OA16334A - Noxious organism control agent - Google Patents
Noxious organism control agent Download PDFInfo
- Publication number
- OA16334A OA16334A OA1201300080 OA16334A OA 16334 A OA16334 A OA 16334A OA 1201300080 OA1201300080 OA 1201300080 OA 16334 A OA16334 A OA 16334A
- Authority
- OA
- OAPI
- Prior art keywords
- group
- substituted
- halogen atom
- formula
- halogen
- Prior art date
Links
- 230000001473 noxious Effects 0.000 title 1
- 241000607479 Yersinia pestis Species 0.000 claims abstract description 181
- 150000001412 amines Chemical class 0.000 claims abstract description 34
- 230000000694 effects Effects 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims description 345
- -1 2,6-dichloro-4-pyridyl group Chemical group 0.000 claims description 312
- 125000005843 halogen group Chemical group 0.000 claims description 222
- 125000000217 alkyl group Chemical group 0.000 claims description 170
- 239000003795 chemical substances by application Substances 0.000 claims description 89
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 claims description 66
- 229910052736 halogen Inorganic materials 0.000 claims description 47
- 150000002367 halogens Chemical class 0.000 claims description 47
- 125000003545 alkoxy group Chemical group 0.000 claims description 34
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 34
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 30
- 125000004448 alkyl carbonyl group Chemical group 0.000 claims description 29
- 239000007787 solid Substances 0.000 claims description 29
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 28
- 239000002689 soil Substances 0.000 claims description 21
- 125000001424 substituent group Chemical group 0.000 claims description 21
- 241000238876 Acari Species 0.000 claims description 20
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 19
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 19
- 239000000969 carrier Substances 0.000 claims description 18
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 16
- 239000000575 pesticide Substances 0.000 claims description 15
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 13
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 12
- 125000000623 heterocyclic group Chemical group 0.000 claims description 12
- 230000003071 parasitic Effects 0.000 claims description 12
- NRKYWOKHZRQRJR-UHFFFAOYSA-N 2,2,2-trifluoroacetamide Chemical compound NC(=O)C(F)(F)F NRKYWOKHZRQRJR-UHFFFAOYSA-N 0.000 claims description 11
- 229910004664 ORa Inorganic materials 0.000 claims description 11
- 241000282465 Canis Species 0.000 claims description 10
- DHQKLWKZSFCKTA-UHFFFAOYSA-N N-[1-[(6-chloropyridin-3-yl)methyl]pyridin-2-ylidene]-2,2,2-trifluoroacetamide Chemical compound FC(F)(F)C(=O)N=C1C=CC=CN1CC1=CC=C(Cl)N=C1 DHQKLWKZSFCKTA-UHFFFAOYSA-N 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 229910004755 ORb Inorganic materials 0.000 claims description 9
- 125000002947 alkylene group Chemical group 0.000 claims description 9
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 9
- 125000004450 alkenylene group Chemical group 0.000 claims description 8
- 125000005196 alkyl carbonyloxy group Chemical group 0.000 claims description 8
- 125000004419 alkynylene group Chemical group 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 8
- 125000004070 6 membered heterocyclic group Chemical group 0.000 claims description 7
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 7
- 241000258242 Siphonaptera Species 0.000 claims description 6
- 125000004414 alkyl thio group Chemical group 0.000 claims description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 6
- 235000015097 nutrients Nutrition 0.000 claims description 6
- ABFADXMVCUMADD-UHFFFAOYSA-N 2,2,2-trifluoro-N-[1-[(6-fluoropyridin-3-yl)methyl]pyridin-2-ylidene]acetamide Chemical compound C1=NC(F)=CC=C1CN1C(=NC(=O)C(F)(F)F)C=CC=C1 ABFADXMVCUMADD-UHFFFAOYSA-N 0.000 claims description 5
- 125000005330 8 membered heterocyclic group Chemical group 0.000 claims description 5
- 230000001276 controlling effect Effects 0.000 claims description 5
- 125000004076 pyridyl group Chemical group 0.000 claims description 5
- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 5
- 125000006584 (C3-C10) heterocycloalkyl group Chemical group 0.000 claims description 4
- 125000002373 5 membered heterocyclic group Chemical group 0.000 claims description 4
- SAILTMJFUSTICR-UHFFFAOYSA-N N-[1-[1-(6-chloropyridin-3-yl)ethyl]pyridin-2-ylidene]-2,2,2-trifluoroacetamide Chemical compound C1=CC=CC(=NC(=O)C(F)(F)F)N1C(C)C1=CC=C(Cl)N=C1 SAILTMJFUSTICR-UHFFFAOYSA-N 0.000 claims description 4
- 239000001963 growth media Substances 0.000 claims description 4
- XWHQQWVKDTVEEJ-UHFFFAOYSA-N 2-chloro-N-[1-[(6-chloropyridin-3-yl)methyl]pyridin-2-ylidene]-2,2-difluoroacetamide Chemical compound FC(F)(Cl)C(=O)N=C1C=CC=CN1CC1=CC=C(Cl)N=C1 XWHQQWVKDTVEEJ-UHFFFAOYSA-N 0.000 claims description 3
- YFSUKTJZKJIUTM-UHFFFAOYSA-N N-[1-[(2-chloropyrimidin-5-yl)methyl]pyridin-2-ylidene]-2,2,2-trifluoroacetamide Chemical compound FC(F)(F)C(=O)N=C1C=CC=CN1CC1=CN=C(Cl)N=C1 YFSUKTJZKJIUTM-UHFFFAOYSA-N 0.000 claims description 3
- YYELCPZJQRYUSB-UHFFFAOYSA-N N-[1-[(6-bromopyridin-3-yl)methyl]pyridin-2-ylidene]-2,2,2-trifluoroacetamide Chemical compound FC(F)(F)C(=O)N=C1C=CC=CN1CC1=CC=C(Br)N=C1 YYELCPZJQRYUSB-UHFFFAOYSA-N 0.000 claims description 2
- NWOFWGTYDVCXRD-UHFFFAOYSA-N N-[1-[(6-chloropyridin-3-yl)methyl]pyridin-2-ylidene]-2,2,3,3,3-pentafluoropropanamide Chemical compound FC(F)(F)C(F)(F)C(=O)N=C1C=CC=CN1CC1=CC=C(Cl)N=C1 NWOFWGTYDVCXRD-UHFFFAOYSA-N 0.000 claims description 2
- 230000001939 inductive effect Effects 0.000 claims description 2
- 125000004433 nitrogen atoms Chemical group N* 0.000 claims 4
- 229910003667 SRa Inorganic materials 0.000 claims 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N acetic acid ethyl ester Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 187
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 153
- 239000000203 mixture Substances 0.000 description 146
- 238000006243 chemical reaction Methods 0.000 description 137
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene dichloride Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 127
- WEVYAHXRMPXWCK-UHFFFAOYSA-N acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 126
- 241000238631 Hexapoda Species 0.000 description 123
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 104
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 101
- HEDRZPFGACZZDS-UHFFFAOYSA-N chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 94
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 87
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 83
- 239000002904 solvent Substances 0.000 description 80
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 74
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 74
- BZKBCQXYZZXSCO-UHFFFAOYSA-N sodium hydride Chemical compound [H-].[Na+] BZKBCQXYZZXSCO-UHFFFAOYSA-N 0.000 description 72
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 64
- 239000000243 solution Substances 0.000 description 63
- 239000002585 base Substances 0.000 description 62
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 60
- 230000002829 reduced Effects 0.000 description 58
- 239000000126 substance Substances 0.000 description 58
- 230000015572 biosynthetic process Effects 0.000 description 51
- 238000003786 synthesis reaction Methods 0.000 description 51
- 230000002194 synthesizing Effects 0.000 description 51
- 239000008079 hexane Substances 0.000 description 50
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 50
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 50
- ZMANZCXQSJIPKH-UHFFFAOYSA-N triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 47
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 46
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 46
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 46
- MVPPADPHJFYWMZ-UHFFFAOYSA-N Chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 44
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 43
- 239000011541 reaction mixture Substances 0.000 description 43
- 230000000749 insecticidal Effects 0.000 description 40
- 238000009472 formulation Methods 0.000 description 39
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 38
- 239000003513 alkali Substances 0.000 description 37
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 35
- 150000002148 esters Chemical class 0.000 description 34
- 238000005160 1H NMR spectroscopy Methods 0.000 description 32
- 239000001184 potassium carbonate Substances 0.000 description 32
- 229910000027 potassium carbonate Inorganic materials 0.000 description 32
- 150000002170 ethers Chemical class 0.000 description 31
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 25
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 25
- 150000008282 halocarbons Chemical class 0.000 description 24
- 150000001408 amides Chemical class 0.000 description 23
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 23
- 238000001914 filtration Methods 0.000 description 23
- 150000002576 ketones Chemical class 0.000 description 23
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 23
- 239000008096 xylene Substances 0.000 description 23
- TVMXDCGIABBOFY-UHFFFAOYSA-N Octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 22
- KLGZELKXQMTEMM-UHFFFAOYSA-N hydride Chemical compound [H-] KLGZELKXQMTEMM-UHFFFAOYSA-N 0.000 description 22
- IMNFDUFMRHMDMM-UHFFFAOYSA-N n-heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 22
- 150000002825 nitriles Chemical class 0.000 description 22
- FXHOOIRPVKKKFG-UHFFFAOYSA-N DMA Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 21
- YMIPTEDANARMCB-UHFFFAOYSA-N N-[(6-chloropyridin-3-yl)methyl]-2-methylsulfanylethanamine Chemical compound CSCCNCC1=CC=C(Cl)N=C1 YMIPTEDANARMCB-UHFFFAOYSA-N 0.000 description 21
- 240000007594 Oryza sativa Species 0.000 description 21
- 235000007164 Oryza sativa Nutrition 0.000 description 21
- 150000001298 alcohols Chemical class 0.000 description 21
- 235000009566 rice Nutrition 0.000 description 21
- 150000003462 sulfoxides Chemical class 0.000 description 21
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-Dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 20
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate dianion Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 20
- 229940117389 Dichlorobenzene Drugs 0.000 description 20
- 241000196324 Embryophyta Species 0.000 description 20
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 20
- 150000003512 tertiary amines Chemical class 0.000 description 20
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 19
- 238000010438 heat treatment Methods 0.000 description 19
- 229910052739 hydrogen Inorganic materials 0.000 description 19
- VLYFRFHWUBBLRR-UHFFFAOYSA-L potassium;sodium;carbonate Chemical compound [Na+].[K+].[O-]C([O-])=O VLYFRFHWUBBLRR-UHFFFAOYSA-L 0.000 description 19
- 150000004820 halides Chemical class 0.000 description 18
- BDERNNFJNOPAEC-UHFFFAOYSA-N propanol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 18
- 238000010898 silica gel chromatography Methods 0.000 description 18
- 239000012141 concentrate Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxyl anion Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 17
- 229920001213 Polysorbate 20 Polymers 0.000 description 16
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N Trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 16
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 16
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 16
- 238000004458 analytical method Methods 0.000 description 15
- 239000007788 liquid Substances 0.000 description 14
- 238000000622 liquid--liquid extraction Methods 0.000 description 14
- 238000000638 solvent extraction Methods 0.000 description 14
- 241001498622 Cixius wagneri Species 0.000 description 13
- 239000005906 Imidacloprid Substances 0.000 description 13
- YWTYJOPNNQFBPC-UHFFFAOYSA-N Imidacloprid Chemical compound [O-][N+](=O)\N=C1/NCCN1CC1=CC=C(Cl)N=C1 YWTYJOPNNQFBPC-UHFFFAOYSA-N 0.000 description 13
- 241001470017 Laodelphax striatella Species 0.000 description 13
- 239000002253 acid Substances 0.000 description 13
- 239000003153 chemical reaction reagent Substances 0.000 description 13
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 13
- 239000000706 filtrate Substances 0.000 description 13
- 239000008187 granular material Substances 0.000 description 13
- 229940056881 imidacloprid Drugs 0.000 description 13
- 241000255925 Diptera Species 0.000 description 12
- 239000000428 dust Substances 0.000 description 12
- 150000008064 anhydrides Chemical class 0.000 description 11
- 239000012074 organic phase Substances 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 150000002829 nitrogen Chemical group 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- SKCNYHLTRZIINA-UHFFFAOYSA-N 2-chloro-5-(chloromethyl)pyridine Chemical compound ClCC1=CC=C(Cl)N=C1 SKCNYHLTRZIINA-UHFFFAOYSA-N 0.000 description 9
- IZBFEHOMQJBHLY-UHFFFAOYSA-M CS=C(SCC)[S-] Chemical compound CS=C(SCC)[S-] IZBFEHOMQJBHLY-UHFFFAOYSA-M 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 9
- BDAGIHXWWSANSR-UHFFFAOYSA-N formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- 239000002917 insecticide Substances 0.000 description 9
- 238000000634 powder X-ray diffraction Methods 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 8
- 241001124076 Aphididae Species 0.000 description 8
- 241001466042 Fulgoromorpha Species 0.000 description 8
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-Bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 8
- QGJOPFRUJISHPQ-UHFFFAOYSA-N carbon bisulphide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 8
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 8
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- 238000009833 condensation Methods 0.000 description 8
- 238000005507 spraying Methods 0.000 description 8
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-Aminopyridine Chemical compound NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 description 7
- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 description 7
- 241001600408 Aphis gossypii Species 0.000 description 7
- 230000001058 adult Effects 0.000 description 7
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- 239000011248 coating agent Substances 0.000 description 7
- 125000004122 cyclic group Chemical group 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000003501 hydroponics Substances 0.000 description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 7
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- KUGLJYVDCCITGB-UHFFFAOYSA-N 2,2,2-trifluoro-N-pyridin-2-ylacetamide Chemical compound FC(F)(F)C(=O)NC1=CC=CC=N1 KUGLJYVDCCITGB-UHFFFAOYSA-N 0.000 description 6
- JVVRCYWZTJLJSG-UHFFFAOYSA-N 4-Dimethylaminophenol Substances CN(C)C1=CC=C(O)C=C1 JVVRCYWZTJLJSG-UHFFFAOYSA-N 0.000 description 6
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- VZGDMQKNWNREIO-UHFFFAOYSA-N Carbon tetrachloride Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 6
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- 241000500437 Plutella xylostella Species 0.000 description 6
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- 235000014113 dietary fatty acids Nutrition 0.000 description 6
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- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 6
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- DLFVBJFMPXGRIB-UHFFFAOYSA-N acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 5
- 239000002671 adjuvant Substances 0.000 description 5
- 230000000240 adjuvant Effects 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
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- 239000003054 catalyst Substances 0.000 description 5
- 238000000113 differential scanning calorimetry Methods 0.000 description 5
- VRZVPALEJCLXPR-UHFFFAOYSA-N ethyl 4-methylbenzenesulfonate Chemical compound CCOS(=O)(=O)C1=CC=C(C)C=C1 VRZVPALEJCLXPR-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
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- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 5
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- 238000000746 purification Methods 0.000 description 5
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- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 description 4
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 description 4
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 4
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- 239000004342 Benzoyl peroxide Substances 0.000 description 4
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- QOSSAOTZNIDXMA-UHFFFAOYSA-N Carbodicyclohexylimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 4
- 102000004190 Enzymes Human genes 0.000 description 4
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- UWVQIROCRJWDKL-UHFFFAOYSA-N oxadixyl Chemical compound CC=1C=CC=C(C)C=1N(C(=O)COC)N1CCOC1=O UWVQIROCRJWDKL-UHFFFAOYSA-N 0.000 description 1
- 230000004783 oxidative metabolism Effects 0.000 description 1
- 229960000321 oxolinic acid Drugs 0.000 description 1
- 230000036961 partial Effects 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- FURYAADUZGZUGQ-UHFFFAOYSA-N phenoxybenzene;sulfuric acid Chemical compound OS(O)(=O)=O.C=1C=CC=CC=1OC1=CC=CC=C1 FURYAADUZGZUGQ-UHFFFAOYSA-N 0.000 description 1
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- 239000003016 pheromone Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000886 photobiology Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
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- 229910052697 platinum Inorganic materials 0.000 description 1
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- 239000003380 propellant Substances 0.000 description 1
- KKMLIVYBGSAJPM-UHFFFAOYSA-L propineb Chemical compound [Zn+2].[S-]C(=S)NC(C)CNC([S-])=S KKMLIVYBGSAJPM-UHFFFAOYSA-L 0.000 description 1
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- QHMTXANCGGJZRX-WUXMJOGZSA-N pymetrozine Chemical compound C1C(C)=NNC(=O)N1\N=C\C1=CC=CN=C1 QHMTXANCGGJZRX-WUXMJOGZSA-N 0.000 description 1
- QHGVXILFMXYDRS-UHFFFAOYSA-N pyraclofos Chemical compound C1=C(OP(=O)(OCC)SCCC)C=NN1C1=CC=C(Cl)C=C1 QHGVXILFMXYDRS-UHFFFAOYSA-N 0.000 description 1
- VKSBNOLDZMDHRV-UHFFFAOYSA-M pyran-2-ylidenemethanolate Chemical compound [O-]C=C1OC=CC=C1 VKSBNOLDZMDHRV-UHFFFAOYSA-M 0.000 description 1
- 239000002728 pyrethroid Substances 0.000 description 1
- DWFZBUWUXWZWKD-UHFFFAOYSA-N pyridaben Chemical compound C1=CC(C(C)(C)C)=CC=C1CSC1=C(Cl)C(=O)N(C(C)(C)C)N=C1 DWFZBUWUXWZWKD-UHFFFAOYSA-N 0.000 description 1
- AEHJMNVBLRLZKK-UHFFFAOYSA-N pyridalyl Chemical group N1=CC(C(F)(F)F)=CC=C1OCCCOC1=C(Cl)C=C(OCC=C(Cl)Cl)C=C1Cl AEHJMNVBLRLZKK-UHFFFAOYSA-N 0.000 description 1
- ZLIBICFPKPWGIZ-UHFFFAOYSA-N pyrimethanil Chemical compound CC1=CC(C)=NC(NC=2C=CC=CC=2)=N1 ZLIBICFPKPWGIZ-UHFFFAOYSA-N 0.000 description 1
- ITKAIUGKVKDENI-UHFFFAOYSA-N pyrimidifen Chemical compound CC1=C(C)C(CCOCC)=CC=C1OCCNC1=NC=NC(CC)=C1Cl ITKAIUGKVKDENI-UHFFFAOYSA-N 0.000 description 1
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- FBQQHUGEACOBDN-UHFFFAOYSA-N quinomethionate Chemical compound N1=C2SC(=O)SC2=NC2=CC(C)=CC=C21 FBQQHUGEACOBDN-UHFFFAOYSA-N 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 101700024412 soti Proteins 0.000 description 1
- 229940014213 spinosad Drugs 0.000 description 1
- DTDSAWVUFPGDMX-UHFFFAOYSA-N spirodiclofen Chemical compound CCC(C)(C)C(=O)OC1=C(C=2C(=CC(Cl)=CC=2)Cl)C(=O)OC11CCCCC1 DTDSAWVUFPGDMX-UHFFFAOYSA-N 0.000 description 1
- GOLXNESZZPUPJE-UHFFFAOYSA-N spiromesifen Chemical compound CC1=CC(C)=CC(C)=C1C(C(O1)=O)=C(OC(=O)CC(C)(C)C)C11CCCC1 GOLXNESZZPUPJE-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 150000003450 sulfenic acids Chemical class 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000008400 supply water Substances 0.000 description 1
- 239000000829 suppository Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- LWLJEQHTPVPKSJ-UHFFFAOYSA-N tebufloquin Chemical compound C1=C(C(C)(C)C)C=C2C(OC(=O)C)=C(C)C(C)=NC2=C1F LWLJEQHTPVPKSJ-UHFFFAOYSA-N 0.000 description 1
- CJDWRQLODFKPEL-UHFFFAOYSA-N teflubenzuron Chemical compound FC1=CC=CC(F)=C1C(=O)NC(=O)NC1=CC(Cl)=C(F)C(Cl)=C1F CJDWRQLODFKPEL-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- WOSNCVAPUOFXEH-UHFFFAOYSA-N thifluzamide Chemical compound S1C(C)=NC(C(F)(F)F)=C1C(=O)NC1=C(Br)C=C(OC(F)(F)F)C=C1Br WOSNCVAPUOFXEH-UHFFFAOYSA-N 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
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- BAKXBZPQTXCKRR-UHFFFAOYSA-N thiodicarb Chemical compound CSC(C)=NOC(=O)NSNC(=O)ON=C(C)SC BAKXBZPQTXCKRR-UHFFFAOYSA-N 0.000 description 1
- QGHREAKMXXNCOA-UHFFFAOYSA-N thiophanate-methyl Chemical compound COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC QGHREAKMXXNCOA-UHFFFAOYSA-N 0.000 description 1
- VJQYLJSMBWXGDV-UHFFFAOYSA-N tiadinil Chemical compound N1=NSC(C(=O)NC=2C=C(Cl)C(C)=CC=2)=C1C VJQYLJSMBWXGDV-UHFFFAOYSA-N 0.000 description 1
- OBZIQQJJIKNWNO-UHFFFAOYSA-N tolclofos-methyl Chemical compound COP(=S)(OC)OC1=C(Cl)C=C(C)C=C1Cl OBZIQQJJIKNWNO-UHFFFAOYSA-N 0.000 description 1
- WPALTCMYPARVNV-UHFFFAOYSA-N tolfenpyrad Chemical compound CCC1=NN(C)C(C(=O)NCC=2C=CC(OC=3C=CC(C)=CC=3)=CC=2)=C1Cl WPALTCMYPARVNV-UHFFFAOYSA-N 0.000 description 1
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- NKNFWVNSBIXGLL-UHFFFAOYSA-N triazamate Chemical compound CCOC(=O)CSC1=NC(C(C)(C)C)=NN1C(=O)N(C)C NKNFWVNSBIXGLL-UHFFFAOYSA-N 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-N trifluoroacetic acid Substances OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
- RROQIUMZODEXOR-UHFFFAOYSA-N triforine Chemical compound O=CNC(C(Cl)(Cl)Cl)N1CCN(C(NC=O)C(Cl)(Cl)Cl)CC1 RROQIUMZODEXOR-UHFFFAOYSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- JARYYMUOCXVXNK-CSLFJTBJSA-N validamycin A Chemical compound N([C@H]1C[C@@H]([C@H]([C@H](O)[C@H]1O)O[C@H]1[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O1)O)CO)[C@H]1C=C(CO)[C@@H](O)[C@H](O)[C@H]1O JARYYMUOCXVXNK-CSLFJTBJSA-N 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000004562 water dispersible granule Substances 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- CHNQZRKUZPNOOH-UHFFFAOYSA-J zinc;manganese(2+);N-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[Zn+2].[S-]C(=S)NCCNC([S-])=S.[S-]C(=S)NCCNC([S-])=S CHNQZRKUZPNOOH-UHFFFAOYSA-J 0.000 description 1
Abstract
Specific amine derivatives have been found to possess excellent activities as pest control agents.
Description
[DESCRIPTION] [Title of Invention] PEST CONTROL AGENT [Technical Field]
The présent invention relates to novel amine dérivatives and pest control agents which use the same.
[Background Art]
Many pest control agents hâve been discovered to date. However, still novel pesticides are desired today owing to, for example, the résistant problem to pesticides and to concerns such as the persistence of the pesticide effects and safety at the time of use.
In paddy rice cultivation in East Asia and Southeast Asia in particular, as indicated in NonPatent Document 1, damage by planthoppers which hâve developed chemical résistance to major insecticides, including neonicotinoids such as imidacloprid and phenylpyrazole pesticides such as fipronil has emerged. As a resuit, spécifie agents for planthoppers that hâve developed résistance are awaited.
With regard to heterocycle-containing amine dérivatives, Patent Document 1 describes monoalkylamine compounds having a cyano group on the nitrogen atom, and the insecticidal activity of such compounds on aphids. However, no spécifie disclosure is made conceming dialkylamine compounds, nor is anything mentioned about the control activity on pests other than aphids.
Patent Document 2 mentions amine dérivatives which contain a 2,6-dichloro-4-pyridyl group and hâve a carboxyl group on the nitrogen atom, as well as the fungicidal activities and insecticidal activities thereof, but discloses no other heterocycles.
In Non-Patent Documents 2 and 3, amine dérivatives which contain a 6-chloro-3-pyridyl group and hâve an acetyl group on the nitrogen atom are disclosed as métabolites or reaction intermediates, but no mention is made of their pest control activities. Non-Patent Document 4 discloses amine dérivatives which contain a 6-chloro-3-pyridyl group and hâve on the nitrogen atom a N-methylcarbamoyl group or a N-formylcarbamoyl group, but makes no mention of the pest control activities thereof.
t i
Patent Document 3 discloses a plurality of compounds having ring structures similar to those of compounds of formula (le), but these are intended for use as herbicides; no mention is made of pest control.
Patent Document 4 discloses the structural formula of N-[1-((6-chloropyridin-3yl)methyl)pyndin-2(1H)-ylidene]-2,2,2-trifluoroacetamide (Table 1, Compound No. 3 in Patent Document 4), but discloses nothing whatsoever concerning the method of préparation. Nor is this compound included in the lists of compounds for which pest control activities were observed (Tables 2 and 3 in Patent Document 4).
Patent Document 5 discloses the structural formula of N-[1-((6-chloropyridin-3yl)methyl)pyridin-2(1H)-ylidene]-2,2,2-trifluoroacetamide (Table 7, Example No. 12 in Patent Document 5), but discloses nothing whatsoever concerning the method of préparation. Nor is this compound mentioned in the examples of compounds having pest control activities which are described in the working examples.
Non-Patent Document 5 discloses a plurality of compounds having ring structures similar to the compounds of subsequently mentioned formula (le), but these are merely disclosed as synthesis intermediates.
Patent Document 6 discloses a plurality of compounds having rings structures similar to the compounds of formula (le), but no mention or suggestion is made concerning compounds having a trifluoroacetic acid imino structure.
[Citation List] [Patent Literatures] [PL 1] Japanese Unexamined Patent Application Publication No. 2003-26661 (JP 2003-26661 A) [PL 2] International Publication No. WO 2002/050035 (WO 2002-050035) [PL 3] European Unexamined Patent Application Publication No. 432600 [PL 4] Japanese Unexamined Patent Application Publication No. Hei 5-78323 (JP 5-78323 A) [PL 5] European Unexamined Patent Application Publication No. 268915 [PL 6] European Unexamined Patent Application Publication No. 259738 f
[Non Patent Literatures] [NPL 1] Pest Management Science, 64(11), 1115-1121 (2008) [NPL 2] Journal of Agricultural and Food Chemistry, 58(4), 2419 (2010) [NPL 3] Pest Management Science, 61 (8), 742 (2005) [NPL 4] Journal of Photochemistry and Photobiology B: Biology, 98(1), 57 (2010) [NPL 5] Chemische Berichte, 88,1103-8 (1955) [Summary of Invention] [Technical Problem]
It is therefore an object of the présent invention to provide novel pest control agents and thereby, in the pest control field, to solve the problems of existing pesticides, such as résistance to the pesticides, persistence of the pesticide effects, and safety at the time of use.
One major object of the invention is to provide pesticides which hâve excellent control effects against the brown rîce planthopper, the white-backed rice planthopper and the small brown planthopper, ail major insect pests today in the field of paddy rice cultivation, which hâve a high activity even against pesticide-resistant planthoppers, and which reduce the chances for the exposure of workers to the pesticide during use in, for example, soil treatment, seed treatment and seedling box treatment and can thus be safely employed.
[Solution to Problem]
The inventors hâve conducted extensive investigations in order to solve the above problems, as a resuit of which they hâve discovered that amine dérivatives of chemical formula (I) hâve excellent activities as pest control agents.
Accordingly, the invention provides:
(1) A pest control agent comprising at least one compound of the following formula (I) or a sait thereof [Chem. 1]
R2 (D (wherein Ar is a phenyl group which may be substituted or a 5- or 6-membered heterocycle which may be substituted;
Ri is a hydrogen atom or a alkyl group;
R2 is a Ci^ alkylcarbonyl group in which the alkyl moiety may be substituted with a halogen atom, a Cu alkyloxycarbonyl group in which the alkyl moiety may be substituted with a halogen atom, a Cw alkylsulfonyl group in which the alkyl moiety may be substituted with a halogen atom, CONReR7, a Ο,Ο'-alkylphosphoryl group in which the alkyl moiety may be substituted with a halogen atom, a cyano group, a formyl group or a nitro group;
R3 is a CAa alkylene group which may be substituted with a halogen atom, a C2.0 alkenylene group which may be substituted with a halogen atom, a CZ8 alkynylene group which may be substituted with a halogen atom, a phenylene group which may be substituted, or a 5- or 6-membered heterocyclic divalent group which may be substituted; and
R4 is a hydrogen atom, a cyano group, a phenyl group which may be substituted, a 3- to 8membered cyclic alkyl group which may be substituted, a 3- to 8-membered heterocyclic which may be substituted, a halogen atom, OR5i OCOR5, OCOOR5, COR5, COOR5, SR5, SOR5] SO2R5, n-co-orb, n-co-srS] n-cs-or8, n-cs-sr8, n-o-co-r8, o-co-r8, o-co-or8, o-co-sr8i oCS-ORb, O-CS-SR8, S-CS-ORa, S-CS-SRs, S-CO-ORb, S-CO-SRe, S-CS-Rs, NR3R1O1 O-CONRSR1O, O-CS-NR9R10, S-CO-NRsR10 or S-CS-NR9R10Î wherein R5 is a C; « alkyl group which may be substituted with a halogen atom, an aryl group which may be substituted with a halogen atom or an aralkyl group which may be substituted with a halogen atom;
R6 and R7 are each independently a hydrogen atom or a Θμο alkyl group which may be substituted with a halogen atom;
R0 is a Ci-g alkyl group which may be substituted, the substituent being a halogen atom, a CM alkyloxycarbonyl group, a Cm alkylcarbonyl group, a benzoyl group which may be substituted with a halogen atom or a Cm alkyl group which may be substituted with a halogen atom, a Cm alkyloxy group or a Cm alkylthio group;
Rs and Rio are each independently a hydrogen atom, a formyl group, a Cm alkyl group which may be substituted with a halogen atom, a Ci.6 alkylcarbonyl group in which the alkyl moiety may be substituted with a halogen atom, a Ci.6 alkylcarbonyloxy group in which the alkyl moiety may be substituted with a halogen atom, a phenyl group which may be substituted (the substituent being a halogen atom, a Cm alkyl group which may be substituted with a halogen atom, or a Cm alkyloxy group which may be substituted with a halogen atom), or a benzyl group which may be substituted (the substituent being a halogen, a Cm alkyl group which may be substituted with a halogen or a Cm alkyloxy group which may be substituted with a halogen), R9 and R10 together form a ring and dénoté a 3- to 10-membered heterocycloalkyl group containing at least one nitrogen atom, or N, R9 and R10 together form a ring and dénoté a 5- or 6-membered aromatic heterocycle containing at least one nitrogen atom, and
N, R2, R3 and R4 may together form a group of formula (E) [Chem. 2]
O (E) wherein Y is a hydrogen atom, a halogen atom, a hydroxyl group, a Cm alkyl group which may be substituted with a halogen atom, a Cm alkyloxy group which may be substituted with a halogen atom, a cyano group, a formyl group or a nitro group, and R9f. is a Cm alkyl group substituted with a halogen or a Cm alkyloxy group which may be substituted with a halogen;
with the proviso that if Ar is a 2,6-dichloro-4-pyridyl group, then R2 is not a Cm alkyloxycarbonyl group in which the alkyl moiety may be substituted with a halogen atom).
t (2) The pest control agent according to (1), wherein Ar in formula (I) is a 6-chloro-3-pyridyl group or a 5-chloro-3-thiazolyl group.
(3) The pest control agent according to (1) or (2), wherein R2 in formula (I) is a alkylcarbonyl group in which the alkyl moiety may be substituted with a halogen atom, a Ci< alkylsulfonyl group in which the alkyl moiety may be substituted with a halogen atom, or a cyano group.
(4) The pest control agent according to (1), wherein the compound of formula (I) is a compound of formula (le) below.
[Chem. 3]
(5) The pest control agent according to (4), wherein R4e in formula (le) is a Ci_6 alkyl group substituted with a halogen atom.
(6) The pest control agent according to (4), wherein Y in formula (le) is a hydrogen atom or a halogen atom.
(7) The pest control agent according to (4), wherein R4e in formula (le) is a C14} alkyl group substituted with a halogen atom, and Y is a hydrogen atom or a halogen atom.
(8) The pest control agent according to (4), wherein the compound of formula (le) is a compound selected from the group consisting of N-[1-((6-chloropyridin-3-yl)methyl)pyridin-2(1 H)-
y I idene]-2, 2,2-trifluoroacetam ide, | N-[1-((6-chloro-5-fluoropyridin-3-yl)methyl)pyridin-2(1H)-ylidine]- |
2, 2,2-trifluoroacetam ide, | N-[1-((6-fluoropyridin-3-yl)methyl)pyridin-2(1H)-ylidene]-2,2,2- |
trifluoroacetamide, | N-[1-((6-bromopyridin-3-yl)methyl)pyridin-2(1H)-ylidene]-2,2,2- |
trifluoroacetamide, | N-[1-(1-(6-chloropyridin-3-yl)ethyl)pyridin-2(1H)-ylidene]-2,2,2- |
trifluoroacetamide, N-ll-ifG-chloropyridin-S-yQmethyhpyridin-ZflHJ-ylidenej-Z^-difluoroacetamide,
2-chlorO'N-[1'((6-chloropyridin-3-yl)methyl)pyridin-2(1H)-ylidene]-2,2-difluoroacetamide, N-[ 1-((26 chloropyrimidin-5-yl)methyl>pyridin-2(1 H)-ylidene]-2,2,2-trifluoroacetamide and N-[1-((6chloropyridin-3-yl)methyl)pyndin-2(1H)-ylîdene]-2,2,3,3,3-pentafluoropropanamide.
(9) The pest control agent according to any one of (1) to (8), which has a pest control activity on at least one type of pest selected from the group consisting of lepidopterous pests, hemipterous pests, thysanopterous pests, dipterous pests, coleopterous pests, animal parasitic fleas and ticks, and canine heartworms, (10) The pest control agent according to any one of (1) to (9), wherein the pest is an agriculture l/horticultural pest or an animal parasitic pest.
(11) The pest control agent according to any one of (1) to (9), wherein the pest is a pesticide-resistant pest.
(12) An amine dérivative of the following formula (I) or a sait thereof [Chem. 4]
R2 (I) (wherein Ar is a phenyl group which may be substituted or a 5- or 6-membered heterocycle which may be substituted;
R; is a hydrogen atom or a Ci.6 alkyl group;
R2 is a Ci-e alkylcarbonyl group in which the alkyl moiety may be substituted with a halogen atom, a C18 alkyloxycarbonyl group in which the alkyl moiety may be substituted with a halogen atom, a alkylsulfonyl group in which the alkyl moiety may be substituted with a halogen atom, CONReR?, a Ο,Ο’-alkylphosphoryl group in which the alkyl moiety may be substituted with a halogen atom, a cyano group, a formyl group or a nitro group;
R3 is a C-i-b alkylene group which may be substituted with a halogen atom, a C2.a alkenylene group which may be substituted with a halogen atom, a C2-0 alkynylene group which
I may be substituted with a halogen atom, a phenylene group which may be substituted, or a 5- or
6-membered heterocyclic divalent group which may be substituted; and
R4 is a hydrogen atom, a cyano group, a phenyl group which may be substituted, a 3- to 8membered cyclic alkyl group which may be substituted, a 3- to 8-membered heterocyclic which may be substituted, a halogen atom, OR5, OCOR5, OCOOR5, CORS, COOR5, SR5, SOR5, SO2R5, N-CO-OR8, N-CO-SRe, N-CS-ORa, N-CS-SRe, N-O-CO-R8, O-CO-R8, O-CO-OR8, O-CO-SR3t OCS-ORe, O-CS-SR8, S-CS-OR8, S-CS-SR8i S-CO-ORs, s-co-sr8, s-cs-r8, nr9r10, o-coNR9R10, O-CS-NR9R10, S-CO-NR9R10 or S-CS-NR9R-io;
wherein R5 is a Cw alkyl group which may be substituted with a halogen atom, an aryl group which may be substituted with a halogen atom or an aralkyl group which may be substituted with a halogen atom;
Re and R? are each independently a hydrogen atom or a Cm alkyl group which may be substituted with a halogen atom;
R8 is a Cb6 alkyl group which may be substituted, the substituent being a halogen atom, a Cm alkyloxycarbonyl group, a Cm alkylcarbonyl group, a benzoyl group which may be substituted with a halogen atom or a Cm alkyl group which may be substituted with a halogen atom, a Cm alkyloxy group or a Cm alkylthio group;
R9 and R10 are each independently a hydrogen atom, a formyl group, a Cb6 alkyl group which may be substituted with a halogen atom, a Cm alkylcarbonyl group in which the alkyl moiety may be substituted with a halogen atom, a C18 alkylcarbonyloxy group in which the alkyl moiety may be substituted with a halogen atom, a phenyl group which may be substituted (the substituent being a halogen atom, a Cm alkyl group which may be substituted with a halogen atom, or a Cm alkyloxy group which may be substituted with a halogen atom), or a benzyl group which may be substituted (the substituent being a halogen, a Cm alkyl group which may be substituted with a halogen or a Cm alkyloxy group which may be substituted with a halogen), R9 and R10 together form a ring and dénoté a 3- to 10-membered heterocycloalkyl group containing at least one nitrogen atom, or N, R9 and R10 together form a ring and dénoté a 5- or 6-membered aromatic heterocycle containing at least one nitrogen atom; and if Ar is a pyridyl group which may be substituted or a pyrimidyl group which may be substituted, N, R2, R3 and R4 may together form a group of formula (E) [Chem. 5]
wherein Y is a hydrogen atom, a halogen atom, a hydroxyl group, a Cm alkyl group which may be substituted with a halogen atom, a Cm alkyloxy group which may be substituted with a halogen atom, a cyano group, a formyl group or a nitro group, and R4e is a Cv5 alkyl group substituted with a halogen or a C(Î alkyloxy group which may be substituted with a halogen;
with the proviso that if Ar is a 2,6-dichloro-4-pyridyl group, then R2 is not a Cm alkyloxycarbonyl group in which the alkyl moiety may be substituted with a halogen atom, and if Ar is a 6-chloro-3-pyridyl group, then Ri is not a hydrogen atom, Y is not a 5-methyl group and R4e is not a CF3 group).
(13) The amine dérivative or a sait thereof according to (12), wherein Ar in formula (!) is a
6-chloro-3-pyridyl group or a 5-chloro-3-thiazolyl group.
(14) The amine dérivative or a sait thereof according to (12) or (13), wherein R2 in formula (!) is a Cm alkylcarbonyl group in which the alkyl moiety may be substituted with a halogen atom, a Cm alkylsulfonyl group in which the alkyl moiety may be substituted with a halogen atom, or a cyano group.
(15) The amine dérivative or a sait thereof according to (12), wherein the compound of formula (I) is a compound of formula (le’) below.
[Chem. 6]
(wherein Ar’ is a pyridyl group which may be substituted or a pyrimidyl group which may be substituted; Y is a hydrogen atom, a halogen atom, a hydroxyl group, a Cw alkyl group which may be substituted with a halogen atom, a alkyloxy group which may be substituted with a halogen atom, a cyano group, a formyl group or a nitro group; and R4e is a alkyl group substituted with a halogen or a CV6 alkyloxy group which may be substituted with a halogen;
with the proviso that if Ar’ is a 6-chloro-3-pyridyl group, then Ri is not a hydrogen atom, Y is not a 5-methyl group and R/.c is not a trifluoromethyl group).
(16) The amine dérivative or a sait thereof according to (15), wherein in formula (le') is a alkyl group substituted with a halogen atom.
(17) The amine dérivative or a sait thereof according to (15), wherein Y in formula (le’) is a hydrogen atom or a halogen atom.
(18) The amine derivatîve or a sait thereof according to (15), wherein R4e in formula (le’) is a alkyl group substituted with a halogen atom and Y is a hydrogen atom or a halogen atom.
(19) The amine derivatîve or a sait thereof according to (15), wherein the compound of formula (le’) is a compound selected from the group consisting of N-[1-((6-chloropyridin-3yl)methyl)pyridin-2(1H)-ylidene]-2,2,2-trifluoroacetamide, N-[1-((6-chloro-5-fluoropyridin-3yl)methyl)pyridin-2(1H)-ylidÎne]-2,2,2-trifluoroacetamide, N-[1-((6-fluoropyridin-3-yl)methyl)pyridin2(1H)-ylidene]-2,2,2-trifluoroacetamide, N-[1-((6-bromopyridin-3-yl)methyl)pyridin-2(1H)-ylidenel2,2,2-trifluoroacetamide, N-[1-(1-(6-chloropyridin-3-yl)ethyl)pyridin-2(1 H)-ylidene]-2,2,2trifluoroacetamide, N-[1-((6-chloropyndin-3-yl)methyl)pyndin-2(1H)-ylidene]-2,2-difluoroaœtamide: 2-chloro-N-[1-((6-chloropyridin-3-yl)methyl)pyridin-2(1H)-ylidene]-2,2-difluoroacetamide, N-[ 1-((2chloropyrimidin-5-yl)methyl)pyridin-2(1 H)-ylidene]-2,2,2-trifluoroacetamide and N-[ 1-((6chloropyridin“3-yl)methyl)pyridin-2(1H)-ylidene]-2,2,3,3,3-pentafluoropropanamide.
(20) The amine dérivative or a sait thereof according to any one of (12) to (19), which has a pest control activîty on at least one type of pest selected from the group consisting of lepidopterous pests, hemipterous pests, thysanopterous pests, dipterous pests, coleopterous pests, animal parasitic fleas and ticks, and canine heartworms.
(21) A method for controlling pests, comprising the step of using the pest control agent according to any one of (1) to (9) or the amine dérivative or a sait thereof according to any one of (12) to (20).
(22) A method for controlling agricultural/horticultural pests, comprising the step of treating plant seeds, roots, tubers, bulbs, rhizomes, soil, a nutrient solution in hydroponics, a solid culture medium in hydroponics, or a carrier for growing plants, with the pest control agent according to any one of (1) to (9) or the amine dérivative or a sait thereof according to any one of (12) to (20), thereby inducing the compound to penetrate and translocate into the plants.
(23) The method according to (21), wherein the pest is an agricultural/horticultural pest or an animal parasitic pest.
(24) The method according to (21), wherein the pest is a pesticide-resistant pest. [Advantageous Effects of Invention]
By using the amine dérivatives of the invention, it is possible to effectively carry out the control of the diamondback moth, the common cutworm, aphids, delphacid planthoppers, thrips and many other pests.
[Brief Description of Drawings] [Fig. 1] FIG 1 is a graph showîng the results of powder x-ray diffraction analysis on the crystals of N-[1-((6-chloropyridin-3-yl)methyl)pyridin-2(1H)-ylidene]-2,2,2-trifluoroacetamide prepared by a first préparation method.
[Fig. 2] FIG 2 is a graph showing the results of differential scanning calorimetry on the crystals of N-[1-((6-chloropyridin-3-yl)methyl)pyridin-2(1H)-ylidene]-2,2,2“trifluoroacetamide prepared by the first préparation method.
I [Fig, 3] FIG 3 is a graph showing the results of powder x-ray diffraction analysis on the crystals of
N-[1-((6-chloropyridin-3-yl)methyl)pyridin-2(1 H)-ylidene]-2,2,2-trifluoroacetamide prepared by a second préparation method.
[Fig. 4] FIG 4 is a graph showing the results of differentiai scanning calorimetry on the crystals of N-[1-((6-chloropyridin-3-yl)methyl)pyridin-2(1H)-ylidene]-2,2,2-trifluoroacetamide prepared by the second préparation method.
[Fig. 5] FIG 5 is a graph showing the results of differentiai scanning calorimetry on the crystals of N-[1-((6-chloropyridin-3-yl)methyl)pyridin-2(1H)-ylidene]-2,2,2-trifluoroacetamide prepared by a third préparation method.
[Fig. 6] FIG. 6 is a graph showing the results of powder x-ray diffraction analysis on the crystals of N-[1-((6-chloropyridin-3-yl)methyl)pyridin-2(1H)-ylidene]-2,2,2-trifluoroacetamide prepared by a fourth préparation method.
[Fig. 7] FIG. 7 is a graph showing the results of differentiai scanning calorimetry on the crystals of N-[1-((6-chloropyridÎn-3-yl)methyl)pyridin-2(1H)-ylidene]-2,2,2-trifluoroacetamide prepared by the fourth préparation method.
[Fig. 8] FIG. 8 is a graph showing the results of differentiai scanning calorimetry on the crystals of N-[1-((6-chloropyridin-3-y[)methyi)pyridin-2(1H)-ylidene]-2,2,2-trifluoroacetamide prepared by a fifth préparation method.
[Description of Embodiments]
In the amine dérivatives of chemical formula (I) which serve as the active ingrédients of the pest control agents provided by the invention, Ar is a phenyl group which may be substituted or a
5- or 6-membered heterocycle which may be substituted, and is preferably a 5- or 6-membered heterocycle which may be substituted.
Exemplary substituents include halogen atoms, ClJt alkyl groups which may be substituted with halogen atoms, alkyloxy groups which may be substituted with halogen atoms, hydroxyl groups, cyano groups and nitro groups. Halogen atoms and CM alkyl groups which may be substituted with halogen atoms are preferred.
Illustrative examples of phenyl groups which may be substituted include a phenyl group, a
3-chlorophenyl group, a 4-chlorophenyl group, a 3-cyanopheny[ group, a 4-cyanophenyl group, a
3- nitrophenyl group, a 4-nitrophenyl group, a 3,5-dichlorophenyl group, a 4-methylphenyl group, a
4- methoxyphenyl group, a 3,5-dibromophenyl group, a 2,4-dibromophenyl group, a 4-fluorophenyl group, a 4-bromophenyl group, a 3-nitro-5-bromophenyl group and a 3,5-bistrifluoromethyphenyl group, A 4-nitrophenyl group, a 4-cyanophenyl group or a 3,5-dibromophenyl group is prefenred.
Illustrative examples of 5- or 6-membered heterocycles which may be substituted include pyridine, thiazole, tetrahydrofuran and furan. 3-Pyridyl groups and 3-thiazolyl groups are preferred. A 6-chloro-3-pyridyl group, a 5-chloro-3-thiazolyl group, a 6-chloro-5-fluoro-3-pyridyl group, a 6bromo-3-pyridyl group, a 6-fluoro-3-pyridyl group, a 5,6-dichloro-3-pyridyl group or a 6trrfluoromethyl-3-pyridyl group is more preferred. A 6-chloro-3-pyridyl group, a 6-fluoro-3-pyridyl group, a 6-chloro-5-fluoro-3-pyridyl group or a 6-bromo-3-pyridyl group is especially preferred.
In chemical formula (I), the “Cvs alkyl group” represented by Rt is an alkyl group having from 1 to 6 cartons that is linear, branched, cyclic or a combination thereof. When a branched or cyclic alkyl group is included, it is apparent that the number of carbons is at least 3. Spécifie examples include a methyl group, an ethyl group, a propyl group, an isopropyl group and a cyclopropyl group. A methyl group or an ethyl group is preferred.
R2 is a alkylcarbonyl group in which the alkyl moiety may be substituted with a halogen atom, a Ci.6 alkyloxycarbonyl group in which the alkyl moiety may be substituted with a halogen atom, a C-|.e alkylsulfonyl group in which the alkyl moiety may be substituted with a halogen atom, CONReR7, a C)4 Ο,Ο’-alkylphosphoryi group in which the alkyl moiety may be substituted with a halogen atom, a cyano group, a formyl group or a nitro group. A C-> alkylcarbonyl group in which the alkyl moiety may be substituted with a halogen atom, a alkylsulfonyl group în which the alkyl moiety may be substituted with a halogen atom, or a cyano group is preferred.
R3 is a alkylene group which may be substituted with a halogen atom, a C2-3 alkenylene group which may be substituted with a halogen atom, a C2.B alkynylene group which may be substituted with a halogen atom, a phenylene group which may be substituted, or a 5- or
6-membered heterocyclic divalent group which may be substituted. A Cm alkylene group which may be substituted with a halogen atom is preferred.
R4 is a hydrogen atom, a cyano group, a phenyl group which may be substituted, a 3- to 8membered cyclic alkyl group which may be substituted, a 3- to 8-membered heterocyclic which may be substituted, a halogen atom, OR5i OCORS, OCOORS, CORS, COOR5, SR6, SOR5, SO2R5, N-CO-ORg, N-CO-SRg, N-CS-ORb, N-CS-SR81 N-O-CO-R8, O-CO-R8: O-CO-ORb, O-CO-SRb, OCS-ORb, O-CS-SR8, S-CS-ORb, S-CS-SR8, S-CO-ORb, S-CO-SRb, S-CS-Rb, nr9r10, o-coNR9R10, O-CS-NR9Riq, S-CO-NRgR-to or S-CS-NR9R1Q.
Here, Rs is a Cm alkyl group which may be substituted with a halogen atom, an aryl group which may be substituted with a halogen atom or an aralkyl group which may be substituted with a halogen atom.
R6 and R7 are each independently a hydrogen atom or a Cm alkyl group which may be substituted with a halogen atom.
R8 is a Ci_6 alkyl group which may be substituted, the substituent being a halogen atom, a Cm alkyloxycarbonyl group, a CM alkylcarbonyl group, a benzoyl group which may be substituted with a halogen atom or a Cm alkyl group which may be substituted with a halogen atom, a Cm alkyloxy group or a C14 alkylthio group.
R9 and R10 are each independently a hydrogen atom, a formyl group, a Cm alkyl group which may be substituted with a halogen atom, a Cm alkylcarbonyl group in which the alkyl moiety may be substituted with a halogen atom, a Cm alkylcarbonyloxy group in which the alkyl moiety may be substituted with a halogen atom, a phenyl group which may be substituted (the substituent being a halogen atom, a Cm alkyt group which may be substituted with a halogen atom, or a Cm alkyloxy group which may be substituted with a halogen atom), or a benzyl group which may be substituted (the substituent being a halogen, a Cm alkyl group which may be substituted with a halogen or a Cm alkyloxy group which may be substituted with a halogen), R9 and R10 together form a ring and dénoté a 3- to 10-membered heterocycloalkyl group containing at least one nitrogen atom, or N, Ra and R10 together form a ring and dénoté a 5- or 6-membered aromatic heterocycle containing at least one nitrogen atom.
i
I t
The C-..6 alkyl group which may be substituted with a halogen atom that is represented by Rs, Re, R/, Ra, Rg and R10 is an alkyl group having from 1 to 6 carbons that is linear, branched, cyclic or a combination thereof, The upper limit in the number of halogen atoms which may be substituted is the number of hydrogen atoms on the alkyl group. When a branched or cyclic alkyl group is included, it is apparent that the number of carbons is at least 3.
Illustrative examples of the “C^ alkyl group which may be substituted with a halogen atom” that is represented by R5 include a methyl group, an ethyl group, an n-propyl group, a difluoromethyl group, a trifluoromethyl group, a chloromethyl group and a 2-trifluoroethyl group.
Illustrative examples of the “C^ alkyl group which may be substituted with a halogen atom that is represented by R6 and R? include a methyl group, an ethyl group, an n-propyl group, a difluoromethyl group, a trifluoromethyl group, a chloromethyl group and a 2-trifluoroethyl group.
Illustrative examples of the “C^ alkyl group which may be substituted with a halogen atom that is represented by Re include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an n-pentyl group, a 2-trifluoroethyl group and a 2-chloroethyl group. A methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group or an π-pentyl group is preferred.
Illustrative examples of the “CV6 alkyl group which may be substituted with a halogen atom that is represented by Rgand R10 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an n-pentyl group, a 2-trifluoroethyl group and a 2chloroethyl group. A methyl group or an ethyl group is preferred.
The alkyl moiety in the “C^ alkylcarbonyl group in which the alkyl moiety may be substituted with a halogen atom” that is represented by R2, R9 and R10, the “C^ alkyloxycarbonyl group in which the alkyl moiety may be substituted with a halogen atom, the “Ci.6 alkylsulfonyl group in which the alkyl moiety may be substituted with a halogen atom and the C^ 0,0'alkylphosphoryl group in which the alkyl moiety may be substituted with a halogen atom that are represented by Rz, and the C14 alkylcarbonyloxy group in which the alkyl moiety may be substituted with a halogen atom” that is represented by R9 and R10 is an alkyl group having from 1 to 6 carbons that is linear, branched, cyclic or a combination thereof. The upper limit in the number of halogen atoms which may be substituted is the number of hydrogen atoms on the alkyl group. When a branched or cyclic alkyl group is included, it is apparent that the number of carbons is at least 3.
Illustrative examples of the “Ci_e alkylcarbonyl group in which the alkyl moiety may be substituted with a halogen atom” that is represented by R2 include an acetyl group, an ethylcarbonyl group, an n-propylcarbonyl group, a difluoroacetyl group, a trifluoroacetyl group, a pentafluoroacetyl group, a chloroacetyl group and a trichloroacetyl group. A trifluoroacetyl group is preferred.
Illustrative examples of the “C^ alkyloxycarbonyl group in which the alkyl moiety may be substituted with a halogen atom that is represented by R2 include a methyloxycarbonyl group, an ethyloxycarbonyl group, an n-propyloxycarbonyl group, a chloromethyloxycarbonyl group and a 2trifluoroethyloxycarbonyl group.
Illustrative examples of the “C^ alkylsulfonyl group in which the alkyl moiety may be substituted with a halogen atom” that is represented by R2 include a methylsulfonyl group, an ethylsulfonyl group, an n-propylsulfonyl group, a difluoromethylsulfonyl group, a trifluoromethylsulfonyl group, a trichloromethylsulfonyl group and a 2-trifluoromethylsulfonyl group. Atrifluoromethylsulfonyl group îs preferred.
Illustrative examples of the “Ci^ Ο,Ο’-alkylphosphoryl group in which the alkyl moiety may be substituted with a halogen atom that is represented by R2 include an Ο,Ο’-dimethylphosphoryl group and an Ο,Ο’-diethylphosphoryl group.
Illustrative examples of the “CM alkylcarbonyl group in which the alkyl moiety may be substituted with a halogen atom that is represented by R5 include an acetyl group, an ethylcarbonyl group, an n-propylcarbonyl group, an isopropylcarbonyl group and a 2chloroethylcarbonyl group.
Illustrative examples of the “C·^ alkylcarbonyl group in which the alkyl moiety may be substituted with a halogen atom” that is represented by Rgand R10 include a methyloxycarbonyl group, an ethyloxycarbonyl group, an n-propyloxycarbonyl group, an isopropyloxycarbonyl group and a 2-chloroethyloxycarbonyl group.
Illustrative examples of the “C« alkylcarbonyloxy group in which the alkyl moiety may be substituted with a halogen atom that is represented by R9and R10 include a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an isopropylcarbonyloxy group and a 2-chioroethylcarbonyloxy group,
The Ci^ alkylene group which may be substituted with a halogen atom” that is represented by R3 îs an alkylene group having from 1 to 8 carbons that is linear, branched, cyclic or a combination thereof. The upper limit in the number of halogen atoms which may be substituted is the number of hydrogen atoms on the alkyl group. When a branched or cyclic alkyl group is included, it is apparent that the number of carbons is at least 3. Illustrative examples include a methylene group, an ethylene group, a propylene group, a butylène group, a fluoromethylene group, a 1-chloroethylene group, a 2-methylethylene group, a cyclopropylene group, a 2-cyclopropylethylene group and a 1,3-cyclopentylene group. A methylene group, an ethylene group or a propylene group is preferred. An ethylene group is more preferred.
The “C2.8 alkenylene group which may be substituted with a halogen atom that is represented by R3 is an alkenylene group having from 2 to 8 carbons that is linear, branched, cyclic or a combination thereof. The upper limit in the number of halogen atoms which may be substituted is the number of hydrogen atoms on the alkyl group. When a branched or cyclic alkyl group is included, it is apparent that the number of carbons is at least 3. Illustrative examples include a vinylene group, a 1-propenylene group, a 2-fluoro-1-propenylene group, a 2-methyl-1propenylene group and a 2-cyclohexen-1,4-ylene group.
The “C2^ alkynylene group which may be substituted with a halogen atom that is represented by R3 is an alkynylene group having from 2 to 8 carbons that is linear, branched, cyclic or a combination thereof. The upper limit in the number of halogen atoms which may be substituted is the number of hydrogen atoms on the alkyl group. When a branched or cyclic alkyl group is included, it is apparent that the number of carbons is at least 3. Illustrative examples include a propynylene group and a butynylene group. 1-Propynylene is preferred.
The “phenylene which may be substituted” that is represented by R3 is a divalent group from which two of the hydrogen atoms on benzene hâve been removed, and wherein the substituents are exemplified by halogen atoms, CM alkyl groups which may be substituted with a halogen atom, alkyloxy groups which may be substituted with a halogen atom, hydroxyl groups, cyano groups and nitro groups. Illustrative examples include a phenylene group, a 4fluorophenylene group and a 2-methylphenylene group.
The “5- or 6-membered heterocyclic divalent group which may be substituted that is represented by R3 is a divalent group from which two of the hydrogen atoms on the 5- or 6membered heterocycle hâve been removed, and wherein the substituents are exemplified by halogen atoms, C,..-. alkyl groups which may be substituted with a halogen atom, alkyloxy groups which may be substituted with a halogen atom, hydroxyl groups, cyano groups and nitro groups. Illustrative examples include a 2-pyridinylene group.
Substituents which may substituted in the “pyridyl group which may be substituted” or the pyrimidyl group which may be substituted that is represented by Ar' in the compound of the formula (le’) are exemplified by halogen atoms, CM alkyl groups which may be substituted with a halogen atom, alkyloxy groups which may be substituted with a halogen atom, hydroxyl groups, cyano groups and nitro groups. Halogen atoms are preferred.
Preferred examples of Ar in the compound of the formula (le) and of Ar' in the compound of the formula (le’) include a 3-pyridyl group, a 6-chloro-3-pyridyl group, a 5-chloro-3-thiazolyl group, a 6-chloro-5-fluoro-3-pyridyl group, a 6-bromo-3-pyridyl group, a 6-fluoro-3-pyridyl group, a 5,6-dichloro-3-pyridyl group, a 6-trifluoromethyl-3-pyridyl group and a 2-chloro-5-pyrimidyl group. A 6-chloro-3-pyridyl group, a 6-fluoro-3-pyridyl group, a 6-chloro-5-fluoro-3-pyridyl group, a 6bromo-3-pyridyl group or a 2-chloro-5-pyrimidyl group is more preferred.
Y in the compounds of formulas (le) and (le’) represents from 1 to 3 substituents which may be the same or different.
The “Cq.6 alkyl group which may be substituted with a halogen atom represented by Y in the compounds of formulas (le) and (le’) is an alkyl group having from 1 to 6 carbons that is linear, branched, cyclic or a combination thereof. The upper limit in the number of halogen atoms which may be substituted is the number of hydrogen atoms on the alkyl group. When a branched or cyclic alkyl group is included, it is apparent that the number of carbons is at least 3.
Illustrative examples include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a t-butyl group, a trifluoromethyl group and a 2-chloroethyl group. A methyl group is preferred.
Illustrative examples ofthe “Cm alkyloxy group which may be substituted with a halogen represented by Y include a methoxy group, an ethoxy group, a trifluomethyl group and a difluoromethyl group.
Preferred examples of Y are a hydrogen atom and halogens, A hydrogen atom is more preferred.
The “Cm alkyl group substituted with a halogen atom represented by R4e in the compounds of formulas (le) and (le') is an alkyl group having from 1 to 6 carbons that is linear, branched, cyclîc or a combination thereof. The upper limit in the number of halogen atoms which are substituted is the number of hydrogen atoms on the alkyl group. When a branched or cyclic alkyl group is included, it is apparent that the number of carbons is at least 3.
Illustrative examples include a trifluoromethyl group, a trichloromethyl group, a difluorochloromethyl group, a difluoromethyl group, a dichloromethyl group, a dibromomethyl group, a chloromethyl group, a difluoroethyl group, a dichloroethyl group, a 2,2,2-trifluoroethyl group, a pentafluoroethyl group and a difluorocyclopropyl group. A trifluoromethyl group, a trichloromethyl group, a dichloromethyl group, a difluoromethyl group, a difluorochloromethyl group, a chloromethyl group or a pentafluoroethyl group is preferred, A trifluoromethyl group, a difluoromethyl group, a difluorochloromethyl group, a chloromethyl group or a pentafluoroethyl group is more preferred.
Illustrative examples of the Cm alkyloxy group which may be substituted with a halogen” represented by R4b include a methoxy group, an ethoxy group, an isopropyloxy group and a trifluoromethoxy group.
Preferred examples of R^ are Cm alkyl groups which may be substituted with a halogen. A trifluoromethyl group, a difluoromethyl group, a difluorochloromethyl group, a chloromethyl group or a pentafluoroethyl group is more preferred.
Salts of the amine dérivatives of chemical formula (I) which act as the active ingrédient in the pest control agent provided by the invention are acid addition salts allowable in agricultural and livestock chemicals. Illustrative examples include hydrochlorides, nitrates, sulfates, phosphates and acétates.
In a preferred form of the compound of formula (l),
Ar is a 4-nitrophenyl group, a 4-cyanophenyl group, a 3,5-dibromophenyl group, a 2,4dibromophenyl group, a 6-chloro-3-pyridyl group, a 5-chloro-3-thiazolyl group, a 6-chloro-5-fluoro3-pyridyl group, a 6-bromo-3-pyridyl group, a 6-fluoro-3-pyridyl group, a 5,6-dichloro-3-pyridyl group or a 6-trifluoromethyl-3-pyridyl group;
Rt is a hydrogen atom or a methyl group;
R2 is a Cm alkylcarbonyl group in which the alkyl moiety may be substituted with a halogen atom, a Cm alkylsutfonyl group in which the alkyl moiety may be substituted with a halogen atom, or a cyano group;
R3 is a methylene group, an ethylene group, a propylene group or a 1-propynylene group; and
Ra is a hydrogen atom, a cyano group, SRs (Rs being a Cm alkyl group which may be substituted with a halogen), S-CS-ORb or S-CS-SRs (Rs being a Cm alkyl group which may be substituted with a halogen).
Preferred compounds are exemplified by the compounds of (i) to (iii) below.
(i) Compounds wherein:
Ar is a 4-cyanophenyl group, a 4-nitrophenyl group, a 3,5-dichlorophenyl group, a 3,5dibromophenyl group, a 2,4-dibromophenyl group, a 4-bromophenyl group, a 3-nitro-5bromophenyl group, a 6-chloro-3-pyridyl group, a 5-chloro-3-thiazolyl group, a 6-chloro-5-fluoro-3pyridyl group or a 6-trifluoromethyl-3-pyridyl group;
R-ι is a hydrogen atom;
R2 is a trifluoromethylsulfonyl group;
R3 is a methylene group, an ethylene group or a 1-propynylene group; and
R4 is a hydrogen atom or a cyano group.
(ii) Compounds wherein:
Ar is a 6-chloro-3-pyridyl group, a 5-chloro-3-thiazolyl group or a 6-trifluoromethyl-3-pyridyl group;
Ri is a hydrogen atom or a methyl group;
R2 is a cyano group or a trifluoromethylcarbonyi group;
R3 is an ethylene group; and
R4 is a hydrogen atom, SRs (Rs being a CM alkyl group which may be substituted with a halogen), S-CS-ORe or S-CS-SR0 (Re being a Cw alkyl group which may be substituted with a halogen).
(iii) Compounds of the formula (le).
Especially preferred compounds are exemplified by the compounds of (i) to (iii) below.
(i) Compounds wherein:
Ar is a 4-cyanophenyl group, a 4-nitrophenyi group, a 3,5-dichlorophenyl group, a 3,5dibromophenyl group, a 2,4-dibromophenyl group, a 4-bromophenyl group, a 3-nitro-5bromophenyl group, a 6-chloro-3-pyridyl group, a 5-chloro-3-thiazolyl group, a 6-chloro-5-fluoro-3pyridyl group or a 6-trïfluoromethyl-3-pyridyl group;
Ri is a hydrogen atom;
R2 is a trifluoromethylsulfonyl group;
R3 is a methylene group, an ethylene group or a 1-propynylene group; and
R4 is a hydrogen atom.
(ii) Compounds wherein:
Ar is a 6-chloro-3-pyridyl group, a 5-chloro-3-thiazolyl group or a 6-trifluoromethyl-3-pyridyl group;
Ri is a hydrogen atom or a methyl group;
R2 is a cyano group or a trifluoromethylcarbonyi group;
R3 is an ethylene group; and
R4 rs SR5 (R5 being a Ci.6 alkyl group which may be substituted with a halogen), S-CS-OR3 or S-CS-SRg (Rb being a C« alkyi group which may be substituted with a halogen).
(iii) Compounds of the formula (le).
Preferred forms of the compound of formula (le) are compounds wherein:
Ar is a 3-pyridyl group, a 6-chloro-3-pyridyl group, a 5-chloro-3-thiazolyl group, a 6-chloro-
5-fluoro-3-pyridyl group, a 6-bromo-3-pyridyl group, a 6-fluoro-3-pyridyl group, a 5,6-dichloro-3pyridyl group, a 6-trifluoromethyl-3-pyridyl group or a 2-chloro-5-pyrimidyl group;
R! is a hydrogen atom, a methyl group or an ethyl group;
Y is a hydrogen atom, a halogen atom or a methyl group; and
R4e rs a trifluoromethyl group, a trichloromethyl group, a dichloromethyl group, a difluoromethyl group, a difluorochloromethyl group, a chloromethyl group or a pentafluoroethyl group.
Compounds wherein:
Ar is a 6-chloro-3-pyridyl group, a 6-fluoro-3-pyridyl group, a 6-chloro-5-fluoro-3-pyridyl group, a 6-bromo-3-pyridyl group or a 2-chloro-5-pyrimidyl group;
Rt is a hydrogen atom or a methyl group;
Y is a hydrogen atom; and
R4e is a trifluoromethyl group, a difluoromethyl group, a difluorochloromethyl group, a chloromethyl group or a pentafluoroethyl group are more preferred.
The compound of chemical formula (t) which serves as the active ingrédient of the pest control agent ofthe invention is preferably a compound which has a control activity (e.g., an insect mortality or knockdown rate of at Ieast 30%, at Ieast 50%, at Ieast 80%, or 100%) in foliar application at 500 ppm, soil drenching treatment at 0.1 mg/seedling, or local application at 2 gg/insect (see the test examples for the invention). Altematively, the compound is one having a control activity (insecticidal effect), as determined by the évaluation of insect mobility, under the root immersion treatment at 20 gg/seedling described in Test Example 15 or under the culturing conditions at about 3 ppm described in Test Example 21.
In foliar application, the compound is more preferably one having a control actîvity at a concentration of below 500 ppm (e.g,, 400 ppm, 300 ppm, 200 ppm, 100 ppm, 50 ppm, 30 ppm, ppm, 5 ppm, 3 ppm, 1.5 ppm, 1.25 ppm, 1 ppm, or 0.5 ppm)
In soit drenching treatment, the compound is more preferably one having a control actîvity 5 at a concentration below 0.1 mg/seedling (e.g., 0.05 mg/seedling, 0.01 mg/seedling, 0.005 mg/seedling, or 0.002 mg/seedling).
In local application, the compound is more preferably one having a control actîvity at a concentration below 2 pg/insect (e.g., 1 pg/insect, 0.5 pg/insect, or 0.2 pg/insect).
In dry film application, the compound is more preferably one having a control actîvity at a 10 concentration below 200 ppm (e.g., 100 ppm, 50 ppm, 30 ppm, or 10 ppm).
In root immersion treatment, the compound is more preferably one having a control actîvity at a concentration below 20 pg/seedling (e.g., 10 pg/seedling, 5 pg/seedling, 2 pg/seedling, 1 pg/seedling, 0.5 pg/seedling, 0.1 pg/seedling, 0.05 pg/seedling, 0Ό3 pg/seedling, or 0.01 pg/seedling).
Illustrative examples of the compounds of the invention are listed in Tables 1 to 5.
Table 1
Compound No. | Ar | Ri | r2 | r4 | |
1 | (il | H | CN | ch:chz | sch3 |
2 | i} | H | CN | CH-CEï | SCH;CH3 |
3 | (2) | H | CN | CHjCHï | SCH;CH;CHs |
4 | (I) | H | CN | CHjCF^CHj | H |
s | ( 1} | H | CN | CH£CH;CHj | SCHj |
6 | 12} | H | CN | CHîCHj | SCSSCH3 |
7 | (2) | H | CN | CHjCHj | SCSSCH:CHj |
Q | (I) | H | CN | CHsCHj | SCSSCHsCH:CHs |
9 | (II) | H | CN | CH£CHj | SCSSCHzCHa |
10 | (21) | H | CN | CH;CH; | SCSSCH;CH;CH3 |
i ** | (2) | H | CN | CHjCHj | OCHj |
12 | (2) | H | CN | CH;CH2CH3CH; | H |
13 | (2) | H | CN | CH- | H |
14 | (2) | H | CN | CHjCHî | H |
15 | (I) | H | CN | CH(CH3)CH; | H |
16 | (2) | H | CN | CHjCHj | N(CHj); |
17 | (2) | H | CN | CH; | (2) |
IB | {I ) | Me | CN | CHjCHj | H |
19 | (21) | H | CN | CH;CHj | H |
20 | (2) | H | COKe | CH;CH; | H |
21 | (2) | H | cocf3 | CH;CH; | H |
22 | (2) | H | COOMe | CH;CH; | H |
23 | (II) | H | CN | CH;CH; | SCHs |
24 | (2) | H | COMe | CH;CE; | S CH; |
2 5 | il) | H | COOPh | CH;CH; | SCHj |
26 | (2) | H | SOOPh | CH;CH; | SCHs |
2~! | (2) | H | COOMe | CH;CHZ | SCHj |
28 | (2) | H | SOOMe | CHjCH, | S CH; |
29 | (2) | H | CHO | CH;CH; | SCHs |
30 | (2) | H | COPh | CHzCH; | SCH3 |
31 | (I) | H | cocf3 | CH;CH; | SCHs |
32 | (21) | H | CN | CH;CE; | SCH;CH3 |
33 | (ï) | H | PO(OC2Hj) - | CH;CH; | SCHs |
34 | (I) | H | coccl3 | CH;CEZ | SCH3 |
35 | phenyl | H | CN | CHjCEj | H |
36 | 3-pyridyl | H | CN | CHjCHj | H |
37 | 4-chlcrc-phenyl | H | CN | CHZCH; | H |
Table 1 (continuée! from the previous page)
38 | phenyl | H | CX | CHj | phenyl |
39 | phenyl | H | COMe | CHîCHï | H |
4 0 | phenyl | H | COOMe | CHîCHî | H |
41 | 3-thienyl | H | CX | CH2CH- | H |
42 | (I) | H | ex | CH2CsC | H |
43 | (1) | H | ex | CH;CH=CH | H |
44 | (D | H | ex | ch2 | phenyl |
45 | 3-cyanophenyl | H | ex | CH2CH2 | H |
46 | é-trifluorcmethyl- 3-pyridyl | H | ex | CH2CH2 | H |
47 | c-trif lucroiaethyl- 3-pyridyl | H | ex | CH2CH2 | SCHs |
48 | €-trifluorcmetnyl- 3-pyridyl | H | ex | ch2ch2 | SCH2CHj |
49 | (!) | H | ex | CH2CH2 | S-CH2-(2furanyl) |
50 | (I) | H | ex | CHjCHj | S-CHj-phenyl |
51 | (1) | H | ex | CH2CH2 | SOO-phenyl |
52 | (I) | H | CN | CH2CH; | S-phenyl |
53 | (1) | H | CN | ch2ch2 | O-phenyl |
54 | (!) | H | CN | CHjCH- | NHCOCHs |
55 | 4-chlcrophenyl | H | CN | ch2 | 4-chlcrophenyl |
56 | (1) | H | CN | CHî | COOMe |
57 | il) | K | CN | ch2ch2 | phenyl |
58 | il) | H | CN | ch2ch2 | COO-phenyl |
59 | il) | H | CN | CH; | CN |
60 | il) | H | CN | CH(Me) | CN |
Table 2
Compound No. | ?_r | R, | r2 | Rs | r4 |
61 | (r) | H | CN | CH;CH; | OCOMe |
62 | (D | H | CN | CH; | sch3 |
63 | (II) | H | CN | CH;CH; | OCOMe |
64 | (II) | H | CN | ch2 | SCH3 |
6S | (II) | H | CN | CH;CH; | COOMe |
66 | (II) | H | CN | CH; | cyclopropyl |
67 | (II) | H | CN | CH (Me) CH | sch3 |
63 | (D | H | CN | 2-thiiranylene | H |
69 | (D | H | CN | 2cxyranylen | H |
70 | (I) | H | CN | CH;CH; | COOMe |
71 | (I) | H | CN | CH; | cyclopropyl |
72 | 5, 6-dichlcrc- 3-pyridyl | H | CN | CH;CH; | S CH; |
73 | (I) | Me | CN | CH;CH; | sch3 |
74 | (II) | H | CN | CH;CH; | S CH; |
75 | (II) | H | CN | CH;CH; | SCHjCHj |
76 | ( I ) | H | CN | 3tetrahydrc-thiophenyl ene | H |
77 | (I) | H | CN | CH(Me)CH | S CH; |
78 | 6-flucro-3pyridyl | H | CN | CH;CH; | S CH; |
79 | 6-chlorc-5fluoro-3pyridyl | H | CN | CH;CH; | S CH; |
SO | 6-chloro-5flucro-3pyridyl | H | CN | CH;CH; | H |
81 | (I) | H | COCFS | CH;CHF | H |
82 | (I) | H | CN | CH;CHF | H |
83 | (I) | H | CN | CH; | (II) |
84 | (I) | H | CN | CH;CH; | OTS |
85 | (I) | H | CN | CH;CH; | SCSN(Et)CH2Ph |
86 | (I) | H | CN | CH;CH; | SCSOEt |
87 | (11) | H | CN | CH;CH; | SCSOEt |
88 | (I) | H | CN | CH;CH; | SCSN(Me)CH2Ph |
89 | (I) | Me | COCFj | CH;CHF | H |
Table 2(continued from the previous page)
SD | (I) | H | CM | CH2CH2 | SCSOiPr |
SI | (I) | H | CN | ch2ch2 | SCSO-npentyl |
92 | (15 | Me | CN | CH-CHF | H |
93 | (3} | H | CN | CH;CH£ | SCSO-n-Pr |
94 | (D | H | CN | ch2ch2 | SCSO-n-Bu |
95 | (II) | H | CN | CH;CF2 | H |
96 | (I) | Me | COCF3 | ch2cf2 | H |
97 | ( I) | H | COCFj | ch2cf: | H |
98 | (I) | H | COCF2CI | ch:cf2 | H |
93 | il) | H | COCCI3 | CHîCFî | H |
100 | (I) | H | CN | CHîCHjCHj | OTs |
101 | (I) | H | CN | CH2CH2CH2 | BCSOEt |
102 | (I) | H | CN | CHîCHïCHî | SCSO-n-Pr |
103 | (I) | H | CN | CHjCHjCHj | SCSN(Et) CH2Ph |
104 | (I) | H | SO2CF3 | ch2cf2 | H |
105 | (I) | Me | cocf3 | ch2ch2 | H |
106 | (I) | Me | COCFS | ch2ch2cf; | H |
107 | (I) | Me | SOjCFj | CHjCHs | H |
1ÛS | ( I ) | Ke | sa2CF3 | ch:cf2 | H |
109 | (I) | Et | cocf3 | CHjCF- | H |
110 | (I) | Et | SO^CFj | CHjCFj | H |
111 | (I) | Et | COCFS | CHjCHs | H |
112 | (I) | Et | so2cf3 | ch:ch2 | H |
113 | (I) | H | CN | CH2CHj | S-CH2-(2imidazolyl) |
114 | 6- trifluoromethy 1-3-pyridyl | Me | so2cf3 | CHjCH2 | H |
115 | 6- trifluoromethy 1-3-pyridyl | Me | COCFS | CH2CH2 | H |
116 | (II) | Me | so2cf3 | CHjCHs | H |
1'7 | (II) | Me | so2cf3 | ch2cf2 | H |
118 | (II) | Et | COCF3 | CH2CF2 | H |
119 | (II) | H | CN | CHSCH=CH | H |
120 | (II) | H | CN | CH2CsC | H |
Table 3
Compound Ne. | Ar | Ri | Rî | r3 | R< |
121 | fil) | H | CN | CH3 | H |
122 | i 11 ) | H | CN | CH2CH2CR2 | H |
123 | (ir) | Et | SO2CF3 | CH.CF, | H |
124 | 2-pyridyl | Me | SO2CF3 | H | |
125 | (II) | Et | S02CF3 | CH:CF: | H |
126 | (II) | Et | cgcf3 | CH2CH2 | H |
127 | (II) | Et | S02CF3 | CH2CH2 | H |
12 S | (I) | H | SO2CF3 | CHjC^C | H |
12 S | d) | H | so-cf3 | CH- | CN |
130 | 4-tri fluoromethyl- 3-pyridyl | H | cocf3 | CH2CH2 | H |
131 | 6-trifluorc-inethyl- 3-pyridyl | H | so2cf3 | CH;CH- | H |
132 | 4-pyridyl | Me | cocf3 | CH3CH2 | H |
133 | 3-pyridyl | Me | cocf3 | CH2CH2 | H |
134 | 2-pyridyl | Me | cocf3 | ch2ch2 | H |
135 | (I) | H | so2cf3 | ch2 | H |
136 | (II) | H | CN | ch2ch2 | OTs |
137 | (II) | H | CN | ch2ch: | SCSOEt |
138 | (II) | H | CN | ch2ch2 | SCSN(CHjPh) Et |
139 | (I) | H | CN | ch2ch2 | s (=0) Ph |
140 | (I) | H | S02CF3 | ch2ch2ch2 | H |
141 | (I) | H | sc2cf3 | ch2ch;ch2ch2 | H |
142 | (I) | H | so:cf3 | ch2ch2 | SOOPh |
143 | ( I ) | H | SO;CF3 | ch2ch2 | OPh |
144 | (I) | H | so2cf3 | ch2ch2 | H |
145 | (I) | H | so2cf3 | ch2ch2ch2 | H |
146 | (I) | H | so2cf3 | ch2ch=ch | H |
147 | (I) | H | so2cf3 | ch2 | Ph |
148 | 4-fluoro-3-pyridyl | H | CN | ch2ch2 | H |
149 | 4-brc-Eio-3-pyridyl | H | CN | ch2ch2 | H |
150 | (I) | H | so2cf3 | ch2ch2 | NMe2 |
151 | (I) | Me | sc3cf3 | ch2ch2 | NMe; |
152 | (I) | H | so2cf3 | CHïCHjCsC | H |
153 | 3-chloro-4-pyridyl | H | CN | ch2ch2 | H |
Table 3(continued from the previous page)
154 | 3-chloro-2-pyridyl | H | CN | ch:ch2 | H |
155 | (I) | H | S02CF3 | CH;CH- | OCH3 |
156 | ( ΙΣ) | H | SOjCF3 | CH;CH; | och3 |
157 | 6-chloro-3- pyridazyl | H | COCF3 | CHjCHj | H |
156 | 3,5-dichlorcphenyl | H | CN | CH;CH; | H |
159 | il) | H | SO2CF3 | ch2ch2 | CN |
160 | il) | H | SO2CF3 | ch2 | COOMe |
161 | (1) | H | SO2CF3 | cn2 | COOH |
162 | 4-fluorophenyl | H | SO2CP3 | ch3ch2 | OCHj |
163 | ÎII) | H | SOjCFj | CH; | CN |
164 | 4-methylphenyl | H | SO2CF3 | CH;CH; | OCH3 |
165 | e-trifLuoromethyl·- 3-pyridyl | H | SO2CF3 | CH; | CN |
166 | 2-pyridyl | H | SO2CF3 | CH;CH; | OCHâ |
167 | 6-chloro-5-fluoro- 3-pyridyl | H | SO2CF3 | CH; | CN |
165 | 3-pyridyl | H | so2cf3 | CH;CH; | och. |
169 | 4-pyridyl | H | SOjCFs | CH;CH; | och3 |
170 | il) | Ke | so2cr3 | CH; | CN |
1 7 1 | (1) | Me | so2cf3 | CH-C=C | H |
172 | (II) | H | so,cf3 | CH;C=C | H |
173 | 6-fluoro-3-pyridyl | H | S02CFs | CH;CH; | OCHS |
174 | 6-brome-3-pyridyl | H | so2cf3 | CH;CH; | OCH3 |
175 | 3,S-dichlorophenyl | Me | cocf3 | CH;CH; | H |
176 | 3,5-dichlorcphenyl | H | cocf3 | CH;CH; | H |
177 | phenyl | H | so3cf3 | CH;CH2 | H |
4 ΊΏ U. ·Γ L.' | (I) | H | so3ch2cf3 | CH2CH; | H |
179 | (I) | H | so£ch2cf3 | ch2c=c | H |
ISO | 3-chlorophenyl | H | SO2CFj | CH;CH; | H |
Table 4
Compound Ne. | Ar | Rl | F.; | Rs | Ri |
181 | 4-chlorophenyl· | H | so2cf3 | ch;ch2 | H |
182 | 3-cyanophenyl | H | SO:CF3 | ch2ch2 | H |
183 | 4-nitrophenyl | H | SO2CF3 | ch2ch2 | H |
184 | 3,5-dichloxophenyl | H | so2cf3 | CHjCaC | H |
185 | 4-methylphenyl· | H | so2cf3 | ch2ch2 | H |
186 | 4-cyanophenyl | H | so2cf3 | ch2ch2 | H |
187 | 4-methozyphenyl· | H | so2cf3 | ch2ch2 | H |
188 | 4 -fluorophenyl | H | so2cr3 | ch2ch2 | H |
183 | 3,5-dibromophenyl | H | so2cf3 | CH2CHs | H |
190 | 4-bromophenyl | H | so2cf3 | ch2ch2 | H |
191 | 3,S-dimethylphenyL | H | so2cf3 | ch2ch2 | H |
192 | 3-nitrophenyl | H | so2cf3 | ch2ch2 | H |
193 | 2,4-dibromophenyl | H | so2cf3 | ch2ch2 | H |
19 4 | 3-nitro-5-brome phenyl. | H | so2cf3 | ch2ch2 | H |
195 | 3,5- bistri fluorcmethylphenyl | H | SO2CFj | ch2ch2 | H |
196 | (1) | H | CN | ch2ch2 | SCS SCHjCOOCHj |
197 | ¢11) | tfe | CN | ch2ch2 | SCSSCH2CH£CH3 |
198 | (Σ) | H | CN | ch2ch2 | SCSSCH2OKe |
199 | i Z) | H | CN | ch2ch2 | SCSSCH2SMe |
200 | il) | H | CN | ch2ch: | SCSSCHsCO-(4tne t hy 1 pheny 1 ) |
201 | 3-tetrahydrofuranyl· | H | CN | ch2ch2 | H |
202 | 3-tetrahydrofuranyl | H | CN | ch2ch2 | SMe |
203 | (1) | H | coph | ch2ch2 | H |
204 | (I) | H | COCH2CH3 | cf2 | H |
205 | ¢1) | H | conh2 | ch2ch2 | H |
206 | (I) | H | CONHMe | ch2ch2 | H |
207 | (I) | H | CONKe2 | CH.CHj | H |
208 | (I) | H | no2 | ch2ch2 | H |
209 | ( Σ ) | H | coccif2 | ch2ch2 | H |
210 | (D | H | CN | phenylene | H |
211 | (I) | Ke | SO2CF3 | ch2 | H |
245 | (I) | H | COMe | ch2 | CN |
24 6 | (I) | H | COCFg | ch2 | CN |
(T): 6-chlcro-3-pyridyl (ΣΣ): 5-chloro~3-thiazoly1
Table 5
Compound No. | Ar | Ri | V | |
212 | 11} | H | cf3 | H |
213 | III) | H | CF3 | H |
214 | (I) | H | OCH3 | H |
215 | (I) | H | CFî | S-Cl |
216 | (D | H | CFS | 5-F |
217 | (I) | H | CF, | 4-C1 |
21B | (II) | H | cr3 | 5-C1 |
219 | (II) | H | CFi | 5“F |
22 D | (II) | H | cf3 | 4-C1 |
221 | (I) | H | cf3 | 3-Ke |
222 | (I) | H | cf3 | 4-He |
223 | (D | H | CF3 | 3-Ke |
224 | phenyl | H | cf3 | H |
2 2 5 | 4-chlorophenyl | H | CFS | H |
226 | 3-pyridyl | H | cf3 | H |
227 | 6-chloro-3-fluoro-3-pyridyl | H | cf3 | H |
223 | 6-tri fluoromethyl-3-pyridyl | H | cf3 | H |
22 9 | 6-flucre-3-pyridyl | H | CF3 | H |
230 | 5,e-dichloro-S-pyridyl | H | cf3 | H |
231 | 6-bromc-3-pyridyl | H | CF3 | H |
2 32 | il) | H | CFs | 4-F |
233 | (D | H | cf3 | 3-P |
234 | (D | H | CHCIî | H |
235 | il) | H | CC13 | H |
236 | (D | H | CH;C1 | H |
23 7 | (D | Ke | CF3 | H |
238 | (D | H | CHFî | H |
239 | (D | H | CFjCl | H |
240 | iD | H | CHClBr | H |
241 | ED | H | CHBr2 | H |
24 2 | (D | H | cf:cf3 | H |
243 | 2-chlcro-5-pyriKiidinyl· | H | cf3 | H |
244 | (D | H | CH;Br | H |
The most preferred compounds are the following which appear in Table 5:
Compound No. 212: N-[1-((6-chloropyridin-3-yl)methyl)pyridin-2(1H)-ylidene]-2,2,2trifluoroacetamide,
Compound No. 227: N-[1-((6-chloro-5-fluoropyridin-3-yl)methyl)pyridin-2(1H)-ylidene]-2]2,2trifluoroacetamide,
Compound No.
229:
N-[1-((6-fluoropyridin-3-yl)methyl)pyridin-2(1H)-ylidene]-2,2,2trifluoroacetamide,
Compound No.
231:
N-[1-((6-bromopyridin-3-yl)methyl)pyridin-2(1 H)-ylidene]-2;2.2trifluoroacetamide,
Compound No.
237:
N-[1-(1-(6-chloropyridin-3-yl)ethyl)pyridin-2(1 H)-ylidene]-2,2,2trifluoroacetamide,
Compound No.
238:
N-[1-((6-chloropyridin-3-yl)methyl)pyridin-2(1H)-ylidene]-2,2difluoroacetamide,
Compound No. 239:
2-chloro-N-[1-((6-chloropyridin-3-yl)methyl)pyridin-2(1H)-ylidene]-2,2difluoroacetamide,
Compound No. 242:
N-[1-((6-chloropyridin-3-yl)methyl)pyridin-2(1H)-ylidene]-2,2,3,3,3pentafluoropropanamide, and
Compound No. 243:
N-[1-((2-chloropyrimidin-5-yl)methyl)pyridin-2(1H)-ylidene]-2,2,2trifluoroacetamide.
Compound No. 212Î in Table 5, N-[1-((6-ch]oropyridin-3-yl)methyl)pyridin-2(1H)-ylidene]l
2,2,2-trifluoroacetamide, has the following physical properties. These properties hâve not been mentioned in any of the prior-art documents.
(a) In powder x-ray diffraction analysis, the compound has diffraction angle peaks at least at the following diffraction angles (2Θ): 8.6+0.20, 14.2±0.2°, 17.5+0.2°, 18.3±0.2°, 19.7+0.2°, 22.3±0.2°, 30.9±0.2°, 35.3+0.2° (b) In differential scanning calorimetry (DSC), the compound exhibits a melting point of 155 to 158°C.
i i
Examples of the types of pests on which pest control agents containing at least one of the j inventive compounds of chemical formula (I) exhibit control effects are given below.
Examples of agricultural/horticultural pests include lepidopterous pests (e.g., common i cutworm, cabbage armyworm, armyworm, cabbage butterfly caterpillar, diamondback moth, beet armyworm, rice stem borer, grass leaf roller, rice green caterpillar, leaf roller moth, codling moth, leaf miner moth, oriental tussock moth, pests belonging to the genus Agrotis (Agrotis spp.), pests belonging to the genus Helicoverpa (Helicoverpa spp.), and pests belonging to the genus Heliothis i (Heliothis spp.)), hemipterous pests (e.g., aphids (Aphididae, Adelgidae, Phylloxeridae) such as i the green peach aphid, cotton aphid, Aphis fabae, corn leaf aphid, pen aphid, foxglove aphid, '
Aphis craccivora, Macrosiphum euphorbiae, Macrosiphum avenae, Methopoiophium dirhodum, grain aphid, Schizaphis graminum, cabbage aphid, turnip aphid, spiraea aphid, rosy apple aphid, woolly apple aphid, Toxoptera aurantii and brown citrus aphid; leafhoppers such as the green rice leafhopper and the tea green leafhopper; planthoppers such as the small brown planthopper and the white-backed rice planthopper; stink bugs such as the white-spotted bug, the southern green stink bug, the brown-winged green bug and the rice leaf bug; whiteflies (Aleyrodidae) such as the silverleaf whitefly, the sweet potato whitefly and the greenhouse whitefly; and scale insects such as Pseudococcus comstocki, the citrus mealybug, the white peach scale and the California red scale (e.g., Diaspididae, Margarodidae, Ortheziidae, Aclerdiae, Dactylopiidae, Kerridae, Pseudococcidae, Coccidae,, Enococcidae, Asterolecaniidae, Beesonidae, Lecanodiaspididae, i
Cerococcidae)), coleopterous pests (e.g., rice water weevil, adzuki bean weevil, yellow mealworm, Western corn root worm, Southern corn root worm, cupreous chafer, soy bean beetle, striped flea beetle, cucurbit leaf beetle, Colorado potato beetle, rice leaf beetle, codling moth larvae and longicorn beetles), pests belonging to the order Acarina (e.g., the two-spotted spider mite, the Kanzawa spider mite and Panonychus citri), hymenopterous pests (e.g., sawflies), orthopterous pests (e.g., grasshoppers and locusts), dipterous pests (e.g., the housefly and leaf miner flies), thysanopterous pests (e.g.; melon thrips and Western flower thrips), and plant parasitic nematodes (the root knot nématode, the root lésion nematode, the rice white-tip nematode and the pine wood nematode). ;
Examples of animal parasitic pests include hard-bodied ticks (e.g., lone star tick, Gulf Coast tick, cattle tick, Rocky Mountain wood tick, West Coast tick, American dog tick, Haemaphysalis campanulata, Haemaphysalis flava, Haemaphysalis longicomis, Haemaphysalis megaspinosa, Ixodes nipponensis, Ixodes ovatus, Western black-legged tick, Ixodes persulcatus, castor bean tick, black-legged tick, Ornithodores moubata and brown dog tick), Cheyletidae spp. (e.g., Cheyletiella blackei and Cheyletiella yasguri), demodex mites (e.g., Demodex canis and Demodex cati), Psoroptidae spp. (e.g., Psoroptes commuais), mange mites (e.g., Chorioptes bovis and Otodectes cynotis), Dermanyssidae spp. (e.g., Omithonyssus sylviarum), parasitoid mites, feather mites (e.g,, Menacanthus comutus and Pterolichus obtusis), Trombiculidae spp. (e.g., Helenicula miyagawai and Leptotrombidium akamusî), fleas, (e.g., the cat flea, dog flea.sticktight flea, hum an flea and Oriental rat flea), chewîng lice (e.g., dog louse, chicken louse), sucking lice (e.g., hog louse, dog sucking louse, body louse, Pediculus humanus, pubic louse, common bed bug), muscid flies, warble flies, stable flies, horse flies, sand files (e.g., biting sand fly), tsetse fly, tabanid flies, aedine mosquitoes (e.g., the Tiger mosquito and yellow fever mosquito), culicîne mosquitoes (e.g., Culex pipiens pallens), anopheline mosquitoes, biting midges, buffalo gnats, assassin bugs, the pharaoh ant, nematodes (e.g., Strongyloididae, Ancylostomatoidea, Strongylida (e.g., Haemonchus contorius, Nippostrongylus brasiliensis), Trichostrongyloldea, Metastrongyloidea (e.g., Metastrongylus apr, Anriostrongylus cantonesis, Aelurostrongylus abstrusus), Oxyuroidea, Haterakoidea (e.g., Ascaridiidae galli), Ascaridoidea (e.g., Anisakis simplex, Ascaris lumbricoides suum, Parascaris equorum, Toxocara canis, Toxocara catî), Spirurida (e.g., Subuluroidea, Gnathostoma spinigerum, Physaloptea praeputialis, Ascarops strongy/ina, Draschia megastoma, Ascaria hamulosa, Dracunculus medinensis), Filaroidea (e.g., Dirofilaria immitis, Wuchereria bancrofti, Onchocerca volvulus, Loa loa), Dioctophymatoidea, Trichinelloidea (e.g., Trichuris vulpis, Trichinella spiralis)), Trematoda (e.g., Schistosoma japonicum, Fasciola spp.), Acanthocephala, Cestoda (e.g., Pseudophyllidea (e.g., Spiromètre erinaceieuropaei), Cyclophyllidea (e.g., Dipylidium caninum)), and Protozoa.
Health pests, nuisance pests, stored grain pests, stored food pests and household pests include mosquitoes (e.g., thé Tiger mosquito and Culex pipiens pallens), cockroaches (e.g., the smoky-brown cockroach, Periplaneta fuliginosa, and the German cockroach), grain mites (e.g., the common grain mite), fties (e.g., the house fly, Sarcophagidae spp., sand Aies, small fruit flies and Chironomidae spp.), buffalo gnats, biting midges, hymenopterous insects (e.g., ants such as Camponotus japonicas and fire ants, and hornets such as the Japanese giant homet), arthropods 5 of the order Isopoda (e.g., the rough woodlouse, wharf roach, pill bug), hemipterous insects (e.g., common bed bug), arthropods of the subphylum Mynapoda (e.g., centipedes, Chilopoda spp., millipedes), arthropods of the order Araneae (e.g., the huntsman spider), coleopterous insects (e.g., ground beetle), arthropods ofthe order Collembola (e.g., Onychiurus folsomi), insects ofthe order Dermaptera (e.g., the giant earwig), insects of the order Orthoptera (e.g., Stenopelmatidae 10 spp.), insects of the order Coleoptera (e.g., adzuki bean weevil, rice weevil, cadelle, rust-red flour beetle, white-marked spider beetle, deathwatch, bark beetles, dermestid beetles, Chlorophorus diadema), insects ofthe order Lepidoptera (e.g., pyralid moths, clothes moths), Hemipeplidae spp., insects of the order Isoptera (e.g., the house termite, western drywood termite, Odontotermes formosanus), and the order Thysanura (e.g., oriental silverfish).
Of these, preferred examples of pests on which suitable use may be made of the inventive pest control agent include lepidopterous pests, hemipterous pests, thysanopterous pests, dipterous pests, coleopterous pests, animal parasitic fleas and ticks, and canine heartworms (e.g., at Ieast one pest selected from the group consisting of diamondback moth, common cutworm, cotton aphid, green peach aphid, small brown planthopper, brown rice planthopper, white-backed 20 rice planthopper, green rice leafhopper, rice leaf bug, brown-winged green bug, western flower thrips, rice leaf beetle, rice water weevil, house fly, Haemaphysalis longicornis and canine heartworm). Hemipterous pests, coleopteous pests and hard-bodied ticks are more preferred. Planthoppers and the green rice leafhopper are especially preferred.
Therefore, the pest control agents provided by the présent invention are exemplified by 25 insecticides for agricultural and horticultural use, control agents for internai animal parasites, control agents for external animal parasites, control agents for sanitary pests, control agents for nuisance pests, control agents for stored grain/stored food pests, and control agents for household i
l pests. Insecticides for agricultural and horticultural use, control agents for internai animal ;
parasites and control agents forexternal animal parasites are preferred.
The pest control agents of the invention may be prepared using, aside from a compound of chemical formula (I), a carrier suitable for the intended method of use.
When the pest control agent of the invention is an agricultural pest control agent, the activei ingrédient is generally mixed with a suitable solid carrier, liquid carrier, gaseous carrier, surfactant,|
i. dispersant and other adjuvants, and the agent is furnished in any desired form, such as ani emulsifiable concentrate, liquid formulation, suspension concentrate, wettable powder, flowable concentrate, dust, granules, tablets, oil solution, aérosol or smoking agent.
Illustrative examples of solid carriers include talc, bentonite, clay, kaolin, diatomaceous earth, vermiculite, white carbon and calcium carbonate.
Illustrative examples of liquid carriers include alcohols such as méthanol, n-hexanol andί i' ethylene glycol, ketones such as acetone, methyl ethyl ketone and cyclohexanone, aliphatic:
hydrocarbons such as n-hexane and kerosene, aromatic hydrocarbons such as toluene, xylene[
F and methyl naphthalene, ethers such as diethyl ether, dloxane and tetrahydrofuran, esters such asj j ethyl acetate, nitriles such as acetonitrile and isobutyronitrile, acid amides such as dimethylformamide and dimethylacetamide, vegetable oils such as soy oil and cottonseed oil, dimethylsulfoxide, and water.
Illustrative examples of gaseous carriers include liquid propane gas, air, nitrogen, carbon dioxide and dimethyl ether.
Surfactants and dispersants which may be used for the purpose of émulsification, dispersion, spreading, sticking and the like include alkylsulfuric acid esters, alkyl(aryl)sulfonic acid salts, polyoxyalkylene alkyl(aryl) ethers, polyol esters, and ligninsulfonic acid salts.j
Adjuvants which may be used for improving the properties of the formulation includel carboxymethylcellulose, gum arable, polyethyiene glycol and calcium stéarate.
The above carriers, surfactants, dispersants and adjuvants may each be used singly or in' combination, as needed.
The active ingrédient content within the above formulation, although not particularly limited, is typically set to from 1 to 75 wt% in emulsifiable concentrâtes, from 0.3 to 25 wt% in dusts, from to 90 wt% in wettable powders, and from 0.5 to 10 wt% in granules.
The compounds of chemical formula (I), formulations containing these compounds, and mixtures of these with other pest control agents may be suitably applied to, for example, insect pests, plants, plant propagation materials (e.g., seeds, plant foliage, roots, germinated plants, and seedlings), soils, nutrient solutions in hydroponics, solid media in hydroponics, or rooms needed to prevent infestation by pests. Plants subjected to such application include genetically modified crops.
Such application may be carried out before and after pest infestation.
In particular, the compounds of chemical formula (le), formulations containing the same, and combinations of these with other pest control agents, by being applied at an effective dose to a target selected from the group consisting of seeds, roots, tubers, buibs, rhizomes, germinated plants, seedlings, soils, nutrient solutions in hydroponics and solid media in hydroponics, and thus being allowed to penetrate and translocate into the plant, are able to control pests.
In cases where the above targets of application are the seeds, roots, tubers, buibs or rhizomes of plants, preferred examples of the method of application are not particularly limited provided pénétration and translocation is unhindered and include, for example, dipping methods, dust coating methods, smearing methods, spraying methods, pellet methods and film coating methods.
in the case of seeds, examples of the method of application include dipping, dust coating, smearing, spraying, pellet application, film coating and fumigation. Dipping is a method for immersing the seeds in a liquid solution of the pest control agent. Dust coating methods include dry dust coating which involves coating the pest control agent in powdered form onto dry seeds, and wet dust coating which involves coating the pest control agent in powdered form onto iightly water-moistened seeds. Other methods are a smearing method for applying the pest control agent in a suspended form onto the surface of seeds within a mixer, and a spraying method for spraying the same onto the surface of the seeds. Additional methods of application include a peliet method in which, when the seeds are formed together with a filler into pellets of a given size and shape, treatment is carried out by mixing the pest control agent with the filler; a film coating method which entails coating the seeds with a film containing the pest control agent; and a fumigation method which entails disinfection of the seeds with the pest control agent that has been gasified within a closed vessel.
In the case of application to germinated plants and seedlings, these plants may be protected by application, via systemic or partial treatment by dipping, following germination and following emergence from the soil, but prior to transplantation.
In the case of application to seeds, roots, tubers, bulbs or rhizomes, an additional considération is planting or dipping the seeds, roots, tubers, bulbs or rhizomes for a time sufficient to allow pénétration and translocation of the pest control agent. In such a case, the time and température at which dipping is carried out may be suitably determined by a person skilled in the art in accordance with the target of application and the type and dose of the chemical. In addition, the pénétration and transiocation time is not subject to any particular limitation, and may be, for example, 1 hour or more. The température during pénétration and translocation is, for example, from 5to 45°C.
Methods of application to the soil are exemplified by the application of the inventive compound, formulations containing the same, or granules of mixtures thereof with other pest control agents, either into soil or onto soil. Preferred soil application methods are spraying, band application, furrow application and planting hole treatment. Here, spraying treatment is surface treatment over the entire surface area to be treated, and encompasses subséquent mechanical introduction into the soil.
Another useful method of soti treatment in volves application by drenching soil with a solution of the inventive compounds, a formulation containing the same, or a mixture thereof with another pest control agent that has been emulsified or dissolved in water.
in the case of application to nutrient solutions in nutricultural Systems for the production of vegetables and flowering plants, such as solid medium cultivation, including hydroponics, sand culture, the nutrient film technique (NFT) and the rock wool technique, it is obvious that the inventive compounds or formulations containing the same, or mixtures of these with other pest control agents, can be directly applied to an artificial plant growth medium containing vermiculite or a solid medium containing an artificial mat for raising seedlings.
In the above application step, the effective dose of the compound of formula (1) or a sait thereof, or of a compound of formula (le) or a sait thereof, is preferably an amount sufficient for the compound of formula (1) or formula (le) to penetrate and translocate in the subséquent pénétration and translocation step.
This effective dose may be suitably decided while taking into considération such factors as the properties of the compound, the type and amount of the target of application, the length of the subséquent pénétration and translocation step, and the température. For example, in the case of application to seeds, the dose of the compound of formula (1) or a sait thereof, or of the compound of formula (le) or a sait thereof, is preferably from 1 g to 10 kg, and more preferably from 10 g to 1 kg, per 10 kg of seed. In the case of application to soil, the dose of the compound of formula (1) or a sait thereof, or of the compound of formula (le) or a sait thereof, is preferably from 0.1 g to 10 kg, and more preferably from 1 g to 10 kg, per 10 ares of cultivated land. In the case of foliar application to plants, the dose of the compound of formula (1 ) or a sait thereof, or of the compound of formula (le) or a sait thereof, is preferably from 0.1 g to 10 kg, and more preferably from 1 g to 1 kg, per 10 areas of cultivated land.
In cases where the pest control agent of the invention is an agent for controlling animal parasitic pests, it may be furnished as, for example, a liquid formulation, an emulsifiable concentrate, liquefied drop formulation, a spray, a foam formulation, tablets, granules, fine granules, a dust, capsules, tablets, a chewable préparation, an injection, a suppository, a cream, a shampoo, a rinse, a resin formulation, a smoking agent or as poisonous bait. Supply as a liquid formulation or a liquid formulation for drop is especially preferred.
In liquid formulations, adjuvants such as common emulsifying agents, dispersants, spreaders, wetting agents, suspending agents preservatives and propellants may also be included, in addition to which ordinary film-forming agents may be included as well. Surfactants which may be used for émulsification, dispersion, spreading, sticking and the like include soaps, polyoxy alkylene alkyl(aryl) ethers, polyoxyethylene alkylallyl ethers, polyoxyethyiene fatty acid esters, higher alcohols and alkyl aryl sulfonates. Examples of dispersants include casein, gelatin, polysaccharides, lignin dérivatives, sugars and synthetic water-soîuble polymers. Examples of spreading and wetting agents include glycerol and polyethylene glycol. Examples of suspending agents include casein, gelatin, hydroxypropyl cellulose and gum arable. Examples of stabilîzers include phenol-based antioxidants (e.g., BHT, BHA), amine-based antioxidants (e.g., diphenylamine), and organosulfur-based antioxidants. Examples of preservatives include methyl p-oxybenzoate, ethyl p-oxybenzoate, propyl p-oxybenzoate and butyl p-oxybenzoate. The above carriers, surfactants, dispersants and adjuvants may each be used, as needed, either singly or as combinations thereof. In addition, fragrances and synergists may also be included. In a liquid formulation, it is suitable for the active ingrédient content in the pest control agents of the invention to be generally from 1 to 75 wt%.
Carriers used for preparing a cream formulation are exemplified by non-volatile hydrocarbons (e.g., liquid paraffin), lanolin fats added with water and oils, higher fatty acids, fatty acid esters, vegetable oils, silicone oils, and water. In addition, emulsifying agents, humectants, antioxidants, fragrances, borax and ultraviolet absorbera may each be used, either singly or in combination thereof, as needed. Examples of emulsifying agents include fatty acid sorbitans, poiyoxyethylene alkyl ethers and fatty acid polyoxyethylenes. An active ingrédient content within the inventive pest control agent of generally from 0.5 to 70 wt% is appropriate in cream formulations.
In the case of capsules, pills or tablets, the active ingrédient within the inventive composition is suitably dîvided up and mixed with a diluting liquid or a carrier such as starch, lactose or talc, in addition to which a disintegrant such as magnésium stéarate and/or a binder are added. if necessary, the formulation may be tableted prior to use.
In the case of injections, préparation must be carried oui as a stérile solution. The injection may include sufficient sait or glucose to render the solution isotonie with blood. Examples of carriers that may be used to préparé the injection include organic solvents such as glycerides, benzyl benzoate, isopropyl myristate, the fatty acid dehvatives of propyîene glycol and other esters, and N-methylpyrrolidone and glycerol formai. An active ingrédient content within the inventive pest control agent of generally from 0.01 to 10 wt% is appropriate in injections.
Examples of carriers for preparing a resin formulation include vinyl chîoride-based polymers and polyuréthane. If necessary, a pîasticizer such as a phthalic acid ester, an adipic acid ester or stearic acid may be added as the base for such formulations. After kneading the active ingrédient into this base, the resin formulation is shaped such as by injection molding, extrusion or molding under applied pressure. In addition, by suitably passing through such steps as molding and cutting, the formulation may be rendered into ear tags for animais and pest control collars for animais.
Examples of carriers for poisoned bait include feed substances and attractants (e.g., cereal flours such as wheat flour and cornmeal, starches such as corn starch and potato starch, sugars such as granular sugar, barley malt and honey, flood flavors such as glycerol, onion flavor and milk flavor, animal-based powders such as silkworm powder and fish powder, and various pheromones). An active ingrédient content within the inventive pest control agent of generally from 0.0001 to 90 wt% is appropriate in poisoned bait.
Pest control may be carried out by administering the inventive pest control agent within the body of the target animal, either orally or by injection, or by applying the inventive pest control agent to ail or part of the body surface of the target animal. Alternatîvely, pest control may also be carried out by coating places where it is expected that pests will invade, parasitize or move through with the pest control agent of the invention.
The pest control agent of the invention may be used directly as is, or may, depending on the particular case, be applied after dilution with, for example, water, a liquid carrier, or a commercial shampoo, rinse, feed or animal bedding.
Also, the pest control agents according to the invention may be used in admixture with other chemicals, such as fungicides, insecticides, acaricides, herbicides, plant growth regulators and fertilizers. Chemicals which may be used in admixture include compounds cited in the Pesticide Manual (13,h édition, pubiished by The British Crop Protection Council) and the Shibuya Index (13th édition, 2008, pubiished by the Shibuya Index Research Group). Spécifie examples of insecticides, acaricides and nematicides include organophosphate compounds such as acephate, dichlorvos, EPN, fenitothion, fenamifos, prothiofos, profenofos, pyraclofos, chlorpyrifos-methyl, diazinon, fosthiazate and imicyafos; carbamate compounds such as methomyl, thiodicarb, aldicarb, oxamyl, propoxur, carbaryl, fenobucarb, ethiofencarb, fenothiocarb, pirimicarb, carbofuran and benfuracarb; nereistoxin dérivatives such as cartap and thiocyclam; organochlorine compounds such as dicofol and tetradifon; pyrethroid compounds such as permethrin, tefluthrin, cypemnethrin, deltamethrin, cyhalothrin, fenvalerate, fluvalinate, ethofenprox and silafluofen; benzoyl urea compounds such as diflubenzuron, teflubenzuron, flufenoxuron and chlorfluazuron; juvénile hormone-like compounds such as methoprene; and molting hormone-like compounds such as chromafenozide. Examples of other compounds include buprofezin, hexythiazox, amitraz, chlordimeform, pyridaben, fenpyroxymate, pyrimidifen, tebufenpyrad, tolfenpyrad, fluacrypyrim, acequinocyl, cyflumetofen, flubendtzmide, ethiprole, fipronil, ethoxazle, imidacloprid, ciothianidin, thiamethoxam, acetamiprîd, nitenpyram, thiazcloprid, dinotefuran, pymetrozine, bifenazate, spirodiclofen, spiromesifen, flonicamid, chlorfenapyr, pyriproxyfen, indoxacarb, pyridalyl, spinosad, avermectin, milbemycin, cyneopyrafen, spinetoram, pyrifluquinazon, chlorantraniliproie, cyantraniliprole, spirotetramat, lepimectin, metafluminzone, pyrafluprole, pyriprole, hydramethylnon, triazamate, sulfoxaflor, flupyradifurone, flometoquin, organometallic compounds, dinitro compounds, organosulfur compounds, urea compounds, triazine compounds and hydrazine compounds.
The pest control agents of the invention may also be used in admixture or concomitantly with microbial pesticides such as BT formulations and entomopathogenic virus formulations.
Examples of fungicides which may be used in admixture or concomitantly include strobilurin compounds such as azoxystrobin, kresoxym-methyl, trifloxystrobin, metominostrobin and orysastrobin; anilinopyrimidine compounds such as mepanipyrim, pyrimethanil and cyprodinil; azole compounds such as triadimefon. bitertanol, triflumîzole, metoconazole, propiconazole, penconazole, flusilazole, myclobutanil, cyproconazole, tebuconazole, hexaconazole, prochloraz and simeconazole; quinoxalîne compounds such as quinomethionate; dithiocarbamate compounds such as maneb, zineb, mancozeb, polycarbamate and propineb; phenylcarbamate 42 compounds such as diethofencarb; organochlorine compounds such as chlorothalonil and quintozene; benzimidazole compounds such as benomyl, thiophanate-methyl and carbendazole; phenylamide compounds such as metalaxyl, oxadixyl, ofurase, benalaxyl, furalaxyl and cyprofuram; sulfenic acid compounds such as dichlofluanid; copper compounds such as copper hydroxide and oxine-copper; isoxazole compounds such as hydroxyisoxazole; organophosphorus compounds such as fosetyl-aluminium and tolclofos-methyl; N-halogenothioalkyl compounds such as captan, captafoi and folpet; dicarboxyimide compounds such as procymidone, iprodione and vinchlozolin; carboxy anîlide compounds such as flutolanil, mepronil, furamepyr, thifluzamide, boscalid and penthîopyrad; morpholine compounds such as fenpropimorph and dimethomorph; organotin compounds such as fenthin hydroxide and fenthin acetate; cyanopyrrole compounds such as fludioxonil and fenpiclonil; and also tricyclazole, pyroquilon, carpropamid, diclocymet, fenoxanil, fthalide, fluazinam, cymoxanil, triforine, pyrifenox, fenarimol, fenpropidin, pencycuron, ferimzone, cyazofamid, iprovalicarb, benthiavaiicarb-isopropyl, iminoctadin-albesilate, cyflufenamid, kasugamycin, validamycin, streptomycin, oxolinic acid, tebufloquin, probenazole, tiadinil and isotianiî.
Methods for Synthesizinq the Compounds of the Invention (1) Compounds of chemical formula (la) below [Chem. 7]
Ar^NR3R4 Ra (la) (wherein Ar is a phenyl group which may be substituted, or a 5- or 6-membered heterocycle which may be substituted;
R? is a Ci.e alkylcarbonyl group in which the alkyl moiety may be substituted with a halogen atom, a C^ alkyloxycarbonyl group in which the alkyl moiety may be substituted with a halogen atom, a C^ alkylsulfonyl group in which the alkyl moiety may be substituted with a halogen atom, CONR6R7 (wherein Ra and R7 are each independently a hydrogen atom or a Cia3 alkyl group which may be substituted with a halogen), a C,.6 Ο,Ο’-alkylphosphoryl group in which the alkyl moiety may be substituted with a halogen atom, a cyano group, a formyl group or a nitro group;
R3 is a C18 alkylene group which may be substituted with a halogen atom, a C2.3 alkenylene group which may be substituted with a halogen atom, a C2.e alkynylene group which may be substituted with a halogen atom, a phenylene group which may be substituted, or a 5- or
6-membered heterocyclic divalent group which may be substituted; and
R4 is a hydrogen atom, a phenyl group which may be substituted, a 3- to 8-membered carbocycle or heterocycle which may be substituted, a halogen atom, OR5, OCOR5, OCOOR5, COR5, COOR5, SR5i SOR5i SO2R5 (wherein R5 is a Cw alkyl group, an aryl group or an aralkyl group, any of which may be substituted with a halogen), N-CO-ORa, N-CO-SRs. N-CS-OR31 N-CSSR8, N-O-CO-RS, O-CO-Ra, O-CO-OR8, O-CO-SR;i, O-CS-OR8) O-CS-SR3, S-CS-ORa, S-CS-SR8, S-CO-ORs, S-CO-SRs (wherein R0 is a alkyl group which may be substituted, the substituent being a halogen, a C-m alkyloxycarbonyl group, a CM alkylcarbonyl group, a benzoyl group which may be substituted with a halogen or a Cu alkyl group which may be substituted with a halogen, a Cm alkyloxy group or a CM alkylthio group), or NR9R10 (wherein Rg and R10 are each independently a hydrogen atom, a CM alkyl group which may be substituted with a halogen, a CM alkylcarbonyl group in which the alkyl moiety may be substituted with a halogen atom, or a Cve alkylcarbonyloxy group in which the alkyl moiety may be substituted with a halogen atom);
with the proviso that when Ar is a 2,6-dichloro-4-pyridyl group, R2 is not a C-|.6 alkyloxycarbonyl group in which the alkyl moiety may be substituted with a halogen atom) may be obtained by reacting, for example, a halide, anhydride or ester of R2 (R2 having the same meaning as defined in above chemical formula (I)) with a compound of the following chemical formula (II) [Chem. 8]
Ar'/^NHR3R4 (wherein Ar, R3 and R4 hâve the same meanings as defined in above chemical formula (I)), either in the presence or absence of a base.
Carboxylic acid halides, carboalkyloxy halides, sulfonyl halides, O.O’-alkylphosphoryl halides, carboxylic anhydrides, dialkyldicarbonates, carboxylic acid esters and carbonic acid esters may be used as the halide, anhydride or ester of R2. For example, the use of acetyl chloride, ethyl chloroformate, methanesulfonyl chloride, diethyl chlorophosphate, trifluoroacetic anhydride or ethyl formate is preferred,
When the reaction is carried out in the presence of a base, the base may be, for example, an alkali métal hydride such as sodium hydride, a carbonate such as potassium carbonate or sodium carbonate, an alkali métal hydroxide such as potassium hydroxide or sodium hydroxide, a tertiary amine such as triethylamine, or a substituted or unsubstituted pyridine compound such as pyridine or 4-dimethylaminopyridine.
The reaction may be carried out in the absence of a solvent or using a solvent which does not affect the reaction. In cases where a solvent is used, solvents such as amides (e.g., dimethylformamide, dimethylacetamide), nitriles (e.g., acetonitrile), sulfoxides (e.g., dimethylsulfoxide), ethers (e.g., diethyl ether, tetrahydrofuran), esters (e.g., ethyl acetate, butyl acetate), aromatic hydrocarbons (e.g., benzene, xylene, toluene), alcohols (e.g,, methanol, éthanol, propanol), ketones (e.g., acetone, methyl ethyl ketone), aliphatic hydrocarbons (e.g., hexane, heptane, octane), halogenated hydrocarbons (e.g., dichloromethane, chloroform, chlorobenzene, dichlorobenzene), or water may be used singly or as combinations of two or more thereof. The use of dimethylformamide, acetonitrile, ethers, dichloromethane, chloroform or the like is preferred.
The reaction may generally be carried out at from -80 to 100°C, and is preferably carried out in the range of 20 to 50°C.
When R2 in the above chemical compound (la) is a alky(carbonyl group in which the alkyl moiety may be substituted with a halogen atom, the compound of formula (la) may be obtained by reacting the compound of chemical formula (11) with a carboxylic acid of the formula R2-COOH (wherein R2 is a C1j6 alkyl group which may be substituted with a halogen atom) in the presence of a dehydration-condensation agent.
A carbodiimide compound such as dicyclohexylcarbodiimide or 1 -ethyl-3-(3dimethylaminopropyl)carbodiimide hydrochloride may be used as the dehydration-condensation agent.
The reaction is preferably carried out using a solvent For example, amides such as dimethylformamide and dimethylacetamide, nitriles such as acetonitrile, sulfoxides such as dimethylsulfoxide, ethers such as diethyl ether and tetrahydrofuran, esters such as ethyl acetate and butyl acetate, aromatic hydrocarbons such as benzene, xylene and toluene, ketones such as acetone and methyl ethyl ketone, aliphatic hydrocarbons such as hexane, heptane and octane, and halogenated hydrocarbons such as dichlorométhane, chloroform, chlorobenzene and dichlorobenzene may be used singly or as combinations of two or more thereof. The use of, for example, dichlorométhane or chloroform is preferred,
The reaction may be carried out at generally from -80 to 100°C, and is preferably carried out in the range of 20 to 50°C.
When R2 in above chemical formula (la) is a cyano group, the compound of formula (la) may be obtained by reacting the compound of formula (II) with a known cyanating reagent, either in the presence or absence of a base.
Cyanating reagents that may be used for this purpose include cyanogen bromide, cyanogen iodide, 1-cyanoimidazole, 1-cyanobenzotriazole, and substituted or unsubstituted benzenesulfonyl cyanide.
When the reaction is carried out in the presence of a base, the base may be, for example, an alkali métal hydride such as sodium hydride, a carbonate such as potassium carbonate or sodium carbonate, an alkali métal acetate such as sodium acetate, a tertiary amine such as triethylamine, or a substituted or unsubstituted pyridine compound such as pyridine or 4dimethylaminopyridîne.
The reaction may be carried out in the absence of a solvent or using a solvent which does not affect the réaction. In cases where a solvent is used, solvents such as amides (e.g., dimethylformamide, dimethylacetamide), nitriles (e.g., acetonitrile), sulfoxides (e.g., dimethylsulfoxide), ethers (e.g., diethyl ether, tetrahydrofuran), esters (e.g., ethyl acetate, butyl
Λ acetate), aromatic hydrocarbons (e.g., benzene, xylene, toluene), alcohols (e.g., methanol, éthanol, propanol), ketones (e.g., acetone, methyl ethyl ketone), aliphatic hydrocarbons (e.g., hexane, heptane, octane), halogenated hydrocarbons (e.g., dichloromethane, chloroform, chlorobenzene, dichlorobenzene), or water may be used singly or as combinations of two or more thereof. The use of an ether such as diethyl ether or tetrahydrofuran, or a halogenated hydrocarbon such as dichloromethane or chloroform is preferred. The reaction may be carried out at generally from 0 to 100°C, although it is préférable to add the cyanating reagent at 0°C and gradually raise the température to about 20 to 50°C.
The cornpound of chemical formula (II) may be synthesized from a cornpound of chemical formula (Ilia) or chemical formula (lllb) below:
[Chem. 9]
Ar^X (ma) (wherein X is a halogen, OTs or Oms) [Chem. 10]
Ar^NH2(ll[b) (wherein Ar has the same meaning as defined in above chemical formula (I)).
When synthesis is carried out from the cornpound of formula (Ilia), the cornpound of formula (II) may be obtained by reacting the cornpound of formula (Ilia) with a cornpound of the chemical formula (IVa) below [Chem. 11] u m'R3R4 h2n (Iva) (wherein R3 and R4 have the same meanings as defined above in chemical formula (I)), either in the presence or absence of a base.
When the reaction is carried in the presence of a base, the base used for this purpose may be, for example, an alkali métal hydride such as sodium hydride, a carbonate such as potassium carbonate or sodium carbonate, an alkali métal hydroxide such as potassium hydroxide or sodium hydroxide, a tertiary amine such as triethylamine, or a substituted or unsubstîtuted pyridine cornpound such as pyridine or 4-dimethylaminopyridine.
t
The réaction may be carried out in the absence of a solvent or using a solvent which does not affect the reaction. In cases where a solvent is used, solvents such as amides (e.g., dimethylformamide, dîmethylacetamide), nitriles (e.g., acetonitrile), sulfoxides (e.g., dimethylsulfoxide), ethers (e.g., diethyl ether, tetrahydrofuran), esters (e.g., ethyl acetate, butyl acetate), aromatic hydrocarbons (e.g., benzene, xylene, toluene), alcohols (e.g., methanol, éthanol, propanol), ketones (e.g., acetone, methyl ethyl ketone), aliphatic hydrocarbons (e.g., hexane, heptane, octane), or halogenated hydrocarbons (e.g., dichloromethane, chloroform, chlorobenzene, dichlorobenzene) may be used singly or as combinations of two or more thereof. The use of dimethylformamide, acetonitrile, an ether, dichloromethane or chloroform is preferred.
The réaction may be carried out at generally from 0 to 200°C, although it is préférable to add the reagent at 0°C, gradually raise the température to about 20 to 50°C, then let the température rise to a higher température as the reaction proceeds.
The amount of the compound of formula (lila) added is preferably not more than one mole per mole of the compound of formula (IVa).
In the case of synthesis from the compound of formula (IIIb), the compound of formula (II) may be obtained by reacting a compound of the following chemical formula (IVb) with the compound of formula (lllb) [Chem. 12]
X^IVb) (wherein R3 and R4 have the same meanings as defined in above chemical formula (I), and X is a halogen atom, OTs or O Ms), either in the presence or absence of a base.
When the réaction is carried in the presence of a base, the base may be, for example, an alkali métal hydride such as sodium hydride, a carbonate such as potassium carbonate or sodium carbonate, an alkali métal hydroxide such as potassium hydroxide or sodium hydroxide, a tertiary amine such as triethylamine, or a substituted or unsubstituted pyridine compound such as pyridine or 4-dimethylaminopyridine.
The reaction may be carried out in the absence of a solvent or using a solvent which does not affect the reaction. In cases where a solvent is used, solvents such as amides (e.g.,
Λ i
dimethylfomnamide, dimethylacetamide), nitriles (e.g., acetonitrile), sulfoxides (e.g., dimethylsulfoxide), ethers (e.g., diethyl ether, tetrahydrofuran), esters (e.g., ethyl acetate, butyî acetate), aromatic hydrocarbons (e.g., benzene, xylene, toluene), alcohols (e.g., méthanol, éthanol, propanol), ketones (e.g., acetone, methyl ethyl ketone), aliphatic hydrocarbons (e.g., hexane, heptane, octane), halogenated hydrocarbons (e.g., dichloromethane, chloroform, chlorobenzene, dichlorobenzene), or water may be used singly or as combinations of two or more thereof. The use of dimethylformamide, acetonitrile, an ether, dichloromethane or chloroform is preferred.
The reaction may be carried out at generally from 0 to 200°C, although it is préférable to add the reagent at 0°C, gradually raise the température to about 20 to 50°C, then let the température rise to a higher température as the reaction proceeds.
The amount of the compound of formula (IVb) added is preferably not more than one mole per mole of the compound of formula (111b).
Altematively, the compound of formula (II) may be obtained by adding a compound of the formula (IVc) below, either in the presence or absence of an acid, to the compound of formula (III b) so as to form an imine, then carrying out a reducing reaction.
[Chem. 13]
R3-R4
0^ R= (IVc) (In the formula, R3· and R3-, which may be the same or different, are each independently a hydrogen atom or a Ci.7 alkyl group, and R3· and R3- may together form a ring, with the provisos that R3· and R3- are not both hydrogen atoms andthat the sum ofthe numbers of carbon atoms on R3· and R3- is smallerthan 7; and R4 has the same meaning as defined in above chemical formula (I))
It is préférable to use a solvent in the reaction. Illustrative examples of solvents that may be used include lower alcohols (e.g., méthanol, éthanol), acetonitrile, dichloromethane and dichloroethane, with the use of méthanol or éthanol being preferred.
τ ln cases where an acid is used, the acid may be, for example, hydrochloric acid, a substituted or unsubstrtuted benzenesulfonic acid, or acetic acid.
The reducing reaction may be carried out using a hydride reducing reagent such as sodium borohydride, sodium cyanoborohydride or sodium triacetoxyborohydride.
Alternative^, the reducing reaction may be carried out by a catalytic hydrogénation réaction using a métal catalyst. Métal catalysts that may be used include palladium, platinum rhodium, nickel and iron.
The reaction may be carried out at generally from 20 to 100°C.
(2) Compounds of the formula (la) may be synthesized from compounds of the following chemical formula (Va) [Chem. 14]
Ar^NH r2 (Va) (wherein Ar and R2 hâve the same meanings as defined in above chemical formula (la).)
A compound of formula (la) can be obtained by reacting a compound of formula (Va) with a compound of the formula X-R3R4 (wherein R3 and R4 hâve the same meanings as defined in above chemical formula (I), and X is a halogen atom), either in the presence or absence of a base.
When the réaction is carried in the presence of a base, the base may be, for example, an alkali métal hydride such as sodium hydride, a carbonate such as potassium carbonate or sodium carbonate, an alkali métal hydroxide such as potassium hydroxide or sodium hydroxide, a tertiary amine such as triethylamine, or a substituted or unsubstituted pyridine compound such as pyridine or 4-dimethylaminopyridjne. The use of an alkali métal hydride such as sodium hydride is preferred.
The reaction may be carried out in the absence of a solvent or using a solvent which does not affect the reaction, ln cases where a solvent is used, solvents such as amides (e.g., dimethylform amide, dimethylacetamide), nitriles (e.g., acetonitrile), sulfoxides (e.g., dimethylsulfoxide), ethers (e.g., diethyl ether, tetrahydrofuran), esters (e.g., ethyl acetate, butyl acetate), aromatic hydrocarbons (e.g., benzene, xylene, toluene), alcohols (e.g., methanol, éthanol, propanol), ketones (e.g., acetone, methyl ethyl ketone), aliphatiç hydrocarbons (e.g., hexane, heptane, octane), halogenated hydrocarbons (e.g., dichloromethane, chloroform, chlorobenzene, dichlorobenzene), or water may be used singly or as combinations of two or more thereof. The use of dimethylformamide, acetonitrile, an ether, dichloromethane or chloroform is preferred.
A compound of formula (Va) can be obtained by reacting a halide, anhydride, ester or the like of formula R2 (wherein R2 has the same meaning as defined în above chemical compound (I)) with a compound of formula (iiIb), either in the presence or absence of a base.
The halide, anhydride, ester or the like of formula R2 which rs used may be, for example, a carboxylic acid halide, a carboalkyloxy halide, a sulfonyl halide, a Ο,Ο’-alkylphosphoryl halide, a carboxylic anhydride, a dialkyl bicarbonate, a carboxylic acid ester, a carbonic acid ester or a cyanohalide.
The reaction is preferably carried out using a solvent, in which case solvents such as amides (e.g., dimethylformamide, dimethylacetamide), nitriles (e.g., acetonitrile), sutfoxides (e.g., dimethylsulfoxide), ethers (e.g., diethyl ether, tetrahydrofuran), esters (e.g., ethyl acetate, butyl acetate), aromatic hydrocarbons (e.g., benzene, xylene, toluene), alcohols (e.g., methanol, éthanol, propanol), ketones (e.g., acetone, methyl ethyl ketone), aliphatiç hydrocarbons (e.g., hexane, heptane, octane), halogenated hydrocarbons (e.g., dichloromethane, chloroform, chlorobenzene, dichlorobenzene), or water may be used singly or as combinations of two or more thereof. The use of an ether such as diethyl ether or tetrahydrofuran is preferred.
When the reaction is carried in the presence of a base, the base may be, for example, an alkali meta! hydride such as sodium hydride, a carbonate such as potassium carbonate or sodium carbonate, an alkaii métal hydroxide such as potassium hydroxide or sodium hydroxide, a tertiary amine such as triethylamine, or a substituted or unsubstituted pyridine compound such as pyridine or 4-dimethylaminopyridîne.
A compound of formula (Va) can be obtained by reacting a compound of formula R2-NH2 (wherein R2 has the same meaning as defined in above chemical compound (I)) with a compound of formula (Ilia), either in the presence or absence of a base.
< »
The use of a solvent in the reaction is preferred, in which case solvents such as amides (e.g., dimethylformamide, dimethylacetamide), nitriles (e.g., acetonitrile), sulfoxides (e.g., dimethylsulfoxide), ethers (e.g., diethyl ether, tetrahydrofuran), esters (e.g., ethyl acetate, butyl acetate), aromatic hydrocarbons (e.g., benzene, xylene, toluene), alcohols (e.g., methanol, éthanol, propanol), ketones (e.g., acetone, methyl ethyl ketone), aliphatic hydrocarbons (e.g., hexane, heptane, octane), halogenated hydrocarbons (e.g., dichloromethane, chloroform, chlorobenzene, dichlorobenzene), or water may be used singly or as combinations of two or more thereof. The use of acetonitrile or the like is preferred.
When the reaction is carried in the presence of a base, the base may be, for example, an alkali métal hydride such as sodium hydride, a carbonate such as potassium carbonate or sodium carbonate, an alkali métal hydroxide such as potassium hydroxide or sodium hydroxide, a tertiary amine such as triethylamine, or a substituted or unsubstituted pyridine compound such as pyridine or 4’dimethylaminopyridine.
(3) Compounds of the formula (la) may also be synthesized from compounds of the following chemical formula (Vb) [Chem. 15]
r2 (Vb) (wherein R2, R3 and R4 hâve the same meanings as defined in above chemical formula (I)).
Compounds of the formula (la) can be obtained by reacting a compound of the formula (Vb) with a compound ofthe formula Ar-CH2-X (wherein Ar has the same meaning as defined in above chemical formula (I), and X is a halogen atom, OTs or OMs), either in the presence or absence of a base.
When the reaction is carried in the presence of a base, the base may be, for example, an alkali métal hydride such as sodium hydride, a carbonate such as potassium carbonate or sodium carbonate, an alkali métal hydroxide such as potassium hydroxide or sodium hydroxide, a tertiary amine such as triethylamine, or a substituted or unsubstituted pyridine compound such as pyridine
A t
or 4-dimethylaminopyridine. The use of an alkali métal hydride such as sodium hydride is preferred,
The reaction may be carried out in the absence of a solvent or using a solvent which does not affect the reaction. In cases where a solvent is used, solvents such as amides (e.g., dimethylfomnamide, dimethylacetamide), nitriles (e.g., acetonitrile), sulfoxides (e.g., dimethylsulfoxide), ethers (e.g., diethyl ether, tetrahydrofuran), esters (e.g., ethyl acetate, butyl acetate), aromatic hydrocarbons (e.g., benzene, xylene, toluene), alcohols (e.g., methanol, éthanol, propanol), ketones (e.g., acetone, methyl ethyl ketone), aliphatic hydrocarbons (e.g., hexane, heptane, octane), halogenated hydrocarbons (e.g., dichloromethane, chloroform, chlorobenzene, dîchlorobenzene), or water may be used singly or as combinations of two or more thereof. The use of dimethylformamide, acetonitrile, an ether, dichloromethane or chloroform is preferred.
The compound of formula (Vb) may be obtained by reacting a halide, anhydride, ester or the like of the formula R2 (wherein R2 has the same meaning as defined in above chemical formula (I)) with a compound ofthe formula (IVa), either in the presence or absence of a base.
Examples of halides, anhydrides and esters of the formula R2 that may be used include carboxylîc acid halides, carboalkyloxy halides, sulfonyl halides, Ο,Ο’-alkylphosphoryl halides, carboxylîc anhydrides, dialkyloxy dicarbonates, carboxylîc acid esters, carbonic acid esters and cyanogen halides.
The use of a solvent in the reaction is preferred. Solvents such as amides (e.g., dimethylformamide, dimethylacetamide), nitriles (e.g., acetonitrile), sulfoxides (e.g., dimethylsulfoxide), ethers (e.g., diethyl ether, tetrahydrofuran), esters (e.g., ethyl acetate, butyl acetate), aromatic hydrocarbons (e.g., benzene, xylene, toluene), alcohols (e.g., methanol, éthanol, propanol), ketones (e.g., acetone, methyl ethyl ketone), aliphatic hydrocarbons (e.g., hexane, heptane, octane), halogenated hydrocarbons (e.g., dichloromethane, chloroform, chlorobenzene, dîchlorobenzene), or water may be used singly or as combinations of two or more thereof. The use of an ether such as diethyl ether or tetrahydrofuran is preferred.
When the reaction is carried in the presence of a base, the base may be, for example, an alkali métal hydride such as sodium hydride, a carbonate such as potassium carbonate or sodium carbonate, an alkali métal hydroxide such as potassium hydroxide or sodium hydroxide, a tertiary amine such as triethylamine, or a substituted or unsubstituted pyridine compound such as pyridine or 4-dimethylaminopyridine.
Alternatively, the compound of formula (Vb) can be obtained by reacting a compound of the formula R2-NH2 (wherein R2 has the same meaning as defined in above chemical compound (I)) with a compound of the formula X-R3R4 (wherein R3 and R4 hâve the same meanings as defined in above chemical formula (I), and X is a halogen atom), either in the presence or absence of a base.
The use of a solvent in the reaction is preferred. Solvents such as amides (e.g., dimethylformamide, dimethylacetamide), nitriles (e.g., acetonitrile), sulfoxides (e.g., dimethylsulfoxide), ethers (e.g., diethyl ether, tetrahydrofuran), esters (e.g,, ethyl acetate, butyl acetate), aromatic hydrocarbons (e.g., benzene, xylene, toluene), alcohols (e.g., methanol, éthanol, propanol), ketones (e.g., acetone, methyl ethyl ketone), aliphatic hydrocarbons (e.g., hexane, heptane, octane), halogenated hydrocarbons (e.g., dichloromethane, chloroform, chlorobenzene, dichlorobenzene), or water may be used singly or as combinations of two or more thereof. The use of acetonitrile or tetrahydrofuran is preferred.
When the reaction is carried in the presence of a base, the base may be, for example, an alkali métal hydride such as sodium hydride, a carbonate such as potassium carbonate or sodium carbonate, an alkali métal hydroxide such as potassium hydroxide or sodium hydroxide, a tertiary amine such as triethylamine, or a substituted or unsubstituted pyridine compound such as pyridine or 4-dimethylaminopyridine.
(4) Compounds of the chemical formula (Ib) below can be obtained by reacting a compound of the formula ArCH2X (wherein X is a halogen atom) with a compound of the formula R2NH2 (wherein R2 has the same meaning as defined in above chemical compound (I)), either in the presence or absence of a base.
[Chem. 16]
Ar N Ar R2 (lb) (In the formula, Ar and R2 hâve the same meanîngs as defîned in above chemical formula (I),)
When the reaction is carried in the presence of a base, the base may be, for example, an alkali métal hydride such as sodium hydride, a carbonate such as potassium carbonate or sodium carbonate, an alkali métal hydroxide such as potassium hydroxide or sodium hydroxide, a tertiary amine such as triethylamine, or a substituted or unsubstituted pyridine compound such as pyridine or 4-dimethylaminopyridine.
The reaction may be carried out in the absence of a solvent or using a solvent which does not affect the reaction. In cases where a solvent is used, solvents such as amides (e.g., dimethylformamide, dimethylacetamide), nitriles (e.g., acetonitrile), sulfoxides (e.g., dimethylsulfoxide), ethers (e.g., diethyl ether, tetrahydrofuran), esters (e.g., ethyl acetate, butyl acetate), aromatic hydrocarbons (e.g., benzene, xylene, toluene), alcohols (e.g., methanol, éthanol, propanol), ketones (e.g., acetone, methyl ethyl ketone), aliphatic hydrocarbons (e.g., hexane, heptane, octane), or halogenated hydrocarbons (e.g., dichloromethane, chloroform, chlorobenzene, dichlorobenzene) may be used singly or as combinations of two or more thereof. The use of acetonitrile is preferred.
The reaction may be carried out at generally from 0 to 200°C, although it is préférable to add the reagent at 20 to 40°C, and to carry out the réaction at 60 to 80°C.
(5) Compounds of the following chemical formula (le) [Chem. 17]
Ri
Ar NR3R4 R2 (le) (wherein R-) is a C^e alkyl group, and Ar, R2, R3 and R4 having the same meanings as defîned in above chemical formula (I)) can be obtained by reacting a halide, anhydride, ester or the like of the formula R2 (R2 having the same meaning as defîned in above chemical formula (I)) with a compound of the formula (Via) below, either in the presence or absence of a base.
[Chem. 18] î1 ArAN-R3R<
H (Via) (In the formula, Ri is a CM alkyl group, and Ar, R3 and Fl, hâve the same meanings as defined in above chemical formula (I).)
Examples of halides, anhydrides and esters of the formula R2 which may be used include carboxylic acid halides, carboalkyloxy halides, suifonyl halides, Ο,Ο'-alkylphosphoryl halides, carboxylic anhydrides, dialkyl dicarbonates, carboxylic acid esters and carbonic acid esters. The use of, for example, acetyl chloride, ethyl chloroformate, methanesulfonyl chloride, diethyl chlorophosphate, trifluoroacetic anhydride or ethyl formate is preferred.
When the reaction is carried in the presence of a base, the base may be, for example, an alkali métal hydride such as sodium hydride, a carbonate such as potassium carbonate or sodium carbonate, an alkali métal hydroxide such as potassium hydroxide or sodium hydroxide, a tertiary amine such as triethylamine, or a substituted or unsubstituted pyridine compound such as pyridine or 4-dimethylaminopyridine.
The reaction may be carried out in the absence of a solvent or using a solvent which does not affect the reaction. In cases where a solvent is used, solvents such as amides (e.g., dimethylformamide, dimethylacetamide), nitriles (e.g., acetonitrile), sulfoxides (e.g., dimethylsulfoxide), ethers (e.g., diethyl ether, tetrahydrofuran), esters (e.g., ethyl acetate, butyl acetate), aromatic hydrocarbons (e.g., benzene, xylene, toluene), alcohols (e.g., méthanol, éthanol, propanol), ketones (e.g., acetone, methyl ethyl ketone), aliphatic hydrocarbons (e.g,, hexane, heptane, octane), halogenated hydrocarbons (e.g., dichloromethane, chloroform, chlorobenzene, dichlorobenzene), or water may be used singly or as combinations of two or more thereof. The use of dimethylformamide, acetonitrile, ethers, dichloromethane or chloroform is preferred.
The reaction may be carried out at generally from -80 to 100°C, although it is préférable to carry out the reaction in the range of 20 to 50°C.
When the alkyl moiety of R2 in the compound of formula (le) is a alkyl carbonyl group which may be substituted with a halogen atom, the compound of formula (le) can be obtained by t
reacting a carboxylic acid of the formula R2-COOH (wherein R? is a alkyl group which may be substituted with a halogen atom) with a compound of the formula (Via) in the presence of a dehydration-condensation agent
A carbodiimide compound such as dicyclohexylcarbodiimide or 1 -ethyl-3-(3dimethylaminopropyl)carbodiimide hydrochloride may be used as the dehydration-condensation agent.
The réaction is preferably carried out using a solvent. Solvents such as amides (e.g., dimethylformamide, dimethylacetamide), nitriles (e.g., acetonitrile), sulfoxides (e.g., dimethylsulfoxide), ethers (e.g., diethyl ether, tetrahydrofuran), esters (e.g., ethyl acetate, butyl acetate), aromatic hydrocarbons (e.g., benzene, xylene, toluene), ketones (e.g., acetone, methyl ethyl ketone), aliphatic hydrocarbons (e.g., hexane, heptane, octane), or halogenated hydrocarbons (e.g., dichloromethane, chloroform, chlorobenzene, dichlorobenzene) may be used singly or as combinations of two or more thereof. The use of dichloromethane or chloroform is preferred.
The reaction may be carried out at generally from -80 to 100°C, although it is préférable to carry out the reaction in the range of 20 to 50°C.
When R2 în the compound of formula (le) is a cyano group, the compound of formula (le) may be obtained by reacting a known cyanaiing reagent with the compound of formula (IVa), either in the presence or absence of a base.
Cyanating reagents which may be used for this purpose include cyanogen bromide, cyanogen iodide, 1-cyanoimidazole, 1-cyanobenzotriazole, and substituted and unsubstituted benzenesulfonyl cyanide.
When the reaction is carried out in the presence of a base, the base used for this purpose may be, for example, an alkali métal hydride such as sodium hydride, a carbonate such as potassium carbonate or sodium carbonate, an alkali métal acetate such as sodium acetate, a tertiary amine such as triethylamîne, or a substituted or unsubstituted pyridine compound such as pyridine or 4-dimethylaminopyridine.
I «
The reaction may be carried out in the absence of a solvent or using a solvent which does not affect the reaction. In cases where a solvent is used, solvents such as amides (e.g., dimethylformamide, dimethylacetamide), nitriles (e.g., acetonitrile), sulfoxides (e.g., dimethylsulfoxide), ethers (e.g., diethyl ether, tetrahydrofuran), esters (e.g., ethyl acetate, butyl acetate), aromatic hydrocarbons (e.g., benzene, xylene, toluene), alcohols (e.g., methanol, éthanol, propanol), ketones (e.g., acetone, methyl ethyl ketone), aliphatic hydrocarbons (e.g., hexane, heptane, octane), halogenated hydrocarbons (e.g., dichlorométhane, chloroform, chlorobenzene, dichlorobenzene), or water may be used singly or as combinations of two or more thereof. The use of an ether such as diethyl ether or tetrahydrofuran, or a halogenated hydrocarbon such as dichlorométhane and chloroform is preferred.
The reaction may be carried out at generally from 0 to 100°C, although it is préférable to add the cyanating reagent at 0°C and gradually raise the température to about 20 to 50°C.
The compound of formula (Via) can be obtained by adding a compound of the formula H2N-R3R4 (wherein R3 and R4 hâve the same meanings as defined in chemical formula (I)) to a compound ofthe following chemicalformula (VII) [Chem. 19] Ar R1 (VII) (wherein Ri is the same as above) in the presence or absence of an acid so as to form an imine, then carrying out a reducing reaction.
The reaction is preferably carried out using a solvent. It is préférable to use a lower alcohol such as methanol or éthanol, or dichlorométhane or chloroform as the solvent, although the use of acetonitrile is also possible.
When an acid is used, the acid may be, for example, hydrochloride acid, a substituted or unsubstituted benzenesulfonic acid, or acetic acid.
The reducing reaction may be carried out using a hydride reducing reagent such as sodium borohydride, sodium cyanoborohydride or sodium triacetoxyborohydride.
I
The reducing reaction may be carried out by a catalyst hydrogénation reaction using a métal catalyst. Métal catalysts that may be used include palladium, platinum, rhodium, nickel and iron.
The reaction may be carried out at a température în the range of generally from 20 to
100°C.
(6) Compounds of the following chemical formula (Id) [Chem, 20]
(Id) (wherein Ar, R2 and Ra hâve the same meanings as defined in above chemical formula (I)) can be obtained by reacting carbon disulfide and a compound of the formula R8-X (wherein R8 has the same meaning as defined in above chemical formula (l), and X is a halogen atom), in the presence of a base, with a compound of the chemical formula (VIII) below that can be synthesized by a method described in the literature (Journal of Médicinal Chemîstry 42(12), 2227-2234 (1999)), [Chem, 21]
NH (VIII) (In the formula, Ar has the same meaning as defined in above chemical formula (I).)
The base used for this purpose may be, for example, an alkali métal hydride such as sodium hydride, a carbonate such as potassium carbonate or copper carbonate, an alkali métal hydroxide such as potassium hydroxide or sodium hydroxide, a métal oxide such as copper oxide or magnésium oxide, a tertiary amine such as triethylamine, or a substituted or unsubstituted pyridine compound such as pyridine or 4-dimethylaminopyridine. The use of a strong base such as potassium t-butylate is preferred.
The reaction may be carried out in the absence of a solvent or using a solvent which does not affect the reaction. In cases where a solvent is used, solvents such as amides (e.g., dimethylformamide, dimethylacetamide), nitriles (e.g., acetonitrile), sulfoxides (e.g., dimethylsulfoxide), ethers (e.g., diethyl ether, tetrahydrofuran), esters (e.g., ethyl acetate, butyl acetate), aromatic hydrocarbons (e.g., benzene, xylene, toluene), alcohols (e.g., méthanol, éthanol, propanol), ketones (e.g., acetone, methyl ethyl ketone), aliphatic hydrocarbons (e.g., hexane, heptane, octane), halogenated hydrocarbons (e.g., dichloromethane, chloroform, chlorobenzene, dichlorobenzene), or water may be used singly or as combinations oftwo or more thereof. The use of an ether such as tetra hydrofuran is preferred.
The reaction may be carried out at generally from -80 to 100°C, although it is préférable to carry out the reaction in the range of 20 to 50°C.
A compound of the chemical formula (le) [Chem. 22]
(wherein Ar, Rj, Y and R4e are the same as defined above) can be obtained by reacting a compound of the formula (IX) below with a compound of the formula ArCH(R-i)X (wherein Ar and R-i are the same as defined above, and X is a halogen, OTs or OMs), in the presence or absence of a base.
[Chem. 23]
(In the reaction, Y and R4e are the same as defined above.)
When the reaction is carried out in the presence of a base, the base may be, for example, an alkali métal hydride such as sodium hydride, a carbonate such as potassium carbonate or sodium carbonate, an alkali meta! hydroxide such as potassium hydroxide or sodium hydroxide, a tertiary amine such as triethylamine, or a substituted or unsubstituted pyridine compound such as pyridine or 4-dimethylaminopyridine.
The reaction may be carried out in the absence of a solvent or using a solvent which does not affect the reaction. In cases where a solvent is used, solvents such as amides (e.g., dimethylforrnamide, dimethylacetamide), nitriles (e.g., acetonitrile), sulfoxides (e.g., dimethylsulfoxide), ethers (e.g., diethyl ether, tetrahydrofuran), esters (e.g., ethyl acetate, butyl acetate), aromatic hydrocarbons (e.g., benzene, xylene, toluene), alcohols (e.g., methanol, éthanol, propanol), ketones (e.g., acetone, methyl ethyl ketone), aliphatic hydrocarbons (e.g., hexane, heptane, octane), or halogenated hydrocarbons (e.g., dichloromethane, chloroform, chlorobenzene, dichlorobenzene) may be used singly or as combinations of two or more thereof. The use of acetonitrile is preferred.
The reaction may be carried out at generally from 0 to 200°C, although it is préférable to add the reagent at 20 to 40°C, and carry out the reaction at 60 to 80°C.
Compounds of the above chemical formula (IX) can be obtained by reacting a cornpound of the formula R4e-C(=O)X, R4e-C(=O)OC(=O)R4e or R4eC(=O)OR’ (wherein X is a halogen atom, OTS or OMs; R’ is a Cm alkyl group; and R4e is as defined above) with a cornpound ofthe formula (IXa) below, either in the presence or absence of a base.
[Chem. 24] NH2 (|Xa) (In the formula, Y is as defined above.)
When the reaction is carried out in the presence of a base, the base may be, for example, an alkali métal hydride such as sodium hydride, a carbonate such as potassium carbonate or sodium carbonate, an alkali métal hydroxide such as potassium hydroxide or sodium hydroxide, a tertiary amine such as triethylamine, or a substituted or unsubstîtuted pyridine cornpound such as pyridine or 4-dimethylaminopyridine.
The reaction may be carried out in the absence of a solvent or using a solvent which does not affect the reaction. In cases where a solvent is used, solvents such as amides (e.g., dimethylforrnamide, dimethylacetamide), nitriles (e.g., acetonitrile), sulfoxides (e.g., dimethylsulfoxide), ethers (e.g,, diethyl ether, tetrahydrofuran), esters (e.g., ethyl acetate, butyl acetate), aromatic hydrocarbons (e.g., benzene, xylene, toluene), alcohols (e.g., methanol, éthanol, propanol), ketones (e.g., acetone, methyl ethyl ketone), aliphatic hydrocarbons (e.g., hexane, heptane, octane), halogenated hydrocarbons (e.g., dichloromethane, chloroform, chlorobenzene, dichlorobenzene), or water may be used singly or as combinations of two or more thereof. The use of dimethylformamide, acetonitrile, ethers, dichloromethane or chloroform is preferred.
The reaction may be carried out at generally from -80 to 100°C, although it is préférable to canry out the reaction in the range of 20 to 50°C.
The compound of above formula (IX) may also be obtaîned by reacting a compound of above formula (IXa) with a carboxylic acid of the formula R.fc-COOH (wherein R<-.e is the same as defined above) using a dehydration-condensation agent, either in the presence or absence of a base.
A carbodiimide compound such as dicyclohexylcarbodiimide or 1-ethyl-3-(3dimethylaminopropyl)carbodiimide hydrochloride may be used as the dehydration-condensation agent.
When the reaction is carried out in the presence of a base, the base may be, for example, a carbonate such as potassium carbonate or sodium carbonate, a tertiary amine such as triethylamine, or a substituted or unsubstituted pyridine compound such as pyridine or 4dimethylaminopyridine.
The reaction is preferably carried out using a solvent. For example, amides (e.g., dimethylformamide, dimethylacetamide), nitriles (e.g., acetonitrile), sulfoxides (e.g., dimethylsulfoxide), ethers (e.g., diethyl ether, tetrahydrofuran), esters (e.g., ethyl acetate, butyl acetate), aromatic hydrocarbons (e.g., benzene, xylene, toluene), ketones (e.g., acetone, methyl ethyl ketone), aliphatic hydrocarbons (e.g., hexane, heptane, octane), or halogenated hydrocarbons (e.g., dichloromethane, chloroform, chlorobenzene, dichlorobenzene) may be used singly or as combinations of two or more thereof. The use of dichloromethane or chloroform is preferred.
f
The reaction may be carried out at generally from -80 to 100°C, although it is préférable to carry out the reaction in the range of 20 to 50°C.
Compounds of above formula (le) can be obtained by reacting a compound of the formula R4e-C(=O)X, R/.e-C(=O)OC(=O)R4e or R4e-C(=O)OR’ (wherein X is a halogen atom, R' is a alkyl group, and R4e is as defined above) with a compound of the formula (IXb) below or a sait thereof, in the presence or absence of a base.
[Chem. 25]
Ar
NH (|Xb) (ln the formula, Ar, R4 and Y are as defined above.)
When the reaction is carried out in the presence of a base, the base may be, for example, an alkali métal hydride such as sodium hydride, a carbonate such as potassium carbonate or sodium carbonate, an alkali métal hydroxide such as potassium hydroxide or sodium hydroxide, a tertiary amine such as triethylamine, or a substituted or unsubstituted pyridine compound such as pyridine or 4-dimethylaminopyridine.
The reaction may be carried out în the absence of a solvent or using a solvent which does not affect the reaction, ln cases where a solvent is used, solvents such as amides (e.g., dimethylformamide, dimethylacetamide), nitriles (e.g., acetonitrile), sulfoxides (e.g., dimethylsulfoxide), ethers (e.g., diethyl ether, tetrahydrofuran), esters (e.g., ethyl acetate, butyl acetate), aromatic hydrocarbons (e.g., benzene, xylene, toluene), alcohols (e.g., methanol, éthanol, propanol), ketones (e.g., acetone, methyl ethyl ketone), aliphatic hydrocarbons (e.g., hexane, heptane, octane), halogenated hydrocarbons (e.g., dichloromethane, chloroform, chlorobenzene, dichlorobenzene), or water may be used singly or as combinations of two or more thereof. The use of dimethylformamide, acetonitrile, ethers, dichloromethane or chloroform is preferred.
The reaction may be carried out at generally from -80 to 100°C, although it is préférable to carry out the reaction in the range of 20 to 50°C.
i i
Compounds of above formula (le) may also be obtained by reacting a compound of the above formula (IXb) or a sait thereof with a carboxylic acid of the formula R4e-COOH (wherein R4e is as defined above) using a dehydration-condensation agent, either in the presence or absence of a base.
A carbodiimrde compound such as dicyclohexylcarbodiimide or 1-ethyl-3-(3dimethylaminopropyl)carbodiimide hydrochloride may be used as the dehydration-condensation agent.
When the reaction is carried out in the presence of a base, the base may be, for example, a carbonate such as potassium carbonate or sodium carbonate, a tertiary amine such as triethylamine, or a substituted or unsubstituted pyridine compound such as pyridine or 4dimethylaminopyridîne.
The reaction is preferably carried out using a solvent. For example, amides (e.g., dimethylformamide, dîmethylacetamide), nitriles (e.g., acetonitrile), sulfoxides (e.g., dimethylsulfoxide), ethers (e.g., diethyl ether, tetrahydrofuran), esters (e.g., ethyl acetate, butyl acetate), aromatic hydrocarbons (e.g., benzene, xylene, toluene), ketones (e.g., acetone, methyl ethyl ketone), aliphatic hydrocarbons (e.g., hexane, heptane, octane), or halogenated hydrocarbons (e.g., dichloromethane, chloroform, chlorobenzene, dichlorobenzene) may be used singly or as combinations of two or more thereof. The use of dichloromethane or chloroform is preferred.
The reaction may be carried out at generally from -80 to 100°C, although it is préférable to carry out the reaction in the range of 20 to 50°C.
Compounds of the above formula (IXb) can be obtained by reacting a compound of above formula (IXa) with a compound of the formula ArCHiR^X (wherein Ar, Rt and X are as defined above), in the presence or absence of a base.
When the reaction is carried out in the presence of a base, the base may be, for example, an alkali métal hydride such as sodium hydride, a carbonate such as potassium carbonate or sodium carbonate, an alkali métal hydroxide such as potassium hydroxide or sodium hydroxide, a i
ι tertiary amine such as triethylamine, or a substituted or unsubstituted pyridine compound such as pyridine or 4-dimethylaminopyridine.
The reaction may be carried out in the absence of a solvent or using a solvent which does not affect the reaction, in cases where a solvent is used, solvents such as amides (e.g., dimethylformamide, dimethylacetamide), nitrites (e.g., acetonitrile), sulfoxides (e.g., dimethylsulfoxide), ethers (e.g., diethyl ether, tetrahydrofuran), esters (e.g., ethyl acetate, butyl acetate), aromatic hydrocarbons (e.g., benzene, xylene, toluene), alcohols (e.g., methanol, éthanol, propanol), ketones (e.g., acetone, methyl ethyl ketone), aliphatic hydrocarbons (e.g., hexane, heptane, octane), halogenated hydrocarbons (e.g., dichloromethane, chloroform, chlorobenzene, dichlorobenzene), or water may be used singly or as combinations of two or more thereof. The use of dimethylformamide, acetonitrile, ethers, dichloromethane or chloroform is preferred.
The reaction may be carried out at generally from -80 to 100°C, although it is préférable to carry out the reaction in the range of 20 to 50°C.
In cases where (le) is synthesized via (IX) from a compound of chemical formula (IXa), or in cases where (le) is synthesized via (IXb) from a compound of chemical formula (IXa), the reactions may be carried out consecutively without removing the (IX) or (IXb), or the reactions from (IXa) to (le) may be allowed to proceed simuîtaneously within the same reaction vessel. [Examples]
Next, the invention is described more fully below by way of working examples, although the invention is not limited by the working examples.
Reference Example 1: 2-chloro-5-[N-(2-methvlthioethvl)]aminomethvlpyridine (Compound 23)
2-methylthioethylamine (3.0 g, 33 mmol) was dissolved in 25 mL of anhydrous dimethylformamide, following which 5.3 g (33 mmol) of 2-chloro-5-chloromethylpyridine, 1.6 g of 60% sodium hydride (net weight, 950 mg; 40 mmol) were added in this order, and stirring at 70DC was carried out for 90 minutes. The reaction mixture was cooled to 0°C and the reaction was brought to completion by adding about 30 mL of water a little at a time, after which the reaction mixture was extracted twice with about 50 mL of dichloromethane. The dichloromethane phase was dried over anhydrous magnésium sulfate, concentrated, and subsequently purifîed by silica gel column chromatography (hexane/ethyl acetate = 1:1 > ethyl acetate ->
dichloromethane/methanol = 1:19 -> dichloromethane/methanol = 1:10), giving 4.6 g ofthe target compound (yield, 64%).
Synthesis Example 1:_______2-chloro-5-fN-cvano-N-(2-methvlthioethyl)1aminomethvlDvndine (Compound 1)
Anhydrous diethyl ether, 4 mL, was added to 123 mg (1.16 mmol) of cyanogen bromide, and the mixture was cooled to 0°C. To this were added, in order, 250 mg (1.16 mmol) of 2-chloro5-[N-(2-methylthioethyl)]aminomethylpyridine (Reference Example 1) dissolved in 3 mL of anhydrous diethyl ether, and 95 mg (1.16 mmol) of sodium acetate, following which the system was stirred overnight at room température. Next, about 10 mL of a 1% aqueous solution of sodium hydroxide was added to the reaction mixture and the mixture was stirred for 1 hour, following which about 20 mL of diethyl ether was added and liquid-liquid extraction was carried out.
ί
The diethyl ether phase was washed with, in order, about 10 mL of water and about 10 mL of 1% hydrochloric acid, then dried over anhydrous magnésium sulfate and concentrated under reduced t
pressure, giving 209 mg of the target compound (yield, 75%).i > » Synthesis Example 2:_______2-chloro-5-iN-fonTivl-N-(2-methvlthÎoethvl)laminomethvlpvridine!
(Compound 29)
Ethyl formate (10 mL) was added to 132 mg (0.61 mmol) of 2-chloro-5-[N-(2methylthio)ethyl]aminomethylpyridine (Reference Example 1), and the system was refluxed for 3 i hours. Once the reaction mixture had returned to room température, the solvent was distilled offE t under reduced pressure, and purification was carried out with silica gel column chromatography (hexane/ethyl acetate = 7:3 —> 1:1 ), giving 159 mg of the target compound (yield, 81 %).j î
Synthesis Example 3: 2-chloro-5-fN-trifluoroacetvl-N-ethvl1aminomethylpyridine (Compound 21)[
ΙΑ solution of 140 mg (0.67 mmol) of trifluoroacetic anhydride dissolved in 5 mL ofI· anhydrous dichloromethane was added dropwise under ice cooling to a solution of 120 mg (0,70) mmol) of ethyl-(2-chloro-5-pyridylmethyl)amine synthesized by the method described in U.S.
Patent Application Publication No. 2009306041 and 101 mg (1 mmol) of triethylamine dissolved in 5 mL of anhydrous dichloromethane. Following dropwise addition, the system was stirred overnight at room température, then the reaction mixture was washed with, in order, ice-cooled 1% aqueous sodium hydroxide, water, 1% hydrochloric acid, then water, and subsequently dried over anhydrous magnésium sulfate. The solvent was distilled off under reduced pressure, giving 107 mg the target compound (yield, 78%).
Synthesis Example 4: 2-chloro-5-(N-cyano-N-2-isopropyl)aminomethvlpyridine (Compound 15)
Acetone (2 mL) and 1 mL of methanol were added to 50 mg (0.26 mmol) of 2-chloro-5aminoethylpyridine, 43 mg (0.52 mmol) of sodium acetate was added, and the mixture was stirred at room température for 4 hours. Next, 30 mg (0.78 mmol) of sodium borohydride was added, and the mixture was stirred at room température for 1 hour. The reaction mixture was filtered and then concentrated, after which ethyl acetate and water were added and liquid-liquid extraction was carried out. The organic phase was dried over anhydrous magnésium sulfate, then concentrated and subsequently purified on a préparative TLC plate, giving 17 mg of 2-chloro-5-[N-(2isopropylaminomethyl)]pyridine (yield, 36%).
Using 57 mg of the resulting 2-chloro-5-[N-(2-isopropylaminomethyl)]pyridine, 54 mg ofthe target compound (yield, 47%) was obtained by the method described in Synthesis Example 1. Synthesis Example 5: 2-chloro-5-fN-cvano-N-(2-propargvl)1aminomethvlpyridine (Compound 42)
2-chloro-5-aminoethylpyridine (1,50 g, 10.6 mmol) was dissolved in 10 mL of anhydrous dimethylformamide, then 486 mg (net weight, 292 mg; 12.7 mmol) of 60% sodium hydride and 1.25 g (10.6 mmol) of propargyl bromide were added in this order, and stirring was carried out at 70°C for 3.5 hours. The reaction mixture was returned to room température and the reaction was stopped by slowly adding water, after which the reaction mixture was extracted with ethyl acetate. The ethyl acetate phase was dried over anhydrous magnésium sulfate and subsequently concentrated, then purified by silica gel column chromatography (hexane/ethyl acetate = 1:1), giving 892 mg of 2-chloro-5-[N-(2-propargyl)]aminomethylpyridîne (yield, 47%).
Using 60 mg of the resulting 2-chloro-5-[N-(2-propargyl)]aminomethylpyridine, 20 mg of the target compound (yield, 30%) was obtained by the method described in Synthesis Example 1.
Synthesis Example 6: 2-chloro-5-[N-cvano-N-(6-chloro-3-Dvridylmethvl)1aminomethvlpyridine (Compound 17)
6-chloro-3-chloromethy(pyridine (648 mg, 4 mmol), 50% aqueous ammonium cyanide solution (100 mg), and potassium carbonate (590 mg, 5 mmol) were suspended in acetonitrile (20 mL), and the mixture was refluxed under heating for 40 hours. The condensate was filtered while hot, the filtrate was concentrated, and the residue was washed with ether and water. The viscous mixture was recrystallized from a small amount of methanol, giving 28 mg of the target compound. 1H-NMR (CDCIs, Ô, ppm): 4.17 (4H, s), 7.40 (2H, d), 7.68 (2H, dd), 8.31 (2H, d)
IR: 2207 (CN)
MS; m/z = 293 (M+H)
Synthesis Example 7: 4-chloro-[N-cvano-N-(4-chlorobenzyl)laminomethvlbenzene (Compound 55)
The target compound was obtained in an amount of 450 mg (yield, 15%) from 1.61 g of 4chlorobenzyl chloride by the same method as in Synthesis Example 6.
1H-NMR (CDCIs, δ, ppm): 4.10 (2H, s), 7.23 (2H, d), 7.36 (2H, d)
MS: m/z = 291 (M+H)
Synthesis Example 8: N-ri-(6-chloro-3-pvridvl)ethyll-N-cvanoethvlamino (Compound 18)
6-chîoro-3-acetylpyridine (1.03 g, 0.3 mmol) and a 30% ethylamine-methanol solution (1.0 mL) were mixed with 8 mL of chloroform, and the mixture was subjected to refluxing, After 8 hours, 1 mL of 30% ethylamine-methanol solution was added and stirring was continued for 12 hours at the same température. The chloroform was distilled off and the residue was dissolved in 10 mL of methanol, then ice-cooled. Sodium borohydride (1 g) was added a little at a time, and the system was stirred ovemight. The methanol was distilled off, and the residue was extracted with acetonitrile. The extract was then concentrated under reduced pressure. Acetonitrile extraction and concentration under reduced pressure were each repeated another two times, following which the residue was dissolved in chloroform, washed with 1% aqueous NaOH, and the chloroform phase was dried over solid KOH. The chloroform was distilled off under reduced pressure, giving 790 mg of crude N-[1 -(6-chloro-3-pyridyl)ethyl]-N-ethylamine product (purity, 80%).
Using 100 mg of the crude N-[1-(6-chloro-3-pyridyl)ethyl]-N-ethylamine thus obtained, 55 mg (yield, 60%) of the target product was obtained by the method described in Synthesîs Example
1.
1H-NMR (CDCI3, δ, ppm): 1,25 (3H, t), 1,66 (3H, d), 2,91 (2H, m), 4.14 (1H, q), 7.37 (1H, d), 7.73 (1H, dd), 8.30(1 H, d) IR: 2211 (CN), 2206 (CN)
Synthesîs Example 9: 2-ÎN-(6-chloro-3-oyridvlmethvl)cvanamidel ethyl methylcarbonotrithioate (Compound 6)
Potassium t-butylate (112 mg, 1 mmol) was added to a solution of (6-chloro-3pyridylmethyl)-2-imino-1,3-thiazolidine (228 mg, 1 mmol), synthesized by a method described in the literature (Journal of Médicinal Chemistry, 42(12), 2227 (1999)), in 15 mL of tetrahydrofuran, and the mixture was stirred for 30 minutes at room température, following which 228 mg (3 mmol) of carbon disulfide was added a little at a time and stirring was continued for 1 hour. Methyl iodide (142 mg, 1 mmol) was added dropwise and the system was stirred for 2 hours. The insoluble solid was removed by filtration through Celite, and the filtrate was concentrated under reduced pressure. The target compound was isolated as a yellow oil from the viscous residue by silica gel column chromatography using ethyl acetate/hexane (1:1 volumétrie ratio) as the developing solvent. The yield was 130 mg (41%).
1H-NMR (CDCIs, δ, ppm): 2.76 (3H, s), 3.31 (2H, t), 3.63 (2H, t), 4.28 (2H, s), 7.38 (1 H, d), 7.73 (1H, dd), 8.35 (1H, d)
IR: 2211 (CN)
Synthesîs Example 10: 2-chloro-54N-trifluorosulfonvl-N-(2-propvnvl)1aminomethvlpyridine (Compound 152)
An amount of 104 mg (0.58 mmol) of 2-chloro-5-[N'(2-propynyl)]aminomethylpyridine obtained by the method described in Synthesîs Example 5 was dissolved in 10 mL of anhydrous dichloromethane, 191 uL (1.16 mmol, 326 mg) of trifluorosulfonic anhydride was added, and the mixture was stirred at room température for 2 hours. After reaction completion, the reaction mixture was diluted by adding dichloromethane, then washed with, in order, a 1% aqueous sodium hydroxide solution and a 1% aqueous hydrochloric acid solution, and subsequently dried over anhydrous magnésium sulfate, concentrated under reduced pressure, and purified by silica gel column chromatography (hexane/ethyl acetate = 2:8), giving 55 mg of the target compound (yield, 30%).
Synthesis Example 11: 2-chloro-5-[N-cvano-N“(cvclopropylmethvl)laminomethvlpyridine (Compound 71)
The N-[(6-chloropyridin-3-yl)methyl]cyanamide (30 mg, 0.18 mL) synthesized by the method in a comparative example was dissolved in 3 mL of anhydrous dimethylformamide, 10 mg of 60% sodium hydride (net weight, 6 mg; 0.26 mmol) was added, and the mixture was stirred at room température for 20 minutes. Next, 52 pg (0.57 mmol) of (chloromethyl)cyclopropane and 5 mg of potassium iodide were added in this order, and the mixture was stirred at room température for 20 hours. Following reaction completion, the reaction was stopped by adding a small amount of water to the reaction mixture, and liquid-liquid extraction was carried out with 1% hydrochloric acid and ethyl acetate. The organic phase was washed with 1% hydrochloric acid, then dried over anhydrous magnésium sulfate, concentrated under reduced pressure, and purified on a préparative TLC plate (one 0.5 mm plate; developed with hexane/ethyl acetate =1:1, giving 18 mg of the target compound (yield, 45%).
Synthesis Example 12: 2-FN-(6-Chloro-3-pvridylmethvl)cvanamide)ethvl O-ethylcarbonodithioate (Compound 86)
1,2-bis(tosyloxy)ethane (8.86 g; 24.0 mmol) was dissolved in 100 mL of anhydrous dimethylformamide, following which 2.00 g (12.0 mmol) of N-[(6-chloropyridin-3yl)methyl]cyanamide synthesized by the method in a comparative example, 500 mg of 60% NaH (net weight, 300 mg; 13.2 mmol) and 44 mg of Kl were added in this order under ice cooling, and the system was stirred at room température for 80 minutes. Following reaction completion, methanol was added a little at a time at 0°C, then the reaction was stopped by adding water. Next, ethyl acetate and 1% hydrochloric acid were added to the system and liquid-liquid extraction was carried out. The organic phase was washed with 1% hydrochloric acid, dried over anhydrous magnésium sulfate and concentrated under reduced pressure, then purified by silica gel column chromatography (hexane/ethyl acetate = 2:8 -> 6:4). When the fractions containing the target compound were collected and concentrated, dimethylformamide remained in the concentrate. Hence, a small amount of ethyl acetate was added and the concentrate was washed twice with 1% hydrochloric acid, then dried over anhydrous magnésium sulfate and concentrated under reduced pressure to remove the dimethylformamide, giving 1.43 g of 2-[N-(6-chloro-3pyridylmethyl)cyanamide]ethyl 4-methylbenzenesulfonate (Compound 84). The yield was 33%.
Anhydrous acetonitrile (3 mL) was added to 45 mg (0.28 mmol) of potassium ethyl xanthate, a solution of 50 mg (0.14 mmol) of 2-[N-(6-chloro-3-pyridylmethyl)cyanamide]ethyl 4methylbenzenesulfonate synthesized by the above-described method dissolved in 2 mL of acetonitrile was added thereto, and the mixture was stirred at 50°C for 50 minutes. Following reaction completion, the reaction mixture was concentrated under reduced pressure, ethyl acetate and 1% hydrochloric acid were added, and liquid-liquid extraction were carried out. The organic phase was dried over anhydrous magnésium sulfate, then concentrated under reduced pressure, purified on a préparative TLC plate (one 0.5 mm plate, liquid-liquid extraction with hexane/ethyl acetate = 2:3), giving 23 mg of the target compound (yield, 18%).
Synthesis_______Example_______13:______________2-[N-(6-chloro-3-pyridvlmethyl)cvanamide1ethyl benzylfethypcarbamodithioate (Compound 85)
Benzyl ethyl amine (55 mg, 0.41 mmol) was dissolved in 5 mL of anhydrous tetrahydrofuran, 46 mg (0.41 mmol) of potassium t-butylate was added, and the mixture was stirred at room température for 20 minutes. Next, 49 qg (62 mg, 0.41 mmol) of carbon disulfide, 50 mg (0.14 mmol) of 2-[N-(6-chloro-3-pyridylmethyl)cyanamide]ethyl 4-methylbenzenesulfonate (Compound 84) synthesized by the method of Synthesis Example 12 dissolved in 3 mL of anhydrous tetrahydrofuran, and 5 mg of potassium iodide were added in this order, and the system was stirred at 40°C for 1 hour. Following reaction completion, a small amount of water was added to stop the reaction, the reaction mixture was filtered using Celite, and the filtrate was concentrated. The concentrate was purified by silica gel column chromatography (hexane/ethyl acetate = 7:3), giving 41 mg of the target compound (yield, 72%).
Tables 6 to 9 below présent spectral data on the compounds obtained in Synthesis
Examples 1 to 13 and on other compounds obtained by similar methods.
In the tables, the synthesis methods are referred to as follows.
A: Methods similar to those used in Synthesis Examples 1 to 5 and 10
B: Methods similar to those used in Synthesis Examples 6 and 7
C: Methods similar to that used in Synthesis Example 8
D: Methods similar to that used in Synthesis Example 9
E: Methods similar to that used in Synthesis Example 11
F: Methods similar to those used in Synthesis Examples 12 and 13
Table 6
Compound Ho. | Syntjinais Method | (CDCI3, 5, ppm) | IR (KBr, v, en’1) ex MS |
1 | A | Z,40 (3M, a}, 7-59 (2H, s), 3,35 (54, a), 4.2? (24, a), 7,.46 {IH, d}, 7.75 C1H, dd), 6.36 <1H, d} | 2211 (CN) |
2 | A | 1,33 (3M, t) , 2-60 (2Hr q), 2.5? [24, t) , 3.34 (2H, t). 4.27 (24, a}, 7.41 (IM, d) , 7.74 |1K, dd}, 3.37 (IH, d) | 2211 (CN) |
3 | A | 0.9» (SM. t), 1-69 (2K, »1t 2.65 (?M, b). î.«6 (2H, t), 3.34 (2H, t}. 4.27 (SH, a), 7.40 |1K, d), 7.74 (1H, dd), 5.36 <1H, d) | 2211 (CN) |
4 | A | 0,97 (3H, t}, 1-69 (2Hr »), 2.02 (24, tj r 4.19 (2Hr s), 7.32 (IH, d). 7.71 (14, dd}, 6,33 (14, 4} | 2209 (CN) |
5 | A | 1.96 |2H, a}, 2.11 t3Hr b)r î.$6 (24, t), 3-11 (24, t), 4.ZI (?H, a), 7.39 (14, d), 7,71 |14, dd), B.35 (14, d) | 2210 (CN) |
C | £ | 2.76 |3H, a), 3.51 (24, t|, 3.6? (24, t}, 4.ZB (24, a), 7.36 (1H. d), 7.73 (IH, dd}, a.35 |1M, d} | 2211 (CN) , njx 31& (M+H) |
7 | £ | 2.36 |3H, t}, 3.30 (SH, t|, 3,36 (24, q}. 3-61 (24, tj, 4.2? (24. a), 7.39 <1H, d), 7.73 (14, dd}, 0.36 (14, dj | m/ï - 332 (M(-K) |
9 | £ | 3.02 134, t), 1.73 (24, )f 3.30 (24, t), 3.34 (24, t), 3.61 (2H, t), 4.27 124, a). 7.30 (14, a), 7.73 (1H, dd), 5.36 (IM, d} | hl/= = 346 (M+H) |
9 | E | 3.37 (SM, t), 2.33 (24, t), 3.36 (2K, q}, 4 42 (24, a), 7.SI (LH. a) | 2213 (CN) , m/z =* 336 (M+HJ |
10 | £ | 1.03 (3M, t}, 1-75 (24, ql3 3.32 (2H, t), 3.36 (24, t), 3.«2 (SH, t), 442 (24, a), 7.SI |1M, fl) | 2214 (CN). m/z - 352 (M+H) |
11 | A | 3.19 (34, t}, 3.35 (3H, a), 3.61 (2H, t), 4.30 (24, a), 7.35 (IH, d). 7.72 (14. dd), B.35 (IH, d) | 2212 (CR) |
12 | A | 0 93 (3H, t), 1.3» (2H, a), 1.63 (2H, π), 2-96 (SM, t) , «.19 (24, «1, 7.39 (14, dj, 7.71 (1H, dd), 5,33 (IH, d) | 2210 (CN) |
13 | A | 2.B3 (34. s), 4.17 [SK, o), 7,41 (1H, d), 7.71 (IX. dû}, 9.34 (14, d) | 2208 (CN) |
14 | A | 1.30 (34, Î), 3.03 [2K, q}, 4.20 (24, a), 7-3» (IH. d), 7.71 (IH, dd], 9.34 (iHr d) | 2210 (CN) |
18 | A | 1,29 (6Mr d) r 3.15 (14, iflpt), 4-20 (2H, a), 7.39 (IX, d) , 7.70 (lfi, dd) , B.34 (14, d) | 2210 (CN) |
1É | A | 2.?3 (6M, a), 2.54 |2H, t}, 3,06 (24, t), 4 2« (24, a), 7.3? <14, d) , 7.73 (IH, dd), 5.34 (IH, d) | 2211 (CN) |
17 | B | 1.66 (1K, v), 1.52 |2H, a}, 2.20 (14, »), 3.03 (IH, }, 3.17 (IH, n), 4.13 (IH, t) , 7.22 (14, ·), 7.68 (14, d), 0.45 (14, d), 5.5? (14, a) | 2207 (CN) |
16 | C | 1.24 <3H, t), 1.63 (3H, d), 2.91 (24, 4), 4.13 (14, q), 7.36 (14, d), 7.72 (IH, dd}, 6.30 (IM, d) | 2206 (CN) |
19 | A | 1.20 <3H, t), 3,03 (24, q), 4.32 (24, a), 7.4? (1H, a) | 2213 (CN) |
20 | A | 1.12, 1.17 (34, t), 212, 2.17 (34, a), 3,29, 3.41 (24, q), 4.53, 4.55 (24, a). 7.24, 7.35 (IH, d), 7.41, 7.63 (24, dd}, B.27 (14, d) | 1635 (ÇaO) |
21 | A | 1.13, 1.26 (3H, t), 33«, 3.44 (2M, q}, 4.60, 4.61 (2H, *), 7.31, 7.35 (14, d), 7.54, 7,61 (Ut. dû), 029. 9.30 (IH, d} | 1691 (C=O) |
22 | À | 1.10 (3M, ], 3-25 (24, a), 3.74 (3X, }. 4 44 (24, a), 7.29 (LH, a), 7.58 (14. a). 5,25 (Ut, } | 1702 (Ç»Q) |
24 | À | 2.12, 2.13 (3H, a), 214, 2 21 (34, a), 2.62, 2.67 (24, t(, 3 46, 3.54 (24, t), 4.«O, 4.63 (24, a), 7.30, 7.36 (14, d), 7.61, 7-63 tlM, <M| , 9.27 (14, d) | m/z = 259 (M+H) |
25 | À | 2 12, 2.13 (3M, a}, 272 (34, t), 3.57, 3.50 (3M, t), 4.59, 4-69 (24, a), 7.07-7.43 (64, a), 7.63 (Ut, dû), 0.37 (LH, d) | m/z 337 (M+H) |
26 | À | 1.98 (34, a), 2.44 (SH, t}, 3-29 (24, t), 4.37 [2H, i}, 7.33 (LH, d), 7,56 (?H, dd)► 7.63 (IH, td), 7.74 (IM, dû], 7.84 |ÎH, dd), 6-23 <1H, d) | m/z - 357 (M+H) |
27 | A | 2.1Ç (3H, a), 2.63 (SM, n), 3.43 (24, El) , 3.76 [3Hr }, 4.52 (SH, a), 7.30 (14, b) . 7.60 (IH, a). 8 30 (IH, ) | m/z = 275 (M+H) |
26 | À | 2.07 (34, a), 2.55 (SH, t), 3.01 (34, a», 3.35 (2K, t), 4.42 (SH, ·), 7.36 (IM, d), 7.60 (IH, dd)f 534 (14, d} | m/z = 295 (M+H) |
29 | A | 2.6», 2,10 (3H, a). 2.57, 2.61 (24, t), 3.3?, 3.42 (SH, t), 452, 4.50 (2H, b), 7.32, 7,37 (IH, ÛJ, 7 56, 7.64 (14, dd}, B.31, 8.32 (14. d) | m/z - 245 (M+H) |
30 | A | 1.00 (3H, »} . S.«0 (24, s), 3.50 (S»f a), *7« (2H. n), 7-32 (14, d), 7.42 (SH. a}, 7.53, 7-69 (14, dd), 8.16 (IM, d) | ül/z - 321 (M+H) |
31 | A | 2.11, 2.13 (3H, n), 2.«7 (24, t), 3.50, 3.59 (24, t), 4.67, 4.74 <24, s), 7.34, 7.3B (IM, d), 7.50, 7.62 (14, dd), 6.30, B.32 (14, d) | m/z = 313 (M+H) |
33 | A | 1.33 (6H, t), 2-0« (34, a), 2.S6 (SM, t), 3.09 (2H, a), 4.06 (4H, a), 4.26 (2K, a), 7,32 (IM, d}, 1-72 (IH, dd), 6,33 (Ut, d) | m/z = 353 (M+H) |
34 | A | 2.13 (3H, a), 2-90 (24, t), 3.14 (SK, t}, 4-19 (24. a), 7.44 (IH, d), 8.17 (1K, dd), 5.47 (IM, d) | m/z = 361 (M+H) |
35 | A | 1.26 |3H, t), 2.9B (24, q), 4.14 (2K, a), 7-35 («H, t>) | m/z 161 (M+H) |
36 | A | 1.29 |3H, t), 3-02 (24, qk, 4.22 (2H, a}, 7.36 (IM, dd), 7.73(1h, dd), 8.56 (LH, d), 8.«2 (14, dd) | m/z - 162 (M+H) |
37 | A | 1.27 |SH, t), 3.ÛD (2H, q) . 4.1« (2H, a), 7.27 (24. d) , 7.35 (2H, d) | m/z 195 (M+H) |
3» | A | 1.12 (3H, t«2), 2.11, 2.1B (34, a), 3.28, 3.43 (2H, t), 4-51, 4.5» (2K, a), 7.S» (SH, > | |
40 | A | 1.07 (3H, rn), 3.25 (24, a), 3.74 (3H, b), <.<7 (2K, a), 7.2B (SH, ) | |
41 | A | 1.25 OH, 8), 2.9» (24, q), 4.20 (2H, *), 7.11 (1K, }, 7.SS (IH, a), 7.36 (14, al | jn/z » 167 (M+H) |
42 | A | 2.56 (IM, t)r 3.61 (2H, d), 4.30 (2H, a), 7.40 (IH, d), 7.73 (2H, dd), 0-39 (14, d} | m/z = 206 (M+H) |
43 | A | 3.62 (2H, dd) , 4.18 (24, a), 5.37(2H, dd«2>, 5.65 (IH, tdd), 7.39 (LH, d), 7.71 |1H, dd), B.33 (14, d) | m/z 208 (M+H) |
44 | A | 4.10 (24, a), 4.17 (2H, e), 7.33 (8M, a), 7.65 (IH, dd), 5.23 (IH, d) | m/z « 258 (M+H) |
45 | A | 1.32 (34, t} , 3-03 (2H, q) , 4.Z3 (24, a), 7-53 (IM. ta) , 7. «4 (3H, B) | m/z « 186 (M+H) |
46 | A | 1.33 (3M, t), 3.06 (2H, q), 4.31 (SH, a), 7.75 (14, Φ, 7.93 (LH, dd). O.«8 (IH, d) | m/z - 230 (M+H) |
47 | A | 2.14 (3H, a), 2-7B (24, b), 3.25 (2H, t). 4-36 (2M, al, 7.76 (14, d), 7.97 (IH, dd), 8.72 (IH, d) | m/z “ 276 (M+H) |
Table 7
Compound No. | Synthesis Mathod | ‘a-WMR (CDC1,, 8, ppn> | IR (KBrr v, ora’1) or MS |
46 | A | 1.2É (3K, t] r i, se (2H. b}, 2,61 {7Hr q). 3,24 (3K, tJ. 4.3$ (2H, »), 7.75 (LH, ûj ,· 7.44 (IH, d), 8,73 (IH, 41 | m/z - 2&C (M+H) |
49 | A | £,7S ¢234. t) r 3.OS (2H, t}, 3,73 [2Hr *). 4.20 (2H, a), 6.1B (1H, d), 6.31 (IH, dd] , 7.sa |LH. d], 7.3E (1H, d), 7,7j (lHr dd), 0,31 UH, d) | m/z = 30S (M+B) |
50 | A | Ζ65 t]r 2.99 UH, t), 3.72 [2Hr c), 4.11 UK, *1, 7.30 (6H, w), 7.64 (IH, 4d] , 6.26 11«, d> | m/z = 316 (M+H) |
51 | A | 3.44 <2*4, ni. 3.46 UH, n) r 4.23 (2H, »). 7.37 (IH, d] t 7.61 i2H, a), 7.10 UH, h) r 7.91 [2HP a) J B.SS (IH, dj | m/z = 335 (M+H) |
52 | A | 3.12 |2H, td), 3.17 (2H, td)r 1.16 (2H, ), 7.31 «6«, *1 j 7.63 (1K, dd), S.25 (1K, b] | ra/i - 304 (M+H) |
53 | A | 3.43 42«. t), 4.1» (2Hr t), 4.3S UH, «), 6-68 UH, d], 7.Q2 {1HP a), 7.31 UH, a). 7.72 (lHr dd), 8,3« (LH, d> | iel/î « 2S3 (M+H) |
54 | A | 2.01 |3H, ) r 3.17 UH, t), 3-50 UH, q), 4.24 (2H, ] , 3.92 [IX, «x·», 7.39 (LH d), 7.69 (LH, dd) , 8.36 (IH, d) | m/z - 253 (M+H) |
55 | B | 4.09 (4H, }, 7,23 (4H, d), 7.3« (4M, d) | πι/ζ » 231 (M+H) |
57 | E | 2.96 (2H. t)r 3.20 (2HP t). 4.07 (2K, e], 7-17 (2H. B), 7-29 (4«r b), 7.42 (IH, dd}, 8.10 (IH, d) | iït/z - 272 (M+H) |
58 | E | 3.43 (2H. t), 4.98 (2K, «|. 4.53 (2«. t), 7.33 (IH. d}, 7.47 [IH, ), 7.60 ilH, b). 7.71 |1H. dd), 6-Q3 (2«. b), 8.3» {IX, d) | m/z =>3X6 (M+H) |
59 | E | 3.90 (SH, }, 4.3« |2Hr 7-45 (LH, d) r 7.14 (IH, dd} P 9.42 (1KP d] | m/z * 207 (M+H) |
61 | E | 2.11 (3H, t)r 3.28 (2R, t|, 4.27 (4H, a) r 7.40 (IH, d), 7.71 UH, dd) , 8-3« (!Hr d) | m/z = 254 (M+H) |
62 | E | 2.25 (3HP *}, 4.17 |2K, *]. 4.33 (2H. ), 7.39 (IH, d), 7-72 (LH, dd] r 8.37 {IX, d) | m/z - 229 (M+H) |
68 | E | 2.21 (lHr dd), 2.58 |1H, dd), 3.08 (2K, b), 3.32 (IH, dd), 431 (2K. Ad), 7.39 (1K. d), 7.72 «1«. dd), B.36 (1«, d) | |
69 | E | 2.60 (IX, dd), 9.88 |2H, b). 3-21 (IH, b)r 3.49 {IH, dd), 4.31 (ZH, }, 7.38 {1H, d). 7.74 (IH, dd), B.39 (IH, d) | |
70 | E | 2.70 UH, t), 3-30 (2H, t), 3.73 (3H, *), 4.25 {2M, «j. 7.3B (LH, d), 7.72 UK, dd), 8,35 (IM, d) | |
71 | E | 0-27 (JH, a), 0/66 UH, B), 1.06 (1H, B), 9.88 (2H, d). 4-36 (2H. >), 7.40 (LH, d) r 7.75 (IH, dd), 8.34 [1H, d) | m/z « 222 (M+K) |
72 | A | 2.14 (SH, *), 2.77 UH, t). 3.23 (2«r t). 4.38 (2H. >), 7.B7 (IH d). 8.28 (IH, d) | m/z = 276 (M+H) |
73 | C | 1.69 (3H, d), 2.90 (3H. «}, 2.77 {2HP a), 3.08 |2K. b), 4-23 (lHr q). 7-38 (IH. d), 7,7« (IH, dd}, 8.33 (IX, d) | m/z k 256 (M+H) |
74 | A | 2.15 (3K, ), 2.76 UH, t), 3.23 {2H, t), 4.24 UH. ), 7.51 (IX, «) | m/z <* 248 (M+H) |
75 | A | 1-27 |3H. t) r 2.58 {2H, q), 2.78 (2Hr t), 3-21 (2H, t) r 4.42 UH, *), 7.51 (IH, ·) | m/z » 262 (M+H) |
76 | A | 2,22 UH, b), 2.92 (6H, n), 3.63 UH, s), 4-26 UH, '] . 7.39 (IH, d), 7.73 ilH, dd}, B. 36 (1H, d)r | m/z = 254 (M+H) |
77 | A | 1.36 (3h, d}r 2.11 (3H, d), Z.£2 |1H, dd), 2.79 (IH, dd) , 3.15 (IH, q). 4-29 UK, d), 4.32 (IH, d), 7.38 {IX, d), ?-7« |1K, dd), 8,37 (IH, d) | m/z = 266 (M+H) |
76 | A | 2-11 (3H, 2.75 [?X, t), 3.21 UH, t) r 4.27 (2H, »), 7.00 (LH, dd), 7.89 {IX, td), 8.1» (IH, d) | m/z = 226 (M+H) |
79 | A | 2.14 UH, ), 2-78 [2XP t), 3.23 (2H, t) r 4.30 UH, ·), 7.59 (1«, dd], 8.21 {IH, e) | m/z - 260 (M+H) |
60 | A | 1.30 (3H, t), 3.01 |2K, q), 4.21 UH, a), 7.54 <1K, d), S.19 (1H, b) | m/z = 214 (M+H) |
61 | À | 3.«0, 3-68j 3.?0 UH, dt>2), 4.60, 4.6» (2Hr tx2) , 4.77P 4.78 (2«, i«2) P 7,33, 7-39 (LH, dx2). 7.55, 7.63 [IH, ddx2), 8,30, 8-33 UH, dxZ) | m/z - 295 (M+H) |
62 | A | 3.30 [2X. dt) , 4,31 UH, «h 4-31-4-73 (2MP a), 7.39 (1H, d), 7.73 (1K, dd) , 8-36 (IH, d) | m/z * 214 (M+H) |
83 | E | 4.18 UHr 4.32 UH, ] , 7.40 [IH, d), 7,48 U*. >) 76» (IX. dd). 0.33 (1H, d) | m/z - 299 (M+H) |
84 | E | 9.4? (3H. s) r 3.31 (2H, t), 4.21 <£Hr t), 4.23 UK, x). 7.37 {3X. n), 7.69 (1H, dd) r 7.79 (ZM, d) r 8.30 (IH, d) | m/z - 366 (M+H) |
65 | F | 1.22 (3«, tï2), 3.36 (2H, tM2), 3.60 (Z*. tï2!. 3.71 (2«, q), 4-02 (2H, q). 4-28, 4-32 {2X, *x2j, 4.94, 5.31 (2H, *xZ). 7.32 {6K, a), 7.?4 (1H, b), B·38 (IH, B] | m/z =*= 405 (M+H) |
56 | F | 1.42 (3H, t) r 3.33 (2H, t), 3.88 UXP t), 4.2B (2H, ) , 4. «3 U*. 4). 7.38 {IX, d), 7.72 tJH. dd), 8.37 (IH, d) | m/z = 316 (M+H) |
86 | F | 3.25, 3.47 {3M, 8*2), 3.36 UH, t*2) , 3-80 (2H, txZ). 4.29. 4.32 (2H, «x2), 4.»8, B.33 UH, *x2), 7.19-7.37 (6H, a), 7.73 UH, ·) . B.41 (IH, a) | m/z » 391 (M+H) |
Θ9 | C | 1.74 UK, a), 3,19 {IH, a), 3.37-3,62 (1H, a}, 4,31-4-66 (2H, a), 5.33 (IH, b], 7.37 UH, dx2)z 7.57, 7.70 [IX, ddx2), 0,35, 8.38 (IH, dxZ) | m/z >299 (M+H) |
90 | F | 1,3» (CM, d), 3.30-3.40 (4H, n) r $73 (IHj a), 7.30 U», d), 7.13 (IH, dd). 8.37 (IH. d] | m/z > 330 (M+H) |
91 | F | 0.92 (3H, t), 1.37 (4KP b), 1.7» (2H, M), 3.31 (2R, t), 3.3a (2H, t), 4,29 UK, *1. 4 57 (2H, t), 7.38 (IH, d), 7.73 (IH, dd), 6.37 (1H, d) | m/z » 350 (M+H) |
92 | C | 1.70 (3X, d), 3.22 42H, a), 4.29 (IH, q}, 4.64 UH, a), 7.39 (IH, d), 7.7« (LK, 8.33 (IXr d) | m/z > 226 (M+R) |
93 | F | 1.00 u«, t), 1-38 |2H, M) , 3.31 (2H, t), 3.38 UK, t). 4.2» (2H, s), 4.53 (2H, t] r 7.38 UH. d), 7.73 UH, dd), 8,37 (LK, d) | m/z - 330 (M+H) |
94 | F | 0,9« (3Mr t), 1.41 (2H, n) r 1.80 (2H, a), 3.31 (ZKr t), 3,36 (2H, t), 4.2$ (2H, *], 4.58 (2H, t), 7.38 UH, H), 7.73 (1H, dd), 8.3« (IH, d] | m/z > 344 (M+H) |
95 | A | 3.68, 3.76 (2H, tdxZ), 4.78, 4-B8 UH, 4*2), 5.85-6.15 UH, b), 7.32. 75« (1K, <x2] | m/z = 309 (M+H) |
96 | C | 1.73 (3H, d), 3.16, 3.49 (ZMr ΔΧ2), 5.27, 5.37 (1K, qx2), 7.33, 7.40 (IX, dx2), 7.56, 7.70 UH, d»2), 8,3« Eix, d) | m/z 317 (M+H) |
97 | À | 3-60, 3.71 (2H, tdxZ), 4.79 UHr ·), 5.B5-6.18 {IX, B), 7.36r 7.40 (lHr dx2). 7.53, 7.60 UH, ddx2k, 6.30, 8.36 {IH, dx2) | m/z ° 303 (M+H) |
Table8
Compound No. | SyDthaaj-A Method | lB-NMR δ. ppm) | IR (KBr, v, cm'1) or MS |
95 | F | 35»r 3,67 |2Xr tdx2), 4,76, 4-93 <2H, ax2)r 8,66-6,17 (LHr b), 7,37, 7.41 (1H, 4x3), 7.53, 7.62 (LH, dx2], B.31, 8.32 (LH, *x2) | m/i = 319 (M4-H) |
99 | A | 3.5» (2Hj B]j 5,11 (2Hr B), 6.10 UN, ), 7.37 [1H, d), 7.60 {1H, d) , 3.32 (LRr ) | m/p -> 351 (M+H) |
100 | F | 2.03 fin, a), 2.47 (3k, «L 3.0» (2Hr t) r 4.12 (2H, t), 4.16 (ÎK, a], 7.38 (38. b) , 1.70 (1H, dd), 7.78 ilH, d), 6-33 (1H, d) | a/z ~ 3B0 (M+H) |
101 | F | 1.43 (3Kr t). 2.10 l?H =)r 3.10 i2Kr t) r 3.2Q (2H. t). 4SI (2H, », 6.66 (2R, q), 7,39 (IR, d), 7.71 (1H, dd), 8,34 (IM, d) | ox/z · 330 (M+H) |
102 | F | 1.00 (2K, t) , 1,83 (2X, q} , 2.11 (2K, q} , 3, Q9 [2H, t) f 3.19 (2H, t) , 4.21 (?KP », 4.55 (M, t) , 7.3B (IN. d), 7.71 |LNr dd), 8.34 (1H, d) | = 344 (M-i-R) |
103 | F | 1.25 |3H, B), 2.12 UH, B), 3.06, 3.12 (2M, tx2) , 3.36, 3.40 (2R, t*?)j 3-71, 4.03 (ZH, qX2) , 4,19, 4.23 (ZH, axZ), 4,94, 5,33 (ZH. b*2) , 7-33 (7H, b), 7,72 (1H, b), 6.33 (IR, a} | m/e 419 (M+-H) |
104 | A | 3.59 (ZH, b), 4,6? |2H, a), 5,77-6.07 flHr n), 7,41 (IX, d), 7.72 (1K, dd), 9.37 (1K, d) | |
105 | C | 1,01, 1.17 (3H, tKZ), 1,72 [3H, dx2} P 3,02-3.54 (2K, b), 5.28, 3.38 (1H, qui), 734, 7.36 (IX, dx 2), 7.57, 7.66 [1H, Odx2), 6.37 (1K, ») | m/z = 281 (M+H) |
107 | C | 1.02 (3H, 1), 1.72 [3H, d), 3.28 [2H, B), 5.25 [1H. q), 7.37 (1H. d), 7.77 (LM. d). 6.44 flKr d) | m/z = 317 (M+H) |
105 | c | 1.70, 1.75 (JH, d»2}r 3.16-3.56 (2M, n), 5.30 ILH, q) , 5.«1-5,96 (1H. m), 7.38. 7.41 (XH, dx2), 7.73 (JH, dd>r 8.43, 8-44 (JH, d*2) | m/z > 353 (M+H) |
109 | c | 1.01 (3K, a), 2.03, 2.Z4 [ZH, BXZ), 3.32, 3.72 [ZH, *xZ), 5.03 (1K, q), 5.60-6.20 (1K, B), 7.37, 7.41 (IM, dx?), 7.60. 7.76 (1H. ddx2}, B.39 (1W, d] | m/z - 331 (M+H) |
119 | c | 0.97 (3Hr t), 2.04-2.32 (2H. », 3.30-3.60 (JK, m) , 5.72-«.00 (1H, » , 7.41 (IR, », 7.72 (IM. m), 8.44 (1H, » | wi/z ° 367 (M+H) |
111 | c | 1.02 (3H, B), 2.00-2.30 (2K, rt} , 2.14-3.26 (2M, B), 4.04-5.12 (LH, B), 7.26-7.34 (LH, a), 7.607.76 (1H, B) , 8.38 [1H, B) | m/s a 295 (M+H) |
lia | c | 0.96, 1.05 (3H, t), 2.06, 2.24 (2Kr ax2) r 3.32 [2H, B). 4.00 (LH, q) , 7.3B (IX, d}r 7.75 (1H, B). B.45 (lHj «) | m/z 331 (M+H) |
114 | c | 1.03 (3X, t), 1.79 (3Mr d). 320-3.45 (2K, m), 5-3? (1H. q}, 7.73 (1H, d), 7.98 (1H, d), 6,82 flH, «) | m/= = 351 (M+H) |
115 | c | 1.03, 1,33 (3H. tx2), 1.78 (IX, d«2). 3.09-3.60 (ZH, a), 5,34 (IM, q), 7.«9- 7.73 (1H, d*?), 7.80. 7,86 (IX, d*», 6,70, 9.71 (1H, dx?) | n/p a 315 (M+H) |
119 | E | 3.63 (ZH, d), 4.33 |2H, «k, 5,39 (ZH, }, 5,63 [1H, ), 7.47 (1H, ) | m/z « 214 (M+H) |
120 | E | 2.85 (1H, t), 3.93 (2H, d). 4,46 [ZH, », 7,55 (1H, c) | m/z a 212 (M+H) |
121 | E | 2.96 (3H, », 4.31 RK, », 7.50 (1H, e) | m/z ~ 188 (M+H) |
122 | E | 096 (3H, », J.89 (2H, H), 2.35 (2H, t), 4-33 (2H, », 7.48 (1H, 6) | m/z = 216 (M+H) |
124 | C | 0.95 (3H, nk . 1.73 (3H, d) , 3.47 (2H, ) , 5.22 (1H, », 7.25 {2H, ». 7.71 (LH, td) , 8.5B (IHj d) | n/z - 283 (M+H9 |
128 | A | 2.50 (1H, t) . 4,23 (2H, », 4.71 [2H, B), 7.61 ilH, d) , 7,75 [1H, dd) , 8.41 (1H, d) | m/z ¢= 313 (M+H) |
129 | A | 3 06 (2H, », 4.85 RH, ». 7.44 (1H, d), 7.74 (1H, dd). 5-44 (1H. d) | m/z - 314 (M+H) |
130 | A | 1.23 (3k, t«2), 3.49 (2H. qxS}, 4-86 (2K, qx2), 7.56 |1H, 4x2), 8.56 (1H, sxZ) , 9.74 (JH, dx2| | m/z =± 3Q1 (M+H) |
131 | A | 1.20 (3H, t) , 3.42 (2H, », 4.61 [£H, ) , 7.7< (1H, d) , 7,SS [1H, dd) , 8.70 (1H, d) | m/z = 337 (M+H) |
132 | C | 1.04, L.1É, 1.31 (3H, tx3), 1.70 [3H, dxZ), 2,00-3,56 (ZK, B), 5.25, 5,40 (1H, qxZ), 7.22, 7,34 (SH, dx?), 8.60, B.«5 (ZK, dxi) | m/z « 247 ÎN+K) |
133 | C | o.»7, l.io OH, tx2), 1.73 (3Hr d}, 3,07-3,52 (2H, », 5,32, 5-52 (1H, qxZ) , 7.34 (1H, a), 7.63, 7.70 (IN, dxZ} , 8,56, 8,60 (1H, dx2) | m/z - 247 (M+H) |
134 | c | 0.92, 1.08 (3H, txzir 1.71 (3H, d), 3.16-3-58 RM, b), 5-28, 5.5? (1K, qx£), 7.20-7.36 (2H. ], 7.6» (1H, Bk, 9.87, 0.62 ilHr dx2k | m/z = 247 (M+H) |
135 | A | 2.04 (3H, », 4.89 (2H, b), 7.39 (1H, d), 7,71 (1H, dd)r 6.34 RH, dk | m/z = 28» ÎM+H) |
136 | E | 2.47 UH, », 3.33 RH, ». 4.22 (ZH, t), 4.39 (2H, ». 7,36 (2H, 4), 7,46 (LHr » r 7,81 (2H, d) | n/z = 372 (M+H} |
137 | F | 1,43 (SU, t) , 3.37 (4H, », 4.43 (2H, », 4.67 (2H, q) , 7.51 [1H, a) | b/z 322 (M+B) |
138 | F | 126 (3H, t)r 3.40 (2H, tK2), 3.60 (2H, tx2), 3-74, 4.0« (2Hr qx2), 4.43, 4.48 (2H, 8X2}, 4.83, 8.30 (2H, ·>2), 7,20-7.40 f$Hr a), 7,53r 7-5« (1H, «x?} | m/z - 411.0286 (M+H) |
139 | A | 2.70 (3H, a), 2.»7 |1H, n), 3.10 (1H, b), 9.81 (2Hr ) r 4.31 (ZH, dd|, 7,40 (1H, dk, 7.76 (lHr dd), 8.40 (1H, d) | m/z - 258 (M+H} |
140 | A | 1.83 (6H, d), 4.24 |lHr n), 4-54 |2H, n), 7.35 IlH, dk. 7.B1 (1H, dd), 8.37 (1H, d) | m/z = 317 (M+H} |
141 | A | 0.83 (3H, t) , 1.22 (2Hr K). 1.55 (2ΚΓ »r 3.2B (2K, H), 4. «1 (2H, B), 7.4D (IR, d) , 7.74 (LK, dd), 8-34 (1H. » | n/z = 331 (M+H) |
142 | A | 3.25 (2M, b), 3.70 (2X, b). 4.60 (2Xr ), 7.24 (2H, n), 7.24-7.63 [7H, Bk, 6.32 (1H, d) | n/2 - 443 (M+H} |
143 | A | 3.70 (2H. », 4.11 (2H, w) r 4.74 (2H, m), 6.81 (2H, al r 7,24 (1H, d|, 7.34 (3Kr », 775 (LHr d) r B.41 (IX, »1 | m/z = 395 (M+H} |
144 | A | 1.16 (3H, t)r 3.3» (2M, a), 4,74 (2Hr a), 7,3» (1H, d), 7.75 (IX, dd|. B.35 (3Hr d) | n/z = 303 (M+H) |
145 | A | 0.94 (3Hr t) r 1,53 (2Hr », 3-25 (2Hr t), 4.55 (2X, ), 7.37 (1K, d}, 7.7« (LH, dd), B.32 (LK, » | m/z 317 (M+H) |
146 | A | 3.9» |2H, »r 4.72 (2M, », 5.22 (lMr dd) . 5.3« (lHr dd) , 5.71 (1H, B), 7.39 (1H, d) , 7.72 (LH, dd), 8.29 [1H, d) | n/z a 315 (M+H) |
147 | A | 6.44 (4H, a) r 7.18 (ZK, »> r 7,25 (1H, d), 7,33 (ZHr », 7.53 (1K, dd), B.Q3 (lKr d) | m/z - 365 (M+H) |
148 | A | 1.30 (3K, t), 3.08 (2H, q}, 4.21 (2Hr a), 7,00 (1H, dd), 7.86 |1H, td), 8.16 (IX, d) | n/z = 180 (M+H) |
149 | A | 1.2» (3K, t), 3.02 (2R, q)r 4-18 (2K, a) r 7-53 (IR, d), 7.«1 (IR, dd), B.32 (lRr d) | m/z 240 (M+H) |
Table 9
C«flfH3Vnd No, | Ayptheaia Mthod | jCDClj, 5j ppm) | IR (XBr, v, ùtt1) or kdâ |
150 | A | 2.15 [SM, 4), 3.36 [Z8, tj , 1-60 («H, Λ) r 7-36 (1K, dk t 7. 7« (1K. 44) , 0-3« (18. d] | st/x a 146 {M+H) |
151 | A | 1.04 (38, t}, 3.37 {28, q] . (.92 iîHr 4*, TJl (IK, □) r 1. BP (IH, dd) , W-17 (18, d) | ra/i ? 901 (M+H) |
152 | A | 7-07 [18. t), Z-43 [33. }. 3.4X ÎÎH, t), , t M [ÎH. } . 7.4Û (18, d) . 7.7β UH. dd) , 6.9« (IR, d) | ra/χ. - 327 (M+H) |
153 | A | 1.37 (33. t). 3-P« [Î8. q). (.21 [38, >], 7.23 (1K, dd] . 7.91 {IM, d), B.42 (18, d} | n/K = 196 (M+R) |
154 | À | 1.3D [JA. t), 3.14 [28. q) , 4.3} [2Ή, 4), 7,3P (1ΗΓ 4), 7.39 (IH, 4), 7,73 (IH, dd] | a/£ a 196 (M+H) |
155 | A | 3.29 (-354, 4), 3.45 [4M. H). 4. SB (2H, ) , 7 3« (1K, «R, 7,74 (1K, 44), 9.37 (18. d] | w/x p= 323 (M+H) |
157 | A | 1.17, 1.91 (9HP t*2|r 3.49, 3.43 UH, q«2), 7.92 (18, d), 7-60 {LH, d) | n/x - 2$B (M+H) |
158 | A | L.3D (38, t), y.Vl [38, qj . 4.13 Um, a), 7.23 {28, ) , 7.95 (IR, >1 | Λ/χ - 229 (M+H) |
159 | A | 2.59 (Î8, a), 3.61 (28. t] . 4.52 (2H, a), 7.43 {IH, d), 7.76 (1K, dd). 0.41 (1Η, 4> | o/e ’ 323 (M+H) |
160 | A | 3.79 (38, 4), 3-»4 [38. ] , 4-71 [ÎH. B], 7.9» [JH, d) , 7.72 (ÏH, dd) , ·,29 (K dj | m/x - »7 (M+H) |
161 | A | 4.03 UH, ), 4-74 (38. P). 7.44 (18, d]. 7.73 {IN, dd). B.31 (18, d) | bl/e - 333 (M+H) |
163 | A | 4.2« (2H. a}. 4.92 (28, }, 7.43 C1H. i] | a/x «< 320 ΓΜ+Η) |
165 | A | 4.02 (29, a), 4.64 |2N, a) , 7.79 (18, d], 0.PB [18, ddl. 9-79 (IM, 4} | m/z a 343 (M+H) |
167 | A | 4.20 (28, *}, 4·S4 (2M, ), 7.3» (18, dd), 9,27 (IN, d) | m/z - 332 (M+H) |
170 | C | l.SO UH. 4). 3.63 UH. d), «27 (IM. d], S.42 (IM. q). 7.43 [IM, d), 7.76 (IH, dd) , 9,47 UK, d) | m/β . 328 (M+H) |
171 | C | 1.0« [28, d), 2.29 (1H. t}. 9.73 (IH, d), 4.17 (18, 4), 5,34 (4M, D , 7-37 UK, d), 1.7fi (18, d), 9.47 {IH, d) | m/z a 327 (M+H) |
172 | A | 2.51 {IH, t), 4.25 UH, M) , 4 . B1 UH, }, 7-5« (18, a) | m/z - 319 (N+R) |
176 | A | 2.63 {9H, t), 3.40 |BH. *), 4 03 (2H, a), ? 94 (28. d). 7.36 {18. d) | hl/z a 335 (M) |
177 | A | l.XJ (9R, t) , 3 9« UK, a) I 4.57 UK, »}, 7.3B (5K, } | |
170 | A | 3.16 OH, ), 3.91 (2H, a), 9. B1 UK, a}, 4.43 (28. f), 7.39 {18. Φ, 7,70 UK. dd) . 0-33 (18, d] | n/z » 317 (M+H) |
179 | A | 2.51 (IH, t), 3.97 (4M, a), 4 57 UK, a), 7.37 UH, d|, 7.79 {1N, dd) , 6.37 (IA, d) | m/z - 327 (M+H) |
Ιθ» | A | 2.24 [3H, t), 3.3» UH, a), 4-SP (2K, a*, 7.2« (2k. a), 7.34 |3K, a) | m/x a 301 (M) |
lai | A | 1,13 (3H, t) , 3.9« (2R, a), 4.C0 UH, ak , 7.30 (2K, 41, 1.36 UH, 4) | m/z = 301 (H) |
162 | A | 1,15 UH, t) , 3.99 UH, a), 4.56 UK, a), 7.54 UK, a), 7.67 [3K, ! | m/z - 292 (H) |
163 | A | 1.14 [2H, t) . 3.42 (3N. a), 4.56 UH, a), 7 · 54 (0H, d) , 9.27 (2H, d) | ft/ï - 312 (M) |
184 | A | 2.50 [IN, t) , 4.00 (38. H). 1.68 UH, a) , 7-27 (2K, a), 7.39 (IH, a) | m/z - 34S (M) |
185 | A | 1.21 [3H, tj, 2,3« {38. t). 3.04 {JH, a), 4.49 {2H, a), 7,20 [2H, d), 7,24 (28. d) | m/z “ 281 (M) |
106 | A | 1.14 [38. t), 3-3» [2H, a). 4.«2 [IM, a), 7.46 {2H, 4), 7.6» [3H, d) | a/< - 292 [MJ |
187 | A | 1.11 (38. t), 3.34 [28, a), 3.62 (38, 4), 4.40 <28, n), «.02 UH, d), 7.2B (28. d) | «/Z - 297 (M) |
188 | A | 1.12 (38, C), 3.36 (2M, ], «-«L (28, o]. 7.97 [3M, a], 7.23 [2H, u] | ca/x a 205 (M) |
189 | A | 3 16 UH, t). 3-40 |ÎH. b}. 4.50 (28, a), 7.43 (38, d] , 7.66 (18, d) | |
190 | A | 1.12 (3K. t), 3.36 (78, a), 4.56 (Î8, }, 7.34 (28, d). 7.92 (2H. d) | eo/z - 345 (H) |
181 | A | 1.12 {SH. t j , 2.32 (CM, 3), 3 36 UH, Bl·., 4.51 (28. a}. «.94 [28, a). 6.97 |1K, a) | h/e « 295 (Mf |
192 | A | 1.17 {3H. + ) . 3-47 (?«, ' ,ÉJ UH, a), 7 62 (18, a), 7.75 (18. d), 020 (IH, a), 9.02 (1«, d) | m/z - 312 (H) |
198 | A | 1,17 (3H. t). 1*3 (2h. a). 4.63 12k, a), 7.37 (IH, d), 7.52 (IH. 44), 1.7« (IH, d) | m/z = 423 (M) |
194 | A | 1.92 UK, t), 3.65 UH, a), 4.60 UK, ») , 1.07 (IH, ». 9.14 (1H, a), 9.39 (lk, a) | n/z a 3»0 (M) |
195 | A | 1.19 {3H, t) , 5.93 UH. a) . 4.66 UH, dk , 7.91 (2H, ) , 7. B9 (lk, ) | m/x a 403 (M> |
196 | E | 3.33 (2H, t), 3,63 UH. t), 3.7« (38. a), 4.19 (2K, », 4.27 (28, 4], 7.3« (IH, d], 7.73 |1K, dd), 0 35 (18. d) | L74Q (C-O), 2212 (CM) |
198 | E | 3-33 (28, t), 3.<9 [38. ), 3.62 [2H, 0}, 4.20 UK, «) 5.4« UH, », 7.09 UH, d), 172 (1K, dd}, B.3« (LK, d) | 22J.2 (£N) |
199 | E | 2.22 (JH, ). 3.» UH, t) , 3.«3 (BH, t). 4-27 UH, a), 4-4« [38. s), 7.39 (IR, d) . 7.73 (1K, Md), B. 3« UK, <0 | 2212 (CN) |
200 | E | 2.44 |3H, 9k, 3.31 (2M, t), 3,62 (2H, t), 4.2« (ÎA, }, 4.BS UH, 4], 7.30 (28, d), 7-39 (18, 4), 7.10 (lk, ddk , 7.90 (2H, d) , 6.34 UK, 4) | 1604 (OQ), 2211 (CM) |
201 | A | 1.22 (38, tk, 1-63 (18, »1, 2-13 (1H, a), 2.69 {18, a), 2.2« {2H, }, 3-04 (BH, P). 3-57 [18, dk - 3.79 (lk, qj. 3.67 (28, B) | 2209 (GM) |
202 | A | 1.64 (18, ), 2-15 [4M, a) , 2.7B (2K, tk , 3,04 (3H, ), 3-2« UH, tk , 3 «9 (18, ddk, 17& [IM, qj , 3.04 UK, *) | 2207 (CN) |
203 | A | 1.12 (38. a). 9.25 (28, a), 4.36 (38, ], 7.32 (38, d], 7.15 (1H. a], B.37 (18. aj | 1632, 1459, 1380 |
204 | A | 1.16, 1.24 (98. tU), 3.31, 3.45 UH, qx2), VM. «.«« (28, **21, 6.16 |2H, bd), 7.31, 7.J( (J.H. d*2k , 1-SS, 7.61 (IH, <JdK2k. < îû ÜK, d) | |
20S | A | 1.14 (3K, t). 3·B3 (2k, q), 4.4B (2K, «}, 5 00 (2Ha brik, 7 Ή UK, d), 7-62 {1H. dd), 6,27 (IM, ) | |
206 | A | 3.13 (3H. t). 2-63 [38, a), 3.30 [3H, q), 4 44 (1K, U**). 4.4» {2H, «), 7.27 {18, dk, 7.64 (LH. 44), 627 (18, 4) | |
207 | A | 3.14 {9k, t), 2.B4 (6H, a), 3.14 (BH, a), 42» (2H, ». 7.2S (1H. d), 7.63 (IH, dk, * 30 (LK, 4) | |
208 | A | 1,19 {9k, t), 2.95 (2H, qk. 5-06 (3K, 7). 7,30 (JH, 4). ? 73 (IH. ddk, S.27 {18, d) | m/z a 216 (M;B) |
211 | C | 1,70 {3r, d.) , 2 B1 (9R, a* , 6.33 UK, q) , 7 36 (IK, 4). 7.71 (lk. dd) . B.4L [18, d] | 1463, 1330, 1237 |
Synthesis Example 14:_______N-[1-((6-chloropvridin-3-vl)methvl'}Dvridin-2('1H)-vlidenel-2.2.2trifluoroacetamide (Compound 212) (1) 2-aminopyridine in an amount of 25 g (270 mmol) was dissolved in 200 mL of anhydrous dichloromethane, 41 mL (30 g, 300 mmol) of triethylamine was added, and the mixture was cooled to 0°C, Next, 38 mL (57 g, 270 mmol) of trifluoroacetic anhydride was added dropwise over 15 minutes, and the mixture was stirred at room température for 2 hours. Following reaction completion, the reaction mixture was poured into about 100 mL of ice water and stirred for 10 minutes. The mixture was then transferred to a separatory funnel and liquid-liquid extraction was carried out. The organic phase was washed twice with 150 mL of water, washed twice with 150 mL of a 1% aqueous HCl solution, then dried over anhydrous magnésium sulfate and concentrated under reduced pressure, giving 36 g of 2,2,2-trrfluoro-N-(pyridin-2(1 H)ylidene)acetamide (yield, 71%).
1H-NMR (CDCI3, δ, ppm): 7.20 (1H, ddd), 7.83 (1H, td), 8.20 (1H, d), 8.35 (1H, d), 10.07 (1H, brs) 13C-NMR (CDCI3i δ, ppm): 115.3, 115.5 (q), 121.6, 139.1, 147.9, 149.5, 155.3 (q)
MS: m/z = 191 (M+H) (2) 2-chloro-5-chloromethyl pyridine in an amount of 20 g (126 mmol) was dissolved in 200 mL of anhydrous acetonitrile, then 24 g (126 mmol) of 2,2,2-trifluoro-N-(pyridin-2(1H)-ylidene)acetamide obtained by the above method and 21 g (151 mmol) of potassium carbonate were added and refluxing under heating was carried out for 6 hours, followed by 10 hours of stirring at room température. Following reaction completion, the reaction mixture was filtered, and the fïltrate was concentrated under reduced pressure. Diethyl ether was added to the concentrate to effect crystallization, and the resulting crystals were collected by filtration, then thoroughly washed with diethyl ether and water. The crystals thus obtained were dried at 60°C and reduced pressure for 1 hour, giving 26 g of the target compound (yield, 66%).
1H-NMR (CDCI3, δ, ppm): 5.57 (2H, s), 6.92 (1H, td), 7.31 (1 H, d), 7.80 (1H, td), 7.87 (1H, dd), 7.99(1 H, dd), 8.48 (2H, m) 13C-NMR (CDCI3, δ, ppm): 53.8, 115.5, 117.2 (q), 122.1, 124.7, 130.0, 139.2, 140.0, 142.5, 149.7,
151.8, 158.9, 163.5 (q)
I J
MS: m/z = 316 (M+H) (3) Powder X-Ray Diffraction Analysis of Crystals
In powder x-ray diffraction analysis, measurement was carried out under the following conditions.
Apparatus: RINT-2200 (Rigaku Corporation)
X-rays: Cu-Ka (40 kV, 20 mA)
Scanning range: 4 to 40°
Sampling width: 0.02°
Scanning rate: 1°/min
The results are given below (FIG. 1).
Diffraction angles (2Θ): 8.7°, 14.2°, 17.5°, 18.3°, 19.8°, 22.4°, 30.9°, 35.3° (4) Differential Scanning Calorimetry (DSC)
In differential scanning calorimetry, measurement was carried out under the following conditions.
Apparatus: DSC-60
Sample cell: aluminum
Température range: 50 to 250°C (température rise rate, 10°C/min)
The results are shown in FIG. 2.
(5) In addition, similar crystals were obtained by using the methods described in (i) to (iv) below (second to fifth préparation methods) to carry out recrystallization. The resulting crystals were subjected to powder x-ray diffraction analysis and differential scanning calorimetry under the same measurement conditions as indicated above.
(i) Second Préparation Method
About 25 mL of hexane and about 25 mL of ethyl acetate were added to Compound 212 (700 mg) and the mixture was heated to 65°C on a hot water bath, effecting complété dissolution. The solution was siowly returned to room température and left to stand overnight. The crystals that precipitated out were collected by filtration and washed with a small amount of a 95:5 solution of hexane and ethyl acetate, The washed crystals were placed in a desiccator and dried for 2 hours under reduced pressure, giving 349 mg of white crystals.
The results of powder x-ray diffraction analysis were as follows (FIG, 3).
Diffraction angle (2Θ): 3,5°, 14.0°, 17.3°, 18,1°, 19,6°, 22,2°, 30.8°, 35,2°
The results of differential scanning analysis are shown in FIG 4.
(ii) Third Préparation Method
An amount of 28 mL of 2-propanol was added to Compound 212 (1.0 g) and the mixture was heated to 65°C on a hot water bath, effecting complété dissolution. The solution was slowly retumed to room température and left to stand overnight, The crystals that precipitated out were collected by filtration and washed with a small amount of 2-propanol. The washed crystals were then placed in a desiccator and dried for 2 hours under reduced pressure, giving 695 mg of white crystals.
The results of differential scanning analysis are shown in FIG. 5.
(iii) Fourth Préparation Method
About 30 mL of toluene was added to Compound 212 (700 mg) and the mixture was heated to 65°C on a hot water bath, effecting complété dissolution. The solution was slowly returned to room température and left to stand overnight, The crystals that precipitated out were collected by filtration and washed with a small amount of toluene. The washed crystals were then placed in a desiccator and dried for 2 hours under reduced pressure, giving 440 mg of white crystals,
The results of powder x-ray diffraction analysis were as follows (FIG 6).
Diffraction angle (2Θ): 8.6°, 14.2°, 17.5°, 18,3°, 19.7°, 22.3°, 30.9°, 35.3°
The results of differential scanning analysis are shown in FIG. 7.
(iv) Fifth Préparation Method
About 2 mL of méthanol and about 2 mL of water were added to Compound 212 (50 mg) and the mixture was heated to 65°C on a hot water bath, effecting dissolution. The solution was retumed to room température and left to stand overnight. The crystals that precipitated out were collected by filtration, giving 16 mg of white crystals,
f ]
i
I The results of differential scanning analysis are shown in FIG. 8.
Synthesis Example 14, Alternative Method for Step (1)
2-amÎnopyridine in an amount of 1.0 g (10.6 mmol) was dissolved in 10 mL of ethyl acetate, following which 1.78 mL (1.2 eq) of triethylamîne was added, then 1.62 mL (1.1 eq) of 5 trifluoroacetic anhydride was added under ice cooling. Stirring was subsequently carried out for 2 hours at room température, then 10 mL of ethyl acetate and 10 mL of water were added, after which the mixture was again stirred and liquid-liquid extraction was carried out. The ethyl acetate phase was washed twice with 10 mL of water, then dried over anhydrous magnésium sulfate and concentrated under reduced pressure, giving 1.56 g of 2,2,2“trifluoro-N-(pyridin-2(1 H)10 ylidene)acetamide (yield, 77.2%).
Synthesis Example 14, Alternative Method 2 for Step (1)
2-aminopyridine in an amount of 0.94 g (10 mmol) was dissolved in 20 mL of tetrahydrofuran (THF), following which 2.84 g (20 mmol) of ethyl trifluoroacetate and 1,22 g (10 mmol) of dimethylaminopyridine were added, and refluxing was carried out for 22 hours. THF was 15 removed by distillation, following which purification was carried out with a silica gel column (developing solvent: 4:1 solution of hexane and ethyl acetate), giving 0.26 g of 2,2,2-trifluoro-N(pyridin-2(1H)-ylidene)acetamide (yield, 13.7%).
Synthesis Example 14, Alternative Method
2-chloro-5-chloromethylpyridine in an amount of 3.00 g (18.6 mmol) was dissolved in 20 20 mL of anhydrous dimethylformamide (DMF), 1.75 g (18.6 mmol) of 2-aminopyridine was added, and the mixture was stirred out at 80°C for 8 hours and at room température for 5 hours. Following reaction completion, DMF was distilled off under reduced pressure and acetonitrile was added, whereupon a solid separated out. The solid was collected by filtration, thoroughly washed with acetonitrile, then dried, giving 2.07 g of 1-[(6-chloropyridin-3-yl)methyl]pyridin-2(1H)-imine 25 hydrochloride (yield, 44%).
1H-NMR (DMSO-de, δ, ppm): 5.65 (2H, s), 6.96 (1H, t), 7.23 (1H, m), 7.57 (1H, d), 7.80 (1H, m), 7.91 (1H,m), 8.28 (1H, m), 8.49 (1H, d), 9.13 (2H, brs)
.......
An amount of 50 mg (0,20 mmol) of 1-[(6-ch1oropyridin-3-yl)methyl]pyndin-2(1 H)-imine hydrochloride obtained by the above method was dissolved in 5 mL of anhydrous dichloromethane, 122 mg (1.00 mmol) of DMAP and 50 mg (0.24 mmol) of trifluoroacetic anhydride were added in this order under ice cooling, and the mixture was stirred for 1 hour at room température. Following reaction completion, the reaction mixture was diluted with dichloromethane, washed with 1% hydrochloric acid, then dried over anhydrous magnésium sulfate. Dichloromethane was removed by distillation under reduced pressure, giving the target cornpound in an amount of 42 mg (yield, 67%). The NMR spectrum agreed with that of the product obtained by the method described above.
Synthesis Example 15: 2l2-dibromo-N-ri-((6-chloropyridin-3-vl)methvl)pyridin-2(1H)-vlidene1acetamide (Cornpound 241)
An amount of 200 mg (0.78 mmol) of 1-[(6-chloropyridin-3-yl)methyl]pyridin-2(1H)-imine hydrochloride obtained in the method described under “Synthesis Example 14, Alternative Method,” 238 mg (1.95 mmol) of DMAP and 224 mg (1.17 mmol) of EDC-HCI were dissolved in 10 mL of anhydrous dichloromethane, following which 101 pL (202 mg, 1.17 mmol) of dibromoacetic acid was added and the mixture was stirred overnight at room température. Following reaction completion, the reaction mixture was diluted with dichloromethane, washed once with water and twice with 1% aqueous HCl, then dried over anhydrous magnésium sulfate and concentrated under reduced pressure, giving the target cornpound in an amount of 50 mg (yield, 15%).
1H-NMR (CDCI3, δ, ppm): 5.56 (2H, s), 5.99 (1H, s), 6.78 (1H, td), 7.33 (1H, d), 7.69 (1 H. td), 7.76 (1 H, dd), 7.93 (1 H, dd), 8.39 (1 H, d), 8.50 (1 H, d) 13C-NMR (CDCI3i δ, ppm): 44.6, 53.1, 113.7, 121.9, 124.8, 130.1, 138.2, 139.7, 141.2, 149.5, 152.0, 159.4, 172.2
Synthesis Example 16: N-[1-((6-chloro-5-fluoropvridin-3-yl)methyl)pyridin-2(1 H)-ylidenel-2,2.2trifluoroacetamide (Cornpound 227)
2-chloro-3-fluoro-5-methylpyridine in an amount of 4.00 g (27.6 mmol) was dissolved in 80 mL of carbon tetrachloride, following which 7.37 g (41.4 mmol) of N-bromosuccinimide and 20 mg of benzoyl peroxide were added and the mixture was refluxed overnight under heating. Following reaction completion, the reaction mixture was retumed to room température, concentrated under reduced pressure, and purified by silica gel column chromatography (hexane/ethyl acetate = 19:1), giving 3.06 g of 5-(bromomethyl)-2-chloro-3-fluoropyridine (yield, 51 %).
1H-NMR (CDCI3, δ, ppm): 4.45 (2H, s), 7.54 (1H, dd), 8.23 (1H, s)
An amount of 50 mg (0.22 mmol) of 5-(bromomethyl)-2-chloro-3-fluoropyridine obtained by the above method was dissolved in 5 mL of anhydrous acetonitrile, following which 42 mg (0.22 mmol) of 2,2,2-trifluoro-N-(pyridin-2(1H)-ylidene)acetamide obtained by the method in “Synthesis Example 14, Step (1)” and 36 mg (0.26 mmol) of potassium carbonate were added in this order and refluxing under heating was carried out for 7 hours. Following reaction completion, the reaction mixture was retumed to room température, the insoluble matter was filtered off, and the filtrate was concentrated under reduced pressure. Diethyl ether was added to the resulting concentrate, whereupon a solid separated out. The solid was collected by filtration and washed with diethyl ether, then dried under reduced pressure in a desiccator, giving the target compound in an amount of 29 mg (yield, 40%).
1H-NMR (CDCIs, δ, ppm): 5.54 (2H, s), 6.89 (1H, td), 7,76 (1H, dd), 7.80 (1 H, td), 7.85 (1H, d), 8.29(1 H, d), 8.57(1 H, d) MS: m/z = 334 (M+H)
Synthesis Example 17:________N-[1-((6-fluoropvridin-3-yl)methvl)pvridin-2(1H)-ylidene)-2,2,2trifluoroacetamide (Compound 229)
2-fluoro-5-methylpyridine in an amount of 500 mg (4.50 mmol) was dissolved in 50 mL of carbon tetrachloride, following which 1.20 g (6.76 mmol) of N-bromosuccinimide and 20 mg of benzoyl peroxide were added and refluxing under heating was carried out for 2.5 hours. Following reaction completion, the reaction mixture was retumed to room température, the solvent was removed by distillation under reduced pressure, and purification was carried out by silica gel column chromatography (hexane/ethyl acetate = 19:1), giving 300 mg of 5-bromomethyl-2fluoropyridine (yield, 35%).
An amount of 57 mg (0.30 mmol) of 5-bromomethyl-2-fluoropyridine obtaîned from the above method was dissolved in 10 mL of anhydrous acetonitrile, following which 57 mg (0.30 mmol) of 2,2,2-trîfluoro-N-(pyridin-2(1H)-ylidene)acetamide synthesized by the method in Synthesis Example 14, Step (1)” and 69 mg (0.50 mmol) of potassium carbonate were added in this order and the mixture was refiuxed under heating for 6 hours. Following reaction completion, the reaction mixture was returned to room température, the insoluble matter was filtered off, and the filtrate was concentrated under reduced pressure. Purification was carried out by silica gel column chromatography (hexane/ethyl acetate = 1:1 -> 3:1), giving 21 mg ofthe target compound (yield, 23%).
1H-NMR (CDCI3, δ, ppm): 5.56 (2H, s), 6.89 (1H, td), 6.94 (1H, d), 7.79 (1H, td), 7.87 (1H, d), 8.03 (1H, m), 8.31 (1H, s), 8.54 (1H, d)
MS: m/z = 300 (M+H)
Synthesis Example 18:_______N-[1-((6-bromoDvridin-3-vl)methyl)pyridin-2(1H)-ylidenel-2.2,2trifluoroacetamide (Compound 231 )
An amount of 500 mg (2.92 mmol) of 2-bromo-5-methylpyridine was dissolved in 15 mL of carbon tetrachloride, following which 623 mg (3.50 mmol) of N-bromosuccinimide and 10 mg of benzoyl peroxide were added and the mixture was refiuxed under heating for 19 hours. Following reaction completion, the reaction mixture was returned to room température and concentrated under reduced pressure, then purified by silica gel column chromatography (hexane/ethyl acetate = 19:1), giving 143 mg of 2-bromo-5-bromomethylpyridine (yield, 20%).
1H-NMR (CDCIa, δ, ppm): 4.42 (2H, s), 7.47 (1H, d), 7.59 (1H, dd), 8.38 (1H, d)
An amount of 70 mg (0.28 mmol) of 2'bromo-5-bromomethylpyridine obtaîned by the above method was dissolved in 10 mL of anhydrous acetonitrile, following which 54 mg (0.28 mmol) of 2,2,2-trifluoro-N-(pyridin-2(1H)-yÎidene)acetamide synthesized by the method described în “Synthesis Example 14, Step (1) and 46 mg (0.34 mmol) of potassium carbonate were added in this order and refluxing was carried out under heating for 6 hours. Following completion of the reaction, the reaction mixture was returned to room température, the insoluble matter was removed by filtration, and the filtrate was concentrated under reduced pressure. Diethyl ether was
ί then added thereto, whereupon a solid separated out. The solid was collected by filtration, washed with diethyl ether, then dried under reduced pressure in a desiccator, giving the target compound in an amount of 81 mg (yield, 82%).
1H-NMR (CDCI3, δ, ppm): 5.52 (2H, s), 6.88 (1H, t), 7.48 (1H, d), 7.78 (2H, m), 7.84 (1H, d), 8.44 5 (1H, d), 8.53 (1H, d)
MS: m/z = 360 (M+H)
Synthesis Example 19:__________2-chloro-N-M -((6-chloropvridin-3-vl)methvl)pyridin-2( 1H)vlidenelacetamide (Compound 236)
An amount of 70 mg (0.27 mmol) of 1-[(6-chloropyridin-3-yl)methyl]pyridin-2(1H)-imine hydrochloride obtained by the method described in “Synthesis Example 14, Alternative Method” was dissolved in 4 mL of anhydrous dichloromethane, following which 82 mg (0.67 mmol) of
DMAP, 25 mg (0.27 mmol) of chloroacetic acid and 62 mg (0,32 mmol) of EDC-HCI were added in this order, and the mixture was stirred overnight at room température. Following reaction completion, the reaction mixture was diluted by adding dichloromethane, washed with water and
1% aqueous HCl, and dried over anhydrous magnésium sulfate, then concentrated under reduced pressure, giving the target compound in an amount of 4 mg (yield, 5%).
1H-NMR (CDCI3, δ, ppm): 4.17 (2H, s), 5.46 (2H, s), 6.64 (1H, td), 7.31 (1 H, d), 7.60 (1 H. td), 7.64 (1 H, dd), 7.80 (1 H, dd), 8.32 (1 H, d), 8.45 (1 H, d)
MS: m/z = 296 (M+H)
Synthesis Example 20:_______N-[ 1 -( 1 -(6-chloropyridin-3-vl)ethvl)py ridin-2( 1 H)-yl idenel-2,2,2trifluoroacetamide (Compound 237)
An amount of 44 mg (0.23 mmol) of 2,2,2-trifluoro-N-(pyridin-2(1H)-ylidene)acetamide obtained by the method in “Synthesis Example 14, Step (1)” was dissolved in 8 mL of anhydrous acetonitrile, following which 72 mg (0.23 mmol) of 1-(6-chloropyridin-3-yl)ethyl 425 methylbenzenesulfonate synthesized by the method described in Biosci. Biotechnol. Biochem.,
67(5), 980-988 (2003) and 38 mg of potassium carbonate were added, and refluxing under heating was carried out for 100 minutes. Following reaction completion, the reaction mixture was retumed to room température, the insoluble matter was removed by filtration, and the filtrate was
I »
concentrated under reduced pressure, The concentrate was purified by silica gel column chromatography (hexane/ethyl acetate = 3:1), giving the target compound in an amount of 24 mg (yield, 32%).
1H-NMR (CDCI3, δ, ppm): 1.89 (3H, d), 6.89 (1H, td), 7.08 (1H, q), 7.32 (1H, d), 7.66 (1H, dd),
7.76 (2H, m), 8.44 (1 H, d), 8.50 (1 H, d) 13C-NMR (CDCIa, δ, ppm): 19.2, 55.1, 115.1, 117.4 (q), 122.0, 124.8, 133.7, 135.2, 138.4, 141.4,
148.6,151.9, 159.1, 163,9 (q)
MS: m/z = 330 (M+H)
Synthesis Example 21 :
N-[ 1 -((6-chloropvrid in-3-vl)methvl) pyridi n-2( 1 H)-ylidenel-2,2difluoroacetamide (Compound 238)
2-aminopyridine in an amount of 400 mg (4.26 mmol) was dissolved in 10 mL of anhydrous dichloromethane, following which 322 pL (490 mg, 5.11 mmol) of difluoroacetic acid, 982 mg (5.10 mmol) of EDC-HCI and 622 mg (5.11 mmol) of DMAP were added, and the mixture was stirred at room température for 61 hours. Following solution completion, the reaction mixture was diluted with dichloromethane, washed once with water and twice with 1% aqueous HCl, then dried over anhydrous magnésium sulfate, and concentrated under reduced pressure, giving 102 mg of 2,2-difluoro-N-(pyridin-2(1H)-ylidene)acetamide (yield, 14%).
H-NMR (CDCI31 δ, ppm): 6.03 (1H, t), 7.15 (1H, m), 7.78 (1H, td), 8.20 (1H, d), 8.34 (1H, dd),
8.72(1 H, brs)
An amount of 100 mg (0.58 mmol) of 2,2-difluoro-N-(pyridin-2(1H)-ylidene)acetamide obtained by the above method was dissolved in 10 mL of anhydrous acetonitrile, then 94 mg (0.58 mmol) of 2-chloro-5-chloromethylpyridine dissolved in 5 mL of anhydrous acetonitrile was added, following which 84 mg (0.63 mmol) of potassium carbonate was added, and refluxing under heating was carried out for 140 minutes. Following reaction completion, the reaction mixture was retumed to room température, the insoluble matter was removed by filtration, and the filtrate was concentrated under reduced pressure. Ether was added to the concentrate, whereupon a solid separated out, The solid was collected by filtration and thoroughly dried, giving 63 mg of the target compound (yield, 37%).
1H-NMR (CDCI3, δ, ppm): 5,52 (2H, s), 5.90 (1 H, t), 6.79 (1H, td), 7.33 (1 H, d), 7.71 (1H, m), 7.77 (1 H, dd), 7.85 (1H, dd), 8.45 (1H, d), 8.50 (1H, d) 13C-NMR (DMSO-ds, δ, ppm): 53,0, 111.0 (t), 115.2, 120.7, 124.7, 131.7, 140.6, 141.6, 143.2, 150.4, 150.9, 158.3, 169.4 (t)
MS: m/z = 298 (M+H)
Synthesis Example 22: 2-chloro-N-[1-(,(6-chloropyridin-3-vl)methyl)pyridin-2(1 HLylidenel-2,2difluoroacetamide (Compound 239)
2-aminopyridine in an amount of 200 mg (2.13 mmol) was dissolved in 5 mL of dichloromethane, following which 491 mg (2.55 mmol) of EDC-HCI, 311 mg (2.55 mmol) of DMAP and 187 pL (2.23 mmol, 290 mg) of chlorodifluoroacetic acid were added in this order and the mixture was stirred overnight. Following reaction completion, the reaction mixture was diluted with dichloromethane, washed with water and 1% hydrochloric acid, then dried over anhydrous magnésium sulfate, giving 105 mg of 2-chloro-2,2-difluoro-N-(pyridin-2(1H)-ylidene)acetamide (yield, 24%).
1H-NMR (CDCI3, δ, ppm): 7.19 (1H, dd), 7.82 (1H, m), 8.18 (1H, d), 8.36 (1 H, d), 9.35 (1H, brs)
An amount of 53 mg (0.33 mmol) of 2-chloro-5-chloromethylpyridine dissolved in 6 mL of anhydrous acetonitrile was added to 68 mg (0.33 mmol) of 2-chloro-2,2-difluoro-N-(pyridin-2(1H)ylidene)acetamide synthesized by the above method, following which 50 mg (0.36 mmol) of potassium carbonate was added and refluxing under heating was carried out for 1 hour. Following reaction completion, the reaction mixture was returned to room température then concentrated under reduced pressure. Diethyl ether was added to the concentrate, whereupon a solid separated out. The solid was collected by filtration and dried, affording the target compound in an amount of 49 mg (yield, 45%).
’H-NMR (CDCI3, δ, ppm): 5.56 (2H, s), 6.92 (1H, t), 7.33 (1H, d), 7.82 (1H, m). 7.91 (1H, dd), 8.02 (1H, d), 8.45 (1H, d), 8.48(1H,d) 13C-NMR (CDCI3i δ, ppm): 53.8, 115.2, 120,1 (t), 122.1, 124. 8. 139.0. 140,0. 142.3, 150.0, 151.9, 159.1,159.1,165.8 (t)
MS: m/z = 332 (M+H)
I
I Synthesis Example 23:_______2.2,2-trichloro-N-[1-((6-chloropyridin-3-yl)methvl)pvridin-2(1H)I i vlidenelacetamide (Compound 235) ί
I An amount of 70 mg (0.27 mmol) of 1-[(6-chloropyridin-3-yl)methyl]pyridin-2(1H)-imine f
I hydrochloride obtained by the method in “Synthesis Example 14, Alternative Method” was dissolved in 4 mL of anhydrous dichloromethane, following which 94 pL (0.68 mmol, 68 mg) of triethylamine and 33 pg (0.27 mmol, 49 mg) of trichloroacetyl chioride were added in this order, ; and the mixture was stirred at room température for 1 hour. Following reaction completion, water i
i was added, stopping the reaction, and liquid-liquid extraction was carried out with ί dichloromethane and water. The organic phase was washed once with water and twice with 1 % hydrochloric acid, then dried over anhydrous magnésium sulfate and concentrated under reduced pressure. Diethyl ether was added to the concentrate, whereupon a solid separated out. The solid was collected by filtration and dried, affording the target compound in an amount of 61 mg (yield, 62%).
1H-NMR (CDCI3, S, ppm): 5.59 (2H, s), 6.86 (1H, t), 7.32 (1H, d), 7.78 (1H, td), 7.91 (2H, m), 8.43 (1H, d),8.50(1H,d)
MS: m/z = 364 (M+H)
Synthesis Example 24: N-[1-((6-chloropvridin-3-vl)methyl)pyridin-2(1H)-vlidenel-2,2,3.3.3pentafluoropropanamide (Compound 242)
2-aminopyridine (300 mg, 3.19 mmol) was dissolved in 15 mL of anhydrous dichloromethane, following which 919 mg (4.78 mmol) of EDC-HCI, 583 mg (4.78 mmol) of DMAP and 397 pL (628 mg, 3.83 mmol) of pentafluoropropionic acid were added in this order and the mixture was stirred overnight at room température. Following reaction completion, the reaction mixture was diluted with dichloromethane, washed once with water and twice with 1 % hydrochloric acid, then dried over anhydrous magnésium sulfate and concentrated under reduced pressure, affording 85 mg of 2,2,3,3,3-pentafluoro-N-(pyridin-2(1H)-ylidene)propanamide (yield, 11%).
To 77 mg (0.32 mmol) of 2I2,3,3,3-pentafluoro-N-(pyridin-2(1 H)-ylidene)propanamide obtained by the above method were added 52 mg (0.32 mmol) of 2-chloro-5-chloromethylpyridine dissolved in 8 mL of anhydrous acetonitrile and 49 mg (0.35 mmol) of potassium carbonate, after ____ j which the mixture was refluxed under heating for 11 hours. Following reaction completion, the i
réaction mixture was retumed to room température, the insoluble matter was removed by filtration, and the filtrate was concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (hexane/ethyl acetate ~ 1:3), affording the target compound in an j 5 amount of 12 mg (yield, 10%).
| 1H-NMR (CDCIa, 5, ppm): 5.56 (2H, s), 6.90(1 H, td), 7.32 (1H, d), 7.79 (2H, m), 7.84 (1H, d), 8.43 (1H,d), 8.56(1 H, d)
MS: m/z = 366 (M+H)
Synthesis Example 25: N-ri-((2-chloropvrimidin-5-vl)methvl)pvridin-2(1H)-ylidene1-2,2l210 trifluoroacetamide (Compound 243)
2-chloro-5-methylpyrïmidine (1.04 g, 8.13 mmol) was dissolved in 30 mL of carbon i
tetrachlcride, 1.73 g (9.75 mmol) of N-bromosuccinimide and 20 mg of benzoyl peroxide were added, and the mixture was refluxed under heating for 6 hours. Following reaction completion, the reaction mixture was returned to room température, concentrated under reduced pressure, and 15 purified by silica gel column chromatography (hexane/ethyl acetate = 3:1), affording 641 mg of 5bromomethyl-2-chloropyridine (yield, 38%).
1H-NMR (CDCI3, Ô, ppm): 4.42 (2H, s), 8.66 (2H, s)
An amount of 104 mg (0.50 mmol) of 5-bromomethyF2-chloropyridine obtained by the above method was dissolved in 6 mL of anhydrous acetonitrile, after which 96 mg (0.50 mmol) of 20 2,2,2-trifluoro-N-(pyridin-2(1H)-ylidene)acetamide obtained by the method in “Synthesis Example
14, Step (1)” and 76 mg (0.55 mmol) of potassium carbonate were added, and the mixture was refluxed under heating for 1 hour. Following reaction completion, the reaction mixture was retumed to room température, the insoluble matter was removed by filtration, and the filtrate was concentrated under reduced pressure. Diethyl ether was added to the concentrate, whereupon a 25 solid separated out. The solid was collected by filtration, washed with diethyl ether, then placed in a desiccator and dried under reduced pressure, affording the target compound in an amount of 92 mg (yield, 58%).
1H-NMR (CDCI3, δ, ppm): 5.54 (2H, s), 6.98 (1H, m), 7.87 (1H, m), 8.18 (1H, m), 8.48 (1H, m),
8.83 (2H, m) 13C-NMR (CDCI3, δ, ppm): 60.0, 115.6, 117.1 (q), 122.1, 127.5, 139.2, 142.9, 158.8, 160.3 (2C),
161.4, 163.8 (q)
MS: m/z=317(M+H)
Spectral data for compounds obtained by methods similar to those in Synthesis Examples to 25 are shown in Tables 10 and 11.
I
Table 10
No, | ‘NMR (CDC1,, 8, ppm) | IRfKBzt, v, cm'1) or MS |
212 | 5,57 (2H, b), 6,92 (IH, td) , 7.31 (IH, d) , 7.80 (IH, td) , 7.87 (IH, dd), 7.99 (IH, dd), B.48 (2H, m) | m/z = 316 (M+H) |
213 | 5.61 (2B, b), 6.93 (IH, dd) , 7.68 (IH, s), 7.83 (IH, td) , 7,97 (IH, d), 8.53 (IH, d) | m/z = 322 (M+H) |
214 | 3.74 (3H, s) , 5.40 (2H, s) , 6.45 (IH, td) , 7.29 (IH, d) , 7.46 (2H, m) , 7.73 (IH, dd) , 8.12 (IH, dd) , 8.40 (IH, d) | m/z = 278 (M+H) |
215 | 5.53 (2H, s), 7.34 (IH, d) , 7.71 (IH, dd) , 7.87 ( IH, dd) , 7,94 (IH, s), 8.49 (IH, d), 8.55 (IH, s) | m/z = 350 (M+H) |
216 | 5.54 (2H, s), 7.34 (IH, d) , 7.70 (IH, m) , 7.S0 (IH, m) , 7.88 (IH, dd), 8.48 (IH, d) , B.64 (IH, m) | m/z = 334 (M+H) |
217 | 5.49 (2H, 3), 6.85 (IH, dd) , 7.35 (IH, d) , 7.76 (IH, dd) , 7.85 (IH, dd), 8.44 (IB, d), 8.62 (IH, s) | m/z = 350 (M+H) |
218 | 5.56 (2H, s) , 7.68 (IH, s) , 7.74 (IH, dd) , 7.84 (IH, d) , B. 58 (IH, d) | m/z = 356 (M+H) |
219 | 5.60 (2H, s), 7.69 (IH, s), 7.72 (IH, td) , 7.86 (IH, m) , 8.67 (IH, m) | m/z = 340 (M+H) |
220 | 5.58 (2H, s), 6.90 (IH, d) , 7.67 (IH, s), 7.90 (IH, d) , 8.61 (IH, s) | m/z = 356 (M+H) |
221 | 2.31 (3H, s) , 5.50 (2H, s) , 6.98 <1H, m) , 7.34 (IH, d) , 7.73 (IH, dd) , 7.77 <2H, ta), 8.42 (IH, d) | m/z = 330 (M+H) |
222 | 2.40 (3H, S) , 5.49 (2H, s) , 6.70 <1H, dd) , 7.32 (IH, d) , 7.70 (IH, d), 7.86 (IB, dd), 8.37 (IH, s), 8.43 (IH, d) | m/z = 330 (M+H) |
223 | 2.29 (3H, s) , 5.52 (2H, s) , 7.32 (IH, d) , 7.62 (IB, s) , 7.65 (IH, dd), 7.88 (IH, dd), 8.46 (IH, d), 8.50 (IH, d) | m/z = 330 (M+H) |
224 | 5.58 (2H, b), 6.81 (IH, m) , 7.37 (4H, m) , 7.77 (2H, m) , 8.50 (IH, d) | m/z = 281 (M+H) |
225 | 5.52 (2B, s) , 6.85 (IH, m) , 7.30 (2H, d) , 7.36 (2H, d) , 7.75 (IH, td), 7.84 (IH, d), 8.47 (IH, d) | m/z - 315 (M+H) |
226 | 5.57 (2H, s), 6.86 (IH, m) , 7.26-7.35 (2H, m) , 7.78 (IH, td) , 7,86 (IH, m), 8.63 (2H, m), 8.67 (IH, d) | m/z = 282 (M+H) |
227 | 5,54 (2H, s), 6.89 (IB, td), 7.76 (IH, dd), 7.80 (IH, td), 7.85 (IH, d), 8.29 (IH, d), 8.57 (IH, d) | m/z = 334 (M+H) |
228 | 5.62 (2H, s) , 6.90 (IH, t) , 7.69 (IH, d) , 7.81 [IH, t) , 7.88 (IH, d), 8.06 (IH, d), 8.56 (IH, d), 8.78 (IH, s) | m/z = 350 (M+H) |
229 | 5.56 (2B, s), 6.89 (IH, td) , 6,94 (IH, d) , 7.79 (IH, td) , 7.87 (IH, d), 8.03 (IH, m), 8.31 (IH, s), 8.54 (IH, d) | m/z = 300 (M+H) |
230 | 5.49 (2H, s), 6.89 (IH, t) , 7.79-7.90 (2H, m) , 8.04 (lfi, d) , 8.37 (IH, d), 8.56 (IH, m) | m/z = 350 (M+H) |
231 | 5.52 (2H, s) , 6.88 (IH, t) , 7.48 (IH, d) , 7.78 (2H, m) , 7.84 (IH, d), 8,44 (IH, d), 8.53 (IH, d) | m/z = 360 (M+H) |
232 | 5.52 {2H, s), 6.71 (IH, m) , 7.35 (IH, d) , 7.86 (IH, dd) , 7.94 (IH, m), 8.33 (IH, dd), 8.44 (IH, d) | m/z = 334 (M+H) |
233 | 5.53 (2H, s) , 6.74 (IH, m) , 7.33 (IH, d) , 7,87 (IH, dd) , 8.07 (IH, m), 8.29 (IH, dd), B.45 (IH, d) | m/z = 334 (M+H) |
234 | 5.54 (2H, s) , 6.02 (IH, s) , 6.77 (IH, t) , 7,32 (IH, m) , 7.69 (IH, m), 7.77 (IH, d), 7.89 (IH, m), 8.42 (IH, m), B.49 (IH, s) | m/z = 330 (M+H) |
Table 11
No, | ‘NMR (CDCIt, 8, ppm) | IR(KBr, v, caT1) or MS |
235 | 5.59 (2H, b), 6.86 (IH, t), 7,32 (IH, d), 7.78 (IH, td) , 7,91 (2H, m), 8.43 (IH, d), 8.50 (IH, d) | m/z = 364 £M+H} |
236 | 4.17 (2H, b), 5.46 <2H, s), 6,64 (IH, td), 7.31 (IH, d) , 7,60 (IH, td), 7.64 (IH, dd), 7.S0 (IH, dd), 8.32 (IH, d), 8.45 (IH, d) | m/z > 296 (M+H) |
237 | 1,β9 (3H, d}, 6.89 (IH, td) , 7.08 (IH, q), 7.32 (IH, d), 7.66 (lHf dd)f 7.76 (2H/ m)f 8.44 (IH, d), 8.50 (IH, d) | m/l = 330 (M+H) |
238 | 5.52 (2H, s), 5.90 (IH, t), 6.79 (IH, td), 7,33 (IH, d), 7.71 (IH, m), 7.77 (IH, dd) , 7.BS {IH, dd), 8.45 (IH, d) , 8.50 (IH, d) | m/z = 298 (M+H) |
239 | 5,56 (2H, s}. 6,92 Î1H, t}, 7,33 (IH, d}, 7,82 (IH, m), 7.91 (IH, dd), 8,02 (IH, d}, 0.45 (XHf d), 8.48 (IH, d} | m/z - 332 (M+H) |
240 | 5.53 (1E, d), 5.58 (lHf d){ 6,06 (IH, s}, 6.76 (XHf td), 7.32 (1E, d)f 7.69 (IH, m), 7.70 (XHf m), 7.90 (IH, dd), 8.40 (IH, d), 8.50 (18, d) | m/z = 374 (M+H) |
241 | 5.56 (2Hr s), 5.99 (1H, e), 6.78 (IH, td}, 7.33 (lHf d) , 7.69 (IH, td), 7,76 (XHf dd), 7.93 (IH, dd) , 8.39 (1H, d) , 8.50 (IH, d) | m/i - 416 (M+H) |
242 | 5.56 (2H, s), 6,90 (1H, td} , 7.32 (IH, d}, 7.79 (2H, m), 7.84 (IH, d), 8.43 (IH, d), 8.56 (XEf d) | m/i = 366 (M+H) |
243 | 5.54 (2H, s), 6.98 (1H, m), 7.87 (IH, m) , 8.18 (1H, m), 8.48 (1H, m) 8.83 (2H, m) | m/ι = 317 (M+H) |
244 | 4.17 (2H, s), 5.46 (2H, s), 6.63 (IH, td), 7.31 (IH, d), 7.60 (IH, td), 7.65 (IH, dd), 7.80 (IH, dd) , 8.32 (IH, d), 8.47 (IH, d) |
Comparative Example 1: N-f(6-chloropvridin-3-vl)methvl1cvanamide (JP 2003-26661 A,
Compound 1)
Cyanogen bromide (220 mg, 2.09 mmol) was dissolved in 10 mL of anhydrous chloroform, and the solution was cooled to 0°C. To this was dropwise added a solution of 500 mg (3.49 mmol) of 2-chloro-5-aminomethylpyridine dissolved in 10 mL of anhydrous chloroform, and the resulting mixture was stirred at 0°C for 1 hour. The réaction mixture was filtered, then water was added and liquid-liquid extraction was carried out, following which the chloroform phase was dried over anhydrous magnésium sulfate and concentrated under reduced pressure. The concentrate was purifîed by silica gel column chromatography (hexane/ethyl acetate = 1:1), giving 122 mg (yield, 35%) of the target compound.
1H-NMR (CDCI3, δ, ppm): 4.21 (2H, s), 5.74 (1H, brs), 7,36 (1H, d), 7.71 (1H, dd), 8.30 (1H, d) 13C-NMR (CDCIg, δ, ppm): 46,5, 116.1, 124.8,131.5,138.9, 148.9, 151.4
MS: m/z = 166 (M-H)
Comparative Example 2: N-f1-((6-chloropyridin-3-vl)methvl)pvridin-2(1H)-vlidene1cvanamide (Patent Document 6, Compound 20) [Chem. 26]
An amount of 128 mg (0.58 mmol) of 1-[(6-chloropyridin-3-yl)methyl]pyridine-2(1H)-imine obtained by the alternative method described in Synthesis Example 14 was dissolved in 5 mL of anhydrous dimethylformamide, NaH (as a 60% dispersion in oil) was added in an amount of 40 mg (net weight, 24 mg; 1.04 mmol), and the mixture was stirred at room température for 30 minutes. Next, 60 mg (0.57 mmol) of cyanogen bromide was added, and the resulting mixture was stirred overnight. Following reaction completion, water and ethyl acetate were added to the reaction mixture and liquid-liquid extraction was carried out. The organic phase was dried over anhydrous magnésium sulfate, then concentrated under reduced pressure. The concentrate was purified on a TLC plate (one 0.5 mm plate, developed with 100% ethyl acetate), giving 14 mg of the target compound (yield, 10%).
1H-NMR (CDCIs, δ, ppm): 5.28 (2H, s), 6.55 (1H, m), 7.33 (2H, m), 7.56 (2H, m), 7.75 (1H, dd), 8.40 (1 H, d)
Comparative Example 3: N-ri-((6-chloropvridin-3-vl)methvl)pyridin-2(2H)-vlidenelacetamide (Patent Document 4, Compound 2)
Anhydrous dichloromethane (20 mL) was added to 118 mg (0.46 mmol) of 1-[(6chloropyridin-3-yl)methyl]pyridine-2(1H)-imine hydrochloride obtained by the alternative method described in Synthesis Example 14, following which 159 pL (1.16 mmol, 116 mg) of triethylamîne and 33 pL of acetyl chloride were added and the mixture was stirred at room température for 15 minutes. The réaction was stopped by adding water to the reaction mixture, and liquid-liquid extraction was carried out with chloroform and water. The organic phase was washed with a saturated aqueous solution of ammonium chloride, then concentrated. With the addition of t
hexane thereto, a solid settled out. The solid was collected by filtration and washed, then thoroughly dried, giving 21 mg ofthe target compound (yield, 17%).
H-NMR (CDCI3, ô, ppm); 2.21 (3H, s), 5.35 (2H, s), 6.46 (1H, m), 7.32 (1H, d), 7.48 (2H, m), 7.75 (1H,d), 8.10 (1H, dd), 8.45(1H,dd)
MS: m/z = 262 (M+H)
Comparative Example 4: 3-[1-((6-chloropvridin-3-vl)methvl)imidazolidin-2-vlidene1-1,1,1trifluoropropan-2-one (Patent Document 5, Example 4) [Chem. 28]
N NH
COCF3
Anhydrous dimethylformamide (15 mL) was added to 1.30 g (33.9 mmol, 780 mg) of NaH (as a 60% dispersion in oil), and the mixture was cooied to 0°C. To this was dropwise added 1.52 mL (1.90 g, 17.0 mmol) of 1,1,1-trifluoroacetone, and stirring was carried out at 0°C for 10 minutes. To this was added 7.0 mL (110 mmol, 8.35 g) of carbon disulfide, and stirring was carried out at 50°C for 1 hour. Next, the reaction mixture was cooied to 0°C, 2.1 mL (34.0 mmol, 4.81 g) of methyl iodide was added, and the mixture was stirred overnight at room température. Following reaction completion, the reaction mixture was poured into ice water and stirring was carried out until the ice completely melted. The reaction mixture was transferred to a separatory funnel and extracted with ethyl acetate. The organic phase was washed with saturated saline, then dried over anhydrous magnésium sulfate and concentrated under reduced pressure. The concentrate was purified by silica gel chromatography (hexane/ethyl acetate = 95:5), and the fractions containing the target compound were collected and concentrated under reduced pressure. Hexane was added thereto, whereupon a solid settled out. The solid was collected by filtration and washed with hexane, then thoroughly dried, giving 460 mg (yield, 13%) of 1,1,1 -trifluoro-4,4bis(methylthio)-3'buten-2-one.
H-NMR (CDCI3, δ, ppm): 2.56 (3H, s), 2.58 (2H, s), 6.25 (1H, s)
Next, 20 mL of ethylenediamine was added to 2.0 g (12.4 mmol) of 2-chloro-5chloromethylpyridine, and the mixture was stirred ovemight. Following reaction completion, the reaction mixture was concentrated under reduced pressure, after which acetonitrile was added and insoluble matter were removed by filtration. The filtrate was concentrated under reduced pressure, giving 2.45 g (yield, 100%) of N-((6-chloropyridin-3-yl)methyl)ethane-1,2-diamine.
A solution of 77 mg (0.42 mmol) of the N-((6-chloropyridin-3-yl)methyl)ethane-1,2-diamine obtained by the foregoing method in 8 mL of anhydrous acetonitrile was added to 60 mg (0.28 mmol) of 1,1,1-trifluoro-4,4-bis(methylthio)-3-buten-2-one obtained by the foregoing method, and the mixture was refluxed under heating for 40 minutes. Following reaction completion, the reaction mixture was returned to room température and concentrated under reduced pressure, after which ethyl acetate and water were added, and liquid-liquid extraction was carried out. The organic phase was washed with anhydrous magnésium sulfate, then concentrated under reduced pressure, and the concentrate was purified by silica gei column chromatography (hexane/ethyl acetate = 3:1), giving 59 mg of the target compound (yield, 69%).
1H-NMR (CDCb, S, ppm): 3.49 (2H, t), 3.78 (2H, t), 4.40 (2H, s), 5.13 (1H, s), 7.37 (1H, d), 7.56 (1H, dd), 8.31 (1H, d), 9.34 (1H, brs) m/z = 306 (M+H)
Comparative Example 5:_______3-[3-((6-chloropvridin-3-vl)methvl)thiazolidin-2-vlidene1-1,1,1 trifluoropropan-2-one (Patent Document 5, Example 3) [Chem. 29]
Γ~\
COCF3
A solution of 36 mg (0.46 mmol) of 2-aminoethanethiol dissolved in 10 mL of éthanol was added to 100 mg (0.46 mmol) of 1,1,1-trifluoro-4,4-bis(methylthio)-3-buten-2-one obtained by the method described in Comparative Example 4, and the mixture was refluxed under heating for 6 hours, then stirred at room température for 13 hours. Following reaction completion, the éthanol was distilled off under reduced pressure, after which the condensate was dissolved in ethyl acetate and washed once with water. The washed product was dried over anhydrous magnésium sulfate, then concentrated under reduced pressure, giving 73 mg (yield, 81%) of 1,1,1-trifluoro-3(thiazolidin-2-ylidene)propan-2-one.
1N-NMR(CDCI3, δ, ppm): 3.35 (2H, m), 4.02 (2H, m), 5.61 (1H, s), 10.40(1 H, brs),
2-chloro-5-chloromethylpyridine (80 mg, 0.50 mmol) dissolved in 8 mL of anhydrous acetonitrile, and potassium carbonate (69 mg, 0.50 mmol) were added to 65 mg (0.33 mmol) of 1,1,1-trifluoro-3-(thiaolidin-2-ylidene)propane-2-one obtained by the foregoing method, and the mixture was refluxed under heating for 2 hours. After reaction completion, the reaction mixture was retumed to room température, insoluble matter was removed by filtration, and the filtrate was concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (hexane/ethyl acetate = 1:1 1:3), giving 53 mg of the target compound (yield,
50%).
1H-NMR (CDCIa, δ, ppm): 3.20 (2H, t), 3.73 (2H, t), 4.61 (2H, s), 5.80 (1H, s), 7.36 (1H, d), 7.53 (1H, dd), 8.31 (1H, d) MS: m/z = 323 (M+H)
Comparative Example 6: 3-f1-((6-chloropvridin-3-vl)methvl)imidazolidin-2-vlidenel-1,1,1,5,5,5hexafluoropentan-2,4-dione (Patent Document 5, Example 5) [Chem. 30] ck n f3coc COCF3
An amount of 31 mg (0.10 mmol) of the 3-[1-((6-chloropyridin-3-yl)methyl)imidazolidin-2ylidene]-1,1,1-trifluoropropan-2-one obtained by the method described in Comparative Example 4 was dissolved in 2 mL of anhydrous dichloromethane, then 20 pL (0.25 mmol, 20 mg) of pyridine and 28 pL (0.20 mmol, 42 mg) of trifluoroacetic anhydride were added in this order, and the mixture was stirred at room température for 30 minutes. The progress of the reaction was checked by thin layer chromatography, whereupon there was found to be some starting material remaining in the system. As a resuit, another 84 pL (0.60 mmol, 62 mg) of trifluoroacetic
anhydride was added, and stirring was carried out for 1 hour at room température. Following reaction completion, the reaction mixture was concentrated under reduced pressure, then purified on a TLC plate (one 0.5 mm plate, developed with hexane/ethyl = 2:8), giving 30 mg ofthe target compound (yield, 75%).
1H-NMR(CD3OD, δ, ppm): 3.87 (4H, m), 4.51 (2H, s), 7.50 (1H, d), 7.82 (1H, dd), 8.35 (1H, d) MS: m/z = 402 (M+H)
Comparative Example 7: N-[1-((6-chloropvridin-3-vl)methvl)imidazolidin-2-ylidene1-2.2.2trifluoroacetamide (Patent Document 5, Example 7) [Chem. 31]
Dimethylcarbonimidodithioate methanesuifonic acid chloride (4.25 g, 18.2 mmol) was dissolved in 30 mL of pyridine, 3.80 mL (5.73 g, 27.3 mmol) of trifluoroacetic anhydride was added dropwise, and the mixture was stirred overnight at room température. The reaction mixture was concentrated under reduced pressure, and subjected to liquid-liquid extraction using dichloromethane and water. The resulting organic phase was dried over anhydrous magnésium sulfate, then concentrated, giving 5.36 g of dimethyl(2,2,2-trifluoroacetyl)carbonimidodithioate (yield, 100%).
N-((6-chloropyridin-3-yl)methyl)ethane-1,2-diamine (4.61 g, 24.9 mmol) was synthesized by the method described in Comparative Example 4. This was dissolved in 40 mL of anhydrous acetonitrile, 4.60 g (21.3 mmol) of the dimethyl(2,2,2-trichloroacetyl)carbonimidodithioate obtained by the above method was added, and the resulting mixture was refluxed under heating for 90 minutes. Following reaction completion, the reaction mixture was returned to room température, after which the solvent was distilled off under reduced pressure. The solid that settled out was collected by filtration and washed with a small amount of acetonitrile, giving 2.17 g ofthe target compound (yield, 33%).
1H-NMR (CDCI3, δ, ppm): 3.50 (2H, m), 376 (2H, m), 4.60 (2H, s). 7.34 (1H, d), 7.70 (1H, dd),
8.33 (1H,d)
Melting point: 168to170°C
Comparative Example 8:_______N-f3-((6-chloropyridin-3-yl)methvl)thiazolidin-2-vlidene1-2,2,2trifluoroacetamide (Patent Document 5, Example 6) [Chem. 32]
Ethanol (20 mL) was added to 77 mg (1.0 mmol) of 2-aminoethanethiol, 216 mmol (1.0 mmol) of the dimethyl(2,2,2-trifluoroacetyl)carbonimidodithioate synthesized by the method described in Comparative Example 7 was added, and the mixture was stirred overnight at room température. Following reaction completion, the solvent was distilled off under reduced pressure, and purification was carried out by silica gel column chromatography (hexane/ethyl acetate = 1:1), giving 100 mg of 2,2,2-trifluoro-N-(thiazolidin'2-ylidene)acetamide (yield, 51%). This reaction was carried out once more by the same synthesis method, giving a combined amount of 350 mg of 2,2,2-trifluoro-N-(thiazolidin-2-ylidene)acetamide.
Dimethylformamide (2 mL) and tetrahydrofuran (18 mL) were added to 162 mg (0.82 mmol) of 2,2,2-trifluoro-N'(thiazolidin-2-ylidene)acetamide obtained by the above-described method, following which 198 mg of 2-chloro-5-chloromethylpyridine and 150 mg (1,09 mmol) of potassium carbonate were added, and the mixture was refluxed under heating for 20 hours. Following reaction completion, the reaction mixture was returned to room température, insoluble matter was filtered off, and the filtrate was concentrated under reduced pressure. The concentrate was purified on a TLC plate (two 0.5 mm plates, developed with 100% ethyl acetate), giving 230 mg of the target compound (yield, 87%).
1H-NMR (CDCI3, δ, ppm): 3.27 (2H, m), 3.73 (2H, m), 4.86 (2H, s), 7.36 (1H, d), 772 (1H, dd), 8.36 (1 H, d)
Melting point: 96°C [EXAMPLE FORMULATIONS]
Formulation Example 1: Granules
Cornpound 1 | 5wt% |
Bentonite | 40 wt% |
Talc | 10 wt% |
Clay | 43 wt% |
Calcium ligninsulfonate | 2 wt% |
The above ingrédients were uniformly ground and mixed, following which water was added and the mixture was thoroughly kneaded. The kneaded material was granulated and dried, giving granules.
Formulation Example 2: Granules
Cornpound 212 | 2 wt% |
Sanx P-252 | 5 wt% |
Binder | 1.5 wt% |
Granulation enhancer | 0.5 wt% |
Clay | 91 wt% |
The above ingrédients were uniformly ground and mixed, following which water was added and the mixture was thoroughly kneaded. The kneaded material was granulated and dried, giving granules.
Formulation Example 3: Wettable Powder
Cornpound 3 | 30 wt% |
Clay | 50 wt% |
White carbon | 2wt% |
Diatomaceous earth | 13wt% |
Calcium ligninsulfonate | 4 wt% |
Sodium lauryl sulfate | 1 wt% |
The above ingrédients were uniformly mixed and ground, giving a wettable powder.
Formulation Example 4: Water Dispersîble Granules
| 4 » i 1 | 16334 | |
1 | Compound 212 | 30 wt% |
Clay | 60 wt% | |
Dextrin | 5 wt% | |
Alkyl-maleic acid copolymer | 4 wt% | |
5 | Sodium lauryl sulfate | 1 wt% |
The above ingrédients were uniformly ground and mixed, following which water was added and the mixture was thoroughly kneaded. The kneaded material was granulated and dried, giving water dispersible granules.
Formulation Example 5: Flowable Concentrate
10 | Compound 8 | 25 wt% |
POE polystyryl phenyl ether sulfate | 5wt% | |
Propylene glycol | 6 wt% | |
Bentonite | 1 wt% | |
Xanthan gum, 1% aqueous solution | 3wt% | |
15 | PRONAL EX-300 (Toho Chemical Industry Co., Ltd.) | 0.05 wt% |
ADDAC 827 (Kl Chemical Industry Co., Ltd.) | 0.02 wt% | |
Water | added to 100 wt% |
The entire amounts of the above ingrédients, excluding the 1% aqueous solution of xanthan gum and a suitable amount of water, were premixed, then ground in a wet grinding mill.
The 1% aqueous solution of xanthan gum and the remaining water were then added to the total
amount of 100 wt%, giving a flowable concentration. Formulation Example 6: Emulsifiable Concentrate | ||
Compound 1 | 15wt% | |
Ν,Ν-dimethylformamide | 20 wt% | |
25 | Solvesso 150 (Exxon Mobil Yugen Kaisha) | 55 wt% |
Polyoxyethylene alkyl aryl ether | 10wt% | |
The above ingrédients were uniformly mixed | and dissolved, giving an emulsifiable | |
concentrate. |
Formulation Example 7: Dust Formulation
Compound 14
Clay
Talc
Calcium stéarate
2wt% wt% wt% wt%
The above ingrédients were uniformiy mixed, giving a dust formulation.
Formulation Example 8: Low-Drift Dust Formulation
Compound 1
Low-drift clay
White carbon wt%
94.5 wt%
2wt%
Calcium stéarate
Light liquid paraffin wt%
0.5 wt%
The above ingrédients were uniformiy mixed, giving a dust formulation.
Formulation Example 9: Fine Granules F
Compound 3
Carrier
White carbon
Hisol SAS-296
2wt% wt% wt% wt%
The above ingrédients were uniformiy mixed, giving a dust formulation.
Formulation Example 10: Liquid formulation for drop
Compound 1
Benzyl alcohol
Propylene carbonate
BHT
10wt%
74.9 wt%
15wt%
0.1 wt%
The above ingrédients were uniformiy mixed, giving a liquefied drop formulation.
Formulation Example 11 : Liquid formulation for drop
Compound 212
Ethanol wt% wt%
100
The above ingrédients were uniformly mixed, giving a liquefied drop formulation. | ||
: | In addition, an example of a mixed formulation containing both a compound of the présent invention and another pest control agent is provided below. Formulation Example 12: Granules | |
5 | Compound 212 | 2 wt% |
Propenazole | 24 wt% | |
Binder | 3.0 wt% | |
Granulation enhancer | 0.5 wt% | |
Clay | 70.5 wt% |
o The above ingrédients were uniformly ground and mixed, following which water was added and the mixture was thoroughly kneaded. The kneaded material was granulated and dried, giving granules.
[TEST EXAMPLES]
Foliar Application Tests
Test Example 1-1: Diamondback Moth Control Test
Leaf dises 5.0 cm in diameter were eut from cabbage plants grown in pots, and these were j sprayed with solutions of the inventive compounds at a predetermined concentration prepared to
50% acetone/water (containing 0,05% Tween 20). The treated leaf dises were air dried, following which second-instar larvae were released onto the dises. The leaf dises and larvae were then held in an incubation chamber at 25°C (16-hour period of light, 8-hour dark period). Three days after released, the numbers of live and dead insects were counted, and the mortality was calculated from the following formula. This was a two-replication test.
Mortality (%) = [number of dead insects/(number of live insects + number of dead insects)] χ 100
From these results, with 500 ppm foliar application, Compounds 9,10, 49,196, 211, 81,82,
89, 92, 104, 107, 108, 109, 110, 111, 112, 114, 128, 131, 140, 141, 144, 145, 146, 152, 165, 167,
170, 171, 172, 176, 179, 180, 181, 183, 184, 186, 188, 189, 190, 193, 194, 212, 219, 226, 227,
229, 230, 234, 235, 237, 239, 240, 241, 242 and 243 exhibited insecticidal activities having at least 80% mortality.
101
Test Example 1-2: Diamondback Moth Control Test
Leaf dises 5.0 cm in diameter were eut from cabbage plants grown in pots, and these were sprayed with solutions of the inventive compounds at a predetermined concentration prepared to 50% acetone/water (contaîning 0.05% Tween 20). The treated leaf dises were air dried, following which second-instar larvae were released onto the dises. The leaf dises and larvae were then held in an incubation chamber at 25°C (16-hour period of light, 8-hour dark period). Three days after released, the numbers of live and dead insects were counted, and the mortality was calculated from the following formula. This was a two-replication test.
Mortality (%) = [number of dead insects/(number of live insects + number of dead insects)] x 100
From these results, with 100 ppm foliar application, Compounds 81, 89, 92, 107, 111, 112, 114, 128, 152, 171, 183, 184, 186, 189, 190, 193, 194, 211, 212, 213, 215, 216, 218, 219, 227, 229, 230, 231, 234, 235, 237, 238, 239, 242 and 243 exhibited insecticidal activities having at least 80% mortality.
Test Example 2: Common Cutworm Control Test
Leaf dises 5.0 cm in diameter were eut from cabbage plants grown in pots, and these were sprayed with solutions of the inventive compounds at a predetermined concentration prepared to 50% acetone/water (contaîning 0.05% Tween 20). The treated leaf dises were air dried, following which third-instar larvae were released onto the dises. The leaf dises and larvae were then held in an incubation chamber at 25°C (16-hour period of light, 8-hour dark period). Three days after released, the numbers of live and dead insects were counted, and the mortality was calculated from the following formula. This was a two-replication test.
Mortality (%) = [number of dead insects/(number of live insects + number of dead insects)] x 100
From these results, with 500 ppm foliar application, Compounds 46, 202, 68, 82, 89, 92, 96, 104, 108, 128, 140, 176, 184, 189, 190, 193, 212, 219, 227, 229, 230 and 239 exhibited insecticidal activities having at least 80% mortality.
Test Example 3-1 : Cotton Aphid Control Test
Leaf dises 2.0 cm in diameter were eut from cucumber plants grown in pots, and these were sprayed with solutions of the inventive compounds at a predetermined concentration
102
i prepared to 50% acetone/water (containing 0.05% Tween 20). The treated leaf dises were air dried, following which first-instar larvae were released onto the dises. The leaf dises and larvae were then held in an incubation chamber at 25°C (16-hour period of light, 8-hour dark period). Three days after released, the numbers of live and dead insects were counted, and the mortality was calculated from the following formula. This was a two-replication test.
Mortality (%) = [number of dead insects/(number of live insects + number of dead insects)] x 100
From these results, with 500 ppm foliar application, Compounds 1, 2, 3, 6, 7, 8, 9, 10, 12,
131, 132, 135, 139, 165, 167, 170, 179, 182, 183, 184, 186, 189, 192, 193, 194, 196, 199, 200,
202, 208, 210, 211, 212, 219, 221, 222, 223, 225, 226, 227, 228, 229, 230, 233, 234, 235, 237,
239 and 243 exhibited insecticidal activities having at least 80% mortality.
By contrast, when Compound 1 (N-[(6-chloropyridin-3-yl)methyl]cyanamide) in Patent
Document 1 (Japanese Patent Application Publication No. 2003-26661) was tested by the same method, the cotton aphid mortality from foliar application at 500 ppm was 65%.
Test Example 3-2: Cotton Aphid Control Test
Leaf dises 2.0 cm in diameter were eut from cucumber plants grown in pots, and these were sprayed with solutions of the inventive compounds at a predetermined concentration prepared to 50% acetone/water (containing 0.05% Tween 20). The treated leaf dises were air dried, following which first-instar larvae were released onto the dises. The leaf dises and larvae were then held in an incubation chamber at 25°C (16-hour period of light, 8-hour dark period). Three days after released, the numbers of live and dead insects were counted, and the mortality was calculated from the following formula. This was a two-replication test.
Mortality (%) = [number of dead insects/(number of live insects + number of dead insects)] x 100
From these results, with 100 ppm foliar application, Compounds 1, 2, 3, 6, 7, 8, 9, 10, 14, 245, 18, 21, 34, 43, 49, 50, 71, 76, 83, 85, 86, 88, 89, 90, 91, 92, 93, 94, 96, 97, 102, 105, 113,
128, 131, 137, 138, 139, 140, 141, 145, 149, 152, 157, 163, 183, 186, 196, 199, 200, 204, 208,
212, 213, 214, 215, 216, 219, 222, 223, 225, 226, 227, 228, 229, 230, 232, 233, 234, 235, 236,
103
237, 238, 239, 240, 241, 242, 243 and 244 exhibited insecticidal activities having at least 80% mortality.
Test Example 3-3 Cotton Aphid Control Test
Leaf dises 2.0 cm in diameter were eut from cucumber plants grown in pots, and these were sprayed with solutions of the inventive compounds at a predetemnined concentration prepared to 50% acetone/water (containing 0.05% Tween 20). The treated leaf dises were air dried, following which first-instar larvae were released onto the dises. The leaf dises and larvae were then held in an incubation chamber at 25°C (16-hour period of light, 8-hour dark period). Three days after released, the numbers of live and dead insects were counted, and the mortality was calculated from the following formula. This was a two-replication test.
Mortality (%) = [number of dead insects/(number of live insects + number of dead insects)] x 100
From these results, with 20 ppm foliar application, Compounds 1, 2, 3, 6, 7, 8, 14, 18, 21, 82, 86, 88, 89, 90, 91, 94, 95, 128, 137, 138, 157, 199, 200, 212, 213, 214, 219, 226, 227, 229, 230, 231, 233, 234, 235, 236, 237, 238, 239, 240, 241, 242, 243 and 244 exhibited insecticidal activities having at least 80% mortality.
Test Example 4: Green Peach Aphid Control Test
Leaf dises 2.8 cm in diameter were eut from cabbage plants grown in pots, and four adult aphids were released onto each dise. One day later, the adults were removed, and the number of first-instar larvae that had been deposited on each leaf dise was adjusted to 10. Next, the leaf dises parasitized by these first instar larvae were sprayed with solutions of the inventive compounds at a predetermined concentration prepared to 50% acetone/water (containing 0.05% Tween 20). The treated leaf dises were air dried, following which covers were placed over the Pétri dishes and the leaf dises and larvae were held in an incubation chamber at 25°C (16-hour period of light, 8-hour dark period). Three days after released, the numbers of live and dead insects were counted, and the mortality was calculated from the following formula. This was a two-replication test.
Mortality (%) = [number of dead insects/(number of live insects + number of dead insects)] χ 100
104
From these results, with 100 ppm foliar application, Compounds 1, 2, 3, 6, 7, 8, 9, 10, 11 and 212 exhibited insecticidal activities having at Ieast 80% mortality.
Test Example 5: Small Brown Planthopper Control Test
Rice seedlings grown in pots were subjected to the foliar application of solutions of the inventive compounds at a predetermined concentration prepared to 50% acetone/water (containing 0.05% Tween 20). The treated seedlings were air dried, following which second-instar larvae were released onto the seedlings. The seedlings and larvae were then held in an incubation chamber at 25°C (16-hour period of light, 8-hour dark period). Three days after released, the numbers of live and dead insects were counted, and the mortality was calculated from the following formula. This was a two-replication test.
Mortality (%) = [number of dead insects/(number of live insects + number of dead insects)] x 100 From these results, with 100 ppm foliar application, Compounds 212, 213, 215, 216, 227, 229 and 230 exhibited insecticidal activities having at Ieast 80% mortality.
Test Example 6: Brown rice Planthopper Control Test
Rice seedlings grown in pots were subjected to the foliar application of solutions of the inventive compounds at a predetermined concentration prepared to 50% acetone/water (containing 0.05% Tween 20). The treated seedlings were air dried, following which second-instar larvae were released onto the seedlings. The seedlings and larvae were then held in an incubation chamber at 25°C (16-hour period of light, 8-hour dark period). Six days after released, the numbers of live and dead insects were counted, and the mortality was calculated from the following formula. This was a two-replication test.
Mortality (%) = [number of dead insects/(number of live insects + number of dead insects)] x 100 From these results, with 100 ppm foliar application, Compounds 1, 2, 3, 6, 7 and 8 exhibited insecticidal activities having at Ieast 80% mortality.
Test Example 7: White-backed Rice Planthopper Control Test
Rice seedlings grown in pots were subjected to the foliar application of solutions of the inventive compounds at a predetermined concentration prepared to 50% acetone/water (containing 0.05% Tween 20). The treated seedlings were air dried, following which second-instar 105
larvae were released onto the seedlings. The seedlîngs and larvae were then held in an incubation chamber at 25°C (16-hour period of light, 8-hour dark period). Four days after released, the numbers of live and dead insects were counted, and the mortality was calculated from the following formula, This was a two-replication test.
Mortality (%) = [number of dead insects/(number of live insects + number of dead insects)] x 100
From these results, with 100 ppm foliar application, Compound 1 exhibited an insecticidal activity having at least 80% mortality.
Test Example 8: Green Rice Leafhopper Control Test
Rice seedlings grown in pots were subjected to the foliar application of solutions of the inventive compounds at a predetermined concentration prepared to 50% acetone/water (containing 0,05% Tween 20). The treated seedlings were air dried, following which second-instar larvae were released onto the seedlings. The seedlings and larvae were then held in an incubation chamber at 25°C (16-hour period of light, 8-hour dark period). Four days after released, the numbers of live and dead insects were counted, and the mortality was calculated from the following formula. This was a two-replication test.
Mortality (%) = [number of dead insects/(numberof live insects + number of dead insects)] χ 100
From these results, with 100 ppm foliar application, Compounds 1 and 212 exhibited insecticidal activities having at least 80% mortality.
Test Example 9: Greenhouse Whitefly Control Test
Adult greenhouse whiteflies were released onto cucumber plants grown in pots, and allowed to laid eggs ovemight. One day after the start of oviposition, the adults were removed, and the plants and eggs were held in an incubation chamber at 25°C (16- hour period of light, 8hour dark period). Three days after the end of oviposition, leaf dises 2.0 cm in diameter were eut from the cucumber plants and, after confirming oviposition thereon, the leaf dises were sprayed with solutions of the inventive compounds at a predetermined concentration prepared to 50% acetone/water (containing 0.05% Tween 20). After spraying, the treated leaf dises were held in an incubation chamber at 25°C (16-hour period of light, 8-hour dark period). Fourteen days after
106 spraying, the numbers of live and dead insects were counted, and the mortality was calculated from the following formula. This was a two-replication test.
Mortality (%) = [(number of oviposited eggs - number of live insects)/number of oviposited eggs] x 100
From these results, with 100 ppm foliar application, Compounds 212, 229 and 230 exhibited high insecticidal activities having at least 80% mortality.
With foliar application at 20 ppm, Compound 213 exhibited a high insecticidal activity having at least 80% a mortality.
Test Example 10-1 : Western FlowerThrips Control Test
Leaf dises 2.8 cm in diameter were eut from bean plants grown in pots, and these were sprayed with solutions of the inventive compounds at a predetermined concentration prepared to 50% acetone/water (containing 0.05% Tween 20). The treated leaf dises were air dried, following which first-instar larvae were released onto the dises. The leaf dises and larvae were then held in an incubation chamber at 25°C (16-hour period of light, 8-hour dark period). Three days after released, the numbers of live and dead insects were counted, and the mortality was calculated from the following formula. This was a two-replication test.
Mortality (%) = [number of dead insects/(number of live insects + number of dead insects)] x 100
From these results, with 500 ppm foliar application, Compounds 49, 50, 85, 86, 90, 91, 93, 94, 104, 107, 108, 114, 128, 131, 135, 137, 140, 141, 144, 145, 146, 147, 152, 167, 170, 171, 172, 176, 181, 182, 183, 184, 186, 189, 190, 193, 196, 199, 200, 208, 211, 212, 222, 226, 227, 229, 230, 231,237, 240, 242 and 243 exhibited high insecticidal activities having at least 80% mortaiity. With 200 ppm foliar application, Compounds 1, 2, 3, 6, 7, 8, 9 and 10 exhibited high insecticidal activities having at least 80% mortality.
Test Example 10-2: Western Fiower Thrips Control Test
Leaf dises 2.8 cm in diameter were eut from bean plants grown in pots, and these were sprayed with solutions of the inventive compounds at a predetermined concentration prepared to 50% acetone/water (containing 0.05% Tween 20). The treated leaf dises were air dried, following which first-instar larvae were released onto the dises. The leaf dises and larvae were then held in
107 an incubation chamber at 25°C (16-hour period of light, 8-hour dark period), Three days after released, the numbers of live and dead insects were counted, and the mortality was calculated from the following formula, This was a two-replication test,
Mortality (%) = [number of dead insects/(number of live insects + number of dead insects)] χ 100
From these results, with 100 ppm foliar application, Compounds 2, 3, 6, 7, 8, 9, 10, 90, 91, 104,128,137,186,193, 212, 213, 216 and 238 exhibited high insecticidal activities having at least 80% mortality.
Test Example 11: Rice Leaf Bug Control Test
Wheat seedling shoots four days after sowing were immersed for 30 seconds in solutions of the inventive compounds at a predetermined concentration prepared to 50% acetone/water (containing 0.05% Tween 20). The treated seedlings were air-dried, then each was placed in a glass cylinder and two second-instar rice leaf bug larvae were released within the same glass cylinder. Following release ofthe insects, the tube was capped and held in an incubation chamber at 25°C (16-hour period of light, 8-hour dark period). In order to supply water to the wheat plant during the test, the plant was allowed to take up water from below the glass cylinder. Three days after released, the numbers of live and dead insects were counted, and the mortality was calculated from the following formula.
Mortality (%) = [number of dead insects/(number of live insects + number of dead insects)] x 100
From these results, with 50 ppm foliar application, Compounds 132, 141, 144, 183, 184, 189, 190, 192, 193, 194, 212, 227, 229, 230, 231, 233, 236, 239, 242 and 243 exhibited high insecticidal activities having at least 80% mortality.
Test Example 12: Brown-Winged Green Bug Control Test
Young apples that had been collected in the field were sprayed with solutions of the inventive compounds at a predetermined concentration prepared to 50% acetone/water (containing 0.05% Tween 20). The treated fruits were air-dried, placed in plastic cups and two adult brown-winged green bugs were released into each cup. Following release of the insects, the fruits and insects were held in an incubation chamber at 25°C (16-hour period of light, 8-hour dark
108
period). Six days after released, the numbers of live and dead insects were counted, and the mortality was calculated from the following formula.
Mortality (%) = [number of dead insects/fnumber of live insects + number of dead insects)] χ 100
From these results, with 50 ppm foliar application, Compound 212 exhibited a high insecticidal activity having at least 80% mortality.
Test Example 13: Rice Leaf Beetle Control Test
The inventive compounds prepared to a predetermined concentration in acetone were locally applied in an amount of 1 pL (per insect) to the backs of field-collected adult beetles using a microsyringe. Following chemical treatment, the beetles were transferred to rice seedlings, with five beetles being placed on each plant, and the seedlings and beetles were held in an incubation chamber at 25°C (16-hour period of light, 8-hour dark period). Forty-eight hours after treatment, the numbers of live and dead insects were counted, and the mortality was calculated from the following formula.
Mortality (%) = [number of dead insects/(number of live insects + number of dead insects)] χ 100
From these results, at a dosage of 0.5 pg/insect, Compounds 1, 8 and 212 exhibited high insecticidal activities having at least 80% mortality.
Test Example 14: House Fly Control Test
The inventive compounds prepared to a predetermined concentration in acetone were applied in an amount of 1 pL (per insect) to the backs of adult female flies raised indoors. Following chemical treatment, the flies were transferred to plastic cups, with five flies being placed in each cup, and held in an incubation chamber at 25°C (16-hour period of light, 8-hour dark period). Twenty-four hours after treatment, the state of knockdown among the flies was observed, and the knockdown rate was calculated from the following formula. The test was carried out as two réplications.
Knockdown rate (%) = [number of knocked down insects/fnumber of live insects + number of knocked down insects)] χ 100
From these results, at a dosage of 2 pg/insect, Compounds 33, 212, 213, 214 and 216 exhibited high insecticidal effects having a knockdown rate of at least 80%,
109
Root Immersion Treatment Test
Test Example 15: Small Brown Planthopper Control Test
Wheat seedling roots 48 hours after sowing were treated with solutions of the inventive compounds at a predetermined concentration prepared to 10% acetone/water, After allowing the roots to absorb the chemical for 72 hours, ten second-instar small brown planthopper larvae were released onto each seedling, The treated seedlings and larvae were then held in an incubation chamber at 25°C (16-hour period of light, 8-hour dark period). Four days after released, the numbers of lîve and dead insects were counted, and the mortality was calculated from the following formula, The test was carried out as two réplications,
Mortality (%) = [number of dead rnsects/(number of live insects + number of dead insects)] x 100
From these results, at a dosage of 20 pg/seedling, Compounds 212, 213, 215, 216, 222, 223, 226, 227, 228, 230, 231, 233, 234, 235, 237, 212, 213, 214, 215, 216, 222, 223, 227, 228, 229, 231,233, 234, 235, 237, 238, 239, 240 and 241 exhibited high insecticidal activities having at least 80% mortality.
Soil Drenching Treatment Tests
Test Example 16: Small Brown Planthopper Control Test
Rice seedlings grown in pots were subjected to soil drenching treatment with solutions of the inventive compounds at a predetermined concentration prepared to 10% acetone/water. Three days following treatment, ten second-instar small brown planthopper larvae were released onto each seedling. The treated seedlings and larvae were then held in an incubation chamber at 25°C (16-hour period of light, 8-hour dark period). Three days after released, the numbers of live and dead insects were counted, and the mortality was calculated from the following formula. The test was carried out as two réplications.
Mortality (%) = [number of dead insects/(number of live insects + number of dead insects)] x 100
From these results, at a dosage of 0.05 mg/seedling, Compounds 212, 227, 229, 231, 233, 237, 238, 239, 242 and 243 exhibited high insecticidal activities having at least 80% mortality, and at a dosage of 0.005 mg/seedling, Compound 212 exhibited a high insecticidal activity having 95% mortality.
110
J | Test Example 17: Whîte-backed Rice Planthopper Control Test i Rice seedlings grown in pots were subjected to soi! drenching treatment with solutions of i
the inventive compounds at a predetermined concentration prepared to 10% acetone/water.
Three days following treatment, ten second-instar whîte-backed rice planthopper larvae were released onto each seedling. The treated seedlings and larvae were then held in an incubation chamber at 25°C (16-hour period of light, 8-hour dark period). Three days after released, the numbers of live and dead insects were counted, and the mortality was calculated from the following formula. The test was carried out as two réplications.
Mortality (%) = [number of dead rnsects/fnumber of live insects + number of dead insects)] x 100
From these results, at a dosage of 0.05 mg/seedling, Compounds 212, 227, 229 and 231 exhibited high insecticidal activities having at least 80% mortality.
Test Example 18: Rice Water Weevil Control Test
Rice seedlings grown in pots were subjected to soil drenching treatment with solutions of the inventive compounds at a predetermined concentration prepared to 10% acetone/water. Two days after treatment, five adult rice water weevils were released onto each seedling. The seedlings and insects were then held în an incubation chamber at 25°C (16-hour period of light, 8- i i
hour dark period). Three days after released, the numbers of live and dead insects were counted, and the mortality was calculated from the following formula. The test was carried out as two réplications.
0 Mortality (%) = [number of dead insects/(number of live insects + number of dead insects)] x 100| i From these results, at a dosage of 0.1 mg/seedling, Compound 212 exhibited a high[ i insecticidal activity having at least 80% mortality.J
Effects on Pests Having a Low Susceptibility to Insecticidesj [
Test Example 19: Brown Rice Planthopper Control Test[
Rice seedlings grown in pots were subjected to soil drenching treatment with solutions of the inventive compounds at a predetermined concentration prepared to 10% acetone/water.[ t
Three days after treatment, ten second-instar brown rice planthopper larvae having a lowy ï
susceptibility to insecticides were released onto each seedling. The seedlings and insects were
111 then held in an incubation chamber at 25°C (16-hour period of light, 8-hour dark period), Three days after released, the numbers of live and dead insects were counted, and the mortality was calculated from the following formula. The test was carried out as two réplications.
Mortality (%) = [number of dead insects/(number of live insects + number of dead insects)] x 100
The pests used in this test were insects that had been raised indoors for successive générations over a long period of tîme (susceptible line), and insects that had been raised indoors for successive générations after being collected (I) in 2007 within Kumamoto Préfecture and (II) in 2005 within Fukuoka Préfecture (field-collected lines).
As a resuit, Compound 212 exhibited a mortality of 100% on ail the lines in treatment at a 10 dosage of 0.05 mg/seedling, and exhibited a mortality of at least 90% on ail the lines at a dosage of 0.005 mg/seedling. By contrast, when applied at a dosage of 0.05 mg/seedling, imidacloprid exhibited a mortality of 100% in the susceptible line and mortalities of 40% on (I) and 60% on (II).
From these results, Compound 212 exhibited a high insecticidal activîty against brown rice planthoppers having a low susceptibility to imidacloprid,
Test Example 20: Small Brown Planthopper Control Test
Rice seedlings grown in pots were subjected to soil drenching treatment with solutions of the inventive compounds at a predetermined concentration prepared to 10% acetone/water. Three days after treatment, ten second-instar small brown planthopper larvae having a low susceptibility to insecticides were released onto each seedling. The seedlings and insects were 20 then held in an incubation chamber at 25°C (16-hour period of light, 8-hour dark period). Three days after released, the numbers of live and dead insects were counted, and the mortality was calculated from the following formula. The test was carried out as two réplications.
Mortality (%) = [number of dead insects/(number of live insects + number of dead insects)] x 100
The pests used in this test were insects that had been raised indoors for successive 25 générations over a long period of time (susceptible line), and insects that had been raised indoors for successive générations after being collected in 2006 within Kumamoto Préfecture (fieldcollected line).
112
1 i ί i •I 1 1 1 Ί | As a resuit, Compound 212 exhibited a mortality of 100% on both lines at a dosage of 0,01 mg/seedling, and exhibited a mortality of at least 90% on both lines at a dosage of 0,005 mg/seedling, By contrast, when applied at a dosage of 0.01 mg/seedling, imidacloprid exhibited a mortality of 100% in the susceptible line and a mortality of 50% in the field-collected line. When |
5 ! 1 ! i 1 i | applied at a dosage of 0.01 mg/seedling, fipronil exhibited a mortality of 100% in the susceptible line and a mortality of 70% in the field-coiiected line. From these results, Compound 212 exhibited a high insecticidal activity against small brown planthoppers having a low susceptibility to imidacloprid and fipronil. Test Example 21: In Vitro Metabolic Tests of Compound 212 and Imidacloprid Usinq House FIv |
i 10 | Crude Enzyme Extract As mentioned in Pest Management Science, 59(3), 347-352 (2003) and the Journal of Pesticide Science, 29(2), 110-116 (2004), imidacloprid is known to be inactivated by incurring oxidative metabolism, which is thought to be one mechanism of acquiring résistance to this agent. The following experîment was carried out to confirm the effects in pests which hâve acquired such |
15 | résistance. An amount of 10 mL of a potassium phosphate buffer solution (pH 7.4, containing 1 mM EDTA) was added to adult house flies (0.645 g), and the flies were thoroughly homogenized in a Physcotron (Niti-On Medical and Physical Instruments Manufacturing Co.). The homogenate was then centrifuged at 10,000 g for 15 minutes. The resulting supernatant was additionally |
20 | centrifuged at 100,000 g for 60 minutes, giving a precipîtate. The precipîtate was dissolved in 1 mL of a potassium phosphate buffer, and the resulting solution was used as the crude enzyme extract. The enzyme extraction operations were ail carried out on ice or at 4°C. The reagents were mixed in the following proportions within a 1.5 mL tube, and the reaction was effected at 25°C for 40 hours. Following the reaction, 1 mL of acetone was added |
25 | and the mixture was stirred, following which the precipîtate that formed was centrifuged at 12,000 rpm for 5 minutes. The supernatant acetone was distilled off, and the precipîtate was injected into a liquid chromatograph-mass spectrometer (LC/MS) and analysis was carried out. Above crude enzyme extract: 300 pL |
113
DMSO solution of compound: 5pL
Glucose 6 phosphorîc acid solution: 5 pL
NADP+ solution: 5 pL
Glucose 6 phosphorîc acid dehydrogenase solution: 5 pL
Potassium phosphate buffer (pH 7.4, containing 1 mM EDTA): 180 pL «Analysis Conditions>
Column: Capcell Pak C18MG
Mobile phase composition:
to 3 minutes: 85% water, 5% acetonitrile, 10% aqueous formic acid solution (0.1% v/v) to 30 minutes: 85 25% water, 5 -> 65% acetonitrile, 10% aqueous formic acid solution (0.1% v/v)
30.1 to 36 minutes: 90% acetonitrile, 10% aqueous formic acid solution (0.1% v/v)
Column température: 40°C
Flow rate: 0.35 mL/min
Injected amount: 100 pL
UV wavelength: Compound 212: 325 nm
Imidacloprid: 300 nm
As a resuit, the sum of the surface area percentages for the métabolites was 0.08% in the case of Compound No. 212 and 2.55% in the case of imidacloprid, indicating that the amount of métabolites of Compound No. 212 was lower than the amount of métabolites of imidacloprid. The above results suggest that Compound 212 can effectively control even résistant pests which metabolically deactivate imidacloprid.
Control Effects on Animal Parasitîc Pests
Test Example 21 : Tick (Haemaphysalis longicomis) Control Test
Glass vials having a capacity of 4 mL were each filled with 30 pL of an acetone solution containing 200 ppm or 10 ppm of the respective compounds. These filled vials were placed on a shaker and air-dried while being spun, thereby forming dry films of the compounds on the inner walls of the vials. After the vials had been dried for at least 24 hours, ten larval ticks
114 (Haemaphysalis longicomis) were released into each vial, following which the vials were capped.
The vials were then left at rest in an incubation chamber at 25°C, 85% humidity and complété darkness. One day after released, the numbers of live and dead ticks were counted, and the mortality was calculated from the following formula. This test was carried out as two réplications.
Mortality (%) = [number of dead ticks/(number of live ticks + number of dead ticks)] x 100
As a resuit, at a dosage of 200 ppm, Compounds 1, 2, 3, 6, 7, 8, 9, 10, 11, 15, 18, 19, 20,
21,39, 41, 42, 43, 45, 49, 50, 53, 58, 61, 72, 86, 88, 89, 91, 92, 93, 94, 96, 97, 101, 102, 105, 107, 108, 109, 111, 112, 114, 115, 119, 120, 130, 131, 132, 135, 137, 138, 165, 196, 199, 200, 204, 212, 213 and 214 exhibited tickcidal effects having ai least 80% mortality.
At a dosage of 10 ppm, Compounds 1, 2, 3, 6, 7, 8, 9, 10, 18, 19, 42, 43, 58, 88, 91, 93,
94,165,196, 208, 212, 213 and 214 exhibited tickcidal effects having at least 80% mortality.
In similar tests, the mortality from treatment with 10 ppm of imidacloprid was 4%.
Test Example 22: Tîck (Haemaphysalis longicomis) Control Test on Body Surface of Mouse
Ventral fur was shaved from an area having a diameter of about 2 cm in mice (ICR, 515 week-old males), and a 15 mL polystyrène conical tube eut to a length of about 1.5 cm was attached to the shaved area using instant glue.
An amount of 20 pL of a 1,000-fold dilution of the pest control agent prepared in the same way as in Formulation Example 11 was added dropwise onto the body surface of the mice within the attached tube. After the solution was allowed to dry thoroughly, ten or more larval ticks (Haemaphysalis longicomis) were released into the tube, which was then capped. Three days after released, the numbers of live and dead ticks were counted, and the mortality was calculated from the following formula.
i
Blood-feeding inhibition (%) = 100 - [number of feeding ticks/(number of live ticks + number of| t
dead ticks)] χ 100î £
As a resuit, Cornpound 212 below exhibited a blood-feeding inhibition of 91%.[ i
Test Example 23: Effects on Canine HeartwormJ
I
The activities of the compounds were evaluated based on changes in the motility off microfilariae in canine heartworm. The respective compounds were dissolved in a RPMI1640[
115 liquid culture medium to a concentration of 3.13 ppm, following which about 20 canine heartworm microfilariae were placed in each culture fluid and cultured at 37°C. The motility of the canine heartworm microfilariae was observed for 48 hours following the start of culturing, and the activities of the compounds were rated according to the following criteria.
Criteria A: At Ieast two-thirds of the heartworms died
B: Substantially ail the heartworms were affected in some way, or at
Ieast one-third died
C: No influence, or less than one-third of the heartworms died
As a resuit, at a dosage of 3.13 ppm, Compounds 1, 2, 6, 7, 8, 9 and 10 had a m icrofi laricidal effect at or higher than level B.
The microfilaricidal effects of Compound Nos. 212, 227, 229, 231, 237, 238, 239, 242 and 243, which are especially preferred compounds according to the invention, are summarized in Table 12.
116
Table 12
TJ P G ta ta 5 £ · d « | ta ® O O» ÇH fi r) | 100 | ||||||||||
' M'...... « V | OH | o Ck w | fi «J | O o —| | ||||||||
H 1 T 1 s | O rt | o o w | O O rd | Q O rd | <· u> | |||||||
U 5> ü ta l· rt P φ £ ta P w X1 W H rt <J | Q m | o o rd | O o rt | Q fi rd | O O rd | fi O rt | O o rd | O o rt | fi O rt | |||
Ο I Æ Ό h ta fi p c; i? ta 5 V fi k, o p £ o u ta u ν Ώ h M -d rt Q V fi ta n? P dE k h h | .3 8 s | Q * CM O | Q C 1-4 | |||||||||
A Ui rj ΓΟ j* >» ·* % g ? Ti u Ü | o ► <O O | O O 1-f | ||||||||||
P d | ο (Ό r o o | o U) | ||||||||||
ê ta | ° w o w | o Ul | ||||||||||
ϋ e | g 4J | ° H o m | o o rt | |||||||||
r. ta | c- & h | °. o w | o Q 1-4 | 40 CM | m CM | |||||||
Pr ta | a ν | 1 in o « | O O rt | |||||||||
m 5 | S ta 3 ? | CM - K“r O | O O rt | Ml i | o Q rd | CD O rt | ||||||
1 s | 8 fi | LO O | Q O H | O <1 | o fi rt | m CM | fi 40 | fi O rt | O O rt | fi O rt | O d rt | |
u 4) ta | P ta | CM | O O rt | n t | e Q rd | m v- | O o rd | o c? rt | O O rt | O a rt | O fi rt | |
M ta | 1 | O CM | o σ 1-4 | o o rd | o o rt | O O rt | d Q rt | a o rt | O o rt | O O rt | ||
C ta | & fi d ‘J | ° w o => | tr» CD | |||||||||
u S u s |ê τί g a > fi â | 0,0 05 | Ml σ» | 40 Γ | O o> | o r | m en | O d | |||||
A § o M ü | O ’ rt O | o o rd | O o rt | fi fi K | σ a rd | 40 Γ | o o rt | O fi | ||||
3 13 o 4Λ | O * Ό d | O o rd | o σ* | o o rd | O O rd | o o rt | fi fi rt | o d rt | O O rt | O a rt | ||
Ή d | § | fi «-> . fi a K | m P | |||||||||
g ifl | P 5’î 1 | OH Ό rt | o o rt | |||||||||
<n | Q O rt | o o rd | S | |||||||||
CD o rt | fi O rt | |||||||||||
ε >- » f i> | o CM | m w | ||||||||||
H ί H ΐ: E g rt fi rt fi ta sV <*a pU rl H | O o rd | o o rt | r» u> | a Ui | m m | m σ. | fi €-· | |||||
O O ul | o o rt | o œ | a o rd | m fi | O m | fi | O O rt | Q O rt | ||||
T5 h rt ta fi P A ta ta | i | CM • r» i—l | o o i-4 | ch | O CO | ** r- | o o rt | <1 fi | O œ | |||
A | ui | m m | fi Q t-4 | U) (Λ | a o rt | CD O rt | o <e | a o rt | ||||
« fi ta s 7 e | o *4 | o Çj | fi O w | fi o rt | o o H | O O rt | <1 fi | fi O rt | fi fi rt | fi o rt | ||
P ta rt M fi O H <J >M | ta u rt | Q O rt | o o rd | O o rd | O o H | O o rt | fi O rd | fi O rt | O O rt | O O rt | ||
A & | o o io | O Q w | O o rd | D O rd | O o rd | O O rd | a o rt | |||||
fi ë 11< v s gï i e | fi ta | o o i-4 | O fi | to n | a i*1 | O | ||||||
! g S u Ij υ HH | r—t O Cm | O O 4ΓΪ | O o Ή | o o rd | a o rd | O | en fi | O | O fi | O fi | d rd | |
U 5 fi JL t» | O CM | O Q •rt | O O rd | d ta1 | O O rt | o o rt | O Ό | d o rt | ||||
f s|s s g 8 8 g | O o rd | O o rt | O O rd | O O rd | O O rt | O O rt | O a rt | d O rd | d d rt | O O rt | ||
§ ne *{ -à ............. | O O jo | O O i—L | O O rd | O O rd | O O rt | fi O . .... | O o rt | fi fi rt | ||||
g Bt3 û | CM rt CM | ΓΟΗ <M | <Λ CM 04 | rt fi 'N | l d CM | CO σι Oi | fi fi 04 | CM M* <M | fi M CM |
117
In addition, the effects against pests having a low susceptibility to insecticides by Compound Nos. 212, 227, 229, 231, 237, 238, 239, 242 and 243, which are especially preferred compounds according to the invention, are summarized in Table 13.
118
Table 13
Small brown planthopper (rice soil drenching) | Brown rice planthopper, Kumamoto low susceptibility (rice soi! drenching) | |||||
0,05 mg/pot | 0,01 mg/pot | 0.005 mg/pot | 0,002 mg/pot | 0,05 mg/pot | 0.005 mg/pot | |
212 | 100 | 100 | 95 | 85 | 100 | 90 |
227 | 90 | 100 | 75 | |||
229 | 100 | 100 | 3Q | |||
231 | 100 | 100 | 70 | |||
237 | 100 | 75 | ||||
238 | 100 | 100 | 33 | |||
239 | 100 | eo | 3ΰ | |||
242 | 100 | |||||
2 4 3 | 100 | |||||
Comparative Example 2 (Patent Document 6, Compound 23) | 20 | |||||
Comparative Example 3 {Patent Document 4, Compound 2) | 10 | |||||
C ompa native Ex ample 4 (Patent Document 5, Example 4} | 100 | 20 | 45 | |||
Comparative Example 5 (Patent Document 5, Example 3) | 95 | 15 | 25 | |||
Comparative Example £ (Patent Document 5, Example 5) | 100 | 20 | 25 | |||
Comparative Examp le 7 (Patent Document 5, Exemple 7) | 63 | 5 | 20 | |||
Comparative Example 8 {Patent Document 5, Example 6) | 20 |
119 [Industrial Applicability]
The amine dérivatives of the présent invention hâve excellent insecticidal effects against the diamondback moth, the common cutworm, the cotton aphid, the small brown planthopper, the brown rice planthopper, the green rice leafhopper, the hard-bodied tîck Haemaphysalis longicomis, 5 and many other pests. Also, they are able to exhibit strong effects even against insects having a low insecticide susceptibility, particularly delphacid planthoppers. Moreover, they are effective also in treating soil and plant cultivation media and, because they are able to mrtigate the chances of worker exposure to chemicals, can be safely used to control pests. Therefore, the présent invention is capable of being highly bénéficiai in the field of pest control.
Claims (12)
- [CLAIMS] [Claim 1] A pest control agent comprising at least one compound of the following formula (I) or a sait thereof [Chem. 1]R2 (D (wherein Ar is a phenyl group which may be substituted or a 5- or 6-membered heterocycle which may be substituted;R] is a hydrogen atom or a C,æ alkyl group;R2 is a Cve alkylcarbonyl group in which the alkyl moiety may be substituted with a halogen atom, a C-|.B alkyloxycarbonyl group in which the alkyl moiety may be substituted with a halogen atom, a C^ alkylsuffonyl group in which the alkyl moiety may be substituted with a halogen atom, CONR6R7, a C^ Ο,Ο'-alkylphosphoryl group in which the alkyl moiety may be substituted with a halogen atom, a cyano group, a formyl group or a nitro group;R3 is a C-i-8 alkylene group which may be substituted with a halogen atom, a C2.3 alkenylene group which may be substituted with a halogen atom, a C2.e alkynylene group which may be substituted with a halogen atom, a phenylene group which may be substituted, or a 5- or 6-membered heterocyclic divalent group which may be substituted; andR4 is a hydrogen atom, a cyano group, a phenyl group which may be substituted, a 3- to 8membered cyclic alkyl group which may be substituted, a 3- to 8-membered heterocyclic which may be substituted, a halogen atom, OR5, OCOR5, OCOORS, COR5, COOR5, SR5l SOR5, SO2R6, N-CO-ORb, N-CO-SRb, N-CS-ORa, N-CS-SRg, N-O-CO-Re, O-CO-Ra, O-CO-OR3, O-CO-SRe, OCS-OR8, O-CS-SR8i S-CS-ORs, S-CS-SRg, S-CO-ORB, S-CO-SRe, S-CS-RB, NR9R1Q, O-CONRgRio, O-CS-NRgR10, S-CO-NR9R10 or S-CS-NR9R10,121 wherein R5 is a Cm alkyl group which may be substituted with a halogen atom, an aryl group which may be substituted with a halogen atom or an aralkyl group which may be substituted with a halogen atom;Rb and R? are each independently a hydrogen atom or a Cm alkyl group which may be substituted with a halogen atom;Ra is a Cm alkyl group which may be substituted, the substituent which may be substituted being a halogen atom, a alkyloxycarbonyl group, a Cm alkylcarbonyl group, a benzoyl group which may be substituted with a halogen atom or a Cm alkyl group which may be substituted with a halogen atom, a Cw alkyloxy group or a Cm alkylthio group;R9 and Ri0 are each independently a hydrogen atom, a formyl group, a C-= alkyl group which may be substituted with a halogen atom, a Cm alkylcarbonyl group in which the alkyl moiety may be substituted with a halogen atom, a Cm alkylcarbonyloxy group in which the alkyl moiety may be substituted with a halogen atom, a phenyl group which may be substituted (the substituent which may be substituted being a halogen atom, a Cm alkyl group which may be substituted with a halogen atom, or a Cm alkyloxy group which may be substituted with a halogen atom), or a benzyl group which may be substituted (the substituent which may be substituted being a halogen, a Cm alkyl group which may be substituted with a halogen or a Cm alkyloxy group which may be substituted with a halogen), R0 and R10 together form a ring and dénoté a 3- to 10-membered heterocycloalkyl group containing at least one nitrogen atom, or N, R9 and R10 together form a ring and dénoté a 5- or 6-membered aromatic heterocycle containing at least one nitrogen atom, andN, Rz, R3 and R4 may together form a group of formula (E) wherein Y is a hydrogen atom, a halogen atom, a hydroxyl group, a Cm alkyl group which may be substituted with a halogen, a Cm alkyloxy group which may be substituted with a halogen, a122I >cyano group, a formyl group or a nitro group, and is a alkyl group substituted with a halogen or a Cm alkyloxy group which may be substituted with a halogen;with the proviso that if Ar is a 2,6-dichloro-4-pyridyl group, then R2 is not a CM alkyloxycarbonyl group in which the alkyl moiety may be substituted with a halogen atom).
- [Claim 2] The pest control agent according to claim 1, wherein Ar in formula (I) is a 6-chloro3-pyridyl group or a 5-chloro-3-thiazolyl group.
- [Claim 3] The pest control agent according to claim 1 or 2, wherein R2 in formula (I) is a Cm alkylcarbonyl group in which the alkyl moiety may be substituted with a halogen atom, a Cm alkylsulfonyl group in which the alkyl moiety may be substituted with a halogen atom, or a cyano group.
- [Claim 4] The pest control agent according to claim 1, wherein the compound of formula (I) is a compound of formula (le) below.[Chem. 3]O (le)
- [Claim 5] The pest control agent according to claim 4, wherein R4e in formula (le) is a Cm alkyl group substituted with a halogen atom.
- [Claim 6] The pest control agent according to claim 4, wherein Y in formula (le) is a hydrogen atom or a halogen atom.
- [Claim 7] The pest control agent according to claim 4, wherein R4e in formula (le) is a Cm alkyl group substituted with a halogen atom, and Y is a hydrogen atom or a halogen atom.
- [Claim 8] The pest control agent according to claim 4, wherein the compound of formula (le) is a compound selected from the group consisting of N-[1-((6-chloropyridin-3-yl)methyl)pyridin2(1 H)-yridene]-2,2,2-trrfluoroacetamide, N-[1 -((6-ch)oro-5-fluoropyridin-3-yl)methyl)pyridin-2(1 H)ylidine]-212,2-trifluoroacetamide, N-[1-((6-fluoropyridîn-3-yl)methyl)pyridin-2(1H)-ylidene]-2,2,2trifluoroacetamide, N-[1-((6-bromopyridin-3-yl)methyl)pyridin-2(1H)-ylidene]-2,2,2123 trifluoroacetamide,N-[1-(1-(6-chloropyridin-3-yl)ethyl)pyridin-2(1 H)-ylidene]-2,2,2trifluoroacetamide, N-D-^e-chloropyridin-S-ylJmethyOpyridin^ll-O-ylÎdenel-Z^-dÎfluoroacetamide, 2-ch loro-N-[ 1 -( (6-c h I o ro py ri d i n-3-y I ) methy I) py rid i n-2 ( 1 H)-y l)dene]-2,2-dif I uoroacetam ide, N-[ 1 -((2chloropyrimidin-5-yl)methyl)pyridin-2(1 H)-ylidene]-2,2,2-trifluoroacetamide and N-[1 -((6chloropyridin-3-yl)methyl)pyridin-2(1H)-ylidene]-2,2,3,3,3-pentafluoropropanamide.
- [Claim 9] The pest control agent according to any one of claims 1 to 8, which has a pest control activity on at least one type of pest selected from the group consisting of lepidopterous pests, hemipterous pests, thysanopterous pests, dipterous pests, coleopterous pests, animal parasitic fleas and ticks, and canine heartworms.
- [Claim 10] The pest control agent according to any one of claims 1 to 9, wherein the pest is an agricultural/horticultural pest or an animal parasitic pest.
- [Claim 11] The pest control agent according to any one of claims 1 to 9, wherein the pest is a pesticide-resistant pest.
- [Claim 12] An amine dérivative of the following formula (I) or a sait thereof [Chem. 4]Ri (D (wherein Ar is a phenyl group which may be substituted or a 5- or 6-membered heterocycle which may be substituted;Ri is a hydrogen atom or a CM alkyl group;R2 is a Cve alkylcarbonyl group in which the alkyl moiety may be substituted with a halogen atom, a C^ alkyloxycarbonyl group in which the alkyl moiety may be substituted with a halogen atom, a C1Æ alkylsulfonyl group in which the alkyl moiety may be substituted with a halogen atom, CONR6R7, a Ο,Ο’-alkylphosphoryl group in which the alkyl moiety may be substituted with a halogen atom, a cyano group, a formyl group or a nitro group;124R3 is a Ci-s alkylene group which may be substituted with a halogen atom, a C2.a alkenylene group which may be substituted with a halogen atom, a C2^ alkynylene group which may be substituted with a halogen atom, a phenylene group which may be substituted, or a 5- or 6-membered heterocyclic divalent group which may be substituted; andR4 is a hydrogen atom, a cyano group, a phenyl group which may be substituted, a 3- to 8membered cyclic alkyl group which may be substituted, a 3- to 8-membered heterocyclic which may be substituted, a halogen atom, ORS, OCOR6, OCOOR6, CORS, COOR5, SR5, SOR5, SO2R5, N-CO-ORa, N-CO-SRa, N-CS-ORa, N-CS-SRa, N-O-CO-R0, O-CO-Re, O-CO-ORa, O-CO-SRa, OCS-ORa, O-CS-SRs, S-CS-ORa, S-CS-SR0I S-CO-ORa, S-CO-SRe, S-CS-Rs, NR9R1Df O-CONRgR10, O-CS-NR9R1Q, S-CO-NR3R10 or S-CS-NRgR-io;wherein R5 is a C-.e alkyl group which may be substituted with a halogen atom, an aryl group which may be substituted with a halogen atom or an aralkyl group which may be substituted with a halogen atom;Ra and R? are each independently a hydrogen atom or a CM alkyl group which may be substituted with a halogen atom;Ra is a Cj.6 alkyl group which may be substituted, the substituent which may be substituted being a halogen atom, a Cm alkyloxycarbonyl group, a CM alkylcarbonyl group, a benzoyl group which may be substituted with a halogen atom or a Cm alkyl group which may be substituted with a halogen atom, a C, < alkyloxy group or a CM alkylthio group;Rs and R10 are each independently a hydrogen atom, a formyl group, a C-t.s alkyl group which may be substituted with a halogen atom, a Cm alkylcarbonyl group in which the alkyl moiety may be substituted with a halogen atom, a Cm alkylcarbonyloxy group in which the alkyl moiety may be substituted with a halogen atom, a phenyl group which may be substituted (the substituent which may be substituted being a halogen atom, a Cm alkyl group which may be substituted with a halogen atom, or a Cm alkyloxy group which may be substituted with a halogen atom), or a benzyl group which may be substituted (the substituent which may be substituted being a halogen, a Cm alkyl group which may be substituted with a halogen or a Cm alkyloxy group which may be substituted with a halogen), R9 and R10 together form a ring and dénoté a 3- to 10-membered125 heterocycîoalkyl group contaîning at least one nitrogen atom, or N, Rg and R10 together form a ring ii and dénoté a 5- or 6-membered aromatic heterocycle contaîning at least one nitrogen atom; and if Ar is a pyridyl group which may be substituted or a pyrimidyl group which may be substituted, N, R2, R3 and R4 may together form a group of formula (E)5 [Chem. 5] wherein Y is a hydrogen atom, a halogen atom, a hydroxy! group, a alkyl group which may be substituted with a halogen atom, a Ci^ alkyloxy group which may be substituted with a halogen atom, a cyano group, a fomnyl group or a nitro group, and R^ is a alkyl group which may be1 o substituted with a halogen or a alkyloxy group which may be substituted with a halogen;with the proviso that if Ar is a 2,6-dichloro-4-pyridyl group, then R2 is not a C14i alkyloxycarbonyl group in which the alkyl moiety may be substituted with a halogen atom, and if Ar!is a 6-chloro-3-pyridyl group, then Ri is not a hydrogen atom, Y is not a 5-methyl group and R4e isj not a trifluoromethyl group).ï i15 [Claim 13] The amine dérivative or a sait thereof according to claim 12, wherein Ar in formulaI i(I) is a 6-chloro-3-pyridyl group or a 5-chloro-3-thiazolyl group.j [Claim 14] The amine dérivative or a sait thereof according to claim 12 or 13, wherein R2 in| iI i formula (I) is a C-^ alkylcarbonyl group in which the alkyl moiety may be substituted with a| halogen atom, a C^ alkylsulfonyl group in which the alkyl moiety may be substituted with a[ ii2 0 halogen atom, or a cyano group.ί [Claim 15] The amine dérivative or a sait thereof according to claim 12, wherein the[ compound of formula (I) is a compound of formula (le’) below.[Chem. 6]126 (wherein Ar' is a pyridyl group which may be substituted or a pyrimidyl group which may be substituted; Y is a hydrogen atom, a halogen atom, a hydroxyl group, a Cm alkyl group which may be substituted with a halogen atom, a Cm alkyloxy group which may be substituted with a halogen atom, a cyano group, a formyl group or a nitro group; and R4e is a Cm alkyl group substituted with a halogen or a Cm alkyloxy group which may be substituted with a halogen;with the proviso that if Ar’ is a 6-chloro-3-pyridyl group, then R, is not a hydrogen atom, Y is not a 5-methyl group and R4e is not a trifluoromethy] group), [Claim 16] The amine dérivative or a sait thereof according to claim 15, wherein R4e in formula (le1) is a Cm alkyl group substituted with a halogen atom, [Claim 17] The amine dérivative or a sait thereof according to claim 15, wherein Y in formula (le1) is a hydrogen atom or a halogen atom.[Claim 18] The amine dérivative or a sait thereof according to claim 15, wherein R4e in formula (le’) is a Cm alkyl group substituted with a halogen atom and Y is a hydrogen atom or a halogen atom.[Claim 19] The amine dérivative or a sait thereof according to claim 15, wherein the compound of formula (le’) is a compound selected from the group consisting of N-[1-((6chloropyridin-3-yl)methyl)pyridin-2(1H)-ylidene]-2,2,2-trifluoroacetamide, N-[1-((6-chloro-5fluoropyridin-S-yOmethylJpyridin^ilHJ-ylidine^^^-trifluoroacetamide, N-[1-((6-fluoropyridin-3yl)methyl)pyridin-2(1 H)-ylidene]-2,2,2-trifluoroacetamide, N-[1 -((6-bromopyridin-3yl)methyl)pyridin-2(1H)-ylidene]-2,2,2-trifluoroacetamide, N-[1-(1-(6-chloropyridin-3-yl)ethyl)pyridin2(1H)-ylidene]-2,2,2-trifluoroacetamide, N-[1-((6-chloropyridin-3-yl)methyl)pyridin-2(1H)-ylidene]2,2-difluorQacetamide, 2-chloro-N-[1-((6-chloropyridin-3-yl)methyl)pyridin-2(1H)-ylidene]-2,2difluoroacetamide, N-[1-((2-chloropyrimidin-5-yl)methyl)pyridin-2(1H)-ylidene]-2,2,2127 trifluoroacetamide and N-[1-((6-chloropyridin-3-yl)methyl)pyridin-2(1 H)-ylidene]-2,2,3,3,3pentafluoropropanamîde.[Claim 20] The amine dérivative or a sait thereof according to any one of claims 12 to 19, which has a pest control activity on at least one type of pest selected from the group consisting of 5 lepidopterous pests, hemipterous pests, thysanopterous pests, dipterous pests, coleopterous pests, animal parasitic fleas and ticks, and canine heartworms.[Claim 21] A method for controlling pests, comprising the step of using the pest control agent according to any one of claims 1 to 9 or the amine dérivative or a sait thereof according to any one of claims 12 to 20.10 [Claim 22] A method for controlling agricultural/horticultural pests, comprising the step of treating plant seeds, roots, tubers, bulbs, rhizomes, soil, a nutrient solution in nutriculture, a solid culture medium in nutriculture, or a carrier for growing plants, with the pest control agent according to any one of claims 1 to 9 or the amine dérivative or a sait thereof according to any one of claims 12 to 20, thereby inducing the compound to penetrate and translocate into the plants.15 [Claim 23] The method according to claim 21, wherein the pest is an agricultural/horticultural pest or an animal parasitic pest [Claim 24] The method according to claim 21, wherein the pest is a pesticide-resistant pest.
Applications Claiming Priority (1)
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JP2010-194584 | 2010-08-31 |
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OA16334A true OA16334A (en) | 2015-05-11 |
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