NO864763L - PESTICIDE 1- (4-PHENOXYPHENYL) -3-BENZOYLURINE INGREDIENTS AND THEIR PREPARATION. - Google Patents
PESTICIDE 1- (4-PHENOXYPHENYL) -3-BENZOYLURINE INGREDIENTS AND THEIR PREPARATION.Info
- Publication number
- NO864763L NO864763L NO864763A NO864763A NO864763L NO 864763 L NO864763 L NO 864763L NO 864763 A NO864763 A NO 864763A NO 864763 A NO864763 A NO 864763A NO 864763 L NO864763 L NO 864763L
- Authority
- NO
- Norway
- Prior art keywords
- compound according
- effective amount
- chlorine
- plague
- bromine
- Prior art date
Links
- 238000002360 preparation method Methods 0.000 title claims description 45
- 239000000575 pesticide Substances 0.000 title claims description 21
- -1 4-PHENOXYPHENYL Chemical class 0.000 title description 5
- 239000004615 ingredient Substances 0.000 title description 3
- 150000001875 compounds Chemical class 0.000 claims description 119
- 239000000460 chlorine Substances 0.000 claims description 36
- 229910052801 chlorine Inorganic materials 0.000 claims description 35
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 33
- 229910052794 bromium Inorganic materials 0.000 claims description 33
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 32
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 31
- 229910052739 hydrogen Inorganic materials 0.000 claims description 30
- 239000001257 hydrogen Substances 0.000 claims description 30
- 206010035148 Plague Diseases 0.000 claims description 29
- 241000607479 Yersinia pestis Species 0.000 claims description 29
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 24
- 229910052731 fluorine Inorganic materials 0.000 claims description 22
- 239000011737 fluorine Substances 0.000 claims description 21
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 229910052736 halogen Inorganic materials 0.000 claims description 16
- 150000002367 halogens Chemical class 0.000 claims description 16
- 150000002431 hydrogen Chemical class 0.000 claims description 13
- GYNAVKULVOETAD-UHFFFAOYSA-N n-phenoxyaniline Chemical compound C=1C=CC=CC=1NOC1=CC=CC=C1 GYNAVKULVOETAD-UHFFFAOYSA-N 0.000 claims description 7
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- 150000003672 ureas Chemical class 0.000 claims description 4
- KCHQIPPONLLUGU-UHFFFAOYSA-N 1-isocyanato-2-phenoxybenzene Chemical compound O=C=NC1=CC=CC=C1OC1=CC=CC=C1 KCHQIPPONLLUGU-UHFFFAOYSA-N 0.000 claims description 2
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims 3
- OBZIZFXJJFVLCZ-UHFFFAOYSA-N 2-chloro-n-[[3-chloro-4-(2,4-dichlorophenoxy)-2,5-dimethylphenyl]carbamoyl]benzamide Chemical group CC=1C(Cl)=C(OC=2C(=CC(Cl)=CC=2)Cl)C(C)=CC=1NC(=O)NC(=O)C1=CC=CC=C1Cl OBZIZFXJJFVLCZ-UHFFFAOYSA-N 0.000 claims 1
- JDGHJIZTUDDDGS-UHFFFAOYSA-N N-[[3-chloro-4-(2,4-dibromophenoxy)-2,5-dimethylphenyl]carbamoyl]-2-fluorobenzamide Chemical group CC=1C(Cl)=C(OC=2C(=CC(Br)=CC=2)Br)C(C)=CC=1NC(=O)NC(=O)C1=CC=CC=C1F JDGHJIZTUDDDGS-UHFFFAOYSA-N 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- WSJKRRDERQFKQB-UHFFFAOYSA-N n-[[3-chloro-4-(2,4-dibromophenoxy)-2,5-dimethylphenyl]carbamoyl]-2,6-difluorobenzamide Chemical group CC=1C(Cl)=C(OC=2C(=CC(Br)=CC=2)Br)C(C)=CC=1NC(=O)NC(=O)C1=C(F)C=CC=C1F WSJKRRDERQFKQB-UHFFFAOYSA-N 0.000 claims 1
- IWCVRYBCFFEJIY-UHFFFAOYSA-N n-[[3-chloro-4-(2,4-dichlorophenoxy)-2,5-dimethylphenyl]carbamoyl]-2-fluorobenzamide Chemical group CC=1C(Cl)=C(OC=2C(=CC(Cl)=CC=2)Cl)C(C)=CC=1NC(=O)NC(=O)C1=CC=CC=C1F IWCVRYBCFFEJIY-UHFFFAOYSA-N 0.000 claims 1
- MYLZWNGISWJVBO-UHFFFAOYSA-N n-[[4-(2,4-dichlorophenoxy)-2,3,5-trimethylphenyl]carbamoyl]-2,6-difluorobenzamide Chemical group CC=1C(C)=C(OC=2C(=CC(Cl)=CC=2)Cl)C(C)=CC=1NC(=O)NC(=O)C1=C(F)C=CC=C1F MYLZWNGISWJVBO-UHFFFAOYSA-N 0.000 claims 1
- CJMWOLXEPQFNCA-UHFFFAOYSA-N n-[[4-(2-bromo-4-chlorophenoxy)-2-chloro-3,5-dimethylphenyl]carbamoyl]-2,6-difluorobenzamide Chemical group ClC=1C(C)=C(OC=2C(=CC(Cl)=CC=2)Br)C(C)=CC=1NC(=O)NC(=O)C1=C(F)C=CC=C1F CJMWOLXEPQFNCA-UHFFFAOYSA-N 0.000 claims 1
- LOUJUMYKQIBTBI-UHFFFAOYSA-N n-[[4-(2-bromo-4-chlorophenoxy)-2-chloro-3,5-dimethylphenyl]carbamoyl]-2-fluorobenzamide Chemical group ClC=1C(C)=C(OC=2C(=CC(Cl)=CC=2)Br)C(C)=CC=1NC(=O)NC(=O)C1=CC=CC=C1F LOUJUMYKQIBTBI-UHFFFAOYSA-N 0.000 claims 1
- AVRSIJPFCMYKEJ-UHFFFAOYSA-N n-[[4-(2-bromo-4-chlorophenoxy)-3-chloro-2,5-dimethylphenyl]carbamoyl]-2-fluorobenzamide Chemical group CC=1C(Cl)=C(OC=2C(=CC(Cl)=CC=2)Br)C(C)=CC=1NC(=O)NC(=O)C1=CC=CC=C1F AVRSIJPFCMYKEJ-UHFFFAOYSA-N 0.000 claims 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- 239000000243 solution Substances 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- 239000000203 mixture Substances 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 239000007787 solid Substances 0.000 description 20
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 238000012360 testing method Methods 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- 238000005481 NMR spectroscopy Methods 0.000 description 13
- 239000011734 sodium Substances 0.000 description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 239000004480 active ingredient Substances 0.000 description 12
- DPYYDZKFFYYPKV-UHFFFAOYSA-N n-[(4-phenoxyphenyl)carbamoyl]benzamide Chemical class C=1C=C(OC=2C=CC=CC=2)C=CC=1NC(=O)NC(=O)C1=CC=CC=C1 DPYYDZKFFYYPKV-UHFFFAOYSA-N 0.000 description 12
- 239000011541 reaction mixture Substances 0.000 description 12
- 241000196324 Embryophyta Species 0.000 description 11
- JRNVZBWKYDBUCA-UHFFFAOYSA-N N-chlorosuccinimide Chemical compound ClN1C(=O)CCC1=O JRNVZBWKYDBUCA-UHFFFAOYSA-N 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 230000004071 biological effect Effects 0.000 description 9
- 239000000725 suspension Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000012267 brine Substances 0.000 description 8
- 239000012043 crude product Substances 0.000 description 8
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 8
- 239000007921 spray Substances 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- HRYILSDLIGTCOP-UHFFFAOYSA-N N-benzoylurea Chemical class NC(=O)NC(=O)C1=CC=CC=C1 HRYILSDLIGTCOP-UHFFFAOYSA-N 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 241000462639 Epilachna varivestis Species 0.000 description 6
- 241000238631 Hexapoda Species 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000003995 emulsifying agent Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- 230000000361 pesticidal effect Effects 0.000 description 6
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 5
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000012954 diazonium Substances 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- 238000003818 flash chromatography Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 235000019198 oils Nutrition 0.000 description 5
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 4
- 241000712024 Brassica rapa var. perviridis Species 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000001989 diazonium salts Chemical class 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 230000026030 halogenation Effects 0.000 description 4
- 238000005658 halogenation reaction Methods 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- WVUJDDBZSITIHW-UHFFFAOYSA-N n-[[3-chloro-4-(2,4-dichlorophenoxy)-2,5-dimethylphenyl]carbamoyl]-2,6-difluorobenzamide Chemical compound CC=1C(Cl)=C(OC=2C(=CC(Cl)=CC=2)Cl)C(C)=CC=1NC(=O)NC(=O)C1=C(F)C=CC=C1F WVUJDDBZSITIHW-UHFFFAOYSA-N 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OBCSCZBVLOZKNS-UHFFFAOYSA-N 2-chloro-4-(2,4-dichlorophenoxy)-3,5-dimethylaniline Chemical compound CC1=CC(N)=C(Cl)C(C)=C1OC1=CC=C(Cl)C=C1Cl OBCSCZBVLOZKNS-UHFFFAOYSA-N 0.000 description 3
- YQZXRKZIGMHKAU-UHFFFAOYSA-N 3-bromo-4-(2-chloro-4-nitrophenoxy)-2,5-dimethylaniline Chemical compound CC1=CC(N)=C(C)C(Br)=C1OC1=CC=C([N+]([O-])=O)C=C1Cl YQZXRKZIGMHKAU-UHFFFAOYSA-N 0.000 description 3
- LKZKKZBOUBHNFG-UHFFFAOYSA-N 3-chloro-2-(2,4-dichlorophenoxy)-1,4-dimethyl-5-nitrobenzene Chemical compound CC1=CC([N+]([O-])=O)=C(C)C(Cl)=C1OC1=CC=C(Cl)C=C1Cl LKZKKZBOUBHNFG-UHFFFAOYSA-N 0.000 description 3
- QCXNFOKUEJMXBS-UHFFFAOYSA-N 3-chloro-4-(2,4-dichlorophenoxy)-2,5-dimethylaniline Chemical compound CC1=CC(N)=C(C)C(Cl)=C1OC1=CC=C(Cl)C=C1Cl QCXNFOKUEJMXBS-UHFFFAOYSA-N 0.000 description 3
- IOOWZEYQYCHTDP-UHFFFAOYSA-N 3-oxononanal Chemical compound CCCCCCC(=O)CC=O IOOWZEYQYCHTDP-UHFFFAOYSA-N 0.000 description 3
- YDKWHCLUFOBYCO-UHFFFAOYSA-N 4-amino-2-bromo-3,6-dimethylphenol Chemical compound CC1=CC(N)=C(C)C(Br)=C1O YDKWHCLUFOBYCO-UHFFFAOYSA-N 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- 244000299507 Gossypium hirsutum Species 0.000 description 3
- 241000255967 Helicoverpa zea Species 0.000 description 3
- 241001477931 Mythimna unipuncta Species 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- QQOMQLYQAXGHSU-UHFFFAOYSA-N 2,3,6-Trimethylphenol Chemical compound CC1=CC=C(C)C(O)=C1C QQOMQLYQAXGHSU-UHFFFAOYSA-N 0.000 description 2
- QFTVNKWBRHTDHE-UHFFFAOYSA-N 2,3-dichloro-4-(2,4-dichlorophenoxy)-5-methylaniline Chemical compound CC1=CC(N)=C(Cl)C(Cl)=C1OC1=CC=C(Cl)C=C1Cl QFTVNKWBRHTDHE-UHFFFAOYSA-N 0.000 description 2
- SUPXYCBYRNOOEQ-UHFFFAOYSA-N 2,5-dichloro-4-(2,4-dichlorophenoxy)-3-methylaniline Chemical compound CC1=C(Cl)C(N)=CC(Cl)=C1OC1=CC=C(Cl)C=C1Cl SUPXYCBYRNOOEQ-UHFFFAOYSA-N 0.000 description 2
- IKFYMZGIAYTIEU-UHFFFAOYSA-N 3-bromo-4-(2,4-dichlorophenoxy)-2,5-dimethylaniline Chemical compound CC1=CC(N)=C(C)C(Br)=C1OC1=CC=C(Cl)C=C1Cl IKFYMZGIAYTIEU-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- 241000255925 Diptera Species 0.000 description 2
- 241000256257 Heliothis Species 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 239000007832 Na2SO4 Substances 0.000 description 2
- 244000061176 Nicotiana tabacum Species 0.000 description 2
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 2
- 244000046052 Phaseolus vulgaris Species 0.000 description 2
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 2
- 231100000674 Phytotoxicity Toxicity 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- ZWWCURLKEXEFQT-UHFFFAOYSA-N dinitrogen pentaoxide Chemical compound [O-][N+](=O)O[N+]([O-])=O ZWWCURLKEXEFQT-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000013020 final formulation Substances 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine hydrate Chemical compound O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 235000014666 liquid concentrate Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000006396 nitration reaction Methods 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000009304 pastoral farming Methods 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical class [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 229950000244 sulfanilic acid Drugs 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- NTBYINQTYWZXLH-UHFFFAOYSA-N 1,2-dichloro-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C(Cl)=C1 NTBYINQTYWZXLH-UHFFFAOYSA-N 0.000 description 1
- UREAJTSNXVIPCP-UHFFFAOYSA-N 2,3,5-trichloro-4-(2,4-difluorophenoxy)aniline Chemical compound ClC1=C(Cl)C(N)=CC(Cl)=C1OC1=CC=C(F)C=C1F UREAJTSNXVIPCP-UHFFFAOYSA-N 0.000 description 1
- DOVNYHFNNRSSEJ-UHFFFAOYSA-N 2,3-dichloro-1,4-dimethyl-5-nitrobenzene Chemical compound CC1=CC([N+]([O-])=O)=C(C)C(Cl)=C1Cl DOVNYHFNNRSSEJ-UHFFFAOYSA-N 0.000 description 1
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- IIFHMPHYPUIXLH-UHFFFAOYSA-N 2-[3-bromo-4-(2-chloro-4-nitrophenoxy)-2,5-dimethylphenyl]-3a,4,5,6,7,7a-hexahydroisoindole-1,3-dione Chemical compound CC1=CC(N2C(C3CCCCC3C2=O)=O)=C(C)C(Br)=C1OC1=CC=C([N+]([O-])=O)C=C1Cl IIFHMPHYPUIXLH-UHFFFAOYSA-N 0.000 description 1
- XWMQHKGQWXULBS-UHFFFAOYSA-N 2-bromo-3,6-dimethyl-4-nitrophenol Chemical compound CC1=CC([N+]([O-])=O)=C(C)C(Br)=C1O XWMQHKGQWXULBS-UHFFFAOYSA-N 0.000 description 1
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- LJYIIVMCAHMDOS-UHFFFAOYSA-N 4-(2,4-dichlorophenoxy)-3,5-dimethylaniline Chemical compound CC1=CC(N)=CC(C)=C1OC1=CC=C(Cl)C=C1Cl LJYIIVMCAHMDOS-UHFFFAOYSA-N 0.000 description 1
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- OZIFWVTUTMBIOH-UHFFFAOYSA-N 4-amino-2,3,6-trimethylphenol Chemical compound CC1=CC(N)=C(C)C(C)=C1O OZIFWVTUTMBIOH-UHFFFAOYSA-N 0.000 description 1
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
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- 229910000564 Raney nickel Inorganic materials 0.000 description 1
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- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 240000006394 Sorghum bicolor Species 0.000 description 1
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- 241000256248 Spodoptera Species 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
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- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
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- 125000002091 cationic group Chemical group 0.000 description 1
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- KSDIHKMNSYWRFB-UHFFFAOYSA-N chrysen-2-amine Chemical compound C1=CC=CC2=CC=C3C4=CC=C(N)C=C4C=CC3=C21 KSDIHKMNSYWRFB-UHFFFAOYSA-N 0.000 description 1
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
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- 235000013305 food Nutrition 0.000 description 1
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- MUTGBJKUEZFXGO-UHFFFAOYSA-N hexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21 MUTGBJKUEZFXGO-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
Foreliggende oppfinnelse angår nye l-(4-fenoksyfenyl)-3-benzoylurinstoff-forbindelser som er brukbare som aktiv forbindelse i pesticide preparater. Oppfinnelsen angår også en fremgangsmåte for fremstilling av disse forbindelser. Videre angår oppfinnelsen pesticide preparater samt en fremgangsmåte for deres bruk. The present invention relates to new 1-(4-phenoxyphenyl)-3-benzoylurea compounds which are usable as an active compound in pesticide preparations. The invention also relates to a method for producing these compounds. Furthermore, the invention relates to pesticide preparations and a method for their use.
I de senere år er et antall benzoylurinstof f-forbindelser angitt i littera- In recent years, a number of benzoyl urea compounds have been reported in the literature
turen som forbindelser med pesticid aktivitet. F.eks. er benzoylureido-difenyletere og deres bruk beskrevet i US-PS 4.005.223, 4.041.177 og 4.068.002. Videre er N-benzoyl-N'-fenoksyfenylurinstoff-forbindelser og deres bruk beskrevet i US-PS 4.399.152, JP søknad 5.5038.357, 5.6092.857 the trip as compounds with pesticide activity. E.g. are benzoylureido-diphenyl ethers and their use described in US-PS 4,005,223, 4,041,177 and 4,068,002. Furthermore, N-benzoyl-N'-phenoxyphenylurea compounds and their use are described in US-PS 4,399,152, JP application 5,5038,357, 5,6092,857
og 5.7002.258. and 5.7002.258.
N-benzoyl-N'-fenoksypyridylurinstoff-forbindelser er beskrevet i EP-PS 0069288. N-benzoyl-N'-phenoxypyridyl urea compounds are described in EP-PS 0069288.
I henhold til dette vil en eller flere av de følgende gjenstander oppnås Accordingly, one or more of the following objects will be achieved
ved gjennomføring av oppfinnelsen. Gjenstand for oppfinnelsen er å tilveiebringe nye l-(4-fenoksyfenyl)-3-benzoylurinstoff-forbindelser. En annen gjenstand for oppfinnelsen er å tilveiebringe visse l-(4-fenoksy-f enyl)-3-benzoylurinstof f-forbindelser som viser utmerket insekticid aktivitet. Ytterligere en- gjenstand ifølge oppfinnelsen er å tilveiebringe nye urinstoff-forbindelser slik som 1-[3-klor-4-(2,4-diklorfenoksy)-2,5-dimetylf enyl]-3- (2,6-dif luorbenzoyl) urinstof f, - 1-[3-klor-4-(2-brom-4-klorfenoksy)-2,5-dimetylfenyl] -3-(2,6-difluorbenzoyl)urinstoff ,1- [3-klor-4-(2-brom-4-klorfenoksy)-2,5-dimetylfenyl] -3-(2-fluorbenzoyl)urinstoff, etc. Ytterligere en gjenstand for oppfinnelsen er å tilveiebringe en fremgangsmåte for fremstilling av de nye benzoylurinstof f-forbindelser. Ytterligere en gjenstand for oppfinnelsen er å tilveiebringe nye pesticide preparater inneholdende de nye benzoylurinstoff-forbindelser som aktiv bestanddel. Ytterligere en gjenstand for oppfinnelsen er å tilveiebringe en fremgangsmåte for å kontrollere pest ved anvendelse av de nye pesticide forbindelser. Disse og andre gjenstander vil lett bli åpenbare for fagmannen ut fra det nedenfor anførte. when carrying out the invention. The object of the invention is to provide new 1-(4-phenoxyphenyl)-3-benzoylurea compounds. Another object of the invention is to provide certain 1-(4-phenoxy-phenyl)-3-benzoylurea compounds which exhibit excellent insecticidal activity. A further object of the invention is to provide new urea compounds such as 1-[3-chloro-4-(2,4-dichlorophenoxy)-2,5-dimethylphenyl]-3-(2,6-difluorobenzoyl) urea f, - 1-[3-chloro-4-(2-bromo-4-chlorophenoxy)-2,5-dimethylphenyl] -3-(2,6-difluorobenzoyl)urea ,1- [3-chloro-4- (2-bromo-4-chlorophenoxy)-2,5-dimethylphenyl]-3-(2-fluorobenzoyl)urea, etc. A further object of the invention is to provide a method for the production of the new benzoyl urea compounds. Another object of the invention is to provide new pesticide preparations containing the new benzoylurea compounds as active ingredient. A further object of the invention is to provide a method for controlling plague using the new pesticidal compounds. These and other items will be readily apparent to the person skilled in the art from what is stated below.
I sitt mest generelle aspekt angår foreliggende oppfinnelse l-(4-fenoksy-fenyl)-3-benzoylurinstoff-forbindelser, pesticide preparater inneholdende disse samt metoder for deres fremstilling. Benzoylurinstof f-forbindelsene ifølge oppfinnelsen kan representeres ved følgende formel: In its most general aspect, the present invention relates to 1-(4-phenoxy-phenyl)-3-benzoylurea compounds, pesticidal preparations containing these and methods for their production. The benzoyl urea compounds according to the invention can be represented by the following formula:
der: there:
X betyr halogen; X means halogen;
X' betyr hydrogen eller halogen; X' means hydrogen or halogen;
X" betyr fluor eller hydrogen, forutsatt at når X' er halogen, er X" X" means fluorine or hydrogen, provided that when X' is halogen, X" is
hydrogen; hydrogen;
R]_, R2og R3uavhengig er metyl, klor eller brom; R1_, R2 and R3 are independently methyl, chlorine or bromine;
R betyr metyl, klor, fluor eller brom; og R means methyl, chlorine, fluorine or bromine; and
R', R" og R'" uavhengig er hydrogen, metyl, klor, fluor eller brom, R', R" and R'" independently are hydrogen, methyl, chlorine, fluorine or bromine,
forutsatt at minst en av R', R" og R"' er forskjellig fra hydrogen. provided that at least one of R', R" and R"' is different from hydrogen.
Som angitt ovenfor angår oppfinnelsen nye l-(4-fenoksyfenyl)-3-benzoylurinstoff-forbindelser, pesticide preparater inneholdende disse samt fremgangsmåter for deres fremstilling og bruk. As stated above, the invention relates to new 1-(4-phenoxyphenyl)-3-benzoylurea compounds, pesticidal preparations containing these as well as methods for their production and use.
Foretrukne benzoylurinstof f-forbindelser innenfor den brede generiske formel (1) er de med formelen: Preferred benzoyl urea compounds within the broad generic formula (1) are those of the formula:
der X, X',<R>lfR2, R3, R, R', R" og R"' er som angitt ovenfor. where X, X', <R>lfR2, R3, R, R', R" and R"' are as indicated above.
Spesielt foretrukket er forbindelser med formelen: Particularly preferred are compounds of the formula:
der X, X', Rj, R2, R3, R og R" er som angitt ovenfor; og where X, X', Rj, R2, R3, R and R" are as indicated above; and
der X, X', R og R" er som angitt ovenfor. where X, X', R and R" are as indicated above.
De følgende benzoylurinstof f-forbindelser som angitt i tabellene A til G er illustrerende for de som omfattes av de ovenfor angitte formler og som kan fremstilles ved oppfinnelsens gjennomføring: The following benzoylurea compounds as indicated in tables A to G are illustrative of those covered by the above formulas and which can be produced by carrying out the invention:
De nye benzoylurinstof f- forbindelser ifølge oppfinnelsen kan hensiktsmessig fremstilles ved en eller flere metoder. F.eks. kan forbindelsene ifølge oppfinnelsen fremstilles ved omsetning av et substituert fenoksyanilin 2 med et benzoylisocyanat 3_ i henhold til skjema I som følger: The new benzoylurea compounds according to the invention can conveniently be prepared by one or more methods. E.g. the compounds according to the invention can be prepared by reacting a substituted phenoxyaniline 2 with a benzoisocyanate 3_ according to scheme I as follows:
hvori X, X', X", Rj, R2, R3, R, R', R" og R"' har den betydning som er gitt for formel 1. wherein X, X', X", Rj, R2, R3, R, R', R" and R"' have the meaning given for formula 1.
Alternativt kan de nye forbindelser fremstilles ved omsetning av et fenoksyfenylisocyanat 4_ med et benzamid 5_ i henhold til skjema II som følger: Alternatively, the new compounds can be prepared by reacting a phenoxyphenyl isocyanate 4_ with a benzamide 5_ according to scheme II as follows:
hvori X, X', X", R1( R2, R3, R, R', R" og R"" har den betydning som er gitt for formel 1. wherein X, X', X", R1( R2, R3, R, R', R" and R"" have the meaning given for formula 1.
De angjeldende forbindelser kan også fremstilles ved omsetning av et benzoylklorid 6_ med et substituert urinstoff 7_ i henhold til skjema III som følger: The compounds in question can also be prepared by reacting a benzoyl chloride 6_ with a substituted urea 7_ according to scheme III as follows:
hvori X, X', X", R^ R2, R3, R, R', R" og R'" har den betydning som er gitt for formel 1. wherein X, X', X", R^ R2, R3, R, R', R" and R'" have the meaning given for formula 1.
Generelt kan de reaksjoner som er vist i reaksjonsskjema I, II og III gjennomføres i organiske opp løsningsmidle r slik som aromatiske hydrokarboner, halogenerte hydrokarboner, etere og lignende. Oppløsnings-midler som toluen, 1,2-dikloretan, diklormetan og p-dioksan er fore trukket. Disse reaksjoner skjer ved temperaturer innen området omgivelsestemperatur til 150° C. In general, the reactions shown in reaction schemes I, II and III can be carried out in organic solvents such as aromatic hydrocarbons, halogenated hydrocarbons, ethers and the like. Solvents such as toluene, 1,2-dichloroethane, dichloromethane and p-dioxane are preferred. These reactions take place at temperatures within the range of ambient temperature to 150° C.
Mellomproduktene som vist i skjema I, II og III kan fremstilles i henhold til generelle prosedyrer. Således kan det substituerte benzoylisocyanat 3_ fremstilles fra det tilsvarende benzamid 5_ ved å følge det som er angitt av Speziale et al., J. Org. Chem., 27, 3742 (1962) som følger: The intermediates shown in Schemes I, II and III can be prepared according to general procedures. Thus, the substituted benzoisocyanate 3_ can be prepared from the corresponding benzamide 5_ by following that indicated by Speziale et al., J. Org. Chem., 27, 3742 (1962) as follows:
hvori X, X' og X" har den samme betydning som i formel 1. in which X, X' and X" have the same meaning as in formula 1.
De substituerte fenoksyaniliner 2_ der Pq ikke er klor eller brom kan fremstilles i henhold til skjema V omfattende omsetning av et substituert fenol 9_ med et klornitrobenzen 8_ som følger: The substituted phenoxyanilines 2_ where Pq is not chlorine or bromine can be prepared according to scheme V involving reaction of a substituted phenol 9_ with a chloronitrobenzene 8_ as follows:
hvori Rj, R2, R3, R, R', R" og R"' har den betydning som er gitt i formel 1, forutsatt at R^ ikke er klor eller brom. Reaksjonen mellom et substituert fenol 9 og et klornitrobenzen 8 for å gi nitroeteren 10 skjer i nærvær av en base i et inert oppløsningsmiddel ved forhøyet temperatur. Baser egnet for denne reaksjon er kaliumkarbonat, natriumhydrid, kaliumhydroksyd og natriumhydroksyd. Egnede oppløsningsmidler er toluen, dimetylformamid og dimetylsulfoksyd. Den ovenfor angitte transformasjon kan gjennomføres i et tofase-reaksjonsmedium i nærvær av en fase-overføringskatalysator. wherein R 1 , R 2 , R 3 , R, R', R" and R"' have the meaning given in formula 1, provided that R 1 is not chlorine or bromine. The reaction between a substituted phenol 9 and a chloronitrobenzene 8 to give the nitroether 10 occurs in the presence of a base in an inert solvent at elevated temperature. Bases suitable for this reaction are potassium carbonate, sodium hydride, potassium hydroxide and sodium hydroxide. Suitable solvents are toluene, dimethylformamide and dimethylsulfoxide. The above-mentioned transformation can be carried out in a two-phase reaction medium in the presence of a phase-transfer catalyst.
Reduksjonen av nitroeteren 10_ til fenoksyanilinet 2_ kan oppnås ved hydrogenering ved bruk av en katalytisk mengde platina eller palladium på trekull eller en Raney-nikkel-katalysator under en hydrogenatmosfære ved et trykk fra 40-200 psi ved omgivelsestrykk. Egnede oppløsnings-midler for hydrogenering inkluderer aromatiske hydrokarboner eller alkoholer. Reduksjonen kan også oppnås ved en kjemisk metode ved bruk av hydrazin og en metallkatalysator slik som beskrevet i Chem. Rev., vol. 65, s. 51.68 (1965). The reduction of the nitroether 10_ to the phenoxyaniline 2_ can be accomplished by hydrogenation using a catalytic amount of platinum or palladium on charcoal or a Raney nickel catalyst under a hydrogen atmosphere at a pressure of 40-200 psi at ambient pressure. Suitable solvents for hydrogenation include aromatic hydrocarbons or alcohols. The reduction can also be achieved by a chemical method using hydrazine and a metal catalyst as described in Chem. Rev., vol. 65, pp. 51.68 (1965).
Isocyanatet 4 kan oppnås ved å omsette det substituerte anilin 2_ med fosgen. Urinstoffet 7_ kan oppnås via omsetning av isocyanat 4 med ammoniumhydroksyd eller gassformig ammoniakk. Disse reaksjoner er illustrert i skjema VI nedenfor som følger: The isocyanate 4 can be obtained by reacting the substituted aniline 2_ with phosgene. The urea substance 7_ can be obtained via reaction of isocyanate 4 with ammonium hydroxide or gaseous ammonia. These reactions are illustrated in Scheme VI below as follows:
hvori Rj, R2, R3, R, R', R" og R'" har den betydning som er gitt i formel 1. wherein Rj, R2, R3, R, R', R" and R'" have the meaning given in formula 1.
De substituerte f enoksyaniliner 2_ der Rj er klor eller brom oppnås ved halogenering av 3,5-disubstituert 4-fenoksyanilin JJ_ som angitt i skjema VII nedenfor som følger: The substituted phenoxyanilines 2_ where Rj is chlorine or bromine are obtained by halogenation of 3,5-disubstituted 4-phenoxyaniline JJ_ as indicated in Scheme VII below as follows:
hvori Ri er klor eller brom og<R>2, R3, R, R', R" og R'" har den betydning som er gitt if ormel 1. Egnede oppløsningsmidler for denne transformering inkluderer halogenalkaner; aromatiske hydrokarboner slik som benzen; eller polare protiske oppløsningsmidler slik som eddiksyre. Halogenering av anilinet 11_ kan gjennomføres ved eksponering til klor eller brom i et egnet oppløsningsmiddel ved lav temperatur eller for-trinnsvis behandling med et N-halogensuccinimid i benzen. Temperaturer nødvendige for reaksjonen varierer i henhold til identiteten til substi-tuentene R2og R^, men ligger generelt innen området 25-80° C. wherein R 1 is chlorine or bromine and <R> 2 , R 3 , R , R', R" and R'" have the meanings given in formula 1. Suitable solvents for this transformation include haloalkanes; aromatic hydrocarbons such as benzene; or polar protic solvents such as acetic acid. Halogenation of the aniline 11_ can be carried out by exposure to chlorine or bromine in a suitable solvent at low temperature or preferably by treatment with an N-halogenosuccinimide in benzene. Temperatures necessary for the reaction vary according to the identity of the substituents R 2 and R 2 , but are generally within the range 25-80° C.
Fenoksyaniliner av type U_ fremstilles ved den metode som er angitt i skjema V ovenfor ved bruk av det 3,4,5-trisubstituerte nitrobenzen 12_ som elektrofil komponent i denne koblingsreaksjon. Klornitrobenzener av type 12_er illustrert som følger: Phenoxyanilines of type U_ are prepared by the method indicated in Scheme V above using the 3,4,5-trisubstituted nitrobenzene 12_ as electrophilic component in this coupling reaction. Chloronitrobenzenes of type 12_are illustrated as follows:
hvori R2og R3har den betydning som er gitt for formel 1. Klornitrobenzener av type 12_ oppnås fra de tilsvarende nitroaniliner via Sandmeyer-prosedyren som angitt av Miller et al. i J. Med. Chem., 23, 1083 (1980). wherein R 2 and R 3 have the meaning given for formula 1. Chloronitrobenzenes of type 12_ are obtained from the corresponding nitroanilines via the Sandmeyer procedure as indicated by Miller et al. in J. Med. Chem., 23, 1083 (1980).
Alternativt kan klornitrobenzener av type 8_ fremstilles ved nitrering av et klorbenzen som illustrert ved syntese av 3,4-diklor-2,5-dimetylnitro-benzen 16_illustrert i skjema VIII som følger: Alternatively, chloronitrobenzenes of type 8_ can be prepared by nitration of a chlorobenzene as illustrated by the synthesis of 3,4-dichloro-2,5-dimethylnitrobenzene 16_ illustrated in Scheme VIII as follows:
Fremstilling av fenoler av typen 9_ illustreres ved elaborering av 4-brom-2-fluorfenol fra 2-fluorfenol ved bruk av den prosedyre som er gitt av Mitchell et al. i J. Org. Chem., 25^4733 (1979). Et annet fenolisk mellomprodukt, 2-brom-4-klorfenol, oppnås på analog måte fra 4-klorfenol. Preparation of phenols of the type 9_ is illustrated by the preparation of 4-bromo-2-fluorophenol from 2-fluorophenol using the procedure given by Mitchell et al. in J. Org. Chem., 25^4733 (1979). Another phenolic intermediate, 2-bromo-4-chlorophenol, is obtained analogously from 4-chlorophenol.
En alternativ vei til fenoksyaniliner av type 2^spesielt fenoksyanilin 21^er angitt i skjema IX nedenfor: An alternative route to type 2 phenoxyanilines^specifically phenoxyaniline 21^is indicated in Scheme IX below:
hvori R]_, R2, R3, R og R" har den betydning som er gitt i formel 1 og R" er klor eller brom. Denne reaksjon involverer kobling av et aminofenol 17 med et 4-klornitrobenzen 18_ i nærvær av en base for derved å gi 4-nitrofenoksyanilin 19_ som beskrevet av Schramm et al. i Ann., 740, 169 wherein R]_, R 2 , R 3 , R and R" have the meaning given in formula 1 and R" is chlorine or bromine. This reaction involves the coupling of an aminophenol 17 with a 4-chloronitrobenzene 18_ in the presence of a base to give 4-nitrophenoxyaniline 19_ as described by Schramm et al. in Ann., 740, 169
(1970). Reaksjonen mellom aminogruppen i. 19_ og cykloheksan-1,2-dikarboksylsyreanhydridet gir imidet 20. * Nitrogruppe- reduksjonen, Sandmeyer-halogenering og beskyttelsesfjerning av aminofunksjonen gir anilinet 2L_ Detaljer for disse transformeringer er gitt i den eksperi-mentelle del nedenfor. ;Aminofenoler av typen 17_ er lett tilgjengelige og kan fremstilles som illustrert ved opparbeiding av aminofenolet 25_ via nitrering av et 2,5-disubstituert fenol 22_ fulgt av halogenering og nitrogruppe reduksjon som angitt i skjema X nedenfor: ; hvori Rj og R3har den betydning som er gitt i formel 1 og Y er brom eller klor. Deres omsetning til mellomproduktet 23_og 24_ ref lekterer det som er beskrevet av Albert og Sears i J. Am. Chem. Soc., 76, 4979 ;(1954). ;En alternativ og komplementær tilnærmelse til aminofenolene 17_ er detaljert i skjema XI som følger: ; hvori R]_, R2og R3har den betydning som er gitt i formel 1. Dette involverer omsetning av et trisubstituert fenol 26_ med et diazoniumsalt fremstilt fra sulfanilsyre for derved å gi mellomproduktet som diazo- ;forbindelse 27 som så reduseres for å få aminofenol 17^Syntese- metodo-logien som ble benyttet her for å oppnå aminofenol et 17_ er som beskrevet av Payne og Weiden i US-PS 3.752.838. ;Forbindelser som beskrives ifølge oppfinnelsen kan benyttes som insekti-cider i henhold til metoder velkjente av fagmannen. Pesticide preparater inneholdende forbindelsene som aktiv bestanddel vil vanligvis omfatte en bærer og/eller et fortynningsmiddel, enten flytende eller fast. ;Egnede flytende fortynningsmidler eller bærere inkluderer vann, petroleumdestillater eller andre flytende bærere med eller uten overflateaktive midler. Flytende konsentrater kan fremstilles ved å oppløse en av disse forbindelser i et ikke-fytotoksisk oppløsningsmiddel slik som aceton, xylen, nitrobenzen, cykloheksanon eller dimetylformamid og å dispergere de aktive bestanddeler i vann ved hjelp av egnede overflateaktive emulgerings- og dispergeringsmidler. ;Valget av dispergerings- og emulgeringsmidler og den mengde som benyttes dikteres av arten av preparatet og midlets evne til å lette disp.ergeringen av den aktive bestanddel. Generelt er det ønskelig å -benyttes så lite som mulig av midlet konsistent med den ønskede disper-sjon av den aktive bestanddel i sprayen, slik at regn ikke reemulgerer den aktive bestanddel etter at den er påført planter, og derved vasker den av planten. Ikke-ioniske, anioniske eller kationiske dispergerings- og emulgeringsmidler kan benyttes, f.eks. kondensasjonsprodukter av alkylenoksyder med fenol og organiske syrer, alkylarylsulfonater, komplekse eteralkoholer, kvaternære ammoniumforbindelser og lignende. ;Ved fremstilling av fuktbare pulvere eller støv eller granulerte preparater blir den aktive bestanddel dispergert i og på en hensiktsmessig findelt fast bærer slik som leire, talkum, bentonitt, diatomejord, fullers jord og lignende. Ved formulering av de fuktbare pulvere kan de ovenfor nevnte dispergeringsmidler så vel som lignosulfonater innarbeides. ;Den nødvendige mengde aktiv bestanddel kan påføres pr. ca. 4 mål i en mengde av 1-200 gallon eller mer flytende bærer og/eller fortynningsmiddel eller i en mengde av 50-500 pund inert fast bærer og/eller fortynningsmiddel. Konsentrasjonen i det flytende konsentrat vil vanligvis variere fra ca. 10-95 vekt-% og i faste formuleringer fra ca. 0,5-90 vekt-%. Tilfredsstillende spray, støv eller granulat for generell bruk inneholder fra ca. 0,25-15 pund aktiv bestanddel pr. ca. 4 mål. ;De her beskrevne pesticider forhindrer angrep av insekter på planter og annet materiale på hvilket pesticidene er påført, og de har en relativt høy restgiftighet. Med henblikk på planter har de en høy sikkerhetsmargin, idet når de benyttes i en tilstrekkelig mengde til å drepe eller avvise insekter, brenner eller skader de ikke planten, og de motstår nedbrytning inkludert av vasking på grunn av regn, dekomponering på grunn av ultrafiolett lys, oksydasjon eller hydrolyse i nærvær av fuktighet eller, til slutt, slik dekomponering , oksydasjon og hydrolyse som i vesentlig grad reduserer de ønskede pesticide karakteristika for de aktive bestanddeler eller å gi disse uønskede karakteristika, f.eks. fytotoksisitet. De aktive bestanddeler er så kjemisk inerte at de nå er kompatible med i det vesentlige enhver annen bestanddel innen sprayspekteret, og de kan benyttes i jord, på frø, på planterøtter uten å skade frø, røtter eller planter. Blandinger av aktive bestanddeler kan benyttes hvis dette er ønskedelig så vel som kombinasjoner av aktive forbindelser ifølge oppfinnelsen med andre biologisk aktive forbindelser eller bestanddeler. ;De følgende eksempler er illustrerende for de metoder som benyttes ved fremstilling av mellomprodukter og forbindelser ifølge oppfinnelsen. For NMR-spektroskopianalyser ble de kjemiske skift angitt i ppm nedstrøms ;TMS. ;EKSEMPEL A ;Fremstilling av 4-( 2, 4- difluorfenoksy)- 2, 3, 5- trikloranilin ;Til en 300 ml rundkolbe ble det chargert 14,9 g (51,4 mmol) 3,5-diklor-4-(2,4-difluorfenoksy)anilin, 7,2 g (53,9 mmol) N-klorsuccinimid (NCS) og 100 ml benzen. Reaksjonsblandingen ble kokt under tilbakeløp i 2 timer, hvoretter ytterligere NCS (350 mg, 2,6 mmol) ble tilsatt. Tilbakeløps-kokingen ble så fortsatt i ytterligere en time. Blandingen ble tillatt avkjøling, fortynnet med 200 ml etylacetat og vasket med H2O, mettet NaHC03og saltoppløsning, tørket over Na2S04og konsentrert under redusert trykk. Den oljeaktige rest ble renset ved flash-kolonnekroma tografi, heksair.toluen 1:1, og man oppnådde 4-(2,4-difluorfenoksy-2,3,5-trikloranilin (9,8 g, 30,2 mmol, 59%) som en mørkebrun olje. Strukturen for dette stoff ble verifisert ved dets Hi-NMR-spektrum (CDCI3) 7,30-6,10 (m 3H; 6,75 (s, 1H), 4,18 (br s, 2H). ;EKSEMPEL B ;Fremstilling av 2- klor- 4-( 2, 4- diklorfenoksy)- 3, 5- dimetylanilin ;Til en 200 ml 3-hals rundkolbe ble det chargert 6,76 g (24,0 mmmol) 4-(2,4-diklorfenoksy)-3,5-dimetylanilin og 48 ml benzen. N-klorsuccinimid (3,85 g, 28,8 mmol) ble så tilsatt og den resulterende heterogene blanding ble omrørt ved romtemperatur i en time. Reaksjonsblandingen ble fortynnet med etylacetat, vasket to ganger med mettet Na2S03~opp-løsning og tørket over Na2S04. Konsentrering under redusert trykk ga råproduktet som en mørk olje. Denne ble filtrert gjennom en kort kolonne av silikagel ved bruk av heksametylacetat i volumforholdet 9:1 som elueringsmiddel. Oppløsningsmiddelfjerning under redusert trykk ga 2-klor-4-(2,4-diklorfenoksy)-3,5-dimetylanilin (6,5 g) forurenset med minst tre andre produkter. Dette materialet ble anbragt i en Parr-kolbe og oppløst i 50 ml toluen. Par r- kolben ble spylt med nitrogen. 650 mg 5% ; platina, på trekull ble tilsatt og blandingen ble hydrogenert i en time ved 40-50 psi og romtemperatur i en Parr-vugge-hydrogenator. Filtrering gjennom en pute av celite, og fjerning av oppløsningsmidlet og flash-kromatografi, heksan: etylacetat 9:1, ga rent 2-klor-4-(2,4-diklorf enoksy)-3,5-dimetylanilin (3,1 g, 9,8 mmol, 41%) som et krystallisert faststoff med et smeltepunkt på 89-93 °C. Elementanalyse for det krystallinske faststoff antydet følgende: ;Analyse: (44H12CI3NO ; ; EKSEMPEL C ;Fremstilling av 2, 5- diklor- 4-( 2, 4- diklorfenoksy)- 3- metylanilin og 2, 3-diklor- 4- ( 2, 4- diklorf enoksy) - 5- metylanilin ;Til en magnetisk omrørt oppløsning av 3-klor-4-(2,4-diklorf enoksy)-5-metylanilin (9,0 g, 29,7 mmol) i 60 ml benzen ble det tilsatt fast N-klorsuccinimid (4,4 g, 32,7 mmol). Blandingen ble omrørt ved romtemperatur i 1,5 time, overført til en skilletrakt og vasket med mettet Na2S03-oppløsning tre ganger, med vann to ganger og med saltoppløsning en gang. Det organiske sjikt ble tørket over Na2S04og konsentrert under redusert trykk hvorved man oppnådde 10,08 g råprodukt som en mørkebrun olje. Flash-kolonnekromatografi på 500 g silikagel, heksanretylacetat 3:1, ga rent 2,5-diklor-4-(2,4-diklorf enoksy)-3-metylanilin (2,85 g, 7,4 mmol, 25%) med et smeltepunkt på 96-97° C og 2,3-diklor-4-(2,4-diklorfenoksy)-5-metylanilin (2,16 g, 6,4 mmol, 22%) med et smeltepunkt på 95 °C. Omkrystallisering av fra metanol ga analytiske prøver. Elementanalyse av prøvene antydet følgende: ;Analyse: (43<H>9CI4NO ; ; EKSEMPEL D ;Fremstilling av 2- brom- 4-( 2- brom- 4- klorfenoksy) - 3, 5- dikloranilin ;Til en magnetisk omrørt oppløsning av 4-(2-brom-4-klorfenoksy)-3,5-dikloranilin (6,38 g, 17,36 mmol) i 35 ml benzen ble det tilsatt N-bromsuccinimid (3,71 g, 20,83 mmol). Reaksjonsblandingen ble omrørt i 2 timer ved romtemperatur, overført til en skilletrakt og vasket to ganger med mettet Na2S03-oppløsning, to ganger med vann og en gang med saltoppløsning. Det organiske laget ble tørket over Na2SC"4 og konsentrert under redusert trykk, hvorved man oppnådde råproduktet som så ble underkastet flash-kolonnekromatografi på 760 g silikagel med heksametylacetat i forholdet 4:1, noe som ga rent 2.brom-4-(2-brom-4-klorfenoksy)-3,5-dikloranilin (5,15 g, 11,53 mmol, 66%). Elementanalyse av produktet indikerte følgende: ;Analyse: C^F^BnChNO ; ; EKSEMPEL E ;Fremstilling av 4- amino- 2, 3, 6- trimetylfenol ;Til en oppløsning av sulfanilsyre (13,0 g, 68 mmol) i 68 ml vann inneholdt i en 250 ml rundkolbe utstyrt med magnetrører, innvendig termometer og isbad, ble det ved 15 °C tilsatt fast Na2SC"3(3,69 g, 34 mmol) fulgt av en oppløsning av NaN02(5,1 g, 74 mmol) i 14 ml vann. Den sistnevnte tilsetning forårsaket en fargeendring fra et melkeaktig-hvit til oransje. En separat 500 ml 3-halskolbe utstyrt med magnetisk rører, innvendig termometer og isbad ble chargert med 12 ml konsentrert saltsyre, 68 g is og oppløsningen av diazoniumsaltet som fremstilt ovenfor. Blandingen ble omrørt ved 15"C i 45 minutter. I mellomtiden ble en tredje kolbe på 1 liter, utstyrt med innvendig termometer, nitrogen-inntak, kondensator, tilsetningstrakt og mekanisk røreverk chargert med 68 ml vann, NaOH (14,96 g, 318 mmol) og 2,3,6-trimetylfenol (9,30 g, 68 mmol). Denne blanding ble avkjølt til 0°C ved hjelp av en is-saltblanding og diazoniumsalt-saltsyreblandingen som fremstilt ovenfor ble tilsatt dråpevis, mens man holdt temperaturen under 5°C. Etter ferdig diazoniumsalttilsetning ble reaksjonsblandingen oppvarmet til 62 "C og fast Na2S2C>4 (3,13 g, 18 mmol) ble tilsatt. Omrøringen ble fortsatt og blandingen oppvarmet til 80 "C, hvoretter ytterligere Na2S204(28,2 g, 162 mmol) ble tilsatt i tre like andeler på 9,4 g hver med 5 minutters intervaller. Blandingen ble oppvarmet til 80 °c under nitrogen i 20 minutter, avkjølt til romtemperatur og filtrert for derved å gi råproduktet som et gult faststoff. Faststoffet ble oppløst i 300 ml etylacetat og vasket med vann. Det organiske sjikt ble tørket over Na2S04og konsentrert under redusert trykk hvorved man oppnådde 4-amino-2,3,6-trimetyl--■fenbri kvantitativt utbytte, forbindelsen ble så brukt med hell i senere reaksjoner uten ytterligere rensing. H^-NMR (CDCI3) 6,30 (s, 1H), 2,11 (s, 9H). ;EKSEMPEL 1 ;Fremstilling av 1-[ 3- klor- 4-( 2, 4- diklorfenoksy)- 2, 5- dimetylfenyl] - 3-( 2,6-difluorbenzoyl) urinstoff ;Del A: Fremstilling av 3- klor- 4-( 2, 4- diklorfenoksy) - 2, 5- dimetylnitro-benzen ;Til en 250 ml 3-hals rundkolbe utstyrt med magnetisk røreverk og nitrogeninnløp ble det chargert 10,0 g (45,44 mmol) 3,4-diklor-2,5-dimetylnitrobenzen, 7,95 g (48,81 mmol) 2,4-diklorfenol, 9,41 g (68,11 mmol) kaliumkarbonat og 60 ml dimetylformamid. Reaksjonsblandingen ble omrørt og oppvarmet til en temperatur av 100 °C i et tidsrom på 20 timer og så avkjølt til romtemperatur, filtrert og konsentrert under redusert trykk. Resten ble fortynnet med metylenklorid og det organiske sjikt ble vasket med 4% NaOH-oppløsning to ganger og så saltoppløsning, tørket gjennom Na2SC>4og konsentrert under redusert trykk for derved å gi råproduktet som en mørkebrun viskøs væske. Tilsetningen av heksan og etylacetat ga et lysebrunt faststoff som ble underkastet Kugelrohr-destillasjon (ca. 180 °C og ca. 0,1 mm kvikksølv) for å oppnå rent 3-klor-4-(2,4-diklorfenoksy)-2,5-dimetylnitrobenzen (7,17 g, 20,7 mmol, 45%) som et gult faststoff med et smeltepunkt på 118-121 °C. NMR-spektroskopisk analyse antydet følgende: H^-NMR (CDCI3) 7,76 (br S, 1H), 7,53 (d, J=2Hz, 1H), 7,12 (d,d; 2,9Hz, 1H), 6,34 (d, J=9Hz, 1H), 2,45 (S, 3H), 2,24 (S, 3H). ;Del B: Fremstilling av 3- klor- 4-( 2, 4- diklorfenoksy)- 2, 5- dimetylanilin Til en 250 ml Parr-flaske ble det chargert 6,59 g (19,01 mmol) 3-klor-4-(2,4-diklorfenoksy)-2,5-dimetylnitrobenzen fremstilt under del A og 15 ml toluen. Flasken ble fylt med nitrogen og 650. mg fast 10% platina på karbon ble tilsatt. Reaksjonsblandingen ble så hydrogenert i 45 minutter ved 43-47 psi hydrogentrykk og romtemperatur på en Parr-vugge-hydrogenator. Katalysatoren ble fjernet ved filtrering gjennom celite og filtratet ble konsentrert under redusert trykk for derved å gi produktet som en tykk gul olje. Tilsetningen av heksan ga rent 3-klor-4-(2,4-diklorf enoksy)-2,5-dimetylanilin (4,82 g, 15,22 mmol, 80%) som et hvitt pulver. NMR-spektroskopiske data antydet følgende: H^-NME (CDCI3) 7,36 (d, J=2Hz, 1H), 6,95 (d,d; J=2,9Hz, 1H), 6,40 (br s, 1H), 6,32 (d, J=9Hz, 1H), 3,54 (br. s, 2H), 2,15 (s, 3H), 2,02 (s, 3H). ;Del C: Fremstilling av 1-[ 3- klor- 4-( 2, 4- diklorfenoksy)- 2, 5- dimetylfenyl] - 3-( 2, 6- difluorbenzoyl) urinstoff Til en magnetisk omrørt oppløsning av 3-klor-4-(2,4-diklorfenoksy) -2,5-dimetylanilin (1,5 g, 4,73 mmol) fremstilt under del B i 15 ml toluen og under nitrogenatmosfære ble det tilsatt ren 2,6-difluorbenzoylisocyanat (1,3 g, 7,10 mmol) og blandingen ble kokt under tiilbakeløp i en time. Reaksjonsblandingen ble tillatt avkjøling og 3 ml heksan ble tilsatt for å indusere krystallisering. Det resulterende presipitat ble filtrert og vasket suksessivt med heksan og toluen for derved å gi rent 1- [3-klor-4-(2,4-diklorf enoksy) -2,5-dimetylfenyl] -3-(2,6-difluorbenzoyl)urinstoff (2,29 g, 4,58 mmol, 97%) som et hvitt faststoff med smeltepunkt 188-190° C. Elementanalyse av.det hvite faststoffet antydet følgende: ;Analyse: C22H15Cl3F2<N>203 ; EKSEMPEL 2 ;Fremstilling av 1-[ 3- brom- 4-( 2, 4- diklorfenoksy)- 2, 5- dimetylfenyl] - 3-( 2,6-di f luo rbenzoyl) ur instof f ;Del A: Fremstilling av 2- brom- 3, 6- dimetyl- 4- nitrofenol ;Til en magnetisk omrørt suspensjon av 2,5-dimetyl-4-nitrofenol (12,70 g, 75,98 mmol) i 150 ml CH2CI2ved romtemperatur ble det porsjonsvis tilsatt N-bromsuccinimid (14,88 g, 83,58 mmol). Blandingen ble hurtig homogen og etter en time antydet tynnsjiktkromatografi med heksametylacetat volumforholdet 3:1, totalt forbruk av utgangsstoffet og dannelse av et enkelt hovedprodukt. 15 ml mettet Na2SC>3-oppløsning ble tilsatt og oppløsningsmidlet ble fjernet under redusert trykk. Etylacetat ble så tilsatt og det organiske sjikt ble vasket med vann og salt-oppløsning, tørket over Na2S04og konsentrert under redusert trykk for derved å gi 2-brom-3,6-dimetyl-4-nitrofenol (13,6 g, 55,3 mmol, 73%) som et rustfarget faststoff. H<*->NMR (CDCI3) 9,26 (br S, 1H), 7,71 (S, 1H), •2,60 (S, 3H), 2,31 (S, 3H). (1970). The reaction between the amino group in 19_ and the cyclohexane-1,2-dicarboxylic anhydride gives the imide 20. * The nitro group reduction, Sandmeyer halogenation and deprotection of the amino function gives the aniline 2L_ Details of these transformations are given in the experimental section below. ;Aminophenols of the type 17_ are readily available and can be prepared as illustrated by working up the aminophenol 25_ via nitration of a 2,5-disubstituted phenol 22_ followed by halogenation and nitro group reduction as indicated in scheme X below: ; wherein Rj and R3 have the meaning given in formula 1 and Y is bromine or chlorine. Their conversion to intermediates 23_and 24_ reflects that described by Albert and Sears in J. Am. Chem. Soc., 76, 4979; (1954). ;An alternative and complementary approach to the aminophenols 17_ is detailed in Scheme XI as follows: ; wherein R]_, R2 and R3 have the meanings given in formula 1. This involves the reaction of a trisubstituted phenol 26_ with a diazonium salt prepared from sulfanilic acid to thereby give the intermediate diazo compound 27 which is then reduced to give aminophenol 17^ The synthesis methodology used here to obtain aminophenol et 17_ is as described by Payne and Weiden in US-PS 3,752,838. Compounds described according to the invention can be used as insecticides according to methods well known to those skilled in the art. Pesticide preparations containing the compounds as active ingredient will usually comprise a carrier and/or a diluent, either liquid or solid. Suitable liquid diluents or carriers include water, petroleum distillates or other liquid carriers with or without surfactants. Liquid concentrates can be prepared by dissolving one of these compounds in a non-phytotoxic solvent such as acetone, xylene, nitrobenzene, cyclohexanone or dimethylformamide and dispersing the active ingredients in water using suitable surface-active emulsifying and dispersing agents. The choice of dispersing and emulsifying agents and the quantity used is dictated by the nature of the preparation and the agent's ability to facilitate the dispersion of the active ingredient. In general, it is desirable to use as little of the agent as possible, consistent with the desired dispersion of the active ingredient in the spray, so that rain does not re-emulsify the active ingredient after it has been applied to plants, thereby washing it off the plant. Non-ionic, anionic or cationic dispersing and emulsifying agents can be used, e.g. condensation products of alkylene oxides with phenol and organic acids, alkylaryl sulphonates, complex ether alcohols, quaternary ammonium compounds and the like. In the production of wettable powders or dust or granulated preparations, the active ingredient is dispersed in and on a suitably finely divided solid carrier such as clay, talc, bentonite, diatomaceous earth, fuller's earth and the like. When formulating the wettable powders, the above-mentioned dispersants as well as lignosulfonates can be incorporated. ;The required amount of active ingredient can be applied per about. 4 measures in a quantity of 1-200 gallons or more of liquid carrier and/or diluent or in a quantity of 50-500 pounds of inert solid carrier and/or diluent. The concentration in the liquid concentrate will usually vary from approx. 10-95% by weight and in fixed formulations from approx. 0.5-90% by weight. Satisfactory sprays, dusts or granules for general use contain from approx. 0.25-15 pounds of active ingredient per about. 4 goals. The pesticides described here prevent attacks by insects on plants and other material to which the pesticides have been applied, and they have a relatively high residual toxicity. For plants, they have a high margin of safety, in that when used in sufficient quantity to kill or repel insects, they do not burn or damage the plant, and they resist degradation including washing due to rain, decomposition due to ultraviolet light , oxidation or hydrolysis in the presence of moisture or, finally, such decomposition, oxidation and hydrolysis as significantly reduce the desired pesticidal characteristics of the active ingredients or to give these undesirable characteristics, e.g. phytotoxicity. The active ingredients are so chemically inert that they are now compatible with essentially any other ingredient within the spray spectrum, and they can be used in soil, on seeds, on plant roots without harming seeds, roots or plants. Mixtures of active ingredients can be used if this is desirable as well as combinations of active compounds according to the invention with other biologically active compounds or ingredients. The following examples are illustrative of the methods used in the production of intermediate products and compounds according to the invention. For NMR spectroscopy analyses, the chemical shifts were given in ppm downstream of ;TMS. EXAMPLE A Preparation of 4-(2,4-difluorophenoxy)-2,3,5-trichloroaniline 14.9 g (51.4 mmol) of 3,5-dichloro-4- (2,4-difluorophenoxy)aniline, 7.2 g (53.9 mmol) of N-chlorosuccinimide (NCS) and 100 ml of benzene. The reaction mixture was refluxed for 2 h, after which additional NCS (350 mg, 2.6 mmol) was added. The reflux was then continued for a further hour. The mixture was allowed to cool, diluted with 200 mL ethyl acetate and washed with H 2 O, saturated NaHCO 3 and brine, dried over Na 2 SO 4 and concentrated under reduced pressure. The oily residue was purified by flash column chromatography, hexair:toluene 1:1, and 4-(2,4-difluorophenoxy-2,3,5-trichloroaniline) was obtained (9.8 g, 30.2 mmol, 59% ) as a dark brown oil. The structure of this substance was verified by its Hi-NMR spectrum (CDCl3) 7.30-6.10 (m 3H; 6.75 (s, 1H), 4.18 (br s, 2H ). ;EXAMPLE B ;Preparation of 2-chloro-4-(2,4-dichlorophenoxy)-3,5-dimethylaniline ;Into a 200 ml 3-necked round flask was charged 6.76 g (24.0 mmol) 4 -(2,4-dichlorophenoxy)-3,5-dimethylaniline and 48 mL of benzene.N-chlorosuccinimide (3.85 g, 28.8 mmol) was then added and the resulting heterogeneous mixture was stirred at room temperature for one hour. was diluted with ethyl acetate, washed twice with sat. eluent Solvent removal below reduced pressure gave 2-chloro-4-(2,4-dichlorophenoxy)-3,5-dimethylaniline (6.5 g) contaminated with at least three other products. This material was placed in a Parr flask and dissolved in 50 ml of toluene. The par r flask was flushed with nitrogen. 650 mg 5%; platinum, on charcoal was added and the mixture was hydrogenated for one hour at 40-50 psi and room temperature in a Parr cradle hydrogenator. Filtration through a pad of celite and removal of the solvent and flash chromatography, hexane:ethyl acetate 9:1, gave pure 2-chloro-4-(2,4-dichlorophenoxy)-3,5-dimethylaniline (3.1 g , 9.8 mmol, 41%) as a crystallized solid with a melting point of 89-93 °C. Elemental analysis for the crystalline solid suggested the following: ;Analysis: (44H12CI3NO ; ; EXAMPLE C ; Preparation of 2, 5- dichloro- 4-( 2, 4- dichlorophenoxy)- 3- methylaniline and 2, 3- dichloro- 4-( 2, 4- dichlorophenoxy)- 5- methylaniline ; To a magnetically stirred To a solution of 3-chloro-4-(2,4-dichlorophenoxy)-5-methylaniline (9.0 g, 29.7 mmol) in 60 ml of benzene was added solid N-chlorosuccinimide (4.4 g, 32, 7 mmol). The mixture was stirred at room temperature for 1.5 hours, transferred to a separatory funnel and washed with saturated Na 2 SO 3 solution three times, with water twice and with brine once. The organic layer was dried over Na 2 SO 4 and concentrated under reduced pressure to give 10.08 g of crude product as a dark brown oil. Flash column chromatography on 500 g silica gel, hexanerethyl acetate 3:1 gave pure 2,5-dichloro-4-(2,4-dichlorophenoxy)-3-methylaniline (2.85 g, 7.4 mmol, 25%) with m.p. 96-97°C and 2,3-dichloro-4-(2,4-dichlorophenoxy)-5-methylaniline (2.16 g, 6.4 mmol, 22%) m.p. 95°C. Recrystallization from methanol gave analytical samples. Elemental analysis of the samples indicated the following: ;Analysis: (43<H>9CI4NO ; ; EXAMPLE D ;Preparation of 2-bromo-4-(2-bromo-4-chlorophenoxy)-3,5-dichloroaniline ;To a magnetically stirred solution of 4-(2-bromo-4-chlorophenoxy)-3,5-dichloroaniline (6.38 g, 17.36 mmol) in 35 ml of benzene was added N-bromosuccinimide (3.71 g, 20.83 mmol). The reaction mixture was stirred for 2 hours at room temperature, transferred to a separatory funnel and washed twice with saturated Na 2 SO 3 solution, twice with water and once with brine. The organic layer was dried over Na 2 SC 4 and concentrated under reduced pressure to give the crude product which was then subjected to flash column chromatography on 760 g of silica gel with hexamethyl acetate in the ratio 4:1, which gave pure 2.bromo-4-(2 -bromo-4-chlorophenoxy)-3,5-dichloroaniline (5.15 g, 11.53 mmol, 66%). Elemental analysis of the product indicated the following: ;Analysis: C^F^BnChNO ; ; EXAMPLE E ; Preparation of 4-amino- 2, 3, 6- trimethylphenol ; To a solution of sulfanilic acid (13.0 g, 68 mmol) in 68 ml of water contained in a 250 ml round bottom flask equipped with a magnetic stirrer, internal thermometer and ice bath, at 15 °C solid Na 2 SC 3 (3.69 g, 34 mmol) was added followed by a solution of NaNO 2 (5.1 g, 74 mmol) in 14 mL of water. The latter addition caused a color change from a milky white to orange. A separate 500 mL 3-necked flask equipped with a magnetic stirrer, internal thermometer, and ice bath was charged with 12 mL of concentrated hydrochloric acid, 68 g of ice, and the solution of the diazonium salt as prepared above. The mixture was stirred at 15"C for 45 minutes. Meanwhile, a third 1-liter flask, equipped with an internal thermometer, nitrogen inlet, condenser, addition funnel, and mechanical stirrer, was charged with 68 mL of water, NaOH (14.96 g, 318 mmol), and 2,3,6-trimethylphenol ( 9.30 g, 68 mmol). This mixture was cooled to 0°C using an ice-salt mixture and the diazonium salt-hydrochloric acid mixture as prepared above was added dropwise, keeping the temperature below 5°C. After complete diazonium salt addition, the reaction mixture was heated to 62 °C and solid Na 2 S 2 C>4 (3.13 g, 18 mmol) was added. Stirring was continued and the mixture was heated to 80 °C, after which additional Na 2 S 2 O 4 (28.2 g, 162 mmol) was added in three equal portions of 9.4 g each at 5 minute intervals. The mixture was heated to 80°C under nitrogen for 20 minutes, cooled to room temperature and filtered to give the crude product as a yellow solid. The solid was dissolved in 300 ml of ethyl acetate and washed with water. The organic layer was dried over Na 2 SO 4 and concentrated under reduced pressure to give 4-amino-2,3,6-trimethyl--■fenbri in quantitative yield, the compound was then successfully used in subsequent reactions without further purification. H 1 H NMR (CDCl 3 ) 6.30 (s, 1H), 2.11 (s, 9H). ; EXAMPLE 1 ; Preparation of 1-[ 3- chloro- 4-( 2, 4- dichlorophenoxy)- 2, 5- dimethylphenyl] - 3-( 2,6-difluorobenzoyl) urea ; Part A: Preparation of 3- chloro- 4-(2,4-dichlorophenoxy)-2,5-dimethylnitro-benzene; 10.0 g (45.44 mmol) of 3,4-dichloro were charged to a 250 ml 3-neck round flask equipped with a magnetic stirrer and nitrogen inlet -2,5-dimethylnitrobenzene, 7.95 g (48.81 mmol) of 2,4-dichlorophenol, 9.41 g (68.11 mmol) of potassium carbonate and 60 ml of dimethylformamide. The reaction mixture was stirred and heated to a temperature of 100 °C for a period of 20 hours and then cooled to room temperature, filtered and concentrated under reduced pressure. The residue was diluted with methylene chloride and the organic layer was washed with 4% NaOH solution twice and then brine, dried over Na2SO4 and concentrated under reduced pressure to give the crude product as a dark brown viscous liquid. The addition of hexane and ethyl acetate afforded a light brown solid which was subjected to Kugelrohr distillation (ca. 180 °C and ca. 0.1 mm Hg) to obtain pure 3-chloro-4-(2,4-dichlorophenoxy)-2, 5-Dimethylnitrobenzene (7.17 g, 20.7 mmol, 45%) as a yellow solid, mp 118-121 °C. NMR spectroscopic analysis suggested the following: H 1 -NMR (CDCl 3 ) 7.76 (br S, 1H), 7.53 (d, J=2Hz, 1H), 7.12 (d,d; 2.9Hz, 1H ), 6.34 (d, J=9Hz, 1H), 2.45 (S, 3H), 2.24 (S, 3H). ;Part B: Preparation of 3-chloro-4-(2,4-dichlorophenoxy)-2,5-dimethylaniline To a 250 ml Parr flask was charged 6.59 g (19.01 mmol) of 3-chloro-4 -(2,4-dichlorophenoxy)-2,5-dimethylnitrobenzene prepared under part A and 15 ml of toluene. The flask was filled with nitrogen and 650 mg of solid 10% platinum on carbon was added. The reaction mixture was then hydrogenated for 45 minutes at 43-47 psi hydrogen pressure and room temperature on a Parr cradle hydrogenator. The catalyst was removed by filtration through celite and the filtrate was concentrated under reduced pressure to give the product as a thick yellow oil. The addition of hexane gave pure 3-chloro-4-(2,4-dichlorophenoxy)-2,5-dimethylaniline (4.82 g, 15.22 mmol, 80%) as a white powder. NMR spectroscopic data suggested the following: H 2 -NME (CDCl 3 ) 7.36 (d, J=2Hz, 1H), 6.95 (d,d; J=2.9Hz, 1H), 6.40 (br s , 1H), 6.32 (d, J=9Hz, 1H), 3.54 (br. s, 2H), 2.15 (s, 3H), 2.02 (s, 3H). ;Part C: Preparation of 1-[ 3- chloro- 4-( 2, 4- dichlorophenoxy)- 2, 5- dimethylphenyl]- 3-( 2, 6- difluorobenzoyl) urea To a magnetically stirred solution of 3-chloro- 4-(2,4-Dichlorophenoxy)-2,5-dimethylaniline (1.5 g, 4.73 mmol) prepared in Part B in 15 mL of toluene and under a nitrogen atmosphere was added pure 2,6-difluorobenzoisocyanate (1,3 g, 7.10 mmol) and the mixture was refluxed for one hour. The reaction mixture was allowed to cool and 3 ml of hexane was added to induce crystallization. The resulting precipitate was filtered and washed successively with hexane and toluene to give pure 1-[3-chloro-4-(2,4-dichlorophenoxy)-2,5-dimethylphenyl]-3-(2,6-difluorobenzoyl )urea (2.29 g, 4.58 mmol, 97%) as a white solid, mp 188-190° C. Elemental analysis of the white solid indicated the following: ;Analysis: C22H15Cl3F2<N>203 ; EXAMPLE 2: Preparation of 1-[3-bromo-4-(2,4-dichlorophenoxy)-2,5-dimethylphenyl]-3-(2,6-difluorobenzoyl) urinstoff; Part A: Preparation of N -bromosuccinimide (14.88 g, 83.58 mmol). The mixture quickly became homogeneous and after one hour thin layer chromatography with hexamethyl acetate indicated the volume ratio 3:1, total consumption of the starting material and formation of a single main product. 15 ml of saturated Na2SO3 solution was added and the solvent was removed under reduced pressure. Ethyl acetate was then added and the organic layer was washed with water and brine, dried over Na 2 SO 4 and concentrated under reduced pressure to give 2-bromo-3,6-dimethyl-4-nitrophenol (13.6 g, 55.3 mmol, 73%) as a rust-colored solid. H<*>NMR (CDCl 3 ) 9.26 (br S, 1H), 7.71 (S, 1H), 2.60 (S, 3H), 2.31 (S, 3H).
Del B: Fremstilling av 4- amino- 2- brom- 3, 6- dimetylfenol Part B: Preparation of 4-amino-2-bromo-3,6-dimethylphenol
Til en Parr-kolbe ble det chargert 2-brom-3~,6-dimetyl-4-nitrofenol (13,6 g, 55,3 mmol) fremstilt i del A samt 50 ml etylacetat. Reaksjons-beholderen ble spylt med nitrogen og 1,36 g 5% platina på trekull ble tilsatt umiddelbart etter spylingen. To a Parr flask was charged 2-bromo-3~,6-dimethyl-4-nitrophenol (13.6 g, 55.3 mmol) prepared in part A and 50 ml of ethyl acetate. The reaction vessel was purged with nitrogen and 1.36 g of 5% platinum on charcoal was added immediately after the purge.
Hydrogeneringen ble gjennomført på en Parr-vugge-hydrogenator i 1,5 time ved et hydrogentrykk på 40-50 psi og ved romtemperatur. Reaksjonsblandingen ble filtrert gjennom celite og konsentrert under redusert trykk og man oppnådde 4-amino-2-brom-3,6-dimetylfenol som et brunt faststoff i kvantitativt utbytte. The hydrogenation was carried out on a Parr cradle hydrogenator for 1.5 hours at a hydrogen pressure of 40-50 psi and at room temperature. The reaction mixture was filtered through celite and concentrated under reduced pressure to give 4-amino-2-bromo-3,6-dimethylphenol as a brown solid in quantitative yield.
h!-NMR (CDCl3-DMSO-d6): 6,40 (S, 1H), 2,17 (br S, 6H). h!-NMR (CDCl 3 -DMSO-d 6 ): 6.40 (S, 1H), 2.17 (br S, 6H).
Del C: Fremstilling av 3- brom- 4-( 2- klor- 4- nitrofenoksy)- 2, 5- dimetylanilin Part C: Preparation of 3-bromo-4-(2-chloro-4-nitrophenoxy)-2,5-dimethylaniline
Til en tørr 250 ml rundkolbe utstyrt med magnetisk røreverk og nitrogen-innløp ble det tilsatt 4-amino-2-brom-3,6-dimetylfenol (11,94 g, 55,3 mmol) fremstilt i del B og 118 ml tørr dimetylsulfoksyd. Kalium-t-butoksyd (7,26 g, 64,65 mmol) ble tilsatt porsjonsvis under nitrogen og blandingen ble omrørt ved romtemperatur i 0,5 timer. Fast 3,4-diklor-nitrobenzen (13,33 g, 70,52 mmol) ble så tilsatt og reaksjonsblandingen ble oppvarmet til 50 °C i 48 timer. Etter avkjøling ble blandingen fortynnet med toluen og vasket suksessivt tre ganger med mettet NH4CI-oppløsning og med 5 %-ig NaOH-oppløsning inntil vaskevannet forble fargeløst. Dette ble fulgt med vaskinger med vann og saltoppløsning, tørking over Na2S04og oppløsningsmiddelfjerning under redusert trykk for derved å oppnå 9,4 g av råproduktet som en mørk rødbrun olje. Flash-kolonnekromatografi på 650 g silikagel med heksanretylacetat i volumforholdet 3:1 ga rent 3-brom-4-(2-klor-4-nitrofenoksy)-2,5-dimetylanilin (4,7 g, 12,6 mmol, 23%) som et gulbrunt faststoff. H^-NMR (CDCI3) 8,42 (d, J=2Hz, 1H), 8,01 (d,d; J=2,9Hz, 1H), 6,55 (d,J=9Hz, 1H), 6,58 (S, 1H), 3,73 (br S, 2H), 2,28 (S, 3H), 2,06 (S, 3H). To a dry 250 mL round bottom flask equipped with a magnetic stirrer and nitrogen inlet was added 4-amino-2-bromo-3,6-dimethylphenol (11.94 g, 55.3 mmol) prepared in Part B and 118 mL of dry dimethyl sulfoxide . Potassium t-butoxide (7.26 g, 64.65 mmol) was added portionwise under nitrogen and the mixture was stirred at room temperature for 0.5 h. Solid 3,4-dichloronitrobenzene (13.33 g, 70.52 mmol) was then added and the reaction mixture was heated to 50 °C for 48 h. After cooling, the mixture was diluted with toluene and washed successively three times with saturated NH 4 Cl solution and with 5% NaOH solution until the wash water remained colorless. This was followed by washings with water and brine, drying over Na 2 SO 4 and solvent removal under reduced pressure to thereby obtain 9.4 g of the crude product as a dark reddish-brown oil. Flash column chromatography on 650 g silica gel with 3:1 v/v hexane-rethyl acetate gave pure 3-bromo-4-(2-chloro-4-nitrophenoxy)-2,5-dimethylaniline (4.7 g, 12.6 mmol, 23% ) as a yellow-brown solid. H 2 NMR (CDCl 3 ) 8.42 (d, J=2Hz, 1H), 8.01 (d,d; J=2.9Hz, 1H), 6.55 (d,J=9Hz, 1H), 6.58 (S, 1H), 3.73 (br S, 2H), 2.28 (S, 3H), 2.06 (S, 3H).
Del D: Fremstilling av 8- [ 3- brom- 4-( 2- klor- 4- nitrofenoksy)- 2, 5- dimetylfenyl] - 8- azabicyklo [ 4. 3. 0] nonan- 7, 9- dion Til en oppløsning av 3-brom-4-(2-klor-4-nitrofenoksy)-2,5-dimetylanilin (4,7 g, 12,65 mmol) fremstilt i del C i 40 ml toluen ble det tilsatt cis-1,2-cykloheksandikarboksylsyreanhydrid (20,48 g, 132,83 mmol) og en spatelspiss toluensulfonsyre. Reaksjonsblandingen ble oppvarmet til tilbakeløp over natt og tillatt avkjøling; vasket fem ganger med 5 %-ig NaOH-oppløsning, tre ganger med vann og en gang med saltoppløsning; tørket over Na2S04og konsentrert under redusert trykk for å oppnå det ønskede råprodukt som en tykk brun olje (5,43 g, 10,69 mmol, 84%) som krystalliserte ved henstand og hadde et smeltepunkt på 187-190 °C. Part D: Preparation of 8- [ 3- bromo- 4-( 2- chloro- 4- nitrophenoxy)- 2, 5- dimethylphenyl] - 8- azabicyclo [ 4. 3. 0] nonane- 7, 9-dione To a To a solution of 3-bromo-4-(2-chloro-4-nitrophenoxy)-2,5-dimethylaniline (4.7 g, 12.65 mmol) prepared in Part C in 40 mL of toluene was added cis-1,2 -cyclohexanedicarboxylic anhydride (20.48 g, 132.83 mmol) and a spatula tip of toluenesulfonic acid. The reaction mixture was heated to reflux overnight and allowed to cool; washed five times with 5% NaOH solution, three times with water and once with saline; dried over Na 2 SO 4 and concentrated under reduced pressure to afford the desired crude product as a thick brown oil (5.43 g, 10.69 mmol, 84%) which crystallized on standing and mp 187-190 °C.
Hi-NMR (CDCI3) 8,40 (d, J=2Hz, 1H), 8,02 (d,d; J=2,9Hz, 1H), 7,00 (br. S, 1H), 6,55 (d, J=9Hz, 1H), 3,10 (M, 2H), 2,21 (br S, 6H), 1,93 (M, 4H), 1,58 (m, 4H). Hi-NMR (CDCl3) 8.40 (d, J=2Hz, 1H), 8.02 (d,d; J=2.9Hz, 1H), 7.00 (br. S, 1H), 6.55 (d, J=9Hz, 1H), 3.10 (M, 2H), 2.21 (br S, 6H), 1.93 (M, 4H), 1.58 (m, 4H).
Del E: Fremstilling av 8- [ 4-( 4- amino- 2- klorfenoksy)- 3- brom- 2,5-dimetylfenyl] - 8- azabicyklo[ 4. 3. 0] nonan- 7, 9- dion Part E: Preparation of 8- [ 4-( 4- amino- 2- chlorophenoxy)- 3- bromo- 2,5-dimethylphenyl]- 8- azabicyclo[ 4. 3. 0] nonane- 7, 9-dione
Til en Parr-kolbe ble det chargert 8- [3-brom-4-(2-klor-4-nitrof enoksy) - 2,5-dimetylfenyl] -8-azabicyklo [4.3.0] nonan-7,9-dion (3,45 g, 6,79 mmol) fremstilt i del D og 100 ml etylacetat. Reaksjonsblandingen ble spylt med nitrogen, 480 mg 5% platina på karbon ble tilsatt og blandingen ble hydrogenert i 1,5 timer ved et hydrogentrykk på 40-50 psi og ved romtemperatur på en Parr-vugge-hydrogenator. Filtrering gjennom celite og konsentrering under redusert trykk ga det ønskede produkt (2,73 g, 5,71 mmol, 84%). H^-NMR (CDC13) 6,93 (br s, 1H), 6,80 (d, J=2Hz, 1H), 6,33 (m, 2H), 3,45 (br s, 2H), 3,06 (br m, 2H), 2,4-1,2 (m, 14H). To a Parr flask was charged 8-[3-bromo-4-(2-chloro-4-nitrophenoxy)-2,5-dimethylphenyl]-8-azabicyclo[4.3.0]nonane-7,9-dione (3.45 g, 6.79 mmol) prepared in Part D and 100 mL of ethyl acetate. The reaction mixture was flushed with nitrogen, 480 mg of 5% platinum on carbon was added and the mixture was hydrogenated for 1.5 hours at a hydrogen pressure of 40-50 psi and at room temperature on a Parr cradle hydrogenator. Filtration through celite and concentration under reduced pressure gave the desired product (2.73 g, 5.71 mmol, 84%). H 3 NMR (CDCl 3 ) 6.93 (br s, 1H), 6.80 (d, J=2Hz, 1H), 6.33 (m, 2H), 3.45 (br s, 2H), 3 .06 (br m, 2H), 2.4-1.2 (m, 14H).
Del F: Fremstilling av 3- brom- 4-( 2, 4- diklorfenoksy)- 2, 5- dimetylanilin Til en iskjølt, magnetisk omrørt oppløsning av NaNO^(420 mg, 6,07 mmol) Part F: Preparation of 3- bromo- 4-( 2, 4- dichlorophenoxy)- 2, 5- dimethylaniline To an ice-cooled, magnetically stirred solution of NaNO^ (420 mg, 6.07 mmol)
i 3,0 ml konsentrert svovelsyre ble det dråpevis tilsatt en oppløsning av 8- [4 -(4- amino-2- klor fenoksy) -3-b rom- 2,5- dimetylf enyl ] -8- azabicyklo-[4.3.0] nonan-7,9-dion (2,66 g, 5,57 mmol) fremstilt i del E i 14 ml eddiksyre, mens den innvendige temperatur ble holdt under 15 °C. Reaksjonsblandingen ble omrørt i 15 minutter ved 15"C og så i 2 timer ved omgivelsestemperatur. I løpet av dette sistnevnte tidsrom ble en ' oppløsning av kobber (I) klorid fremstilt som følger: Til en oppløsning fremstilt fra CuS04-(H20)5(4,85 g, 19,44 mmol), NaCl (830 mg, 14,20 •mmol) og 22 ml vann ble det. under nitrogen tilsatt en oppløsning fremstilt fra NaHS03(780 mg, 7,46 mmol), NaOH (450 mg, 9,56 mmol) og 4 ml vann. Blandingen ble rystet forsiktig og supernatanten ble dekantert av. Det kremfargede presipitat ble vasket tre ganger med vann inntil den dekanterte supernatant var fargeløs. 12 ml konsentrert saltsyre ble så tilsatt, noe som ga en blek grønn oppløsning inneholdende kobber(I)klorid. Til denne oppløsning ble det dråpevis tilsatt diazoniumsalt i eddiksyre/H2S04og blandingen ble omrørt i 0,5 timer. Reaksjonsblandingen ble fortynnet med etylacetat og vasket med mettet Na2S03~oppløsning, vann og saltoppløsning; tørket Na2S04og konsentrert under redusert trykk for derved å gi råproduktet (2,4 g, 4,8 mmol, 86%) som et gyldent faststoff. in 3.0 ml of concentrated sulfuric acid, a solution of 8-[4-(4-amino-2-chlorophenoxy)-3-brom-2,5-dimethylphenyl]-8-azabicyclo-[4.3 was added dropwise. 0] nonane-7,9-dione (2.66 g, 5.57 mmol) prepared in Part E in 14 mL of acetic acid, while maintaining the internal temperature below 15 °C. The reaction mixture was stirred for 15 minutes at 15°C and then for 2 hours at ambient temperature. During this latter time a solution of copper (I) chloride was prepared as follows: To a solution prepared from CuSO4-(H2O)5( 4.85 g, 19.44 mmol), NaCl (830 mg, 14.20 mmol) and 22 mL of water was added under nitrogen to a solution prepared from NaHSO 3 (780 mg, 7.46 mmol), NaOH (450 mg, 9.56 mmol) and 4 mL of water. The mixture was shaken gently and the supernatant was decanted off. The cream-colored precipitate was washed three times with water until the decanted supernatant was colorless. 12 mL of concentrated hydrochloric acid was then added, giving a pale green solution containing copper(I) chloride. To this solution was added dropwise the diazonium salt in acetic acid/H2SO4 and the mixture was stirred for 0.5 hours. The reaction mixture was diluted with ethyl acetate and washed with saturated Na2SO3 solution, water and brine; dried Na2SO4 and concentrated under reduced pressure to thereby give the crude product (2.4 g, 4.8 mmol, 86%) as a golden solid.
Råproduktet (2,0 g, 4,02 mmol) ble oppløst 8 ml metanol og hydrazin-monohydrat (20,1 g, 402 mmol) ble tilsatt dråpevis. Blandingen ble oppvarmet til tilbakeløp i 48 timer, avkjølt og fortynnet med etylacetat og vann. 2% vandig saltsyre ble tilsatt inntil den vandige fase var homogen. Det organiske sjikt ble så vasket tre ganger med vann og saltoppløsning, tørket over Na2S04og konsentrert under redusert trykk for derved å oppnå det ønskede produkt (1,10 g, 3,05 mmol, 76%) som en oransje olje som langsomt krystalliserte ved henstand. The crude product (2.0 g, 4.02 mmol) was dissolved in 8 mL of methanol and hydrazine monohydrate (20.1 g, 402 mmol) was added dropwise. The mixture was heated to reflux for 48 hours, cooled and diluted with ethyl acetate and water. 2% aqueous hydrochloric acid was added until the aqueous phase was homogeneous. The organic layer was then washed three times with water and brine, dried over Na 2 SO 4 and concentrated under reduced pressure to give the desired product (1.10 g, 3.05 mmol, 76%) as an orange oil which slowly crystallized on standing. .
Hi-NMR (CDCI3) 7,45 (d, J=2Hz, 1H), 7,05 (d,d; J=2,9Hz, 1H), Hi-NMR (CDCl 3 ) 7.45 (d, J=2Hz, 1H), 7.05 (d,d; J=2.9Hz, 1H),
6,54 (br S, 1H), 6,37 (d, J=9Hz, 1H), 3,63 (br S, 2H), 2,26 (S, 3H), 2,06 (S, 3H). 6.54 (br S, 1H), 6.37 (d, J=9Hz, 1H), 3.63 (br S, 2H), 2.26 (S, 3H), 2.06 (S, 3H) .
Del G: Fremstilling av l-( 3- brom- 4-( 2, 4- diklorfenoksy)- 2, 5- dimetylfenyl)- 3-( 2, 6- difluorbenzoyl) urinstoff Part G: Preparation of 1-(3-bromo-4-(2,4-dichlorophenoxy)-2,5-dimethylphenyl)-3-(2,6-difluorobenzoyl)urea
Til en magntisk omrørt oppløsning av 3-brom-4-(2,4-diklorfenoksy) -2,5-dimetylanilin (960 mg, 2,67 mmol) fremstilt i del F, i 5 ml heksamtoluen 1:1, ble det tilsatt ren 2,6-difluorbenzoylisocyanat (490 mg, 2,67 mmol) og blandingen ble omrørt under nitrogenatmosfære i 10 minutter. Det resulterende presipitat ble samlet på en filtertrakt, vasket med toluen og tørket for derved å oppnå det ønskede produkt (1,26 g, 2,3 mmol, 87%) som et hvitaktig pulver med et smeltepunkt på 205-209° C. NMR-spektroskopisk analyse antydet følgende: H^-NMR (CDCI3) 11,60 (br s, 1H), 10,17 (br s, 1H), 8,00-7,10 (m, 6H), 6,43 (d, J=9Hz, 1H), 2,39 (s, 3H), 2,11 (s, 3H). To a magnetically stirred solution of 3-bromo-4-(2,4-dichlorophenoxy)-2,5-dimethylaniline (960 mg, 2.67 mmol) prepared in Part F, in 5 mL of hexamtoluene 1:1, was added neat 2,6-difluorobenzoisocyanate (490 mg, 2.67 mmol) and the mixture was stirred under a nitrogen atmosphere for 10 minutes. The resulting precipitate was collected on a filter funnel, washed with toluene and dried to afford the desired product (1.26 g, 2.3 mmol, 87%) as an off-white powder with a melting point of 205-209°C. NMR -spectroscopic analysis suggested the following: H 2 NMR (CDCl 3 ) 11.60 (br s, 1H), 10.17 (br s, 1H), 8.00-7.10 (m, 6H), 6.43 ( d, J=9Hz, 1H), 2.39 (s, 3H), 2.11 (s, 3H).
EKSEMPLENE 3 - 102 EXAMPLES 3 - 102
På en måte som antydet i de ovenfor angitte eksempler og ved å bruke et av de synteseskjemaer som tidligere er beskrevet ble andre urinstof f-forbindelser fremstilt. Identiteten av disse for den generiske formel og de analytiske data er gitt i tabell I nedenfor: In a manner as indicated in the examples given above and by using one of the synthesis schemes previously described, other urea compounds were prepared. The identity of these for the generic formula and the analytical data is given in Table I below:
Visse representative eksempler på de nye forbindelser ble evaluert for å bestemme deres pesticide virkning mot visse insekter inkludert en larve og en bille. De nye forbindelser ble også prøvet på fytotoksisitet på viktige økonomiske avlinger inkludert prydbønne, agurk og durra. De nye forbindelser ble ytterligere evaluert på giftighet overfor pattedyr. Certain representative examples of the new compounds were evaluated to determine their pesticidal activity against certain insects including a caterpillar and a beetle. The new compounds were also tested for phytotoxicity on important economic crops including ornamental bean, cucumber and sorghum. The new compounds were further evaluated for mammalian toxicity.
Suspensjoner av prøveforbindelser ble fremstilt ved å oppløse 100 mg forbindelse i en 1,5 ml dimetylformamid og så å tilsette 8,5 ml av en acetonoppløsning inneholdende 0,25% av et alkylfenoksypolyetoksyetanol-overflateaktivt middel som emulgerings- eller dispergeringsmiddel. Den resulterende oppløsning ble blandet i 30 ml vann for derved å gi grovt regnet 40 ml av en suspensjon inneholdende forbindelsen i findelt form. Den således fremstilte suspensjon inneholdt 2,5 vekt-% forbindelse. Prøvekonsentrasjonen i ppm på vektbasis som ble benyttet i prøvene nedenfor ble oppnådd ved egnet fortynning av, utgangssuspensjonen med vann. Sonikering ble benyttet der det var nødvendig for å oppnå en homogen suspensjon. Prøveprosedyrene var som følger: Suspensions of test compounds were prepared by dissolving 100 mg of compound in 1.5 ml of dimethylformamide and then adding 8.5 ml of an acetone solution containing 0.25% of an alkylphenoxypolyethoxyethanol surfactant as an emulsifier or dispersant. The resulting solution was mixed in 30 ml of water to give roughly 40 ml of a suspension containing the compound in finely divided form. The thus prepared suspension contained 2.5% by weight of compound. The sample concentration in ppm on a weight basis used in the samples below was obtained by suitable dilution of the starting suspension with water. Sonication was used where necessary to achieve a homogeneous suspension. The test procedures were as follows:
Hærmygg- bladsprayprøve Army midge leaf spray test
Larver av "southern" hærmygg (Spodoptera eidania (Cram.)) på Tendergreen bønneplante ved en temperatur av 80°± 5°F og en relativ fuktighet på 50 ± 5 % utgjorde prøveinsektene. Larvae of "southern" armyworm (Spodoptera eidania (Cram.)) on Tendergreen bean plant at a temperature of 80°± 5°F and a relative humidity of 50 ± 5% constituted the test insects.
Prøveforbindelsene ble formulert ved å fortynne utgangssuspensjonen med vann for derved å gi en suspensjon inneholdende prøveforbindelsen i den konsentrasjon (i deler prøveforbindelse pr. million deler sluttformulering) som angitt i tabellene nedenfor. Pottede tendergreen-bønneplanter av standard høyde og vekt ble anbragt på et dreiebord og besprøytet med 100 ml prøveforbindelseformulering ved bruk av en DeVilbiss-sprøytepistol ved et lufttrykk på 40 psig. Denne påføring som varte i .25 sekunder var tilstrekkelig til å fukte planten til avrenning. Som en kontroll ble 100 ml vann-aceton-emulgeringsmiddeloppløsning uten prøveforbindelse også sprøytet på infiserte planter. Etter tørking ble de parrede blader separert og hver ble anbragt i en 9 cm Petri-skål utforet med fuktet filterpapir. Fem tilfeldig valgte larver ble innført i hver skål og skålene ble lukket. De lukkede skåler ble merket og holdt ved 80-85"F i 5 dager. Selv om larven lett kunne konsumere det hele blad i løpet av 24 timer, ble det ikke tilført mere næring. Larver som ikke var i stand til å bevege lengderetningen av kroppen selv ved stimulering med prikking, ble ansett døde. Prosent dødelighet ble skrevet ned for forskjellige konsentrasjonsnivåer. The test compounds were formulated by diluting the starting suspension with water to thereby give a suspension containing the test compound at the concentration (in parts test compound per million parts final formulation) as indicated in the tables below. Potted tender green bean plants of standard height and weight were placed on a rotary table and sprayed with 100 ml of test compound formulation using a DeVilbiss spray gun at an air pressure of 40 psig. This application lasting .25 seconds was sufficient to wet the plant until runoff. As a control, 100 ml water-acetone emulsifier solution without test compound was also sprayed on infected plants. After drying, the paired leaves were separated and each was placed in a 9 cm Petri dish lined with moistened filter paper. Five randomly selected larvae were introduced into each dish and the dishes were closed. The closed dishes were labeled and held at 80-85"F for 5 days. Although the larva could easily consume the entire leaf within 24 hours, no additional food was added. Larvae that were unable to move longitudinally off the body even when stimulated by pricking, was considered dead.Percent mortality was recorded for different concentration levels.
Mexikansk bønnebille- bladsprayprøve Mexican bean beetle foliar spray test
Tredje stadiums larver av den mexikanske bønnebille (Ephilachna varivestis, Muls.) som beitet på Tendergreen-bønneplanter ved en temperatur av 80° ± 5° F og 50 ± 5 % relativ fuktighet, var prøve-insektene. Third instar larvae of the Mexican bean beetle (Ephilachna varivestis, Muls.) grazing on Tendergreen bean plants at a temperature of 80° ± 5° F and 50 ± 5% relative humidity were the test insects.
Prøveforbindelsene ble formulert ved å fortynne utgangssuspensjonen med The test compounds were formulated by diluting the starting suspension with
vann for derved å gi en suspensjon inneholdende prøveforbindelsen i den konsentrasjon (i deler prøveforbindelse pr. million deler sluttformulering) water to thereby give a suspension containing the test compound at that concentration (in parts test compound per million parts final formulation)
som angitt i tabellene nedenfor. Pottede tendergreen-bønneplanter av standard høyde og vekt ble anbragt på et dreiebord og besprøytet med 100 ml prøveforbindelseformulering ved bruk av en DeVilbiss-sprøytepistol ved et lufttrykk på 40 psig. Denne påføring som varte i 25 sekunder var tilstrekkelig til å fukte planten til avrenning. Som en kontroll ble 100 ml<y>ann-aceton-emulgeringsmiddeloppløsriing uten prøveforbindelse også ~ sprøytet på infiserte planter. Etter tørking ble de parrede blader separert as indicated in the tables below. Potted tender green bean plants of standard height and weight were placed on a rotary table and sprayed with 100 ml of test compound formulation using a DeVilbiss spray gun at an air pressure of 40 psig. This application lasting 25 seconds was sufficient to wet the plant until runoff. As a control, 100 ml<y>ann-acetone emulsifier solution without test compound was also ~ sprayed on infected plants. After drying, the paired leaves were separated
og hver ble anbragt i en 9 cm Petri-skål utforet med fuktet filterpapir. Fem tilfeldig valgte larver ble innført i hver skål og skålene ble lukket. and each was placed in a 9 cm Petri dish lined with moistened filter paper. Five randomly selected larvae were introduced into each dish and the dishes were closed.
De lukkede skåler ble merket og holdt ved en temperatur av 80°± 5°F i The sealed dishes were labeled and maintained at a temperature of 80°± 5°F i
5 dager. Selv om larvene lett kunne spise bladet i løpet av 24-48 timer, 5 days. Although the larvae could easily eat the leaf within 24-48 hours,
ble det ikke tilsatt mer næring. Larver som ikke kunne bevege kropps-lengden, selv ved stimulering, ble ansett døde. no more nutrition was added. Larvae that could not move their body length, even when stimulated, were considered dead.
Tobakk " Budworm"- og bomull " Bollworm"- bladsprayprøve Tobacco "Budworm" and cotton "Bollworm" leaf spray test
Annet stadium larver av tobakk "budworm" med en vekt på ca. 2,5 mg (Heliothis virescens, F.) og bomulls "bollworm" med en vekt på ca. 2,5 Second stage larvae of tobacco "budworm" with a weight of approx. 2.5 mg (Heliothis virescens, F.) and cotton "bollworm" with a weight of approx. 2.5
mg (Heliothis zea. (Boddie)), begge kommersielt oppnådd og beitende på kunstig diett ved en temperatur av 80°± 5° F og en relativ fuktighet på mg (Heliothis zea. (Boddie)), both commercially obtained and grazing on artificial diets at a temperature of 80°± 5° F and a relative humidity of
50 ± 5 % utgjorde prøveinsektene. 50 ± 5% constituted the test insects.
Ved bruk av en prosedyre tilsvarende den ovenfor angitte, men ved å benytte bomullsplanter i stedet for prydbønner, ble behandlede og tørkede bomullsblader innført i 9 cm Petri-skåler som var organisert i gruppe på 10 skålsett. En tilfeldig valgt larve ble innført i hver skål i et 10 skålsett og skålen ble lukket. De lukkede skåler ble merket og holdt ved 80"± 5"F i 5 dager. Larver som ikke var i stand til å bevege lengden av kroppen, selv ved stimulering, ble ansett døde. Dødelighetsprosenten ble notert for de forskjellige konsentrasjonsnivåer. Using a procedure similar to that stated above, but using cotton plants instead of ornamental beans, treated and dried cotton leaves were introduced into 9 cm Petri dishes which were organized into groups of 10 dish sets. A randomly selected larva was introduced into each dish in a 10 dish set and the dish was closed. The closed dishes were labeled and held at 80"± 5"F for 5 days. Larvae that were unable to move the length of their body, even when stimulated, were considered dead. The mortality rate was noted for the different concentration levels.
De biologiske egenskaper for visse representative eksempler av forbindelsene ifølge oppfinnelsen er angitt i tabellene II, III, IV, V og VI nedenfor. The biological properties for certain representative examples of the compounds according to the invention are set out in Tables II, III, IV, V and VI below.
Eksemplene 103 - 108 og Sammenlignende eksempler A- D Examples 103-108 and Comparative Examples A-D
For å demonstrere den forbedrede biologiske aktivitet mot "Southern" hærmygg og mexikansk bønnebille ble representative l-(4-fenoksyfenyl)-3-benzoylurinstof f-forbindelser ifølge oppfinnelsen sammenlignet med kjente forbindelser. Resultatene er angitt i tabell III nedenfor. Fra de data som er gitt i tabell III er det klart atl-(4-fenoksyfenyl)-3-benzoylurinstof f -forbindelsene ifølge oppfinnelsen tilveiebringer betydelig forbedret biologisk aktivitet mot "Southern" hærmygg og mexikansk bønnebille sammenlignet med kjente forbindelser. Som brukt i tabell III ble forbindelsen i sammenligningseksempel A fremstilt på en måte tilsvarende det som er beskrevet i US-PS 4.399.152. Forbindelsen i sammenligningseksempel B ble fremstilt i henhold til US-PS 4.068.002. Forbindelsene i sammenligningseksempel C ble fremstilt i henhold til EP-PS 0069288. Forbindelsen ifølge sammenligningseksempel D ble fremstilt tilsvarende JP-PS 5.5038.357. To demonstrate the improved biological activity against "Southern" armyworm and Mexican bean beetle, representative 1-(4-phenoxyphenyl)-3-benzoylurea compounds of the invention were compared with known compounds. The results are set out in Table III below. From the data given in Table III, it is clear that the atl-(4-phenoxyphenyl)-3-benzoylurea compounds according to the invention provide significantly improved biological activity against "Southern" armyworm and Mexican bean beetle compared to known compounds. As used in Table III, the compound in Comparative Example A was prepared in a manner similar to that described in US-PS 4,399,152. The compound in Comparative Example B was prepared according to US-PS 4,068,002. The compounds in comparative example C were prepared according to EP-PS 0069288. The compound according to comparative example D was prepared according to JP-PS 5.5038.357.
Eksemplene 109 - 144 og sammenligningseksemplene E - H Examples 109-144 and Comparative Examples E-H
For ytterligere å vise den forbedrede biologiske aktivitet mot mexikansk bønnebille ble representative 1 - (4-f enoksyf enyl)-3-benzoylurinstof f - forbindelser ifølge oppfinnelsen sammenlignet . med kjente forbindelser. Resultatene er angitt i tabell IV nedenfor. ^ Fra de data som finnes i tabell IV, er det klart at 1-(4-f enoksyf enyl)-3-benzoylurinstof f-forbindelsene ifølge oppfinnelsen gir sterkt forbedret biologisk aktivitet mot mexikansk bønnebille sammenlignet med de kjente forbindelser. I tabell IV ble forbindelsen fra sammenligningseksempel E fremstilt i henhold til US-PS 4.399.152, forbindelsen i sammenligningseksempel F ble fremstilt tilsvarende US-PS 4.005.223, forbindelsen i sammenligningseksempel G ble fremstilt i henhold til US-PS 4.005.223 og forbindelsen fra sammenligningseksempel H ble fremstilt i henhold til US-PS 4.041.177. To further demonstrate the improved biological activity against the Mexican bean beetle, representative 1-(4-phenoxyphenyl)-3-benzoylurea compounds according to the invention were compared. with known compounds. The results are set out in Table IV below. ^ From the data found in Table IV, it is clear that the 1-(4-phenoxyphenyl)-3-benzoylurea compounds according to the invention provide greatly improved biological activity against the Mexican bean beetle compared to the known compounds. In Table IV, the compound of Comparative Example E was prepared according to US-PS 4,399,152, the compound of Comparative Example F was prepared according to US-PS 4,005,223, the compound of Comparative Example G was prepared according to US-PS 4,005,223 and the compound from Comparative Example H was prepared according to US-PS 4,041,177.
Eksemplene 115 - 121 og sammenligningseksemplene I - K Examples 115 - 121 and Comparative Examples I - K
For ytterligere å vise den forbedrede biologiske aktivitet mot "Southern" hærmygg, ble representative 1-(4-f enoksyf enyl)-3-benzoylurinstof f-forbindelser ifølge oppfinnelsen sammenlignet med kjente forbindelser. Resultatene er gitt i tabell V nedenfor. Fra de i tabell V gitte data er det klart at 1-(4-f enoksy f enyl)-3-benzoylurinstoff-forbindelsene ifølge oppfinnelsen gir betydelig forbedret biologisk aktivitet mot "Southern" hærmygg sammenlignet med kjente forbindelser. Som brukt i tabell V ble forbindelsene i sammenligningseksempel I fremstilt i henhold til US-PS 4.005.223, i sammenligningseksempel J i henhold til US-PS 4.041.177 og forbindelsen ifølge eksempel K i henhold til JP-PS 5.6092.857. To further demonstrate the improved biological activity against "Southern" army mosquitoes, representative 1-(4-phenoxyphenyl)-3-benzoylurea compounds of the invention were compared with known compounds. The results are given in Table V below. From the data given in Table V, it is clear that the 1-(4-phenoxy phenyl)-3-benzoylurea compounds according to the invention provide significantly improved biological activity against "Southern" army mosquitoes compared to known compounds. As used in Table V, the compounds in Comparative Example I were prepared according to US-PS 4,005,223, in Comparative Example J according to US-PS 4,041,177 and the compound of Example K according to JP-PS 5,6092,857.
Eksemplene 122 - 124 og sammenligningseksempler L og M Examples 122 - 124 and Comparative Examples L and M
For å vise den forbedrede biologiske aktivitet mot Heliothis ssp. ble representative 1 - (4-f enoksyf enyl) -3-benzoylurinstof f-forbindelser ifølge oppfinnelsen sammenlignet med kjente forbindelser. Resultatene er angitt i tabell VI nedenfor. Fra de data som er gitt i tabell VI, er det klart at 1-(4-f enoksyf enyl)-3-benzoylurinstof f-forbindelsene ifølge oppfinnelsen gir en vesentlig forbedret biologisk aktivitet mot Heliothis spp. sammenlignet med kjente forbindelser. Som benyttet i tabell VI ble forbindelsen i sammenligningseksempel L og M fremstilt i henhold til US-PS 4.005.223. To show the improved biological activity against Heliothis ssp. were representative 1-(4-phenoxyphenyl)-3-benzoylurea compounds according to the invention compared to known compounds. The results are set out in Table VI below. From the data given in Table VI, it is clear that the 1-(4-phenoxyphenyl)-3-benzoylurea compounds according to the invention provide a significantly improved biological activity against Heliothis spp. compared to known compounds. As used in Table VI, the compound in Comparative Examples L and M was prepared according to US-PS 4,005,223.
Eksemplene illustrerer oppfinnelsen uten å begrense den og modifika-sjoner og utførelsesformer kan skje uten å gå utenfor oppfinnelsens ånd og ramme. The examples illustrate the invention without limiting it and modifications and embodiments can take place without going outside the spirit and scope of the invention.
Claims (67)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US71778485A | 1985-03-29 | 1985-03-29 | |
| PCT/US1986/000317 WO1986005780A1 (en) | 1985-03-29 | 1986-02-20 | Pesticidal 1-(4-phenoxyphenyl)-3-benzoyl urea compounds and process for preparation |
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| NO864763D0 NO864763D0 (en) | 1986-11-26 |
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