剂存在下引起酰化,比如碘化2-氯-1-甲基吡啶鎓、N,N′-二环己基碳二亚胺、1-(3-二甲基氨基丙基)-3-乙基碳二亚胺和N,N′-羰基二咪唑,任选地在碱如三乙胺或吡啶存在下,在适宜溶剂比如四氢呋喃、二氯甲烷或乙腈中。适宜的方法由例如W.Zhang和G.Pugh,Tetrahedron Lett.,(1999),40(43),7595-7598;T.Isobe和T.Ishikawa,J.Org.Chem.,(1999),64(19),6984-6988以及K.Nicolaou,T.Montagnon,G.Vassilikogiannakis,C.Mathison,J.Am.Chem.Soc.,(2005),127(24),8872-8888所描述。
环1,3-二酮的磷酰化可以使用磷酰卤或硫代磷酰卤和碱由与例如L.Hodakowski,US4409153所描述的那些相类似的方法引起。
式(A)化合物的磺酰化可以使用烷基或芳基磺酰卤,优选在至少1当量碱存在下,由例如C.Kowalski和K.Fields,J.Org.Chem.,(1981),46,197-201的方法来达成。
式(A)化合物,其中Y是S(O)m且m是1或2,可以通过氧化按照与E.Fehnel和A.Paul,J.Am.Chem.Soc.,(1955),77,4241-4244类似的方法,制备自式(A)化合物,其中Y是S。
用与US4209532中描述的那些类似的方法,优选在酸或碱存在下,任选在适宜溶剂存在下,式(A)化合物可以通过环化式(B)化合物,其中R是氢或烷基,来制得。式(B)化合物特别设计为式(I)化合物合成中的中间体。其中R是氢的式(B)化合物在酸性条件下可以环化,优选在强酸如硫酸、多磷酸或Eaton试剂存在下,任选在适宜溶剂如乙酸、甲苯或二氯甲烷存在下。
式(B) 式(A)
式(B)化合物,其中R是烷基(优选甲基或乙基)可以在酸性或碱性条件下环化,优选在至少1当量强碱如叔丁醇钾、二异丙氨基锂或氢化钠存在下,在溶剂如四氢呋喃、二甲亚砜或N,N-二甲基甲酰胺中。
式(B)化合物,其中R是H,可以由与例如T.Wheeler,US4209532描述的那些相类似的方法通过在标准条件下皂化式(C)化合物,其中R′是烷基(优选甲基或乙基)来制备,随后酸化反应混合物引起脱羧。
式(C) 式(B)
式(B)化合物,其中R是H,可以在已知条件下,例如在酸催化剂存在下,与烷醇,ROH加热,酯化为式(B)化合物,其中R是烷基。
式(C)化合物,其中R是烷基,可以通过在酸性或碱性条件下用适宜的式(E)酰氯处理式(D)化合物来制备。适宜酸包括强酸比如硫酸。适宜的碱包括叔丁醇钾、二(三甲基甲硅烷基)氨基钠、二异丙氨基锂,并且反应优选在适宜溶剂中(比如四氢呋喃或甲苯)于-80℃至30℃的温度下进行:另选地,式(C)化合物,其中R是H,可以通过在适宜溶剂(比如四氢呋喃或甲苯)中于适宜温度(-80℃至30℃)下用适宜的碱(比如叔丁醇钾、二(三甲基甲硅烷基)氨基钠和二异丙氨基锂)处理式(D)化合物,并使所获阴离子与适宜的式(F)酸酐反应来制备:
在碱存在下
式(D)化合物是已知化合物,或者可以通过已知方法制备自已知化合物。
式(E)化合物可以通过用烷醇,R-OH处理,随后通过在已知条件下将所得酸用氯化试剂如草酰氯或二氯亚砜处理,制备自式(F)化合物(参见,例如,C.Rouvier.Tetrahedron Lett.,(1984),25,(39),4371;D.Walba和M.Wand,Tetrahedron Lett.,(1982),23,4995;J.Cason,Org.Synth.Coll.卷III,(1955),169)。
式(F) 式(E)
式(F)化合物可以通过将式(G)化合物用脱水剂如酸酐处理来制得(描述于,例如J.Cason,Org.Synth.Coll.卷IV,(1963),630)。优选酸酐是乙酸酐。
式(G) 式(F)
式(G)化合物可以通过皂化式(H)酯,其中R”和R″′是适宜烷基,随后将所得酸脱羧来制得。适宜烷基是C1-C6烷基,尤其是甲基或乙基。引起皂化的适宜方法是已知的,包括例如将式(H)酯用适宜碱如氢氧化钠或氢氧化钾的水溶液处理,并将反应混合物用酸比如盐酸酸化促进脱羧。
式(H) 式(G)
式(H)化合物可以通过将式(J)化合物在碱性条件下与丙二酸二烷基酯比如丙二酸二甲酯或丙二酸二乙酯反应来制得。优选的包括醇钠碱比如甲醇钠和乙醇钠,反应优选在溶剂如甲醇、乙醇或甲苯进行。
式(J) 式(H)
式(J)化合物是已知化合物,或者可以通过已知方法制备自已知化合物。
式(B)化合物,其中R和R5都是H,也可以经由水解和脱羧式(K)化合物来制得,而该式(K)化合物可以通过在适宜碱比如甲醇钠或乙醇钠,在适宜溶剂比如甲醇、乙醇或甲苯中将丙二酸二烷基酯(优选丙二酸二甲酯或丙二酸二乙酯)加成至式(L)化合物来制得。式(L)化合物,可以按照已知方法(参见,例如J.March,Advanced OrganicChemistry,第3版,第835-841页,John Wiley and Sons Inc.1985),通过Knoevenagel缩合式(M)醛与式(N)β-酮酯,其中R″″是烷基,来制得。式(N)化合物可以按照文献中描述的方法(参见,例如J.Wemple等人,Synthesis,(1993),290-292;J.Bowman,J.Chem.Soc.,(1950),322)通过转化为相应的酰氯并且随后反应给出式(N)β-酮酯制备自式(D)化合物,其中R是H。
式(M)化合物是已知化合物,或者可以通过已知方法制备自已知化合物。
其它式(A)化合物可以通过在已知条件下将式(O)的2-重氮环己烷-1,3-二酮与式(P)化合物反应来制得。适宜方法包括光敏化重氮酮分解(参见,例如T.Wheeler,J.Org.Chem.,(1979),44,4906),或通过在已知条件下于适宜溶剂中使用适宜金属催化剂比如乙酸铑、氯化铜或三氟甲磺酸铜(参见,例如M.Oda等人,Chem.Lett.(1987),1263)。在式(P)化合物在室温下是液体的情况下,这些反应可以不需任何溶剂而进行。式(P)化合物是已知化合物,或者可以通过已知方法制备自已知化合物。
式(O) 式(P) 式(A)
式(O)化合物可以通过将式(Q)化合物用重氮转移试剂比如甲苯磺酰叠氮化物或甲磺酰叠氮化物和碱来处理来制得,按照例如T.Ye和M.McKervey(Chem.Rev.,(1994),94,1091-1160)、H.Stetter和K.Kiehs(Chem.Ber.,(1965),98,1181)和D.Taber等人(J.Org.Chem.,(1986),51,4077)所描述。
式(Q) 式(O)
式(Q)化合物可以在已知条件下经由水解和脱羧式(R)化合物来制得。优选R″是甲基或乙基。
式(R) 式(Q)
式(R)化合物可以通过在碱性条件下将式(S)化合物与丙二酸二烷基酯反应来制得。优选所述丙二酸二烷基酯是丙二酸二甲酯或丙二酸二乙酯,所述碱是金属醇盐比如甲醇钠或乙醇钠,反应在适宜溶剂比如甲醇、乙醇或甲苯中进行。
式(S) 式(R)
式(S)化合物是已知的,或者可以通过已知方法制备自已知化合物。
其它式(A)化合物可以通过将式(Y)碘内鎓盐,其中Ar是任选取代的苯基,在适宜钯催化剂、碱存在下和在适宜溶剂中与式(Z)芳基硼酸反应来制得。
式(Y) 式(Z) 式(A)
适宜的钯催化剂通常是钯(II)或钯(0)配合物,例如二卤化钯(II),乙酸钯(II)、硫酸钯(II)、二氯化二(三苯基膦)钯(II)、二氯化二(三环戊基膦)钯(II)、二氯化二(三环己基膦)钯(II)、二(二苯亚甲基丙酮丙酮)钯(0)或四(三苯基膦)-钯(0)。所述钯催化剂也可以通过与希望的配体配合从钯(II)或钯(0)化合物“原位”制得,例如将要配合的钯(II)盐,例如二氯化钯(II)(PdCl2)或乙酸钯(II)(Pd(OAc)2)与希望的配体一起,例如三苯基膦(PPh3)、三环戊基膦或三环己基膦、2-二环己基-膦-2′,6′-二甲氧基联苯或2-二环己基膦-2′,4′,6′-三异丙基联苯以及所选溶剂,与式(Y)化合物、式(Z)芳基硼酸和碱组合。还适宜的二齿配体是,例如1,1′-二(二苯基膦基)二茂铁或1,2-二(二苯基膦基)乙烷。通过加热反应介质,对C-C偶联反应所希望的钯(II)配合物或钯(0)配合物由此“原位”形成,接着引发所述C-C偶联反应。
所述钯催化剂的用量是0.001-50mol%,优选量是0.1-15mol%,基于式(Y)化合物。反应还可以在其他添加剂比如四烷基铵盐,例如溴化四丁基铵存在下进行。优选所述钯催化剂是乙酸钯,所述碱是氢氧化锂而所述溶剂是1,2-二甲氧基乙烷水溶液。
式(Y)化合物可以按照K.Schank和C.Lick,Synthesis(1983),392;R.Moriarty等人,J.Am.Chem.Soc,(1985),107,1375,或Z.Yang等人,Org.Lett.,(2002),4(19),3333的方法通过在溶剂中比如水或者醇水溶液比如乙醇水溶液用高价碘试剂比如(二乙酰氧基)碘苯或亚碘酰苯和碱比如碳酸钠水溶液、氢氧化锂或氢氧化钠处理来制备自式(Q)化合物:
式(Z)芳基硼酸可以通过已知方法(参见,例如,W.Thompson和J.Gaudino,J.Org.Chem,(1984),49,5237以及R.Hawkins等人,J.Am.Chem.Soc.,(1960),82,3053)制备自式(AA)芳基卤,其中Hal是溴或碘。例如,式(AA)芳基卤可以在适宜溶剂,优选二乙醚或四氢呋喃中,在-80℃至30℃的温度下用烷基锂或烷基镁卤化物处理,所得芳基镁或芳基锂试剂可以随后与硼酸三烷基酯(优选硼酸三甲酯)反应给出芳基硼酸二烷基酯,其可以在酸性条件下水解为希望的式(Z)硼酸。
式(AA) 式(Z)
另选地,式(AA)化合物可以在已知条件下与双(频那醇)二硼反应(参见,例如N.Miyaura等人,J.Org.Chem.,(1995),60,7508),所得芳基硼酸酯在酸性条件下水解给出式(Z)硼酸。
式(AA)芳基卤化物可以通过已知方法例如Sandmeyer反应经由相应重氮鎓盐制备自式(BB)苯胺。
式(BB)苯胺是已知化合物或者可以通过已知方法制备自已知化合物。
式(BB) 式(AA)
其它式(A)化合物,其中R2是任选取代芳基或杂芳基,可以在已知条件下(参见,例如F.Bellina,A.Carpita和R.Rossi,Synthesis,(2004),15,2419-2440和A.Suzuki,Journal ofOrganometallic Chemistry,(2002),653,83)在适宜钯催化剂和碱存在下制备自式(CC)化合物,其中X′是原子或适于与芳基-或杂芳基-硼酸偶联的基团。适宜原子和基团X′包括三氟甲磺酸盐和卤素,尤其是氯、溴和碘。
式(CC) 式(A)
类似地,式(A)化合物,其中R3是任选取代的芳基或杂芳基,可以在类似的钯催化条件下制备自式(DD)化合物,其中X′如前文所定义,和适宜的芳基-或杂芳基-硼酸。
式(DD) 式(A)
式(CC)和式(DD)化合物可以通过前文所描述的一种或多种方法分别制备自式(EE)和式(FF)化合物。
式(EE) 式(FF)
式(EE)和式(FF)化合物可以通过已知方法制备自已知化合物。
式(CC)化合物可以通过将式(O)化合物与式(GG)化合物在与前文将式(O)化合物转化为式(A)化合物所描述的那些相类似的条件下反应来制得。
式(CC) 式(O) 式(DD)
类似地,式(DD)化合物可以在类似条件下制备自式(O)化合物和式(HH)化合物。
另外式(I)化合物,其中G是C1-4烷基,可以通过将式X化合物(JJ),其中G是C1-4烷基而Hal是卤素优选溴或碘,与式(Z)芳基硼酸在适宜钯催化剂和碱存在下,优选在适宜配体存在下,在适宜溶剂中反应来制得。优选钯催化剂是乙酸钯,碱是磷酸钾,配体是2-二环己基膦-2′,6′-二甲氧基联苯而溶剂是甲苯。
式(JJ) 式(Z) 式(A)
其中,G是C1-4烷基
式(JJ)化合物可以通过卤化式(Q)化合物,随后将所得式(KK)卤化物用C1-4卤代烷或原甲酸三-C1-4-烷基酯在已知条件下烷基化来制得,例如R.Shepherd和A.White(J.Chem.Soc.Perkin Trans.1(1987),2153)和Y.-L.Lin等人(Bioorg.Med.Chem.(2002),10,685-690)的方法。另选地,式(JJ)化合物可以通过将式(Q)化合物用C1-4卤代烷或原甲酸三-C1-4-烷基酯烷基化,并在已知条件下卤化式(LL)烯酮来制得。
式(I)化合物,其中G是H,可以通过优选在酸催化剂比如盐酸存在下和任选在适宜溶剂比如四氢呋喃存在下水解制备自式(I)化合物,其中G是C1-4烷基。
其他式(A)化合物可以通过将式(Q)化合物与式(MM)有机铅试剂在例如由J.Pinhey,Pure and Appl.Chem.,(1996),第68卷,第4期,第819-824页和M.Moloney等人,Tetrahedron Lett.,(2002),43,3407-3409描述的条件下反应来制得。式(MM)有机铅试剂可以制备自式(Z)硼酸和式(NN)锡烷,或通过按照已知方法用四乙酸铅直接高铅酸化(plumbation)式(OO)化合物来制得。
另外的式(A)化合物可以通过将式(Q)化合物与适宜三芳基铋化合物在例如由A.Yu.Fedorov等人,Russ.Chem.Bull.Int.Ed.,(2005),第54卷,第11期,第2602-2611页和P.Koech和M.Krische,J.Am.Chem.Soc.,(2004),第126卷,第17期,第5350-5351页(2004)及其参考文献中描述的条件下反应来制得。
本发明式(I)化合物可以如合成所得以未修饰的形式用作除草剂,但是通常使用如载体、溶剂和表面活性物质的制剂助剂以各种方式将它们制剂成除草组合物。所述制剂可以是各种物理形式,例如粉剂、凝胶剂、可湿性粉剂、水分散性粒剂、水分散性片剂、泡腾压缩片剂、乳油、可微乳化浓剂、水乳剂、可流动油剂、水分散剂、油分散剂、悬乳剂、微胶囊悬浮剂、乳粒剂、可溶液剂、水溶性浓剂(具有作为载体的水或可与水混合的有机溶剂)、浸渍的聚合物膜的形式或已知自例如the Manual on Development and Use of FAOSpecifications for Plant Protection Products,第5版,1999的其它形式。这些制剂可以直接使用或在使用前稀释。稀释的制剂可以用例如水、液体肥料、微量营养素、生物体、油或溶剂来制备。
这些制剂可以这样制备,例如通过将活性成分与制剂助剂混合而得到细分的固体、颗粒、溶液、分散液或乳液形式的组合物。活性成分还可以与其它助剂一起制剂,例如细分的固体、矿物油、植物油、改性的植物油、有机溶剂、水、表面活性物质或其组合。活性成分还可以包含在包含聚合物的非常细小的微胶囊中。微胶囊在多孔载体中包含活性成分。这使得活性成分能够以受控量(例如缓释)被释放入其环境。微胶囊通常具有0.1到500微米的直径。它们包含活性成分,按胶囊重量计约25到95%。活性成分可以以整块固体形式、固体或液体分散体中的微粒形式或者适宜的溶液形式存在。包封膜包含,例如,天然或合成树胶、纤维素、苯乙烯-丁二烯共聚物、聚丙烯腈、聚丙烯酸酯、聚酯、聚酰胺、聚脲、聚氨酯或化学改性的聚合物和淀粉黄原酸酯或者其它本领域技术人员已知的相关聚合物。另选地,可以形成很细的微胶囊,其中活性成分以基础物质固体基体中的细分颗粒形式存在,但在此情况下微胶囊未被包封。
适于制备本发明组合物的制剂助剂本身是已知的。可以用作液体载体的有:水、甲苯、二甲苯、石油醚、植物油、丙酮、甲乙酮、环己酮、酸酐、乙腈、苯乙酮、乙酸戊酯、2-丁酮、碳酸亚丁酯、氯苯、环己烷、环己醇、乙酸烷基酯、二丙酮醇、1,2-二氯丙烷、二乙醇胺、对二乙苯、二甘醇、二甘醇松香酸酯、二甘醇丁基醚、二甘醇乙基醚、二甘醇甲基醚、N,N-二甲基甲酰胺、二甲亚枫、1,4-二氧六环、一缩二丙二醇、一缩二丙二醇甲基醚、一缩二丙二醇二苯甲酸酯、diproxitol、烷基吡咯烷酮、乙酸乙酯、2-乙基己醇、碳酸亚乙酯、1,1,1-三氯乙烷、2-庚酮、α-蒎烯、d-柠檬烯、乳酸乙酯、乙二醇、乙二醇丁基醚、乙二醇甲基醚、γ-丁内酯、甘油、乙酸甘油酯、二乙酸甘油酯、三乙酸甘油酯、十六烷、己二醇、乙酸异戊酯、乙酸异冰片酯、异辛烷、异佛尔酮、异丙基苯、肉豆蔻酸异丙酯、乳酸、十二胺、异亚丙基丙酮、甲氧基丙醇、甲基异戊基酮、甲基异丁基酮、月桂酸甲酯、辛酸甲酯、油酸甲酯、二氯甲烷、间二甲苯、正己烷、正辛胺、十八烷酸、辛胺乙酸盐、油酸、油酰基胺、邻二甲苯、苯酚、聚乙二醇(PEG400)、丙酸、乳酸丙酯、碳酸亚丙酯、丙二醇、丙二醇甲基醚、对二甲苯、甲苯、磷酸三乙酯、三甘醇、二甲苯磺酸、烷烃、矿物油、三氯乙烯、全氯乙烯、乙酸乙酯、乙酸戊酯、乙酸丁酯、丙二醇甲基醚、二甘醇甲基醚、甲醇、乙醇、异丙醇和如异戊醇、四氢糠醇、己醇、辛醇的更聚合物量的醇、乙二醇、丙二醇、甘油、N-甲基-2-吡咯烷酮等。为稀释浓缩物,一般选择水作载体。适宜的固体载体是,例如,滑石、二氧化钛、叶蜡石粘土、硅土、绿坡缕石粘土、硅藻土、石灰石、碳酸钙、膨润土、蒙脱石钙、棉籽壳、粗麦粉、大豆面粉、浮石、木屑、落花生(ground walnut)壳、木质素以及例如CFR 180.1001.(c)&(d)中描述的类似物质。
大量表面活性物质可以被有利地用在固体和液体制剂中,特别是在使用前可用载体稀释的那些制剂中。表面活性物质可以是阴离子、阳离子、非离子或聚合物的,它们还可用作乳化剂、湿润剂或悬浮剂或用于其他目的。典型的表面活性物质包括,例如,烷基硫酸盐,比如月桂基硫酸二乙醇铵;烷基芳基磺酸盐,比如十二烷基苯磺酸钙;烷基苯酚-环氧烷烃的加成产物,比如乙氧基化壬基苯酚;醇-环氧烷烃的加成产物,比如乙氧基化十三烷醇;皂,比如硬脂酸钠;烷基萘磺酸盐,比如二丁基萘磺酸钠;磺基琥珀酸盐的二烷基酯,比如磺基琥珀酸钠二(2-乙基己基)酯;山梨糖醇酯,比如山梨糖醇油酸酯;季铵,比如氯化月桂基三甲基铵,聚脂肪酸乙二醇酯,比如聚硬脂酸乙二醇酯;环氧乙烷和环氧丙烷的嵌段共聚物;单-和二-烷基磷酸酯的盐;还有在例如″McCutcheon′s Detergents and EmulsifiersAnnual″MC Publishing Corp.,Ridgewood New Jersey,1981中描述的其它物质。
通常可以用在农药制剂中的其它助剂可以包括结晶抑制剂、粘度改性物质、悬浮剂、染料、抗氧化剂、起泡剂、光吸收剂、混合助剂、消泡剂、配位剂、中和或pH-改性物质以及缓冲剂、腐蚀-抑制剂、香料、湿润剂、吸收改善剂、微量营养素、增塑剂、助流剂、润滑剂、分散剂、增稠剂、防冻剂、杀微生物剂以及液体和固体肥料。
所述制剂还可以包含额外的活性物质,例如其它除草剂、除草剂安全剂、植物生长调节剂、杀真菌剂或杀虫剂。
本发明组合物还可以包括添加剂,其包含植物或动物来源的油、矿物油、这样的油的烷基酯或者这样的油和油衍生物的混合物。用于本发明组合物中的油添加剂的量一般是从0.01到10%,基于喷雾混合物。例如,可以在制备出喷雾混合物后可将油添加剂以希望的浓度加至喷雾槽。优选的油添加剂包含矿物油或植物来源的油,例如菜籽油、橄榄油或向日葵油、乳化植物油如(-PoulencCanada Inc.)、植物来源的油的烷基酯如甲基衍生物或者动物来源的油如鱼油或牛脂。优选的添加剂包含,例如,作为活性成分基本上80%重量的鱼油烷基酯和15%重量的甲基化菜籽油,还有5%重量的惯用乳化剂和pH改性剂。特别优选的油添加剂包含C8-C22脂肪酸的烷基酯,特别是C12-C18脂肪酸的甲基衍生物,例如重要的月桂酸、棕榈酸和油酸的甲酯。这些酯已知为月桂酸甲酯(CAS-111-82-0)、棕榈酸甲酯(CAS-112-39-0)和油酸甲酯(CAS-112-62-9)。优选的脂肪酸甲酯衍生物是2230和2231(Cognis GmbH)。这些油衍生物和其它油衍生物也已知自the Compendium of HerbicideAdjuvants,第5版,Southern Illinois University,2000。
油添加剂的施用和作用还可以通过将其与表面活性物质如非离子、阴离子或阳离子表面活性剂组合来改善。适宜的阴离子、非离子和阳离子表面活性剂的实例见于WO 97/34485的第7页和第8页。优选的表面活性物质是十二烷基苄磺酸盐类的阴离子表面活性剂,特别是其钙盐,以及乙氧基化脂肪醇类的非离子表面活性剂。特别优选乙氧基化的C12-C22脂肪醇,具有5-40的乙氧基化度。可商购表面活性剂的实例是Genapol型(Clariant AG)。还优选的是硅酮表面活性剂,特别是多烷基氧化物改性的七甲基三硅氧烷,其可作为例如Silwet L-购得,以及全氟化表面活性剂。相对总添加剂的表面活性物质浓度一般从1到30%重量。包含油或矿物油或其衍生物与表面活性剂的混合物的添加剂实例是Edenor ME(Syngenta AG,CH)和(BP Oil UK Limited,GB)。
所述表面活性物质还可以单独用于制剂中,即不加油添加剂。
此外,向油添加剂/表面活性剂混合物中添加有机溶剂可以有助于作用的进一步增强。适宜的溶剂是,例如,Solvesso((ESSO)和Aromatic(Exxon公司)。这种溶剂的浓度可以是总重量的10到80%。这种可以与溶剂混合的油添加剂描述于例如US-A-4 834 908中,其中公开的可商购油添加剂称为(BASF公司)。本发明优选的又一种油添加剂是(Syngenta CropProtection Canada)。
除了上面列出的油添加剂,为了增强本发明组合物的作用,还可以将烷基吡咯烷酮制剂(例如)加入喷雾混合物。还可以使用合成网络结构(lattices)制剂,比如,例如聚丙烯酰胺、聚乙烯化合物或聚-1-p-薄荷烯(例如或)。包含丙酸的溶液,例如Eurogkem Pen-e-也可以混入喷雾混合物中作为活性增强剂。
除草制剂通常包含从0.1到99%重量、特别是从0.1到95%重量的式(I)化合物以及从1到99.9%重量的制剂助剂,其优选包括从0到25%重量的表面活性物质。虽然商业产品优选制剂为浓缩剂,但是终端用户通常采用稀释的制剂。
式(I)化合物的施用率可以在宽范围内变化并且取决于土壤性质、施用方法(出苗前或出苗后;拌种;向种畦中施用;免耕施用等)、作物植物、要防治的杂草或禾本科草、主要气候条件和其它受施用方法控制的因素、施用时间和目标作物。本发明式I化合物通常以1-4000g/ha、特别是5-1000g/ha的比率施用。
优选的制剂特别地具有下述组成:
(%=重量百分比):
乳油:
活性成分: 1-95%,优选60-90%
表面活性剂: 1-30%,优选5-20%
液体载体: 1-80%,优选1-35%
粉剂:
活性成分: 0.1-10%,优选0.1-5%
固体载体: 99.9-90%,优选99.9-99%
浓悬浮剂:
活性成分: 5-75%,优选10-50%
水: 94-24%,优选88-30%
表面活性剂: 1-40%,优选2-30%
可湿性粉剂:
活性成分: 0.5-90%,优选1-80%
表面活性剂: 0.5-20%,优选1-15%
固体载体: 5-95%,优选15-90%
颗粒剂:
活性成分: 0.1-30%,优选0.1-15%
固体载体: 99.5-70%,优选97-85%
下述实施例进一步举例说明而不是限制本发明。
F1.乳油 a) b) c) d)
活性成分 5% 10% 25% 50%
十二烷基苯磺酸钙 6% 8% 6% 8%
蓖麻油聚乙二醇醚 4% - 4% 4%
(36mol环氧乙烷)
辛基苯酚聚乙二醇醚 - 4% - 2%
(7-8mol环氧乙烷)
NMP - - 10% 20%
芳族烃混合物C9-C12 85% 78% 55% 16%
可用水稀释该浓缩液配制任意希望浓度的乳液。
F2.溶液 a) b) c) d)
活性成分 5% 10% 50% 90%
1-甲氧基-3-(3-甲氧基-
丙氧基)-丙烷 - 20% 20% -
聚乙二醇MW 400 20% 10% - -
NMP - - 30% 10%
芳族烃混合物C9-C12 75% 60% - -
该溶液适于以微滴剂形式的施用。
F3.可湿性粉剂 a) b) c) d)
活性成分 5% 25% 50% 80%
木质素磺酸钠 4% - 3% -
月桂基硫酸钠 2% 3% - 4%
二异丁基萘磺酸钠
十二烷基苯磺酸钙 - 6% 5% 6%
辛基苯酚聚乙二醇醚 - 1% 2% -
(7-8mol环氧乙烷)
高分散硅酸 1% 3% 5% 10%
高岭土 88% 62% 35% -
该活性成分与助剂充分地混合,所述混合物在合适的研磨机中充分研磨,得到可湿性粉剂,其可加水稀释给出任意要求浓度的悬浮剂。
F4.包覆颗粒剂 a) b) c)
活性成分 0.1% 5% 15%
高分散硅酸 0.9% 2% 2%
无机载体 99.0% 93% 83%
(直径0.1-1mm)
例如CaCO3或SiO2
该活性成分溶于二氯甲烷,将溶液喷涂于载体上,接着在真空中蒸除溶剂。
F5.包覆颗粒剂 a) b) c)
活性成分 0.1% 5% 15%
聚乙二醇MW 200 1.0% 2% 3%
高分散硅酸 0.9% 1% 2%
无机载体 98.0% 92% 80%
(直径0.1-1mm)
例如CaCO3或SiO2
在搅拌机中,将充分研磨的活性成分均匀地涂布至用聚乙二醇湿润的载体。通过这种方式获得无尘的包覆颗粒剂。
F6.挤出颗粒剂 a) b) c) d)
活性成分 0.1% 3% 5% 15%
木质素磺酸钠 1.5% 2% 3% 4%
羧甲基纤维素 1.4% 2% 2% 2%
高岭土 97.0% 93% 90% 79%
用助剂与活性成分混合并研磨,用水润湿此混合物。所获混合物挤出后在空气流中干燥。
F7.粉剂 a) b) c)
活性成分 0.1% 1% 5%
滑石 39.9% 49% 35%
高岭土 60.0% 50% 60%
通过混合活性成分和载体并在合适的研磨机中研磨所述混合物获得即用粉剂。
F8.浓悬浮剂 a) b) c) d)
活性成分 3% 10% 25% 50%
乙二醇 5% 5% 5% 5%
壬基苯酚聚乙二醇醚 - 1% 2% -
(15mol环氧乙烷)
木质素磺酸钠 3% 3% 4% 5%
羧甲基纤维素 1% 1% 1% 1%
37%甲醛水溶液 0.2% 0.2% 0.2% 0.2%
硅油乳液 0.8% 0.8% 0.8% 0.8%
水 87% 79% 62% 38%
用助剂与充分研磨的活性成分密切混合,得到浓悬浮剂,用水稀释后者可制备任意要求浓度的悬浮剂。
本发明也涉及选择性防治有用植物作物中的禾本科草和杂草的方法,其包含用式(I)化合物处理所述有用植物或其栽培区域或场所。
其中可以使用本发明组合物的有用植物作物尤其包括谷物、棉花、大豆、糖用甜菜、甘蔗、种植园作物、油菜、玉米和稻,并且用于非选择性杂草防治。术语“作物”应被理解为还包括通过常规育种法或基因工程使其耐受除草剂或除草剂类(例如ALS、GS、EPSPS、PPO、ACCase和HPPD抑制剂)的作物。通过常规育种法使其耐受例如咪唑啉酮类如甲氧咪草烟的作物的实例是夏季油菜(芸苔)。通过基因工程方法使之耐受除草剂的作物的实例包括抗草甘膦和抗草铵膦的玉米,该品种可根据商品名和购得。要防治的杂草可以是单子叶和双子叶杂草,比如,例如,繁缕属(Stellaria)、旱金莲属(Nasturtium)、剪股颖属(Agrostis)、马唐属(Digitaria)、燕麦属(Avena)、狗尾草属(Setaria)、白芥属(Sinapis)、黑麦草属(Lolium)、茄属(Solanum)、稗属(Echinochloa)、莞草属(Scirpus)、雨久花属(Monochoria)、慈姑属(Sagittaria)、雀麦属(Bromus)、看麦娘属(Alopecurus)、蜀黍属(Sorghum)、筒轴茅属(Rottboellia)、莎草属(Cyperus)、苘麻属(Abutilon)、黄花捻属(Sida)、苍耳属(Xanthium)、苋属(Amaranthus)、藜属(Chenopodium)、番薯属(Ipomoea)、菊属(Chrysanthemum)、猪殃殃属(Galium)、堇菜属(Viola)和婆婆纳属(Veronica)。
作物还被理解为通过基因工程方法使其对有害昆虫有抗性的那些,例如Bt玉米(对欧洲玉米螟有抗性)、Bt棉花(对棉铃象有抗性)以及Bt马铃薯(对马铃薯叶甲有抗性)。Bt玉米的实例是(Syngenta Seeds)的Bt-176杂交玉米。该Bt毒素是由苏云金杆菌(Bacillus thuringiensis)土壤细菌天然形成的蛋白。毒素和能合成这种毒素的转基因植物的实例描述于EP-A-451878、EP-A-374753、WO 93/07278、WO 95/34656、WO 03/052073和EP-A-427 529中。包含一种或多种编码杀虫抗性和表达一种或多种毒素的基因的转基因植物实例是(玉米)、Yield(玉米)、(棉花)、(棉花)、(马铃薯)、和植物作物和其种子材料可以对除草剂有抗性,而且同时对昆虫摄食有抗性(“叠加的”转基因事件)。种子例如可以具有表达杀虫活性Cry3蛋白并在同时有草甘膦耐受性的能力。术语“作物”应被理解为还包括通过常规育种法或基因工程获得的作物,其包含所谓的输出特性(例如改进的味道、贮藏稳定性、营养成分)。
栽培区域应被理解为包括其中已经生长了作物植物的土地以及计划用于这些作物植物的栽培的土地。
本发明式(I)化合物还可以与一种或多种其它除草剂组合使用。式(I)化合物的下述混合物特别重要。优选地,式(I)化合物是下述表1-151中列出的化合物:
式I化合物+乙草胺、式I化合物+三氟羧草醚、式I化合物+三氟羧草醚-钠盐、式I化合物+苯草醚、式I化合物+丙烯醛、式I化合物+甲草胺、式I化合物+禾草灭、式I化合物+烯丙基醇、式I化合物+莠灭津、式I化合物+氨唑草酮、式I化合物+酰嘧磺隆、式I化合物+氨基吡啶酸、式I化合物+杀草强、式I化合物+氨基磺酸铵、式I化合物+莎稗磷、式I化合物+磺草灵、式I化合物+莠去津、式I+艾维激素(aviglycine)、式I+唑啶草酮、式I化合物+四唑嘧磺隆、式I化合物+BCPC、式I化合物+氟丁酰草胺、式I化合物+草除灵、式I+苯硫酰草胺(bencarbazone)、式I化合物+乙丁氟灵、式I化合物+呋草磺、式I化合物+苄嘧磺隆、式I化合物+苄嘧磺隆-甲酯、式I化合物+地散磷、式I化合物+灭草松、式I化合物+双苯嘧草酮、式I化合物+双环磺草酮、式I化合物+吡草酮、式I化合物+甲羧除草醚、式I化合物+双丙氨膦、式I化合物+双草醚、式I化合物+双草醚-钠盐、式I化合物+硼砂、式I化合物+除草定、式I化合物+溴丁酰草胺、式I+溴酚肟、式I化合物+溴苯腈、式I化合物+丁草胺、式I化合物+氟丙嘧草酯、式I化合物+抑草磷、式I化合物+双丁乐灵、式I化合物+丁苯草酮、式I化合物+丁草敌、式I化合物+二甲胂酸、式I化合物+氯酸钙、式I化合物+唑草胺、式I化合物+双酰草胺、式I化合物+唑草酯、式I化合物+唑草酯-乙酯、式I化合物+CDEA、式I化合物+CEPC、式I化合物+氯甲丹、式I化合物+氯甲丹-甲酯、式I化合物+氯草敏、式I化合物+氯嘧磺隆、式I化合物+氯嘧磺隆-乙酯、式I化合物+氯代乙酸、式I化合物+绿麦隆、式I化合物+氯苯胺灵、式I化合物+氯磺隆、式I化合物+氯酞酸、式I化合物+氯酞酸甲酯、式I化合物+吲哚酮草酯、式I化合物+环庚草醚、式I化合物+醚磺隆、式I化合物+咯草隆、式I化合物+烯草酮、式I化合物+炔草酸、式I化合物+炔草酯、式I化合物+异噁草酮、式I化合物+稗草胺、式I化合物+二氯吡啶酸、式I化合物+氯磺草胺、式I化合物+氯磺草胺-甲酯、式I化合物+CMA、式I化合物+4-CPB、式I化合物+CPMF、式I化合物+4-CPP、式I化合物+CPPC、式I化合物+甲酚、式I化合物+苄草隆、式I化合物+氰胺、式I化合物+氰草津、式I化合物+环草敌、式I化合物+环丙嘧磺隆、式I化合物+噻草酮、式I化合物+氰氟草酯、式I化合物+氰氟草酯-丁酯、式I化合物+2,4-滴、式I化合物+3,4-DA、式I化合物+杀草隆、式I化合物+茅草枯、式I化合物+棉隆、式I化合物+2,4-滴丁酸、式I化合物+3,4-滴丁酸、式I化合物+2,4-DEB、式I化合物+甜菜安、式I+敌草净、式I化合物+麦草畏、式I化合物+敌草腈、式I化合物+邻二氯苯、式I化合物+对二氯苯、式I化合物+2,4-滴丙酸、式I化合物+高2-4-滴丙酸、式I化合物+禾草灵、式I化合物+禾草灵-甲酯、式I化合物+双氯磺草胺、式I化合物+野燕枯、式I化合物+野燕枯甲硫酸盐、式I化合物+吡氟草胺、式I化合物+氟吡草腙、式I化合物+噁唑隆、式I化合物+哌草丹、式I化合物+二甲草胺、式I化合物+异戊净、式I化合物+二甲噻草胺、式I化合物+二甲噻草胺-P、式I化合物+噻节因、式I化合物+二甲基次胂酸、式I化合物+氨氟灵、式I化合物+特乐酚、式I化合物+双苯酰草胺、式I+异丙净、式I化合物+敌草快、式I化合物+二溴敌草快、式I化合物+氟硫草定、式I化合物+敌草隆、式I化合物+二硝酚、式I化合物+3,4-DP、式I化合物+DSMA、式I化合物+EBEP、式I化合物+茵多酸、式I化合物+茵草敌、式I化合物+禾草畏、式I化合物+乙丁烯氟灵、式I化合物+胺苯磺隆、式I化合物+胺苯磺隆-甲酯、式I+乙烯利、式I化合物+乙呋草磺、式I化合物+氯氟草醚、式I化合物+乙氧嘧磺隆、式I化合物+乙氧苯草胺、式I化合物+噁唑禾草灵-P、式I化合物+精噁唑禾草灵、式I化合物+四唑酰草胺、式I化合物+硫酸亚铁、式I化合物+精麦草伏、式I化合物+啶嘧磺隆、式I化合物+双氟磺草胺、式I化合物+吡氟禾草灵、式I化合物+吡氟禾草灵-丁酯、式I化合物+精吡氟禾草灵、式I化合物+精吡氟禾草灵-丁酯、式I+异丙吡草酯、式I化合物+氟酮磺隆、式I化合物+氟酮磺隆-钠盐、式I化合物+氟吡磺隆、式I化合物+氯乙氟灵、式I化合物+氟噻草胺、式I化合物+氟哒嗪草酯、式I化合物+氟哒嗪草酯、式I+氟节胺、式I化合物+唑嘧磺草胺、式I化合物+氟烯草酸、式I化合物+氟烯草酸-戊基、式I化合物+丙炔氟草胺、式I+氟炔草胺(flumipropin)、式I化合物+伏草隆、式I化合物+乙羧氟草醚、式I化合物+乙羧氟草醚-乙酯、式I+fluoxaprop、式I+氟胺草唑、式I+氟丙草定(flupropacil)、式I化合物+四氟丙酸、式I化合物+氟啶嘧磺隆、式I化合物+氟啶嘧磺隆、式I化合物+芴丁酯、式I化合物+氟啶草酮、式I化合物+氟咯草酮、式I化合物+氯氟吡氧乙酸、式I化合物+呋草酮、式I化合物+氟噻甲草酸(fluthiacet)、式I化合物+氟噻乙草酯、式I化合物+氟磺胺草醚、式I化合物+甲酰胺磺隆、式I化合物+杀木膦、式I化合物+草铵膦、式I化合物+草铵膦-铵、式I化合物+草甘膦、式I化合物+氯吡嘧磺隆、式I化合物+氯吡嘧磺隆-甲酯、式I化合物+氟吡禾灵、式I化合物+精氟吡禾灵、式I化合物+氟乳醚、式I化合物+环嗪酮、式I化合物+咪草酸、式I化合物+咪草酸-甲基、式I化合物+甲氧咪草烟、式I化合物+甲基咪草烟、式I化合物+咪唑烟酸、式I化合物+咪唑喹啉酸、式I化合物+咪唑乙烟酸、式I化合物+唑吡嘧磺隆、式I化合物+茚草酮、式I化合物+碘甲烷、式I化合物+碘甲磺隆、式I化合物+碘甲磺隆-甲酯-钠盐、式I化合物+碘苯腈、式I化合物+异丙隆、式I化合物+异噁隆、式I化合物+异噁草胺、式I化合物+异噁氯草酮、式I化合物+异噁唑草酮、式I+异噁草醚、式I化合物+特胺灵、式I化合物+乳氟禾草灵、式I化合物+环草定、式I化合物+利谷隆、式I化合物+MAA、式I化合物+MAMA、式I化合物+2甲4氯、式I化合物+硫代2甲4氯乙酯、式I化合物+2甲4氯丁酸、式I化合物+2甲4氯丙酸、式I化合物+高2甲4氯丙酸、式I化合物+苯噻酰草胺、式I化合物+氟磺酰草胺、式I化合物+甲磺胺磺隆、式I化合物+甲磺胺磺隆-甲酯、式I化合物+甲基磺草酮、式I化合物+百亩、式I化合物+噁唑酰草胺、式I化合物+苯嗪草酮、式I化合物+吡草胺、式I化合物+甲基苯噻隆、式I+灭草唑、式I化合物+甲基胂酸、式I化合物+甲基杀草隆、式I化合物+异硫氰酸甲酯、式I化合物+吡喃隆、式I+溴谷隆、式I化合物+异丙甲草胺、式I化合物+高效异丙甲草胺、式I化合物+磺草唑胺、式I化合物+甲氧隆、式I化合物+嗪草酮、式I化合物+甲磺隆、式I化合物+甲磺隆-甲酯、式I化合物+MK-616、式I化合物+禾草敌、式I化合物+绿谷隆、式I化合物+MSMA、式I化合物+萘丙胺、式I化合物+萘氧丙草胺、式I化合物+萘草胺、式I+NDA-402989、式I化合物+草不隆、式I化合物+烟嘧磺隆、式I+氟氯草胺、式I+n-甲基草甘膦、式I化合物+壬酸、式I化合物+氟草敏、式I化合物+油酸(脂肪酸)、式I化合物+坪草丹、式I化合物+嘧苯胺磺隆、式I化合物+安磺灵、式I化合物+丙炔噁草酮、式I化合物+噁草酮、式I化合物+环氧嘧磺隆、式I化合物+噁嗪草酮、式I化合物+乙氧氟草醚、式I化合物+百草枯、式I化合物+二氯化百草枯、式I化合物+克草敌、式I化合物+二甲戊乐灵、式I化合物+五氟磺草胺、式I化合物+五氯酚、式I化合物+甲氯酰草胺、式I化合物+环戊噁草酮、式I化合物+烯草胺、式I化合物+石油、式I化合物+甜菜宁、式I化合物+甜菜宁-乙酯、式I化合物+胺氯吡啶酸、式I化合物+氟吡草胺、式I化合物+唑啉草酯(pinoxaden)、式I化合物+哌草磷、式I化合物+亚砷酸钾、式I化合物+叠氮化钾、式I化合物+丙草胺、式I化合物+氟嘧磺隆、式I化合物+氟嘧磺隆、式I化合物+氨氟乐灵、式I化合物+氟唑草胺、式I化合物+环苯草酮(profoxydim)、式I+调环酸钙、式I化合物+扑灭通、式I化合物+扑草净、式I化合物+毒草胺、式I化合物+敌稗、式I化合物+喔草酯、式I化合物+扑灭津、式I化合物+苯胺灵、式I化合物+异丙草胺、式I化合物+丙苯磺隆、式I化合物+丙苯磺隆-钠盐、式I化合物+炔苯酰草胺、式I化合物+苄草丹、式I化合物+氟磺隆、式I化合物+双唑草腈、式I化合物+氯吡草酸(pyraflufen)、式I化合物+吡草醚、式I+吡砜氟酮(pyrasulfotole)、式I化合物+吡唑特、式I化合物+吡嘧磺隆、式I化合物+吡嘧磺隆-乙酯、式I化合物+苄草唑、式I化合物+嘧啶肟草醚、式I化合物+稗草畏、式I化合物+哒草酚(pyridafol)、式I化合物+哒草特、式I化合物+环酯草醚、式I化合物+嘧草醚(pyriminobac)、式I化合物+嘧草醚、式I化合物+嘧氟磺草胺(pyrimisulfan)、式I化合物+嘧草硫醚、式I化合物+嘧草硫醚钠盐、式I+吡异噁砜(pyroxasulfone)(KIH-485)、式I+嘧吡草胺(pyroxulam)、式I化合物+二氯喹啉酸、式I化合物+喹草酸、式I化合物+灭藻醌、式I化合物+喹禾灵、式I化合物+精喹禾灵、式I化合物+砜嘧磺隆、式I化合物+稀禾定、式I化合物+环草隆、式I化合物+西玛津、式I化合物+西草净、式I化合物+SMA、式I化合物+亚砷酸钠、式I化合物+叠氮化钠、式I化合物+氯酸钠、式I化合物+磺草酮、式I化合物+甲磺草胺、式I化合物+甲嘧磺隆、式I化合物+甲嘧磺隆-甲酯、式I化合物+草硫膦、式I化合物+磺酰磺隆、式I化合物+硫酸、式I化合物+焦油、式I化合物+草芽畏、式I化合物+三氯乙酸、式I化合物+三氯乙酸钠、式I+牧草胺、式I化合物+丁噻隆、式I+特呋磺草酮(tefuryltrione)、式1化合物+氟磺草酮(tembotrione)、式I化合物+吡喃草酮、式I化合物+特草定、式I化合物+特丁通、式I化合物+特丁津、式I化合物+特丁净、式I化合物+甲氧噻草胺、式I化合物+噻氟隆、式I化合物+噻唑烟酸、式I化合物+噻吩磺隆、式I化合物+噻砜草胺(thiencarbazone)、式I化合物+噻吩磺隆-甲酯、式I化合物+杀草丹、式I化合物+仲草丹、式I化合物+异噁砜酮(topramezone)、式I化合物+苯草酮、式I化合物+野燕畏、式I化合物+醚苯磺隆、式I化合物+三嗪氟草胺、式I化合物+苯磺隆、式I化合物+苯磺隆-甲酯、式I化合物+杀草畏、式I化合物+三氯吡氧乙酸、式I化合物+草达津、式I化合物+三氟啶磺隆、式I化合物+三氟啶磺隆-钠盐、式I化合物+氟乐灵、式I化合物+氟胺磺隆、式I化合物+氟胺磺隆-甲酯、式I化合物+三羟基三嗪、式I化合物+抗倒酯、式I化合物+三氟甲磺隆、式I化合物+[3-[2-氯-4-氟-5-(1-甲基-6-三氟甲基-2,4-二氧代-1,2,3,4-四氢嘧啶-3-基)苯氧基]-2-吡啶基氧基]乙酸乙酯(CAS RN 353292-31-6)、式I化合物+4-羟基-3-[[2-[(2-甲氧基乙氧基)甲基]-6-(三氟甲基)-3-吡啶]羰基]-二环[3.2.1]辛-3-烯-2-酮(CAS RN 352010-68-5)、式I化合物+2-氯-5-[3,6-二氢-3-甲基-2,6-二氧代-4-(三氟甲基)-1(2H)-嘧啶基]-4-氟-N-[[甲基(1-甲基乙基)氨基]磺酰基]苯甲酰胺(CAS RN 372137-35-4)和式I化合物+4-羟基-3-[[2-(3-甲氧基丙基)-6-(二氟甲基)-3-吡啶基]羰基]二环[3.2.1]辛-3-烯-2-酮。
参照例如The Pesticide Manual,第12版(BCPC),2000中的内容,式(I)化合物的混配物还可以是酯或盐的形式。
式(I)化合物与混配物的混合比优选为1∶100到1000∶1。所述混合物可以有利地用于上面提及的制剂中(在此情况下“活性成分”涉及式(I)化合物与混配物的各种混合物)。
本发明式(I)化合物还可以与安全剂组合使用。优选地,在这些混合物中,式(I)化合物是后文表1-151列出的那些化合物之一。特别考虑与安全剂的下述混合物:
式(I)化合物+解毒喹,式(I)化合物+解毒喹酸及其盐,式(I)化合物+解草唑,式(I)化合物+解草唑酸及其盐,式(I)化合物+吡唑解草酯,式(I)化合物+吡唑解草酯(mefenpyr diacid),式(I)化合物+双苯噁唑酸-乙酯,式(I)化合物+双苯噁唑酸,式(I)化合物+呋喃解草唑,式(I)化合物+呋喃解草唑R异构体,式(I)化合物+解草酮,式(I)化合物+烯丙酰草胺,式(I)化合物+AD-67,式(I)化合物+解草腈,式(I)化合物+解草胺腈,式(I)化合物+解草胺腈Z-异构体,式(I)化合物+解草啶,式(I)化合物+环酰磺草胺(cyprosulfamide),式(I)化合物+酞酐,式(I)化合物+解草安,式(I)化合物+N-(2-甲氧基苯甲酰基)-4-[(甲基氨基羰基)氨基]苯磺酰胺,式(I)化合物+CL 304,415,式(I)化合物+吡嘧草酮(dicyclonon),式(I)化合物+肟草安,式(I)化合物+解草烯,式(I)化合物+R-29148和式(I)化合物+PPG-1292。还可以观察到式(I)化合物+杀草隆,式(I)化合物+2甲4氯,式(I)化合物+2甲4氯丙酸和式(I)化合物+高2甲4氯丙酸的安全效果。
上述提及的安全剂和除草剂描述于,例如the PesticideManual,第12版,British Crop Protection Council,2000。R-29148例如由P.B.Goldsbrough等人,Plant Physiology,(2002),第130卷第1497-1505页及其中的参考文献所描述,PPG-1292已知于WO09211761且N-(2-甲氧基苯甲酰基)-4-[(甲基氨基羰基)氨基]苯磺酰胺已知于EP365484。
根据本发明的式(I)化合物还可以与上述提及的共-除草剂和安全剂组合使用形成包含式(I)化合物、共-除草剂和安全剂的三元混合物。
实施例1
制备2-(2,6-二乙基-4-甲基苯基)-5-[2-(乙硫基)丙基]环己烷-
1,3-二酮(化合物编号T7,表T1)
步骤1
将乙硫醇(1.48ml,20.0mmol)滴加至1.66ml丁烯醛(1.66ml,20.0mmol)和0.02ml三乙胺(0.02ml,0.1mmol)的混合物,混合物在室温下搅拌4小时,然后减压浓缩给出3-(乙硫基)丁醛(2.66g),是黄色液体,将其不加进一步纯化用于后续步骤。
步骤2
将1-三苯基亚正膦基-2-丙酮(12.77g,40.0mmol)加至3-(乙硫基)丁醛(5.30g,40.0mmol)的二氯甲烷(100ml)溶液,混合物在回流下加热24小时。反应混合物冷却至室温,溶剂真空蒸发给出米色固体。将粗产品溶于1∶1的己烷∶乙醚混合物(弃去不溶物质),随后减压浓缩给出橙色油状物,将其进一步通过柱色谱法在硅胶上纯化,给出6-(乙硫基)庚-3-烯-2-酮,是黄色油状物。
步骤3
将经己烷洗涤的钠(0.73g,32.0mmol)加至乙醇(40ml)中,在0℃下于氮气下搅拌。搅拌2小时后,将丙二酸二乙酯(4.64g,29.0mmol)的乙醇(20ml)溶液在5分钟内滴加,加入完成后即除去冷却浴,使反应混合物温热至室温。反应混合物在室温下搅拌1小时,然后再次冷却至0℃。
将6-(乙硫基)庚-3-烯-2-酮(4.2g,24.0mmol)的(20ml)乙醇溶液在10分钟内滴加。加入完成后即除去冷却浴,使反应混合物温热至室温。反应混合物在室温下搅拌24小时,然后倾入2M盐酸水溶液(200ml)。反应混合物用二氯甲烷萃取,合并的有机萃取物在无水硫酸镁上干燥,过滤,滤液真空蒸发给出黄色胶状物,将其溶于2M氢氧化钠水溶液(75ml)和丙-2-醇(25ml)的混合物,随后在室温下搅拌44小时。减压除去部分溶剂(大约1/4到1/2),加入浓盐酸小心地酸化反应混合物至pH 2。反应混合物加热至70℃,在70℃下保持30分钟,除去热源,使反应冷却至室温。反应混合物用乙酸乙酯萃取,合并的有机萃取物在无水硫酸镁上干燥,过滤,真空蒸发滤液,给出黄色胶状物。进一步通过柱色谱法在硅胶上纯化提供5-[(2-乙硫基)丙基)环-己烷-1,3-二酮,是黄色胶状物。
步骤4
制备5-(2-乙硫基)丙基)环己烷-1,3-二酮(2.50g,11.7mmol)和碳酸钠(1.24g,11.7mmol)的水(35ml)/乙醇(5ml)溶液,随后于室温下在5分钟内滴加至(二乙酰氧基碘)苯(3.76g,11.7mmol)和碳酸钠(1.24g,11.7mmol)在水(40ml)中的混合物。在室温下搅拌反应混合物2小时,然后用二氯甲烷萃取。合并有机萃取物,在无水硫酸镁上干燥,过滤,真空蒸发滤液,给出碘内鎓盐,不加进一步纯化用于后续步骤。
步骤5
在氮气氛下将步骤4中制备的碘内鎓盐(1.90g,4.56mmol)、2,6-二乙基-4-甲基-苯基硼酸(1.05g,5.48mmol)、乙酸钯(II)(0.082g,0.36mmol)、一水合氢氧化锂(0.766g,18.24mmol)与1,2-二甲氧基乙烷(40ml)和水(10ml)的混合物一起搅拌,随后加热至50℃持续4.75小时。将混合冷却至室温,通过C盐过滤,C盐用2M盐酸水溶液(80ml)和40ml乙酸乙酯(40ml)洗涤。将混合物倾入分液漏斗,分离有机层,水层用乙酸乙酯萃取。合并有机萃取物,在无水硫酸钠上干燥,过滤,真空浓缩滤液,给出褐色胶状物。通过柱色谱法在硅胶上纯化给出2-(2,6-二乙基-4-甲基苯基)-5-[2-(乙硫基)丙基]-环己烷-1,3-二酮,是淡黄色胶状物。
δH(CDCl3)6.98(d,2H),5.52(d,1H),2.93-2.83(m,1H),2.21-2.76(m,11H),2.33(s,3H),1.78-1.59(m,2H),1.34(dd,3H),1.27(m,3H),1.08(m,6H)
实施例2
制备9-(2,6-二乙基-4-甲基苯基)-3-氧杂螺[5.5]十一烷-8,10-
二酮(化合物编号T22,表T1)
步骤1
向5℃的氢氧化钾(12.85g,0.229mol)的水(50ml)/乙醇(200ml)溶液加入2-氧代丙基磷酸二甲酯(38.0g,0.229mol),随后滴加四氢吡喃-4-酮(15ml,16.4g,0.163mol)。在室温下搅拌澄清的溶液5小时。
减压从反应混合物中除去大部分溶剂,残余物用叔丁基甲基醚和水稀释。分离有机层,水层用叔丁基甲基-醚萃取两次,合并的有机层在无水硫酸钠上干燥,过滤,真空浓缩滤液。
粗产品通过减压蒸馏纯化,给出18.8g(82%)产品,沸点为102-104℃/12毫巴。1H-NMR显示产品为希望的1-(四氢吡喃-4-亚基)丙-2-酮和异构体1-(3,6-二氢-2H-吡喃-4-基)丙-2-酮的4∶1-混合物,将其不加进一步纯化用于后续步骤。
步骤2
向步骤1产品(13.18g,94.0mmol)在室温下的100ml乙醇(100ml)溶液,加入丙二酸二乙酯(14.3ml,15.09g;94.2mmol),随后滴加~2.72M乙醇钠的乙醇(36.6ML~94.1mmol)溶液。在室温下搅拌溶液3小时,然后在回流下搅拌1小时。
将溶剂从反应混合物减压除去,固体残余物溶于12N氢氧化钠水溶液(150ml),在室温下搅拌过夜。将碱性混合物水溶液用叔丁基甲基醚洗涤一次,然后用浓盐酸酸化至pH 2-3,温热至70℃持续2小时。混合物水溶液用乙酸乙酯和二氯甲烷萃取,合并有机相,在无水硫酸钠上干燥,过滤,真空浓缩滤液。将固体残余物溶于叔丁基甲基醚,搅拌混合物,通过过滤收集灰白色固体,给出3-氧杂螺[5.5]十一烷-8,10-二酮(12.3g),m.p.162-164℃。
步骤3
0℃下,将3-氧杂螺[5.5]十一烷-8,10-二酮(5.47g,30.0mmol)在水(50ml)和乙醇(16ml)的混合物中搅拌,加入一水合氢氧化锂(2.52g,60.0mmol)。当溶液变得澄清后,立即加入(二乙酰氧基碘)苯(9.65g,30.0mmol),混合物在0℃下搅拌45分钟,随后在室温下搅拌3小时。
将反应混合物用1,2-二甲氧基乙烷(200ml)稀释,在0℃下加入2,6-二乙基-4-甲基苯基硼酸(6.50g,33.8mmol)、乙酸钯(II)(0.5g,2.23mmol)和一水合氢氧化锂(5.05g,120.0mmol)。将混合物温热至50℃,当其在大约1-2小时变粘稠后,再用水和1,2-二甲氧基乙烷(50+50ml)的混合物再次稀释。在再加入催化量的乙酸钯(II)之后,搅拌在50℃下持续大约16小时。
反应混合物用乙酸乙酯和水稀释,碱性水层用乙酸乙酯萃取两次。弃去合并的有机层,水相再用乙酸乙酯稀释,在0℃下用4N盐酸水溶液酸化至pH 2-3。分离有机层,水层用乙酸乙酯萃取两次,合并的有机相在无水硫酸钠上干燥,过滤,真空浓缩滤液。
粗产品先用快速过滤(乙酸乙酯/己烷3∶1)纯化,随后通过快速色谱法(乙酸乙酯/己烷3∶2→2∶1)纯化。将浓缩后获得的黄色油状物溶于4∶1的己烷∶叔丁基甲基-醚混合物,搅拌混合物,通过过滤收集灰白色固体,给出9-(2,6-二乙基-4-甲基苯基)-3-氧杂螺[5.5]十一烷-8,10-二酮,m.p.139-141℃。
δH(CDCl3)6.97(s,2H),5.83(br s,1H),3.72(t,4H),2.59(br s,4H),2.39-2.27(m,4H),2.32(s,3H),1.69(t,4H),1.06(t,6H)
实施例3
制备2-(2,6-二乙基-4-甲基苯基)-5-[2-(乙基磺酰基)丙基]环
己烷-1,3-二酮(化合物编号28,表T1)
将35%的过氧乙酸乙酸溶液(0.3ml,1.55mmol)滴加至2-(2,6-二乙基-4-甲基苯基)-5-[2-(乙硫基)丙基]环己烷-1,3-二酮(0.17g,0.47mmol)的二氯甲烷(5ml)溶液,将反应混合物在室温下搅拌2小时,然后将其放置过夜。反应混合物用二氯甲烷稀释,用15%焦亚硫酸钠水溶液和盐水洗涤,在无水硫酸镁上干燥,过滤,真空蒸发滤液。残余物通过柱色谱法在硅胶上纯化,给出2-(2,6-二乙基-4-甲基苯基)-5-[2-(乙基磺酰基)丙基]-环己烷-1,3-二酮,m.p.62-65℃。
δH(CDCl3)6.99(s,2H),5.67(d,1H),3.16-3.05(m,1H),3.01(q,2H),2.80-2.61(m,2H),2.55-2.13(m,7H),2.33(s,3H),1.82-1.60(m,2H),1.48-1.38(m,6H),1.08(q,6H)
实施例4
制备2-(2,6-二乙基-4-甲基苯基)-5-[2-(乙基亚磺酰基)丙基]-
环己烷-1,3-二酮(化合物编号T29,表T1)
在0℃下,将70%的3-过氧苯甲酸(0.104g,0.42mmol)的二氯甲烷(2ml)溶液滴加至2-(2,6-二乙基-4-甲基苯基)-5-[2-(乙硫基)丙基]环-己烷-1,3-二酮(0.17g,0.47mmol)的二氯甲烷(3ml)溶液,反应混合物在0℃下搅拌1小时,然后将之在室温下放置过夜。反应混合物用二氯甲烷稀释,用15%焦亚硫酸钠水溶液和盐水洗涤,在无水硫酸镁上干燥,过滤,真空蒸发滤液。残余物通过柱色谱法在硅胶上纯化,给出2-(2,6-二乙基-4-甲基苯基)-5-[2-(乙基亚磺酰基)丙基]环己烷-1,3-二酮,m.p.58-61℃。
δH(CDCl3)6.98(s,2H),6.00(br s,1H),2.87-2.18(m,12H),2.33(s,3H),1.81-1.52(m,2H),1.44-1.23(m,6H),1.08(q,6H)
实施例5
制备9-(5-(4′-氯苯基)-2-乙基苯基)-3-氧杂螺[5.5]十一烷-
8,10-二酮(化合物编号T4,表T1)
步骤1
将按照实施例2中提供的方法所制备的3-氧杂螺[5.5]十一烷-8,10-二酮(14.0g,77.0mol)加至碳酸钠(16.32g,0.154mol)在水(200ml)和乙醇(50ml)混合物中的溶液,混合物在室温下搅拌5分钟,然后在冰浴中冷却至5℃。将(二乙酰氧基碘)苯(24.77g,77.0mmol)在5分钟内分批加入,一旦加入完成,即在5℃下搅拌反应混合物15分钟,然后移去冷却浴,混合物在室温下搅拌4小时。沉淀通过过滤收集,用水洗涤,干燥,给出希望的碘内鎓盐(28.2g),是膏状固体。
步骤2
在氮气氛下,将步骤1中制备的碘内鎓盐(1.0g,2.6mmol)、5-(4-氯苯基)-2-乙基苯基硼酸(0.745g,2.86mmol)、乙酸钯(II)(0.047g,0.21mmol)和一水合氢氧化锂(0.437g,10.4mmol)的混合物在1,2-二甲氧基乙烷(24ml)和水(6ml))中一起搅拌,搅拌混合物,加热至50℃持续5.5小时。将反应混合物冷却至室温,通过C盐过滤,用100ml水和40ml乙酸乙酯洗涤,将滤液倾入分液漏斗。分离有机相,水层用乙酸乙酯萃取。弃去有机萃取物。
水相通过加入浓盐酸酸化至pH2,然后用乙酸乙酯萃取。有机萃取物在无水硫酸镁上干燥,过滤,真空蒸发滤液,给出褐色胶状物。通过柱色谱法在硅胶上进一步纯化,给出9-(5-(4′-氯苯基)-2-乙基苯基)-3-氧杂螺[5.5]十一烷-8,10-二酮,是无色固体,m.p.94.5-97.5℃。
δH(CDCl3)7.53(dd,1H),7.50-7.45(m,2H),7.43-7.36(m,3H),7.20(d,1H),5.79(s,1H),3.75(m,4H),2.65(s,2H),2.59(q,2H),2.45(m,2H),1.72(t,4H)1.13(t,3H)
实施例6
制备9-(3,5-二甲基联苯-4-基)-3-氧杂螺[5.5]十一烷-8,10-二
酮(化合物编号T73,表T1)
向3-氧杂螺[5.5]十一烷-8,10-二酮(0.182g,1mmol)和4-二甲基氨基-吡啶(0.61g;5mmol)的混合物加入无水氯仿(4ml),在氮气氛下于室温下搅拌混合物,直至固体溶解。向此溶液中随后加入无水甲苯(2ml),然后加入3,5-二甲基联苯-4-基三乙酸铅(1.2mmol)的氯仿溶液。反应混合物在回流下加热1小时,然后冷却至室温,用2N盐酸水溶液酸化至pH=1,过滤,滤液用二氯甲烷萃取(2X40ml)。合并有机萃取物,在无水硫酸镁上干燥,过滤,真空蒸发滤液。残余物通过柱色谱法在硅胶上纯化,给出9-(3,5-二甲基联苯基-4-基)-3-氧杂-螺[5.5]十一烷-8,10-二酮。
δH(CDCl3)7.57(d,2H),7.42(dd,2H),7.35(d,1H),7.33(s,2H),5.91(bs,1H),3.73(dd,4H),2.64(s,2H),2.58(s,2H),2.14(s,6H);1.72(dd,4H)
下述表T1中的化合物可以通过类似方法使用合适的原料制得。
表T1
注:化合物的HPLC-MS表征使用Agilent 1100 Series HPLC来分析,配有Waters Atlantis dC18柱(柱长20mm,柱内径3mm,粒径3微米,温度40℃),Waters光电二极管阵列和MicromassZQ2000。分析根据下述梯度表使用3分钟的运行时间来进行:
时间(分) | 溶剂A(%) | 溶剂B(%) | 流量(ml/mn) | 压力(巴) |
0.00 | 90.0 | 10.0 | 1.700 | 400 |
2.50 | 0.0 | 100 | 1.700 | 400 |
2.80 | 0.00 | 100 | 1.700 | 400 |
2.90 | 90.0 | 10.0 | 1.700 | 400 |
溶剂A:H2O/CH3CN 90/10,含0.1% HCOOH
溶剂B:0.1% HCOOH的CH3CN溶液
对每个化合物得到的特征值是保留时间(按分钟记录)和分子离子,一般为如表T1中列出的阳离子M+H+。
下文表1-84的化合物可以以类似方式获得。
书写形式C.C用于在下表中表示在这2个碳原子间存在三键。比如,CH2C.CH表示炔丙基。
表1:
本表包含下述类型的646个化合物,
其中X、R2、R3和R4定义如下:
化合物编号 | R6 | R7 | X | R8 |
1.1 | H | H | O | CH2CH3 |
1.2 | H | H | O | CH2CH2CH3 |
1.3 | H | H | O | CH(CH3)2 |
1.4 | H | H | O | CH2CH2CH2CH3 |
1.5 | H | H | O | CH2CH(CH3)2 |
1.6 | H | H | O | CH(CH3)CH2CH3 |
1.7 | H | H | O | C(CH3)3 |
1.8 | H | H | O | CH2CH2CH2CH2CH3 |
1.9 | H | H | O | CH2CH2CH(CH3)2 |
1.10 | H | H | O | CH2C(CH3)3 |
1.11 | H | H | O | CH2CH(CH3)CH2CH3 |
1.12 | H | H | O | CH(CH3)CH2CH2CH3 |
1.13 | H | H | O | C(CH3)2CH2CH3 |
1.14 | H | H | O | CH2CH=CH2 |
1.15 | H | H | O | CH2CH=CHCH3 |
1.16 | H | H | O | CH2CH=C(CH3)2 |
1.17 | H | H | O | CH2C(CH3)=CH2 |
1.18 | H | H | O | CH2C(CH3)=CHCH3 |
1.19 | H | H | O | CH2C(CH3)=C(CH3)2 |
1.20 | H | H | O | CH(CH3)CH=CH2 |
1.21 | H | H | O | CH(CH3)CH=CHCH3 |
1.22 | H | H | O | CH(CH3)CH=C(CH3)2 |
1.23 | H | H | O | C(CH3)2CH=CH2 |
1.24 | H | H | O | C(CH3)2CH=CHCH3 |
1.25 | H | H | O | C(CH3)2CH=C(CH3)2 |
1.26 | H | H | O | CH2CH=CHCl |
1.27 | H | H | O | CH2CH=CCl2 |
1.28 | H | H | O | CH2CCl=CHCl |
化合物编号 | R6 | R7 | X | R8 |
1.29 | H | H | O | CH2CCl=CCl2 |
1.30 | H | H | O | CH2CH=CF2 |
1.31 | H | H | O | CH2CF=CF2 |
1.32 | H | H | O | CH2C.CH |
1.33 | H | H | O | CH2C.CCH3 |
1.34 | H | H | O | CH2C.CCH2CH3 |
1.35 | H | H | O | CH(CH3)C.CH |
1.36 | H | H | O | CH(CH3)C.CCH3 |
1.37 | H | H | O | CH(CH3)C.CCH2CH3 |
1.38 | H | H | O | C(CH3)2C.CH |
1.39 | H | H | O | C(CH3)2C.CCH3 |
1.40 | H | H | O | C(CH3)2C.CCH2CH3 |
1.41 | H | H | O | 环丙基 |
1.42 | H | H | O | 环丁基 |
1.43 | H | H | O | 环戊基 |
1.44 | H | H | O | 环己基 |
1.45 | H | H | O | CH2CF3 |
1.46 | H | H | O | CH2CH2CF3 |
1.47 | H | H | O | CH2-环丙基 |
1.48 | H | H | O | CH2-环丁基 |
1.49 | H | H | O | CH2-环戊基 |
1.50 | H | H | O | CH2-环己基 |
1.51 | H | H | O | CH2OCH3 |
1.52 | H | H | O | CH2OCH2CH3 |
1.53 | H | H | O | CH2CH2OCH3 |
1.54 | H | H | O | CH2CH2OCH2CH3 |
1.55 | CH3 | H | O | CH3 |
1.56 | CH3 | H | O | CH2CH3 |
化合物编号 | R6 | R7 | X | R8 |
1.57 | CH3 | H | O | CH2CH2CH3 |
1.58 | CH3 | H | O | CH(CH3)2 |
1.59 | CH3 | H | O | CH2CH2CH2CH3 |
1.60 | CH3 | H | O | CH2CH(CH3)2 |
1.61 | CH3 | H | O | CH(CH3)CH2CH3 |
1.62 | CH3 | H | O | C(CH3)3 |
1.63 | CH3 | H | O | CH2CH2CH2CH2CH3 |
1.64 | CH3 | H | O | CH2CH2CH(CH3)2 |
1.65 | CH3 | H | O | CH2C(CH3)3 |
1.66 | CH3 | H | O | CH2CH(CH3)CH2CH3 |
1.67 | CH3 | H | O | CH(CH3)CH2CH2CH3 |
1.68 | CH3 | H | O | C(CH3)2CH2CH3 |
1.69 | CH3 | H | O | CH2CH=CH2 |
1.70 | CH3 | H | O | CH2CH=CHCH3 |
1.71 | CH3 | H | O | CH2CH=C(CH3)2 |
1.72 | CH3 | H | O | CH2C(CH3)=CH2 |
1.73 | CH3 | H | O | CH2C(CH3)=CHCH3 |
1.74 | CH3 | H | O | CH2C(CH3)=C(CH3)2 |
1.75 | CH3 | H | O | CH(CH3)CH=CH2 |
1.76 | CH3 | H | O | CH(CH3)CH=CHCH3 |
1.77 | CH3 | H | O | CH(CH3)CH=C(CH3)2 |
1.78 | CH3 | H | O | C(CH3)2CH=CH2 |
1.79 | CH3 | H | O | C(CH3)2CH=CHCH3 |
1.80 | CH3 | H | O | C(CH3)2CH=C(CH3)2 |
1.81 | CH3 | H | O | CH2CH=CHCl |
1.82 | CH3 | H | O | CH2CH=CCl2 |
1.83 | CH3 | H | O | CH2CCl=CHCl |
1.84 | CH3 | H | O | CH2CCl=CCl2 |
化合物编号 | R6 | R7 | X | R8 |
1.85 | CH3 | H | O | CH2CH=CF2 |
1.86 | CH3 | H | O | CH2CF=CF2 |
1.87 | CH3 | H | O | CH2C.CH |
1.88 | CH3 | H | O | CH2C.CCH3 |
1.89 | CH3 | H | O | CH2C.CCH2CH3 |
1.90 | CH3 | H | O | CH(CH3)C.CH |
1.91 | CH3 | H | O | CH(CH3)C.CCH3 |
1.92 | CH3 | H | O | CH(CH3)C.CCH2CH3 |
1.93 | CH3 | H | O | C(CH3)2C.CH |
1.94 | CH3 | H | O | C(CH3)2C.CCH3 |
1.95 | CH3 | H | O | C(CH3)2C.CCH2CH3 |
1.96 | CH3 | H | O | 环丙基 |
1.97 | CH3 | H | O | 环丁基 |
1.98 | CH3 | H | O | 环戊基 |
1.99 | CH3 | H | O | 环己基 |
1.100 | CH3 | H | O | CH2CF3 |
1.101 | CH3 | H | O | CH2CH2CF3 |
1.102 | CH3 | H | O | CH2-环丙基 |
1.103 | CH3 | H | O | CH2-环丁基 |
1.104 | CH3 | H | O | CH2-环戊基 |
1.105 | CH3 | H | O | CH2-环己基 |
1.106 | CH3 | H | O | CH2OCH3 |
1.107 | CH3 | H | O | CH2OCH2CH3 |
1.108 | CH3 | H | O | CH2CH2OCH3 |
1.109 | CH3 | H | O | CH2CH2OCH2CH3 |
1.110 | CH3 | CH3 | O | CH3 |
1.111 | CH3 | CH3 | O | CH2CH3 |
1.112 | CH3 | CH3 | O | CH2CH2CH3 |
化合物编号 | R6 | R7 | X | R8 |
1.113 | CH3 | CH3 | O | CH(CH3)2 |
1.114 | CH3 | CH3 | O | CH2CH2CH2CH3 |
1.115 | CH3 | CH3 | O | CH2CH(CH3)2 |
1.116 | CH3 | CH3 | O | CH(CH3)CH2CH3 |
1.117 | CH3 | CH3 | O | C(CH3)3 |
1.118 | CH3 | CH3 | O | CH2CH2CH2CH2CH3 |
1.119 | CH3 | CH3 | O | CH2CH2CH(CH3)2 |
1.120 | CH3 | CH3 | O | CH2C(CH3)3 |
1.121 | CH3 | CH3 | O | CH2CH(CH3)CH2CH3 |
1.122 | CH3 | CH3 | O | CH(CH3)CH2CH2CH3 |
1.123 | CH3 | CH3 | O | C(CH3)2CH2CH3 |
1.124 | CH3 | CH3 | O | CH2CH=CH2 |
1.125 | CH3 | CH3 | O | CH2CH=CHCH3 |
1.126 | CH3 | CH3 | O | CH2CH=C(CH3)2 |
1.127 | CH3 | CH3 | O | CH2C(CH3)=CH2 |
1.128 | CH3 | CH3 | O | CH2C(CH3)=CHCH3 |
1.129 | CH3 | CH3 | O | CH2C(CH3)=C(CH3)2 |
1.130 | CH3 | CH3 | O | CH(CH3)CH=CH2 |
1.131 | CH3 | CH3 | O | CH(CH3)CH=CHCH3 |
1.132 | CH3 | CH3 | O | CH(CH3)CH=C(CH3)2 |
1.133 | CH3 | CH3 | O | C(CH3)2CH=CH2 |
1.134 | CH3 | CH3 | O | C(CH3)2CH=CHCH3 |
1.135 | CH3 | CH3 | O | C(CH3)2CH=C(CH3)2 |
1.136 | CH3 | CH3 | O | CH2CH=CHCl |
1.137 | CH3 | CH3 | O | CH2CH=CCl2 |
1.138 | CH3 | CH3 | O | CH2CCl=CHCl |
1.139 | CH3 | CH3 | O | CH2CCl=CCl2 |
1.140 | CH3 | CH3 | O | CH2CH=CF2 |
化合物编号 | R6 | R7 | X | R8 |
1.141 | CH3 | CH3 | O | CH2CF=CF2 |
1.142 | CH3 | CH3 | O | CH2C.CH |
1.143 | CH3 | CH3 | O | CH2C.CCH3 |
1.144 | CH3 | CH3 | O | CH2C.CCH2CH3 |
1.145 | CH3 | CH3 | O | CH(CH3)C.CH |
1.146 | CH3 | CH3 | O | CH(CH3)C.CCH3 |
1.147 | CH3 | CH3 | O | CH(CH3)C.CCH2CH3 |
1.148 | CH3 | CH3 | O | C(CH3)2C.CH |
1.149 | CH3 | CH3 | O | C(CH3)2C.CCH3 |
1.150 | CH3 | CH3 | O | C(CH3)2C.CCH2CH3 |
1.151 | CH3 | CH3 | O | 环丙基 |
1.152 | CH3 | CH3 | O | 环丁基 |
1.153 | CH3 | CH3 | O | 环戊基 |
1.154 | CH3 | CH3 | O | 环己基 |
1.155 | CH3 | CH3 | O | CH2CF3 |
1.156 | CH3 | CH3 | O | CH2CH2CF3 |
1.157 | CH3 | CH3 | O | CH2-环丙基 |
1.158 | CH3 | CH3 | O | CH2-环丁基 |
1.159 | CH3 | CH3 | O | CH2-环戊基 |
1.160 | CH3 | CH3 | O | CH2-环己基 |
1.161 | CH3 | CH3 | O | CH2OCH3 |
1.162 | CH3 | CH3 | O | CH2OCH2CH3 |
1.163 | CH3 | CH3 | O | CH2CH2OCH3 |
1.164 | CH3 | CH3 | O | CH2CH2OCH2CH3 |
1.165 | H | H | S | CH2CH3 |
1.166 | H | H | S | CH2CH2CH3 |
1.167 | H | H | S | CH(CH3)2 |
1.168 | H | H | S | CH2CH2CH2CH3 |
化合物编号 | R6 | R7 | X | R8 |
1.169 | H | H | S | CH2CH(CH3)2 |
1.170 | H | H | S | CH(CH3)CH2CH3 |
1.171 | H | H | S | C(CH3)3 |
1.172 | H | H | S | CH2CH2CH2CH2CH3 |
1.173 | H | H | S | CH2CH2CH(CH3)2 |
1.174 | H | H | S | CH2C(CH3)3 |
1.175 | H | H | S | CH2CH(CH3)CH2CH3 |
1.176 | H | H | S | CH(CH3)CH2CH2CH3 |
1.177 | H | H | S | C(CH3)2CH2CH3 |
1.178 | H | H | S | CH2CH=CH2 |
1.179 | H | H | S | CH2CH=CHCH3 |
1.180 | H | H | S | CH2CH=C(CH3)2 |
1.181 | H | H | S | CH2C(CH3)=CH2 |
1.182 | H | H | S | CH2C(CH3)=CHCH3 |
1.183 | H | H | S | CH2C(CH3)=C(CH3)2 |
1.184 | H | H | S | CH(CH3)CH=CH2 |
1.185 | H | H | S | CH(CH3)CH=CHCH3 |
1.186 | H | H | S | CH(CH3)CH=C(CH3)2 |
1.187 | H | H | S | C(CH3)2CH=CH2 |
1.188 | H | H | S | C(CH3)2CH=CHCH3 |
1.189 | H | H | S | C(CH3)2CH=C(CH3)2 |
1.190 | H | H | S | CH2CH=CHCl |
1.191 | H | H | S | CH2CH=CCl2 |
1.192 | H | H | S | CH2CCl=CHCl |
1.193 | H | H | S | CH2CCl=CCl2 |
1.194 | H | H | S | CH2CH=CF2 |
1.195 | H | H | S | CH2CF=CF2 |
1.196 | H | H | S | CH2C.CH |
化合物编号 | R6 | R7 | X | R8 |
1.197 | H | H | S | CH2C.CCH3 |
1.198 | H | H | S | CH2C.CCH2CH3 |
1.199 | H | H | S | CH(CH3)C.CH |
1.200 | H | H | S | CH(CH3)C.CCH3 |
1.201 | H | H | S | CH(CH3)C.CCH2CH3 |
1.202 | H | H | S | C(CH3)2C.CH |
1.203 | H | H | S | C(CH3)2C.CCH3 |
1.204 | H | H | S | C(CH3)2C.CCH2CH3 |
1.205 | H | H | S | 环丙基 |
1.206 | H | H | S | 环丁基 |
1.207 | H | H | S | 环戊基 |
1.208 | H | H | S | 环己基 |
1.209 | H | H | S | CH2CF3 |
1.210 | H | H | S | CH2CH2CF3 |
1.211 | H | H | S | CH2-环丙基 |
1.212 | H | H | S | CH2-环丁基 |
1.213 | H | H | S | CH2-环戊基 |
1.214 | H | H | S | CH2-环己基 |
1.215 | CH3 | H | S | CH3 |
1.216 | CH3 | H | S | CH2CH3 |
1.217 | CH3 | H | S | CH2CH2CH3 |
1.218 | CH3 | H | S | CH(CH3)2 |
1.219 | CH3 | H | S | CH2CH2CH2CH3 |
1.220 | CH3 | H | S | CH2CH(CH3)2 |
1.221 | CH3 | H | S | CH(CH3)CH2CH3 |
1.222 | CH3 | H | S | C(CH3)3 |
1.223 | CH3 | H | S | CH2CH2CH2CH2CH3 |
1.224 | CH3 | H | S | CH2CH2CH(CH3)2 |
化合物编号 | R6 | R7 | X | R8 |
1.225 | CH3 | H | S | CH2C(CH3)3 |
1.226 | CH3 | H | S | CH2CH(CH3)CH2CH3 |
1.227 | CH3 | H | S | CH(CH3)CH2CH2CH3 |
1.228 | CH3 | H | S | C(CH3)2CH2CH3 |
1.229 | CH3 | H | S | CH2CH=CH2 |
1.230 | CH3 | H | S | CH2CH=CHCH3 |
1.231 | CH3 | H | S | CH2CH=C(CH3)2 |
1.232 | CH3 | H | S | CH2C(CH3)=CH2 |
1.233 | CH3 | H | S | CH2C(CH3)=CHCH3 |
1.234 | CH3 | H | S | CH2C(CH3)=C(CH3)2 |
1.235 | CH3 | H | S | CH(CH3)CH=CH2 |
1.236 | CH3 | H | S | CH(CH3)CH=CHCH3 |
1.237 | CH3 | H | S | CH(CH3)CH=C(CH3)2 |
1.238 | CH3 | H | S | C(CH3)2CH=CH2 |
1.239 | CH3 | H | S | C(CH3)2CH=CHCH3 |
1.240 | CH3 | H | S | C(CH3)2CH=C(CH3)2 |
1.241 | CH3 | H | S | CH2CH=CHCl |
1.242 | CH3 | H | S | CH2CH=CCl2 |
1.243 | CH3 | H | S | CH2CCl=CHCl |
1.244 | CH3 | H | S | CH2CCl=CCl2 |
1.245 | CH3 | H | S | CH2CH=CF2 |
1.246 | CH3 | H | S | CH2CF=CF2 |
1.247 | CH3 | H | S | CH2C.CH |
1.248 | CH3 | H | S | CH2C.CCH3 |
1.249 | CH3 | H | S | CH2C.CCH2CH3 |
1.250 | CH3 | H | S | CH(CH3)C.CH |
1.251 | CH3 | H | S | CH(CH3)C.CCH3 |
1.252 | CH3 | H | S | CH(CH3)C.CCH2CH3 |
化合物编号 | R6 | R7 | X | R8 |
1.253 | CH3 | H | S | C(CH3)2C.CH |
1.254 | CH3 | H | S | C(CH3)2C.CCH3 |
1.255 | CH3 | H | S | C(CH3)2C.CCH2CH3 |
1.256 | CH3 | H | S | 环丙基 |
1.257 | CH3 | H | S | 环丁基 |
1.258 | CH3 | H | S | 环戊基 |
1.259 | CH3 | H | S | 环己基 |
1.260 | CH3 | H | S | CH2CF3 |
1.261 | CH3 | H | S | CH2CH2CF3 |
1.262 | CH3 | H | S | CH2-环丙基 |
1.263 | CH3 | H | S | CH2-环丁基 |
1.264 | CH3 | H | S | CH2-环戊基 |
1.265 | CH3 | H | S | CH2-环己基 |
1.266 | CH3 | CH3 | S | CH3 |
1.267 | CH3 | CH3 | S | CH2CH3 |
1.268 | CH3 | CH3 | S | CH2CH2CH3 |
1.269 | CH3 | CH3 | S | CH(CH3)2 |
1.270 | CH3 | CH3 | S | CH2CH2CH2CH3 |
1.271 | CH3 | CH3 | S | CH2CH(CH3)2 |
1.272 | CH3 | CH3 | S | CH(CH3)CH2CH3 |
1.273 | CH3 | CH3 | S | C(CH3)3 |
1.274 | CH3 | CH3 | S | CH2CH2CH2CH2CH3 |
1.275 | CH3 | CH3 | S | CH2CH2CH(CH3)2 |
1.276 | CH3 | CH3 | S | CH2C(CH3)3 |
1.277 | CH3 | CH3 | S | CH2CH(CH3)CH2CH3 |
1.278 | CH3 | CH3 | S | CH(CH3)CH2CH2CH3 |
1.279 | CH3 | CH3 | S | C(CH3)2CH2CH3 |
1.280 | CH3 | CH3 | S | CH2CH=CH2 |
化合物编号 | R6 | R7 | X | R8 |
1.281 | CH3 | CH3 | S | CH2CH=CHCH3 |
1.282 | CH3 | CH3 | S | CH2CH=C(CH3)2 |
1.283 | CH3 | CH3 | S | CH2C(CH3)=CH2 |
1.284 | CH3 | CH3 | S | CH2C(CH3)=CHCH3 |
1.285 | CH3 | CH3 | S | CH2C(CH3)=C(CH3)2 |
1.286 | CH3 | CH3 | S | CH(CH3)CH=CH2 |
1.287 | CH3 | CH3 | S | CH(CH3)CH=CHCH3 |
1.288 | CH3 | CH3 | S | CH(CH3)CH=C(CH3)2 |
1.289 | CH3 | CH3 | S | C(CH3)2CH=CH2 |
1.290 | CH3 | CH3 | S | C(CH3)2CH=CHCH3 |
1.291 | CH3 | CH3 | S | C(CH3)2CH=C(CH3)2 |
1.292 | CH3 | CH3 | S | CH2CH=CHCl |
1.293 | CH3 | CH3 | S | CH2CH=CCl2 |
1.294 | CH3 | CH3 | S | CH2CCl=CHCl |
1.295 | CH3 | CH3 | S | CH2CCl=CCl2 |
1.296 | CH3 | CH3 | S | CH2CH=CF2 |
1.297 | CH3 | CH3 | S | CH2CF=CF2 |
1.298 | CH3 | CH3 | S | CH2C.CH |
1.299 | CH3 | CH3 | S | CH2C.CCH3 |
1.300 | CH3 | CH3 | S | CH2C.CCH2CH3 |
1.301 | CH3 | CH3 | S | CH(CH3)C.CH |
1.302 | CH3 | CH3 | S | CH(CH3)C.CCH3 |
1.303 | CH3 | CH3 | S | CH(CH3)C.CCH2CH3 |
1.304 | CH3 | CH3 | S | C(CH3)2C.CH |
1.305 | CH3 | CH3 | S | C(CH3)2C.CCH3 |
1.306 | CH3 | CH3 | S | C(CH3)2C.CCH2CH3 |
1.307 | CH3 | CH3 | S | 环丙基 |
1.308 | CH3 | CH3 | S | 环丁基 |
化合物编号 | R6 | R7 | X | R8 |
1.309 | CH3 | CH3 | S | 环戊基 |
1.310 | CH3 | CH3 | S | 环己基 |
1.311 | CH3 | CH3 | S | CH2CF3 |
1.312 | CH3 | CH3 | S | CH2CH2CF3 |
1.313 | CH3 | CH3 | S | CH2-环丙基 |
1.314 | CH3 | CH3 | S | CH2-环丁基 |
1.315 | CH3 | CH3 | S | CH2-环戊基 |
1.316 | CH3 | CH3 | S | CH2-环己基 |
1.317 | H | H | S(O) | CH3 |
1.318 | H | H | S(O) | CH2CH3 |
1.319 | H | H | S(O) | CH2CH2CH3 |
1.320 | H | H | S(O) | CH(CH3)2 |
1.321 | H | H | S(O) | CH2CH2CH2CH3 |
1.322 | H | H | S(O) | CH2CH(CH3)2 |
1.323 | H | H | S(O) | CH(CH3)CH2CH3 |
1.324 | H | H | S(O) | C(CH3)3 |
1.325 | H | H | S(O) | CH2CH2CH2CH2CH3 |
1.326 | H | H | S(O) | CH2CH2CH(CH3)2 |
1.327 | H | H | S(O) | CH2C(CH3)3 |
1.328 | H | H | S(O) | CH2CH(CH3)CH2CH3 |
1.329 | H | H | S(O) | CH(CH3)CH2CH2CH3 |
1.330 | H | H | S(O) | C(CH3)2CH2CH3 |
1.331 | H | H | S(O) | CH2CH=CH2 |
1.332 | H | H | S(O) | CH2CH=CHCH3 |
1.333 | H | H | S(O) | CH2CH=C(CH3)2 |
1.334 | H | H | S(O) | CH2C(CH3)=CH2 |
1.335 | H | H | S(O) | CH2C(CH3)=CHCH3 |
1.336 | H | H | S(O) | CH2C(CH3)=C(CH3)2 |
化合物编号 | R6 | R7 | X | R8 |
1.337 | H | H | S(O) | CH(CH3)CH=CH2 |
1.338 | H | H | S(O) | CH(CH3)CH=CHCH3 |
1.339 | H | H | S(O) | CH(CH3)CH=C(CH3)2 |
1.340 | H | H | S(O) | C(CH3)2CH=CH2 |
1.341 | H | H | S(O) | C(CH3)2CH=CHCH3 |
1.342 | H | H | S(O) | C(CH3)2CH=C(CH3)2 |
1.343 | H | H | S(O) | CH2CH=CHCl |
1.344 | H | H | S(O) | CH2CH=CCl2 |
1.345 | H | H | S(O) | CH2CCl=CHCl |
1.346 | H | H | S(O) | CH2CCl=CCl2 |
1.347 | H | H | S(O) | CH2CH=CF2 |
1.348 | H | H | S(O) | CH2CF=CF2 |
1.349 | H | H | S(O) | CH2C.CH |
1.350 | H | H | S(O) | CH2C.CCH3 |
1.351 | H | H | S(O) | CH2C.CCH2CH3 |
1.352 | H | H | S(O) | CH(CH3)C.CH |
1.353 | H | H | S(O) | CH(CH3)C.CCH3 |
1.354 | H | H | S(O) | CH(CH3)C.CCH2CH3 |
1.355 | H | H | S(O) | C(CH3)2C.CH |
1.356 | H | H | S(O) | C(CH3)2C.CCH3 |
1.357 | H | H | S(O) | C(CH3)2C.CCH2CH3 |
1.358 | H | H | S(O) | 环丙基 |
1.359 | H | H | S(O) | 环丁基 |
1.360 | H | H | S(O) | 环戊基 |
1.361 | H | H | S(O) | 环己基 |
1.362 | H | H | S(O) | CH2CF3 |
1.363 | H | H | S(O) | CH2CH2CF3 |
1.364 | H | H | S(O) | CH2-环丙基 |
化合物编号 | R6 | R7 | X | R8 |
1.365 | H | H | S(O) | CH2-环丁基 |
1.366 | H | H | S(O) | CH2-环戊基 |
1.367 | H | H | S(O) | CH2-环己基 |
1.368 | H | H | S(O) | CH2OCH3 |
1.369 | H | H | S(O) | CH2OCH2CH3 |
1.370 | H | H | S(O) | CH2CH2OCH3 |
1.371 | H | H | S(O) | CH2CH2OCH2CH3 |
1.372 | CH3 | H | S(O) | CH3 |
1.373 | CH3 | H | S(O) | CH2CH3 |
1.374 | CH3 | H | S(O) | CH2CH2CH3 |
1.375 | CH3 | H | S(O) | CH(CH3)2 |
1.376 | CH3 | H | S(O) | CH2CH2CH2CH3 |
1.377 | CH3 | H | S(O) | CH2CH(CH3)2 |
1.378 | CH3 | H | S(O) | CH(CH3)CH2CH3 |
1.379 | CH3 | H | S(O) | C(CH3)3 |
1.380 | CH3 | H | S(O) | CH2CH2CH2CH2CH3 |
1.381 | CH3 | H | S(O) | CH2CH2CH(CH3)2 |
1.382 | CH3 | H | S(O) | CH2C(CH3)3 |
1.383 | CH3 | H | S(O) | CH2CH(CH3)CH2CH3 |
1.384 | CH3 | H | S(O) | CH(CH3)CH2CH2CH3 |
1.385 | CH3 | H | S(O) | C(CH3)2CH2CH3 |
1.386 | CH3 | H | S(O) | CH2CH=CH2 |
1.387 | CH3 | H | S(O) | CH2CH=CHCH3 |
1.388 | CH3 | H | S(O) | CH2CH=C(CH3)2 |
1.389 | CH3 | H | S(O) | CH2C(CH3)=CH2 |
1.390 | CH3 | H | S(O) | CH2C(CH3)=CHCH3 |
1.391 | CH3 | H | S(O) | CH2C(CH3)=C(CH3)2 |
1.392 | CH3 | H | S(O) | CH(CH3)CH=CH2 |
化合物编号 | R6 | R7 | X | R8 |
1.393 | CH3 | H | S(O) | CH(CH3)CH=CHCH3 |
1.394 | CH3 | H | S(O) | CH(CH3)CH=C(CH3)2 |
1.395 | CH3 | H | S(O) | C(CH3)2CH=CH2 |
1.396 | CH3 | H | S(O) | C(CH3)2CH=CHCH3 |
1.397 | CH3 | H | S(O) | C(CH3)2CH=C(CH3)2 |
1.398 | CH3 | H | S(O) | CH2CH=CHCl |
1.399 | CH3 | H | S(O) | CH2CH=CCl2 |
1.400 | CH3 | H | S(O) | CH2CCl=CHCl |
1.401 | CH3 | H | S(O) | CH2CCl=CCl2 |
1.402 | CH3 | H | S(O) | CH2CH=CF2 |
1.403 | CH3 | H | S(O) | CH2CF=CF2 |
1.404 | CH3 | H | S(O) | CH2C.CH |
1.405 | CH3 | H | S(O) | CH2C.CCH3 |
1.406 | CH3 | H | S(O) | CH2C.CCH2CH3 |
1.407 | CH3 | H | S(O) | CH(CH3)C.CH |
1.408 | CH3 | H | S(O) | CH(CH3)C.CCH3 |
1.409 | CH3 | H | S(O) | CH(CH3)C.CCH2CH3 |
1.410 | CH3 | H | S(O) | C(CH3)2C.CH |
1.411 | CH3 | H | S(O) | C(CH3)2C.CCH3 |
1.412 | CH3 | H | S(O) | C(CH3)2C.CCH2CH3 |
1.413 | CH3 | H | S(O) | 环丙基 |
1.414 | CH3 | H | S(O) | 环丁基 |
1.415 | CH3 | H | S(O) | 环戊基 |
1.416 | CH3 | H | S(O) | 环己基 |
1.417 | CH3 | H | S(O) | CH2CF3 |
1.418 | CH3 | H | S(O) | CH2CH2CF3 |
1.419 | CH3 | H | S(O) | CH2-环丙基 |
1.420 | CH3 | H | S(O) | CH2-环丁基 |
化合物编号 | R6 | R7 | X | R8 |
1.421 | CH3 | H | S(O) | CH2-环戊基 |
1.422 | CH3 | H | S(O) | CH2-环己基 |
1.423 | CH3 | H | S(O) | CH2OCH3 |
1.424 | CH3 | H | S(O) | CH2OCH2CH3 |
1.425 | CH3 | H | S(O) | CH2CH2OCH3 |
1.426 | CH3 | H | S(O) | CH2CH2OCH2CH3 |
1.427 | CH3 | CH3 | S(O) | CH3 |
1.428 | CH3 | CH3 | S(O) | CH2CH3 |
1.429 | CH3 | CH3 | S(O) | CH2CH2CH3 |
1.430 | CH3 | CH3 | S(O) | CH(CH3)2 |
1.431 | CH3 | CH3 | S(O) | CH2CH2CH2CH3 |
1.432 | CH3 | CH3 | S(O) | CH2CH(CH3)2 |
1.433 | CH3 | CH3 | S(O) | CH(CH3)CH2CH3 |
1.434 | CH3 | CH3 | S(O) | C(CH3)3 |
1.435 | CH3 | CH3 | S(O) | CH2CH2CH2CH2CH3 |
1.436 | CH3 | CH3 | S(O) | CH2CH2CH(CH3)2 |
1.437 | CH3 | CH3 | S(O) | CH2C(CH3)3 |
1.438 | CH3 | CH3 | S(O) | CH2CH(CH3)CH2CH3 |
1.439 | CH3 | CH3 | S(O) | CH(CH3)CH2CH2CH3 |
1.440 | CH3 | CH3 | S(O) | C(CH3)2CH2CH3 |
1.441 | CH3 | CH3 | S(O) | CH2CH=CH2 |
1.442 | CH3 | CH3 | S(O) | CH2CH=CHCH3 |
1.443 | CH3 | CH3 | S(O) | CH2CH=C(CH3)2 |
1.444 | CH3 | CH3 | S(O) | CH2C(CH3)=CH2 |
1.445 | CH3 | CH3 | S(O) | CH2C(CH3)=CHCH3 |
1.446 | CH3 | CH3 | S(O) | CH2C(CH3)=C(CH3)2 |
1.447 | CH3 | CH3 | S(O) | CH(CH3)CH=CH2 |
1.448 | CH3 | CH3 | S(O) | CH(CH3)CH=CHCH3 |
化合物编号 | R6 | R7 | X | R8 |
1.449 | CH3 | CH3 | S(O) | CH(CH3)CH=C(CH3)2 |
1.450 | CH3 | CH3 | S(O) | C(CH3)2CH=CH2 |
1.451 | CH3 | CH3 | S(O) | C(CH3)2CH=CHCH3 |
1.452 | CH3 | CH3 | S(O) | C(CH3)2CH=C(CH3)2 |
1.453 | CH3 | CH3 | S(O) | CH2CH=CHCl |
1.454 | CH3 | CH3 | S(O) | CH2CH=CCl2 |
1.455 | CH3 | CH3 | S(O) | CH2CCl=CHCl |
1.456 | CH3 | CH3 | S(O) | CH2CCl=CCl2 |
1.457 | CH3 | CH3 | S(O) | CH2CH=CF2 |
1.458 | CH3 | CH3 | S(O) | CH2CF=CF2 |
1.459 | CH3 | CH3 | S(O) | CH2C.CH |
1.460 | CH3 | CH3 | S(O) | CH2C.CCH3 |
1.461 | CH3 | CH3 | S(O) | CH2C.CCH2CH3 |
1.462 | CH3 | CH3 | S(O) | CH(CH3)C.CH |
1.463 | CH3 | CH3 | S(O) | CH(CH3)C.CCH3 |
1.464 | CH3 | CH3 | S(O) | CH(CH3)C.CCH2CH3 |
1.465 | CH3 | CH3 | S(O) | C(CH3)2C.CH |
1.466 | CH3 | CH3 | S(O) | C(CH3)2C.CCH3 |
1.467 | CH3 | CH3 | S(O) | C(CH3)2C.CCH2CH3 |
1.468 | CH3 | CH3 | S(O) | 环丙基 |
1.469 | CH3 | CH3 | S(O) | 环丁基 |
1.470 | CH3 | CH3 | S(O) | 环戊基 |
1.471 | CH3 | CH3 | S(O) | 环己基 |
1.472 | CH3 | CH3 | S(O) | CH2CF3 |
1.473 | CH3 | CH3 | S(O) | CH2CH2CF3 |
1.474 | CH3 | CH3 | S(O) | CH2-环丙基 |
1.475 | CH3 | CH3 | S(O) | CH2-环丁基 |
1.476 | CH3 | CH3 | S(O) | CH2-环戊基 |
化合物编号 | R6 | R7 | X | R8 |
1.477 | CH3 | CH3 | S(O) | CH2-环己基 |
1.478 | CH3 | CH3 | S(O) | CH2OCH3 |
1.479 | CH3 | CH3 | S(O) | CH2OCH2CH3 |
1.480 | CH3 | CH3 | S(O) | CH2CH2OCH3 |
1.481 | CH3 | CH3 | S(O) | CH2CH2OCH2CH3 |
1.482 | H | H | SO2 | CH3 |
1.483 | H | H | SO2 | CH2CH3 |
1.484 | H | H | SO2 | CH2CH2CH3 |
1.485 | H | H | SO2 | CH(CH3)2 |
1.486 | H | H | SO2 | CH2CH2CH2CH3 |
1.487 | H | H | SO2 | CH2CH(CH3)2 |
1.488 | H | H | SO2 | CH(CH3)CH2CH3 |
1.489 | H | H | SO2 | C(CH3)3 |
1.490 | H | H | SO2 | CH2CH2CH2CH2CH3 |
1.491 | H | H | SO2 | CH2CH2CH(CH3)2 |
1.492 | H | H | SO2 | CH2C(CH3)3 |
1.493 | H | H | SO2 | CH2CH(CH3)CH2CH3 |
1.494 | H | H | SO2 | CH(CH3)CH2CH2CH3 |
1.495 | H | H | SO2 | C(CH3)2CH2CH3 |
1.496 | H | H | SO2 | CH2CH=CH2 |
1.497 | H | H | SO2 | CH2CH=CHCH3 |
1.498 | H | H | SO2 | CH2CH=C(CH3)2 |
1.499 | H | H | SO2 | CH2C(CH3)=CH2 |
1.500 | H | H | SO2 | CH2C(CH3)=CHCH3 |
1.501 | H | H | SO2 | CH2C(CH3)=C(CH3)2 |
1.502 | H | H | SO2 | CH(CH3)CH=CH2 |
1.503 | H | H | SO2 | CH(CH3)CH=CHCH3 |
1.504 | H | H | SO2 | CH(CH3)CH=C(CH3)2 |
化合物编号 | R6 | R7 | X | R8 |
1.505 | H | H | SO2 | C(CH3)2CH=CH2 |
1.506 | H | H | SO2 | C(CH3)2CH=CHCH3 |
1.507 | H | H | SO2 | C(CH3)2CH=C(CH3)2 |
1.508 | H | H | SO2 | CH2CH=CHCl |
1.509 | H | H | SO2 | CH2CH=CCl2 |
1.510 | H | H | SO2 | CH2CCl=CHCl |
1.511 | H | H | SO2 | CH2CCl=CCl2 |
1.512 | H | H | SO2 | CH2CH=CF2 |
1.513 | H | H | SO2 | CH2CF=CF2 |
1.514 | H | H | SO2 | CH2C.CH |
1.515 | H | H | SO2 | CH2C.CCH3 |
1.516 | H | H | SO2 | CH2C.CCH2CH3 |
1.517 | H | H | SO2 | CH(CH3)C.CH |
1.518 | H | H | SO2 | CH(CH3)C.CCH3 |
1.519 | H | H | SO2 | CH(CH3)C.CCH2CH3 |
1.520 | H | H | SO2 | C(CH3)2C.CH |
1.521 | H | H | SO2 | C(CH3)2C.CCH3 |
1.522 | H | H | SO2 | C(CH3)2C.CCH2CH3 |
1.523 | H | H | SO2 | 环丙基 |
1.524 | H | H | SO2 | 环丁基 |
1.525 | H | H | SO2 | 环戊基 |
1.526 | H | H | SO2 | 环己基 |
1.527 | H | H | SO2 | CH2CF3 |
1.528 | H | H | SO2 | CH2CH2CF3 |
1.529 | H | H | SO2 | CH2-环丙基 |
1.530 | H | H | SO2 | CH2-环丁基 |
1.531 | H | H | SO2 | CH2-环戊基 |
1.532 | H | H | SO2 | CH2-环己基 |
化合物编号 | R6 | R7 | X | R8 |
1.533 | H | H | SO2 | CH2OCH3 |
1.534 | H | H | SO2 | CH2OCH2CH3 |
1.535 | H | H | SO2 | CH2CH2OCH3 |
1.536 | H | H | SO2 | CH2CH2OCH2CH3 |
1.537 | CH3 | H | SO2 | CH3 |
1.538 | CH3 | H | SO2 | CH2CH3 |
1.539 | CH3 | H | SO2 | CH2CH2CH3 |
1.540 | CH3 | H | SO2 | CH(CH3)2 |
1.541 | CH3 | H | SO2 | CH2CH2CH2CH3 |
1.542 | CH3 | H | SO2 | CH2CH(CH3)2 |
1.543 | CH3 | H | SO2 | CH(CH3)CH2CH3 |
1.544 | CH3 | H | SO2 | C(CH3)3 |
1.545 | CH3 | H | SO2 | CH2CH2CH2CH2CH3 |
1.546 | CH3 | H | SO2 | CH2CH2CH(CH3)2 |
1.547 | CH3 | H | SO2 | CH2C(CH3)3 |
1.548 | CH3 | H | SO2 | CH2CH(CH3)CH2CH3 |
1.549 | CH3 | H | SO2 | CH(CH3)CH2CH2CH3 |
1.550 | CH3 | H | SO2 | C(CH3)2CH2CH3 |
1.551 | CH3 | H | SO2 | CH2CH=CH2 |
1.552 | CH3 | H | SO2 | CH2CH=CHCH3 |
1.553 | CH3 | H | SO2 | CH2CH=C(CH3)2 |
1.554 | CH3 | H | SO2 | CH2C(CH3)=CH2 |
1.555 | CH3 | H | SO2 | CH2C(CH3)=CHCH3 |
1.556 | CH3 | H | SO2 | CH2C(CH3)=C(CH3)2 |
1.557 | CH3 | H | SO2 | CH(CH3)CH=CH2 |
1.558 | CH3 | H | SO2 | CH(CH3)CH=CHCH3 |
1.559 | CH3 | H | SO2 | CH(CH3)CH=C(CH3)2 |
1.560 | CH3 | H | SO2 | C(CH3)2CH=CH2 |
化合物编号 | R6 | R7 | X | R8 |
1.561 | CH3 | H | SO2 | C(CH3)2CH=CHCH3 |
1.562 | CH3 | H | SO2 | C(CH3)2CH=C(CH3)2 |
1.563 | CH3 | H | SO2 | CH2CH=CHCl |
1.564 | CH3 | H | SO2 | CH2CH=CCl2 |
1.565 | CH3 | H | SO2 | CH2CCl=CHCl |
1.566 | CH3 | H | SO2 | CH2CCl=CCl2 |
1.567 | CH3 | H | SO2 | CH2CH=CF2 |
1.568 | CH3 | H | SO2 | CH2CF=CF2 |
1.569 | CH3 | H | SO2 | CH2C.CH |
1.570 | CH3 | H | SO2 | CH2C.CCH3 |
1.571 | CH3 | H | SO2 | CH2C.CCH2CH3 |
1.572 | CH3 | H | SO2 | CH(CH3)C.CH |
1.573 | CH3 | H | SO2 | CH(CH3)C.CCH3 |
1.574 | CH3 | H | SO2 | CH(CH3)C.CCH2CH3 |
1.575 | CH3 | H | SO2 | C(CH3)2C.CH |
1.576 | CH3 | H | SO2 | C(CH3)2C.CCH3 |
1.577 | CH3 | H | SO2 | C(CH3)2C.CCH2CH3 |
1.578 | CH3 | H | SO2 | 环丙基 |
1.579 | CH3 | H | SO2 | 环丁基 |
1.580 | CH3 | H | SO2 | 环戊基 |
1.581 | CH3 | H | SO2 | 环己基 |
1.582 | CH3 | H | SO2 | CH2CF3 |
1.583 | CH3 | H | SO2 | CH2CH2CF3 |
1.584 | CH3 | H | SO2 | CH2-环丙基 |
1.585 | CH3 | H | SO2 | CH2-环丁基 |
1.586 | CH3 | H | SO2 | CH2-环戊基 |
1.587 | CH3 | H | SO2 | CH2-环己基 |
1.588 | CH3 | H | SO2 | CH2OCH3 |
化合物编号 | R6 | R7 | X | R8 |
1.589 | CH3 | H | SO2 | CH2OCH2CH3 |
1.590 | CH3 | H | SO2 | CH2CH2OCH3 |
1.591 | CH3 | H | SO2 | CH2CH2OCH2CH3 |
1.592 | CH3 | CH3 | SO2 | CH3 |
1.593 | CH3 | CH3 | SO2 | CH2CH3 |
1.594 | CH3 | CH3 | SO2 | CH2CH2CH3 |
1.595 | CH3 | CH3 | SO2 | CH(CH3)2 |
1.596 | CH3 | CH3 | SO2 | CH2CH2CH2CH3 |
1.597 | CH3 | CH3 | SO2 | CH2CH(CH3)2 |
1.598 | CH3 | CH3 | SO2 | CH(CH3)CH2CH3 |
1.599 | CH3 | CH3 | SO2 | C(CH3)3 |
1.600 | CH3 | CH3 | SO2 | CH2CH2CH2CH2CH3 |
1.601 | CH3 | CH3 | SO2 | CH2CH2CH(CH3)2 |
1.602 | CH3 | CH3 | SO2 | CH2C(CH3)3 |
1.603 | CH3 | CH3 | SO2 | CH2CH(CH3)CH2CH3 |
1.604 | CH3 | CH3 | SO2 | CH(CH3)CH2CH2CH3 |
1.605 | CH3 | CH3 | SO2 | C(CH3)2CH2CH3 |
1.606 | CH3 | CH3 | SO2 | CH2CH=CH2 |
1.607 | CH3 | CH3 | SO2 | CH2CH=CHCH3 |
1.608 | CH3 | CH3 | SO2 | CH2CH=C(CH3)2 |
1.609 | CH3 | CH3 | SO2 | CH2C(CH3)=CH2 |
1.610 | CH3 | CH3 | SO2 | CH2C(CH3)=CHCH3 |
1.611 | CH3 | CH3 | SO2 | CH2C(CH3)=C(CH3)2 |
1.612 | CH3 | CH3 | SO2 | CH(CH3)CH=CH2 |
1.613 | CH3 | CH3 | SO2 | CH(CH3)CH=CHCH3 |
1.614 | CH3 | CH3 | SO2 | CH(CH3)CH=C(CH3)2 |
1.615 | CH3 | CH3 | SO2 | C(CH3)2CH=CH2 |
1.616 | CH3 | CH3 | SO2 | C(CH3)2CH=CHCH3 |
化合物编号 | R6 | R7 | X | R8 |
1.617 | CH3 | CH3 | SO2 | C(CH3)2CH=C(CH3)2 |
1.618 | CH3 | CH3 | SO2 | CH2CH=CHCl |
1.619 | CH3 | CH3 | SO2 | CH2CH=CCl2 |
1.620 | CH3 | CH3 | SO2 | CH2CCl=CHCl |
1.621 | CH3 | CH3 | SO2 | CH2CCl=CCl2 |
1.622 | CH3 | CH3 | SO2 | CH2CH=CF2 |
1.623 | CH3 | CH3 | SO2 | CH2CF=CF2 |
1.624 | CH3 | CH3 | SO2 | CH2C.CH |
1.625 | CH3 | CH3 | SO2 | CH2C.CCH3 |
1.626 | CH3 | CH3 | SO2 | CH2C.CCH2CH3 |
1.627 | CH3 | CH3 | SO2 | CH(CH3)C.CH |
1.628 | CH3 | CH3 | SO2 | CH(CH3)C.CCH3 |
1.629 | CH3 | CH3 | SO2 | CH(CH3)C.CCH2CH3 |
1.630 | CH3 | CH3 | SO2 | C(CH3)2C.CH |
1.631 | CH3 | CH3 | SO2 | C(CH3)2C.CCH3 |
1.632 | CH3 | CH3 | SO2 | C(CH3)2C.CCH2CH3 |
1.633 | CH3 | CH3 | SO2 | 环丙基 |
1.634 | CH3 | CH3 | SO2 | 环丁基 |
1.635 | CH3 | CH3 | SO2 | 环戊基 |
1.636 | CH3 | CH3 | SO2 | 环己基 |
1.637 | CH3 | CH3 | SO2 | CH2CF3 |
1.638 | CH3 | CH3 | SO2 | CH2CH2CF3 |
1.639 | CH3 | CH3 | SO2 | CH2-环丙基 |
1.640 | CH3 | CH3 | SO2 | CH2-环丁基 |
1.641 | CH3 | CH3 | SO2 | CH2-环戊基 |
1.642 | CH3 | CH3 | SO2 | CH2-环己基 |
1.643 | CH3 | CH3 | SO2 | CH2OCH3 |
1.644 | CH3 | CH3 | SO2 | CH2OCH2CH3 |
化合物编号 | R6 | R7 | X | R8 |
1.645 | CH3 | CH3 | SO2 | CH2CH2OCH3 |
1.646 | CH3 | CH3 | SO2 | CH2CH2OCH2CH3 |
表2:
本表包含下述类型的646个化合物,
其中X、R6、R7和R8如表1所定义。
表3:
本表包含下述类型的646个化合物,
其中X、R6、R7和R8如表1所定义。
表4
表4包含下述类型的646个化合物,
其中X、R6、R7和R8如表1所定义。
表5:
本表包含下述类型的646个化合物,
其中X、R6、R7和R8如表1所定义。
表6:
本表包含下述类型的646个化合物,
其中X、R6、R7和R8如表1所定义。
表7:
本表包含下述类型的646个化合物,
其中X、R6、R7和R8如表1所定义。
表8:
本表包含下述类型的646个化合物,
其中X、R6、R7和R8如表1所定义。
表9:
本表包含下述类型的646个化合物,
其中X、R6、R7和R8如表1所定义。
表10:
本表包含下述类型的646个化合物,
其中X、R6、R7和R8如表1所定义。
表11:
本表包含下述类型的646个化合物,
其中X、R6、R7和R8如表1所定义。
表12
本表包含下述类型的646个化合物,
其中X、R6、R7和R8如表1所定义。
表13
本表包含下述类型的646个化合物,
其中X、R6、R7和R8如表1所定义。
表14
本表包含下述类型的646个化合物,
其中X、R6、R7和R8如表1所定义。
表15
本表包含下述类型的646个化合物,
其中X、R6、R7和R8如表1所定义。
表16
本表12包含下述类型的646个化合物,
其中X、R6、R7和R8如表1所定义。
表17
本表包含下述类型的646个化合物,
其中X、R6、R7和R8如表1所定义。
表18
本表包含下述类型的646个化合物,
其中X、R6、R7和R8如表1所定义。
表19:
本表包含下述类型的646个化合物,
其中X、R6、R7和R8如表1所定义。
表20
本表包含下述类型的646个化合物,
其中X、R6、R7和R8如表1所定义。
表21
本表包含下述类型的646个化合物,
其中X、R6、R7和R8如表1所定义。
表22
本表包含下述类型的646个化合物,
其中X、R6、R7和R8如表1所定义。
表23
本表12包含下述类型的646个化合物,
其中X、R6、R7和R8如表1所定义。
表24
本表包含下述类型的646个化合物,
其中X、R6、R7和R8如表1所定义。
表25
本表包含下述类型的646个化合物,
其中X、R6、R7和R8如表1所定义。
表26:
本表包含下述类型的618个化合物,
其中X、R6、R7和R8定义如下:
化合物编号 | R6 | R7 | X | R8 |
26.1 | H | H | O | CH3 |
26.2 | H | H | O | CH2CH3 |
26.3 | H | H | O | CH2CH2CH3 |
26.4 | H | H | O | CH(CH3)2 |
化合物编号 | R6 | R7 | X | R8 |
26.5 | H | H | O | CH2CH2CH2CH3 |
26.6 | H | H | O | CH2CH(CH3)2 |
26.7 | H | H | O | CH(CH3)CH2CH3 |
26.8 | H | H | O | C(CH3)3 |
26.9 | H | H | O | CH2CH2CH2CH2CH3 |
26.10 | H | H | O | CH2CH2CH(CH3)2 |
26.11 | H | H | O | CH2C(CH3)3 |
26.12 | H | H | O | CH2CH(CH3)CH2CH3 |
26.13 | H | H | O | CH(CH3)CH2CH2CH3 |
26.14 | H | H | O | C(CH3)2CH2CH3 |
26.15 | H | H | O | CH2CH=CH2 |
26.16 | H | H | O | CH2CH=CHCH3 |
26.17 | H | H | O | CH2CH=C(CH3)2 |
26.18 | H | H | O | CH2C(CH3)=CH2 |
26.19 | H | H | O | CH2C(CH3)=CHCH3 |
26.20 | H | H | O | CH2C(CH3)=C(CH3)2 |
26.21 | H | H | O | CH(CH3)CH=CH2 |
26.22 | H | H | O | CH(CH3)CH=CHCH3 |
26.23 | H | H | O | CH(CH3)CH=C(CH3)2 |
26.24 | H | H | O | C(CH3)2CH=CH2 |
26.25 | H | H | O | C(CH3)2CH=CHCH3 |
26.26 | H | H | O | C(CH3)2CH=C(CH3)2 |
26.27 | H | H | O | CH2CH=CHCl |
26.28 | H | H | O | CH2CH=CCl2 |
26.29 | H | H | O | CH2CCl=CHCl |
26.30 | H | H | O | CH2CCl=CCl2 |
26.31 | H | H | O | CH2CH=CF2 |
26.32 | H | H | O | CH2CF=CF2 |
化合物编号 | R6 | R7 | X | R8 |
26.33 | H | H | O | CH2C.CH |
26.34 | H | H | O | CH2C.CCH3 |
26.35 | H | H | O | CH2C.CCH2CH3 |
26.36 | H | H | O | CH(CH3)C.CH |
26.37 | H | H | O | CH(CH3)C.CCH3 |
26.38 | H | H | O | CH(CH3)C.CCH2CH3 |
26.39 | H | H | O | C(CH3)2C.CH |
26.40 | H | H | O | C(CH3)2C.CCH3 |
26.41 | H | H | O | C(CH3)2C.CCH2CH3 |
26.42 | H | H | O | 环丙基 |
26.43 | H | H | O | 环丁基 |
26.44 | H | H | O | 环戊基 |
26.45 | H | H | O | 环己基 |
26.46 | H | H | O | CH2CF3 |
26.47 | H | H | O | CH2CH2CF3 |
26.48 | H | H | O | CH2-环丙基 |
26.49 | H | H | O | CH2-环丁基 |
26.50 | H | H | O | CH2-环戊基 |
26.51 | H | H | O | CH2-环己基 |
26.52 | H | H | O | CH2OCH3 |
26.53 | H | H | O | CH2OCH2CH3 |
26.54 | H | H | O | CH2CH2OCH3 |
26.55 | H | H | O | CH2CH2OCH2CH3 |
26.56 | CH3 | H | O | CH3 |
26.57 | CH3 | H | O | CH2CH3 |
26.58 | CH3 | H | O | CH2CH2CH3 |
26.59 | CH3 | H | O | CH(CH3)2 |
26.60 | CH3 | H | O | CH2CH2CH2CH3 |
化合物编号 | R6 | R7 | X | R8 |
26.61 | CH3 | H | O | CH2CH(CH3)2 |
26.62 | CH3 | H | O | CH(CH3)CH2CH3 |
26.63 | CH3 | H | O | C(CH3)3 |
26.64 | CH3 | H | O | CH2CH2CH2CH2CH3 |
26.65 | CH3 | H | O | CH2CH2CH(CH3)2 |
26.66 | CH3 | H | O | CH2C(CH3)3 |
26.67 | CH3 | H | O | CH2CH(CH3)CH2CH3 |
26.68 | CH3 | H | O | CH(CH3)CH2CH2CH3 |
26.69 | CH3 | H | O | C(CH3)2CH2CH3 |
26.70 | CH3 | H | O | CH2CH=CH2 |
26.71 | CH3 | H | O | CH2CH=CHCH3 |
26.72 | CH3 | H | O | CH2CH=C(CH3)2 |
26.73 | CH3 | H | O | CH2C(CH3)=CH2 |
26.74 | CH3 | H | O | CH2C(CH3)=CHCH3 |
26.75 | CH3 | H | O | CH2C(CH3)=C(CH3)2 |
26.76 | CH3 | H | O | CH(CH3)CH=CH2 |
26.77 | CH3 | H | O | CH(CH3)CH=CHCH3 |
26.78 | CH3 | H | O | CH(CH3)CH=C(CH3)2 |
26.79 | CH3 | H | O | C(CH3)2CH=CH2 |
26.80 | CH3 | H | O | C(CH3)2CH=CHCH3 |
26.81 | CH3 | H | O | C(CH3)2CH=C(CH3)2 |
26.82 | CH3 | H | O | CH2CH=CHCl |
26.83 | CH3 | H | O | CH2CH=CCl2 |
26.84 | CH3 | H | O | CH2CCl=CHCl |
26.85 | CH3 | H | O | CH2CCl=CCl2 |
26.86 | CH3 | H | O | CH2CH=CF2 |
26.87 | CH3 | H | O | CH2CF=CF2 |
26.88 | CH3 | H | O | CH2C.CH |
化合物编号 | R6 | R7 | X | R8 |
26.89 | CH3 | H | O | CH2C.CCH3 |
26.90 | CH3 | H | O | CH2C.CCH2CH3 |
26.91 | CH3 | H | O | CH(CH3)C.CH |
26.92 | CH3 | H | O | CH(CH3)C.CCH3 |
26.93 | CH3 | H | O | CH(CH3)C.CCH2CH3 |
26.94 | CH3 | H | O | C(CH3)2C.CH |
26.95 | CH3 | H | O | C(CH3)2C.CCH3 |
26.96 | CH3 | H | O | C(CH3)2C.CCH2CH3 |
26.97 | CH3 | H | O | 环丙基 |
26.98 | CH3 | H | O | 环丁基 |
26.99 | CH3 | H | O | 环戊基 |
26.100 | CH3 | H | O | 环己基 |
26.101 | CH3 | H | O | CH2CF3 |
26.102 | CH3 | H | O | CH2CH2CF3 |
26.103 | CH3 | H | O | CH2-环丙基 |
26.104 | CH3 | H | O | CH2-环丁基 |
26.105 | CH3 | H | O | CH2-环戊基 |
26.106 | CH3 | H | O | CH2-环己基 |
26.107 | CH3 | H | O | CH2OCH3 |
26.108 | CH3 | H | O | CH2OCH2CH3 |
26.109 | CH3 | H | O | CH2CH2OCH3 |
26.110 | CH3 | H | O | CH2CH2OCH2CH3 |
26.111 | CH3 | CH3 | O | CH3 |
26.112 | CH3 | CH3 | O | CH2CH3 |
26.113 | CH3 | CH3 | O | CH2CH2CH3 |
26.114 | CH3 | CH3 | O | CH(CH3)2 |
26.115 | CH3 | CH3 | O | CH2CH2CH2CH3 |
26.116 | CH3 | CH3 | O | CH2CH(CH3)2 |
化合物编号 | R6 | R7 | X | R8 |
26.117 | CH3 | CH3 | O | CH(CH3)CH2CH3 |
26.118 | CH3 | CH3 | O | C(CH3)3 |
26.119 | CH3 | CH3 | O | CH2CH2CH2CH2CH3 |
26.120 | CH3 | CH3 | O | CH2CH2CH(CH3)2 |
26.121 | CH3 | CH3 | O | CH2C(CH3)3 |
26.122 | CH3 | CH3 | O | CH2CH(CH3)CH2CH3 |
26.123 | CH3 | CH3 | O | CH(CH3)CH2CH2CH3 |
26.124 | CH3 | CH3 | O | C(CH3)2CH2CH3 |
26.125 | CH3 | CH3 | O | CH2CH=CH2 |
26.126 | CH3 | CH3 | O | CH2CH=CHCH3 |
26.127 | CH3 | CH3 | O | CH2CH=C(CH3)2 |
26.128 | CH3 | CH3 | O | CH2C(CH3)=CH2 |
26.129 | CH3 | CH3 | O | CH2C(CH3)=CHCH3 |
26.130 | CH3 | CH3 | O | CH2C(CH3)=C(CH3)2 |
26.131 | CH3 | CH3 | O | CH(CH3)CH=CH2 |
26.132 | CH3 | CH3 | O | CH(CH3)CH=CHCH3 |
26.133 | CH3 | CH3 | O | CH(CH3)CH=C(CH3)2 |
26.134 | CH3 | CH3 | O | C(CH3)2CH=CH2 |
26.135 | CH3 | CH3 | O | C(CH3)2CH=CHCH3 |
26.136 | CH3 | CH3 | O | C(CH3)2CH=C(CH3)2 |
26.137 | CH3 | CH3 | O | CH2CH=CHCl |
26.138 | CH3 | CH3 | O | CH2CH=CCl2 |
26.139 | CH3 | CH3 | O | CH2CCl=CHCl |
26.140 | CH3 | CH3 | O | CH2CCl=CCl2 |
26.141 | CH3 | CH3 | O | CH2CH=CF2 |
26.142 | CH3 | CH3 | O | CH2CF=CF2 |
26.143 | CH3 | CH3 | O | CH2C.CH |
26.144 | CH3 | CH3 | O | CH2C.CCH3 |
化合物编号 | R6 | R7 | X | R8 |
26.145 | CH3 | CH3 | O | CH2C.CCH2CH3 |
26.146 | CH3 | CH3 | O | CH(CH3)C.CH |
26.147 | CH3 | CH3 | O | CH(CH3)C.CCH3 |
26.148 | CH3 | CH3 | O | CH(CH3)C.CCH2CH3 |
26.149 | CH3 | CH3 | O | C(CH3)2C.CH |
26.150 | CH3 | CH3 | O | C(CH3)2C.CCH3 |
26.151 | CH3 | CH3 | O | C(CH3)2C.CCH2CH3 |
26.152 | CH3 | CH3 | O | 环丙基 |
26.153 | CH3 | CH3 | O | 环丁基 |
26.154 | CH3 | CH3 | O | 环戊基 |
26.155 | CH3 | CH3 | O | 环己基 |
26.156 | CH3 | CH3 | O | CH2CF3 |
26.157 | CH3 | CH3 | O | CH2CH2CF3 |
26.158 | CH3 | CH3 | O | CH2-环丙基 |
26.159 | CH3 | CH3 | O | CH2-环丁基 |
26.160 | CH3 | CH3 | O | CH2-环戊基 |
26.161 | CH3 | CH3 | O | CH2-环己基 |
26.162 | CH3 | CH3 | O | CH2OCH3 |
26.163 | CH3 | CH3 | O | CH2OCH2CH3 |
26.164 | CH3 | CH3 | O | CH2CH2OCH3 |
26.165 | CH3 | CH3 | O | CH2CH2OCH2CH3 |
26.166 | H | H | S | CH3 |
26.167 | H | H | S | CH2CH3 |
26.168 | H | H | S | CH2CH2CH3 |
26.169 | H | H | S | CH(CH3)2 |
26.170 | H | H | S | CH2CH2CH2CH3 |
26.171 | H | H | S | CH2CH(CH3)2 |
26.172 | H | H | S | CH(CH3)CH2CH3 |
化合物编号 | R6 | R7 | X | R8 |
26.173 | H | H | S | C(CH3)3 |
26.174 | H | H | S | CH2CH2CH2CH2CH3 |
26.175 | H | H | S | CH2CH2CH(CH3)2 |
26.176 | H | H | S | CH2C(CH3)3 |
26.177 | H | H | S | CH2CH(CH3)CH2CH3 |
26.178 | H | H | S | CH(CH3)CH2CH2CH3 |
26.179 | H | H | S | C(CH3)2CH2CH3 |
26.180 | H | H | S | CH2CH=CH2 |
26.181 | H | H | S | CH2CH=CHCH3 |
26.182 | H | H | S | CH2CH=C(CH3)2 |
26.183 | H | H | S | CH2C(CH3)=CH2 |
26.184 | H | H | S | CH2C(CH3)=CHCH3 |
26.185 | H | H | S | CH2C(CH3)=C(CH3)2 |
26.186 | H | H | S | CH(CH3)CH=CH2 |
26.187 | H | H | S | CH(CH3)CH=CHCH3 |
26.188 | H | H | S | CH(CH3)CH=C(CH3)2 |
26.189 | H | H | S | C(CH3)2CH=CH2 |
26.190 | H | H | S | C(CH3)2CH=CHCH3 |
26.191 | H | H | S | C(CH3)2CH=C(CH3)2 |
26.192 | H | H | S | CH2CH=CHCl |
26.193 | H | H | S | CH2CH=CCl2 |
26.194 | H | H | S | CH2CCl=CHCl |
26.195 | H | H | S | CH2CCl=CCl2 |
26.196 | H | H | S | CH2CH=CF2 |
26.197 | H | H | S | CH2CF=CF2 |
26.198 | H | H | S | CH2C.CH |
26.199 | H | H | S | CH2C.CCH3 |
26.200 | H | H | S | CH2C.CCH2CH3 |
化合物编号 | R6 | R7 | X | R8 |
26.201 | H | H | S | CH(CH3)C.CH |
26.202 | H | H | S | CH(CH3)C.CCH3 |
26.203 | H | H | S | CH(CH3)C.CCH2CH3 |
26.204 | H | H | S | C(CH3)2C.CH |
26.205 | H | H | S | C(CH3)2C.CCH3 |
26.206 | H | H | S | C(CH3)2C.CCH2CH3 |
26.207 | H | H | S | 环丙基 |
26.208 | H | H | S | 环丁基 |
26.209 | H | H | S | 环戊基 |
26.210 | H | H | S | 环己基 |
26.211 | H | H | S | CH2CF3 |
26.212 | H | H | S | CH2CH2CF3 |
26.213 | H | H | S | CH2-环丙基 |
26.214 | H | H | S | CH2-环丁基 |
26.215 | H | H | S | CH2-环戊基 |
26.216 | H | H | S | CH2-环己基 |
26.217 | CH3 | H | S | CH3 |
26.218 | CH3 | H | S | CH2CH3 |
26.219 | CH3 | H | S | CH2CH2CH3 |
26.220 | CH3 | H | S | CH(CH3)2 |
26.221 | CH3 | H | S | CH2CH2CH2CH3 |
26.222 | CH3 | H | S | CH2CH(CH3)2 |
26.223 | CH3 | H | S | CH(CH3)CH2CH3 |
26.224 | CH3 | H | S | C(CH3)3 |
26.225 | CH3 | H | S | CH2CH2CH2CH2CH3 |
26.226 | CH3 | H | S | CH2CH2CH(CH3)2 |
26.227 | CH3 | H | S | CH2C(CH3)3 |
26.228 | CH3 | H | S | CH2CH(CH3)CH2CH3 |
化合物编号 | R6 | R7 | X | R8 |
26.229 | CH3 | H | S | CH(CH3)CH2CH2CH3 |
26.230 | CH3 | H | S | C(CH3)2CH2CH3 |
26.231 | CH3 | H | S | CH2CH=CH2 |
26.232 | CH3 | H | S | CH2CH=CHCH3 |
26.233 | CH3 | H | S | CH2CH=C(CH3)2 |
26.234 | CH3 | H | S | CH2C(CH3)=CH2 |
26.235 | CH3 | H | S | CH2C(CH3)=CHCH3 |
26.236 | CH3 | H | S | CH2C(CH3)=C(CH3)2 |
26.237 | CH3 | H | S | CH(CH3)CH=CH2 |
26.238 | CH3 | H | S | CH(CH3)CH=CHCH3 |
26.239 | CH3 | H | S | CH(CH3)CH=C(CH3)2 |
26.240 | CH3 | H | S | C(CH3)2CH=CH2 |
26.241 | CH3 | H | S | C(CH3)2CH=CHCH3 |
26.242 | CH3 | H | S | C(CH3)2CH=C(CH3)2 |
26.243 | CH3 | H | S | CH2CH=CHCl |
26.244 | CH3 | H | S | CH2CH=CCl2 |
26.245 | CH3 | H | S | CH2CCl=CHCl |
26.246 | CH3 | H | S | CH2CCl=CCl2 |
26.247 | CH3 | H | S | CH2CH=CF2 |
26.248 | CH3 | H | S | CH2CF=CF2 |
26.249 | CH3 | H | S | CH2C.CH |
26.250 | CH3 | H | S | CH2C.CCH3 |
26.251 | CH3 | H | S | CH2C.CCH2CH3 |
26.252 | CH3 | H | S | CH(CH3)C.CH |
26.253 | CH3 | H | S | CH(CH3)C.CCH3 |
26.254 | CH3 | H | S | CH(CH3)C.CCH2CH3 |
26.255 | CH3 | H | S | C(CH3)2C.CH |
26.256 | CH3 | H | S | C(CH3)2C.CCH3 |
化合物编号 | R6 | R7 | X | R8 |
26.257 | CH3 | H | S | C(CH3)2C.CCH2CH3 |
26.258 | CH3 | H | S | 环丙基 |
26.259 | CH3 | H | S | 环丁基 |
26.260 | CH3 | H | S | 环戊基 |
26.261 | CH3 | H | S | 环己基 |
26.262 | CH3 | H | S | CH2CF3 |
26.263 | CH3 | H | S | CH2CH2CF3 |
26.264 | CH3 | H | S | CH2-环丙基 |
26.265 | CH3 | H | S | CH2-环丁基 |
26.266 | CH3 | H | S | CH2-环戊基 |
26.267 | CH3 | H | S | CH2-环己基 |
26.268 | CH3 | CH3 | S | CH3 |
26.269 | CH3 | CH3 | S | CH2CH3 |
26.270 | CH3 | CH3 | S | CH2CH2CH3 |
26.271 | CH3 | CH3 | S | CH(CH3)2 |
26.272 | CH3 | CH3 | S | CH2CH2CH2CH3 |
26.273 | CH3 | CH3 | S | CH2CH(CH3)2 |
26.274 | CH3 | CH3 | S | CH(CH3)CH2CH3 |
26.275 | CH3 | CH3 | S | C(CH3)3 |
26.276 | CH3 | CH3 | S | CH2CH2CH2CH2CH3 |
26.277 | CH3 | CH3 | S | CH2CH2CH(CH3)2 |
26.278 | CH3 | CH3 | S | CH2C(CH3)3 |
26.279 | CH3 | CH3 | S | CH2CH(CH3)CH2CH3 |
26.280 | CH3 | CH3 | S | CH(CH3)CH2CH2CH3 |
26.281 | CH3 | CH3 | S | C(CH3)2CH2CH3 |
26.282 | CH3 | CH3 | S | CH2CH=CH2 |
26.283 | CH3 | CH3 | S | CH2CH=CHCH3 |
26.284 | CH3 | CH3 | S | CH2CH=C(CH3)2 |
化合物编号 | R6 | R7 | X | R8 |
26.285 | CH3 | CH3 | S | CH2C(CH3)=CH2 |
26.286 | CH3 | CH3 | S | CH2C(CH3)=CHCH3 |
26.287 | CH3 | CH3 | S | CH2C(CH3)=C(CH3)2 |
26.288 | CH3 | CH3 | S | CH(CH3)CH=CH2 |
26.289 | CH3 | CH3 | S | CH(CH3)CH=CHCH3 |
26.290 | CH3 | CH3 | S | CH(CH3)CH=C(CH3)2 |
26.291 | CH3 | CH3 | S | C(CH3)2CH=CH2 |
26.292 | CH3 | CH3 | S | C(CH3)2CH=CHCH3 |
26.293 | CH3 | CH3 | S | C(CH3)2CH=C(CH3)2 |
26.294 | CH3 | CH3 | S | CH2CH=CHCl |
26.295 | CH3 | CH3 | S | CH2CH=CCl2 |
26.296 | CH3 | CH3 | S | CH2CCl=CHCl |
26.297 | CH3 | CH3 | S | CH2CCl=CCl2 |
26.298 | CH3 | CH3 | S | CH2CH=CF2 |
26.299 | CH3 | CH3 | S | CH2CF=CF2 |
26.300 | CH3 | CH3 | S | CH2C.CH |
26.301 | CH3 | CH3 | S | CH2C.CCH3 |
26.302 | CH3 | CH3 | S | CH2C.CCH2CH3 |
26.303 | CH3 | CH3 | S | CH(CH3)C.CH |
26.304 | CH3 | CH3 | S | CH(CH3)C.CCH3 |
26.305 | CH3 | CH3 | S | CH(CH3)C.CCH2CH3 |
26.306 | CH3 | CH3 | S | C(CH3)2C.CH |
26.307 | CH3 | CH3 | S | C(CH3)2C.CCH3 |
26.308 | CH3 | CH3 | S | C(CH3)2C.CCH2CH3 |
26.309 | CH3 | CH3 | S | 环丙基 |
26.310 | CH3 | CH3 | S | 环丁基 |
26.311 | CH3 | CH3 | S | 环戊基 |
26.312 | CH3 | CH3 | S | 环己基 |
化合物编号 | R6 | R7 | X | R8 |
26.313 | CH3 | CH3 | S | CH2CF3 |
26.314 | CH3 | CH3 | S | CH2CH2CF3 |
26.315 | CH3 | CH3 | S | CH2-环丙基 |
26.316 | CH3 | CH3 | S | CH2-环丁基 |
26.317 | CH3 | CH3 | S | CH2-环戊基 |
26.318 | CH3 | CH3 | S | CH2-环己基 |
26.319 | H | H | S(O) | CH3 |
26.320 | H | H | S(O) | CH2CH3 |
26.321 | H | H | S(O) | CH2CH2CH3 |
26.322 | H | H | S(O) | CH(CH3)2 |
26.323 | H | H | S(O) | CH2CH2CH2CH3 |
26.324 | H | H | S(O) | CH2CH(CH3)2 |
26.325 | H | H | S(O) | CH(CH3)CH2CH3 |
26.326 | H | H | S(O) | C(CH3)3 |
26.327 | H | H | S(O) | CH2CH2CH2CH2CH3 |
26.328 | H | H | S(O) | CH2CH2CH(CH3)2 |
26.329 | H | H | S(O) | CH2C(CH3)3 |
26.330 | H | H | S(O) | CH2CH(CH3)CH2CH3 |
26.331 | H | H | S(O) | CH(CH3)CH2CH2CH3 |
26.332 | H | H | S(O) | C(CH3)2CH2CH3 |
26.333 | H | H | S(O) | CH2CH=CH2 |
26.334 | H | H | S(O) | CH2CH=CHCH3 |
26.335 | H | H | S(O) | CH2CH=C(CH3)2 |
26.336 | H | H | S(O) | CH2C(CH3)=CH2 |
26.337 | H | H | S(O) | CH2C(CH3)=CHCH3 |
26.338 | H | H | S(O) | CH2C(CH3)=C(CH3)2 |
26.339 | H | H | S(O) | CH(CH3)CH=CH2 |
26.340 | H | H | S(O) | CH(CH3)CH=CHCH3 |
化合物编号 | R6 | R7 | X | R8 |
26.341 | H | H | S(O) | CH(CH3)CH=C(CH3)2 |
26.342 | H | H | S(O) | C(CH3)2CH=CH2 |
26.343 | H | H | S(O) | C(CH3)2CH=CHCH3 |
26.344 | H | H | S(O) | C(CH3)2CH=C(CH3)2 |
26.345 | H | H | S(O) | CH2CH=CHCl |
26.346 | H | H | S(O) | CH2CH=CCl2 |
26.347 | H | H | S(O) | CH2CCl=CHCl |
26.348 | H | H | S(O) | CH2CCl=CCl2 |
26.349 | H | H | S(O) | CH2CH=CF2 |
26.350 | H | H | S(O) | CH2CF=CF2 |
26.351 | H | H | S(O) | CH2C.CH |
26.352 | H | H | S(O) | CH2C.CCH3 |
26.353 | H | H | S(O) | CH2C.CCH2CH3 |
26.354 | H | H | S(O) | CH(CH3)C.CH |
26.355 | H | H | S(O) | CH(CH3)C.CCH3 |
26.356 | H | H | S(O) | CH(CH3)C.CCH2CH3 |
26.357 | H | H | S(O) | C(CH3)2C.CH |
26.358 | H | H | S(O) | C(CH3)2C.CCH3 |
26.359 | H | H | S(O) | C(CH3)2C.CCH2CH3 |
26.360 | H | H | S(O) | 环丙基 |
26.361 | H | H | S(O) | 环丁基 |
26.362 | H | H | S(O) | 环戊基 |
26.363 | H | H | S(O) | 环己基 |
26.364 | H | H | S(O) | CH2CF3 |
26.365 | H | H | S(O) | CH2CH2CF3 |
26.366 | H | H | S(O) | CH2-环丙基 |
26.357 | H | H | S(O) | CH2-环丁基 |
26.358 | H | H | S(O) | CH2-环戊基 |
化合物编号 | R6 | R7 | X | R8 |
26.359 | H | H | S(O) | CH2-环己基 |
26.360 | H | H | S(O) | CH2OCH3 |
26.361 | H | H | S(O) | CH2OCH2CH3 |
26.362 | H | H | S(O) | CH2CH2OCH3 |
26.363 | H | H | S(O) | CH2CH2OCH2CH3 |
26.364 | CH3 | H | S(O) | CH3 |
26.365 | CH3 | H | S(O) | CH2CH3 |
26.366 | CH3 | H | S(O) | CH2CH2CH3 |
26.367 | CH3 | H | S(O) | CH(CH3)2 |
26.368 | CH3 | H | S(O) | CH2CH2CH2CH3 |
26.369 | CH3 | H | S(O) | CH2CH(CH3)2 |
26.370 | CH3 | H | S(O) | CH(CH3)CH2CH3 |
26.371 | CH3 | H | S(O) | C(CH3)3 |
26.372 | CH3 | H | S(O) | CH2CH2CH2CH2CH3 |
26.373 | CH3 | H | S(O) | CH2CH2CH(CH3)2 |
26.374 | CH3 | H | S(O) | CH2C(CH3)3 |
26.375 | CH3 | H | S(O) | CH2CH(CH3)CH2CH3 |
26.376 | CH3 | H | S(O) | CH(CH3)CH2CH2CH3 |
26.377 | CH3 | H | S(O) | C(CH3)2CH2CH3 |
26.378 | CH3 | H | S(O) | CH2CH=CH2 |
26.379 | CH3 | H | S(O) | CH2CH=CHCH3 |
26.380 | CH3 | H | S(O) | CH2CH=C(CH3)2 |
26.381 | CH3 | H | S(O) | CH2C(CH3)=CH2 |
26.382 | CH3 | H | S(O) | CH2C(CH3)=CHCH3 |
26.383 | CH3 | H | S(O) | CH2C(CH3)=C(CH3)2 |
26.384 | CH3 | H | S(O) | CH(CH3)CH=CH2 |
26.385 | CH3 | H | S(O) | CH(CH3)CH=CHCH3 |
26.386 | CH3 | H | S(O) | CH(CH3)CH=C(CH3)2 |
化合物编号 | R6 | R7 | X | R8 |
26.387 | CH3 | H | S(O) | C(CH3)2CH=CH2 |
26.388 | CH3 | H | S(O) | C(CH3)2CH=CHCH3 |
26.389 | CH3 | H | S(O) | C(CH3)2CH=C(CH3)2 |
26.390 | CH3 | H | S(O) | CH2CH=CHCl |
26.391 | CH3 | H | S(O) | CH2CH=CCl2 |
26.392 | CH3 | H | S(O) | CH2CCl=CHCl |
26.393 | CH3 | H | S(O) | CH2CCl=CCl2 |
26.394 | CH3 | H | S(O) | CH2CH=CF2 |
26.395 | CH3 | H | S(O) | CH2CF=CF2 |
26.396 | CH3 | H | S(O) | CH2C.CH |
26.397 | CH3 | H | S(O) | CH2C.CCH3 |
26.398 | CH3 | H | S(O) | CH2C.CCH2CH3 |
26.399 | CH3 | H | S(O) | CH(CH3)C.CH |
26.400 | CH3 | H | S(O) | CH(CH3)C.CCH3 |
26.401 | CH3 | H | S(O) | CH(CH3)C.CCH2CH3 |
26.402 | CH3 | H | S(O) | C(CH3)2C.CH |
26.403 | CH3 | H | S(O) | C(CH3)2C.CCH3 |
26.404 | CH3 | H | S(O) | C(CH3)2C.CCH2CH3 |
26.405 | CH3 | H | S(O) | 环丙基 |
26.406 | CH3 | H | S(O) | 环丁基 |
26.407 | CH3 | H | S(O) | 环戊基 |
26.408 | CH3 | H | S(O) | 环己基 |
26.409 | CH3 | H | S(O) | CH2CF3 |
26.410 | CH3 | H | S(O) | CH2CH2CF3 |
26.411 | CH3 | H | S(O) | CH2-环丙基 |
26.412 | CH3 | H | S(O) | CH2-环丁基 |
26.413 | CH3 | H | S(O) | CH2-环戊基 |
26.414 | CH3 | H | S(O) | CH2-环己基 |
化合物编号 | R6 | R7 | X | R8 |
26.415 | CH3 | CH3 | S(O) | CH3 |
26.416 | CH3 | CH3 | S(O) | CH2CH3 |
26.417 | CH3 | CH3 | S(O) | CH2CH2CH3 |
26.418 | CH3 | CH3 | S(O) | CH(CH3)2 |
26.419 | CH3 | CH3 | S(O) | CH2CH2CH2CH3 |
26.420 | CH3 | CH3 | S(O) | CH2CH(CH3)2 |
26.421 | CH3 | CH3 | S(O) | CH(CH3)CH2CH3 |
26.422 | CH3 | CH3 | S(O) | C(CH3)3 |
26.423 | CH3 | CH3 | S(O) | CH2CH2CH2CH2CH3 |
26.424 | CH3 | CH3 | S(O) | CH2CH2CH(CH3)2 |
26.425 | CH3 | CH3 | S(O) | CH2C(CH3)3 |
26.426 | CH3 | CH3 | S(O) | CH2CH(CH3)CH2CH3 |
26.427 | CH3 | CH3 | S(O) | CH(CH3)CH2CH2CH3 |
26.428 | CH3 | CH3 | S(O) | C(CH3)2CH2CH3 |
26.429 | CH3 | CH3 | S(O) | CH2CH=CH2 |
26.430 | CH3 | CH3 | S(O) | CH2CH=CHCH3 |
26.431 | CH3 | CH3 | S(O) | CH2CH=C(CH3)2 |
26.432 | CH3 | CH3 | S(O) | CH2C(CH3)=CH2 |
26.433 | CH3 | CH3 | S(O) | CH2C(CH3)=CHCH3 |
26.434 | CH3 | CH3 | S(O) | CH2C(CH3)=C(CH3)2 |
26.435 | CH3 | CH3 | S(O) | CH(CH3)CH=CH2 |
26.436 | CH3 | CH3 | S(O) | CH(CH3)CH=CHCH3 |
26.437 | CH3 | CH3 | S(O) | CH(CH3)CH=C(CH3)2 |
26.438 | CH3 | CH3 | S(O) | C(CH3)2CH=CH2 |
26.439 | CH3 | CH3 | S(O) | C(CH3)2CH=CHCH3 |
26.440 | CH3 | CH3 | S(O) | C(CH3)2CH=C(CH3)2 |
26.441 | CH3 | CH3 | S(O) | CH2CH=CHCl |
26.442 | CH3 | CH3 | S(O) | CH2CH=CCl2 |
化合物编号 | R6 | R7 | X | R8 |
26.443 | CH3 | CH3 | S(O) | CH2CCl=CHCl |
26.444 | CH3 | CH3 | S(O) | CH2CCl=CCl2 |
26.445 | CH3 | CH3 | S(O) | CH2CH=CF2 |
26.446 | CH3 | CH3 | S(O) | CH2CF=CF2 |
26.447 | CH3 | CH3 | S(O) | CH2C.CH |
26.448 | CH3 | CH3 | S(O) | CH2C.CCH3 |
26.449 | CH3 | CH3 | S(O) | CH2C.CCH2CH3 |
26.450 | CH3 | CH3 | S(O) | CH(CH3)C.CH |
26.451 | CH3 | CH3 | S(O) | CH(CH3)C.CCH3 |
26.452 | CH3 | CH3 | S(O) | CH(CH3)C.CCH2CH3 |
26.453 | CH3 | CH3 | S(O) | C(CH3)2C.CH |
26.454 | CH3 | CH3 | S(O) | C(CH3)2C.CCH3 |
26.455 | CH3 | CH3 | S(O) | C(CH3)2C.CCH2CH3 |
26.456 | CH3 | CH3 | S(O) | 环丙基 |
26.457 | CH3 | CH3 | S(O) | 环丁基 |
26.458 | CH3 | CH3 | S(O) | 环戊基 |
26.459 | CH3 | CH3 | S(O) | 环己基 |
26.460 | CH3 | CH3 | S(O) | CH2CF3 |
26.461 | CH3 | CH3 | S(O) | CH2CH2CF3 |
26.462 | CH3 | CH3 | S(O) | CH2-环丙基 |
26.463 | CH3 | CH3 | S(O) | CH2-环丁基 |
26.464 | CH3 | CH3 | S(O) | CH2-环戊基 |
26.465 | CH3 | CH3 | S(O) | CH2-环己基 |
26.466 | H | H | SO2 | CH3 |
26.467 | H | H | SO2 | CH2CH3 |
26.468 | H | H | SO2 | CH2CH2CH3 |
26.469 | H | H | SO2 | CH(CH3)2 |
26.470 | H | H | SO2 | CH2CH2CH2CH3 |
化合物编号 | R6 | R7 | X | R8 |
26.471 | H | H | SO2 | CH2CH(CH3)2 |
26.472 | H | H | SO2 | CH(CH3)CH2CH3 |
26.473 | H | H | SO2 | C(CH3)3 |
26.474 | H | H | SO2 | CH2CH2CH2CH2CH3 |
26.475 | H | H | SO2 | CH2CH2CH(CH3)2 |
26.476 | H | H | SO2 | CH2C(CH3)3 |
26.477 | H | H | SO2 | CH2CH(CH3)CH2CH3 |
26.478 | H | H | SO2 | CH(CH3)CH2CH2CH3 |
26.479 | H | H | SO2 | C(CH3)2CH2CH3 |
26.480 | H | H | SO2 | CH2CH=CH2 |
26.481 | H | H | SO2 | CH2CH=CHCH3 |
26.482 | H | H | SO2 | CH2CH=C(CH3)2 |
26.483 | H | H | SO2 | CH2C(CH3)=CH2 |
26.484 | H | H | SO2 | CH2C(CH3)=CHCH3 |
26.485 | H | H | SO2 | CH2C(CH3)=C(CH3)2 |
26.486 | H | H | SO2 | CH(CH3)CH=CH2 |
26.487 | H | H | SO2 | CH(CH3)CH=CHCH3 |
26.488 | H | H | SO2 | CH(CH3)CH=C(CH3)2 |
26.489 | H | H | SO2 | C(CH3)2CH=CH2 |
26.490 | H | H | SO2 | C(CH3)2CH=CHCH3 |
26.491 | H | H | SO2 | C(CH3)2CH=C(CH3)2 |
26.492 | H | H | SO2 | CH2CH=CHCl |
26.493 | H | H | SO2 | CH2CH=CCl2 |
26.494 | H | H | SO2 | CH2CCl=CHCl |
26.495 | H | H | SO2 | CH2CCl=CCl2 |
26.496 | H | H | SO2 | CH2CH=CF2 |
26.497 | H | H | SO2 | CH2CF=CF2 |
26.498 | H | H | SO2 | CH2C.CH |
化合物编号 | R6 | R7 | X | R8 |
26.499 | H | H | SO2 | CH2C.CCH3 |
26.500 | H | H | SO2 | CH2C.CCH2CH3 |
26.501 | H | H | SO2 | CH(CH3)C.CH |
26.502 | H | H | SO2 | CH(CH3)C.CCH3 |
26.503 | H | H | SO2 | CH(CH3)C.CCH2CH3 |
26.504 | H | H | SO2 | C(CH3)2C.CH |
26.505 | H | H | SO2 | C(CH3)2C.CCH3 |
26.506 | H | H | SO2 | C(CH3)2C.CCH2CH3 |
26.507 | H | H | SO2 | 环丙基 |
26.508 | H | H | SO2 | 环丁基 |
26.509 | H | H | SO2 | 环戊基 |
26.510 | H | H | SO2 | 环己基 |
26.511 | H | H | SO2 | CH2CF3 |
26.512 | H | H | SO2 | CH2CH2CF3 |
26.513 | H | H | SO2 | CH2-环丙基 |
26.514 | H | H | SO2 | CH2-环丁基 |
26.515 | H | H | SO2 | CH2-环戊基 |
26.516 | H | H | SO2 | CH2-环己基 |
26.517 | CH3 | H | SO2 | CH3 |
26.518 | CH3 | H | SO2 | CH2CH3 |
26.519 | CH3 | H | SO2 | CH2CH2CH3 |
26.520 | CH3 | H | SO2 | CH(CH3)2 |
26.521 | CH3 | H | SO2 | CH2CH2CH2CH3 |
26.522 | CH3 | H | SO2 | CH2CH(CH3)2 |
26.523 | CH3 | H | SO2 | CH(CH3)CH2CH3 |
26.524 | CH3 | H | SO2 | C(CH3)3 |
26.525 | CH3 | H | SO2 | CH2CH2CH2CH2CH3 |
26.526 | CH3 | H | SO2 | CH2CH2CH(CH3)2 |
化合物编号 | R6 | R7 | X | R8 |
26.527 | CH3 | H | SO2 | CH2C(CH3)3 |
26.528 | CH3 | H | SO2 | CH2CH(CH3)CH2CH3 |
26.529 | CH3 | H | SO2 | CH(CH3)CH2CH2CH3 |
26.530 | CH3 | H | SO2 | C(CH3)2CH2CH3 |
26.531 | CH3 | H | SO2 | CH2CH=CH2 |
26.532 | CH3 | H | SO2 | CH2CH=CHCH3 |
26.533 | CH3 | H | SO2 | CH2CH=C(CH3)2 |
26.534 | CH3 | H | SO2 | CH2C(CH3)=CH2 |
26.535 | CH3 | H | SO2 | CH2C(CH3)=CHCH3 |
26.536 | CH3 | H | SO2 | CH2C(CH3)=C(CH3)2 |
26.537 | CH3 | H | SO2 | CH(CH3)CH=CH2 |
26.538 | CH3 | H | SO2 | CH(CH3)CH=CHCH3 |
26.539 | CH3 | H | SO2 | CH(CH3)CH=C(CH3)2 |
26.540 | CH3 | H | SO2 | C(CH3)2CH=CH2 |
26.541 | CH3 | H | SO2 | C(CH3)2CH=CHCH3 |
26.542 | CH3 | H | SO2 | C(CH3)2CH=C(CH3)2 |
26.543 | CH3 | H | SO2 | CH2CH=CHCl |
26.544 | CH3 | H | SO2 | CH2CH=CCl2 |
26.545 | CH3 | H | SO2 | CH2CCl=CHCl |
26.546 | CH3 | H | SO2 | CH2CCl=CCl2 |
26.547 | CH3 | H | SO2 | CH2CH=CF2 |
26.548 | CH3 | H | SO2 | CH2CF=CF2 |
26.549 | CH3 | H | SO2 | CH2C.CH |
26.550 | CH3 | H | SO2 | CH2C.CCH3 |
26.551 | CH3 | H | SO2 | CH2C.CCH2CH3 |
26.552 | CH3 | H | SO2 | CH(CH3)C.CH |
26.553 | CH3 | H | SO2 | CH(CH3)C.CCH3 |
26.554 | CH3 | H | SO2 | CH(CH3)C.CCH2CH3 |
化合物编号 | R6 | R7 | X | R8 |
26.555 | CH3 | H | SO2 | C(CH3)2C.CH |
26.556 | CH3 | H | SO2 | C(CH3)2C.CCH3 |
26.557 | CH3 | H | SO2 | C(CH3)2C.CCH2CH3 |
26.558 | CH3 | H | SO2 | 环丙基 |
26.559 | CH3 | H | SO2 | 环丁基 |
26.560 | CH3 | H | SO2 | 环戊基 |
26.561 | CH3 | H | SO2 | 环己基 |
26.562 | CH3 | H | SO2 | CH2CF3 |
26.563 | CH3 | H | SO2 | CH2CH2CF3 |
26.564 | CH3 | H | SO2 | CH2-环丙基 |
26.565 | CH3 | H | SO2 | CH2-环丁基 |
26.566 | CH3 | H | SO2 | CH2-环戊基 |
26.567 | CH3 | H | SO2 | CH2-环己基 |
26.568 | CH3 | CH3 | SO2 | CH3 |
26.569 | CH3 | CH3 | SO2 | CH2CH3 |
26.570 | CH3 | CH3 | SO2 | CH2CH2CH3 |
26.571 | CH3 | CH3 | SO2 | CH(CH3)2 |
26.572 | CH3 | CH3 | SO2 | CH2CH2CH2CH3 |
26.573 | CH3 | CH3 | SO2 | CH2CH(CH3)2 |
26.574 | CH3 | CH3 | SO2 | CH(CH3)CH2CH3 |
26.575 | CH3 | CH3 | SO2 | C(CH3)3 |
26.576 | CH3 | CH3 | SO2 | CH2CH2CH2CH2CH3 |
26.577 | CH3 | CH3 | SO2 | CH2CH2CH(CH3)2 |
26.578 | CH3 | CH3 | SO2 | CH2C(CH3)3 |
26.579 | CH3 | CH3 | SO2 | CH2CH(CH3)CH2CH3 |
26.580 | CH3 | CH3 | SO2 | CH(CH3)CH2CH2CH3 |
26.581 | CH3 | CH3 | SO2 | C(CH3)2CH2CH3 |
26.582 | CH3 | CH3 | SO2 | CH2CH=CH2 |
化合物编号 | R6 | R7 | X | R8 |
26.583 | CH3 | CH3 | SO2 | CH2CH=CHCH3 |
26.584 | CH3 | CH3 | SO2 | CH2CH=C(CH3)2 |
26.585 | CH3 | CH3 | SO2 | CH2C(CH3)=CH2 |
26.586 | CH3 | CH3 | SO2 | CH2C(CH3)=CHCH3 |
26.587 | CH3 | CH3 | SO2 | CH2C(CH3)=C(CH3)2 |
26.588 | CH3 | CH3 | SO2 | CH(CH3)CH=CH2 |
26.589 | CH3 | CH3 | SO2 | CH(CH3)CH=CHCH3 |
26.590 | CH3 | CH3 | SO2 | CH(CH3)CH=C(CH3)2 |
26.591 | CH3 | CH3 | SO2 | C(CH3)2CH=CH2 |
26.592 | CH3 | CH3 | SO2 | C(CH3)2CH=CHCH3 |
26.593 | CH3 | CH3 | SO2 | C(CH3)2CH=C(CH3)2 |
26.594 | CH3 | CH3 | SO2 | CH2CH=CHCl |
26.595 | CH3 | CH3 | SO2 | CH2CH=CCl2 |
26.596 | CH3 | CH3 | SO2 | CH2CCl=CHCl |
26.597 | CH3 | CH3 | SO2 | CH2CCl=CCl2 |
26.598 | CH3 | CH3 | SO2 | CH2CH=CF2 |
26.599 | CH3 | CH3 | SO2 | CH2CF=CF2 |
26.600 | CH3 | CH3 | SO2 | CH2C.CH |
26.601 | CH3 | CH3 | SO2 | CH2C.CCH3 |
26.602 | CH3 | CH3 | SO2 | CH2C.CCH2CH3 |
26.603 | CH3 | CH3 | SO2 | CH(CH3)C.CH |
26.604 | CH3 | CH3 | SO2 | CH(CH3)C.CCH3 |
26.605 | CH3 | CH3 | SO2 | CH(CH3)C.CCH2CH3 |
26.606 | CH3 | CH3 | SO2 | C(CH3)2C.CH |
26.607 | CH3 | CH3 | SO2 | C(CH3)2C.CCH3 |
26.608 | CH3 | CH3 | SO2 | C(CH3)2C.CCH2CH3 |
26.609 | CH3 | CH3 | SO2 | 环丙基 |
26.610 | CH3 | CH3 | SO2 | 环丁基 |
化合物编号 | R6 | R7 | X | R8 |
26.611 | CH3 | CH3 | SO2 | 环戊基 |
26.612 | CH3 | CH3 | SO2 | 环己基 |
26.613 | CH3 | CH3 | SO2 | CH2CF3 |
26.614 | CH3 | CH3 | SO2 | CH2CH2CF3 |
26.615 | CH3 | CH3 | SO2 | CH2-环丙基 |
26.616 | CH3 | CH3 | SO2 | CH2-环丁基 |
26.617 | CH3 | CH3 | SO2 | CH2-环戊基 |
26.618 | CH3 | CH3 | SO2 | CH2-环己基 |
表27:
本表包含下述类型的618个化合物,
其中X、R6、R7和R8如表26所定义。
表28:
本表包含下述类型的618个化合物,
其中X、R6、R7和R8如表26所定义。
表29:
本表包含下述类型的618个化合物,
其中X、R6、R7和R8如表26所定义。
表30:
本表包含下述类型的618个化合物,
其中X、R6、R7和R8如表26所定义。
表31:
本表包含下述类型的618个化合物,
其中X、R6、R7和R8如表26所定义。
表32:
本表包含下述类型的618个化合物,
其中X、R6、R7和R8如表26所定义。
表33:
本表包含下述类型的618个化合物,
其中X、R6、R7和R8如表26所定义。
表34:
本表包含下述类型的618个化合物,
其中X、R6、R7和R8如表26所定义。
表35:
本表包含下述类型的618个化合物,
其中X、R6、R7和R8如表26所定义。
表36:
本表包含下述类型的618个化合物,
其中X、R6、R7和R8如表26所定义。
表37:
本表包含下述类型的618个化合物,
其中X、R6、R7和R8如表26所定义。
表38:
本表包含下述类型的618个化合物,
其中X、R6、R7和R8如表26所定义。
表39:
本表包含下述类型的618个化合物,
其中X、R6、R7和R8如表26所定义。
表40:
本表包含下述类型的618个化合物,
其中X、R6、R7和R8如表26所定义。
表41:
本表包含下述类型的618个化合物,
其中X、R6、R7和R8如表26所定义。
表42:
本表包含下述类型的618个化合物,
其中X、R6、R7和R8如表26所定义。
表43:
本表包含下述类型的618个化合物,
其中X、R6、R7和R8如表26所定义。
表44:
本表包含下述类型的618个化合物,
其中X、R6、R7和R8如表26所定义。
表45:
本表包含下述类型的618个化合物,
其中X、R6、R7和R8如表26所定义。
表46:
本表包含下述类型的618个化合物,
其中X、R6、R7和R8如表26所定义。
表47:
本表包含下述类型的618个化合物,
其中X、R6、R7和R8如表26所定义。
表48:
本表包含下述类型的618个化合物,
其中X、R6、R7和R8如表26所定义。
表49:
本表包含下述类型的618个化合物,
其中X、R6、R7和R8如表26所定义。
表50:
本表包含下述类型的618个化合物,
其中X、R6、R7和R8如表26所定义。
表51:
本表包含下述类型的220个化合物,
其中X和R4定义如下:
化合物编号 | X | R8 |
51.1 | O | CH3 |
51.2 | O | CH2CH3 |
51.3 | O | CH2CH2CH3 |
51.4 | O | CH(CH3)2 |
51.5 | O | CH2CH2CH2CH3 |
51.6 | O | CH2CH(CH3)2 |
51.7 | O | CH(CH3)CH2CH3 |
51.8 | O | C(CH3)3 |
化合物编号 | X | R8 |
51.9 | O | CH2CH2CH2CH2CH3 |
51.10 | O | CH2CH2CH(CH3)2 |
51.11 | O | CH2C(CH3)3 |
51.12 | O | CH2CH(CH3)CH2CH3 |
51.13 | O | CH(CH3)CH2CH2CH3 |
51.14 | O | C(CH3)2CH2CH3 |
51.15 | O | CH2CH=CH2 |
51.16 | O | CH2CH=CHCH3 |
51.17 | O | CH2CH=C(CH3)2 |
51.18 | O | CH2C(CH3)=CH2 |
51.19 | O | CH2C(CH3)=CHCH3 |
51.20 | O | CH2C(CH3)=C(CH3)2 |
51.21 | O | CH(CH3)CH=CH2 |
51.22 | O | CH(CH3)CH=CHCH3 |
51.23 | O | CH(CH3)CH=C(CH3)2 |
51.24 | O | C(CH3)2CH=CH2 |
51.25 | O | C(CH3)2CH=CHCH3 |
51.26 | O | C(CH3)2CH=C(CH3)2 |
51.27 | O | CH2CH=CHCl |
51.28 | O | CH2CH=CCl2 |
51.29 | O | CH2CCl=CHCl |
51.30 | O | CH2CCl=CCl2 |
51.31 | O | CH2CH=CF2 |
51.32 | O | CH2CF=CF2 |
51.33 | O | CH2C.CH |
51.34 | O | CH2C.CCH3 |
51.35 | O | CH2C.CCH2CH3 |
51.36 | O | CH(CH3)C.CH |
化合物编号 | X | R8 |
51.37 | O | CH(CH3)C.CCH3 |
51.38 | O | CH(CH3)C.CCH2CH3 |
51.39 | O | C(CH3)2C.CH |
51.40 | O | C(CH3)2C.CCH3 |
51.41 | O | C(CH3)2C.CCH2CH3 |
51.42 | O | 环丙基 |
51.43 | O | 环丁基 |
51.44 | O | 环戊基 |
51.45 | O | 环己基 |
51.46 | O | CH2CF3 |
51.47 | O | CH2CH2CF3 |
51.48 | O | CH2-环丙基 |
51.49 | O | CH2-环丁基 |
51.50 | O | CH2-环戊基 |
51.51 | O | CH2-环己基 |
51.52 | O | CH2OCH3 |
51.53 | O | CH2OCH2CH3 |
51.54 | O | CH2CH2OCH3 |
51.55 | O | CH2CH2OCH2CH3 |
51.56 | S | CH3 |
51.57 | S | CH2CH3 |
51.58 | S | CH2CH2CH3 |
51.59 | S | CH(CH3)2 |
51.60 | S | CH2CH2CH2CH3 |
51.61 | S | CH2CH(CH3)2 |
51.62 | S | CH(CH3)CH2CH3 |
51.63 | S | C(CH3)3 |
51.64 | S | CH2CH2CH2CH2CH3 |
化合物编号 | X | R8 |
51.65 | S | CH2CH2CH(CH3)2 |
51.66 | S | CH2C(CH3)3 |
51.67 | S | CH2CH(CH3)CH2CH3 |
51.68 | S | CH(CH3)CH2CH2CH3 |
51.69 | S | C(CH3)2CH2CH3 |
51.70 | S | CH2CH=CH2 |
51.71 | S | CH2CH=CHCH3 |
51.72 | S | CH2CH=C(CH3)2 |
51.73 | S | CH2C(CH3)=CH2 |
51.74 | S | CH2C(CH3)=CHCH3 |
51.75 | S | CH2C(CH3)=C(CH3)2 |
51.76 | S | CH(CH3)CH=CH2 |
51.77 | S | CH(CH3)CH=CHCH3 |
51.78 | S | CH(CH3)CH=C(CH3)2 |
51.79 | S | C(CH3)2CH=CH2 |
51.80 | S | C(CH3)2CH=CHCH3 |
51.81 | S | C(CH3)2CH=C(CH3)2 |
51.82 | S | CH2CH=CHCl |
51.83 | S | CH2CH=CCl2 |
51.84 | S | CH2CCl=CHCl |
51.85 | S | CH2CCl=CCl2 |
51.86 | S | CH2CH=CF2 |
51.87 | S | CH2CF=CF2 |
51.88 | S | CH2C.CH |
51.89 | S | CH2C.CCH3 |
51.90 | S | CH2C.CCH2CH3 |
51.91 | S | CH(CH3)C.CH |
51.92 | S | CH(CH3)C.CCH3 |
化合物编号 | X | R8 |
51.93 | S | CH(CH3)C.CCH2CH3 |
51.94 | S | C(CH3)2C.CH |
51.95 | S | C(CH3)2C.CCH3 |
51.96 | S | C(CH3)2C.CCH2CH3 |
51.97 | S | 环丙基 |
51.98 | S | 环丁基 |
51.99 | S | 环戊基 |
51.100 | S | 环己基 |
51.101 | S | CH2CF3 |
51.102 | S | CH2CH2CF3 |
51.103 | S | CH2-环丙基 |
51.104 | S | CH2-环丁基 |
51.105 | S | CH2-环戊基 |
51.106 | S | CH2-环己基 |
51.107 | S | CH2OCH3 |
51.108 | S | CH2OCH2CH3 |
51.109 | S | CH2CH2OCH3 |
51.110 | S | CH2CH2OCH2CH3 |
51.111 | S(O) | CH3 |
51.112 | S(O) | CH2CH3 |
51.113 | S(O) | CH2CH2CH3 |
51.114 | S(O) | CH(CH3)2 |
51.115 | S(O) | CH2CH2CH2CH3 |
51.116 | S(O) | CH2CH(CH3)2 |
51.117 | S(O) | CH(CH3)CH2CH3 |
51.118 | S(O) | C(CH3)3 |
51.119 | S(O) | CH2CH2CH2CH2CH3 |
51.120 | S(O) | CH2CH2CH(CH3)2 |
化合物编号 | X | R8 |
51.121 | S(O) | CH2C(CH3)3 |
51.122 | S(O) | CH2CH(CH3)CH2CH3 |
51.123 | S(O) | CH(CH3)CH2CH2CH3 |
51.124 | S(O) | C(CH3)2CH2CH3 |
51.125 | S(O) | CH2CH=CH2 |
51.126 | S(O) | CH2CH=CHCH3 |
51.127 | S(O) | CH2CH=C(CH3)2 |
51.128 | S(O) | CH2C(CH3)=CH2 |
51.129 | S(O) | CH2C(CH3)=CHCH3 |
51.130 | S(O) | CH2C(CH3)=C(CH3)2 |
51.131 | S(O) | CH(CH3)CH=CH2 |
51.132 | S(O) | CH(CH3)CH=CHCH3 |
51.133 | S(O) | CH(CH3)CH=C(CH3)2 |
51.134 | S(O) | C(CH3)2CH=CH2 |
51.135 | S(O) | C(CH3)2CH=CHCH3 |
51.136 | S(O) | C(CH3)2CH=C(CH3)2 |
51.137 | S(O) | CH2CH=CHCl |
51.138 | S(O) | CH2CH=CCl2 |
51.139 | S(O) | CH2CCl=CHCl |
51.140 | S(O) | CH2CCl=CCl2 |
51.141 | S(O) | CH2CH=CF2 |
51.142 | S(O) | CH2CF=CF2 |
51.143 | S(O) | CH2C.CH |
51.144 | S(O) | CH2C.CCH3 |
51.145 | S(O) | CH2C.CCH2CH3 |
51.146 | S(O) | CH(CH3)C.CH |
51.147 | S(O) | CH(CH3)C.CCH3 |
51.148 | S(O) | CH(CH3)C.CCH2CH3 |
化合物编号 | X | R8 |
51.149 | S(O) | C(CH3)2C.CH |
51.150 | S(O) | C(CH3)2C.CCH3 |
51.151 | S(O) | C(CH3)2C.CCH2CH3 |
51.152 | S(O) | 环丙基 |
51.153 | S(O) | 环丁基 |
51.154 | S(O) | 环戊基 |
51.155 | S(O) | 环己基 |
51.156 | S(O) | CH2CF3 |
51.157 | S(O) | CH2CH2CF3 |
51.158 | S(O) | CH2-环丙基 |
51.159 | S(O) | CH2-环丁基 |
51.160 | S(O) | CH2-环戊基 |
51.161 | S(O) | CH2-环己基 |
51.162 | S(O) | CH2OCH3 |
51.163 | S(O) | CH2OCH2CH3 |
51.164 | S(O) | CH2CH2OCH3 |
51.165 | S(O) | CH2CH2OCH2CH3 |
51.166 | SO2 | CH3 |
51.167 | SO2 | CH2CH3 |
51.168 | SO2 | CH2CH2CH3 |
51.169 | SO2 | CH(CH3)2 |
51.170 | SO2 | CH2CH2CH2CH3 |
51.171 | SO2 | CH2CH(CH3)2 |
51.172 | SO2 | CH(CH3)CH2CH3 |
51.173 | SO2 | C(CH3)3 |
51.174 | SO2 | CH2CH2CH2CH2CH3 |
51.175 | SO2 | CH2CH2CH(CH3)2 |
51.176 | SO2 | CH2C(CH3)3 |
化合物编号 | X | R8 |
51.177 | SO2 | CH2CH(CH3)CH2CH3 |
51.178 | SO2 | CH(CH3)CH2CH2CH3 |
51.179 | SO2 | C(CH3)2CH2CH3 |
51.180 | SO2 | CH2CH=CH2 |
51.181 | SO2 | CH2CH=CHCH3 |
51.182 | SO2 | CH2CH=C(CH3)2 |
51.183 | SO2 | CH2C(CH3)=CH2 |
51.184 | SO2 | CH2C(CH3)=CHCH3 |
51.185 | SO2 | CH2C(CH3)=C(CH3)2 |
51.186 | SO2 | CH(CH3)CH=CH2 |
51.187 | SO2 | CH(CH3)CH=CHCH3 |
51.188 | SO2 | CH(CH3)CH=C(CH3)2 |
51.189 | SO2 | C(CH3)2CH=CH2 |
51.190 | SO2 | C(CH3)2CH=CHCH3 |
51.191 | SO2 | C(CH3)2CH=C(CH3)2 |
51.192 | SO2 | CH2CH=CHCl |
51.193 | SO2 | CH2CH=CCl2 |
51.194 | SO2 | CH2CCl=CHCl |
51.195 | SO2 | CH2CCl=CCl2 |
51.196 | SO2 | CH2CH=CF2 |
51.197 | SO2 | CH2CF=CF2 |
51.198 | SO2 | CH2C.CH |
51.199 | SO2 | CH2C.CCH3 |
51.200 | SO2 | CH2C.CCH2CH3 |
51.201 | SO2 | CH(CH3)C.CH |
51.202 | SO2 | CH(CH3)C.CCH3 |
51.203 | SO2 | CH(CH3)C.CCH2CH3 |
51.204 | SO2 | C(CH3)2C.CH |
化合物编号 | X | R8 |
51.205 | SO2 | C(CH3)2C.CCH3 |
51.206 | SO2 | C(CH3)2C.CCH2CH3 |
51.207 | SO2 | 环丙基 |
51.208 | SO2 | 环丁基 |
51.209 | SO2 | 环戊基 |
51.210 | SO2 | 环己基 |
51.211 | SO2 | CH2CF3 |
51.212 | SO2 | CH2CH2CF3 |
51.213 | SO2 | CH2-环丙基 |
51.214 | SO2 | CH2-环丁基 |
51.215 | SO2 | CH2-环戊基 |
51.216 | SO2 | CH2-环己基 |
51.217 | SO2 | CH2OCH3 |
51.218 | SO2 | CH2OCH2CH3 |
51.219 | SO2 | CH2CH2OCH3 |
51.220 | SO2 | CH2CH2OCH2CH3 |
表52:
本表包含下述类型的220个化合物,
其中X和R8如表51所定义。
表53:
本表包含下述类型的220个化合物,
其中X和R8如表51所定义。
表54:
本表包含下述类型的220个化合物,
其中X和R8如表51所定义。
表55:
本表包含下述类型的220个化合物,
其中X和R8如表51所定义。
表56:
本表包含下述类型的220个化合物,
其中X和R8如表51所定义。
表57:
本表包含下述类型的220个化合物,
其中X和R8如表51所定义。
表58:
本表包含下述类型的220个化合物,
其中X和R8如表51所定义。
表59:
本表包含下述类型的220个化合物,
其中X和R8如表51所定义。
表60:
本表包含下述类型的220个化合物,
其中X和R8如表51所定义。
表61:
本表包含下述类型的220个化合物,
其中X和R8如表51所定义。
表62:
本表包含下述类型的220个化合物,
其中X和R8如表51所定义。
表63:
本表包含下述类型的220个化合物,
其中X和R8如表51所定义。
表64:
本表包含下述类型的220个化合物,
其中X和R8如表51所定义。
表65:
本表包含下述类型的220个化合物,
其中X和R8如表51所定义。
表66:
本表包含下述类型的220个化合物,
其中X和R8如表51所定义。
表67:
本表包含下述类型的220个化合物,
其中X和R8如表51所定义。
表68:
本表包含下述类型的220个化合物,
其中X和R8如表51所定义。
表69:
本表包含下述类型的220个化合物,
其中X和R8如表51所定义。
表70:
本表包含下述类型的220个化合物,
其中X和R8如表51所定义。
表71:
本表包含下述类型的220个化合物,
其中X和R8如表51所定义。
表72:
本表包含下述类型的220个化合物,
其中X和R8如表51所定义。
表73:
本表包含下述类型的220个化合物,
其中X和R8如表51所定义。
表74:
本表包含下述类型的220个化合物,
其中X和R8如表51所定义。
表75:
本表包含下述类型的220个化合物,
其中X和R8如表51所定义。
表76:
本表包含下述类型的12个化合物
其中n、X、R5、R6、R7和R8定义如下:
化合物编号 | n | X | R5 | R6 | R7 | R8 |
76.1 | 1 | O | CH2 | H | H | CH2 |
76.2 | 1 | O | CH2CH2 | H | H | CH2 |
76.3 | 2 | O | CH2 | H | H | CH2 |
76.4 | 1 | S | CH2 | H | H | CH2 |
76.5 | 1 | S | CH2CH2 | H | H | CH2 |
76.6 | 2 | S | CH2 | H | H | CH2 |
76.7 | 1 | S(O) | CH2 | H | H | CH2 |
76.8 | 1 | S(O) | CH2CH2 | H | H | CH2 |
76.9 | 2 | S(O) | CH2 | H | H | CH2 |
76.10 | 1 | SO2 | CH2 | H | H | CH2 |
76.11 | 1 | SO2 | CH2CH2 | H | H | CH2 |
76.12 | 2 | SO2 | CH2 | H | H | CH2 |
表77:
本表包含下述类型的12个化合物
其中n、X、R5、R6、R7和R8如表76所定义。
表78:
本表包含下述类型的12个化合物
其中n、X、R5、R6、R7和R8如表76所定义。
表79:
本表包含下述类型的12个化合物
其中n、X、R5、R6、R7和R8如表76所定义。
表80:
本表包含下述类型的12个化合物
其中n、X、R5、R6、R7和R8如表76所定义。
表81:
本表包含下述类型的12个化合物
其中n、X、R5、R6、R7和R8如表76所定义。
表82:
本表包含下述类型的12个化合物
其中n、X、R5、R6、R7和R8如表76所定义。
表83:
本表包含下述类型的12个化合物
其中n、X、R5、R6、R7和R8如表76所定义。
表84:
本表包含下述类型的12个化合物
其中n、X、R5、R6、R7和R8如表76所定义。
表85:
本表包含下述类型的12个化合物
其中n、X、R5、R6、R7和R8如表76所定义。
表86:
本表包含下述类型的12个化合物
其中n、X、R5、R6、R7和R8如表76所定义。
表87:
本表包含下述类型的12个化合物
其中n、X、R5、R6、R7和R8如表76所定义。
表88:
本表包含下述类型的12个化合物
其中n、X、R5、R6、R7和R8如表76所定义。
表89:
本表包含下述类型的12个化合物
其中n、X、R5、R6、R7和R8如表76所定义。
表90:
本表包含下述类型的12个化合物
其中n、X、R5、R6、R7和R8如表76所定义。
表91:
本表包含下述类型的12个化合物
其中n、X、R5、R6、R7和R8如表76所定义。
表92:
本表包含下述类型的12个化合物
其中n、X、R5、R6、R7和R8如表76所定义。
表93:
本表包含下述类型的12个化合物
其中n、X、R5、R6、R7和R8如表76所定义。
表94:
本表包含下述类型的12个化合物
其中n、X、R5、R6、R7和R8如表76所定义。
表95:
本表包含下述类型的12个化合物
其中n、X、R5、R6、R7和R8如表76所定义。
表96:
本表包含下述类型的12个化合物
其中n、X、R5、R6、R7和R8如表76所定义。
表97:
本表包含下述类型的12个化合物
其中n、X、R5、R6、R7和R8如表76所定义。
表98:
本表包含下述类型的12个化合物
其中n、X、R5、R6、R7和R8如表76所定义。
表99:
本表包含下述类型的12个化合物
其中n、X、R5、R6、R7和R8如表76所定义。
表100:
本表包含下述类型的12个化合物
其中n、X、R5、R6、R7和R8如表76所定义。
表101:
本表包含下述类型的12个化合物
其中X、R6、R7和R8定义如下:
化合物编号 | X | R6 | R7 | R8 |
101.1 | O | CH2 | H | CH2 |
101.2 | O | CH2CH2 | H | CH2 |
101.3 | O | CH2CH2 | H | CH2CH2 |
101.4 | S | CH2 | H | CH2 |
101.5 | S | CH2CH2 | H | CH2 |
101.6 | S | CH2CH2 | H | CH2CH2 |
101.7 | S(O) | CH2 | H | CH2 |
101.8 | S(O) | CH2CH2 | H | CH2 |
101.9 | S(O) | CH2CH2 | H | CH2CH2 |
101.10 | SO2 | CH2 | H | CH2 |
101.11 | SO2 | CH2CH2 | H | CH2 |
101.12 | SO2 | CH2CH2 | H | CH2CH2 |
表102:
本表包含下述类型的12个化合物
其中X、R6、R7和R8如表101所定义。
表103:
本表包含下述类型的12个化合物
其中X、R6、R7和R8如表101所定义。
表104:
本表包含下述类型的12个化合物
其中X、R6、R7和R8如表101所定义。
表105:
本表包含下述类型的12个化合物
其中X、R6、R7和R8如表101所定义。
表106:
本表包含下述类型的12个化合物
其中X、R6、R7和R8如表101所定义。
表107:
本表包含下述类型的12个化合物
其中X、R6、R7和R8如表101所定义。
表108:
本表包含下述类型的12个化合物
其中X、R6、R7和R8如表101所定义。
表109:
本表包含下述类型的12个化合物
其中X、R6、R7和R8如表101所定义。
表110
本表包含下述类型的12个化合物
其中X、R6、R7和R8如表101所定义。
表111:
本表包含下述类型的12个化合物
其中X、R6、R7和R8如表101所定义。
表112:
本表包含下述类型的12个化合物
其中X、R6、R7和R8如表101所定义。
表113:
本表包含下述类型的12个化合物
其中X、R6、R7和R8如表101所定义。
表114:
本表包含下述类型的12个化合物
其中X、R6、R7和R8如表101所定义。
表115:
本表包含下述类型的12个化合物
其中X、R6、R7和R8如表101所定义。
表116:
本表包含下述类型的12个化合物
其中X、R6、R7和R8如表101所定义。
表117:
本表包含下述类型的12个化合物
其中X、R6、R7和R8如表101所定义。
表118:
本表包含下述类型的12个化合物
其中X、R6、R7和R8如表101所定义。
表119:
本表包含下述类型的12个化合物
其中X、R6、R7和R8如表101所定义。
表120:
本表包含下述类型的12个化合物
其中X、R6、R7和R8如表101所定义。
表121:
本表包含下述类型的12个化合物
其中X、R6、R7和R8如表101所定义。
表122:
本表包含下述类型的12个化合物
其中X、R6、R7和R8如表101所定义。
表123:
本表包含下述类型的12个化合物
其中X、R6、R7和R8如表101所定义。
表124:
本表包含下述类型的12个化合物
其中X、R6、R7和R8如表101所定义。
表125:
本表包含下述类型的12个化合物
其中X、R6、R7和R8如表101所定义。
表126:
本表包含下述类型的16个化合物
其中X和R8定义如下:
化合物编号 | X | R8 |
126.1 | O | CH3 |
126.2 | O | CH2CH3 |
126.3 | O | CH(CH3)2 |
126.4 | O | CF3 |
126.5 | S | CH3 |
126.6 | S | CH2CH3 |
126.7 | S | CH(CH3)2 |
化合物编号 | X | R8 |
126.8 | S | CF3 |
126.9 | S(O) | CH3 |
126.10 | S(O) | CH2CH3 |
126.11 | S(O) | CH(CH3)2 |
126.12 | S(O) | CF3 |
126.13 | SO2 | CH3 |
126.14 | SO2 | CH2CH3 |
126.15 | SO2 | CH(CH3)2 |
126.16 | SO2 | CF3 |
表127
本表包含下述类型的16个化合物
其中n和R8如表126所定义。
表128
本表包含下述类型的16个化合物
其中n和R8如表126所定义。
表129
本表包含下述类型的16个化合物
其中n和R8如表126所定义。
表130
本表包含下述类型的16个化合物
其中n和R8如表126所定义。
表131
本表包含下述类型的16个化合物
其中n和R8如表126所定义。
表132
本表包含下述类型的16个化合物
其中n和R8如表126所定义。
表133
本表包含下述类型的16个化合物
其中n和R8如表126所定义。
表134
本表包含下述类型的16个化合物
其中n和R8如表126所定义。
表135
本表包含下述类型的16个化合物
其中n和R8如表126所定义。
表136
本表包含下述类型的16个化合物
其中n和R8如表126所定义。
表137
本表包含下述类型的16个化合物
其中n和R8如表126所定义。
表138
本表包含下述类型的16个化合物
其中n和R8如表126所定义。
表139
本表包含下述类型的16个化合物
其中n和R8如表126所定义。
表140
本表包含下述类型的16个化合物
其中n和R8如表126所定义。
表141
本表包含下述类型的16个化合物
其中n和R8如表126所定义。
表142
本表包含下述类型的16个化合物
其中n和R8如表126所定义。
表143
本表包含下述类型的16个化合物
其中n和R8如表126所定义。
表144
本表包含下述类型的16个化合物
其中n和R8如表126所定义。
表145
本表包含下述类型的16个化合物
其中n和R8如表126所定义。
表146
本表包含下述类型的16个化合物
其中n和R8如表126所定义。
表147
本表包含下述类型的16个化合物
其中n和R8如表126所定义。
表148
本表包含下述类型的16个化合物
其中n和R8如表126所定义。
表149
本表包含下述类型的16个化合物
其中n和R8如表126所定义。
表150
本表包含下述类型的16个化合物
其中n和R8如表126所定义。
表151
本表包含下述类型的16个化合物
其中n和R8如表126所定义。
实施例7
制备9-(2,6-二乙基-4-甲基苯基)-10-氧代-3-氧杂螺[5.5]十
一-8-烯基3,3-二甲基丁酸酯(化合物编号P6,表T2)
将叔丁基乙酰氯(0.049g,0.36mmol)的二氯甲烷(2ml)溶液滴加至9-(2,6-二乙基-4-甲基苯基)-3-氧杂螺[5.5]十一烷-8,10-二酮(0.10g,0.3mmol)和三乙胺(0.036g,0.36mmol)的二氯甲烷(2ml)溶液,反应混合物在室温下搅拌过夜。混合物用饱和碳酸氢钠水溶液洗涤,真空蒸发溶剂。残余物进一步通过柱色谱法在硅胶上纯化,给出希望的产物。
δH(CDCl3)6.87(s,2H),3.75(m,4H),2.78(s 2H),2.64(s,2H),2.33(m,4H),2.28(s,3H),1.74(m,4H),1.07(t,6H),0.79(s,9H)
实施例8
制备9-(2,6-二乙基-4-甲基苯基)-10-丙-2-炔氧基-3-氧杂螺
[5.5]十一-9-烯-8-酮(化合物编号P31,表T2)
将炔丙基溴(0.043g,0.36mmol)的丙酮(2ml)溶液滴加至9-(2,6-二乙基-4-甲基苯基)-3-氧杂螺[5.5]十一烷-8,10-二酮(0.10g,0.3mmol)和碳酸钾(0.05g,0.36mmol)在丙酮(3ml)中的混合物,反应回流过夜。溶剂真空蒸发,残余物溶于乙酸乙酯,用2N氢氧化钠水溶液洗涤。有机相真空浓缩,残余物通过柱色谱法在硅胶上进一步纯化,给出希望的化合物,是无色胶状物。
δH(CDCl3)6.92(s,2H),4.50(s,2H),3.76(t,4H),2.85(s,2H),2.60(s,2H),2.56(t,1H),2.32(m,7H),1.74(t,4H),1.07(t,6H)
表T2中的其它化合物可以通过类似方法使用合适的原料制得。
表T2
重要中间体的实验方法。
实施例1A
制备2,6-二乙基-4-甲基苯基硼酸
向于-78℃的25g(110mmol)2,6-二乙基-4-甲基溴苯(按WO2000078712的描述制备)的240ml四氢呋喃溶液中在10分钟内滴加~1.6M丁基锂的己烷(75ml,120mmol)溶液。在-78℃下搅拌混合物10分钟,然后一次加入硼酸三甲酯(24.6ml,22.9g;220mmol),在-78℃下继续搅拌30分钟。除去冷却浴,在1小时内将溶液温热至室温,用2N盐酸水溶液(140ml)淬灭。
分离有机层,水相用1∶1的二乙醚∶己烷萃取三次。合并有机萃取物,在无水硫酸钠上干燥,过滤,真空浓缩滤液。将油状残余物在搅拌下溶于己烷,通过过滤收集白色固体,给出2,6-二乙基-4-甲基苯基硼酸。浓缩滤液,通过柱色谱法在硅胶上纯化,给出更多量的希望的产物。获得16.6g(78%)合并收率的2,6-二乙基-4-甲基苯基硼酸。
实施例1B
制备5-(4-氯苯基)-2-甲基苯基硼酸
步骤1
将4-氯苯基硼酸(20.2g,0.13mol)和四(三苯基膦)钯(0)(3.7g,0.003mol)加至5-溴-2-甲基苯胺(20g,0.1mol)的1,2-二甲氧基乙烷(200ml)溶液。在20℃搅拌反应混合物15分钟后,将20%碳酸钠水溶液(300ml)加至混合物,在回流所得混合物24小时。将反应混合物冷却至室温,用(600ml)水稀释,用乙酸乙酯萃取。合并的有机萃取物在无水硫酸钠上干燥,过滤,真空蒸发滤液。进一步通过柱色谱法在硅胶上纯化残余物,用7%的乙酸乙酯/己烷洗脱,给出5-(4-氯苯基)-2-甲基苯胺(21.0g)。
步骤2
将氢溴酸(48%重量水溶液,120ml)滴加至5-(4-氯苯基)-2-甲基苯胺(21g,0.09mol)的水(80ml)悬浮液,搅拌混合物直到固体溶解。将混合物冷却至-5℃,滴加亚硝酸钠(10.12g,0.14mol)水溶液(50ml),保持温度为0-5℃。搅拌反应混合物1小时,随后加至0℃的预先冷却的溴化亚铜(17.9g,0.12mol)的氢溴酸(48%重量水溶液,120ml)溶液。搅拌反应混合物,使其温热至室温过夜。混合物用乙酸乙酯萃取,合并有机萃取物,在无水硫酸钠上干燥,过滤,真空浓缩滤液。进一步通过柱色谱法在硅胶上纯化残余物,用2%乙酸乙酯/己烷洗脱,给出5-(4-氯苯基)-2-甲基-1-溴苯(15.0g)。
步骤3
将5-(4-氯苯基)-2-甲基-1-溴苯(5.0g,0.02mol)溶于THF(125ml),将温度调为-78℃。在30分钟内滴加正丁基锂(1.33摩尔每升的己烷溶液,17.3ml),保持温度为大约-78℃。反应混合物在-78℃下搅拌1.5小时,然后滴加硼酸三甲酯(2.58g,0.024mol),搅拌反应混合物3.5小时,将之温热至0℃。然后滴加2N盐酸水溶液(50ml),滴加完成之后混合物搅拌2小时。真空浓缩混合物除去大部分四氢呋喃,接着用水(~80ml)稀释并用乙醚萃取。合并有机萃取物,在无水硫酸钠上干燥,过滤,真空浓缩滤液。通过快速柱色谱法在硅胶上进一步纯化残余物,用7%乙酸乙酯/己烷洗脱,给出5-(4-氯苯基)-2-甲基苯基硼酸(2.5g)。
实施例1C
制备5-(4-氯苯基)-2-乙基苯基硼酸
步骤1
将硝酸铵(39.6g,0.49mol)分批加至冷却的(冰浴)4-乙基苯胺(20g,0.16mol)的浓硫酸(100ml)溶液,通过外部冷却保持温度为-10℃至0℃。搅拌反应混合物2小时,倾至碎冰上,通过过滤收集沉淀。用水分散固体,加入稀氢氧化钠水溶液中和溶液,用乙酸乙酯萃取。合并有机萃取物,在无水硫酸钠上干燥,过滤,真空浓缩滤液,给出4-乙基-3-硝基苯胺(20g)。
步骤2
将氢溴酸(48%重量水溶液,240ml)滴加至4-乙基-3-硝基苯胺(20g,0.12mol)的水(80ml)悬浮液,搅拌混合物直至固体溶解。将混合物冷却至-5℃,滴加亚硝酸钠(19.8g,0.28mol)水溶液(100ml),保持温度为0至5℃。一旦完成加入,除去冷却浴,在室温下搅拌反应混合物1小时。将混合物滴加至0℃的预先冷却的溴化亚铜(22.4g,0.16mol)的氢溴酸(48%重量水溶液)溶液。搅拌反应混合物并使其在3小时内温热至室温。用乙醚萃取混合物,合并有机萃取物,在无水硫酸钠上干燥,过滤,真空浓缩滤液。通过柱色谱法在硅胶上进一步纯化残余物,用己烷洗脱,给出4-溴-1-乙基-2-硝基苯(18g)。
步骤3
将氯化铵(12.5g,0.2mol)的水(30ml)溶液加至锌粉(35.7g,0.5mol)和4-溴-1-乙基-2-硝基苯(18g,0.07mol)在甲醇(720ml)和水(180ml)中的混合物。反应混合物回流1小时,然后冷却至室温,通过硅藻土塞过滤。真空浓缩混合物,然后用水稀释,用乙酸乙酯萃取。合并的有机萃取物用水和盐水洗涤,在无水硫酸钠上干燥,过滤,真空浓缩滤液,产生5-溴-2-乙基苯胺(14g),不加进一步纯化用于后续步骤。
步骤4
将4-氯苯基硼酸(13.2g,0.08mol)和四(三苯基膦)钯(0)(2.4g,0.002mol)加至5-溴-2-乙基苯胺(14.1g,0.07mol)的1,2-二甲氧基乙烷(140ml)溶液。在20℃搅拌反应混合物15分钟后,将20%碳酸钠水溶液(300ml)加至混合物,在回流下加热所得混合物24小时。将反应混合物冷却至室温,用水稀释,用乙酸乙酯萃取。合并的有机萃取物在无水硫酸钠上干燥,过滤,真空蒸发滤液。残余物通过柱色谱法在硅胶上进一步纯化,用5%的乙酸乙酯/己烷洗脱,给出5-(4-氯苯基)-2-乙基苯胺(14.3g)。
步骤5
将氢溴酸(48%重量水溶液,85ml)滴加至5-(4-氯苯基)-2-乙基苯胺(14.3g,0.062mol)的水(57ml)悬浮液,搅拌混合物。将混合物冷却至-5℃,滴加亚硝酸钠(5.07g,0.072mol)水溶液(25ml),保持温度为0-5℃。搅拌反应混合物1小时,随后加至0℃的预先冷却的溴化亚铜(9g,0.062mol)的氢溴酸(48%重量水溶液,64ml)溶液。搅拌反应混合物,将其温热至室温过夜。混合物用水稀释,用二乙醚萃取,合并有机萃取物,在无水硫酸钠上干燥,过滤,真空浓缩滤液。残余物通过柱色谱法在硅胶上进一步纯化,用2%的乙酸乙酯/己烷洗脱,给出5-(4-氯苯基)-2-乙基-1-溴苯(10g)。
步骤6
将5-(4-氯苯基)-2-乙基-1-溴苯(10g,0.03mol)溶于THF(250ml),调节至温度-78℃。在30分钟内滴加正丁基锂(1.33摩尔浓度的己醇溶液,34.6ml),温度保持在大约-78℃。搅拌反应混合物1.5小时,然后滴加硼酸三甲酯(4.9g,0.05mol),搅拌反应混合物2小时。滴加2N盐酸水溶液(100ml),加入完成后搅拌混合物2小时。浓缩混合物除去大部分四氢呋喃,用水稀释,用乙醚萃取。有机萃取物用水和盐水洗涤,合并,在无水硫酸钠上干燥,过滤,真空蒸发滤液。通过快速柱色谱法在硅胶上进一步纯化残余物,用7%乙酸乙酯/己烷洗脱,给出5-(4-氯-苯基)-2-甲基苯基硼酸(5.4g)。
实施例1D
制备3,5-二甲基联苯基硼酸
在-78℃下,将叔丁基锂(1.7M己烷溶液,36.2ml,62.6mmol)滴加至3,5-二甲基联苯(7.27g;28mmol)的无水四氢呋喃(150ml)溶液,在氮气氛下搅拌30分钟。加入硼酸三甲酯(9.54ml;84mmol),所得混合物在-78℃下搅拌30分钟,然后将之温热至室温。反应混合物用盐酸水溶液酸化,用乙醚(2x150ml)萃取。合并有机层,在无水硫酸镁上干燥,过滤,真空蒸发滤液,给出黄色固体。粗产品与异己烷研磨,过滤,给出3,5-二甲基联苯基硼酸(5.89g),是白色固体。
实施例1E
制备3,5-二甲基联苯-4-基三乙酸铅
在氮气氛下,向40℃的四乙酸铅(4.3g,9.7mmol)无水氯仿(15ml)溶液中一批加入3,5-二甲基联苯-4-基硼酸(2.0g;8.8mmol)。混合物在40℃下搅拌4小时,然后冷却至室温。沉淀通过过滤除去,滤液随后通过基于硅藻土上的碳酸钾塞,除去乙酸。真空蒸发滤液,提供3,5-二甲基联苯-4-基三乙酸铅(3.37g)。
生物实施例
将单子叶和双子叶测试植物在罐中播种于经消毒的标准土壤中。栽培1天后(苗前)或栽培10天后(苗后),在温室中于受控条件下,用含水喷雾溶液来喷雾植株,所述喷雾溶液得自工业级活性成分在0.6ml丙酮和含10.6%Emulsogen EL(登录号61791-12-6)、42.2%N-甲基吡咯烷酮、42.2%二丙二醇单甲醚(登录号34590-94-8)和0.2%X-77(登录号11097-66-8)的45ml制剂溶液中的制剂。然后在温室中于最佳条件下生长供测试植物,直到14或15天后(苗后)和20天后(苗前),评价供测试植物(100=损伤全部植物;0=未损伤植物)。
测试植物:
大穗看麦娘(Alopecurus myosuroides)(ALOMY)、野燕麦(Avenafatua)(AVEFA)、黑麦草属(Lolium perenne)(LOLPE)、法式狗毛草(Setaria faberi)(SETFA)、马唐(Digitaria sanguinalis)(DIGSA)、西来稗(Echinochloa crus-calli)(ECHCG)
苗前活性
苗后活性
Claims (48)
1.式(I)化合物
其中
R1是甲基、乙基、正丙基、异丙基、环丙基、卤代甲基、卤代乙基、卤素、乙烯基、乙炔基、甲氧基、乙氧基、卤代甲氧基或卤代乙氧基,
R2和R3彼此独立地是氢、卤素、C1-C6烷基、C1-C6卤代烷基、C1-C6烷氧基、C1-C6卤代烷氧基、C2-C6烯基、C2-C6卤代烯基、C2-C6炔基、C3-C6烯氧基、C3-C6卤代烯氧基、C3-C6炔氧基、C3-C6环烷基、C1-C6烷硫基、C1-C6烷基亚磺酰基、C1-C6烷基磺酰基、C1-C6烷基磺酰氧基、C1-C6卤代烷基磺酰氧基、氰基、硝基、苯基、被下述基团取代的苯基:C1-C4烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、氰基、硝基、卤素、C1-C3烷硫基、C1-C3烷基亚磺酰基或C1-C3烷基磺酰基,或杂芳基或被下述基团取代的杂芳基:C1-C4烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、氰基、硝基、卤素、C1-C3烷硫基、C1-C3烷基亚磺酰基或C1-C3烷基磺酰基,
R4是氢、甲基、乙基、正丙基、异丙基、卤代甲基、卤代乙基、卤素、乙烯基、乙炔基、甲氧基、乙氧基、卤代甲氧基或卤代乙氧基,
n是0、1、2或3,
X是O、S、S(O)或S(O)2,
R5是氢或甲基,
R6和R7彼此独立地是氢、甲基或乙基,其中,当n是2或3时,4个或6个取代基R6和R7的含义不必相同,
R8是C1-C18烷基、C1-C18卤代烷基、C3-C7环烷基、被甲基或乙基取代的C3-C7环烷基、C1-C6烷氧基C1-C12烷基、C1-C6烷硫基C1-C12烷基、C3-C18烯基或被卤素取代的C3-C18烯基、C3-C18炔基或被卤素取代的C3-C18炔基,或
R5,当n表示1或2时,与R8一起形成C2-C5亚烷基链,其是未经取代的或者被甲基或乙基取代,或C2-C5亚烯基链,其是未经取代的或者被甲基或乙基取代,其中,当n是2时,4个取代基R6和R7的含义不必相同,或
R6,当n表示1时,与R5、R7和R8之一一起形成C2-C5亚烷基链,其是未经取代的或者被甲基或乙基取代,或C2-C5亚烯基链,其是未经取代的或者被甲基或乙基取代,和
G是氢、碱金属、碱土金属、锍,铵或潜伏基团。
2.根据权利要求1的化合物,其中R1是甲基、乙基、乙烯基、乙炔基、甲氧基或卤素。
3.根据权利要求2的化合物,其中R1是甲基、乙基、甲氧基或卤素。
4.根据权利要求3的化合物,其中R1是甲基或乙基。
5.根据权利要求1的化合物,其中R2是氢、卤素、甲基、乙基、苯基或被下述基团取代的苯基:C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、氰基、硝基、卤素、C1-C3烷硫基、C1-C3烷基亚磺酰基或C1-C3烷基磺酰基。
6.根据权利要求5的化合物,其中R2是甲基。
7.根据权利要求1的化合物,其中R3是氢、卤素、甲基、乙基、苯基或被下述基团取代的苯基:C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、氰基、硝基、卤素、C1-C3烷硫基、C1-C3烷基亚磺酰基或C1-C3烷基磺酰基。
8.根据权利要求1的化合物,其中R2和R3彼此独立地是氢、甲基、乙基、卤素、任选被取代的苯基或任选被取代的杂芳基。
9.根据权利要求1的化合物,其中R4是氢、甲基、乙基、乙烯基或乙炔基。
10.根据权利要求9的化合物,其中R4是氢、甲基或乙基。
11.根据权利要求1的化合物,其中R5是氢。
12.根据权利要求1的化合物,其中R6和R7各自是氢。
13.根据权利要求1的化合物,其中R6和R7是甲基或乙基。
14.根据权利要求1的化合物,其中R6是氢,R7是甲基或乙基。
15.根据权利要求1的化合物,其中R8,当X表示S(O)或S(O)2时,是C1-C18烷基、C3-C7环烷基、被甲基或乙基取代的C3-C7环烷基、C1-C6烷氧基C1-C12烷基、C1-C6烷硫基C1-C12烷基、C3-C18烯基、C3-C18炔基或被卤素取代的C3-C18炔基。
16.根据权利要求15的化合物,其中R8是C1-C6烷基或C3-C7环烷基。
17.根据权利要求16的化合物,其中R8是甲基、乙基或丙基。
18.根据权利要求1的化合物,其中R8,当X表示O或S时,是甲基、乙基、丙基、丁基、戊基或己基、C7-C18烷基、C3-C7环烷基、被甲基或乙基取代的C3-C7环烷基、C1-C6烷氧基C1-C12烷基、C1-C6烷硫基C1-C12烷基、C3-C18烯基、C3-C18炔基或被卤素取代的C3-C18炔基。
19.根据权利要求18的化合物,其中R8是甲基、乙基或丙基。
20.根据权利要求19的化合物,其中R8是乙基或丙基。
21.根据权利要求1的化合物,其中R8,当X表示S(O)或S(O)2时,是C1-C18烷基、C3-C7环烷基、被甲基或乙基取代的C3-C7环烷基、C1-C6烷氧基C1-C12烷基、C1-C6烷硫基C1-C12烷基、C3-C18烯基、C3-C18炔基或被卤素取代的C3-C18炔基以及R6和R7是甲基或乙基,或R6是氢和R7是甲基或乙基。
22.根据权利要求1的化合物,其中R8-X-[CR6R7]1-不是CH3OCH2-和CH3SCH2-。
23.根据权利要求1的化合物,其中G是C(Xa)-Ra或C(Xb)-Xc-Rb。
24.根据权利要求1的化合物,其中G是氢、碱金属或碱土金属。
25.根据权利要求24的化合物,其中G是氢。
26.根据权利要求1的化合物,其中n是1或2。
27.根据权利要求1的化合物,其中R5,当n表示1或2时,与R8一起形成C2-C5亚烷基链。
28.根据权利要求1的化合物,其中R5,当n表示1时,与R8一起形成亚丙基链以及R6和R7各自是氢。
29.根据权利要求1的化合物,其中R5,当n表示1或2时,与R8一起形成亚乙基链以及R6和R7各自是氢。
30.根据权利要求29的化合物,其中n表示2。
31.根据权利要求1的化合物,其中R5,当n表示1或2时,与R8一起形成亚乙基链以及R6和R7各自是氢和X是O。
32.根据权利要求1的化合物,其中R5,当n表示1或2时,与R8一起形成亚乙基链以及R6和R7各自是氢,X是S(O)或S(O)2。
33.根据权利要求1的化合物,其中R1、R2和R4彼此独立地是甲基或乙基,R3是氢。
34.根据权利要求1的化合物,其中R1是甲基或乙基,R2是氢,R3是苯基或被下述基团取代的苯基:C1-C4烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、氰基、硝基或卤素,或杂芳基或被下述基团取代的杂芳基:C1-C4烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、氰基、硝基或卤素。
35.根据权利要求1的化合物,其中R1是甲基或乙基,R2是苯基或被下述基团取代的苯基:C1-C4烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、氰基、硝基或卤素,或者杂芳基或被下述基团取代的杂芳基:C1-C4烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧基、氰基、硝基或卤素,R3是氢和R4是氢、甲基或乙基。
41.制备式(I)化合物的方法,其中G是H,其包含在酸性条件下水解式(I)化合物,其中G是C1-C4烷基。
43.式(Y)化合物
其中R5、R6、R7、R8和X以及n具有权利要求1中赋予它们的含义,且A r是任选被取代的芳族环。
44.在有用植物作物中防治禾本科草和杂草的方法,其包含将除草有效量的式(I)化合物或者包含这种化合物的组合物施用至植物或其场所。
45.一种除草组合物,其除包含制剂助剂外包含除草有效量的式(I)化合物。
46.根据权利要求45的组合物,其除包含式(I)化合物外包含其它除草剂作为混配物。
47.根据权利要求45的组合物,其除包含式(I)化合物外包含安全剂。
48.根据权利要求45的组合物,其除包含式(I)化合物外包含作为混配物的其它除草剂和安全剂。
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CN107200701A (zh) * | 2017-07-03 | 2017-09-26 | 江苏威格瑞斯化工有限公司 | 一种合成环己烯酮类除草剂关键中间体的方法 |
CN107162945A (zh) * | 2017-07-03 | 2017-09-15 | 江苏威格瑞斯化工有限公司 | 一种合成烯草酮的方法 |
CN111868034A (zh) * | 2018-03-13 | 2020-10-30 | 先正达参股股份有限公司 | 作为除草剂的螺环环己二酮衍生物 |
CN111868034B (zh) * | 2018-03-13 | 2023-12-01 | 先正达参股股份有限公司 | 作为除草剂的螺环环己二酮衍生物 |
CN113412256A (zh) * | 2019-02-11 | 2021-09-17 | 先正达农作物保护股份公司 | 除草化合物 |
CN113412256B (zh) * | 2019-02-11 | 2024-01-19 | 先正达农作物保护股份公司 | 除草化合物 |
CN113423693A (zh) * | 2019-02-22 | 2021-09-21 | 先正达农作物保护股份公司 | 除草化合物 |
CN113423693B (zh) * | 2019-02-22 | 2024-02-02 | 先正达农作物保护股份公司 | 除草化合物 |
CN114222733A (zh) * | 2019-07-31 | 2022-03-22 | 先正达农作物保护股份公司 | 环状二酮作为除草化合物 |
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JP5524629B2 (ja) | 2014-06-18 |
WO2008110308A3 (en) | 2008-12-11 |
WO2008110308A2 (en) | 2008-09-18 |
JP2010520867A (ja) | 2010-06-17 |
GB0704652D0 (en) | 2007-04-18 |
AU2008226027B2 (en) | 2014-01-30 |
CO6220851A2 (es) | 2010-11-19 |
US8084649B2 (en) | 2011-12-27 |
KR20090119931A (ko) | 2009-11-20 |
AU2008226027A1 (en) | 2008-09-18 |
CN102007097B (zh) | 2014-07-23 |
AR068967A1 (es) | 2009-12-23 |
US20100173774A1 (en) | 2010-07-08 |
RU2009136671A (ru) | 2011-04-20 |
EP2121584A2 (en) | 2009-11-25 |
CA2679194A1 (en) | 2008-09-18 |
BRPI0808693A2 (pt) | 2014-09-09 |
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