CN1147193A - 杀虫剂n-(取代芳甲基)-4-[双(取代苯基)哌啶 - Google Patents
杀虫剂n-(取代芳甲基)-4-[双(取代苯基)哌啶 Download PDFInfo
- Publication number
- CN1147193A CN1147193A CN95192801A CN95192801A CN1147193A CN 1147193 A CN1147193 A CN 1147193A CN 95192801 A CN95192801 A CN 95192801A CN 95192801 A CN95192801 A CN 95192801A CN 1147193 A CN1147193 A CN 1147193A
- Authority
- CN
- China
- Prior art keywords
- phenyl
- hydrogen
- alkyl
- group
- trifluoromethoxyphen
- 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.)
- Pending
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 title claims abstract description 28
- 150000003053 piperidines Chemical class 0.000 title claims description 133
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 title claims description 8
- 230000000749 insecticidal effect Effects 0.000 title description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 80
- 239000001257 hydrogen Substances 0.000 claims abstract description 60
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 60
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 48
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 43
- 150000002367 halogens Chemical group 0.000 claims abstract description 43
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 22
- 150000001204 N-oxides Chemical class 0.000 claims abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 125000001188 haloalkyl group Chemical group 0.000 claims abstract description 15
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical group FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011737 fluorine Chemical group 0.000 claims abstract description 14
- 229910052731 fluorine Chemical group 0.000 claims abstract description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 125000001072 heteroaryl group Chemical group 0.000 claims abstract description 5
- -1 nitro, amino Chemical group 0.000 claims description 170
- 239000000203 mixture Substances 0.000 claims description 90
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 41
- 241000238631 Hexapoda Species 0.000 claims description 35
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 29
- 239000001301 oxygen Substances 0.000 claims description 29
- 229910052760 oxygen Inorganic materials 0.000 claims description 29
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 16
- 125000004414 alkyl thio group Chemical group 0.000 claims description 15
- 239000000460 chlorine Substances 0.000 claims description 15
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 15
- 241000607479 Yersinia pestis Species 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 125000005133 alkynyloxy group Chemical group 0.000 claims description 10
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 8
- 125000003282 alkyl amino group Chemical group 0.000 claims description 8
- CUCJJMLDIUSNPU-UHFFFAOYSA-N 1-oxidopiperidin-1-ium Chemical compound [O-][NH+]1CCCCC1 CUCJJMLDIUSNPU-UHFFFAOYSA-N 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 150000001336 alkenes Chemical group 0.000 claims description 7
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 7
- 125000004457 alkyl amino carbonyl group Chemical group 0.000 claims description 7
- 125000003806 alkyl carbonyl amino group Chemical group 0.000 claims description 7
- 125000004448 alkyl carbonyl group Chemical group 0.000 claims description 7
- 125000003368 amide group Chemical group 0.000 claims description 7
- 125000005359 phenoxyalkyl group Chemical group 0.000 claims description 7
- SETHSKIRVBKZTB-UHFFFAOYSA-N NC([O])=O Chemical compound NC([O])=O SETHSKIRVBKZTB-UHFFFAOYSA-N 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 125000004466 alkoxycarbonylamino group Chemical group 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 4
- 150000001721 carbon Chemical group 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000005112 cycloalkylalkoxy group Chemical group 0.000 claims description 4
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 4
- VBWQIRPJIODGDU-UHFFFAOYSA-N CC(=CC)C.[O] Chemical compound CC(=CC)C.[O] VBWQIRPJIODGDU-UHFFFAOYSA-N 0.000 claims description 3
- 125000005278 alkyl sulfonyloxy group Chemical group 0.000 claims description 3
- 125000000304 alkynyl group Chemical group 0.000 claims description 3
- 125000005336 allyloxy group Chemical group 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 claims description 3
- 125000004672 ethylcarbonyl group Chemical group [H]C([H])([H])C([H])([H])C(*)=O 0.000 claims description 3
- 125000005280 halo alkyl sulfonyloxy group Chemical group 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 claims 1
- 239000002917 insecticide Substances 0.000 abstract description 13
- 150000002431 hydrogen Chemical group 0.000 abstract 2
- 125000006413 ring segment Chemical group 0.000 abstract 1
- 125000001424 substituent group Chemical group 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 99
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 70
- 239000003921 oil Substances 0.000 description 57
- 239000000243 solution Substances 0.000 description 54
- 239000000376 reactant Substances 0.000 description 51
- 238000006243 chemical reaction Methods 0.000 description 48
- 239000000543 intermediate Substances 0.000 description 48
- 239000002585 base Substances 0.000 description 47
- 239000007787 solid Substances 0.000 description 46
- 238000003756 stirring Methods 0.000 description 41
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 40
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 36
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 34
- 238000012360 testing method Methods 0.000 description 29
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 28
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 28
- 239000000047 product Substances 0.000 description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 27
- 125000004494 ethyl ester group Chemical group 0.000 description 26
- 239000012141 concentrate Substances 0.000 description 25
- 239000000706 filtrate Substances 0.000 description 25
- 238000002360 preparation method Methods 0.000 description 24
- SRJOCJYGOFTFLH-UHFFFAOYSA-N isonipecotic acid Chemical compound OC(=O)C1CCNCC1 SRJOCJYGOFTFLH-UHFFFAOYSA-N 0.000 description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- 239000003480 eluent Substances 0.000 description 20
- 239000012044 organic layer Substances 0.000 description 20
- 235000002639 sodium chloride Nutrition 0.000 description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 17
- 238000010898 silica gel chromatography Methods 0.000 description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 15
- 239000007788 liquid Substances 0.000 description 15
- 239000000126 substance Substances 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 239000003153 chemical reaction reagent Substances 0.000 description 14
- 235000019198 oils Nutrition 0.000 description 14
- 229920006395 saturated elastomer Polymers 0.000 description 14
- 230000008569 process Effects 0.000 description 12
- 239000011780 sodium chloride Substances 0.000 description 11
- 229960002668 sodium chloride Drugs 0.000 description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 241000256244 Heliothis virescens Species 0.000 description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 10
- 239000000284 extract Substances 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- 239000011777 magnesium Substances 0.000 description 10
- 229910052749 magnesium Inorganic materials 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- WRPIDJDJEGLKFA-UHFFFAOYSA-N 1-bromo-3,4,5-trifluoro-2-methoxybenzene Chemical compound COC1=C(F)C(F)=C(F)C=C1Br WRPIDJDJEGLKFA-UHFFFAOYSA-N 0.000 description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 8
- CSJLBAMHHLJAAS-UHFFFAOYSA-N diethylaminosulfur trifluoride Chemical compound CCN(CC)S(F)(F)F CSJLBAMHHLJAAS-UHFFFAOYSA-N 0.000 description 8
- 230000007613 environmental effect Effects 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 229910052938 sodium sulfate Inorganic materials 0.000 description 8
- 235000011152 sodium sulphate Nutrition 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 230000009036 growth inhibition Effects 0.000 description 7
- 230000000361 pesticidal effect Effects 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- 239000007818 Grignard reagent Substances 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 241000256247 Spodoptera exigua Species 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- DPZNOMCNRMUKPS-UHFFFAOYSA-N resorcinol dimethyl ether Natural products COC1=CC=CC(OC)=C1 DPZNOMCNRMUKPS-UHFFFAOYSA-N 0.000 description 6
- 238000009736 wetting Methods 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- 244000045195 Cicer arietinum Species 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 5
- 241000255993 Trichoplusia ni Species 0.000 description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- 229960001866 silicon dioxide Drugs 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- UDQTXCHQKHIQMH-KYGLGHNPSA-N (3ar,5s,6s,7r,7ar)-5-(difluoromethyl)-2-(ethylamino)-5,6,7,7a-tetrahydro-3ah-pyrano[3,2-d][1,3]thiazole-6,7-diol Chemical compound S1C(NCC)=N[C@H]2[C@@H]1O[C@H](C(F)F)[C@@H](O)[C@@H]2O UDQTXCHQKHIQMH-KYGLGHNPSA-N 0.000 description 4
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- 229940125936 compound 42 Drugs 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- 239000011550 stock solution Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- 229910052727 yttrium Inorganic materials 0.000 description 4
- WGFNXGPBPIJYLI-UHFFFAOYSA-N 2,6-difluoro-3-[(3-fluorophenyl)sulfonylamino]-n-(3-methoxy-1h-pyrazolo[3,4-b]pyridin-5-yl)benzamide Chemical compound C1=C2C(OC)=NNC2=NC=C1NC(=O)C(C=1F)=C(F)C=CC=1NS(=O)(=O)C1=CC=CC(F)=C1 WGFNXGPBPIJYLI-UHFFFAOYSA-N 0.000 description 3
- PYRKKGOKRMZEIT-UHFFFAOYSA-N 2-[6-(2-cyclopropylethoxy)-9-(2-hydroxy-2-methylpropyl)-1h-phenanthro[9,10-d]imidazol-2-yl]-5-fluorobenzene-1,3-dicarbonitrile Chemical compound C1=C2C3=CC(CC(C)(O)C)=CC=C3C=3NC(C=4C(=CC(F)=CC=4C#N)C#N)=NC=3C2=CC=C1OCCC1CC1 PYRKKGOKRMZEIT-UHFFFAOYSA-N 0.000 description 3
- FMKGJQHNYMWDFJ-CVEARBPZSA-N 2-[[4-(2,2-difluoropropoxy)pyrimidin-5-yl]methylamino]-4-[[(1R,4S)-4-hydroxy-3,3-dimethylcyclohexyl]amino]pyrimidine-5-carbonitrile Chemical compound FC(COC1=NC=NC=C1CNC1=NC=C(C(=N1)N[C@H]1CC([C@H](CC1)O)(C)C)C#N)(C)F FMKGJQHNYMWDFJ-CVEARBPZSA-N 0.000 description 3
- VVCMGAUPZIKYTH-VGHSCWAPSA-N 2-acetyloxybenzoic acid;[(2s,3r)-4-(dimethylamino)-3-methyl-1,2-diphenylbutan-2-yl] propanoate;1,3,7-trimethylpurine-2,6-dione Chemical compound CC(=O)OC1=CC=CC=C1C(O)=O.CN1C(=O)N(C)C(=O)C2=C1N=CN2C.C([C@](OC(=O)CC)([C@H](C)CN(C)C)C=1C=CC=CC=1)C1=CC=CC=C1 VVCMGAUPZIKYTH-VGHSCWAPSA-N 0.000 description 3
- GAPGQBDURBPRLG-UHFFFAOYSA-N 3-chloro-4-methoxybenzoyl chloride Chemical compound COC1=CC=C(C(Cl)=O)C=C1Cl GAPGQBDURBPRLG-UHFFFAOYSA-N 0.000 description 3
- 102000004377 Thiopurine S-methyltransferases Human genes 0.000 description 3
- 108090000958 Thiopurine S-methyltransferases Proteins 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001350 alkyl halides Chemical class 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 235000019994 cava Nutrition 0.000 description 3
- SOIODWSIJIUYHX-UHFFFAOYSA-N chlorobenzene;methane Chemical compound C.ClC1=CC=CC=C1 SOIODWSIJIUYHX-UHFFFAOYSA-N 0.000 description 3
- 229940127113 compound 57 Drugs 0.000 description 3
- 238000010908 decantation Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
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- 238000002474 experimental method Methods 0.000 description 3
- 230000009969 flowable effect Effects 0.000 description 3
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical class FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 3
- 229910001623 magnesium bromide Inorganic materials 0.000 description 3
- 238000003359 percent control normalization Methods 0.000 description 3
- QARVLSVVCXYDNA-UHFFFAOYSA-N phenyl bromide Natural products BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 3
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- 238000004809 thin layer chromatography Methods 0.000 description 3
- 239000000080 wetting agent Substances 0.000 description 3
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 2
- IMPIIVKYTNMBCD-UHFFFAOYSA-N 2-phenoxybenzaldehyde Chemical compound O=CC1=CC=CC=C1OC1=CC=CC=C1 IMPIIVKYTNMBCD-UHFFFAOYSA-N 0.000 description 2
- QBWKPGNFQQJGFY-QLFBSQMISA-N 3-[(1r)-1-[(2r,6s)-2,6-dimethylmorpholin-4-yl]ethyl]-n-[6-methyl-3-(1h-pyrazol-4-yl)imidazo[1,2-a]pyrazin-8-yl]-1,2-thiazol-5-amine Chemical compound N1([C@H](C)C2=NSC(NC=3C4=NC=C(N4C=C(C)N=3)C3=CNN=C3)=C2)C[C@H](C)O[C@H](C)C1 QBWKPGNFQQJGFY-QLFBSQMISA-N 0.000 description 2
- IBCQUQXCTOPJOD-UHFFFAOYSA-N 3-chloro-4-methoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C=C1Cl IBCQUQXCTOPJOD-UHFFFAOYSA-N 0.000 description 2
- DPBWFNDFMCCGGJ-UHFFFAOYSA-N 4-Piperidine carboxamide Chemical class NC(=O)C1CCNCC1 DPBWFNDFMCCGGJ-UHFFFAOYSA-N 0.000 description 2
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
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- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 238000003747 Grignard reaction Methods 0.000 description 2
- LVDRREOUMKACNJ-BKMJKUGQSA-N N-[(2R,3S)-2-(4-chlorophenyl)-1-(1,4-dimethyl-2-oxoquinolin-7-yl)-6-oxopiperidin-3-yl]-2-methylpropane-1-sulfonamide Chemical compound CC(C)CS(=O)(=O)N[C@H]1CCC(=O)N([C@@H]1c1ccc(Cl)cc1)c1ccc2c(C)cc(=O)n(C)c2c1 LVDRREOUMKACNJ-BKMJKUGQSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 244000046052 Phaseolus vulgaris Species 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- LJOOWESTVASNOG-UFJKPHDISA-N [(1s,3r,4ar,7s,8s,8as)-3-hydroxy-8-[2-[(4r)-4-hydroxy-6-oxooxan-2-yl]ethyl]-7-methyl-1,2,3,4,4a,7,8,8a-octahydronaphthalen-1-yl] (2s)-2-methylbutanoate Chemical compound C([C@H]1[C@@H](C)C=C[C@H]2C[C@@H](O)C[C@@H]([C@H]12)OC(=O)[C@@H](C)CC)CC1C[C@@H](O)CC(=O)O1 LJOOWESTVASNOG-UFJKPHDISA-N 0.000 description 2
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- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 2
- OAYLNYINCPYISS-UHFFFAOYSA-N ethyl acetate;hexane Chemical compound CCCCCC.CCOC(C)=O OAYLNYINCPYISS-UHFFFAOYSA-N 0.000 description 2
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- 229910052740 iodine Inorganic materials 0.000 description 2
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- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 231100000225 lethality Toxicity 0.000 description 2
- 239000012280 lithium aluminium hydride Substances 0.000 description 2
- 239000006210 lotion Substances 0.000 description 2
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 2
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- DYGBNAYFDZEYBA-UHFFFAOYSA-N n-(cyclopropylmethyl)-2-[4-(4-methoxybenzoyl)piperidin-1-yl]-n-[(4-oxo-1,5,7,8-tetrahydropyrano[4,3-d]pyrimidin-2-yl)methyl]acetamide Chemical compound C1=CC(OC)=CC=C1C(=O)C1CCN(CC(=O)N(CC2CC2)CC=2NC(=O)C=3COCCC=3N=2)CC1 DYGBNAYFDZEYBA-UHFFFAOYSA-N 0.000 description 2
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- 239000003960 organic solvent Substances 0.000 description 2
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- 239000002245 particle Substances 0.000 description 2
- BZCGWAXQDLXLQM-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O.ClP(Cl)(Cl)=O BZCGWAXQDLXLQM-UHFFFAOYSA-N 0.000 description 2
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- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
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- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
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- BEOOHQFXGBMRKU-UHFFFAOYSA-N sodium cyanoborohydride Chemical compound [Na+].[B-]C#N BEOOHQFXGBMRKU-UHFFFAOYSA-N 0.000 description 2
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- 239000004562 water dispersible granule Substances 0.000 description 2
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- NHOWDZOIZKMVAI-UHFFFAOYSA-N (2-chlorophenyl)(4-chlorophenyl)pyrimidin-5-ylmethanol Chemical compound C=1N=CN=CC=1C(C=1C(=CC=CC=1)Cl)(O)C1=CC=C(Cl)C=C1 NHOWDZOIZKMVAI-UHFFFAOYSA-N 0.000 description 1
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- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- UNILWMWFPHPYOR-KXEYIPSPSA-M 1-[6-[2-[3-[3-[3-[2-[2-[3-[[2-[2-[[(2r)-1-[[2-[[(2r)-1-[3-[2-[2-[3-[[2-(2-amino-2-oxoethoxy)acetyl]amino]propoxy]ethoxy]ethoxy]propylamino]-3-hydroxy-1-oxopropan-2-yl]amino]-2-oxoethyl]amino]-3-[(2r)-2,3-di(hexadecanoyloxy)propyl]sulfanyl-1-oxopropan-2-yl Chemical compound O=C1C(SCCC(=O)NCCCOCCOCCOCCCNC(=O)COCC(=O)N[C@@H](CSC[C@@H](COC(=O)CCCCCCCCCCCCCCC)OC(=O)CCCCCCCCCCCCCCC)C(=O)NCC(=O)N[C@H](CO)C(=O)NCCCOCCOCCOCCCNC(=O)COCC(N)=O)CC(=O)N1CCNC(=O)CCCCCN\1C2=CC=C(S([O-])(=O)=O)C=C2CC/1=C/C=C/C=C/C1=[N+](CC)C2=CC=C(S([O-])(=O)=O)C=C2C1 UNILWMWFPHPYOR-KXEYIPSPSA-M 0.000 description 1
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- 235000009496 Juglans regia Nutrition 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-diisopropylethylamine Substances CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 1
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- 125000002877 alkyl aryl group Chemical group 0.000 description 1
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- MCQRPQCQMGVWIQ-UHFFFAOYSA-N boron;methylsulfanylmethane Chemical compound [B].CSC MCQRPQCQMGVWIQ-UHFFFAOYSA-N 0.000 description 1
- NNTOJPXOCKCMKR-UHFFFAOYSA-N boron;pyridine Chemical compound [B].C1=CC=NC=C1 NNTOJPXOCKCMKR-UHFFFAOYSA-N 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
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- 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 1
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- RDEWTAHSEKSPPT-UHFFFAOYSA-N ethyl 2-(bromomethyl)benzoate Chemical compound CCOC(=O)C1=CC=CC=C1CBr RDEWTAHSEKSPPT-UHFFFAOYSA-N 0.000 description 1
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- 239000011521 glass Substances 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- TWBYWOBDOCUKOW-UHFFFAOYSA-N isonicotinic acid Chemical compound OC(=O)C1=CC=NC=C1 TWBYWOBDOCUKOW-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
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- LULAYUGMBFYYEX-UHFFFAOYSA-N metachloroperbenzoic acid Natural products OC(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- YYERFRCBHRNMTB-UHFFFAOYSA-N n,n-diethylpiperidine-1-carboxamide Chemical class CCN(CC)C(=O)N1CCCCC1 YYERFRCBHRNMTB-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 230000001069 nematicidal effect Effects 0.000 description 1
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- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- UYDLBVPAAFVANX-UHFFFAOYSA-N octylphenoxy polyethoxyethanol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(OCCOCCOCCOCCO)C=C1 UYDLBVPAAFVANX-UHFFFAOYSA-N 0.000 description 1
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- 230000024241 parasitism Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000005648 plant growth regulator Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- KSAVQLQVUXSOCR-UHFFFAOYSA-M sodium lauroyl sarcosinate Chemical compound [Na+].CCCCCCCCCCCC(=O)N(C)CC([O-])=O KSAVQLQVUXSOCR-UHFFFAOYSA-M 0.000 description 1
- 229920005552 sodium lignosulfonate Polymers 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
-
- 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
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
-
- 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
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
-
- 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
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
-
- 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
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/60—1,4-Diazines; Hydrogenated 1,4-diazines
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
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- A—HUMAN NECESSITIES
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Abstract
披露了结构(I)的化合物、其相应的N-氧化物和农业上可接受的盐作为有效的杀虫剂,其中Q选自氢、羟基和氟;R选自具有5-6个环原子的杂芳基,以及(II),其中V是氢、卤素、烷基等;W和X分别选自许多种取代基,Y和Z分别选自氢和烷氧基;W和X可一起构成-OCH2CH2O-等;R1和R2分别选自取代的苯基。同时还披露了这些化合物的制备方法。
Description
本发明涉及控制害虫的方法。特别涉及向需要控制害虫的场所使用某种N-(取代芳甲基)-4-[双(取代苯基)甲基]哌啶进行虫害控制。尽管该类化合物不全具有新颖性,但是这些化合物的杀虫效果是以前所未知的。
已经披露了许多N-(取代芳甲基)-4-[双(取代)苯基甲基]哌啶的衍生物作为心血管药或抗过敏剂。南非专利No.8,604-552A披露下列通式化合物的这种用途:其中:p是0,1,或2;A首选(inter alia)氢或羟基;m为1-6;Q是-CH-,-CH2-或-CH(OH)-;d和n为0或1,虚线表示符合碳化合价的双键;Ar、D和R首选自
X、Y和Z选自不同的取代基,包括氢、低级烷基、卤素、硝基、氰基、氨基、烷氧基、硫代烷基、羰基或磺酰基;
B首选硫或氧。
所披露的专利中有几个附加条件,并且还披露了这些化合物的药学上可接受的盐具有相同的效果。
美国专利4,628,095披露了下列通式的化合物作为心血管药物:
其中,
Ar是苯基,可任意地为卤素所取代;
R是低级烷氧基或二(低级烷基)氨基;
R1是氢、低级烷氧基羰基、羧基或低级烷基氨基羰基;
n是0或1,当R1为氢时,n是1。
现在发现:具有下列结构的化合物、它们的相应的N-氧化物以及它们的农业上可接受的盐具有杀虫活性:其中,Q选自氢、羟基和氟;R选自具有5-6个环原子的杂芳基,以及
其中,
V是氢、卤素、烷基、卤代烷基或烷氧基;
W是氢、卤素、烷基、卤烷基、烷氧基、苯氧基或苯基烷氧基;
X是氢、羟基、卤素、烷基、烷氧基烷基、烷氧基、环烷基烷氧基、卤代烷氧基、烯氧基、卤代烯氧基、炔氧基、烷基甲硅烷氧基、烷硫基、卤代烷硫基、氰基、氰烷氧基、硝基、氨基、一烷基氨基、二烷基氨基、烷基氨基烷氧基、烷基羰基氨基、烷基羰基、烷氧基羰基氨基、烷氧基羰基、烷基氨基羰基、氨基羰基氧基、苯基、苯基烷氧基、苯氧基或苯氧基烷基,每个苯环可任意地被卤素、烷氧基或卤代烷氧基所取代;
Y和Z分别选自氢和烷氧基;
W和X一起形成-OCH2CH2O-、-CH2C(CH3)2O-或-OC(CH3)2O-;
R1和R2分别选自被卤素、烷基、卤代烷基、卤代烷氧基、烷基磺酰氧基和卤代烷基磺酰氧基所取代的苯基;
n是1、2或3;
所附加的条件是每个脂族部分所含有的碳原子数不大于6,卤素指氯或氟,并且在氨基氮上的每个烷基取代基含有1-3个碳原子。
其中
V选自氢和卤素;
Y和Z分别为氢;
W选自氢、卤素和烷氧基;
X选自氢、羟基、卤素、烷基、卤代烷基、烯基、炔基、烷氧基、烯氧基、炔氧基、卤代烷氧基、烷硫基、卤代烷硫基、一烷基氨基、二烷基氨基、烷氧基烷基、烷氧基烷氧基、烷基羰基、烷氧基羰基、烷基氨基羰基、烷基羰基氨基、氨基羰基氧基、烷氧基羰基氨基、氰基、苯基、苯氧基、苯氧基烷基,和任意取代的苯基烷氧基;
W和X一起形成-OCH2CH2O-、-CH2C(CH3)2O-或-OC(CH3)2O-;
R1和R2分别选自被卤素或卤代烷氧基所取代的苯基;
n是1、2或3;
所附加的条件是R1或R2之一是对位取代的苯基。
最好的化合物是:
V选自氢和氟;
Y和Z分别为氢;
W选自氢、卤素、甲氧基和乙氧基;
X选自氢、卤素、甲基、甲氧基、乙氧基、正丙氧基、正丁氧基、全氟乙氧基、全氟乙硫基、氰基、苯基、苯氧基、苯基甲氧基、二甲基氨基、乙氧基甲基、乙基羰基、乙氧基羰基、烯丙氧基、炔丙氧基、2-甲基丙氧基、环丙基甲氧基、2-氯-2-丙烯氧基、2-甲基-2-丙烯氧基、3-甲基-2-丁烯氧基、氰基甲氧基、2-丁炔氧基和乙基羰基氨基;
W和X一起形成-CH2C(CH3)2O-;
n是1;
R1和R2分别为对三氟甲氧基苯基,并且各个脂族部分所含的碳原子数不大于5,及其它们的N-氧化物和盐。
本发明化合物的制备方法通常为熟悉本领域的人所了解。在反应流程图1所示的方法中(其中R1和R2相同),哌啶-4-基羧酸乙酯与经适当取代的卤代烷(如4-甲氧基苯基溴甲烷)或经适当取代的醛(如对苯氧基苯甲醛)反应,生成相应的N-取代的烷基哌啶-4-基羧酸乙酯(A)。然后用2摩尔当量以上适当取代的卤化物的格氏试剂(如4-三氟甲氧基苯基溴化镁)对中间体(A)进行处理,生成所要求的N-(取代烷基)-4-[双(取代)羟甲基]哌啶(I)(如N-(4-甲氧基苯基甲基)-4-[双(4-三氟甲氧基苯基)羟甲基]哌啶(化合物24))。实施例1-3、5、6和10对这些反应的过程进行了详细的描述。
在R1和R2相同的场合的另一个方法中,(见反应流程图2)使用了D.A.Walsh等人的方法(J.Med.Chem.1989,32,105-118)。在该方法中,使哌啶-4-基羧酸乙酯在碱性条件下与二乙基氨基甲酰氯反应,生成相应的中间体N-二乙基氨基羰基哌啶-4-基羧酸乙酯(B)。用大于2摩尔当量的适当取代的卤化物的格氏试剂对中间体(B)进行处理,生成相应的N-二乙基氨基羰基-4-[双(取代)羟甲基]哌啶(C)。用氢化铝锂处理中间体(C),生成4-[双(取代)羟甲基]哌啶(II),例如4-[双(4-三氟甲氧基苯基)羟甲基]哌啶。如反应流程图2C中所示,用适当取代的烷基卤化物或适当取代的醛处理中间体(II),如前面所描述的那样,得到要求的N-(取代烷基)-4-[双(取代)羟甲基]哌啶(I),如N-(4-乙氧基羰基苯基甲基)-4-[双(4-三氟甲氧基苯基)羟甲基]哌啶(化合物57)。实施例7对该反应的过程进行了详细的描述。
用上述方法制备中间体(II)的产量相对较低。为改进中间体(II)的产量,使用了两种合成该中间体的合成路径。
合成中间体(II)可选用的第一条路径可见反应流程图2A,在10%的钯炭的存在下用甲酸铵处理N-苯基甲基-4-[双(取代)羟甲基]哌啶(I)(如N-苯基甲基-4-[双(4-三氟甲氧基苯基)羟甲基]哌啶)的盐酸盐(D),很容易地得到中间体(II)。如反应流程图2C中所示,再次处理中间体(II),得到要求的N-(取代烷基)-4-[双(取代)羟甲基]哌啶(I),例如N-[4-(甲基羰基氨基)苯基甲基]-4-[双(4-三氟甲氧基苯基)羟甲基]哌啶(化合物66)。实施例12详细描述了该反应的过程。
在第二个可选用的合成中间体(II)的路径(参见反应流程图2B)中,哌啶-4-基羧酸乙酯与大于2摩尔当量的适当取代的卤化物的格氏试剂反应,生成相应的4-[双(取代)羟甲基]哌啶(E)。然后制得中间体(E)的盐酸盐(F),并在氧化铂的存在下对得到的盐酸盐(F)进行氢化,生成相应的盐酸4-[双(取代)羟甲基]哌啶(IIA)。如反应流程图2C中所示,在碱性条件下中间体(IIA)再进行反应,得到要求的N-(取代烷基)-4-[双(取代)羟甲基]哌啶(I),例如N-[4-(2-丙炔-1-基氧基)苯基甲基]-4-[双(4-三氟甲氧基苯基)羟甲基]哌啶(化合物65)。实施例11详细地说明了该反应的过程。
如反应流程图2C所示,在碱性条件下使上述中间体4-[双(取代)羟甲基]哌啶(II)与适当取代的酰氯(如3-氯-4-甲氧基苯甲酰氯)反应,生成相应的N-(取代羰基)-4-[双(取代)羟甲基]哌啶(G)。用甲硼烷-二甲硫配合物还原中间体(G),得到要求的N-(取代烷基)-4-[双(取代)羟甲基]哌啶(I),例如N-(3-氯-4-甲氧基苯基甲基)-4-[双(4-三氟甲氧基苯基)羟甲基]哌啶(化合物44)。实施例8详细地说明了该反应的过程。
反应流程图3显示了当R1和R2不相同时所使用的方法。在该方法中,在碱性条件下使4-氨基羰基哌啶与适当取代的卤烷(如对丙氧基苯基氯甲烷)反应,生成相应的N-(取代烷基)-4-氨基羰基哌啶(H)。用磷酰氯处理中间体(H),生成相应的N-(取代烷基)-4-氰基哌啶(J),使中间体(J)再与适当取代的卤化物的格氏试剂(如4-三氟甲氧基苯基溴化镁)反应,生成相应的N-(取代烷基)-4-(取代羰基)哌啶(K)。使中间体(K)与另一适当取代的卤化物的格氏试剂(如4-氯苯基溴化镁)反应,得到要求的N-(取代烷基)-4-[双(取代)羟甲基]哌啶(I),例如N-(4-丙氧基苯基甲基)-4-[(4-三氟甲氧基苯基)-(4-氯苯基)羟甲基]哌啶。实施例4详细地说明了该反应的过程。
如反应流程图4所示,还可以使用本领域中众所周知的方法使本发明的N-(取代烷基)-4-[双(取代)羟甲基]哌啶(I)反应,制得其它具有杀虫活性的化合物,这也包括在本发明的范围内。
在两步反应中,用在1,2-二甲氧基乙烷中的Lawesson氏试剂处理化合物(I)(如N-(4-丙氧基苯基甲基)-4-[双(4-三氟甲氧基苯基)羟甲基]哌啶(实施例10中制得),生成相应的N-(取代烷基)-4-[双(取代)巯基甲基]哌啶(L),在浓氢氧化铵和1,3-环己二烯的存在下,在甲醇中用Ranry镍还原化合物(L),生成要求的脱羟基的N-(取代烷基)-4-[双(取代)甲基]哌啶(IB)。实施例13详细描述了该反应的过程。
在另一个一步反应中,通过在二氯甲烷中将N-(取代烷基)-4-[双(取代)羟甲基]哌啶(I)以三氟乙酸和三乙基甲硅烷还原制得脱羟化合物(IB)。实施例14详细地描述了该反应的过程。
还可以使N-(取代烷基)-4-[双(取代)羟甲基]哌啶(I)(如N-(4-丙氧基苯基甲基)-4-[双(4-三氟甲氧基苯基)羟甲基]哌啶)在二氯甲烷中以二乙基氨基三氟化硫(DAST)进行脱羟和氟化,产生相应的N-(取代烷基)-4-[双(取代)氟甲基]哌啶(IC)。实施例15详细地描述了该反应的过程。
空白页
本发明的范围还包括上述方法制得的化合物的N-氧化物(IA)。该N-氧化物是通过用氧化剂(如间氯过氧化苯甲酸)氧化上述化合物制备的(如N-[4-(2-丙烯-1基氧基)苯基甲基]-4-[双(4-三氟甲氧基苯基)羟甲基]哌啶(化合物42)生成相应的N-氧化物(如N-[4-(2-丙烯-1基氧基)苯基甲基]-4-[双(4-三氟甲氧基苯基)羟甲基]哌啶N-氧化物(化合物43))。实施例9详细地描述了该反应的过程。
实施例1
合成N-(4-甲氧基苯基甲基)-4-[双(4-三氟甲氧基苯基)羟甲基]
哌啶(化合物24)
向搅拌的1.1克(0.045摩尔)镁屑(turning)在30ml二乙醚中的混合物中滴入15ml 11.0克(0.045摩尔)对三氟甲氧基溴苯在30ml二乙醚中的溶液。一旦反应开始,在45分钟内分批加入其余15ml该溴化物的溶液。当反应平息后,在5分钟内滴入5.0克(0.018摩尔)N-(4-甲氧基苯基甲基)哌啶-4-基羧酸乙酯在20ml二乙醚中的溶液。加料完成后,将反应混合物加热回流并搅拌约30分钟。然后使反应混合物冷却至环境温度并搅拌约18小时,然后滴入饱和氯化铵水溶液以中止反应。此时混合物在水和二乙醚之间进行分配。分离出二乙醚层并依次用饱和氯化钠溶液和水进行洗涤。有机层用硫酸镁干燥并过滤。滤液在减压下浓缩得油状残留物,对该油用硅胶柱色谱进行分离纯化,用10%二乙醚的己烷溶液、100%二乙醚和10%甲醇的二乙醚溶液作为洗脱液。合并含产品的部份,并在减压下浓缩,得到6.7gN-(4-甲氧基苯基甲基)-4-[双(4-三氟甲氧基苯基)羟甲基]哌啶,m.p.86-96℃。NMR谱与所描述的结构相符合。
实施例2
合成N-(4-苯氧基苯基甲基)-4-[双(4-三氟甲氧基苯基)羟甲基]
哌啶(化合物60)
步骤A合成中间体N-(4-苯氧基苯基甲基)哌啶-4-基羧酸乙酯
向搅拌的5.0克(0.025摩尔)苯氧基苯甲醛和4.0克(0.025摩尔)哌啶-4-基羧酸乙酯在25ml甲醇中的溶液中一次性加入1.6克(0.025摩尔)氰基硼氢化钠。加料完成后,滴加饱和的氯化氢甲醇溶液直至反应混合物的pH值约为6.0。然后在环境温度下将反应混合物搅拌约22小时,然后再加入饱和氯化氢甲醇溶液将pH调至约5.5-6.0。将反应混合物倒入350ml 0.1M氢氧化钾水溶液中。得到的混合物用二乙醚萃取(萃取三次,每次125ml),合并的萃取液用饱和氯化钠水溶液洗涤一次。有机层用硫酸钠干燥并过滤。滤液在减压下浓缩至剩下残余物,用1∶1乙酸乙酯/己烷作洗脱液用硅胶柱色谱对该残余物进行分离纯化。合并并浓缩含产品的部份,得到5.9克N-(4-苯氧基苯基甲基)哌啶-4-基羧酸乙酯,NMR谱与所描述的结构相符合。
步骤B合成N-(4-苯氧基苯基甲基)-4-[双(4-三氟甲氧基苯基)羟甲基]
哌啶(化合物60)
该化合物以类似于实施例1的方法制得,使用2.0克(0.006摩尔)N-(4-苯氧基苯基甲基)哌啶-4-基羧酸乙酯,7.1克(0.029摩尔)对三氟甲氧基溴苯以及0.7克(0.030摩尔)镁屑在二乙醚中作为反应试剂。与实施例1中的反应所不同的是使用少量的(10滴)1,2-二溴乙烷以引发格氏反应。所得到的N-(4-苯氧基苯基甲基)-4-[双(4-三氟甲氧基苯基)羟甲基]哌啶的量为0.7克。NMR谱与所描述的结构相符合。
实施例3
合成N-[2-(4-甲氧基苯基)乙基]-4-[双(4-三氟甲氧基苯基)羟甲基]
哌啶(化合物25)
步骤A合成中间体N-[2-(4--甲氧基苯基)乙基]哌啶-4-基羧酸乙酯
在下面制备中使用G.D.Maynard等人在Bioorganic & Medicinal ChemistryLetters,3(4),pp.753-756,1993中所报导的N-烷基化反应条件。将搅拌的5.0克(0.032摩尔)哌啶-4-基羧酸乙酯、5.4克(0.032摩尔)1-(2-氯乙基)-4-甲氧基苯和4.4克(0.032摩尔)碳酸钾在50ml经干燥的N,N-二甲基甲酰胺中的混合物在70℃加热约16小时。反应混合物冷却后,使之在二乙醚和水之间分配。分离有机层并依次用水、饱和氯化钠水溶液对其进行洗涤。有机层用硫酸镁干燥并过滤。滤液在减压下浓缩至剩下残余物,以二乙醚/己烷混合物作为洗脱液用硅胶柱色谱对该残余物进行分离纯化。合并含产品的部份并在减压下浓缩,得到2.4克N-[2-(4-甲氧基苯基)乙基]哌啶-4-基羧酸乙酯。NMR谱与所描述的结构相符合。
步骤B合成N-[2-(4-甲氧基苯基)乙基]-4-[双(4-三氟甲氧基苯基)羟甲基]
哌啶(化合物25)
该化合物以类似于实施例1的方法制得,使用1.6克(0.005摩尔)N-[2-(4-甲氧基苯基)乙基]哌啶-4-基羧酸乙酯、2.4克(0.010摩尔)对三氟甲氧基溴苯以及0.3克(0.011摩尔)镁屑在约35ml二乙醚中作为反应试剂。与实施例1中的反应所不同的是格氏反应一开始,就向对三氟甲氧基溴苯的二乙醚溶液中加入N-[2-(4-甲氧基苯基)乙基]哌啶-4-基羧酸乙酯。然后将该组合物滴入反应混合物中,从而在形成格氏试剂的同时就将哌啶-4-基羧酸酯加入反应混合物中。加料完成后,将该反应混合物在环境温度下搅拌约18小时。然后滴入饱和氯化铵水溶液以中止反应。反应混合物用二氯甲烷萃取,合并得到的萃取液,依次用稀盐酸水溶液、饱和氯化钠水溶液洗涤。有机层用硫酸镁干燥并过滤。滤液在减压下浓缩至剩下残余物,以二乙醚/己烷和乙酸乙酯/甲醇的组合物作为洗脱液用硅胶柱色谱对该残余物进行分离纯化。为得到纯的产品,需进行以二乙醚作为洗脱液的第二次硅胶柱色谱分离纯化,合并含产品的部份并在减压下浓缩,得到0.3克N-[2-(4-甲氧基苯基)乙基]-4-[双(4-三氟甲氧基苯基)羟甲基]哌啶。NMR谱与所描述的结构相符合。
实施例4
合成N-(4-丙氧基苯基甲基)-4-[(4-三氟甲氧基苯基)-(4-氯苯基)羟甲基]
哌啶(化合物7)
步骤A合成中间体4-氰基-N-(4-丙氧基苯基甲基)哌啶
在下面的两步制备中使用R.A.Farr等人在J.Org.Chem.1981,46,1212-1215中所报导的方法。将强烈搅拌的16.5克(0.129摩尔)4-氨基羰基哌啶、25.0克(0.135摩尔)对丙氧基苯基氯甲烷和19.4克(0.193摩尔)碳酸氢钾在200ml甲苯中的溶液加热回流6.5小时。反应混合物冷却后,加入水并用乙酸乙酯进行萃取。萃取液用饱和氯化钠水溶液洗涤两次。有机层用硫酸镁干燥并过滤。滤液在减压下浓缩至剩下固态残余物,将该固态残余物在戊烷中形成淤浆(slurried)并过滤,得到28.2克4-氨基羰基-N-(4-丙氧基苯基甲基)哌啶,m.p.为142-146℃。NMR谱与所描述的结构相符合。
在环境温度下搅拌27.0克(0.10摩尔)4-氨基羰基-N-(4-丙氧基苯基甲基)哌啶在200ml 1,2-二氯乙烷中的混合物,然后依次加入8.0克(0.14摩尔)氯化钠、9.2克(0.06摩尔)磷酰氯。然后将反应混合物加热回流并搅拌约1.75小时。使该反应混合物冷却至环境温度并加入约350ml水。分离出水层,用二乙醚洗涤两次,然后用5%氢氧化钠水溶液碱化。用二乙醚对该混合物萃取两次。合并得到的萃取液,用饱和氯化钠水溶液洗涤。有机层用硫酸镁干燥并经一层硅胶过滤。用1000ml二乙醚洗涤该硅胶层,合并得到的洗脱液,在减压下浓缩,得到14.5克4-氰基-N-(4-丙氧基苯基甲基)哌啶,NMR谱与所描述的结构相符合。
步骤B合成N-(4-丙氧基苯基甲基)-4-(4-三氟甲氧基苯基羰基)
哌啶中间体
该化合物以类似于实施例3步骤B的方法制得,使用5.0克(0.019摩尔)4-氰基-N-(4-丙氧基苯基甲基)哌啶、10.7克(0.045摩尔)对三氟甲氧基溴苯、1.1克(0.045摩尔)镁屑以及碘(催化剂)在155ml四氢呋喃中作为反应试剂。产生3.9克N-(4-丙氧基苯基甲基)-4-(4-三氟甲氧基苯基羰基)哌啶。NMR谱与所描述的结构相符合。
步骤C合成N-(4-丙氧基苯基甲基)-4-[(4-三氟甲氧基苯基)-(4-氯苯基)
羟甲基]哌啶(化合物7)
搅拌0.6g(0.0014摩尔)N-(4-丙氧基苯基甲基)-4-(4-三氟甲氧基苯基羰基)哌啶在15ml四氢呋喃中的溶液,然后向该搅拌的溶液中慢慢加入1.8ml对氯苯基溴化镁(0.0018摩尔,1M,在二乙醚中)。加料完成后,将反应混合物加热至65℃并搅拌3.5小时,然后将该反应混合物冷却至环境温度,并搅拌约18小时。再将该反应混合物倒入50ml冰和75ml氯化铵饱和水溶液组成的混合物中,搅拌该混合物直至冰融化,然后用乙酸乙酯萃取。得到的萃取液用硫酸钠干燥并过滤。滤液在减压下浓缩至剩下残余物,将该残余物溶解在沸腾的石油醚中,并用脱色炭处理。再加入硅藻土进行搅拌,得到的混合物经活性硅酸镁层进行过滤。用30%丙酮的二氯甲烷溶液洗涤该硅酸镁层。合并滤液和洗涤液并在减压下浓缩之,得到0.4gN-(4-丙氧基苯基甲基)-4-[(4-三氟甲氧基苯基)-(4-氯苯基)羟甲基]哌啶。NMR谱与所描述的结构相符合。
实施例5
合成N-[4-(2-丙烯-1-基氧基)苯基甲基]-4-[双(4-三氟甲氧基苯基) 羟甲基]
哌啶(化合物42)
步骤A合成N-[4-(2-丙烯-1-基氧基)苯基甲基]哌啶-4-基羧酸乙酯中间体
在下述制备中使用A.E.Moormann在Syn.Comm.,23(6),789-795(1993)中报导的反应条件。向4.8g(0.030摩尔)哌啶4-基羧酸乙酯和4.9g(0.030摩尔)4-(2-丙烯-1-基氧基)苯甲醛在50ml乙醇中的溶液在搅拌下加入3.8ml(0.030摩尔)甲硼烷-吡啶配合物。加料完成后,在环境温度下将反应混合物搅拌约18小时。然后将反应混合物加水溶解,用二氯甲烷萃取。有机层用水洗涤并用硫酸镁干燥。过滤混合物,并在减压下浓缩滤液,得到9.0gN-[4-(2-丙烯-1-基氧基)苯基甲基]哌啶-4-基羧酸乙酯。其NMR谱与所描述的结构相符合。
步骤B合成N-[4-(2-丙烯-1-基氧基)苯基甲基]-4-[双(4-三氟甲氧基苯基)
羟甲基]哌啶(化合物42)
用相似于实施例2步骤B的方法制备本化合物,使用3.8g(0.013摩尔)N-[4-(2-丙烯-1-基氧基)苯基甲基]哌啶-4-基羧酸乙酯,15.0g(0.063摩尔)对三氟甲氧基溴苯,1.5g(0.060摩尔)镁屑和约10滴1,2-二溴乙烷在二乙醚中作为反应试剂,得到约0.3gN-[4-(2-丙烯-1-基氧基)苯基甲基]-4-[双(4-三氟甲氧基苯基)羟甲基]哌啶。其NMR谱与所描述的结构相符。
实施例6
合成N-(2,6-二甲氧基苯基甲基)-4-[双(4-三氟甲氧基苯基)羟甲基]
哌啶(化合物38)
步骤A合成2,6-二甲氧基苯基溴甲烷中间体
将5.7g(0.034摩尔)2,6-二甲氧基苯基甲醇在40ml浓氢溴酸中的混合物在环境温度下搅拌约1小时后,将该反应混合物以二乙醚溶解。向该混合物中加入固体氯化钠使之分相,分离有机层并在减压下浓缩之,得到约4.7g2,6-二甲氧基苯基溴甲烷。立即将该混合物用于下一步反应中。
步骤B合成N-(2,6-二甲氧基苯基甲基)哌啶-4-基羧酸乙酯中间体
将搅拌的4.7g(0.020摩尔)2,6-二甲氧基苯基溴甲烷,3.2g(0.020摩尔)哌啶-4-基羧酸乙酯在100ml乙腈中的溶液和23.5g(0.200摩尔)50%在Celite助滤剂上的溴化钾加热回流约18小时,然后冷却并过滤该反应混合物。在减压下将滤液浓缩至剩下残余物,用乙酸乙酯在己烷中的混合液作为洗脱液,对该残余物进行硅胶柱色谱分离。合并含产物的部份并在减压下浓缩至剩下残余物。用薄层色谱分析该残余物得知它不纯,使用乙酸乙酯在己烷中的混合液和甲醇在乙酸乙酯中的混合液作为洗脱液,对该残余物再次进行硅胶柱色谱分离。合并含产物的部份并在减压下浓缩之,得到约1克N-(2,6-二甲氧基苯基甲基)哌啶-4-基羧酸乙酯。其NMR谱与所描述的结构相符。
步骤C合成N-(2,6-二甲氧基苯基甲基)-4-[双(4-三氟甲氧基苯基)羟甲基]
哌啶(化合物38)
用相似于实施例2步骤B的方法制备本化合物,使用1.0g(0.003摩尔)N-(2,6-二甲氧基苯基甲基)哌啶-4-基羧酸乙酯,3.7g(0.015摩尔)对三氟甲氧基溴苯,0.4g(0.015摩尔)镁屑和10滴1,2-二溴乙烷在20ml二乙醚中作为反应试剂,得到约0.9gN-(2,6-二甲氧基苯基甲基)-4-[双(4-三氟甲氧基苯基)羟甲基]哌啶。其NMR谱与所描述的结构相符。
实施例7
合成N-(4-乙氧基羰基苯基甲基)-4-[双(4-三氟甲氧基苯基)羟甲基]
哌啶(化合物57)
步骤A合成N-(二乙基氨基羰基)-4-[双(4-三氟甲氧基苯基)羟甲基]哌啶
中间体
用相似于实施例1的方法制备本化合物,使用25.7g(0.10摩尔)N-(二乙基氨基羰基)哌啶4-基羧酸乙酯,61.1g(0.25摩尔)对三氟甲氧基溴苯,5.7g(0.23摩尔)镁屑在390ml四氢呋喃中作为反应试剂,得到43.8gN-(二乙基氨基羰基)-4-[双(4-三氟甲氧基苯基)羟甲基]哌啶。m.p.165-166℃,其NMR谱与所描述的结构相符。
步骤B合成4-[双(4-三氟甲氧基苯基)羟甲基]哌啶中间体,以及N-甲基
-4-[双(4-三氟甲氧基苯基)羟甲基]哌啶(化合物9)
将7.7g(0.203摩尔)氢化铝锂在150ml无水四氢呋喃中的悬浮液在搅拌下冷却至约15℃,然后以15分钟的时间滴加43.3g(0.081摩尔)N-(二乙基氨基羰基)-4-[双(4-三氟甲氧基苯基)羟甲基]哌啶在约250ml无水四氢呋喃中的溶液。加料完成后,在约15-20℃搅拌该反应混合物约5分钟,然后加热回流并搅拌约18小时。将反应混合物冷却至环境温度并放置24小时。再将其冷却至0-10℃,并在30分钟时间内依次滴加7.7ml水、23ml 3N氢氧化钠水溶液以及7.7ml水。在加料过程中保持反应混合物的温度为0-10℃。加料完成后,将反应混合物搅拌约75分钟并过滤,得到一种粘稠固体。将该固体与少量四氢呋喃一起搅拌并过滤。在50-55℃减压浓缩得到的滤液,直至粘性残余物固化。将得到的固体溶解在温热(31-33℃)的石油醚中,然后在干冰/丙酮浴中冷却得到的溶液。沉积在烧瓶壁上的固态产物通过先滗去石油醚随后将固体悬浮在二乙醚中进行收集。在减压下浓缩收集到的混合物,得到6.8g固态残余物。对该固态样品进行NMR分析。其NMR谱无确定的结果,丢弃该固态样品。将滗出的石油醚在减压下进行浓缩,得到约26g粘性的残余物。将该残余物溶解在温热的氯仿中并用硅胶柱色谱进行分离,用20%甲醇的氯仿溶液开始洗脱。合并经薄层色谱鉴定的适当的部份并在减压下浓缩之,得到9.4g固体,mp为123-128℃,NHR和质谱显示该固体是N-甲基-4-[双(4-三氟甲氧基苯基)羟甲基]哌啶(化合物9)。将洗脱液由20%甲醇在氯仿中的溶液改成30%甲醇在氯仿中的溶液,继续进行柱色谱分离。合并也经薄层色谱鉴定的其他部份,并在减压下浓缩之,得到7.4g固体,NMR和质谱显示该固体是要求的4-[双(4-三氟甲氧基苯基)羟甲基]哌啶中间体。
步骤C合成N-(4-乙氧基羰基苯基甲基)-4-[双(4-三氟甲氧基苯基)羟甲基]
哌啶(化合物57)
使用D.A.Walsh等在J.Med.Chem.1989,32,105-118,报导的方法,将0.5g(0.001摩尔)4-[双(4-三氟甲氧基苯基)羟甲基]哌啶(由本实施例的步骤B制得),0.3g(0.001摩尔)对溴甲基苯甲酸乙酯以及0.5g(0.004摩尔)碳酸钾在15mlN,N-二甲基甲酰胺中的搅拌的混合物加热至95℃并搅拌约16小时。然后将反应混合物倒入50ml冰水中并搅拌15分钟。使用3份(每份75ml)二乙醚对该混合物进行萃取,合并萃取液,使用2份(每份75ml)氯化钠饱和水溶液进行洗涤。有机层用硫酸镁干燥并过滤。在减压下浓缩滤液,得到0.1g油状残留物。水层再用3份(每份100ml)乙酸乙酯进行萃取。萃取液合并,用100ml氯化钠饱和水溶液洗涤。用硫酸钠干燥有机层并过滤之,滤液在减压下浓缩,得到0.8g油状残留物,使用30%乙酸乙酯的戊烷溶液作为洗脱液,对该残留物进行硅胶柱色谱分离。合并含产物的部份并减压浓缩之,得到0.3gN-(4-乙氧基羰基苯基甲基)-4-[双(4-三氟甲氧基苯基)羟甲基]哌啶。其NMR谱与所描述的结构相符合。
实施例8
合成N-(3-氯-4-甲氧基苯基甲基)-4-[双(4-三氟甲氧基苯基)羟甲基]
哌啶(化合物44)
步骤A合成N-(3-氯-4-甲氧基苯基羰基)-4-[双(4-三氟甲氧基苯基)羟甲基]
哌啶中间体
将0.22g(0.0012摩尔)3-氯-4-甲氧基苯甲酸在少量的四氢呋喃和氯仿中的搅拌的溶液冷却至0℃,并滴加0.12ml(0.0014摩尔)草酰氯。加料完成后,使反应混合物温热至环境温度并搅拌约3.5小时,然后在减压下浓缩反应混合物,得到3-氯-4-甲氧基苯甲酰氯,将其溶解在少量的四氢呋喃中待用。
在单独的反应容器中,对0.5g(0.0012摩尔)4-[双(4-三氟甲氧基苯基)羟甲基]哌啶(由实施例7步骤B制得)和0.09g(0.0012摩尔)吡啶在少量的四氢呋喃中的溶液进行搅拌,接着加入上面制得的3-氯-4-甲氧基苯甲酰氯在四氢呋喃中的溶液,加料完成后,将反应混合物在环境温度下搅拌约15分钟,然后过滤除去白色固体,将滤液搅拌约18小时后,使之在乙酸乙酯和氯化钠饱和水溶液之间进行分配,使分离得到的有机层流过硅胶柱。然后用50%乙酸乙酯的己烷溶液进行洗脱。合并含产物的部份并在减压下浓缩之,得到0.62gN-(3-氯-4-甲氧基苯基羰基)-4-[双(4-三氟甲氧基苯基)羟甲基]哌啶,其NMR谱与所描述的结构相符合。
步骤B合成N-(3-氯-4-甲氧基苯基甲基)-4-[双(4-三氟甲氧基苯基)羟甲基]
哌啶(化合物44)
缓慢地向0.50g(0.0008摩尔)N-(3-氯-4-甲氧基苯基羰基)-4-[双(4-三氟甲氧基苯基)羟甲基]哌啶在5ml四氢呋喃中的搅拌的溶液中加入0.42ml(0.0040摩尔)甲硼烷-二甲硫配合物(10M在BH3中)。加料完成后,将反应混合物在环境温度下搅拌约18小时,接着使反应混合物在冰浴中冷却,然后缓慢地加入20ml甲醇以中止反应。在减压下将反应混合物浓缩至剩下残余物,再加入20ml甲醇并搅拌,然后再在减压下浓缩之。再次重复加入20ml甲醇并将溶液减压浓缩至残余物的过程。使残余物在乙酸乙酯和水之间分配并将得到的混合物搅拌15分钟,分离出有机层,用氯化钠饱和水溶液洗涤之,接着用硫酸钠干燥。将混合物过滤,滤液在减压下浓缩至残余物。用乙酸乙酯-己烷混合液作为洗脱液,对得到的残余物进行硅胶柱色谱分离。合并含产物的部份并在减压下浓缩之,得到0.13g N-(3-氯-4-甲氧基苯基甲基)-4-[双(4-三氟甲氧基苯基)羟甲基]哌啶。其NMR谱与描述的结构相符合。
实施例9
合成N-[4-(2-丙烯-1-基氧基)苯基甲基]-4-[双(4-三氟甲氧基苯基)羟甲基]
哌啶N-氧化物(化合物43)
向0.5g(0.0008摩尔)N-[4-(2-丙烯-1-基氧基)苯基甲基]-4-[双(4-三氟甲氧基苯基)羟甲基]哌啶(化合物42,由实施例5制得)在10ml氯仿中的搅拌的溶液中加入0.3g(0.0008摩尔)50%3-氯过氧苯甲酸。加料完成后,将反应混合物在环境温度下搅拌约2小时。然后依次用碳酸氢钠饱和水溶液和氯化钠饱和水溶液洗涤反应混合物。用硫酸镁干燥有机层并过滤,在减压下将滤液浓缩至残余物,使用乙酸乙酯-己烷混合液作为洗脱液对得到的残余物进行硅胶柱色谱分离。合并含产物的部份并将其在减压下浓缩至残余物。将该残余物在高真空下进一步浓缩,得到约0.2gN-[4-(2-丙烯-1-基氧基)苯基甲基]-4-[双(4-三氟甲氧基苯基)羟甲基]哌啶N-氧化物。其NMR谱与描述的结构相符合。
实施例10
合成N-(4-丙氧基苯基甲基)-4-[双(4-三氟甲氧基苯基)羟甲基]
哌啶(化合物29)
步骤A合成N-(4-丙氧基苯基甲基)哌啶-4-基羧酸乙酯中间体
用相似于实施例2步骤A的方法制备本化合物,使用5.3g(0.032摩尔)对丙氧基苯甲醛,5.0g(0.032摩尔)哌啶-4-基羧酸乙酯,2.0g(0.032摩尔)氰基硼氢化钠(sodium cyanoborohydride)和氯化氢的甲醇溶液在30ml甲醇中作为反应试剂,得到2.6gN-(4-丙氧基苯基甲基)哌啶-4-基羧酸乙酯。其NMR谱与所描述的结构相符合。
步骤B合成N-(4-丙氧基苯基甲基)-4-[双(4-三氟甲氧基苯基)羟甲基]
哌啶(化合物29)
使用相似于实施例1的方法制备本化合物,使用1.5g(0.005摩尔)N-(4-丙氧基苯基甲基)哌啶-4-基羧酸乙酯,3.6g(0.015摩尔)4-三氟甲氧基溴苯,0.4g(0.015摩尔)镁屑以及碘(催化剂)在40ml四氢呋喃中作为反应试剂,得到1.1gN-(4-丙氧基苯基甲基)-4-[双(4-三氟甲氧基苯基)羟甲基]哌啶,其NMR谱与所描述的结构相符合。
实施例11
合成N-[4-(2-丙炔-1-基氧基)苯基甲基]-4-[双(4-三氟甲氧基苯基)羟甲基]
哌啶(化合物65)
步骤A合成4-[双(4-三氟甲氧基苯基)羟甲基]吡啶中间体
使用相似于实施例1的方法制备本化合物,使用10.9g(0.067摩尔)吡啶-4-基羧酸乙酯,40.3g(0.167摩尔)4-三氟甲氧基溴苯,4.1g(0.023摩尔)镁屑在约275ml二乙醚中作为反应试剂,使用20-90%乙酸乙酯的己烷溶液作为洗脱液对粗产品进行硅胶柱色谱纯化,合并含产物的部份并在减压下浓缩至固态残余物。用己烷将该固体研制(triturated)三次,得到17.7g4-[双(4-三氟甲氧基苯基)羟甲基]吡啶,其NMR谱与所描述的结构相符合。
步骤B合成盐酸4-[双(4-三氟甲氧基苯基)羟甲基]吡啶中间体
向17.6g(0.041摩尔)4-[双(4-三氟甲氧基苯基)羟甲基]吡啶在200ml二乙醚中的搅拌的溶液中加入约20ml饱和的氯化氢乙醇溶液,加料完成后,使反应混合物冷却以促进产物的沉淀。如果不出现固体沉淀,则可在反应混合物上面通过氮气流1小时使其缓慢地浓缩。如果在此期间固体沉淀还不析出,则可加入二乙醚并继续在反应混合物上面通过氮气流。最后将反应混合物在减压下浓缩至近于,此时形成固体沉淀。将得到的固体悬浮在约10ml新鲜的二乙醚中,过滤后得到9.3g盐酸4-[双(4-三氟甲氧基苯基)羟甲基]吡啶。其NMR谱与描述的结构相符合。
步骤C合成盐酸4-[双(4-三氟甲氧基苯基)羟甲基]哌啶中间体
在Parr氢化器中,在50psi氢气压力下,将2.0g(0.004摩尔)盐酸4-[双(4-三氟甲氧基苯基)羟甲基]吡啶和催化量的氧化铂在125ml甲醇中的溶液氢化。完成氢化所需的时间约2小时。然后过滤除去催化剂。将滤液浓缩至约20ml体积,加入80ml二乙醚并将得到的溶液放置于冰箱中。过滤收集生成的固体沉淀,得到约0.4g产物。在减压下浓缩滤液,得到另外1.9g产物。合并两份固体产物,得到2.3g盐酸4-[双(4-三氟甲氧基苯基)羟甲基]哌啶。其NMR谱与描述的结构相符合。
步骤D合成N-[4-(2-丙炔-1-基氧基)苯基甲基]-4-[双(4-三氟甲氧基苯基)
羟甲基]哌啶(化合物65)
将0.8g(0.0016摩尔)盐酸4-[双(4-三氟甲氧基苯基)羟甲基]哌啶,0.3g(0.0016摩尔)4-(2-丙炔-1-基氧基)苯基氯甲烷以及0.5g(0.0079摩尔)在Celite助滤剂上的氟化钾在50ml乙腈中的搅拌的混合物加热回流约1.3小时。然后加入0.5ml(过量)三乙胺,此时反应混合物变成均相的溶液。加料完成后,再将反应混合物加热回流18小时。接着将反应混合物冷却、过滤,并在减压下将滤液浓缩至剩下残余物,用10-70%二乙醚在己烷中的混合液作为洗脱液对残余物进行硅胶柱色谱分离。合并含产物的部份并在减压下浓缩之,得到0.6gN-[4-(2-丙炔-1-基氧基)苯基甲基]-4-[双(4-三氟甲氧基苯基)羟甲基]哌啶。其NMR谱与描述的结构相符合。
实施例12
合成N-[4-(甲基羰基氨基)苯基甲基]-4-[双(4-三氟甲氧基苯基)羟甲基]
哌啶(化合物66)
步骤A合成N-苯基甲基基-4-[双(4-三氟甲氧基苯基)羟甲基]哌啶
(化合物13)中间体
该化合物以类似于实施例3步骤B的方法制得,使用6.0克(0.024摩尔)N-苯基甲基哌啶-4-基羧酸乙酯、1.8克(0.073摩尔)镁屑,17.5克(0.073摩尔)对三氟甲氧基溴苯在约80ml四氢呋喃中作为反应试剂。产生9.7克N-苯基甲基-4-[双(4-三氟甲氧基苯基)羟甲基]哌啶。NMR谱与所描述的结构相符合。
步骤B合成盐酸N-苯基甲基-4-[双(4-三氟甲氧基苯基)羟甲基]哌啶中间体
在下面两步制备中使用P.J.Gillgan等人在J.Med.Chem.1992,4344-4361中所报导的反应条件。将1.0g(0.002摩尔)N-苯基甲基-4-[双(4-三氟甲氧基苯基)羟甲基]哌啶在30ml二乙醚中的搅拌的溶液冷却至0℃,通入氯化氢气体。形成油状的(oily)固体沉淀。沉淀完全后,将反应混合物用入25ml己烷溶解并在冰箱中放置约18小时。然后滗去沉淀上层的清液。将沉淀与约20ml二乙醚一起搅拌,混合物在减压下浓缩至剩下残余物。得到的固体残余物与约20ml己烷一起搅拌,随后从固体上滗去己烷,并在减压下干燥得到的固体,得到0.8g盐酸N-苯基甲基-4-[双(4-三氟甲氧基苯基)羟甲基]哌啶。其NMR谱与描述的结构相符合。
步骤C合成4-[双(4-三氟甲氧基苯基)羟甲基]哌啶中间体
在氮气氛中将0.8g10%钯炭(催化剂)放入反应容器中,仔细地向反应容器中加入25ml经氮气吹洗的甲醇、0.8g(0.001摩尔)盐酸N-苯基甲基-4-[双(4-三氟甲氧基苯基)羟甲基]哌啶在10ml甲醇中的溶液以及0.9g(0.010摩尔)甲酸铵。加料完成后,将反应混合物加热回流约45分钟。然后使反应混合物冷却至环境温度并用1∶1二氯甲烷/甲醇稀释之。通过硅藻土/玻璃纤维层过滤该反应混合物,在约30℃、减压下将滤液浓缩至剩下残余物。将得到的残余物溶于约70ml冰/水中并用5%氢氧化钠水溶液碱化。用二氯甲烷萃取该混合物,并用氯化钠饱和水溶液洗涤萃取液。然后用硫酸钠干燥有机层。过滤混合物并在减压下将滤液浓缩至剩下残余物。将该残余物与石油醚一起搅拌,然后过滤得到0.5g固态4-[双(4-三氟甲氧基苯基)羟甲基]哌啶。其NMR谱与描述的结构相符合。
步骤D合成N-[4-(甲基羰基氨基)苯基甲基]-4-[双(4-三氟甲氧基苯基)
羟甲基]哌啶(化合物66)
向0.4g(0.0008摩尔)4-[双(4-三氟甲氧基苯基)羟甲基]哌啶在10ml甲硫醚中的搅拌的溶液中加入0.2g(0.0008摩尔)4-(甲基羰基氨基)苯基氯甲烷和0.6ml(0.003摩尔)N,N-二异丙基乙胺的混合物。加料完成后,在环境温度将反应混合物搅拌约18小时,然后使该反应混合物在碳酸氢钠饱和水溶液和乙酸乙酯之间分配。分离出有机层并用氯化钠饱和水溶液洗涤之。然后在减压下将有机层浓缩至残余物,用二氯甲烷和10-50%丙酮在二氯甲烷中的混合液作为洗脱液对该残余物进行硅胶柱色谱分离。合并含产物的部份并在减压下浓缩之,得到约0.3gN-[4-(甲基羰基氨基)苯基甲基]-4-[双(4-三氟甲氧基苯基)羟甲基]哌啶。其NMR谱与所描述的结构相符合。
实施例13
合成N-(4-丙氧基苯基甲基)-4-[双(4-三氟甲氧基苯基)甲基]
哌啶(化合物104)
步骤A合成N-(4-丙氧基苯基甲基)-4-[双(4-三氟甲氧基苯基)巯甲基]
哌啶中间体
在氮气氛中,搅拌2.3g(0.004摩尔)N-(4-丙氧基苯基甲基)-4-[双(4-三氟甲氧基苯基)羟甲基]哌啶(由实施例10制得)在约13.4ml 1,2-二甲氧基乙烷中的溶液,并加入1.3g(0.003摩尔)2,4-双(4-甲氧基苯基)-1,3-二硫杂-2,4-二磷杂环丁烷-2,4-二硫化物(Lawesson氏试剂)。将反应混合物加热至约80-85℃,再加入0.3g(0.0007摩尔)Lawesson氏试剂。将反应混合物搅拌10分钟,再加入0.3g(0.0007摩尔)Lawesson氏试剂。再将反应混合物搅拌10分钟后,加入第三份0.3g(0.0007摩尔)Lawesson氏试剂。通过与二氯甲烷共沸,除去1,2-二甲氧基乙烷溶剂。在减压下将得到的二氯甲烷溶液浓缩至残余物,并将该残余物加至本反应的前面一批(previous run,0.001摩尔))的粗产品中。分别使用甲苯、二氯甲烷和丙酮2∶1∶1的混合液作为洗脱液,对合并后的产物进行硅胶柱色谱分离。合并含产品的部份并在减压下浓缩之,得到约3.8g不纯的产物。使用二氯甲烷和1-2%丙酮-二氯甲烷混合液作为洗脱液对该产物再次进行硅胶柱色谱分离。合并含产物的部份并在减压下浓缩之,得到1.2gN-(4-丙氧基苯基甲基)-4-[双(4-三氟甲氧基苯基)巯甲基]哌啶。其NMR谱与描述的结构相符合。
步骤B合成N-(4-丙氧基苯基甲基)-4-[双(4-三氟甲氧基苯基)甲基]
哌啶中间体(化合物104)
向15.4g(过量)Raney镍(50%,在水中的悬浮液)、7.7ml 1,3-环己二烯和13.1ml浓氢氧化铵在105ml甲醇中的搅拌的混合物中加入0.8g(0.0013摩尔)N-(4-丙氧基苯基甲基)-4-[双(4-三氟甲氧基苯基)巯甲基]哌啶在50ml乙醇中的溶液。加料完成后,将反应混合物加热回流并搅拌约30分钟。然后使反应混合物冷却,并与本反应前面两小批(earlier runs,每批0.00017摩尔)相合并。经硅藻土层对合并产物进行过滤。用乙醇洗涤该硅藻土层,并合并滤液和洗液。在减压下将洗液/滤液合并浓缩至残余物,用乙酸乙酯稀释该残余物并用氯化钠饱和水溶液洗涤之。有机层用硫酸钠干燥并过滤,在减压下将滤液浓缩至残余物。用二氯甲烷和2-4%丙酮-二氯甲烷作为洗脱液对该残余物进行硅胶柱色谱分离纯化,合并含产物的部份并在减压下浓缩之,得到0.3gN-(4-丙氧基苯基甲基)-4-[双(4-三氟甲氧基苯基)甲基]哌啶。其NMR谱与所描述的结构相符合。
实施例14
合成N-(4-甲氧基苯基甲基)-4-[双(4-乙基苯基)甲基]哌啶(化合物103)
向搅拌的1.0g(0.002摩尔)N-(4-甲氧基苯基甲基)-4-[双(4-乙基苯基)羟甲基]哌啶(用实施例1的方法制得)在10ml二氯甲烷中的溶液中缓慢地加入1.1ml(0.007摩尔)三乙基甲硅烷,接着加入1.0ml(0.013摩尔)三氟乙酸。将反应化合物在环境温度下搅拌5小时。然后用固体碳酸钠中和反应混合物。使该混合物在100ml二氯甲烷和50ml水之间分配,分离有机层并用二份各为50ml的氯化钠饱和水溶液洗涤。用硫酸钠干燥有机层并过滤之。在减压下将滤液浓缩至残余物。使用25%丙酮-二氯甲烷作为洗脱液对该残余物进行制备薄层色谱纯化,得到约0.5gN-(4-甲氧基苯基甲基)-4-[双(4-乙基苯基)甲基]哌啶。其NMR谱与描述的结构相符合。
实施例15
合成N-(4-丙氧基苯基甲基)-4-[双(4-三氟甲氧基苯基)氟甲基]
哌啶(化合物105)
将搅拌的0.6g(0.001摩尔)N-(4-丙氧基苯基甲基)-4-[双(4-三氟甲氧基苯基)羟甲基]哌啶(实施例10制得)在15ml二氯甲烷中的溶液冷却至-78℃,用注射器向该溶液中加入0.15ml(0.001摩尔)二乙基氨基三氟化硫(DAST)。加料完成后,将反应混合物加热至环境温度并搅拌约18小时。随后将反应混合物倒入冰水中。用2份50ml的二氯甲烷萃取该混合物。用硫酸钠干燥合并的萃取液并过滤之。在减压下将滤液浓缩至残余物。使用5-15%丙酮-二氯甲烷作为洗脱液对残余物进行硅胶柱色谱分离。合并含产物的部份并在减压下浓缩之,得到约0.1gN-(4-丙氧基苯基甲基)-4-[双(4-三氟甲氧基苯基)氟甲基]哌啶。其NMR谱与所描述的结构相符合。
使用上面例举的方法所制得的典型化合物列于表1。其特征性质列于表2。
生物数据
将候选的杀虫剂混入人工饲料中以便用下列方法评估对烟芽夜蛾(Heliothisvirescens[Fabricius])的杀虫活性。制备供试化学物(50-0.005nM)的二甲亚砜储备溶液以便各种比例的使用。将100微升的各种储备溶液在手工搅拌下加至50ml熔融(65-70℃)的麦芽基人工饲料中。将含有供试化学物的50ml熔融饲料均匀地倒入具有25穴的5列塑料盘的每一侧外面二列的20个穴中(盘中每个穴约1cm深,开口3cm边缘4cm)。将仅含二甲亚砜(用量同供试化学物处理过的饲料中的用量)的熔融饲料倒入盘中第三列(中间)的5个穴中。因此,每个塑料盘含有一种使用比例的一种供试化学物以及未经处理的对照组。以摩尔浓度的负对数表示的使用比例,以及用于制备各种使用比例的相应储备溶液的浓度列于下面:
储备溶液 使用比例
50μM 4
5 5
0.5 6
0.05 7
0.005 8
将单个重量均约为5mg的二龄烟芽夜蛾幼虫放入各个穴中。当寄生完成后,用普通的家用平面熨斗将一片透明的塑料膜热封在塑料盘的上面。将塑料盘在25℃、60%相对湿度的生长室内放置5天。将光照设置在14小时有光照、10小时黑暗。经过5天试验后,得到昆虫的死亡率数据,并对存活的昆虫称重。比较以经处理的饲料喂养的存活的昆虫与以未经处理的饲料喂养的昆虫的重量,可得到各种试验化学物造成的生长抑制百分数。如有可能从这些数据的线性回归,可得到各种试验化学物达到50%生长抑制(pI50)时的负对数浓度。同样,如有可能,可得到50%死亡率(pLC50)时的试验化学物的负对数浓度。
对饲料试验中具有高pI50值的候选杀虫剂进行杀灭烟芽夜蛾、甜菜夜蛾、(Spodoptera exigua[Hubner])、粉纹夜蛾(Trichoplusia ni[Hubner])的杀虫活性试验(叶片评价)。
在杀灭烟芽夜蛾和甜菜夜蛾的试验中,对9天龄的鹰嘴豆植物(Cicerarietinum)叶片的上表面和下表面以20psi的液量喷洒试验化学物溶液,使得试验化学物的使用比例高达1000ppm。用于制备供试化学物溶液的溶剂为10%丙酮或甲醇(v/v)和0.1%辛基苯氧基聚乙氧基乙醇表面活性剂在蒸馏水中的混合液。进行四次平行测定,试验化学物的每种使用浓度喷洒一株鹰嘴豆植物。将经处理的植物移至遮阳蓬下直至喷洒物干燥。
将上述分别经试验化学物处理的每一次平行试验的4株鹰嘴豆植物在刚高出土壤的茎处割断而从盆中移出。从每一次平行试验的四株植物上切下的叶片和茎分别放入8盎司纸杯中,每一杯中含一湿滤纸。将5个二龄(6天龄)烟芽夜蛾或甜菜夜蛾(7-8天龄)放入各个杯中,此时应注意别使昆虫受伤害。在各个杯上盖上不透明的塑料盖,然后将其放入25℃、50%相对湿度的生长室进行96小时试验(exposure)。经96小时试验后,打开杯子,清点死亡的、垂死的和活着的昆虫的数目。使用昆虫计数,以控制百分数表示试验化学物的效果。控制百分数是试验中死亡昆虫的总数(TD)加上垂死昆虫的总数(TM)与昆虫总数之比:
%控制=[(TD+TM)/TI]×100%
还对试验植物的状态进行观察以比较相对于未处理的对照组的植物毒性和施药损害(feeding damage)。
使用相同于上面的方法对粉纹夜蛾进行叶片试验,不同之处在于用印度青刀豆植物(Phaseolus vulgaris)代替鹰嘴豆植物。
本发明化合物在饲料试验中具有杀灭烟芽夜蛾的活性。化合物22、24、27、28、29、34、39、42、43、46、47、48、52、55、57、65、68、78、79、80、88、89、90、92、94、96、97、98和102都具有6.0或更高的pI50值。表3给出了在饲料试验中化合物的杀虫活性值。
本发明化合物在叶片试验中也显示出良好至优秀的杀灭烟芽夜蛾、甜菜夜蛾和粉纹夜蛾的杀虫活性。由表4可见,许多化合物在100ppm的使用比例、在叶片试验中对一种或多种试验昆虫具有80%或更高的控制百分数。
为了在杀虫上使用,通过混合有效量的杀虫剂与本领域中常用毒物、使活性成分分散以满足具体要求的助剂以及载体,将活性化合物制成杀虫剂组合物,发现制剂和使用方式会影响杀虫剂在给定的应用中的杀虫活性。因此,为了用于农业中,根据要求的使用方式,本杀虫化合物常制备成相对较大粒径的颗粒、水溶性或水分散性颗粒、粉剂、可湿性粉剂、可乳化浓缩物、溶液或其他几种已知类型的制剂中的任何一种。
这些杀虫剂组合物可以以水稀的喷雾剂或粉剂或颗粒剂施加在要求控制虫害的区域。这些制剂可含有低至0.1%、0.2%、或0.5%至高达95%(重量)或更高的活性成分。
粉剂是活性成分和细分的固体(如滑石粉、天然粘土、硅藻土)、粉末(如胡桃壳粉和棉籽(cottonseed)粉)以及其它作为杀虫剂的分散剂和载体的有机或无机固体混合而成的可自由流动的混合物。这些细分的固体的平均粒度小于约50微米。用于本发明的典型粉末制剂含有1.0份(或更少)杀虫化合物和99.0份滑石粉。
可湿性粉剂是容易分散在水或其它分散剂中的细分颗粒。可湿性粉剂主要以干粉或在水中或其它液体中的乳浊液用于需要控制虫害的场合。用于可湿性粉剂的常用的载体包括漂白土、高岭土、二氧化硅和其它高吸附性、容易湿润的无机稀释剂。随载体的吸附性的不同,常将可湿性粉剂制成含有5-80%的活性成分,并且还常使之含有少量的湿润剂、分散剂或乳化剂以促进其分散。例如,可用的可湿性粉剂含有80.8份杀虫化合物、17.9份Palmetto粘土和1.0份木素磺酸钠以及0.3份磺化脂肪酸聚酯湿润剂。
其它可用作杀虫剂的有用的制剂是可乳化的浓缩物(ECs),该浓缩物是可分散在水或其它分散剂中的均相的液态组合物,并且可完全由杀虫化合物和液态或固态的乳化剂组成,或还含有液态载体(如二甲苯、重芳香石脑油、异佛尔酮或其它非挥发性有机溶剂)。为用于杀虫,这些浓缩物常分散在水或其它液态载体中,并且常以喷雾剂的形式喷洒在需处理的区域。杀虫剂组合物中主要活性成分的重量百分比可随该组合物施加的方式不同而不同,但通常含有0.5-95%(按杀虫剂组合物的重量计)的活性成分。
可流动的制剂相似于ECs,不同之处在于活性成分悬浮在液态载体(通常是水)中。如ECs一样,可流动制剂可含有少量的表面活性剂,所含的活性成分的量为0.5-95%,常为10-50%(按组合物的重量计)。在应用时,可流动制剂可用水或其它液态载体稀释,并常以喷雾剂的形式喷洒在需处理的区域。
用于农业制剂中的具体湿润剂、分散剂或乳化剂包括(但不限于)烷基和烷芳基磺酸盐和硫酸盐以及它们的钠盐;烷芳基聚醚醇;硫酸化高级醇;聚环氧乙烷;磺化动植物油;磺化石油润滑油;脂肪酸多元醇酯以及这类酯的环氧乙烷加成物;以及长链硫醇和环氧乙烷的加成物。在商业上还可得到许多其它类型的有用的表面活性剂。当使用表面活性剂时,其含量常占组合物重量的1-15%。
其它有用的制剂包括活性成分悬浮在相对非挥发性溶剂(如水、玉米油、煤油、丙二醇或其它合适的溶剂)中形成的悬浮剂。
其它能作为杀虫剂使用的有用的制剂还包括活性成分在溶剂中形成的简单的溶液,在这种溶剂(如丙酮、烷基化的萘、二甲苯或其它有机溶剂)中,活性成分能以要求的浓度完全溶解。杀虫剂载带在相对粗糙颗粒上的颗粒制剂对空中撒布或透过覆盖作物的株冠(cover crop canopy)特别有效。还可使用加压喷雾(常形成气溶胶),其中低沸点分散溶剂载体(如二氧化碳、丙烷或丁烷)蒸发使活性成分分散成细分状态。在本发明化合物的杀虫应用中,水溶性或水分散性颗粒也是有用的制剂。这类颗粒制剂是可自由流动的、非粉状的并且容易溶解在水中或与水溶混。描述在美国专利3,920,442中的可溶解的或可分散的颗粒制剂对本发明杀虫化合物是有用的。农民在耕地上使用时,可用水将颗粒制剂、可乳化的浓缩物、可流动的浓缩物、溶液等稀释至活性成分的浓度约为0.1%或0.2%至1.5%或2%。
本发明杀虫化合物可与其它杀虫剂、杀真菌剂、杀线虫剂、植物生长调节素、肥料或其它农用化学物一起制成制剂和/或一起使用。在用本发明活性化合物(无论单独或与其它农用化学物一起形成制剂)控制虫害时,可将有效量和浓度的活性化合物施加至需要控制虫害的部位。该部位可以是例如害虫本身、带害虫的植物或害虫的栖息地。当该部位是土壤(如已种植或将种植农作物的土壤)时,该活性化合物的组合物可施加在或任意地掺入土壤。在许多应用场合,该有效量可低至如约10-500g/ha,最好约100-250g/ha。
显然,在不偏离本发明的发明思想以及权利要求所限定的范围的情况下,可对本发明化合物的制剂和使用进行改进。
表1
其中R是 R1和R2是化合物n V W X Y Z13 1 H H H H H14 1 Cl H H H H15 1 H H Cl H H16 1 H H F H H17 1 H H -CH3 H H18 1 H H -CH(CH3)2 H H19 1 H H -C(CH3)3 H H20 1 H -CF3 H H H21 1 H H OH H H22 1 -OCH3 H H H H23 1 H -OCH3 H H H24 1 H H -OCH3 H H25 2 H H -OCH3 H H26 3 H H -OCH3 H H27 1 H -OC2H5 H H H28 1 H H -OC2H5 H H29 1 H H n-OC3H7 H H30 1 H H -OCH(CH3)2 H H31 1 H H -OCH2CH2CH(CH3)2 H H32 1 H H -OCHF2 H H33 1 H H -OCF3 H H34 1 H -CH3 -OCH3 H H35 1 -OCH3 -OCH3 H H H36 1 -OCH3 -H -OCH3 H H37 1 -OCH3 H H -OCH3 H38 1 -OCH3 H H H -OCH339 1 H -OCH3 -OCH3 H H40 1 -OCH3 H -OCH3 H -OCH341 1 H -OCH3 -OCH3 -OCH3 H42 1 H H -OCH2CH=CH2 H H43 1 H H -OCH2CH=CH2 H H
一种N-氧化物44 1 H Cl -OCH3 H H45 1 Cl H -OC2H5 H H46 1 H F -OCH3 H H47 1 H F -OC2H5 H H48 1 H F n-OC3H7 H H49 1 H H -OSi(CH3)2C(CH3)3 H H50 1 H H -SCH3 H H51 1 H H -SC2F5 H H52 1 H H -CH2OC2H5 H H53 1 H H -CN H H54 1 H H -NO2 H H55 1 H H -N(CH3)2 H H56 1 H H -C(=O)C2H5 H H57 1 H H -CO2C2H5 H H58 1 H H 苯基 H H59 1 H 苯氧基 H H H60 1 H H 苯氧基 H H61 1 H H 苯氧基甲基 H H62 1 H 苯基甲氧基H H H63 1 H H 苯基甲氧基 H H64 1 H HH H65 1 H H -OCH2C≡CH H H66 1 H H -NH(C=O)CH3 H H67 1 H -OCH2CH2O- H H68 1 H -CH2C(CH3)2O- H H69 1 H -OC(CH3)2O- H H
其中n是1,R1和R2是化合物 R73 -CH2-C(Cl)=C(Cl)274
75
76
77
其中R是 R1和R2是化合物 n V W X Y Z78 1 H H n-OC4H9 H H79 1 H H -OCH2CHCH3)2 H H80 1 H H
H H81 1 H H n-OC5H11 H H82 1 Cl H n-OC3H7 H H83 1 -C2H5H n-OC3H7 H H84 1 -CF3 H n-OC3H7 H H85 1 H -CH3 n-OC3H7 H H86 1 H -C2H5 n-OC3H7 H H87 1 H H -O(CH2)3N(CH3)2 H H88 1 H H -OCH2C(Cl)=CH2 H H89 1 H H -OCH2CH=CHCl H H
顺式异构体90 1 H H -OCH2CH=CHCl H H
反式异构体91 1 H H -OCH2CH=CCl2 H H92 1 H H -OCH2C(CH3)=CH2 H H93 1 H H -OCH2CH=C(CH3)2 H H94 1 H H -OCH2CH=C(CH3)2 H H
一种N-氧化物95 1 H H -O(CH2)3CH=CH2 H H96 1 H H -OCH2C≡N97 1 H H -OCH2C≡CH H H
一种N-氧化物98 1 H H -OCH2C≡CCH3 H H99 1 H H -SO2C2F5 H H100 1 H H -NH2 H H101 1 H H -NHC3H7 H H102 1 H H -NH(C=O)C2H5 H H其中n是1,R是V,W,Y和Z是氢化合物 X R1 R2103 -OCH3 104 n-OC3H7 其中n是1,R是V,W,Y和Z是氢化合物X R1 R2105 n-OC3H7
表2
特 征 数 据1 C23H28F3NO3 90-93℃2 C29H40F3NO3 油3 C26H32F3NO3 油4 C25H30F3NO3 油5 C29H32F3NO3 ---6 C26H25Cl2F2NO2 油7 C29H31ClF3NO3 油8 C30H34F3NO3 油9 C22H21F6NO3 123-128℃10 C24H25F6NO3 浆状物11 C27H31F6NO3 油12 C26H24F6N2O3 55-59℃13 C27H25F6NO3 胶质油14 C27H24ClF6NO3 油15 C27H24ClF6NO3 油16 C27H24F7NO3 固体17 C28H27F6NO3 油18 C30H31F6NO3 油19 C31H33F6NO3 75-80℃20 C28H24F9NO3 油21 C27H25F6NO4 半固体22 C28H27F6NO4 50℃23 C28H27F6NO4 蜡状固体24 C28H27F6NO4 86-96℃25 C29H29F6NO4 凝胶26 C30H31F6NO4 粘性油27 C29H29F6NO4 油28 C29H29F6NO4 油29 C30H31F6NO4 油30 C30H31F6NO4 ---31 C32H35F6NO4 油32 C28H25F8NO4 油33 C28H24F9NO4 液体34 C29H29F6NO4 粘石油35 C29H29F6NO5 半固体36 C29H29F6NO5 液体37 C29H29F6NO5 油38 C29H29F6NO5 半固体39 C29H29F6NO5 油40 C30H31F6NO6 蜡状固体41 C30H31F6NO6 油42 C30H29F6NO4 液体43 C30H29F6NO5 固体44 C28H26ClF6NO4 无色稠油45 C29H28ClF6NO4 油46 C28H26F7NO4 油47 C29H28F7NO4 油48 C30H30F7NO4 油49 C33H39F6NO4Si 53-57℃50 C28H27F6NO3S 53-55℃51 C29H24F11NO3S 油52 C30H31F6NO4 粘性油53 C28H24F6N2O3 109-110℃54 C27H24F6N2O5 96-98℃55 C29H30F6N2O3 55-62℃56 C30H29F6NO4 无定型固体57 C30H29F6NO5 油58 C33H29F6NO3 65-70℃59 C33H29F6NO4 液体60 C33H29F6NO4 油61 C33H29F6NO4 油62 C34H31F6NO4 胶质固体63 C34H31F6NO4 胶质固体64 C34H30F7NO4 半固体65 C30H27F6NO4 液体66 C29H28F6N2O4 油67 C29H27F6NO5 油68 C31H31F6NO4 油69 C30H29F6NO5 油70 C28H31Cl2NO2 泡沫体71 C30H31F6NO4 油72 C27H30F3NO4 油73 C23H20Cl3NO3 泡沫体74 C25H23F6NO3S 粘性油75 C29H30F6N2O4 树胶76 C24H21F6N3O3 61-64℃77 C31H31F6NO4 胶质固体78 C31H33F6NO4 油79 C31H33F6NO4 55-56℃80 C31H31F6NO4 液体81 C32H35F6NO4 无色粘性油82 C30H30ClF6N2O4 半固体83 C32H35F6NO4 粘性油84 C31H30F9NO4 粘性油85 C31H33F6NO4 粘性油86 C32H35F6NO4 粘性油87 C32H36F6N2O4 胶质固体88 C30H28ClF6NO4 油89 C30H28ClF6NO4 油90 C30H28ClF6NO4 油91 C30H27Cl2F6NO4 油92 C31H31F6NO4 半固体93 C32H33F6NO4 油94 C32H33F6NO5 160-163℃95 C32H33F6NO4 油96 C29H26F6N2O4 半固体97 C30H27F6NO5 固体98 C31H29F6NO4 浆状物99 C29H24F11NO4S 78-81℃100 C27H26F6N2O3 68.0-71.0℃101 C30H32F6N2O3 油102 C30H30F6N2O4 96-101℃
103 C30H37NO 油
104 C30H31F6NO3 油
105 C30H30F7NO3 油
表3
混入烟芽夜蛾的饲料后的杀虫活性化合物 使用 生长抑制 pI504 %死亡5 pLC506
比例1 百分数2,31 4 22 <4.0 0 ---2 4 99 5.4 30 <4.03 4 53 4.1 0 ---4 4 51 4.0 0 ---5 4 51 4.0 0 ---6 4 95 5.1 5 <3.57 4 100 5.9 100 4.68 4 56 4.0 0 ---9 3.5 16 --- 0 ---10 4 69 4.3 0 ---11 4 76 4.6 0 ---12 4 20 --- 0 ---13 4 100 5.6 60 4.214 4 97 5.1 0 <3.515 4 100 5.6 90 4.516 4 99 5.6 85 4.517 4 100 5.7 90 4.518 4 90 4.7 0 ---19 4 87 4.5 0 ---20 4 69 4.0 0 ---21 4 100 5.6 75 4.222 4 100a 6.0 70a 4.3a23 4 99 5.6 30 <4.024 4 100a 6.1a 100a 4.6a25 4 98 5.6 25 <4.026 4 98 5.1 15 ---27 5 100 6.2 80 3.428 4 100b 6.5b 100b 5.4a29 4 100 6.5 100 5.831 4 100 5.7 100 5.032 4 100 5.6 100 4.533 4 99 5.4 65 4.234 4 100 6.0 90 4.535 4 99 5.2 55 4.236 4 100 5.5 95 4.537 4 98 5.3 35 4.038 4 99 5.0 45 4.139 4 100 6.2 100 4.640 4 98 5.4 30 <4.641 4 97 5.1 0 <4.642 4 100 6.5 100 5.543 4 100 6.4 100 5.544 4 100 5.6 65 4.345 4 100 5.6 100 4.946 4 100 6.2 100 4.947 4 100 6.4 100 5.548 4 100 6.4 100 5.649 4 77 4.6 0 ---50 4 98 5.0 40 <4.051 3.5 -10 --- 0 ---52 4 100b 6.2 100b 4.6b53 4 97 5.7 25 <4.054 4 81 4.7 0 ---55 4 100b 6.0b 100b 4.5b56 4 95 5.1 5 ---57 4 100b 6.2b 100b 5.3b58 4 100 5.6 100 4.859 4 82 4.5 0 <3.560 4 100 5.8 100 5.4b61 4 84 5.2 0 ---62 4 0 3.6 0 ---63 4 100 5.9 90 4.564 4 100 5.4 60 4.365 4 100b 6.1b0 100b 4.9b66 4 95 4.7 0 ---67 4 100 5.5 70 4.368 4 100 6.0 55 4.169 4 100 5.5 55 4.170 4 99 5.7 35 ---71 4 91 4.7 5 ---72 4 56 4.1 0 ---73 4 8 --- 0 ---74 4 99 5.4 60 4.275 4 100 5.6 100 4.976 4 3 --- 0 ---77 4 20 --- 0 ---78 4 100a 7.0a 100a 5.8a79 4 100 6.0 100 5.580 4 100 6.2 100 5.581 4 100 5.5 100 5.282 4 100 5.2 100 4.683 4 99 5.1 70 4.384 4 40 <4.0 0 ---85 4 100 5.6 100 5.586 4 100 5.4 100 4.687 4 34 3.9 0 ---88 4 100 6.1 100 5.189 4 100 >6.0 100 5.590 4 100a 6.1a 100a 5.1a91 4 100 5.4 0 4.292 4 100 6.2 100 4.993 4 100 5.6 100 4.694 4 100 6.3 100 5.695 4 100 5.6 100 5.096 4 100 6.2 100 4.697 4 100 6.3 100 4.698 4 100 6.1 100 4.899 4 0 --- 0 ---100 4 98 5.4 20 <3.5101 4 99 5.5 0 4.21024 100a 6.0a 100a 4.8a1034 75 4.3 0 ---1044 100 5.8 100 5.51054 100 5.6 100 5.0注:
1.使用比例以试验化合物在饲料中的摩尔浓度的负
对数表示。
2.生长抑制百分数由每个使用比例的试验组中的昆虫的总重量(IW)相对于未处理的对照组中的昆虫的总重量(IW)得到:
%生长抑制=[IW(对照组)-IW(试验组)/IW(对照组)]×100
3.负的生长抑制百分数指试验结束后试验组的昆虫重量重于对照组的昆虫重量。
4.pI50是在试验组中达到50%生长抑制时的试验化合物的浓度的负对数。
5.死亡百分数来自于相对于试验中所用的昆虫总数(TI)的死亡昆虫数(TD):
%死亡=TD/TI×100
6.pLC50是使试验昆虫达到50%死亡率时的试验化学物浓度的负对数。
a三次试验的平均值
b二次试验的平均值表4进行叶片喷洒时的杀虫活性
控 制 百 分 比1化合物 使用比例 TBW2 CL3 BAW4
(ppm)2 100 10 79 07 100 15 100 6013 100 5 100 015 100 20 100 3516 100 15 37 517 100 6 96* 3920 100 0 60 021 100 0 95 2522 100 20 97* 5323 100 0 97* 024 100 80 100 5527 100 45 100 6528 100 95* 100* 90*29 100 100* 97* 100*31 100 95 21 8132 100 97* 100* 85*33 100 21 60 1534 100 35 100 6336 100 33 100 7538 100 11 5 039 100 100 100 4240 100 5 25 541 100 5 --- 042 100 95* 100* 93*43 100 92* 100* 95*44 100 20 100 4545 100 90 85 9546 100 73* 100* 95*47 100 97* 87* 97*48 100 100* 65* 95*51 100 0 15 052 100 11 100 6053 100 28 --- 554 100 65 0 6355 100 25 100 557 100 100 90 10058 100 95 10 9059 100 0 0 1060 100 95 35 10064 100 11 25 067 100 100 90 9568 100 15 0 069 100 12 67 1078 100 100 100 6579 100 100 100 10080 100 100 100 10085 100 85 80 7888 100 72* 90* 3589 100 95 95 8590 100 85 100 8094 100 90 95 ---104 100 95* 90* 98*
1.%控制来自死亡昆虫的总数(TD)加上垂死昆虫的总数(TM)与所试验的昆虫的总数(TI)之比:
%控制=(TD+TM)/TI×100
2.TBW是烟芽夜蛾
3.CL是粉纹夜蛾
4.BAW是甜菜夜蛾
*指一次以上的试验的平均数
权利要求书
按照条约第19条的修改
1.一种具有如下通式的化合物:其中,Q选自氢、羟基和氟;
其中
V选自氢、卤素、烷基、卤代烷基和烷氧基;
W选自氢、卤素、烷基、卤代烷基、烷氧基、苯氧基以及苯基烷氧基;
X选自氢、羟基、卤素、烷基、烷氧基烷基、烷氧基、环烷基烷氧基、卤代烷氧基、烯氧基、卤代烯氧基、炔氧基、烷基甲硅烷氧基、烷硫基、卤代烷硫基、氰基、氰烷氧基、硝基、氨基、一烷基氨基、二烷基氨基、烷基氨基烷氧基、烷基羰基氨基、烷氧基羰基氨基、烷基羰基、烷氧基羰基、烷基氨基羰基、氨基羰基氧基、苯基、苯基烷氧基、苯氧基和苯氧基烷基,每个苯环可任意地被卤素、烷氧基或卤代烷氧基所取代;
Y和Z分别选自氢和烷氧基;
W和X一起形成-OCH2CH2O-、-CH2C(CH3)2O-或-OC(CH3)2O-;
R1和R2分别选自被卤代烷基或卤代烷氧基所取代的苯基;
n是1、2或3;
所附加的条件是每个脂族部分所含有的碳原子数不大于6,卤素指氯或氟,并且在氨基氮上的每个烷基取代基含有1-3个碳原子,
以及相应的N-氧化物和农业上可接受的盐。
其中
V选自氢和卤素;
Y和Z分别为氢;
W选自氢、卤素和烷氧基;
X选自氢、羟基、卤素、烷基、卤代烷基、链烯基、炔基、烷氧基、烯氧基、炔氧基、卤代烷氧基、烷硫基、卤代烷硫基、一烷基氨基、二烷基氨基、烷氧基烷基、烷氧基烷氧基、烷基羰基、烷氧基羰基、烷基氨基羰基、烷基羰基氨基、氰基、苯基、苯氧基、苯氧基烷基,和任意取代的苯基烷氧基;
W和X一起形成-OCH2CH2O-、-CH2C(CH3)2O-或-OC(CH3)2O-;
R1和R2卤代烷氧基所取代的苯基;
n是1、2或3;
所附加的条件是R1和R2中的一个是对位取代的苯基,
以及相应的N-氧化物和农业上可接受的盐。
3.如权利要求2所述的化合物,其中
V选自氢和氟;
W选自氢、卤素、甲氧基和乙氧基;
X选自氢、卤素、甲基、甲氧基、乙氧基、正丙氧基、正丁氧基、全氟乙氧基、全氟乙硫基、氰基、苯基、苯氧基、苯基甲氧基、二甲基氨基、乙氧基甲基、乙基羰基、乙氧基羰基、烯丙氧基、炔丙氧基、2-甲基丙氧基、环丙基甲氧基、2-氯-2-丙烯氧基、2-甲基-2-丙烯氧基、3-甲基-2-丁烯氧基、氰基甲氧基、2-丁炔氧基和乙基羰基氨基;
W和X一起形成-CH2C(CH3)2O-;
n是1;
R1和R2分别为对三氟甲氧基苯基,
及其它们的N-氧化物和农业上可接受的盐。
4.如权利要求3所述的化合物,其中W选自氢、氟和甲氧基。
5.如权利要求4所述的化合物,其中W是氢。
6.如权利要求5所述的化合物,其中V是氢,X是正丙氧基、环丙基甲氧基、乙氧基羰基或乙氧基,及其相应的N-氧化物。
7.如权利要求6所述的化合物,为N-(4-乙氧基苯基甲基)-4-[双(4-三氟甲氧基苯基)羟甲基]哌啶。
8.如权利要求6所述的化合物,为N-(4-正丙氧基苯基甲基)-4-[双(4-三氟甲氧基苯基)羟甲基]哌啶。
9.如权利要求6所述的化合物,为N-(4-乙氧基羰基苯基甲基)-4-[双(4-三氟甲氧基苯基)羟甲基]哌啶。
10.如权利要求6所述的化合物,为N-(4-环丙基甲氧基苯基甲基)-4-[双(4-三氟甲氧基苯基)羟甲基]哌啶。
11.如权利要求6所述的化合物,为N-(4-正丙氧基苯基甲基)-4-[双(4-三氟甲氧基苯基)羟甲基]哌啶N-氧化物。
12.如权利要求6所述的化合物,为N-(4-环丙基甲氧基苯基甲基)-4-[双(4-三氟甲氧基苯基)羟甲基]哌啶N-氧化物。
13.一种组合物,含有有效杀虫量的下面通式的化合物:其中,Q选自氢、羟基和氟;
R选自具有5或6个环原子和1或2个杂原子的杂芳基、以及
其中
V选自氢、卤素、烷基、卤代烷基和烷氧基;
W选自氢、卤素、烷基、卤代烷基、烷氧基、苯氧基以及苯基烷氧基;
X选自氢、羟基、卤素、烷基、烷氧基烷基、烷氧基、环烷基烷氧基、卤代烷氧基、烯氧基、卤代烯氧基、炔氧基、烷基甲硅烷氧基、烷硫基、卤代烷硫基、氰基、氰烷氧基、硝基、氨基、一烷基氨基、二烷基氨基、烷基氨基烷氧基、烷基羰基氨基、烷氧基羰基氨基、烷基羰基、烷氧基羰基、烷基氨基羰基、氨基羰基氧基、苯基、苯基烷氧基、苯氧基和苯氧基烷基,每个苯环可任意地被卤素、烷氧基或卤代烷氧基所取代;
Y和Z分别选自氢和烷氧基;
W和X一起形成-OCH2CH2O-、-CH2C(CH3)2O-或-OC(CH3)2O-;
R1和R2分别选自被卤素、烷基、卤代烷基、卤代烷氧基、烷基磺酰氧基和卤代烷基磺酰氧基所取代的苯基;
n是1、2或3;
所附加的条件是每个脂族部分所含有的碳原子数不大于6,卤素指氯或氟并且在氨基氮上的每个烷基取代基含有1-3个碳原子,
以及相应的N-氧化物和农业上可接受的盐,
以及与之相混合的至少一种农业上可接受的填充剂或助剂。
14.一种控制虫害的方法,包括向需要控制虫害的区域施加有效杀虫量的如权利要求1所述的组合物。
15.一种控制虫害的方法,包括向需要控制虫害的区域施加有效杀虫量的如权利要求13所述的组合物。
Claims (14)
其特征在于
V选自氢、卤素、烷基、卤代烷基和烷氧基;
W选自氢、卤素、烷基、卤代烷基、烷氧基、苯氧基以及苯基烷氧基;
X选自氢、羟基、卤素、烷基、烷氧基烷基、烷氧基、环烷基烷氧基、卤代烷氧基、烯氧基、卤代烯氧基、炔氧基、烷基甲硅烷氧基、烷硫基、卤代烷硫基、氰基、氰烷氧基、硝基、氨基、一烷基氨基、二烷基氨基、烷基氨基烷氧基、烷基羰基氨基、烷氧基羰基氨基、烷基羰基、烷氧基羰基、烷基氨基羰基、氨基羰基氧基、苯基、苯基烷氧基、苯氧基和苯氧基烷基,每个苯环可任意地被卤素、烷氧基或卤代烷氧基所取代;
Y和Z分别选自氢和烷氧基;
W和X一起形成-OCH2CH2O-、-CH2C(CH3)2O-或-OC(CH3)2O-;
R1和R2分别选自被卤素、烷基、卤代烷基、卤代烷氧基、烷基磺酰氧基和卤代烷基磺酰氧基所取代的苯基;
n是1、2或3;
所附加的条件是每个脂族部分所含有的碳原子数不大于6,卤素指氯或氟并且在氨基氮上的每个烷基取代基含有1-3个碳原子,
以及相应的N-氧化物和农业上可接受的盐。
其特征在于
V选自氢和卤素;
Y和Z分别为氢;
W选自氢、卤素和烷氧基;
X选自氢、羟基、卤素、烷基、卤代烷基、链烯基、炔基、烷氧基、烯氧基、炔氧基、卤代烷氧基、烷硫基、卤代烷硫基、一烷基氨基、二烷基氨基、烷氧基烷基、烷氧基烷氧基、烷基羰基、烷氧基羰基、烷基氨基羰基、烷基羰基氨基、氰基、苯基、苯氧基、苯氧基烷基,和任意取代的苯基烷氧基;
W和X一起形成-OCH2CH2O-、-CH2C(CH3)2O-或-OC(CH3)2O-;
R1和R2分别选自被卤素或卤代烷氧基所取代的苯基;
n是1、2或3;
所附加的条件是R1和R2中的一个是对位取代的苯基,
以及相应的N-氧化物和农业上可接受的盐。
3.如权利要求2所述的化合物,其特征在于
V选自氢和氟;
W选自氢、卤素、甲氧基和乙氧基;
X选自氢、卤素、甲基、甲氧基、乙氧基、正丙氧基、正丁氧基、全氟乙氧基、全氟乙硫基、氰基、苯基、苯氧基、苯基甲氧基、二甲基氨基、乙氧基甲基、乙基羰基、乙氧基羰基、烯丙氧基、炔丙氧基、2-甲基丙氧基、环丙基甲氧基、2-氯-2-丙烯氧基、2-甲基-2-丙烯氧基、3-甲基-2-丁烯氧基、氰基甲氧基、2-丁炔氧基和乙基羰基氨基;
W和X一起形成-CH2C(CH3)2O-;
n是1;
R1和R2分别为对三氟甲氧基苯基,
及其它们的N-氧化物和农业上可接受的盐。
4.如权利要求3所述的化合物,其特征在于W选自氢、氟和甲氧基。
5.如权利要求4所述的化合物,其特征在于W是氢。
6.如权利要求5所述的化合物,其特征在于V是氢,X是正丙氧基、环丙基甲氧基、乙氧基羰基或乙氧基,及其相应的N-氧化物。
7.如权利要求6所述的N-(4-乙氧基苯基甲基)-4-[双(4-三氟甲氧基苯基)羟甲基]哌啶化合物。
8.如权利要求6所述的N-(4-正丙氧基苯基甲基)-4-[双(4-三氟甲氧基苯基)羟甲基]哌啶化合物。
9.如权利要求6所述的N-(4-乙氧基羰基苯基甲基)-4-[双(4-三氟甲氧基苯基)羟甲基]哌啶化合物。
10.如权利要求6所述的N-(4-环丙基甲氧基苯基甲基)-4-[双(4-三氟甲氧基苯基)羟甲基]哌啶化合物。
11.如权利要求6所述的N-(4-正丙氧基苯基甲基)-4-[双(4-三氟甲氧基苯基)羟甲基]哌啶N-氧化物。
12.如权利要求6所述的N-(4-环丙基甲氧基苯基甲基)-4-[双(4-三氟甲氧基苯基)羟甲基]哌啶N-氧化物。
13.一种由有效杀虫量的如权利要求1所述的化合物和至少一种农业上可接受的填充剂或助剂相混合而成的组合物。
14.一种控制虫害的方法,其特征在于向需要控制虫害的区域施加有效杀虫量的如权利要求13所述的组合物。
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US20403394A | 1994-03-01 | 1994-03-01 | |
US08/204,033 | 1994-03-01 |
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CN1147193A true CN1147193A (zh) | 1997-04-09 |
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CN95192801A Pending CN1147193A (zh) | 1994-03-01 | 1995-02-28 | 杀虫剂n-(取代芳甲基)-4-[双(取代苯基)哌啶 |
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US (2) | US5639763A (zh) |
EP (1) | EP0748159A4 (zh) |
JP (1) | JPH09505080A (zh) |
KR (1) | KR970701497A (zh) |
CN (1) | CN1147193A (zh) |
AP (1) | AP9600855A0 (zh) |
AU (1) | AU694192B2 (zh) |
BG (1) | BG100815A (zh) |
BR (1) | BR9506972A (zh) |
CA (1) | CA2184576A1 (zh) |
CZ (1) | CZ256496A3 (zh) |
GT (1) | GT199500011A (zh) |
HU (1) | HU215401B (zh) |
IL (1) | IL112832A0 (zh) |
NO (1) | NO963641L (zh) |
OA (1) | OA10725A (zh) |
PL (1) | PL316082A1 (zh) |
SK (1) | SK112596A3 (zh) |
WO (1) | WO1995023507A1 (zh) |
ZA (1) | ZA951702B (zh) |
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CN104302623A (zh) * | 2012-05-01 | 2015-01-21 | 住友化学株式会社 | 哌啶化合物及其有害生物防除用途 |
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US5795901A (en) * | 1996-07-02 | 1998-08-18 | Fmc Corporation | Insecticidal N-(substituted arylmethyl)-4- bis(substituted aryl)hydroxymethyl!piperidinium salts |
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ATE327230T1 (de) | 2000-01-20 | 2006-06-15 | Eisai Co Ltd | Piperidinverbindungen und diese enthaltenden medikamente |
US6989394B2 (en) * | 2000-09-01 | 2006-01-24 | Syngenta Crop Protection, Inc. | Tetrahydropyridines |
KR100394030B1 (ko) * | 2001-01-15 | 2003-08-06 | 앰코 테크놀로지 코리아 주식회사 | 적층형 반도체 패키지 |
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JP2006511621A (ja) * | 2002-12-18 | 2006-04-06 | エフ エム シー コーポレーション | N―(置換アリールメチル)―4―(二置換メチル)ピペリジン及びピペラジン |
EP1620401A4 (en) | 2003-04-30 | 2008-08-13 | Bayer Cropscience Ag | PHENYL SUBSTITUTED CYCLIC DERIVATIVES |
JP2007508306A (ja) * | 2003-10-10 | 2007-04-05 | エフ エム シー コーポレーション | N−置換アザ環状体 |
JP4585818B2 (ja) * | 2004-09-10 | 2010-11-24 | 日本エンバイロケミカルズ株式会社 | シロアリ防除剤 |
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KR101997596B1 (ko) * | 2016-07-04 | 2019-07-08 | 주식회사 엘지화학 | 변성제, 변성 공액디엔계 중합체 및 이를 포함하는 고무 조성물 |
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-
1995
- 1995-02-16 US US08/389,675 patent/US5639763A/en not_active Expired - Lifetime
- 1995-02-28 KR KR1019960704824A patent/KR970701497A/ko not_active Application Discontinuation
- 1995-02-28 SK SK1125-96A patent/SK112596A3/sk unknown
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- 1995-02-28 CN CN95192801A patent/CN1147193A/zh active Pending
- 1995-02-28 PL PL95316082A patent/PL316082A1/xx unknown
- 1995-02-28 CA CA002184576A patent/CA2184576A1/en not_active Abandoned
- 1995-02-28 EP EP95911986A patent/EP0748159A4/en not_active Ceased
- 1995-02-28 AP APAP/P/1996/000855A patent/AP9600855A0/en unknown
- 1995-02-28 WO PCT/US1995/002473 patent/WO1995023507A1/en not_active Application Discontinuation
- 1995-02-28 AU AU19351/95A patent/AU694192B2/en not_active Ceased
- 1995-02-28 CZ CZ962564A patent/CZ256496A3/cs unknown
- 1995-02-28 JP JP7522973A patent/JPH09505080A/ja active Pending
- 1995-02-28 BR BR9506972A patent/BR9506972A/pt unknown
- 1995-03-01 GT GT199500011A patent/GT199500011A/es unknown
- 1995-03-01 IL IL11283295A patent/IL112832A0/xx unknown
-
1996
- 1996-03-01 ZA ZA951702A patent/ZA951702B/xx unknown
- 1996-08-30 NO NO963641A patent/NO963641L/no unknown
- 1996-09-02 OA OA60882A patent/OA10725A/en unknown
- 1996-09-02 BG BG100815A patent/BG100815A/xx unknown
-
1999
- 1999-09-02 US US09/388,592 patent/US6214845B1/en not_active Expired - Fee Related
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102190609A (zh) * | 2010-03-16 | 2011-09-21 | 凯惠科技发展(上海)有限公司 | 3-氯-4-甲氧基过氧苯甲酸及其中间体,及制备方法 |
CN104302623A (zh) * | 2012-05-01 | 2015-01-21 | 住友化学株式会社 | 哌啶化合物及其有害生物防除用途 |
Also Published As
Publication number | Publication date |
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CA2184576A1 (en) | 1995-09-08 |
ZA951702B (en) | 1996-12-02 |
EP0748159A4 (en) | 1997-11-19 |
NO963641D0 (no) | 1996-08-30 |
US6214845B1 (en) | 2001-04-10 |
JPH09505080A (ja) | 1997-05-20 |
AU1935195A (en) | 1995-09-18 |
NO963641L (no) | 1996-10-30 |
SK112596A3 (en) | 1997-03-05 |
HU215401B (hu) | 1998-12-28 |
IL112832A0 (en) | 1995-06-29 |
WO1995023507A1 (en) | 1995-09-08 |
PL316082A1 (en) | 1996-12-23 |
KR970701497A (ko) | 1997-04-12 |
AP9600855A0 (en) | 1996-10-31 |
BG100815A (en) | 1997-10-31 |
OA10725A (en) | 2002-12-04 |
EP0748159A1 (en) | 1996-12-18 |
MX9603762A (es) | 1997-10-31 |
AU694192B2 (en) | 1998-07-16 |
BR9506972A (pt) | 1997-09-23 |
GT199500011A (es) | 1996-08-22 |
US5639763A (en) | 1997-06-17 |
HUT75053A (en) | 1997-03-28 |
HU9602388D0 (en) | 1996-10-28 |
CZ256496A3 (en) | 1997-02-12 |
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