KR830001087B1 - Process for preparing cyclopropane carboxylic acid ester - Google Patents
Process for preparing cyclopropane carboxylic acid ester Download PDFInfo
- Publication number
- KR830001087B1 KR830001087B1 KR1019790000617A KR790000617A KR830001087B1 KR 830001087 B1 KR830001087 B1 KR 830001087B1 KR 1019790000617 A KR1019790000617 A KR 1019790000617A KR 790000617 A KR790000617 A KR 790000617A KR 830001087 B1 KR830001087 B1 KR 830001087B1
- Authority
- KR
- South Korea
- Prior art keywords
- cyclopropane
- hydrogen
- peak
- dimethyl
- cyano
- Prior art date
Links
- YMGUBTXCNDTFJI-UHFFFAOYSA-N cyclopropanecarboxylic acid Chemical compound OC(=O)C1CC1 YMGUBTXCNDTFJI-UHFFFAOYSA-N 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title description 2
- 239000001257 hydrogen Substances 0.000 claims description 74
- 229910052739 hydrogen Inorganic materials 0.000 claims description 74
- -1 5-benzyl-3-furylmethyl group Chemical group 0.000 claims description 46
- 239000000460 chlorine Substances 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 18
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 12
- 229910052801 chlorine Inorganic materials 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 7
- AFVLVVWMAFSXCK-VMPITWQZSA-N alpha-cyano-4-hydroxycinnamic acid Chemical group OC(=O)C(\C#N)=C\C1=CC=C(O)C=C1 AFVLVVWMAFSXCK-VMPITWQZSA-N 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 125000001424 substituent group Polymers 0.000 claims description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims 1
- 239000011630 iodine Substances 0.000 claims 1
- 229910052740 iodine Inorganic materials 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 80
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 59
- 239000000203 mixture Substances 0.000 description 53
- 150000001875 compounds Chemical class 0.000 description 46
- 239000000243 solution Substances 0.000 description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 17
- 230000000749 insecticidal effect Effects 0.000 description 17
- 239000000047 product Substances 0.000 description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- 125000001495 ethyl group Polymers [H]C([H])([H])C([H])([H])* 0.000 description 16
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 16
- 229940126062 Compound A Drugs 0.000 description 14
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 14
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 10
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 239000004480 active ingredient Substances 0.000 description 9
- GKIRPKYJQBWNGO-OCEACIFDSA-N clomifene Chemical compound C1=CC(OCCN(CC)CC)=CC=C1C(\C=1C=CC=CC=1)=C(\Cl)C1=CC=CC=C1 GKIRPKYJQBWNGO-OCEACIFDSA-N 0.000 description 9
- 239000003480 eluent Substances 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 241001465754 Metazoa Species 0.000 description 8
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 7
- 238000003556 assay Methods 0.000 description 7
- 150000007942 carboxylates Chemical class 0.000 description 7
- 238000004587 chromatography analysis Methods 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- GXUQMKBQDGPMKZ-CQSZACIVSA-N (2s)-2-hydroxy-2-(3-phenoxyphenyl)acetonitrile Chemical compound N#C[C@@H](O)C1=CC=CC(OC=2C=CC=CC=2)=C1 GXUQMKBQDGPMKZ-CQSZACIVSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 5
- 241000257159 Musca domestica Species 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 239000000575 pesticide Substances 0.000 description 5
- 230000003389 potentiating effect Effects 0.000 description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- 241001638456 Manica Species 0.000 description 4
- 241000257226 Muscidae Species 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 241000607479 Yersinia pestis Species 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000002983 circular dichroism Methods 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 4
- 239000004495 emulsifiable concentrate Substances 0.000 description 4
- 239000000546 pharmaceutical excipient Substances 0.000 description 4
- 229960005235 piperonyl butoxide Drugs 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- GXUQMKBQDGPMKZ-AWEZNQCLSA-N (2r)-2-hydroxy-2-(3-phenoxyphenyl)acetonitrile Chemical compound N#C[C@H](O)C1=CC=CC(OC=2C=CC=CC=2)=C1 GXUQMKBQDGPMKZ-AWEZNQCLSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 241000255925 Diptera Species 0.000 description 3
- 241000238631 Hexapoda Species 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000895 acaricidal effect Effects 0.000 description 3
- 239000000642 acaricide Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- ZOOSILUVXHVRJE-UHFFFAOYSA-N cyclopropanecarbonyl chloride Chemical compound ClC(=O)C1CC1 ZOOSILUVXHVRJE-UHFFFAOYSA-N 0.000 description 3
- GVJHHUAWPYXKBD-UHFFFAOYSA-N d-alpha-tocopherol Natural products OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 3
- 239000005645 nematicide Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 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
- 230000000699 topical effect Effects 0.000 description 3
- 238000002211 ultraviolet spectrum Methods 0.000 description 3
- CYCYDSJDZNVSPP-QRHDOFTISA-N (1r,3r)-3-(1,2-dibromo-2,2-dichloroethyl)-2,2-dimethylcyclopropane-1-carboxylic acid Chemical compound CC1(C)[C@H](C(Br)C(Cl)(Cl)Br)[C@H]1C(O)=O CYCYDSJDZNVSPP-QRHDOFTISA-N 0.000 description 2
- NUQSJBAQSZZDJA-OVEKKEMJSA-N (1r,3s)-2,2-dimethyl-3-(1,2,2,2-tetrachloroethyl)cyclopropane-1-carboxylic acid Chemical compound CC1(C)[C@@H](C(Cl)C(Cl)(Cl)Cl)[C@H]1C(O)=O NUQSJBAQSZZDJA-OVEKKEMJSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- OPLCSTZDXXUYDU-UHFFFAOYSA-N 2,4-dimethyl-6-tert-butylphenol Chemical compound CC1=CC(C)=C(O)C(C(C)(C)C)=C1 OPLCSTZDXXUYDU-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 241000254086 Tribolium <beetle> Species 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- SESFRYSPDFLNCH-UHFFFAOYSA-N benzyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC1=CC=CC=C1 SESFRYSPDFLNCH-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000005998 bromoethyl group Chemical group 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 2
- 229940005991 chloric acid Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000013601 eggs Nutrition 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000000361 pesticidal effect Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 2
- VSBCUTLTLUSECJ-OVEKKEMJSA-N (1R)-cis-2,2-dimethyl-3-(1,2,2,2-tetrabromoethyl)cyclopropanecarboxylic acid Chemical compound CC1(C)[C@@H](C(Br)C(Br)(Br)Br)[C@H]1C(O)=O VSBCUTLTLUSECJ-OVEKKEMJSA-N 0.000 description 1
- JKFYLGGLNVXKOL-OVEKKEMJSA-N (1r,3s)-3-(2,2-dibromo-1,2-dichloroethyl)-2,2-dimethylcyclopropane-1-carbonyl chloride Chemical compound CC1(C)[C@@H](C(Cl)C(Cl)(Br)Br)[C@H]1C(Cl)=O JKFYLGGLNVXKOL-OVEKKEMJSA-N 0.000 description 1
- LLMLSUSAKZVFOA-XINAWCOVSA-N (1r,3s)-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropane-1-carboxylic acid Chemical compound CC1(C)[C@H](C=C(Cl)Cl)[C@H]1C(O)=O LLMLSUSAKZVFOA-XINAWCOVSA-N 0.000 description 1
- SJVFWGWIAVNCCC-UHFFFAOYSA-N 1,1-dimethyl-2-(1,2,2,2-tetrabromoethyl)cyclopropane Chemical compound CC1(C)CC1C(Br)C(Br)(Br)Br SJVFWGWIAVNCCC-UHFFFAOYSA-N 0.000 description 1
- QPQGJXICNIIBCY-UHFFFAOYSA-N 1,2,2,2-tetrabromoethyl cyclopropanecarboxylate Chemical compound C1(CC1)C(=O)OC(C(Br)(Br)Br)Br QPQGJXICNIIBCY-UHFFFAOYSA-N 0.000 description 1
- FPIPGXGPPPQFEQ-UHFFFAOYSA-N 13-cis retinol Natural products OCC=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- XPSKXQAQGYAGLO-UHFFFAOYSA-N 2-[4-[2-(2-butoxyethoxy)ethoxy]butan-2-yl]-1,3-benzodioxole Chemical compound C(OCCOCCOCCCC)CC(C)C1OC2=CC=CC=C2O1 XPSKXQAQGYAGLO-UHFFFAOYSA-N 0.000 description 1
- GXUQMKBQDGPMKZ-UHFFFAOYSA-N 2-hydroxy-2-(3-phenoxyphenyl)acetonitrile Chemical compound N#CC(O)C1=CC=CC(OC=2C=CC=CC=2)=C1 GXUQMKBQDGPMKZ-UHFFFAOYSA-N 0.000 description 1
- VOEOAOWTEZOVCB-UHFFFAOYSA-N 3-(2,2-dibromo-1,2-dichloroethyl)-2,2-dimethylcyclopropane-1-carboxylic acid Chemical compound CC1(C)C(C(Cl)C(Cl)(Br)Br)C1C(O)=O VOEOAOWTEZOVCB-UHFFFAOYSA-N 0.000 description 1
- MDIQXIJPQWLFSD-UHFFFAOYSA-N 3-(2,2-dibromoethenyl)-2,2-dimethylcyclopropane-1-carboxylic acid Chemical compound CC1(C)C(C=C(Br)Br)C1C(O)=O MDIQXIJPQWLFSD-UHFFFAOYSA-N 0.000 description 1
- AFJWMGOTLUUGHF-UHFFFAOYSA-N 4,5,6,7-tetrahydroisoindole-1,3-dione Chemical compound C1CCCC2=C1C(=O)NC2=O AFJWMGOTLUUGHF-UHFFFAOYSA-N 0.000 description 1
- 206010063409 Acarodermatitis Diseases 0.000 description 1
- 241001124076 Aphididae Species 0.000 description 1
- ZEFJUGDBANTUFU-UHFFFAOYSA-N C1(CC1)C(=O)O.[Cl] Chemical compound C1(CC1)C(=O)O.[Cl] ZEFJUGDBANTUFU-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 235000016071 Cordyline australis Nutrition 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 235000019750 Crude protein Nutrition 0.000 description 1
- ZAKOWWREFLAJOT-CEFNRUSXSA-N D-alpha-tocopherylacetate Chemical compound CC(=O)OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C ZAKOWWREFLAJOT-CEFNRUSXSA-N 0.000 description 1
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 238000007698 E/Z-isomerization reaction Methods 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 240000004658 Medicago sativa Species 0.000 description 1
- 235000017587 Medicago sativa ssp. sativa Nutrition 0.000 description 1
- 241000244206 Nematoda Species 0.000 description 1
- JBZRLVKMCLOFLG-UHFFFAOYSA-N O=S=Cl Chemical compound O=S=Cl JBZRLVKMCLOFLG-UHFFFAOYSA-N 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 241000786363 Rhampholeon spectrum Species 0.000 description 1
- 244000126647 Roystonea oleracea Species 0.000 description 1
- 235000008947 Roystonea oleracea Nutrition 0.000 description 1
- 235000001601 Sabal palmetto Nutrition 0.000 description 1
- 241000447727 Scabies Species 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 240000004460 Tanacetum coccineum Species 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 244000098338 Triticum aestivum Species 0.000 description 1
- FPIPGXGPPPQFEQ-BOOMUCAASA-N Vitamin A Natural products OC/C=C(/C)\C=C\C=C(\C)/C=C/C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-BOOMUCAASA-N 0.000 description 1
- 229930003268 Vitamin C Natural products 0.000 description 1
- 229930003427 Vitamin E Natural products 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- ROVGZAWFACYCSP-MQBLHHJJSA-N [2-methyl-4-oxo-3-[(2z)-penta-2,4-dienyl]cyclopent-2-en-1-yl] (1r,3r)-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropane-1-carboxylate Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OC1C(C)=C(C\C=C/C=C)C(=O)C1 ROVGZAWFACYCSP-MQBLHHJJSA-N 0.000 description 1
- 210000001015 abdomen Anatomy 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 125000005907 alkyl ester group Chemical class 0.000 description 1
- FPIPGXGPPPQFEQ-OVSJKPMPSA-N all-trans-retinol Chemical compound OC\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-OVSJKPMPSA-N 0.000 description 1
- IZZOKZMGQDMCAE-XQZFLANJSA-N alpha-L-Rhap-(1->2)-[beta-D-GlcpNAc-(1->3)]-alpha-L-Rhap-(1->3)-alpha-L-Rhap-(1->2)-[beta-D-GlcpNAc-(1->3)]-alpha-L-Rhap Chemical compound O[C@@H]1[C@H](O)[C@@H](O)[C@H](C)O[C@H]1O[C@@H]1[C@H](O[C@H]2[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](O)[C@H](C)O[C@H]1O[C@H]1[C@@H](O)[C@H](O[C@@H]2[C@@H]([C@@H](O)[C@H](C)O[C@H]2O)O[C@H]2[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)NC(C)=O)O[C@@H](C)[C@@H]1O IZZOKZMGQDMCAE-XQZFLANJSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- RTEXIPZMMDUXMR-UHFFFAOYSA-N benzene;ethyl acetate Chemical compound CCOC(C)=O.C1=CC=CC=C1 RTEXIPZMMDUXMR-UHFFFAOYSA-N 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 229960002903 benzyl benzoate Drugs 0.000 description 1
- MDHYEMXUFSJLGV-UHFFFAOYSA-N beta-phenethyl acetate Natural products CC(=O)OCCC1=CC=CC=C1 MDHYEMXUFSJLGV-UHFFFAOYSA-N 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002316 fumigant Substances 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 1
- 210000001035 gastrointestinal tract Anatomy 0.000 description 1
- 238000003197 gene knockdown Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 230000002147 killing effect Effects 0.000 description 1
- 230000001418 larval effect Effects 0.000 description 1
- 231100000636 lethal dose Toxicity 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 229940029985 mineral supplement Drugs 0.000 description 1
- 235000020786 mineral supplement Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 235000013379 molasses Nutrition 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 239000008194 pharmaceutical composition Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000004591 piperonyl group Chemical group C(C1=CC=2OCOC2C=C1)* 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- 229940015367 pyrethrum Drugs 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 208000005687 scabies Diseases 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000003431 steroids Chemical class 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229930003799 tocopherol Natural products 0.000 description 1
- 229960001295 tocopherol Drugs 0.000 description 1
- 239000011732 tocopherol Substances 0.000 description 1
- 235000010384 tocopherol Nutrition 0.000 description 1
- 229940042585 tocopherol acetate Drugs 0.000 description 1
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 235000019155 vitamin A Nutrition 0.000 description 1
- 239000011719 vitamin A Substances 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 229940045997 vitamin a Drugs 0.000 description 1
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/62—Use of additives, e.g. for stabilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
내용 없음.No content.
Description
본 발명은 폴리할로겐화 치환체를 함유하는 시클로프로판 카르 복실산 에스테르의 제조방법에 관한 것이다.The present invention relates to a process for the preparation of cyclopropane carboxylic acid esters containing polyhalogenated substituents.
"폴리할로겐화 치환체를 함유하는 새로운 시클로프로판 카르복실산의 에스테르"제하의 1977년 9월 20일자 특허출원 2215(1961-F/a)에는 다음의 일반식(I)과 같은 화합물 및 이들의 가능한 모든 이성체들이 언급되어 있다.Patent application 2215 (1961-F / a) dated Sep. 20, 1977 under "Ester of a new cyclopropane carboxylic acid containing polyhalogenated substituents" includes compounds of the following general formula (I) and all possible Isomers are mentioned.
여기서 X1,X2,X3은 불소, 염소, 혹은 브롬원자를 나타내며, R은 치환가능한 벤질기, 5-벤질-3-퓨릴메틸그룹, 2-메틸 3-알킬 4-옥소시클로펜-2-테닐그룹 또는 관련된 그룹들, 3-패녹시벤질, α-시아노 3-페녹시벤질, 또는 α-에티닐 3-페녹시벤질 그룹 또는 관련된 그룹들, 또는 3,4,5,6-테트라 하이드로프탈이미도 메틸그룹 또는 관련된 그룹들의 하나등을 의미한다.Wherein X 1 , X 2 , X 3 represents a fluorine, chlorine or bromine atom, R represents a substituted benzyl group, 5-benzyl-3-furylmethyl group, 2-methyl 3-alkyl 4-oxocyclophen-2 -Tenyl group or related groups, 3-phenoxybenzyl, α-cyano 3-phenoxybenzyl, or α-ethynyl 3-phenoxybenzyl group or related groups, or 3,4,5,6-tetra Hydrophthalimide also means methyl group or one of related groups.
구조식(I)의 에스테르는 다수의 이성체 형태로서 존재할 수 있으며 실제로 일반식(I)의 에테르중에서 산성분을 형성하는 시클로프로판 카르복실산은 시클로프로판 고리의 1위치와 3위치에 비대칭 탄소원자들과 3위치의 폴리할로겐화된 에틸측쇄의 1'위치에 비대칭 탄소를 지니고 있다.The esters of formula (I) may exist in many isomeric forms, and in fact, the cyclopropane carboxylic acid, which forms an acid component in the ether of formula (I), has asymmetric carbon atoms at positions 1 and 3 of the cyclopropane ring and 3 It has an asymmetric carbon at the 1 'position of the polyhalogenated ethyl side chain at the position.
구조식(I)의 에스테르의 알코올 부분을 구성하는 알코올 ROH는 하나 또는 그 이상의 비대칭 탄소원자를 및/또는 E/Z이성화를 야기하는 한개 또는 그 이사의 이중결합을 가질 수 있음은 상기의 참중문헌에 언급되어 있다.It is mentioned in the literature above that the alcohol ROH constituting the alcoholic moiety of the ester of formula (I) may have one or more asymmetric carbon atoms and / or one or more double bonds thereof which cause E / Z isomerization. It is.
또한 치환체 X1및 X2가 동일한 경우 시클로프로판 고리의 1 및 3위치의 비대칭 탄소원자들의 고정된 스테로이드 배위와 알코올성부분의 명확한 입체화학적 구조에 대하여 1'위치의 비대칭 탄소원자의 존재에 따라 구조식(I)로 표시되는 에스테르 또는 상응하는 산의 두가지 부분입체 이성질체가 존재할 수 있음도 상기 참증에 언급되어 있다.In addition, when the substituents X 1 and X 2 are identical, the structural formula (I) depends on the immobilized steroid coordination of the asymmetric carbon atoms at the 1 and 3 positions of the cyclopropane ring and the presence of the asymmetric carbon atom at the 1 'position for the clear stereochemical structure of the alcoholic moiety It is also mentioned in the foregoing that there may be two diastereoisomers of the ester or corresponding acid represented by).
일반적으로 이들 이성체들은 순수한 상태로 분리 고립될 수 있으며 앞으로 이들을 이성체(A)와 (B)로 지칭하기도 한다.In general, these isomers can be isolated and isolated in the pure state, and they are sometimes referred to as isomers (A) and (B).
일반식(I)로 표시되는 화합물의 제조방법, 일반식(I)의 화합물을 함유하는 살충제 조성물 및 질소의 치료를 위해 수의학적으로 사용되는 약제조성물, 살균제 조성물들에 관하여는 앞에서의 참조문헌에서 이미 알려진 바 있다.For the preparation of the compound represented by the general formula (I), the pesticide composition containing the compound of the general formula (I) and the pharmaceutical composition used for the treatment of nitrogen, veterinary compositions, fungicide compositions in the above references It is already known.
본 발명의 목적은 구조식(I)에서 치환체 X1,X2,X3및 R이 지니는 중요성을 새로운 실시예들과 함께 예증하려는 것이다. 따라서 이성체(A)나 이성체(B), 또는 이들 이성체의 혼합물의 형태로 구조식(I)과 같은 화합물을 다루고 있다. 이들 화합물에는 다음과 같은 것들이 있다.It is an object of the present invention to illustrate, with new embodiments, the importance of substituents X 1 , X 2 , X 3 and R in formula (I). Therefore, compounds such as formula (I) are dealt with in the form of isomers (A), isomers (B), or mixtures of these isomers. These compounds include the following.
-(S)α-시아노 3-페녹시벤질(1R, 트랜스) 2,2-디메틸 3-2',2'-디클로로 1',2'-디브로모에틸)시클로프로판-1-카르복실레이트 ;-(S) α-cyano 3-phenoxybenzyl (1R, trans) 2,2-dimethyl 3-2 ', 2'-dichloro 1', 2'-dibromoethyl) cyclopropane-1-carboxyl Rate;
-(S)α-시아노 3-페녹시 벤질(1R, 시스) 2,2-디메틸 3-(2',2'-디브로모 1',2'-디클로로 에틸)시클로프로판-1-카르복실레이트 ;-(S) α-cyano 3-phenoxy benzyl (1R, cis) 2,2-dimethyl 3- (2 ', 2'-dibromo 1', 2'-dichloroethyl) cyclopropane-1-car Carboxylate;
-3,4,5,6-테트라히드로프탈리미도 메틸(1R, 트랜스) 2,2-디메틸 3-(1',2',2',2'-테트라브로모에틸)시클로프로판-1-카르복실레이트 ;-3,4,5,6-tetrahydrophthalimido methyl (1R, trans) 2,2-dimethyl 3- (1 ', 2', 2 ', 2'-tetrabromoethyl) cyclopropane-1- Carboxylate;
-3,4,5,6-테트라히드로프탈리미도 메틸(1R, 시스) 2,2-디메틸 3-(1',2',2',2'-테트라브로모에틸) 시클로프로판-1-카르복실레이트 ;-3,4,5,6-tetrahydrophthalimido methyl (1R, cis) 2,2-dimethyl 3- (1 ', 2', 2 ', 2'-tetrabromoethyl) cyclopropane-1- Carboxylate;
-(S(α-시아노 3-페녹시벤질(1R, 시스) 2,2-디메틸 3-(1',2',2',2'-테트라클로로에틸) 시클로프로판-1-카르복실레이트 ;-(S (α-cyano 3-phenoxybenzyl (1R, cis) 2,2-dimethyl 3- (1 ', 2', 2 ', 2'-tetrachloroethyl) cyclopropane-1-carboxylate ;
-(R)α-시아노 3-페녹시벤질(1R, 시스) 2,2-디메틸 3-(1',2',2',2'-테트라클로로에틸) 시클로프로판-1-카르복실레이트 ;-(R) α-cyano 3-phenoxybenzyl (1R, cis) 2,2-dimethyl 3- (1 ', 2', 2 ', 2'-tetrachloroethyl) cyclopropane-1-carboxylate ;
-(S)α-시아노 3-페녹시벤질(1R, 트랜스) 2,2-디메틸 3-(2',2'-디클로로 1',2'-디브로모에틸) 시클로프로판-1-카르복실레이트.-(S) α-cyano 3-phenoxybenzyl (1R, trans) 2,2-dimethyl 3- (2 ', 2'-dichloro 1', 2'-dibromoethyl) cyclopropane-1-car Carboxylate.
이들 화합물들은 이하에서 "γ"화합물이라 칭하여지고 있다.These compounds are referred to hereinafter as "γ" compounds.
(S)α-시아노 3-페녹시벤질(1R, 시스) 2,2-디메틸 3-(2',2'-디클로로 1',2'-디브로모에틸) 시클로프로판1-카르복실레이트는 앞서의 참조 문헌에서 이미 언급되어 있다. (S)α-시아노 3-페녹시벤질(1R, 트랜스) 2,2-디메틸 3-(2',2'-디브로모 1',2'-디클로로에틸)시클로프로판-1-카르복실레이트와 (S)α-시아노 3-페녹시벤질(1R, 트랜스) 2,2-디메틸 3-(1',2',2',2'-테트라클로로에틸)시클로프로판-1-카르복실레이트는 상기의 참조문헌에 나타나 있는 방법에 따라 상응하는 산들을 이후의 실시예 3에서 언급된 방법과 유사한 방법에 의해 (S)α-시아노 3-페녹시 벤질알콜로 상응하는 산을 에스레르화시켜 제조한다. (R)α-시아노 3-페녹시벤질은 실시에 6예 나타나 있는 방법에 따라 (R)α-시아노 3-페녹시 벤질알코올에 의해 상응하는 산을 에스테르화시켜 얻는다.(S) α-cyano 3-phenoxybenzyl (1R, cis) 2,2-dimethyl 3- (2 ', 2'-dichloro 1', 2'-dibromoethyl) cyclopropane1-carboxylate Is already mentioned in the above references. (S) α-cyano 3-phenoxybenzyl (1R, trans) 2,2-dimethyl 3- (2 ', 2'-dibromo 1', 2'-dichloroethyl) cyclopropane-1-carboxyl (S) α-cyano 3-phenoxybenzyl (1R, trans) 2,2-dimethyl 3- (1 ', 2', 2 ', 2'-tetrachloroethyl) cyclopropane-1-carboxyl The rate is determined according to the method shown in the above references to the corresponding acid with (S) α-cyano 3-phenoxy benzyl alcohol by a method similar to that mentioned in Example 3 below. It is prepared by oxidization. (R) α-cyano 3-phenoxybenzyl is obtained by esterifying the corresponding acid with (R) α-cyano 3-phenoxy benzyl alcohol according to the method shown in Example 6 in the Examples.
본 발명에서는 특히 시스 구조와 트랜스 구조의 광학이성체들의 혼합물 형태로의 "γ"화합물들을 다루고 있다. 이들 화합물 가운데에서는 특히 시스 구조와 트랜스 구조의 구성비가 무게비로 20/80, 50/50, 또는 80/20인 혼합물 형태로된 것들을 들 수 있다.The present invention specifically addresses "γ" compounds in the form of a mixture of optical isomers of the cis structure and the trans structure. Among these compounds are those in the form of mixtures, in particular the composition ratio of the cis structure and the trans structure is 20/80, 50/50, or 80/20 by weight.
본 발명의 목적은 특화 다음의 일반식(I)의 화합물을 포함하는 시스 및 특랜스 구조의 혼합물이나 "γ"화합물들을 제조하는 방법을 제공하려는 것이다.It is an object of the present invention to provide a mixture of cis and special lance structures or "γ" compounds comprising a compound of formula (I) following specialization.
이 제조방법에서는 구조식(Ⅱ)의 적절한 산들을 시클로프판의 측쇄상에 Cl2나Br2를 고착시킬 수 있는 염소화 작용제나 브롬화 작용제와 반응시키고 있다.In this production method, the appropriate acids of formula (II) are reacted with chlorinating or brominating agents capable of fixing Cl 2 or Br 2 on the side chain of the cyclopropane.
여기서 X1,X2는 상기와 같다.X 1 and X 2 are the same as above.
본 발명의 목적은 또한 "γ"화합물 또는 앞에서 정의한 혼합물들의 제조방법을 제공하려는 것이며 상기와 같이 반응시켜 구조식(Ⅲ)의 산을 얻고 이 산이 산의 작용 유도체를 ROH 알코올이나 그의 기능유도체와 반응시키고 있다.It is also an object of the present invention to provide a process for the preparation of "γ" compounds or mixtures as defined above, by reacting as described above to obtain an acid of formula (III) which reacts the functional derivative of the acid with ROH alcohol or a functional derivative thereof. have.
상기식에서 X3는 이중결합상에 고정돈 할로겐을 나타낸다. 상기의 산(Ⅱ)의 할로겐화제로는 특히 염소나 브롬이 사용되고 상기의 산(Ⅱ)의 할로겐화는 초산, 사염화탄소, 클로로포름, 메틸렌클로라이드와 같이 염소나 브롬과 반응하지 않는 유기용매중에서 진행된다. 알코올 ROH나 알코올의 관능성 유도체와 에스레르화 반응에 사용되는 구조식(Ⅱ)의 산의 관능성 유도체에는 염소, 안하이드라이드, 혼합한 하이드 라이드, 저급알킬에스레르, 금속염 또는 산(Ⅱ)의 유기염기의 염이 있으며 알코올의 관능성 유도체로는 염소, 브롬 또는 그 알코올의 술폰산염이 있다.In the above formula, X 3 represents a fixed halogen on the double bond. Chlorine or bromine are used as the halogenating agent of the acid (II), and the halogenation of the acid (II) proceeds in an organic solvent which does not react with chlorine or bromine such as acetic acid, carbon tetrachloride, chloroform and methylene chloride. The functional derivatives of alcohol ROH or the functional derivatives of alcohols and of the acid of structural formula (II) used in the esterification reaction include chlorine, anhydride, mixed hydrides, lower alkyl esters, metal salts or acids (II). There are salts of organic bases and functional derivatives of alcohols include chlorine, bromine or sulfonates of the alcohols.
본 발명에 의한 화합물들의 살충효과는 특히 집파리, 스포돕테레라 리토탈리스의 유충, 에피라크나 바리베스트리스의 유충, 에데스에짚리의 유충, 블라렐라게트마니카, 디스데트쿠스파시아투스, 시토필루스그라나리우스와 트리블리움카스타노움 등에 효과가 있다. "γ"화합물은 광학적인 안정성이 매우 크며 농경분야의 해충들을 박멸시키는데 사용하는 것을 적합하다. 예컨데 이들 화합물들은 진딧물, 레피도프레타의 유층 및 클레옵레타의 방제에 효과적이다. 1헥타아르당 이들 화합물의 유효성분 1-100g을 투여하는 것이 일반적인데 이들은 또한 가정용 살충제로서도 사용할 수 있다.Insecticidal effects of the compounds according to the invention are particularly larvae of housefly, spodidoterra litolithis, larvae of epiracha or bariberistris, larvae of edes etilli, blalarge manica, disedcus spatiatus, It is effective against Cytophilus granarius and Triblyum castanoum. "γ" compounds have very high optical stability and are suitable for use in combating pests in agriculture. For example, these compounds are effective in controlling aphids, oily layers of lepidodopreta, and cleopettas. It is common to administer 1-100 g of these compounds per hectare, which can also be used as household pesticides.
본 발명의 유효성분에 다른 살충제를 첨가하여 사용할 수 있으며, 이들 조성물들은 분제, 입제, 현탁제, 유제, 용액, 에어로졸용액, 가연성스트립, 미끼밥 또는 이러한 종류의 화합물에 사용되는 다른 여려 약제의 형태로 제제할 수 있다. 유효성분 이외에 이들 조성물들은 혼합물의 분산을 균일하게 해 주는 부형제(賦刑制), 비이온성 계면활성제등을 함유하는데, 사용되는 부형제로는 물, 알코올, 탄화수소 또는 기타 유기용매, 광유, 동·식물성유와 같은 액체, 활석, 점토, 실리케이트 또는 키젤기와 같은 분말 또는 관상분체(또는 피레쓰럼 마르크)와 같은 가연성 고체가 있다.Other pesticides may be added to the active ingredients of the present invention, and these compositions may be in the form of powders, granules, suspensions, emulsions, solutions, aerosol solutions, flammable strips, bait rice or other various agents used in these kinds of compounds. It can be formulated as. In addition to the active ingredients, these compositions contain excipients, nonionic surfactants, and the like, which make the mixture evenly dispersed. Excipients used include water, alcohols, hydrocarbons or other organic solvents, mineral oils, animal and vegetable compounds. Liquids such as oil, talc, clays, silicates or combustible solids such as powders or tubular powders (or pyrethrum marks).
본 발명의 화합물들의 살충작용을 높이기 위한 상승제로는 1-(2,5,8-트리옥사도데실 2-프로필 4,5-메틸렌디옥시) 벤젠(또는 피페로닐 부록사이드), N-(2-에틸텝틸) 바이스클로[2,2-1]-텝텐-2,3-디카르복시미드와 피페로닐-비스-2-(2'-n-부톡시 에톡시)에틸 아세탈(또는 트로피랄) 등이 있다.Synergists to enhance the pesticidal action of the compounds of the present invention include 1- (2,5,8-trioxadodecyl 2-propyl 4,5-methylenedioxy) benzene (or piperonyl appendoxide), N- ( 2-ethylptyl) bisclo [2,2-1] -tetene-2,3-dicarboximide and piperonyl-bis-2- (2'-n-butoxy ethoxy) ethyl acetal (or tropic) ).
본 발명에 따른 살충제 조성물은 중량으로 0.005%-10%의 활성성분을 함유한다.The pesticide composition according to the present invention contains 0.005% -10% active ingredient by weight.
본 발명의 목적은 좀더 구체적으로 말하자면 살충제 조성물을 제공하려는 것으로서 그 활성성분으로는 (S)α-시아노 3-페녹시벤질 1R, 트랜스 2,2-디메틸 3-(2',2'-디클로로 1',2'-디브로모에틸)시클로프로판-1-카르복실레이드의 이성체 A와 B, 또는 그 이성체 A와 B의 혼합물이 이용된다.The object of the present invention is to provide a pesticide composition more specifically, the active ingredient is (S) α-cyano 3-phenoxybenzyl 1R, trans 2,2-dimethyl 3- (2 ', 2'-dichloro Isomers A and B of 1 ', 2'-dibromoethyl) cyclopropane-1-carboxylate or mixtures of isomers A and B are used.
"γ" 화합물은 또한 비활성도 지니고 있는데 이것은 테트라니쿠스 우트리카에 대한 실험으로부터 명백해진다. 이와같은 용도로 사용되는 경우에는 중량으로 1-80%의 활성성분을 함유하는 엽면 분무용수화제 또는 1-500g/ι의 활성성분을 함유하는 면면 분무용액제를 사용하는 것이 좋으며 0.05-3% (중량)의 활성성분을 함유하는 엽면 산포용 분제를 사용할 수도 있다. 살선충제로 사용하기 위해서는 300-500g/ι의 활성성분을 함유하는 토양처리액을 사용하는 것이 좋다.The "γ" compound also has an inactivation, which is evident from experiments on tetranicus utrica. When used for this purpose, it is recommended to use a foliar spray solution containing 1-80% of the active ingredient by weight or a cotton spray solution containing 1-500 g / ι of the active ingredient, and 0.05-3% (by weight). It is also possible to use a powder for foliar scattering containing the active ingredient. In order to use as a nematicide, it is recommended to use a soil treatment solution containing 300-500 g / ι active ingredient.
본 발명에 의한 조성물을 살비제에 대해서는 1헥타르당 1-100g, 살선충제에 대해서는 10-200g의 활성성분을 사용하는 것이 좋다. 또한 본 발명의 화합물들은 동물에 기생하는 계선충이나 옴의 방제용으로도 사용될 수 있다. 전기 조성물은 외부경로를 통해서 사용할 수 있으나 비 경구 또는 소화기관을 통해서 투여할 수도 있다. 이들 조성물에 상승 효과제로서 피레트리노이드를 첨가 사용하는 것이 유리하다.The composition according to the present invention preferably uses 1-100 g per hectare for acaricides and 10-200 g for nematicides. The compounds of the present invention can also be used for controlling parasitic nematodes or scabies in animals. The electrical composition can be used via external routes but can also be administered orally or through the digestive tract. It is advantageous to add and use pyretrinoid as a synergist in these compositions.
또한 상기 조성물을 수의용으로 사용하기 위하여 일정량의 동물사료와 혼합하는 것이 편리하다. 예를 들면 0.002-0.4%의 α-시아노 3-페녹시벤질1R, 트랜스 2,2-디메틸 3-(2',2'-디클로로 1',2'-디브로모에틸)시클로프로판-1-카르복실레이트를 함유하는 동물사료 화합물을 사용하는 것이 가능하다. 이들 조성물을 동물사료용으로 사용하는 경우에는 일정량의 동물용사료 화합물과 적어도 "γ"화합물 또는 이후에 설명되는 입체 이성질체의 혼합물을 함유함을 특징으로 한다.It is also convenient to mix the composition with a certain amount of animal feed for veterinary use. For example 0.002-0.4% α-cyano 3-phenoxybenzyl1R, trans 2,2-dimethyl 3- (2 ', 2'-dichloro 1', 2'-dibromoethyl) cyclopropane-1 It is possible to use animal feed compounds containing carboxylates. When these compositions are used for animal feed, they are characterized by containing a certain amount of a animal feed compound and a mixture of at least a "γ" compound or a stereoisomer described later.
실시예 1 : 3,4,5,6-테트라히드로프탈리미도메틸(1R, 시스) -2,2-디메틸-3-(1',2',2',2'-테트라브모토에틸)시클로프로판-1-카르복실테이트Example 1 3,4,5,6-tetrahydrophthalimidomethyl (1R, cis) -2,2-dimethyl-3- (1 ', 2', 2 ', 2'-tetramomotoethyl) Cyclopropane-1-carboxylate
단계 A : (1R, 시스) 2,2-디메틸 3-(1',2',2',2'-테드라브로모에틸) 시클로프로판-1-카르복실산.Step A: (1R, Cis) 2,2-Dimethyl 3- (1 ', 2', 2 ', 2'-tetrabromoethyl) cyclopropane-1-carboxylic acid.
사염화탄소 150㎤에 19.4g의 (1R, 시스 2,2-디메틸 3-(2',2'-디브로모비닐) 시클로프로판-1-카르복실산을 도입하고 사염화탄소 22㎤중에 브롬 10.4g이 함유된 용액을 가하여 20℃에서 1시간동안 농축시키고 감압하에서 증발건조시키면 31.4g의 생성물(융점 145℃)을 얻는다. 이를 사염화탄소 110㎤중에서 재결정시키면 22.12g의 원하는 생성물을 얻는다. 융점=150℃이 생성물은 두 이성체(A)와 (B)의 혼합물인데 이는 NMR스팩트럼으로부터 명백하다. 실제로 NMR 스팩트럼은 화합물이 개미날 메틸의 수소에 해당되는 1.31-1.43에서 피크를 갖는다는 사실을 분명히 하여 주며 아울러 단일 브롬화된 비대칭 탄소상에 고착된 수소에 해당되는 5.33-5.66에서의 피크를 가지는 화합물, 그리고 게미날메틸의 수소에 해당되는 1.28-4.48ppm에서의 피크 및 단일 브롬화된 비대칭 탄소상에 고착돈 수소에 해당되는 4.24-5.34ppm에서의 피크를 가지는 또 다른 화합물의 존재를 밝혀준다.19.4 g of (1R, cis 2,2-dimethyl 3- (2 ', 2'-dibromovinyl) cyclopropane-1-carboxylic acid is introduced into 150 cm 3 of carbon tetrachloride and 10.4 g of bromine is contained in 22 cm 3 of carbon tetrachloride. The solution was added, concentrated for 1 hour at 20 ° C. and evaporated to dryness under reduced pressure to yield 31.4 g of product (melting point 145 ° C.) which was recrystallized in 110 cm 3 carbon tetrachloride to give 22.12 g of desired product. Is a mixture of the two isomers (A) and (B), which is evident from the NMR spectrum, which actually clarifies the fact that the compound has a peak at 1.31-1.43, corresponding to hydrogen of antyl methyl, Having a peak at 5.33-5.66 corresponding to hydrogen fixed on asymmetric carbon, and a peak at 1.28-4.48 ppm corresponding to hydrogen of geminmethyl and a single brominated asymmetric carbon With a peak at 4.24-5.34ppm corresponding to the hydrogen addition gives out the presence of other compounds.
위에서 얻은 혼합물(융점=150℃)의 분석은 다음과 같다.The analysis of the mixture obtained above (melting point = 150 ° C.) is as follows.
C8H10Br4O2(457.804)C 8 H 10 Br 4 O 2 (457.804)
계산치 ; C% 20.99 H% 2.20 Br% 69.82Calculated value; C% 20.99 H% 2.20 Br% 69.82
측정치 : 20.9 2.2 70.2Measured value: 20.9 2.2 70.2
단계 B : (1R, 시스)2,2-디메틸3-(1',2',2',2'-테트타브로모에틸 시클로프로판-1-카르복실산클로라이드Step B: (1R, cis) 2,2-dimethyl3- (1 ', 2', 2 ', 2'-tettabromoethyl cyclopropane-1-carboxylic acid chloride
유화에테르(비점 35-75℃) 179㎤중에 디메틸포름아미드 0.2㎤와 티오닐클로라이드 8.5㎤를 도입하고 환류로 잡아 염화메틸렌 150㎤에 단계 A에서 얻은 산물 35.76g이 들이 있는 용액을 가하고 환류로 2시간 교반시킨 뒤, 냉각, 농축, 증류 건조시킨 다음 톨루엔을 가하여 다시 농축물을 감압하에서 증류건조시켜 38g의 조산물(융점 =88℃)을 얻는다.0.2 cm 3 of dimethylformamide and 8.5 cm 3 of thionyl chloride were introduced into 179 cm 3 of emulsified ether (boiling point 35-75 ° C.), and reflux was added to a solution containing 35.76 g of the product obtained in step A to 150 cm 3 of methylene chloride. After stirring for a period of time, the mixture was cooled, concentrated and distilled to dryness, then toluene was added, and the concentrate was further distilled off under reduced pressure to obtain 38 g of crude product (melting point = 88 DEG C).
단계 C : 3,4,5,6-테드라하이드로프탈이미도 메틸 (1R, 시스)2,2-디메틸-3-(1',2',2',2'-테트라브로모에틸 시클로프로판-1-카르복실레이트Step C: 3,4,5,6-Tetrahydrophthalimido methyl (1R, cis) 2,2-dimethyl-3- (1 ', 2', 2 ', 2'-tetrabromoethyl cyclo Propane-1-carboxylate
네오피나미늄 2.9g을 함유하는 앞단계의 생성물 7.7g의 전술한 산클로라이드를 50㎤의 무수벤젠에 넣고 0℃까지 냉각하여 교반하면서 3g의 피리딘을 가하여 상온으로 될 때 18시간동안 교반하고 반응혼합물을 묽은 염산용액에 부은 다음 벤젠으로 추출하고 중탄산나트륨 용액으로 세척한다. 이를 중성으로 될 때까지 물로 수세하고 유기상을 분리한 다음 황산마그네슘으로 건조시켜 여과시킨 다음 감압농축하면 10g의 조(粗)생성물이 얻어진다. 이것을 실리카를 써서 크로마토 그래피에 의해 정화하면(용리액 : 벤젠 : 에틸아세테이트 95:5) 3.3g의 3,4,5,6-테트라히드로프탈리미도메틸(1R, 시스)2,2-디메틸3-(1',2',2',2'-테트라브로모에틸) 시클로프로판-1-카트복실레이트의 이성체 A와 B의 혼합물이 얻어지는데, 이때 이성체 B는 0.5g이다. 이성체 A와 B의 혼합물 형태로 얻어진 생성물의 특성은 다음과 같다.7.7 g of the above-mentioned acid chloride containing 2.9 g of neofinaminium was added to 50 cm 3 of anhydrous benzene, cooled to 0 ° C., and stirred for 18 hours when 3 g of pyridine was added to room temperature, followed by stirring. Is poured into diluted hydrochloric acid solution, extracted with benzene and washed with sodium bicarbonate solution. It was washed with water until neutral, the organic phase was separated, dried over magnesium sulfate, filtered and concentrated under reduced pressure to give 10 g of crude product. This was purified by chromatography using silica (eluent: benzene: ethyl acetate 95: 5) 3.3 g of 3,4,5,6-tetrahydrophthalimidomethyl (1R, cis) 2,2-dimethyl3- A mixture of isomers A and B of (1 ', 2', 2 ', 2'-tetrabromoethyl) cyclopropane-1-carboxylate is obtained, wherein isomer B is 0.5 g. The properties of the product obtained in the form of a mixture of isomers A and B are as follows.
[20]20 D=-21.5°±1°(C=1%, 벤젠)[20] 20 D = -21.5 ° ± 1 ° (C = 1%, benzene)
분석 :C17H19Br4NO3분자량=620.982Assay: C 17 H 19 Br 4 NO 3 Molecular weight = 620.982
이론치 : C% 32.88 H% 3.08 N% 2.25 Br% 51.47Theoretic Value: C% 32.88 H% 3.08 N% 2.25 Br% 51.47
실측치 ; 33.8 3.2 2.1 50.2Found value; 33.8 3.2 2.1 50.2
자외선스펙트럼(에탄올) :UV Spectrum (Ethanol):
변곡점 218nm E1 1=243Inflection point 218 nm E 1 1 = 243
최대 =223nm E1 1=275 ε=17100Max = 223 nm E 1 1 = 275 ε = 17100
최대 = 229nm E1 1=269 ε=16700Max = 229 nm E 1 1 = 269 ε = 16700
변곡점 238nm E1 1=170 ε=10500Inflection point 238nm E 1 1 = 170 ε = 10500
변곡점= 295nm E1 1=8Inflection point = 295 nm E 1 1 = 8
N.M.R. 스펙트럼(듀데로클로로포름)N.M.R. Spectrum (Duderochloroform)
4.98-5.17 p.p.m. 에서 피크 : 이성체 B의 에틸 측쇄의 1'위치에 있는 수소.4.98-5.17 p.p.m. Peak in: Hydrogen at 1 'position of the ethyl side chain of Isomer B.
1.2-1.45 p.p.m. 에서 피크 : 이성체 B의 제미날메틸의 수소.1.2-1.45 p.p.m. Peak in: Hydrogen of Geminimethyl of Isomer B.
5.17-5.38 p.p.m. 에서 피크 : 이성체 A의 에틸 측쇄의 1'위치에 있는 수소.5.17-5.38 p.p.m. Peak in: Hydrogen at 1 'position of the ethyl side chain of Isomer A.
1.2-1.38 p.p.m. 에서 피크 : 이성체 A의 제미날메틸의 수소.1.2-1.38 p.p.m. Peak in: Hydrogen of the Geminalmethyl of Isomer A.
1.58-2.08 p.p.m. 에서 피크 : 시클로프로필의 수소 및 시클로헥실의 메틸렌1.58-2.08 p.p.m. Peak in: Hydrogen of cyclopropyl and methylene of cyclohexyl
2.33 p.p.m. 에서 피크 : 시클로헥실의 메틸렌의 수소.2.33 p.p.m. Peak in: Methyl hydrogen of cyclohexyl.
5.33--5.70 p.p.m. 에서 피크 : COOCH2N 기의 수소.Peak at 5.33--5.70 ppm: hydrogen of COOCH 2 N group.
이성체 B의 형태로 얻어지는 생성물의 특성 :Properties of the product obtained in the form of isomer B:
[α]20 D=+725±2.5°(C=0.5%, 벤젠)[α] 20 D = + 725 ± 2.5 ° (C = 0.5%, benzene)
분석 : C17H19Br4NO4분자량=620.982Assay: C 17 H 19 Br 4 NO 4 Molecular weight = 620.982
이론치 : C% 32.88 H% 3.08 N% 2.25 Br% 51.47Theoretic Value: C% 32.88 H% 3.08 N% 2.25 Br% 51.47
실측치 ; 35.5 3.3 2.2 50.1Found value; 35.5 3.3 2.2 50.1
자외선 스펙트럼 ;Ultraviolet spectrum;
변곡점 =218nm E1 1=248 최대 = 223nm E1 1=278Inflection point = 218 nm E 1 1 = 248 max = 223 nm E 1 1 = 278
최대 = 228-229nm E1 1=272Max = 228-229 nm E 1 1 = 272
변곡점= 238nm E1 1=172 변곡점= 295nm E1 1=7Inflection point = 238nm E 1 1 = 172 Inflection point = 295nm E 1 1 = 7
NMR 스펙트럼(듀레로클로로포름)NMR Spectrum (Durerochloroform)
4.98-5.16p.p.m.에서 피크 : 에틸측쇄의 위치 11에 있는 수소.Peak at 4.98-5.16 ppm: hydrogen at position 1 1 of the ethyl side chain.
1.21-1.45p.p.m.에서 피크 : 제미날메틸의 수소.Peak at 1.21-1.45p.p.m .: Hydrogen of Geminalmethyl.
1.5-2p.p.m.에서 피크 : 시클로프로필의 수소와 시클로 헥실의 위치의 메틸렌.Peak at 1.5-2p.p.m .: Methylene in position of hydrogen in cyclopropyl and cyclohexyl.
2.38p.p.m.에서 피크 : 시클로헥실의 메틸렌의 수소.Peak at 2.38p.p.m .: Hydrogen of methylene of cyclohexyl.
5.38-5.57 및 5.57-5.75p.p.m.에서 피크 : COOCH2N기의 수소.Peaks at 5.38-5.57 and 5.57-5.75 ppm: Hydrogen in COOCH 2 N group.
실시예 2 : 3,4,5,6-테트라히드로프탈리미도 메틸(1R, 트랜스) 2,2-디메틸 3-(1',2',2',2'-테트타 브로모에틸)시클로프로판-1-카르복실레이트Example 2 3,4,5,6-tetrahydrophthalimido methyl (1R, trans) 2,2-dimethyl 3- (1 ', 2', 2 ', 2'-tetta bromoethyl) cyclo Propane-1-carboxylate
단계 A : (1R, 트랜스) 2,2-디메틸 3-(1',2',2',2'-테트타 브로모에틸)시클로프로판-1-카르복실산.Step A: (1R, trans) 2,2-Dimethyl 3- (1 ', 2', 2 ', 2'-tetta bromoethyl) cyclopropane-1-carboxylic acid.
이 화합물은 (1R, 트랜스) 2,2-디메틸 3-(2',2'- 브로모비닐) 시클로프로판-1-카트복실산, 이성체(A)와 (B)의 혼합물들을 브롬화시켜 얻는다.This compound is obtained by bromination of a mixture of (1R, trans) 2,2-dimethyl 3- (2 ', 2'-bromovinyl) cyclopropane-1-carboxylic acid, isomers (A) and (B).
NMR 스펙트럼NMR Spectrum
1.30-1.40p.p.m. 에서 피크(시클로프로판 2위치의 메틸의 수소)1.30-1.40p.p.m. Peak in (hydrogen of methyl at cyclopropane 2-position)
1.97-2.37, 1.65-1.74p.p.m. 에서 피크(시클로프로판의 1,3위치의 수소)1.97-2.37, 1.65-1.74p.p.m. Peak at (hydrogen at position 1,3 of cyclopropane)
4.30-4.47,및 4.47-4.65p.p.m. 에서 피크(에틸의 1'위치의 수소)4.30-4.47, and 4.47-4.65 p.p.m. Peak in (hydrogen at 1'position of ethyl)
9.63p.p.m. 에서 피크(카르복실의 수소)9.63p.p.m. Peak in (hydrogen of carboxyl)
단계 B : (1R, 트랜스 2,2-디메틸 3-)1',2',2',2'- 테트라브로모에틸) 시클로프로판-1-카르복실산 클로라이드.Step B: (1R, trans 2,2-dimethyl 3-) 1 ', 2', 2 ', 2'-tetrabromoethyl) cyclopropane-1-carboxylic acid chloride.
단계 A의 생성물에 티오닐염소를 작용시켜 다음 단계에서 사용되는 염소산을 얻는다.Thionylchlorine is reacted with the product of step A to obtain chloric acid for use in the next step.
IR 스펙트럼(클로로포름)IR spectrum (chloroform)
1778㎝-1에서 흡수.Absorbed at 1778 cm -1 .
단계 C : 3,4,5,6-테트라히드로프탈이미도-매틸 (1R, 트랜스) 2,2-디메틸 3-(1',2',2',2'- 테트라브로모에틸) 시클로프로판-1-카트복실레이트Step C: 3,4,5,6-Tetrahydrophthalimido-matyl (1R, trans) 2,2-dimethyl 3- (1 ', 2', 2 ', 2'-tetrabromoethyl) cyclopropane -1-carboxylate
앞 단계의 생성물 7.7g을 실시예 1의 단계 C에서와 동일한 방법으로 처리하면 9.2g의 조생성물이 얻어지는데 이것을 실리카를 써서 크로마토그래피에의해 정화한다.7.7 g of the product of the previous step was treated in the same manner as in step C of Example 1 to give 9.2 g of crude product which was purified by chromatography using silica.
(용리액 ; 벤젠 에틸아세테이트 9;1).(Eluent; benzene ethyl acetate 9; 1).
이를 결정화시킨 다음 생성물을 석유 에테르에 넣고 (40°-70℃)진공여과하여 건조하면 5.4g의 3,4,5,6-테트라히드로프탈리미도메틸(1R, 트랜스)2,2-디메틸 3-(1',2',2',2'- 테트라브로모에틸) 시클로프로판-1-카트복실레이트를 얻는다.After crystallization, the product was placed in petroleum ether (40 ° -70 ° C.) and vacuum filtered to dry 5.4 g of 3,4,5,6-tetrahydrophthalimidomethyl (1R, trans) 2,2-dimethyl 3 -(1 ', 2', 2 ', 2'-tetrabromoethyl) cyclopropane-1-carboxylate is obtained.
이성체 A와 B의 혼합물로서 용융점은 124°Melting point 124 ° as a mixture of isomers A and B
[α]20 D=-1°±1°(C=1%, 벤젠)[α] 20 D = -1 ° ± 1 ° (C = 1%, benzene)
분석 :C17H19Br4NO4분자량=620.982Assay: C 17 H 19 Br 4 NO 4 Molecular weight = 620.982
이론치 : C% 32.88 H% 3.08 Br% 51.47 N% 2.25Theoretic Value: C% 32.88 H% 3.08 Br% 51.47 N% 2.25
실측치 ; 33.1 3.2 51.1 2.1Found value; 33.1 3.2 51.1 2.1
자외선스펙트럼(에탄올)UV spectrum (ethanol)
최대 =224nm E1 1=274 ε=17000 최대 = 228nm E1 1=269 ε=16700Max = 224 nm E 1 1 = 274 ε = 17000 max = 228 nm E 1 1 = 269 ε = 16700
변곡점 =235nm E1 1=167 ε=10400 변곡점 = 280nm E1 1=9Inflection point = 235 nm E 1 1 = 167 ε = 10400 Inflection point = 280 nm E 1 1 = 9
NMR 스펙트럼(듀테로 클로로포름)NMR Spectrum (Dutetro Chloroform)
1.25-1.30-1.31p.p.m. 에서 피크 : 제미날메틸의 수소1.25-1.30-1.31 p.p.m. Peak in: Geminimethylmethyl Hydrogen
1.58-2.16p.p.m. 에서 피크시클로프로필의 수소 및 시클로 덱실의 β위치의 메틸렌1.58-2.16p.p.m. Hydrogen at peak cyclopropyl and methylene at β-position of cyclodexyl at
2.16-2.5p.p.m. 에서 피크 : 시클로덱실의 α위치의 메틸렌의 수소.2.16-2.5p.p.m. Peak in: Hydrogen of methylene at α position of cyclodexyl.
5.51 과 5.55p.p.m. 에서 피크 : COOCH2N기의 특징.Peak at 5.51 and 5.55ppm: Characteristics of COOCH 2 N group.
실시예 3 : (S)α-시아노 3-페녹시벤질(1R, 트랜스)2,2-디메틸 3-(2',2'-디클로로1',21-디브로모에틸) 시클로프로판-1-카르복실레이트Example 3: (S) α-cyano 3-phenoxybenzyl (1R, trans) 2,2-dimethyl 3- (2 ', 2'-dichloro1', 2 1 -dibromoethyl) cyclopropane- 1-carboxylate
단계 A : (1R, 트랜스)2,2-디메틸 3-(2',2'-디클로로 1',2'-디브로모에틸) 시클로프로판-1-카르복실산)Step A: (1R, trans) 2,2-Dimethyl 3- (2 ', 2'-dichloro 1', 2'-dibromoethyl) cyclopropane-1-carboxylic acid)
(1R, 트랜스) 2,2-디메틸 3-(2',2'-디클로로비닐)시클로프로판-1-카르복실산에 브롬을 작용시켜 (1R, 트랜스) 2,2-디메틸 3-(2',2'-디클로로 1',2'-디브로모에틸) 시클로프로판-1-카르복실산, 그리고 그의 이성체(A)와 (B)를 얻는다.(1R, trans) 2,2-dimethyl 3- (2 ', 2'-dichlorovinyl) cyclopropane-1-carboxylic acid with bromine to react (1R, trans) 2,2-dimethyl 3- (2' , 2'-dichloro 1 ', 2'-dibromoethyl) cyclopropane-1-carboxylic acid, and isomers (A) and (B) thereof are obtained.
NMR 스펙트럼NMR Spectrum
1.17-1.37p.p.m. 에서 피크(시클로프로판의 2위치에틸의 수소)1.17-1.37p.p.m. Peak at (hydrogen 2-position ethyl in cyclopropane)
1.65-1.73-1.03-2.03p.p.m.에서 피크(시클로프로판의 1위치 수소)Peak at 1.65-1.73-1.03-2.03p.p.m. (1-position hydrogen of cyclopropane)
4.23-4.45 그리고 4.45-4.62p.p.m. 에서 프크 (시클로프로판의 3위치에틸의 1'위치의 수소)4.23-4.45 and 4.45-4.62 p.p.m. Fruc (hydrogen at 1 'position of 3-position ethyl of cyclopropane)
단게 B : (1R, 트랜스) 2,2-디메틸 3-(2',2'-디클로로1',2'-디브로모에틸) 시클로프로판-1-카르복실산Step B: (1R, trans) 2,2-dimethyl 3- (2 ', 2'-dichloro1', 2'-dibromoethyl) cyclopropane-1-carboxylic acid
클로라이드Chloride
앞 단계 A에서 얻은 산에 티오닐클로라이드를 작용시켜 원하는 생성물을 얻는다.Thionylchloride is applied to the acid obtained in the previous step A to obtain the desired product.
IR 스펙트럼(클로로포름)IR spectrum (chloroform)
1777㎝-1에서 흡수Absorbed at 1777 cm -1
단계 C : (S)α-시아노 3-페녹시벤질(1R, 트랜스) 2,2-디메틸 3-(2',2'-디클로로1',2'-디브로모에틸) 시클로프로판-1-카르복실레이트Step C: (S) α-cyano 3-phenoxybenzyl (1R, trans) 2,2-dimethyl 3- (2 ', 2'-dichloro1', 2'-dibromoethyl) cyclopropane-1 Carboxylate
2.6g의 (S)α-시아노 3-페녹시 벤질알콜을 함유하는 앞 단계의 생성물 4.45g을 무수벤젠 100㎤와 혼합한다. 이를 15℃까지 냉각시킨 다음 5㎤의 피리딘 용액을 -20㎤의 무수벤젠에 첨가한다. 상온에서 3시간 동안 교반하고 반응혼합물을 100㎤의 2N염산에 가하여 유기상을 분리하고 물로 세척한 다음 감압하에서 농축건조시킨다. 실리카를 써서 크로마토그래피에 의해 정제하면(용리액 : 벤젠 4.9g의 (S)α-시아노 3-페녹시벤질(1R, 트랜스) 2,2-디메틸 3-(2',2'-디클로로-1',2'-디브로모에틸) 시클로프로판-1-카르복실레이트가 이성체 A와 B의 혼합물의 형태로 얻어진다.4.45 g of the product of the previous step containing 2.6 g of (S) α-cyano 3-phenoxy benzyl alcohol is mixed with 100 cm 3 of anhydrous benzene. It is cooled to 15 ° C. and then 5 cm 3 of pyridine solution is added to -20 cm 3 of anhydrous benzene. After stirring for 3 hours at room temperature, the reaction mixture was added to 100 cm 3 of 2N hydrochloric acid to separate the organic phase, washed with water, and concentrated to dryness under reduced pressure. Purification by chromatography using silica (eluent: 4.9 g of (S) α-cyano 3-phenoxybenzyl (1R, trans) 2,2-dimethyl 3- (2 ', 2'-dichloro-1) ', 2'-dibromoethyl) cyclopropane-1-carboxylate is obtained in the form of a mixture of isomers A and B.
[α]D 20=0°(벤젠)[α] D 20 = 0 ° (benzene)
분석 :C22H19Cl2O3N 분자량=576.12Assay: C 22 H 19 Cl 2 O 3 N Molecular weight = 576.12
이론치 : C% 45.86 H% 3.32 Br% 27.74 Cl% 12.31 N% 2.43Theoretic Value: C% 45.86 H% 3.32 Br% 27.74 Cl% 12.31 N% 2.43
실측치 ; 46.0 3.4 27.5 12.2 2.2Found value; 46.0 3.4 27.5 12.2 2.2
원편광이색성Circular dichroism
287nm에서 최대 Δε=+0.12Δε max at 287nm = + 0.12
282nm에서 최대 Δε=+0.11Max Δε = + 0.11 at 282 nm
265nm에서 최대 Δε=+0.042Max Δε = + 0.042 at 265nm
NMR 스펙트럼NMR Spectrum
1.20-1.26-1.31p.p.m. 에서 피크 : 제미날메틸의 수소1.20-1.26-1.31 p.p.m. Peak in: Geminimethylmethyl Hydrogen
4.20-4.35 와 4.36-4.52p.p.m. 에서 피크 : 에틸사슬의 위치 1'에 있는 수소4.20-4.35 and 4.36-4.52p.p.m. Peak in: Hydrogen at position 1 'of ethyl chain
1.68-1.78, 1.57-2.07, 1.97-2.42p.p.m. 에서 피크 :시클로 프로필의 수소1.68-1.78, 1.57-2.07, 1.97-2.42 p.p.m. Peak at: Hydrocyclopropyl Hydrogen
6.42p.p.m. 에서 피크 : COOCHCN기의 수소6.42p.p.m. Peak in: Hydrogen of COOCHCN Group
6.92-7.58p.p.m. 에서 피크 : 방향족핵의 수소.6.92-7.58p.p.m. Peak in: Hydrogen of aromatic nuclei.
단계 D : (S)α-시아노 3-페녹시 벤질(1R, 트랜스)2,2-디메틸 3-(2',2'-디클로로1',2'-디브로모에틸) 시클로프로판-1-카르복실레이트의 이성체 A와 B의 분리Step D: (S) α-cyano 3-phenoxy benzyl (1R, trans) 2,2-dimethyl 3- (2 ', 2'-dichloro1', 2'-dibromoethyl) cyclopropane-1 Separation of Isomers A and B of the Carboxylate
전술한 방법에 의해 얻어진 (S)α-시아노 3-페녹시벤질(1R, 트랜스) 2,2-디메틸 3-디클로로 1',2'-디브로모에틸) 시클로프로판-1-카르복실레이트의 이성체 A와 B의 혼합물 4.69g을 실리카를 써서 크로마토그래피법으로 분리하면 다음의 이성체 A : B가 분리된다. 이때 용리액은 헥산/펜탄/에테트/아세토니트릴/이소프로판올 혼합물(30 : 12 : 0.4 : 1.2 : 0.3)이다.(S) α-cyano 3-phenoxybenzyl (1R, trans) 2,2-dimethyl 3-dichloro 1 ', 2'-dibromoethyl) cyclopropane-1-carboxylate obtained by the method described above 4.69 g of the mixture of isomers A and B of was separated by chromatography using silica to separate the following isomers A: B. At this time, the eluent is hexane / pentane / etet / acetonitrile / isopropanol mixture (30: 12: 0.4: 1.2: 0.3).
1.258g의 이성체 A [α]D 20=+35.5±2.5°(C=0.5% 벤젠)1.258 g of isomer A [α] D 20 = + 35.5 ± 2.5 ° (C = 0.5% benzene)
0.980g의 이성체 B [α]D 20=-17.5±2°(C=0.8% 벤젠)0.980 g of isomer B [α] D 20 = -17.5 ± 2 ° (C = 0.8% benzene)
한편 본 실시예에서 사용한 (S)α-시아노 3-페녹시벤질 알코올은 본 출원인의 프랑스 특허출원제 78.02.621호(제목 : 광학활성 치환 벤젠 알코올의 제조방법)에 그 제조방법이 기술되어 있는데, 그 에를 들면 다음과 같다.Meanwhile, the preparation method of (S) α-cyano 3-phenoxybenzyl alcohol used in this example is described in the French Patent Application No. 78.02.621 (Title: Method for preparing optically active substituted benzene alcohol) of the present applicant. For example,
단계 A : (1R, 55)6,6-디메틸 4(R)[(S)-시아노(3'-페녹시페닐)메톡시] 3-옥사바이시클로(3-1-0)헥산-2-온과(1R, 5S)6,6-디메틸 54(R)[(R(-시아노 93'-페녹시페닐)메톡시]3-옥사바이시클로(3-1-0)헥산-2-온 의혼합물Step A: (1R, 55) 6,6-Dimethyl 4 (R) [(S) -cyano (3'-phenoxyphenyl) methoxy] 3-oxabicyclo (3-1-0) hexane-2 -Warm and (1R, 5S) 6,6-dimethyl 54 (R) [(R (-cyano 93'-phenoxyphenyl) methoxy] 3-oxabicyclo (3-1-0) hexane-2- Whole mixture
22.5g의 (R,S)α-시아노 3-페녹시 벤질알코올, 9.46g의 (1R, 3S)시스 2,2-디페닐 3-(디히드록시메틸) 시클로프로판-1-카르복실산 락톤, 0.15g의 모노히드 레이티드파라톨루엔 술폰산을 혼합하여 10-2mmHg의 진공하에서 80℃로 2시간동안 유지시킨 다음 생성된 물을 증류하여 제거한다. 이것을 20℃로 냉각하면 (1R, 5S) 6,6-디메틸 4(R) [(S)-시아노 (3'-페녹시페닐)메톡시]3-옥사바이시클로 (3-1-0)-헥산-2-온과 (1R, 5S) 6,6-디메틸 4(R)[(R)-시아노 (3'-페녹시페닐)메톡시] 3-옥사-바이시클로 (3-1-0)헥산-2-온의조 혼합물 30.7g을 얻으며 이때의 불순물은 주로 미반응 반응물이다) 혼합물22.5 g of (R, S) α-cyano 3-phenoxy benzyl alcohol, 9.46 g of (1R, 3S) cis 2,2-diphenyl 3- (dihydroxymethyl) cyclopropane-1-carboxylic acid Lactone, 0.15 g of monohydrated paratoluene sulfonic acid was mixed and maintained at 80 ° C. for 2 hours under a vacuum of 10 −2 mmHg, and the resulting water was distilled off. This was cooled to 20 ° C. (1R, 5S) 6,6-dimethyl 4 (R) [(S) -cyano (3'-phenoxyphenyl) methoxy] 3-oxabicyclo (3-1-0) -Hexan-2-one and (1R, 5S) 6,6-dimethyl 4 (R) [(R) -cyano (3'-phenoxyphenyl) methoxy] 3-oxa-bicyclo (3-1- 0) 30.7 g of a bath mixture of hexane-2-one are obtained, at which time the impurities are mainly unreacted reactants)
단계 B : (1R, 5S) 6,6-디메틸 4(R)[(S)-시아노 (3'-페녹시페닐메톡시]3-옥사-바이시클로 (3-1-0)헥산-2-온 ;Step B: (1R, 5S) 6,6-Dimethyl 4 (R) [(S) -cyano (3'-phenoxyphenylmethoxy] 3-oxa-bicyclo (3-1-0) hexane-2 -On ;
단계 A에서 얻어진 혼합물을 실리카겔을 써서 크로마토 그래프 분리를 하면(용리액 : 벤젠과 에틸아세테이트 혼합물(95:5) 10.9의 (1R, 5S) 6,6-디메틸 4(R)[(S)-시아노(3'-페녹시페닐)메톡시] 3-옥사바이시클로 (3-1-0)헥산-2-온을 얻는다.The mixture obtained in step A was chromatographed using silica gel (eluent: benzene and ethyl acetate mixture (95: 5) (1R, 5S) 6,6-dimethyl 4 (R) [(S) -cyano of 10.9. (3'-phenoxyphenyl) methoxy] 3-oxabicyclo (3-1-0) hexan-2-one.
융점=126℃, [α]D 20=-71° (C=1%, 벤젠).Melting point = 126 ° C., [α] D 20 = −71 ° (C = 1%, benzene).
단계 C : (S)α-시아노 3-페녹시벤질알코올Step C: (S) α-cyano 3-phenoxybenzyl alcohol
100㎤의 디옥산과 50㎤의 물의 혼합물에 앞 단계 B에서 얻어진 (1R, 5S) 6,6-디메틸 4(R)((S)-시아노 (3'-페녹시페닐)메톡시]3-옥사바이시클로(3-1-0) 헥산-2-온 10g을 넣고 1g의 모노하이드레이티드 파라톨루엔 술폰산을 가한다음 반응혼합물을 환류시켜 23시간 동안 유지시키고 감압하에서 증류시켜 최초의 부피의 1/2이 될 때까지 농축한 다음 에틸에테르를 가하고 교반하여 유기상을 분리시키고 수세한 다음 건조시키고 감압하에서 증류에 의하여 건조농축시킨다. 이 잔사(9.5g)를 실리카겔을 써서 크로마토그래프 분리시키면(용리액 : 벤젠과 에틸아세테이트 혼합물(9:1) 6.1g의 (S)α-시아노 3-페녹시 벤질 알코올 [a]D 20=-16.5°±1.5°(C=0.8%, 벤젠)이 얻어진다.(1R, 5S) 6,6-dimethyl 4 (R) ((S) -cyano (3'-phenoxyphenyl) methoxy] 3 obtained in the previous step B in a mixture of 100 cm 3 dioxane and 50 cm 3 water Add 10 g of oxabicyclo (3-1-0) hexane-2-one, add 1 g of monohydrated paratoluene sulfonic acid, keep the reaction mixture at reflux for 23 hours, distilled under reduced pressure to obtain the initial volume of 1 Concentrate to 2, add ethyl ether, stir to separate the organic phase, wash, dry and concentrate by distillation under reduced pressure.The residue (9.5 g) is chromatographed using silica gel (eluent: 6.1 g of (S) α-cyano 3-phenoxy benzyl alcohol [a] D 20 = -16.5 ° ± 1.5 ° (C = 0.8%, benzene) of 6.1 g of benzene and ethyl acetate mixture (9: 1) are obtained.
NMR 스펙트럼(듀테로클로로포름)NMR Spectrum (Duterochloroform)
3.25p.p.m.에서 피크 : 알코올기의 수소.Peak at 3.25p.p.m .: Hydrogen of alcohol group.
5.42p.p.m.에서 피크: 니트릴기와 같은 탄소원자에 붙은 수소.Peak at 5.42 p.m .: Hydrogen attached to a carbon atom, such as a nitrile group.
실시예 4 : (S)α-시아노 3-페녹시 벤질(1R, 시스)2,2-디메틸 3-(2',2'-디브로모 1',2'-디클로로에틸) 시클로프로판-1-카르복실레이트)Example 4 (S) α-cyano 3-phenoxy benzyl (1R, cis) 2,2-dimethyl 3- (2 ', 2'-dibromo 1', 2'-dichloroethyl) cyclopropane- 1-carboxylate)
단계 A : (1R, 시스 2,2-디메틸 3-(2',2'-디브로모 1',2'-디클로로에틸) 시클로프로판-1-카르복실산Step A: (1R, cis 2,2-dimethyl 3- (2 ', 2'-dibromo 1', 2'-dichloroethyl) cyclopropane-1-carboxylic acid
-15℃에서 거품을 이루어주면서 사염화탄소 30㎤중에 염소 11.8g을 가한 다음 -10℃에서 염화메틸렌 37㎤와 (1R, 시스)2,2-디메틸 3-(2',2'-디브로모비닐)시클로프로판-1-카르복실산 24g의 용액을 서서히 가하고 0℃에서 30분, 다시 25℃에서 2시간 동안 교반시킨후 감압농축시키고 사염화탄소로부터 재결정시키면 7.4g의 원하는 산을 얻는다.11.8 g of chlorine was added to 30 cm 3 of carbon tetrachloride while bubbling at -15 ° C, and 37 cm 3 of methylene chloride and (1R, cis) 2,2-dimethyl 3- (2 ', 2'-dibromovinyl) were added at -10 ° C. A solution of 24 g of cyclopropane-1-carboxylic acid was slowly added, stirred at 0 ° C. for 30 minutes, again at 25 ° C. for 2 hours, concentrated under reduced pressure and recrystallized from carbon tetrachloride to yield 7.4 g of the desired acid.
(융점=134℃ : 이성체(A)와 (B)의 혼합물).(Melting point = 134 ° C .: mixture of isomers (A) and (B)).
NMR 스펙트럼NMR Spectrum
1.32-1.44 및 1.28-1.48p.p.m.에서 피크(시클로프로판의 2위치 메틸의 수소)Peaks at 1.32-1.44 and 1.28-1.48 p.p.m. (Hydrogen of 2-position methyl in cyclopropane)
5.08-5.45 및 4.67-5.0p.p.m.에서 피크(시클로프로판의 3위치 에틸사슬의 1' 위치수소)Peaks at 5.08-5.45 and 4.67-5.0 p.p.m. (1'-position hydrogen in 3-position ethyl chain of cyclopropane)
10.1p.p.m.에서 피크(카르복실의 수소)Peak at 10.1 p.m. (hydrogen of carboxyl)
단계 B : (1R, 시스) 2,2-디메틸 3-(2',2'-디브로모 1',2'-디클로로에틸)시클로프로판-1-카르복실산 클로라이드Step B: (1R, cis) 2,2-dimethyl 3- (2 ', 2'-dibromo 1', 2'-dichloroethyl) cyclopropane-1-carboxylic acid chloride
앞 단계 A에서 얻은 산에 피리딘 존재하에서 티오닐클로라이드를 작용시켜 원하는 생성물을 얻는다.The acid obtained in step A is subjected to thionylchloride in the presence of pyridine to give the desired product.
단계 C : (S)-α-시아노 3-페녹시벤질(1R, 시스) 2,2-디메틸 3-(2',2'-디브로모 1',2'-디클로로에틸(시클로프로판 카르복실레이드)Step C: (S) -α-cyano 3-phenoxybenzyl (1R, cis) 2,2-dimethyl 3- (2 ', 2'-dibromo 1', 2'-dichloroethyl (cyclopropane carboxy) Box Raid)
2.5g의 (S)α-시아노 3-페녹시벤질을 함유하는 앞 단계에서 얻은 염소산과 무수벤젠 100㎤를 혼합시킨다. 이를 15℃까지 냉각하고 4㎤의 피리딘 용액을 20㎤의 무수벤젠에 넣는다. 상온에서 4시간동안 교반하고 반응 혼합물을 100㎤의 2N염산에 부어 유기상을 분리시키고 수세한 다음 건조시키고 감압하에서 건조농축시킨 뒤 실리카를 써서 크로마토 그래피 시키면(용리액 : 석유에테르(40°-70℃) 이소프로필에레트(100-200) (S)α-시아노 3-페녹시벤질(1R, 시스)2,2-디메틸 3-(2',2'-디브로모 1',2'-디클로로에틸)시클로프로판-1-카르복실레이트가 얻어지는데 이때 이성체 A가 1.8g(Rf=0.30), 이성체 B가 1.4g(Rf=0.25)얻어진다.The hydrochloric acid obtained in the previous step containing 2.5 g of (S) α-cyano 3-phenoxybenzyl and 100 cm 3 of anhydrous benzene are mixed. It is cooled to 15 ° C. and 4 cm 3 of pyridine solution is placed in 20 cm 3 of anhydrous benzene. After stirring for 4 hours at room temperature, the reaction mixture was poured into 100 cm 3 of 2N hydrochloric acid, the organic phase was separated, washed with water, dried, concentrated under reduced pressure and chromatographed with silica (eluent: petroleum ether (40 ° -70 ° C)). Isopropyl ether (100-200) (S) α-cyano 3-phenoxybenzyl (1R, cis) 2,2-dimethyl 3- (2 ', 2'-dibromo 1', 2'-dichloro Ethyl) cyclopropane-1-carboxylate is obtained with 1.8 g (Rf = 0.30) of isomer A and 1.4 g (Rf = 0.25) of isomer B.
이성체 A의 물리적시험Physical Test of Isomer A
[α]D 20=-21°±1°(C=1%, 벤젠)[α] D 20 = -21 ° ± 1 ° (C = 1%, benzene)
원편광이색성Circular dichroism
300nm에서 최대 : Δε=-0.003Max at 300nm: Δε = -0.003
288nm에서 최대 : Δε=+0.29Max at 288nm: Δε = + 0.29
264nm에서 최대 : Δε=+0.11Max at 264nm: Δε = + 0.11
232nm에서 최대 : Δα=-1.8Max at 232nm: Δα = -1.8
NMR 스펙트럼(듀테로클로로포름)NMR Spectrum (Duterochloroform)
1.28-1.37p.p.m에서 피크 : 제미날메틸의 수소Peak at 1.28-1.37p.p.m: Hydrogen of Geminalmethyl
5.05-5.10-5.18-5.23p.p.m에서 피크 : 에틸측쇄의 위치 1'에 있는 수소Peak at 5.05-5.10-5.18-5.23p.p.m: hydrogen at position 1 'of the ethyl side chain
1.83-2.10p.p.m에서 피크 : 시클로프로필의 수소.Peak at 1.83-2.10p.p.m: hydrogen of cyclopropyl.
6.38p.p.m에서 피크 : COOCHCN기의 수소.Peak at 6.38p.p.m: Hydrogen of COOCHCN group.
6.92-7.55p.p.m에서 피크 : 방향족 핵의 수소.Peak at 6.92-7.55p.p.m: hydrogen in aromatic nuclei.
이성체 B의 물리적시험 :Physical test of isomer B:
[α]D 20=+80°±2.5°(C=1%, 벤젠)[α] D 20 = + 80 ° ± 2.5 ° (C = 1%, benzene)
원편광이색성 :Circular dichroism:
288nm에서 최대 : Δε =+0.22Max at 288nm: Δε = + 0.22
263nm에서 변곡 : Δε=+0.62Inflection at 263nm: Δε = + 0.62
220nm에서 최대 : Δε=+3.7Max at 220nm: Δε = + 3.7
NMR 스펙트럼(듀테로클로로포름)NMR Spectrum (Duterochloroform)
1.23-1.38p.p.m에서 피크 : 제미날메틸의 수소Peak at 1.23-1.38p.p.m: Hydrogen of Geminalmethyl
4.6-4.95p.p.m에서 피크 :에틸측쇄의 위치 1'에 있는 소수The decimal at position 1 'of the peak: ethyl side chain at 4.6-4.95 p.p.m
1.75-2.16p.p.m에서 피크 :시클로프로필의 수소Peak at 1.75-2.16p.p.m: Hydrogen of cyclopropyl
6.38p.p.m에서 피크 : COOCHCN기의 수소Peak at 6.38p.p.m: Hydrogen of COOCHCN group
6.88-7.57p.p.m에서 피크 : 방향족 핵의 수소.Peak at 6.88-7.57p.p.m: hydrogen in aromatic nuclei.
실시예 5 : (S)α-시아노 3-페녹시벤질(1R, 시스 2,2디메틸 3-1',2',2',2'-테트라클로로에틸)시클로프로판-1-카르복실레이트Example 5 (S) α-cyano 3-phenoxybenzyl (1R, cis 2,2dimethyl 3-1 ', 2', 2 ', 2'-tetrachloroethyl) cyclopropane-1-carboxylate
단계 A : (1R, 시스)2,2-디메틸 3-(1',2',2',2'-테트라 클로로에틸) 시클로프로판-1-카르복실산Step A: (1R, cis) 2,2-dimethyl 3- (1 ', 2', 2 ', 2'-tetra chloroethyl) cyclopropane-1-carboxylic acid
사염화탄소 30cm중에 염소거품을 포화될때까지 30분에 걸쳐 도입하고(염소 11.8g이 용해된다)(1R,시스) 2,2-디메틸 3-(2',2'디클로로비닐) 시클로프로판-1-카르볼실산 16.7g과 염화메틸렌 40㎤의 용액을 0℃이하의 온도에서 가한 뒤 0℃에서 24시간동안 적어준 다음 반응 혼합물의 온도를 +25℃로 올린 후 이 온도에서 3시간동안 교반한 뒤 질소를 불어 넣어 과량의 염소를 제거하고 감압하에서 중류, 농축 건조시킨 후 잔사를 시클로헥산과 에틸아세테이트(8 : 2) 혼합물로 요출시키면 실리카겔상에서 크로마토 그라피하고 유화에테르(비점 35-37℃)로부터 결정화 시키면 3.14g의 원하는 생성물(1R,시스) 2,2-디메틸 3-(1',2',2',2'-테트라클로로에틸)시클로프로판-1-카르복실산 (융점=144℃)을 얻는다.Chlorine bubbles are introduced in 30 cm of carbon tetrachloride over 30 minutes until saturated (11.8 g of chlorine is dissolved) (1R, cis) 2,2-dimethyl 3- (2 ', 2'dichlorovinyl) cyclopropane-1-car A solution of 16.7 g of volsylic acid and 40 cm 3 of methylene chloride was added at a temperature of 0 ° C. or lower, and then the resultant was added at 0 ° C. for 24 hours. Blow off the excess chlorine, remove the excess chlorine under reduced pressure, concentrate and dry, remove the residue with a mixture of cyclohexane and ethyl acetate (8: 2), chromatograph on silica gel and crystallize from emulsified ether 3.14 g of the desired product (1R, cis) 2,2-dimethyl 3- (1 ', 2', 2 ', 2'-tetrachloroethyl) cyclopropane-1-carboxylic acid (melting point = 144 ° C.) Get
분석 : C8H10Cl4O2(297.98)Assay: C 8 H 10 Cl 4 O 2 (297.98)
계산치 : C% 34.3 H% 3.6 Cl% 50.6Calculated Value: C% 34.3 H% 3.6 Cl% 50.6
측정치 : 34.3 3.7 50.3Measured value: 34.3 3.7 50.3
NMR 스펙트럼(듀테로클로로포름)NMR Spectrum (Duterochloroform)
1.26-1.42p.p.m 및 1.30-1.42 p.p.m.에서 피크 : 제미날 메틸의 수소의 특성Peaks at 1.26-1.42p.p.m and 1.30-1.42p.p.m .: Properties of Hydrogen of Gemini Methyl
4.67-5.17p.p.m 및 5.08-5.43 p.p.m.에서 피크 : 치환 에밀 측쇄의 1'위치에 수소의 특성.Peaks at 4.67-5.17p.p.m and 5.08-5.43p.p.m .: Properties of hydrogen at 1'position of substituted Emile side chain.
1.67-2.0p.p.m.에서 피크 : 시클로프로필의 수소의 특성.Peak at 1.67-2.0 p.m .: Properties of hydrogen of cyclopropyl.
10.2p.p.m.에서 피크 : 카르복실의 하이드록사이드의 특성.Peak at 10.2 p.m .: Properties of carboxyl hydroxide.
단계 B : (1R, 시스)2,2-디메틸 3-(1',2',2',2'-택트라 콜로로에틸) 시클로프로판-1-카르복실산 염소Step B: (1R, cis) 2,2-Dimethyl 3- (1 ', 2', 2 ', 2'-tactra coloethyl) cyclopropane-1-carboxylic acid chlorine
유화에테르 60㎤(비점(35-70℃)와 티오닐클로라이드 8.7㎤의 혼합물중에 단계 A의 생성물 6.75g을 도입하고 환류로 잡은 뒤 4시간 30분간 유지시킨 후감압하에서 증류농축 건조시키고 벤젠을 가한 다음 건조 농축시켜서 다음 단계에서 사용되는 (1R, 시스)2,2-디메틸 3-(1',2',2',2'-테트라클로로에틸) 시클로프로판-1-카르복실산 염소의조산물을 얻는다.6.75 g of the product of step A was introduced in a mixture of 60 cm 3 of emulsified ether (boiling point (35-70 ° C.) and 8.7 cm 3 of thionyl chloride), held at reflux and maintained for 4 hours and 30 minutes. A crude product of (1R, cis) 2,2-dimethyl 3- (1 ', 2', 2 ', 2'-tetrachloroethyl) cyclopropane-1-carboxylic acid chlorine which is then concentrated to dryness and used in the next step. Get
단계 C : (S)α-시아노 3-페녹 시벤질(1R, 시스) 2,2-디메틸 3-(1',2',2',2'-테트라클로로에틸) 시클로프로판-1-카르복실레이트Step C: (S) α-cyano 3-phenoxy cibenzyl (1R, cis) 2,2-dimethyl 3- (1 ', 2', 2 ', 2'-tetrachloroethyl) cyclopropane-1-car Carboxylate
2.6g의 (S)α-시아노 3-페녹시벤질알코올을 함유하는 앞단계의 생성물인 염소산 3.19g을 30㎤의 무수벤젠에 넣는다. 얼음을 채운 냉각조에서 이를 냉각시키고 3㎤의 피리딘을 서서히 가한 다음 상온에서 24시간 교반하고 반응 혼합물을 냉각된 묽은 염산에 붓는다. 이를 벤젠으로 추출하고 유기상을 분리시킨 다음 중탄산나트륨 용액으로 세척하고 수세한 뒤 황산나트륨으로 건조시키고 여과하여 감압농축 시킨다.3.19 g of chloric acid, the previous product containing 2.6 g of (S) α-cyano 3-phenoxybenzyl alcohol, are placed in 30 cm 3 of anhydrous benzene. Cool it in an ice bath filled with ice, slowly add 3 cm 3 of pyridine, stir at room temperature for 24 hours, and pour the reaction mixture into cold diluted hydrochloric acid. It is extracted with benzene, the organic phase is separated, washed with sodium bicarbonate solution, washed with water, dried over sodium sulfate, filtered and concentrated under reduced pressure.
이것을 실리카를 써서 크로마토그래피법으로 정제하면(용리액 : 벤제/시클로헥산 7:3)(S)α-시아노 3-페녹시벤질(1R, 시스)2,2-디메틸 3-(1',2',2',2'-테트라클로로에틸) 시클로프로판-1-카르복실레이트가 이성체 A와 B의 혼합물의 형태로 얻어지는데 이때 이성체 A는 2.258g, 이성체 A B는 1.48g이다.Purification by chromatography using silica (eluent: benze / cyclohexane 7: 3) (S) α-cyano 3-phenoxybenzyl (1R, cis) 2,2-dimethyl 3- (1 ', 2 ', 2', 2'-Tetrachloroethyl) cyclopropane-1-carboxylate is obtained in the form of a mixture of isomers A and B with 2.258 g of isomer A and 1.48 g of isomer AB.
이성체 A의 물리분석 :Physical Analysis of Isomer A:
[α]D 20=+35.5±2°(C=0.6%, 벤젠)[α] D 20 = + 35.5 ± 2 ° (C = 0.6%, benzene)
분석 : C22H19Cl4NO3487.213Assay: C 22 H 19 Cl 4 NO 3 487.213
이론치 : C% 54.23 H% 3.93 N% 2.87 Cl% 29.1Theoretic Value: C% 54.23 H% 3.93 N% 2.87 Cl% 29.1
실측치 : 54.4 3.8 2.8 28.5Found: 54.4 3.8 2.8 28.5
NMR 스펙트럼(듀데로클로로포름)NMR Spectrum (Duderochloroform)
1.28-137p.p.m.에서 피크 : 제미날 메틸의 수소Peak at 1.28-137p.p.m .: Hydrogen of Gemini Methyl
1.75-2.08p.p.m.에서 피크 : 시클로프로필의 수소Peak at 1.75-2.08p.p.m .: Hydrogen of cyclopropyl
5.07-5.25p.p.m.에서 피크 : 에틸측쇄의 위치 1에 있는 수소Peak at 5.07-5.25p.p.m.: Hydrogen at position 1 of the ethyl side chain
6.35p.p.m.에서 피크 : COOCHCN기의 수소Peak at 6.35p.p.m .: Hydrogen of COOCHCN group
6.92-7.58p,p,m.에서 피크 : 방향족 핵의 수소Peak at 6.92-7.58p, p, m .: Hydrogen of aromatic nucleus
이성체 A와 B의 혼합물의 물리분석Physical Analysis of Mixtures of Isomers A and B
[α]D 20=-33.5°±2.5°(C=0.4%, 벤젠)[α] D 20 = -33.5 ° ± 2.5 ° (C = 0.4%, benzene)
분석 : C22H19Cl4NO3=487.213Analysis: C 22 H 19 Cl 4 NO 3 = 487.213
이론치 : C% 54.23 H% 3.93 N% 2.87 Cl% 29.1Theoretic Value: C% 54.23 H% 3.93 N% 2.87 Cl% 29.1
실측치 : 54.5 3.9 2.8 28.8Found: 54.5 3.9 2.8 28.8
NMR 스펙트럼(듀테로클로로포름)NMR Spectrum (Duterochloroform)
1.2-1.35p.p.m.에서 피크 : 이성체 R의 제미날메틸의 수소Peak at 1.2-1.35p.p.m .: Hydrogen of Geminalmethyl of Isomer R
1.27-1.35p.p.m.에서 피크 : 이성체 S의 제미날메틸의 수소Peak at 1.27-1.35p.p.m .: Hydrogen of Geminimethyl of Isomer S
1.75-2.08p.p.m.에서 피크 : 시클로프로필을 수소Peak at 1.75-2.08p.p.m .: Cyclopropyl Hydrogen
4.77-4.94p.p.m.에서 피크 : 에틸측쇄의 위치 1'에 있는 수소Peak at 4.77-4.94p.p.m.: Hydrogen at position 1 'of the ethyl side chain
5.08-5.26p.p.m.에서 피크 : 에틸측쇄의 위치 1'에 있는 수소Peak at 5.08-5.26p.p.m.: Hydrogen at position 1 'of the ethyl side chain
6.35-6.37p.p.m.에서 피크 : COOCHCN기의 수소Peak at 6.35-6.37p.p.m .: Hydrogen of COOCHCN group
7.93-7.38p.p.m.에서 피크 : 방향족핵의 수소Peak at 7.93-7.38p.p.m .: Hydrogen of Aromatic Nucleus
실시예 6 : (R)α-시아노 3-페녹시벤질(1R, 트랜스) 2,2-디메틸 3-(2',2'-디클로로 1',2'-디브로모에틸)시클로프로판-1-카르복실레이트Example 6: (R) α-cyano 3-phenoxybenzyl (1R, trans) 2,2-dimethyl 3- (2 ', 2'-dichloro 1', 2'-dibromoethyl) cyclopropane- 1-carboxylate
실시예 3의 단계 C에서와 같이 하는데 이에서는 실시예 3의 단계 B에서 얻은 2g의 (1R, 트랜스) 2,2-디메틸 3-(2',2') 디클로로 1',2'-디브로모에틸)시클로프로판-1-카르복실산 클로라이드와 1.1g의 (R)α-시아노 3-페녹시벤질 알코올을 반응시키면 1.4g의 (R)α-시아노 3-페녹 시벤질(1R, 트랜스) 2,2-디메틸 3-(2',2'-디클로로 1',2'-디브로모메틸)시클로프로-1-판카르복실레이트가 이성체 A와 B의 혼합물 형태로 얻어진다.As in Step C of Example 3, wherein 2 g of (1R, trans) 2,2-dimethyl 3- (2 ', 2') dichloro 1 ', 2'-dibro obtained in Step B of Example 3 Moethyl) cyclopropane-1-carboxylic acid chloride and 1.1 g of (R) α-cyano 3-phenoxybenzyl alcohol reacted with 1.4 g of (R) α-cyano 3-phenoxy sibenzyl (1R, Trans) 2,2-dimethyl 3- (2 ', 2'-dichloro 1', 2'-dibromomethyl) cyclopro-1-pancarboxylate is obtained in the form of a mixture of isomers A and B.
[α]D 20=-28°±2°(C=0.7%, 벤젠)[α] D 20 = -28 ° ± 2 ° (C = 0.7%, benzene)
분석 : C22H19Br2Cl2NO3분자량=576.22Assay: C 22 H 19 Br 2 Cl 2 NO 3 Molecular weight = 576.22
이론치 : C% 45.87 H% 3.32 N% 2.43 Cl% 12.31 Br% 27.74Theoretic value: C% 45.87 H% 3.32 N% 2.43 Cl% 12.31 Br% 27.74
실측치 : 46.3 3.3 2.4 12.5 27.4Found: 46.3 3.3 2.4 12.5 27.4
NMR 스펙트럼)듀테로클로로포름)NMR spectrum) deuterochloroform)
1.31-1.35p.p.m.에서 피크 : 제미날 메틸의 수소Peak at 1.31-1.35p.p.m .: Hydrogen of Gemini Methyl
1.66-2.42p.p.m.에서 피크 : 시클로프로필의 수소Peak at 1.66-2.42p.p.m .: Hydrogen of Cyclopropyl
4.23-4.42p.p.m.,4.42-4.58 p.p.m.에서 피크‥에틸측쇄의 위치 1'에 있는 수소.4.23-4.42 p.m., 4.42-4.58 Hydrogen at position 1 'of the peak-ethyl side chain at p.p.m.
6.47p.p.m.에서 피크 : COOCHEN기의 수소.Peak at 6.47p.p.m .: Hydrogen of COOCHEN group.
6.92-7.58p.p.m.에서 피크 : 방향족핵의 수소Peak at 6.92-7.58p.p.m .: Hydrogen of Aromatic Nucleus
원편광이색성(디옥산)Circular dichroism (dioxane)
219nm에서 최대 : ε=-5.4 280에서 최대 : ε=-0.28Maximum at 219 nm: ε = -5.4 Maximum at 280: ε = -0.28
285에서 최대 : ε=-0.27Max at 285: ε = -0.27
실리카를 이용하는 크로마토그래피법에 의하여 이성체 A와 B를 분리하였으며 이때 용리액을 헥산/펜탄/에테르(7-2.8-0.17)혼합물이었다.Isomers A and B were separated by chromatography using silica, at which time the eluent was a hexane / pentane / ether (7-2.8-0.17) mixture.
이성체 A :Isomer A:
NMR 스펙트럼(듀테로클로포름)NMR Spectrum (Duteclochloroform)
1.32-1.37p.p.m.에서 피크 : 제미날메틸의 수소Peak at 1.32-1.37p.p.m .: Hydrogen of Geminimethyl
1.66-1.76p.p.m.에서 피크 : 시클로프로판의 수소Peak at 1.66-1.76p.p.m .: Hydrogen of cyclopropane
2.08-2.17p.p.m.에서 피크 : 시클로프로판의 수소Peak at 2.08-2.17p.p.m .: Hydrogen of cyclopropane
2.29-2.35p.p.m.에서 시클로프로판의 수소Hydrogen of cyclopropane at 2.29-2.35p.p.m.
4.2-4.37p.p.m.에서 피크 : 에틸측쇄의 위치 1'에 있는 수소Peak at 4.2-4.37p.p.m .: Hydrogen at position 1 'of ethyl side chain
6.42p.p.m.에서 피크 : COOCHCN기의 수소Peak at 6.42p.p.m .: Hydrogen of COOCHCN group
6.92-7.58p.p.m.에서 피크 : 방향족핵의 수소Peak at 6.92-7.58p.p.m .: Hydrogen of Aromatic Nucleus
이성체 B :Isomer B:
NMR 스펙트럼(듀테로클로로포름)NMR Spectrum (Duterochloroform)
4.37-4.53p.p.m.에서 피크 : 에틸측쇄의 위치 1'에 있는 수소 이때 사용된 (R)α-시아노 3-페녹 시벤질알코올은 다음과 같은 방법에 따라 제조하였다.Peak at 4.37-4.53p.p.m.: Hydrogen at position 1 ′ of the ethyl side chain. The (R) α-cyano 3-phenoxy sibenzyl alcohol used at this time was prepared according to the following method.
단계 A : (1R, 5S) 6,6-디메틸(4(R)[(R)시아노(3'-페녹시 페닐)메톡시] 3-옥사 비시클로(3-1-0) 헥사-2-논Step A: (1R, 5S) 6,6-Dimethyl (4 (R) [(R) cyano (3'-phenoxyphenyl) methoxy] 3-oxabicyclo (3-1-0) hexa-2 Rice fields
실시예 3의 단계 B에서 시작되는 크로마토그래피를 계속하여 7.32g의 원하는 산물을 얻는다.The chromatography starting in step B of Example 3 is continued to yield 7.32 g of the desired product.
[α]D 20=-120°±2.5°(C=0.9%, 벤젠)[α] D 20 = -120 ° ± 2.5 ° (C = 0.9%, Benzene)
단계 B : (R)α-시아노 3-페녹시 벤질알콜Step B: (R) α-cyano 3-phenoxy benzyl alcohol
실시예 3의 단계 C에서 언급된 방법과 유사한 방법으로 하여 앞단계에서 얻은 12.8g의 출발물질로부터 5g의 원하는 산물을 얻는다.5 g of the desired product are obtained from 12.8 g of starting material obtained in the previous step by a similar method as described in step C of Example 3.
[α]D 20=-11°±2°(C=0.5%, 벤젠)[α] D 20 = -11 ° ± 2 ° (C = 0.5%, benzene)
실시예 7 : (S)α-시아노 3-페녹시벤질(1R, 트랜스 2,2-디메틸 3-(2',2'-디클로로 1',2'-디브로메틸) 시클로 프로판-1-카르복실레이트(화합물 A), (S)α-시아노 3-페녹시벤질(1R, 시스) 2,2-디메틸 3-(2',2'-디브로모 1',2'-디클로로에틸)시클로프로판-1-카르복실레이트의 이성체 A(화합물)및 이성체 B(화합물 C)의 살충활성시험Example 7 (S) α-cyano 3-phenoxybenzyl (1R, trans 2,2-dimethyl 3- (2 ', 2'-dichloro 1', 2'-dibromethyl) cyclopropane-1- Carboxylate (Compound A), (S) α-cyano 3-phenoxybenzyl (1R, cis) 2,2-dimethyl 3- (2 ', 2'-dibromo 1', 2'-dichloroethyl Insecticidal Activity of Isomer A (Compound) and Isomer B (Compound C) of Cyclopropane-1-carboxylate
(1) 집파리에 대한 화합물 A,B,C의 치사활성시험.(1) Killing activity test of compounds A, B, and C on housefly.
시험곤충은 4일생 암컷 집파리이다. 1μ의 아세톤 용액을 파리의 배면 가슴부에 아놀드 미량조작기를 이용하여 국소 처리법으로 시험하였다. 1회 처리당 50마리의 파리를 이용하였으며 처리 24시간 후의 치사율을 조사하였다.Test insects are four-day-old female house flies. An acetone solution of 1 μ was tested by topical treatment using an Arnold micromanipulator in the back chest of the fly. Fifty flies were used per treatment and mortality was examined 24 hours after treatment.
상승효과나 피페로닐 부톡사이드(1부의 시험 화합물당 10부의 상승효과제)를 사용하지 않고 시험하였고 그 결과는 다음의 표에 50%의 벌레를 죽이는데 요하는 양을 LD50으로 하여 표시했다.It was tested without the use of synergistic effects or piperonyl butoxide (10 parts synergist per test compound) and the results are shown in the following table as the amount required to kill 50% of worms as LD 50 .
결론 : 화합물 A,B,C는 집파리에 대해서 매우 강한 살충작용을 나타내었다.CONCLUSIONS: Compounds A, B and C showed very strong insecticidal action against housefly.
(2) 집파리에 대한 화합물 A,B,C의 녹다운(knock-down)활성 시험.(2) Knock-down activity test of compounds A, B, and C on housefly.
시험곤충은 4일생 암컷 집파리이다.Test insects are four-day-old female house flies.
컨스(KEARNS)와 마취(MARCH)실에서 아세톤과 등유(2×0.2㎤을 사용)를 용제로 하여 화합물들을 직접 분무하였다. 1회 처리당 50마리의 파리를 사용했다.Compounds were directly sprayed with acetone and kerosene (using 2 × 0.2 cm 3) as solvents in KEARNS and MARCH chambers. 50 flies were used per treatment.
처음 10분은 매분마다 조사하였고 16분에 측정하였으며 통상의 방법에 의하여 KT50을 결정하였다. 시험결과를 다음의 표에 정리하였다.The first 10 minutes were checked every minute and measured at 16 minutes and KT 50 was determined by conventional methods. The test results are summarized in the following table.
결론 : 화합물 A,B,C는 집파리에 대하여 능력을 가지고 있다.Conclusions: Compounds A, B, and C have the capacity for houseflies.
(3) 화합물 A를 연기발생 코일의 형태로 사용하는 경우의 집파리에 대한 살충활성.(3) Insecticidal activity against housefly when Compound A is used in the form of a smoke generating coil.
연기발생코일의 중성담체를 아세톤 용액에 활성성분과 함께 함침시켰다.The neutral carrier of the smoke generating coil was impregnated with the active ingredient in the acetone solution.
초자로 만든 밀폐된 실린더(용량 13.50㎝)에 20마리의 암컷 집파리(4-5일생)를 넣고 2분동안 한쪽 끝이 타고 있는 연기발생 코일을 도입시켰다. 매분당의 녹 다운 여부검사를 행하여 5분 후 모든 파리가 녹 다운 된 후에 시험을 끝냈다. 각각의 투여량에 대하여 3번씩 시험하였다.Twenty female house flies (4-5 days old) were placed in a sealed cylinder made of choza (13.50 cm) and a smoke-coiled coil with one end burned for 2 minutes was introduced. The test was carried out every 5 minutes, and after 5 minutes all flies were knocked down to complete the test. Three trials were made for each dose.
결론 : 화합물 A를 훈증제(fumigant)로서 사용하였을 때 좋은 살충활성을 나타내었다.Conclusion: Compound A showed good insecticidal activity when used as a fumigant.
(4) 스포도프테라 리로탈리스 유충에 대한 화합물 A,B,C의 살충활성(4) Insecticidal Activities of Compounds A, B, and C on Spodofterra rotalilis Larva
시험할 생성물의 아세톤용액 1μι를 각개 유충의 배면 가슴부에 가하였다. 제4유충단계에 있는 스포도프테라리토탈리스 유충 15마리를 매회 투여시에 사용하였다. 처리 후 각개 유층들을 인공 배양기에 넣고 24시간 동안 효율조사를 하고(처리하지 않은 경우에 대한 %치사율) 48시간 후에 각개 유충당 치사량 50(LD50)의 나노그램양을 결정했다.1 μιη acetone solution of the product to be tested was added to the rear chest of each larva. Fifteen Spodofteraritotalis larvae in the fourth larva stage were used at each administration. After treatment, the individual oil layers were placed in an artificial incubator for 24 hours (% mortality for untreated) and 48 hours later, the amount of nanograms of LD 50 per individual larvae was determined.
시험결과를 다음의 표에 정리하였다.The test results are summarized in the following table.
결론 : 화합물 A,B,C는 스포도프테라리토탈리스 유충에 대하여 강력한 살충효과를 가지고 있다.CONCLUSIONS: Compounds A, B, and C have potent insecticidal effects against Spodopteraritotalis larvae.
(5) 에피라크나 바리베스트리스 유충에 대한 살충활성 스포도프 테라에 대해서 앞서 시험한 방법으로 국소처리 하였다. 버금끝마디 유충단계에 있는 유충을 사용하였으며 처리 휴유충을 통으로 먹었다. 처리한지 72시간 후에 치사여부를 조사하였으며(5) Insecticidal activity against epiraces and baribestris larvae The topical treatment was done topically by the method previously tested. The larvae at the end of the larva stage were used and the treated larvae were eaten through the barrel. 72 hours after treatment, the mortality was checked.
시험결과를 다음표에 정리하여 나타내었다.The test results are summarized in the following table.
결론 : 화합물 A,B,C는 에피라크나 바리베스트리스 유충에 대하여 강력한 살충작용이 있으며 특히 화합물 A가 더욱 효과적이다.CONCLUSIONS: Compounds A, B, and C have potent insecticidal effects against epirak and baribestris larvae, especially compound A.
(6) 화합물 A의 에데스 에짚티에 대한 살충활성(6) Insecticidal Activity of Compound A on Eddes ettyti
370ml용량의 입이 넓은 병속에 200ml의 물을 넣었다. 각개의 용기에 들어있는 물을 시험할 화합물을 함유하고 있는 1ml의 아세톤 용액으로 처리하고 각각 10마리씩의 에데스에짚티 유충(최종유충단계)을 감염시켰다. 유층을 49ml의 물로 옮겼다. 감염시킨 지 24-48시간 후에 효쪽을 조사하였는데 시험도중 각각의 용기들은 항온기에서 25℃로 유지되었다.200 ml of water was placed in a wide bottle of 370 ml. The water contained in each container was treated with 1 ml of acetone solution containing the compound to be tested and each 10 edes etymtee larvae (final larval stage) were infected. The oil layer was transferred to 49 ml of water. Efficacy was examined 24-48 hours after infection, and each vessel was kept at 25 ° C in a thermostat during the test.
시험결과를 요약하면 다음과 같다.The test results are summarized as follows.
결론 : 화합물 A는 에데스 에짚티에 대하여 강력한 살충작용이 있다.CONCLUSIONS: Compound A has a potent insecticidal action against Edes etunty.
(7) 화합물 A의 블타텔라제트 마니카에 대한 살충활성(7) Insecticidal Activity of Compound A on Blotellazet Manica
이 시험은 국소처리법으로 시행하였다. 길이 기준에 따라서 선택된 수컷 블라델라제트 마니카 성충의 두번째와 세번째 상의 다리 사이로 시험할 화합물이 함유된 2μι의 아세톤 용액을 가하였다. 처리 후 시험 해충을 약광(弱光)하에서 20℃로 유지시키고 먹이를 주었다.This test was performed by topical treatment. A 2 μιη acetone solution containing the compound to be tested was added between the legs of the second and third phases of the male Bladelazette Manica adults selected according to the length criteria. After treatment test pests were kept at 20 ° C. under low light and fed.
투여량은 10-7.5-5-3.75ng/마리이었다.Dosage was 10-7.5-5-3.75 ng / mari.
실시한지 24시간, 48시간 및 6일 후에 조사를 하였으며 매해충당의 LD50을 나노그램으로 표시한 결과를 다음표에 나타내었다.After 24 hours, 48 hours, and 6 days after the irradiation, the results were expressed in nanograms of LD 50 per insect pest in the following table.
결론 : 화합물 A는 블라텔라제트 마니카에 대하여 강력한 살충작용이 있다.CONCLUSIONS: Compound A has a potent insecticidal action against blatelazette manica.
(8) 화합물 A의 디스데르쿠스 파시아루스에 대한 살충활성 각개 해충의 복부 가슴에 시험할 화합물의 아세톤 용액 1μι를 가하였다. 투여량은 3.75-2.5-1.25-1-0.625ng/마리이며 처리 24시간, 48시간 및 5일 후에 효율을 조사하고 그 결과를 다음표에 나타내었다.(8) Insecticidal activity of compound A against disdercus paciarus 1 μιη of acetone solution of the compound to be tested was added to the abdomen chest of each pest. Dosage was 3.75-2.5-1.25-1-0.625 ng / mari and the efficiency was investigated 24 hours, 48 hours and 5 days after treatment and the results are shown in the following table.
결론 : 화합물 A는 디스데르쿠스 파시아루스에 대하여 강력한 살충작용이 있다.Conclusion: Compound A has a potent insecticidal action against Disdercus paciarus.
(9) 화합물 A의 시토필루스그라나리우스와 트리볼리블리움 카스타늄에 대한 살충활성(9) Insecticidal Activities of Compound A on Cytophilus granarius and Tribolybium castanium
감염된 밀에 대하여 직접 분무하여 시험하였다. 1ι용량의 회전증발기(작동중인것)에 들어있는 100g의 밀에 시험할 화합물의 아세톤용액 5ml와 0.1㎤의 용액을 분무하였다. 50마리의 시토필루스 또는 트리볼리움을 인공적으로 감염시켰다. 매투여량 마다 7일 후 % 사망율을 측정하고 100마리에 대한 평균값을 취하여 치사농도를 p.p.m. 단위로 결정하였다.Test was by direct spraying on infected wheat. Into a milliliter of 100 g of a 1 e volume rotary evaporator (operating) was sprayed with 5 ml of acetone solution of the compound to be tested and a solution of 0.1 cm 3. Fifty Cytophilus or Tribolium were artificially infected. Percent mortality was measured after 7 days per dose and the mean value for 100 animals was taken to determine the lethal concentration. Determined in units.
결론 : 화합물 A는 시로필루스 그라나리우스와 트리볼리움 카스타늄에 대하여 좋은 살충활성을 가지고 있다.Conclusion: Compound A has good insecticidal activity against Sirophyllus granarius and Tribolium castanium.
실시예 8 : 화합물 A의 테트라리쿠스 우트리케에 대한 살비활성 :Example 8 Acaricide Activity of Tetralicus Utrique of Compound A:
콩잎 1장당 10마리의 암컷 테트라니쿠스우르티케를 감염시키고 그 둘레에 끈끈이 덫을 침투시켰다. 암컷을 24시간 동안 놓아 둔 다음 제거하고 잎을 잘라서 알을 두개의 그룹으로 감염시켰다.Ten female tetranicus urtices were infected per bean leaf and a sticky trap was infiltrated around them. The females were allowed to stand for 24 hours, then removed and their leaves cut to infect the eggs in two groups.
(가) 첫번째 그룹은 시험할 화합물로 처리하였다.(A) The first group was treated with the compound to be tested.
1헥타아르당 50g 및 25g의 농도를 사용하여 시험할 화합물의 수용액 0.5㎝을 매 잎사귀에 분무하였다.Each leaf was sprayed with 0.5 cm of an aqueous solution of the compound to be tested using concentrations of 50 g and 25 g per hectare.
(나) 두번째 그룹은 화합물로 처리하지 않은 것으로서 비교를 위한 것이다. 처리를 시작한지 9일 후에 살아있는 성충, 알, 유층의 수를 측정하였으며 각각의 % 사망율을 다음표에 정리하였다.(처리하지 않은 것과의 비교에 의한 것임).(B) The second group is not treated with compounds and is for comparison. Nine days after the start of treatment, the number of living adults, eggs, and stratums was measured and the percentage mortality of each is summarized in the following table (by comparison with untreated).
결론 : 화합물 A는 테트라니쿠스우트티케에 대해 괄목할 만한 살충 능력을 가지고 있다.CONCLUSIONS: Compound A has remarkable pesticidal ability against tetranikusuttice.
실시예 9 : 살충제의 조성 : 유화 가능한 농축물을 완전히 혼합하여 제조하였다.Example 9 Composition of Insecticide: An emulsifiable concentrate was prepared by thoroughly mixing.
-(S)α-시아노 3-페녹시벤질 1R, 트랜스 2,2-디메틸 3-(2',2'-디클로로 1',2'-디브로모에틸)시클로프로판-1-카르복실레이트……………………0.015g-(S) α-cyano 3-phenoxybenzyl 1R, trans 2,2-dimethyl 3- (2 ', 2'-dichloro 1', 2'-dibromoethyl) cyclopropane-1-carboxylate … … … … … … … … 0.015 g
-피페로닐 부톡사이드……………………………………………………0.5gPiperonyl butoxide; … … … … … … … … … … … … … … … … … … … 0.5g
-토파놀 A…………………………………………………………………0.1gTopanol A... … … … … … … … … … … … … … … … … … … … … … … … … 0.1g
-크실렌……………………………………………………………………99.385g-xylene… … … … … … … … … … … … … … … … … … … … … … … … … … 99.385 g
실시예 10 : 살충제의조성 : 유화가능한 농축물을 다음과 같이 제조하였다.Example 10 Composition of Insecticide: An emulsifiable concentrate was prepared as follows.
-(S)α-시아노 3α패녹시벤질 1R, 트랜스 2,2-디메틸 3-(2',2'-디클로로 1',2'-디브로모에틸)시클로프로판-1--(S) α-cyano 3α phenoxybenzyl 1R, trans 2,2-dimethyl 3- (2 ', 2'-dichloro 1', 2'-dibromoethyl) cyclopropane-1-
카르복실레이트……………………………………………………………1.5gCarboxylate… … … … … … … … … … … … … … … … … … … … … … … 1.5 g
-트윈 80……………………………………………………………………20gTwin 80 … … … … … … … … … … … … … … … … … … … … … … … … … 20 g
-토파놀 A……………………………………………………………………0.1gTopanol A... … … … … … … … … … … … … … … … … … … … … … … … … … 0.1g
-크실렌………………………………………………………………………78.4g-xylene… … … … … … … … … … … … … … … … … … … … … … … … … … … 78.4 g
실시예 11 : 살비제의 조성Example 11 Composition of Acaricide
유화 가능한 농축물은 다음 화합물을 함유한다.Emulsifiable concentrates contain the following compounds.
(S)α-시아노 3-페녹시벤질 1R, 트랜스 2,2-디메틸 3-(2',2'-디클로로 1',2'-디브로모에틸 시클로프로판-1-카르복실레이트 20%(무게%), 나트록스 4851(술포네이트와 결합된 에틸렌옥사이드 트리글리세라이드로서 산가 1.5)6.5%, 아트록스 4855(술포네이트와 결합된 에틸렌 옥사이드트리글리세라이드로서 산가 : 3)3.3%와 크실렌 70.2%(S) α-cyano 3-phenoxybenzyl 1R, trans 2,2-dimethyl 3- (2 ', 2'-dichloro 1', 2'-dibromoethyl cyclopropane-1-carboxylate 20% (Weight%), natrox 4851 (acid value 1.5 as ethylene oxide triglyceride combined with sulfonate) 6.5%, atrox 4855 (ethylene value as ethylene oxide triglyceride combined with sulfonate: 3) 3.3% and xylene 70.2%
실시예 12 : 살선충제의 조성Example 12 Composition of Nematicides
유화 가능한 농축물은 다음 화합물들을 함유한다.Emulsifiable concentrates contain the following compounds.
(S)α-시아노 3-페녹시벤질 1R, 트랜스 2,2-디메틸 3-(2',2'-디클로로 1',2'-디브로모에틸)시클로프로판-1-카르복실레이트 45%(무게%). 아트록스 4851 6.4%, 아트록스 4855 3.2%, 크실렌 45.4%.(S) α-cyano 3-phenoxybenzyl 1R, trans 2,2-dimethyl 3- (2 ', 2'-dichloro 1', 2'-dibromoethyl) cyclopropane-1-carboxylate 45 %(weight%). Atrox 4851 6.4%, Atrox 4855 3.2%, Xylene 45.4%.
실시예 13 : 살옥소드제의 조성Example 13 Composition of Axoxide Agent
이 용액은 다음과 같은 조성을 갖는다.This solution has the following composition.
(S)α-시아노 3-페녹시벤질 1R, 트랜스 2,2-디메틸 3-(2',2'-디클로로 1',2'-디브로모에틸)시클로프로판-1-(S) α-cyano 3-phenoxybenzyl 1R, trans 2,2-dimethyl 3- (2 ', 2'-dichloro 1', 2'-dibromoethyl) cyclopropane-1-
카르복실레이트…………………………………0.5gCarboxylate… … … … … … … … … … … … … 0.5g
플리소트베이트 80………………………………10gPlissobate 80... … … … … … … … … … … … 10 g
트리톤 100…………………………………………25gTriton 100... … … … … … … … … … … … … … … … 25 g
토코페롤 아세레이트………………………………1gTocopherol acerate… … … … … … … … … … … … 1 g
에탄올, q.s…………………………………………100mlEthanol, q.s... … … … … … … … … … … … … … … … 100 ml
이 용액을 물로 50배로 희석하여 외부에 사용된다.The solution is diluted 50 times with water and used externally.
실시예 15 : 살옥소드제의 조성Example 15 Composition of Axoxide
주입 가능한 용액은 다음과 같은 조성을 갖는다.Injectable solutions have the following composition:
-(S)α-시아노 3-페녹시벤질 1R, 트랜스 2,2-디메틸 3-(2',2'-디클로로 1',2'-디브로모에틸) 시클로프로판-1-(S) α-cyano 3-phenoxybenzyl 1R, trans 2,2-dimethyl 3- (2 ', 2'-dichloro 1', 2'-dibromoethyl) cyclopropane-1
-카르복실레이트……………………………………………………2g-Carboxylate... … … … … … … … … … … … … … … … … … … … 2 g
-피페로닐 부톡사이드…………………………………………6.65gPiperonyl butoxide; … … … … … … … … … … … … … … … 6.65 g
-토코페롤 아세테이트…………………………………………0.33gTocopherol acetate. … … … … … … … … … … … … … … … 0.33 g
-유성부형제(油性賦形劑)*, q.s………………………………100㎤Oily excipient * , qs... … … … … … … … … … … … 100 cm3
*이 유성부형제는 29g의 벤질벤조에이트와 충분한 양의 땅콩기름으로 만들며 전체부피는 100㎤이다. * This oily excipient is made up of 29g of benzylbenzoate and enough peanut oil and total volume is 100cm3.
실시 15 : 예동물사료용 조성물Embodiment 15: Composition for Animal Feed
기본사료로서 옥수수, 탈수시킨 자주 개자리, 밀짚, 당밀로 가당된 양배추-야자케이크, 요소, 비타민화된 광물성 보조제를 사용했다. 이 사료는 적어도 11%이상의 조 단백질제(이것의 2.5%는 요소로부터 취한것임) : 지방질 2.5% 및 15%정도의 셀룰로오즈제, 6%의 광물제 및 14%의 수분을 함유한다.As basic feed, corn, dehydrated alfalfa, straw, molasses cabbage- palm cake, urea, and vitaminized mineral supplements were used. This feed contains at least 11% crude protein (2.5% of which is taken from urea): 2.5% fat and 15% cellulose, 6% mineral and 14% water.
사용된 사료는 100kg당 82 사료단위로서 사료 100kg은 910,000I.U.의 비타민 A, 910.000 I.U. D3, 의 비타민 156mg의 비타민 E와 150mg의 비타민 C를 함유한다. 이 사료에 0.04kg의 (S)α-시아노 3-페녹시 벤질 1R, 트랜스 2,2-디메틸 3-(2',2'-디클로로 1',2'-디브로모에틸) 시클로프로판-1-카르복실레이트를 넣는다.The feed used was 82 feed units per 100 kg, with 100 kg of feed containing 910,000 IU of vitamin A, 910.000 IU D 3 , 156 mg of vitamin E and 150 mg of vitamin C. 0.04 kg (S) α-cyano 3-phenoxy benzyl 1R, trans 2,2-dimethyl 3- (2 ', 2'-dichloro 1', 2'-dibromoethyl) cyclopropane- Add 1-carboxylate.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019790000617A KR830001087B1 (en) | 1979-02-28 | 1979-02-28 | Process for preparing cyclopropane carboxylic acid ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019790000617A KR830001087B1 (en) | 1979-02-28 | 1979-02-28 | Process for preparing cyclopropane carboxylic acid ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR830000675A KR830000675A (en) | 1983-04-18 |
| KR830001087B1 true KR830001087B1 (en) | 1983-06-02 |
Family
ID=19210933
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1019790000617A KR830001087B1 (en) | 1979-02-28 | 1979-02-28 | Process for preparing cyclopropane carboxylic acid ester |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR830001087B1 (en) |
-
1979
- 1979-02-28 KR KR1019790000617A patent/KR830001087B1/en active
Also Published As
| Publication number | Publication date |
|---|---|
| KR830000675A (en) | 1983-04-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE2365555C2 (en) | ||
| CA1242733A (en) | Cyclopropane carboxylic acid esters containing a polyhalogenic substituent, preparation process insecticide composition containing same | |
| US3981903A (en) | Cyclopropane carboxylic acid esters | |
| DK164740B (en) | ESTERS OF CYCLOPROPANCARBOXYLIC ACIDS CONDUCTED WITH PYRETHRIC ACID, AND THEIR PREPARATION AND PREPARATIONS CONTAINING THEREOF TO CONTROL PARASITES | |
| CS203967B2 (en) | Insecticide means | |
| US4310542A (en) | Novel cyclopropane carboxylic acid esters | |
| JPS64363B2 (en) | ||
| JPH02233644A (en) | New 2,2-dimethyl-3-(2- monohaloethenyl)cyclopropanecarboxylic acid derivative,preparation thereof,and use thereof as insecticide | |
| JPH0692356B2 (en) | Ester of cyclopropanecarboxylic acid having cyano group, its production method and its use as insecticide and acaricide | |
| US3835220A (en) | Insecticidal composition comprising vinylcyclopropanecarboxylates | |
| JPH02225442A (en) | New florinated derivative of 3-ethenyl-2,2- dimethylcyclopropanecarboxylic acid, preparation thereof, use thereof as insecticide, and composition containing same | |
| CA1222250A (en) | Cyclopropane carboxylic acid derivatives, their preparation and their use in pest control | |
| DD143849A6 (en) | INSECTICIDES, ACARICIDES AND NEMATICIDES | |
| DE3781092T2 (en) | AETHYLENIC OXIME DERIVATIVES OF CYCLOPROPANCARBONIC ACID ESTERS, METHODS AND INTERMEDIATE PRODUCTS FOR THE PRODUCTION THEREOF AND THEIR USE FOR CONTROLLING PARASITES. | |
| KR830001087B1 (en) | Process for preparing cyclopropane carboxylic acid ester | |
| JPH0465823B2 (en) | ||
| US3758504A (en) | Vinylcyclopropanecarboxylates | |
| EP0335801A2 (en) | Process for the preparation of trifluoromethylvinyl derivatives from the corresponding halovinyl derivatives | |
| JPH07149693A (en) | New ester derived from 2,2-dimethyl-3-(3,3,3- trifluoro-1-propenyl)cyclopropanecarboxylic acid, its production and its use as insect extermination agent | |
| CZ278747B6 (en) | Insecticidal, acaricidal and nematocidal agent and process for preparing an active component thereof | |
| HU184693B (en) | Process for preparing new alpha-cyano-3-phenoxy-benzyl-esters and insecticide, nematocide and acaricide compositions containing such compounds as active substances | |
| JPH0456818B2 (en) | ||
| CA1203246A (en) | Cyclopropane carboxylic acid and (5) cyano (4-fluoro-3-phenoxyphenyl) methylic alcohol ester, preparation process, and use as pesticid and compositions containing them | |
| KR820000008B1 (en) | Process for preparing esters of phthal imido methyl cyclopropane carboxylic acid | |
| JPS6075445A (en) | Novel derivative 2,2-dimethyl-3-(2-fluoro- 3-oxo-3-(1,1-dimethylethoxy)-1-propenyl) cyclopropanecarboxylic acid |