JP2935127B2 - Cyclohexane derivative or its salt, its production method, its use and its use - Google Patents
Cyclohexane derivative or its salt, its production method, its use and its useInfo
- Publication number
- JP2935127B2 JP2935127B2 JP11253590A JP11253590A JP2935127B2 JP 2935127 B2 JP2935127 B2 JP 2935127B2 JP 11253590 A JP11253590 A JP 11253590A JP 11253590 A JP11253590 A JP 11253590A JP 2935127 B2 JP2935127 B2 JP 2935127B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- carbon atoms
- alkyl group
- atom
- hydrogen atom
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 150000003839 salts Chemical class 0.000 title claims description 42
- 238000004519 manufacturing process Methods 0.000 title description 43
- 125000000113 cyclohexyl group Chemical class [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 title 1
- 125000004432 carbon atom Chemical group C* 0.000 claims description 216
- 125000000217 alkyl group Chemical group 0.000 claims description 97
- 150000001934 cyclohexanes Chemical class 0.000 claims description 58
- 150000001875 compounds Chemical class 0.000 claims description 57
- 125000005843 halogen group Chemical group 0.000 claims description 53
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 48
- -1 phenylcarbonyloxy group Chemical group 0.000 claims description 47
- 125000003545 alkoxy group Chemical group 0.000 claims description 31
- 229910052799 carbon Inorganic materials 0.000 claims description 27
- 125000001424 substituent group Chemical group 0.000 claims description 27
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 23
- 239000004480 active ingredient Substances 0.000 claims description 22
- 239000002917 insecticide Substances 0.000 claims description 22
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 20
- 241000607479 Yersinia pestis Species 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 125000004414 alkyl thio group Chemical group 0.000 claims description 17
- 241000258937 Hemiptera Species 0.000 claims description 14
- 125000001188 haloalkyl group Chemical group 0.000 claims description 14
- 125000003342 alkenyl group Chemical group 0.000 claims description 13
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- 125000004644 alkyl sulfinyl group Chemical group 0.000 claims description 11
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 9
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 8
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 7
- 230000000749 insecticidal effect Effects 0.000 claims description 7
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 7
- 125000005196 alkyl carbonyloxy group Chemical group 0.000 claims description 6
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 6
- 125000005359 phenoxyalkyl group Chemical group 0.000 claims description 6
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 6
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 5
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- 125000005108 alkenylthio group Chemical group 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 241000238631 Hexapoda Species 0.000 claims description 3
- 125000006350 alkyl thio alkyl group Chemical group 0.000 claims description 3
- 125000004438 haloalkoxy group Chemical group 0.000 claims description 3
- 125000004440 haloalkylsulfinyl group Chemical group 0.000 claims description 3
- 125000004441 haloalkylsulfonyl group Chemical group 0.000 claims description 3
- 125000004995 haloalkylthio group Chemical group 0.000 claims description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 238000006462 rearrangement reaction Methods 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims 20
- 125000004429 atom Chemical group 0.000 claims 2
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims 2
- 125000005201 cycloalkylcarbonyloxy group Chemical group 0.000 claims 2
- 239000004615 ingredient Substances 0.000 claims 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 102
- 238000006243 chemical reaction Methods 0.000 description 97
- 235000019439 ethyl acetate Nutrition 0.000 description 34
- 239000000047 product Substances 0.000 description 32
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 27
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 24
- 239000012442 inert solvent Substances 0.000 description 24
- 239000000243 solution Substances 0.000 description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- 238000010898 silica gel chromatography Methods 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 230000000704 physical effect Effects 0.000 description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- 239000000284 extract Substances 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000007810 chemical reaction solvent Substances 0.000 description 12
- 239000002904 solvent Substances 0.000 description 10
- 239000013076 target substance Substances 0.000 description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 240000007594 Oryza sativa Species 0.000 description 8
- 241001674048 Phthiraptera Species 0.000 description 8
- 150000007530 organic bases Chemical class 0.000 description 8
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 7
- 235000007164 Oryza sativa Nutrition 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000002585 base Substances 0.000 description 7
- 235000013312 flour Nutrition 0.000 description 7
- 150000007529 inorganic bases Chemical class 0.000 description 7
- 235000009566 rice Nutrition 0.000 description 7
- MWFMGBPGAXYFAR-UHFFFAOYSA-N 2-hydroxy-2-methylpropanenitrile Chemical compound CC(C)(O)C#N MWFMGBPGAXYFAR-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 5
- 235000013399 edible fruits Nutrition 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 235000013311 vegetables Nutrition 0.000 description 5
- 241001466042 Fulgoromorpha Species 0.000 description 4
- 241001556089 Nilaparvata lugens Species 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- 150000008065 acid anhydrides Chemical class 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 230000002140 halogenating effect Effects 0.000 description 4
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 238000000638 solvent extraction Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- FXYSLMWUJOJBBA-UHFFFAOYSA-N 3-hydroxycyclohex-2-en-1-one Chemical compound OC1=CC(=O)CCC1 FXYSLMWUJOJBBA-UHFFFAOYSA-N 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000002671 adjuvant Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohex-2-enone Chemical compound O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 150000002825 nitriles Chemical class 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 241000207199 Citrus Species 0.000 description 2
- 241000586568 Diaspidiotus perniciosus Species 0.000 description 2
- 244000068988 Glycine max Species 0.000 description 2
- 235000010469 Glycine max Nutrition 0.000 description 2
- 244000299507 Gossypium hirsutum Species 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229920001732 Lignosulfonate Polymers 0.000 description 2
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 244000070406 Malus silvestris Species 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 241000526145 Psylla Species 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 240000003768 Solanum lycopersicum Species 0.000 description 2
- 241000018135 Trialeurodes Species 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- XTKDAFGWCDAMPY-UHFFFAOYSA-N azaperone Chemical compound C1=CC(F)=CC=C1C(=O)CCCN1CCN(C=2N=CC=CC=2)CC1 XTKDAFGWCDAMPY-UHFFFAOYSA-N 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 235000020971 citrus fruits Nutrition 0.000 description 2
- 150000004292 cyclic ethers Chemical class 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- YMGUBTXCNDTFJI-UHFFFAOYSA-N cyclopropanecarboxylic acid Chemical compound OC(=O)C1CC1 YMGUBTXCNDTFJI-UHFFFAOYSA-N 0.000 description 2
- 239000012351 deprotecting agent Substances 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000002552 dosage form Substances 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011403 purification operation Methods 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 235000012222 talc Nutrition 0.000 description 2
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 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
- 239000011345 viscous material Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- BTUGGGLMQBJCBN-UHFFFAOYSA-N 1-iodo-2-methylpropane Chemical compound CC(C)CI BTUGGGLMQBJCBN-UHFFFAOYSA-N 0.000 description 1
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- YNJSNEKCXVFDKW-UHFFFAOYSA-N 3-(5-amino-1h-indol-3-yl)-2-azaniumylpropanoate Chemical compound C1=C(N)C=C2C(CC(N)C(O)=O)=CNC2=C1 YNJSNEKCXVFDKW-UHFFFAOYSA-N 0.000 description 1
- TVZRAEYQIKYCPH-UHFFFAOYSA-N 3-(trimethylsilyl)propane-1-sulfonic acid Chemical compound C[Si](C)(C)CCCS(O)(=O)=O TVZRAEYQIKYCPH-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 description 1
- 244000215068 Acacia senegal Species 0.000 description 1
- 241000292372 Aleurocanthus spiniferus Species 0.000 description 1
- 241001132873 Aleyrodes lonicerae Species 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000368260 Aonidia Species 0.000 description 1
- 241001414828 Aonidiella aurantii Species 0.000 description 1
- 241000254123 Bemisia Species 0.000 description 1
- 241000254127 Bemisia tabaci Species 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- RJAVNXCUGWTHCR-UHFFFAOYSA-N CCC(=O)C1=C(O)CC(CC1=O)c1c(C)nn(C)c1SC Chemical compound CCC(=O)C1=C(O)CC(CC1=O)c1c(C)nn(C)c1SC RJAVNXCUGWTHCR-UHFFFAOYSA-N 0.000 description 1
- QQXJEHOOZZEHHX-UHFFFAOYSA-N CCCCCCCCn1nc(C)c(C2CC(O)=C(C(=O)C3CC3)C(=O)C2)c1S(C)=O Chemical compound CCCCCCCCn1nc(C)c(C2CC(O)=C(C(=O)C3CC3)C(=O)C2)c1S(C)=O QQXJEHOOZZEHHX-UHFFFAOYSA-N 0.000 description 1
- PMPONQMYNMSBOI-UHFFFAOYSA-N CCn1nc(C)c(C2CC(O)=C(C(=O)C3CC3)C(=O)C2)c1SC Chemical compound CCn1nc(C)c(C2CC(O)=C(C(=O)C3CC3)C(=O)C2)c1SC PMPONQMYNMSBOI-UHFFFAOYSA-N 0.000 description 1
- SEUOLIGXAKQCRD-UHFFFAOYSA-N CCn1nc(Cl)c(C2CC(O)=C(C(=O)C3CC3)C(=O)C2)c1SC Chemical compound CCn1nc(Cl)c(C2CC(O)=C(C(=O)C3CC3)C(=O)C2)c1SC SEUOLIGXAKQCRD-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- UBHCJPMTTNFZPV-UHFFFAOYSA-N Cc1nn(C=C)c(C)c1C1CC(O)=C(C(=O)C2CC2)C(=O)C1 Chemical compound Cc1nn(C=C)c(C)c1C1CC(O)=C(C(=O)C2CC2)C(=O)C1 UBHCJPMTTNFZPV-UHFFFAOYSA-N 0.000 description 1
- 241000813632 Ceroplastes pseudoceriferus Species 0.000 description 1
- 241000675108 Citrus tangerina Species 0.000 description 1
- 240000008067 Cucumis sativus Species 0.000 description 1
- 235000009849 Cucumis sativus Nutrition 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 241001205778 Dialeurodes citri Species 0.000 description 1
- 241000526125 Diaphorina citri Species 0.000 description 1
- QWDBCIAVABMJPP-UHFFFAOYSA-N Diisopropyl phthalate Chemical compound CC(C)OC(=O)C1=CC=CC=C1C(=O)OC(C)C QWDBCIAVABMJPP-UHFFFAOYSA-N 0.000 description 1
- IYXGSMUGOJNHAZ-UHFFFAOYSA-N Ethyl malonate Chemical compound CCOC(=O)CC(=O)OCC IYXGSMUGOJNHAZ-UHFFFAOYSA-N 0.000 description 1
- 241001281764 Furcifer Species 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 241000578422 Graphosoma lineatum Species 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 240000007049 Juglans regia Species 0.000 description 1
- 235000009496 Juglans regia Nutrition 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 241001470017 Laodelphax striatella Species 0.000 description 1
- 241000131091 Lucanus cervus Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 240000000249 Morus alba Species 0.000 description 1
- 235000008708 Morus alba Nutrition 0.000 description 1
- 241000699670 Mus sp. Species 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 description 1
- 244000061176 Nicotiana tabacum Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 239000012425 OXONE® Substances 0.000 description 1
- 241000902235 Oides Species 0.000 description 1
- 241000237502 Ostreidae Species 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 229920001213 Polysorbate 20 Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 241000220324 Pyrus Species 0.000 description 1
- 244000088401 Pyrus pyrifolia Species 0.000 description 1
- 235000001630 Pyrus pyrifolia var culta Nutrition 0.000 description 1
- 241000208422 Rhododendron Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 241000176085 Sogatella Species 0.000 description 1
- 244000061458 Solanum melongena Species 0.000 description 1
- 235000002597 Solanum melongena Nutrition 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 241000337870 Stephanitis pyri Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 241000018137 Trialeurodes vaporariorum Species 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 241000219094 Vitaceae Species 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- JJLCLURDDMPLME-UHFFFAOYSA-N [5-(1,3-dimethylpyrazol-4-yl)-3-oxocyclohexen-1-yl] propanoate Chemical compound C1C(OC(=O)CC)=CC(=O)CC1C1=CN(C)N=C1C JJLCLURDDMPLME-UHFFFAOYSA-N 0.000 description 1
- GENRYDDYRWSWKB-UHFFFAOYSA-N [5-(2,5-dimethylpyrazol-3-yl)-3-oxocyclohexen-1-yl] propanoate Chemical compound C1C(OC(=O)CC)=CC(=O)CC1C1=CC(C)=NN1C GENRYDDYRWSWKB-UHFFFAOYSA-N 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 150000001266 acyl halides Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 125000004849 alkoxymethyl group Chemical group 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 235000021016 apples Nutrition 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000002361 compost Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000006254 cycloalkyl carbonyl group Chemical group 0.000 description 1
- YZTQMWLHGYAGPI-UHFFFAOYSA-N cyclohex-2-en-1-one;hydrochloride Chemical compound Cl.O=C1CCCC=C1 YZTQMWLHGYAGPI-UHFFFAOYSA-N 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 235000021021 grapes Nutrition 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000011081 inoculation Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- FMKOJHQHASLBPH-UHFFFAOYSA-N isopropyl iodide Chemical compound CC(C)I FMKOJHQHASLBPH-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 235000021332 kidney beans Nutrition 0.000 description 1
- LULAYUGMBFYYEX-UHFFFAOYSA-N metachloroperbenzoic acid Natural products OC(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 1
- PVWOIHVRPOBWPI-UHFFFAOYSA-N n-propyl iodide Chemical compound CCCI PVWOIHVRPOBWPI-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 235000020636 oyster Nutrition 0.000 description 1
- 235000021017 pears Nutrition 0.000 description 1
- 230000000361 pesticidal effect Effects 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- MQHNKCZKNAJROC-UHFFFAOYSA-N phthalic acid dipropyl ester Natural products CCCOC(=O)C1=CC=CC=C1C(=O)OCCC MQHNKCZKNAJROC-UHFFFAOYSA-N 0.000 description 1
- 239000010665 pine oil Substances 0.000 description 1
- 239000000419 plant extract Substances 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 239000000244 polyoxyethylene sorbitan monooleate Substances 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- OKBMCNHOEMXPTM-UHFFFAOYSA-M potassium peroxymonosulfate Chemical compound [K+].OOS([O-])(=O)=O OKBMCNHOEMXPTM-UHFFFAOYSA-M 0.000 description 1
- HDMGAZBPFLDBCX-UHFFFAOYSA-N potassium;sulfooxy hydrogen sulfate Chemical compound [K+].OS(=O)(=O)OOS(O)(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229910052903 pyrophyllite Inorganic materials 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical class [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
【発明の詳細な説明】 本発明は一般式（IA） ［式中、R1′は水素原子、エチル基、ｎ−プロピル
基、ｎ−ブチル基、ｉ−ブチル基又はｓ−ブチル基を示
し、R2′は水素原子、ハロゲン原子 又は炭素原子数１〜５のアルキル基を示し、R3′はハ
ロゲン原子、炭素原子数１〜５のアルキル基、炭素原子
数１〜５のアルコキシ基、炭素原子数１〜５のアルキル
チオ基、炭素原子数１〜５のアルキルスルフィニル基、
炭素原子数１〜５のアルキルスルホニル基又は−Ｎ
（R7′）R8′（式中、R7′及びR8′は同一若しくは異な
っても良く、水素原子又は炭素原子数１〜３のアルキル
基を示し、R7′及びR8′は４〜６のメチレン基で結合さ
れても良い。）を示し、R4′は水素原子、炭素原子数１
〜５のアルキル基又は炭素原子数２〜５のアルコキシカ
ルボニル基を示し、R5′は水酸基、フェニルカルボニル
オキシ基又は同一若しくは異なっても良く、ハロゲン原
子、炭素原子数１〜３のアルキル基若しくは炭素原子数
１〜３のアルコキシ基から選択される１〜５個の置換基
をフェニル環上に有するフェニルカルボニルオキシ基を
示し、R6′は炭素原子数１〜５のアルキル基、炭素原子
数３〜６のシクロアルキル基又は炭素原子数１〜３のア
ルキル基により置換されたシクロアルキル基を示す。） 但し、R1′がエチル基を、R2′がメチル基を、R3′が
ハロゲン原子又はメチルチオ基を、R4′が水素原子を及
びR5′が水酸基を同時に示す場合、R6′はエチル基又は
ｎ−プロピル基を除く。］ で表されるシクロへキサン誘導体又はその塩類、及び一
般式（IB） ［式中、R1は水素原子、炭素原子数１〜16のアルキル
基、炭素原子数１〜５のハロアルキル基、炭素原子数２
〜５のアルケニル基、炭素原子数２〜５のアルコキシア
ルキル基、フェニル基、同一若しくは異なっても良く、
ハロゲン原子、炭素原子数１〜３のアルキル基若しくは
炭素原子数１〜３のアルコキシ基から選択される１〜５
個の置換基を有するフェニル基、ベンジル基又は同一若
しくは異なっても良く、ハロゲン原子、炭素原子数１〜
３のアルキル基若しくは炭素原子数１〜３のアルコキシ
基から選択される１〜５個の置換基を有するベンジル基
を示し、R2は水素原子、ハロゲン原子、炭素原子数１〜
５のアルキル基、炭素原子数１〜５のハロアルキル基、
フェニル基又は同一若しくは異なっても良く、ハロゲン
原子、炭素原子数１〜３のアルキル基若しくは炭素慮原
子数１〜３のアルコキシ基から選択される１〜５個の置
換基を有するフェニル基を示し、R3は水素原子、ハロゲ
ン原子、炭素原子数１〜５のアルキル基、炭素原子数１
〜５のハロアルキル基、炭素原子数１〜５のアルコキシ
基、炭素原子数１〜５のハロアルコキシ基、炭素原子数
１〜５のアルキルチオ基、炭素原子数１〜５のハロアル
キルチオ基、炭素原子数１〜５のアルキルスルフィニル
基、炭素原子数１〜５のハロアルキルスルフィニル基、
炭素原子数１〜５のアルキルスルホニル基、炭素原子数
１〜５のハロアルキルスルホニル基、フェノキシ基、同
一若しくは異なっても良く、ハロゲン原子、炭素原子数
１〜３のアルキル基若しくは炭素原子数１〜３のアルコ
キシ基から選択される１〜５個の置換基を有するフェノ
キシ基、フェニルチオ基、同一若しくは異なっても良
く、ハロゲン原子、炭素原子数１〜３のアルキル基若し
くは炭素原子数１〜３のアルコキシ基から選択される１
〜５個の置換基を有するフェニルチオ基、−Ｎ（R7）R8
（式中、R7及びR8は同一若しくは異なっても良く、水素
原子又は炭素原子数１〜３のアルキル基を示し、R7及び
R8は４〜６のメチレン基で結合されても良い。）又は炭
素原子数２〜５のアルキルカルボニルオキシ基を示し、
R2及びR3は一緒になって炭素原子数２〜５のメチレン基
を示すこともできる。R4は水素原子、炭素原子数１〜５
のアルキル基又は炭素原子数２〜５のアルコキシカルボ
ニル基を示し、R5水酸基、ハロゲン原子、炭素原子数１
〜５のアルキルチオ基、炭素原子数１〜５のアルケニル
チオ基、−Ｎ（R9）R10（式中、R9及びR10は同一若しく
は異なっても良く、水素原子、炭素原子数１〜３のアル
キル基又は炭素原子数１〜３のアルケニル基を示
す。）、炭素原子数２〜８のアルキルカルボニルオキシ
基、シクロアルキルの炭素原子数が３〜６シクロアルキ
ルカルボニルオキシ基、フェニルカルボニルオキシ基又
は同一若しくは異なっても良く、ハロゲン原子、炭素原
子数１〜３のアルキル基若しくは炭素原子数１〜３のア
ルコキシ基から選択される１〜５個の置換基をフェニル
環上に有するフェニルカルボニルオキシ基を示し、R6は
炭素原子数１〜18のアルキル基、炭素原子数３〜６のシ
クロアルキル基、同一又は異なっても良く、ハロゲン原
子若しくは炭素原子数１〜３のアルキル基により置換さ
れたシクロアルキル基、炭素原子数２〜17のアルケニル
基、炭素原子数２〜８のアルコキシアルキル基、炭素原
子数２〜８のアルキルチオアルキル基、フェノキシアル
キル基又は同一若しくは異なっても良く、ハロゲン原
子、炭素原子数１〜３のアルキル基若しくは炭素原子数
１〜３のアルキル基から選択される１〜５個の置換基を
フェニル環上に有するフェノキシアルキル基を示す。］
で表されるシクロへキサン誘導体又はその塩類及び該化
合物の製造方法及び該化合物を有効成分として含有する
ことを特徴とする殺虫剤並びに殺虫方法に関するもので
ある。DETAILED DESCRIPTION OF THE INVENTION The present invention provides a compound represented by the general formula (IA) [Wherein R 1 ′ represents a hydrogen atom, an ethyl group, an n-propyl group, an n-butyl group, an i-butyl group or an s-butyl group, and R 2 ′ represents a hydrogen atom, a halogen atom or a carbon atom having 1 carbon atom. And R 3 ′ is a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkylthio group having 1 to 5 carbon atoms, An alkylsulfinyl group of 5,
An alkylsulfonyl group having 1 to 5 carbon atoms or -N
(R 7 ′) R 8 ′ (wherein, R 7 ′ and R 8 ′ may be the same or different and represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R 7 ′ and R 8 ′ R 4 ′ may be a hydrogen atom or a carbon atom having 1 to 4 carbon atoms.
Represents an alkyl group having 5 to 5 carbon atoms or an alkoxycarbonyl group having 2 to 5 carbon atoms, and R 5 ′ may be a hydroxyl group, a phenylcarbonyloxy group or may be the same or different, a halogen atom, an alkyl group having 1 to 3 carbon atoms or A phenylcarbonyloxy group having 1 to 5 substituents selected from an alkoxy group having 1 to 3 carbon atoms on a phenyl ring, wherein R 6 ′ is an alkyl group having 1 to 5 carbon atoms, A cycloalkyl group substituted by a cycloalkyl group having 3 to 6 or an alkyl group having 1 to 3 carbon atoms is shown. ) However, 'the ethyl group, R 2' R 1 a is a methyl group, indicating 'a halogen atom or a methylthio group, R 4' R 3 is Oyobi a hydrogen atom R 5 'is a hydroxyl group simultaneously, R 6 'Excludes an ethyl group or an n-propyl group. ] The cyclohexane derivative represented by these, or its salts, and general formula (IB) [Wherein, R 1 represents a hydrogen atom, an alkyl group having 1 to 16 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms, and 2 carbon atoms.
5 to 5 alkenyl groups, an alkoxyalkyl group having 2 to 5 carbon atoms, a phenyl group, which may be the same or different,
1 to 5 selected from a halogen atom, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms
Phenyl group having two substituents, a benzyl group or the same or different, a halogen atom, a carbon atom number of 1 to
A benzyl group having 1 to 5 substituents selected from an alkyl group of 3 or an alkoxy group of 1 to 3 carbon atoms, wherein R 2 is a hydrogen atom, a halogen atom,
5 alkyl groups, haloalkyl groups having 1 to 5 carbon atoms,
A phenyl group or a phenyl group which may be the same or different and has 1 to 5 substituents selected from a halogen atom, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms. , R 3 are a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, 1 carbon atom
Haloalkyl group having 1 to 5 carbon atoms, alkoxy group having 1 to 5 carbon atoms, haloalkoxy group having 1 to 5 carbon atoms, alkylthio group having 1 to 5 carbon atoms, haloalkylthio group having 1 to 5 carbon atoms, carbon atom An alkylsulfinyl group having 1 to 5 carbon atoms, a haloalkylsulfinyl group having 1 to 5 carbon atoms,
An alkylsulfonyl group having 1 to 5 carbon atoms, a haloalkylsulfonyl group having 1 to 5 carbon atoms, a phenoxy group, which may be the same or different, a halogen atom, an alkyl group having 1 to 3 carbon atoms or 1 to carbon atoms. A phenoxy group having 1 to 5 substituents selected from 3 alkoxy groups, a phenylthio group, which may be the same or different, a halogen atom, an alkyl group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms. 1 selected from an alkoxy group
Phenylthio group having 5 substituents, -N (R 7) R 8
(Wherein, R 7 and R 8 may be the same or different, represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R 7 and
R 8 may be linked by 4 to 6 methylene groups. ) Or an alkylcarbonyloxy group having 2 to 5 carbon atoms,
R 2 and R 3 may together represent a methylene group having 2 to 5 carbon atoms. R 4 is a hydrogen atom, having 1 to 5 carbon atoms
Represents an alkyl group or an alkoxycarbonyl group having 2 to 5 carbon atoms, wherein R 5 is a hydroxyl group, a halogen atom,
5 alkylthio group, alkenylthio group having 1 to 5 carbon atoms, -N (R 9) R 10 ( wherein, R 9 and R 10 may be the same or different, a hydrogen atom, 1 to carbon atoms 3 alkyl group or alkenyl group having 1 to 3 carbon atoms), alkylcarbonyloxy group having 2 to 8 carbon atoms, cycloalkylcarbonyl group having 3 to 6 carbon atoms of cycloalkyl, phenylcarbonyloxy Phenylcarbonyl having 1 to 5 substituents on the phenyl ring which may be the same or different and may be the same or different and are selected from a halogen atom, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms indicates an oxy group, R 6 may alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, the same or different, several halogen atoms or carbon atoms 1 A cycloalkyl group substituted by an alkyl group having 3 carbon atoms, an alkenyl group having 2 to 17 carbon atoms, an alkoxyalkyl group having 2 to 8 carbon atoms, an alkylthioalkyl group having 2 to 8 carbon atoms, a phenoxyalkyl group or the same or It may be different, and represents a phenoxyalkyl group having 1 to 5 substituents selected from a halogen atom, an alkyl group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms on a phenyl ring. ]
And a method for producing the compound, an insecticide containing the compound as an active ingredient, and an insecticide method.
特開昭62−４号、特開平１−25762号、同第１−11067
4号、同１−193250号等に本発明の一般式（IB）で表さ
れるシクロヘキサン誘導体またはその塩類の一部の化合
物が開示されているが、一般式（IA）で表されるシクロ
ヘキサン誘導体又はその塩類は全く開示されておらず、
一般式（IA）及び一般式（IB）で表されるシクロヘキサ
ン誘導体またはその塩類が殺虫作用を有することは全く
開示されておらず、且つ示唆もされていない。JP-A-62-4, JP-A-1-25762, 1-111067
Nos. 4, 1 and 193250 disclose the cyclohexane derivative represented by the general formula (IB) of the present invention or some of its salts, but the cyclohexane derivative represented by the general formula (IA) is disclosed. Or its salts are not disclosed at all,
There is no disclosure or suggestion that the cyclohexane derivatives represented by the general formulas (IA) and (IB) or salts thereof have an insecticidal action.
本発明者等は新規な殺虫剤を創出すべく鋭意研究を重
ねた結果、一般式（IA）で表されるシクロヘキサン誘導
体又はその塩類が文献未記載の新規化合物であり、一般
式（IA）で表されるシクロヘキサン誘導体又はその塩類
を含む一般式（IB）で表されるシクロヘキサン誘導体又
はその塩類が顕著な殺虫作用を有することを見出し、本
発明を完成させたものである。The present inventors have conducted intensive studies to create a novel insecticide, and as a result, a cyclohexane derivative represented by the general formula (IA) or a salt thereof is a novel compound not described in the literature, and a compound represented by the general formula (IA) The present inventors have found that a cyclohexane derivative or a salt thereof represented by the general formula (IB) containing the cyclohexane derivative or a salt thereof has a remarkable insecticidal action, and completed the present invention.
本発明の一般式（IA）で表されるシクロへキサン誘導
体又はその塩類は以下に示す互変異性体を有し、本発明
はこれらの互変異性体をも包含するものである。The cyclohexane derivative represented by the general formula (IA) of the present invention or a salt thereof has the following tautomers, and the present invention also includes these tautomers.
（式中、R1′、R2′、R3′、R4′及びR6′は前記に同
じ。） 一般式（IB）で表されるシクロへキサン誘導体又はそ
の塩類も同様に互変異性体を有する。 (In the formula, R 1 ′, R 2 ′, R 3 ′, R 4 ′ and R 6 ′ are the same as described above.) The cyclohexane derivative represented by the general formula (IB) or a salt thereof is also tautomeric. Has a sexual body.
本発明の一般式（IA）又は（IB）で表されるシクロヘ
キサン誘導体の塩類としては無機塩基又は有機塩基を挙
げることができ、無機塩基としては、例えば塩酸、硫
酸、硝酸等の無機酸類、ナトリウム、カリウム等のアル
カリ金属類、カルシウム、マグネシウム、バリウム等の
アルカリ土類金属類、アルミニウム、スズ、鉄、ニッケ
ル、亜鉛等の金属類等との塩類、有機塩基としては、例
えばジエチルアミン、トリエタノールアミン、トリエチ
ルアミン、ジメチルアミノピリジン、ピロール、モルホ
リン、DBU（1.8−ジアザビシクロ［5.4.0.］−７−ウン
デセン）等の有機塩基類、パラトルエンスルホン酸、ト
リフルオロ酢酸、シュウ酸等の有機酸類との塩類を例示
することができるが、本発明はこれらの塩類に限定され
るものではない。Examples of the salts of the cyclohexane derivative represented by the general formula (IA) or (IB) of the present invention include an inorganic base or an organic base. Examples of the inorganic base include inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid; , Alkali metals such as potassium, alkaline earth metals such as calcium, magnesium and barium, salts with metals such as aluminum, tin, iron, nickel and zinc, and organic bases such as diethylamine and triethanolamine. , Triethylamine, dimethylaminopyridine, pyrrole, morpholine, organic bases such as DBU (1.8-diazabicyclo [5.4.0.]-7-undecene), and organic acids such as paratoluenesulfonic acid, trifluoroacetic acid and oxalic acid. Salts can be exemplified, but the present invention is not limited to these salts.
本発明の一般式（IA）又は（IB）で表されるシクロへ
キサン誘導体又はその塩類の代表的な製造方法として
は，例えば以下に図示する製造方法を例示することがで
きる。As a typical production method of the cyclohexane derivative represented by the general formula (IA) or (IB) of the present invention or a salt thereof, for example, the production method shown below can be exemplified.
尚、一般式（IA）で表されるシクロへキサン誘導体又
はその塩類は一般式（IB）で表されるシクロへキサン誘
導体又はその塩類に包含されるので、代表例として一般
式（IB）で表されるシクロへキサン誘導体又はその塩類
を例示する。Since the cyclohexane derivative represented by the general formula (IA) or a salt thereof is included in the cyclohexane derivative represented by the general formula (IB) or a salt thereof, the cyclohexane derivative represented by the general formula (IB) is a representative example. Examples of the cyclohexane derivative or salts thereof are shown below.
（式中、R1，R2，R3，R4及びR6は前記に同じ。） 即ち、一般式（II）で表される化合物を不活性溶媒及
び触媒の存在下に転位反応を行うことにより一般式（Ｉ
−１）で表されるシクロヘキサン誘導体又はその塩類を
製造することができる。 (In the formula, R 1 , R 2 , R 3 , R 4 and R 6 are the same as described above.) That is, the compound represented by the general formula (II) is subjected to a rearrangement reaction in the presence of an inert solvent and a catalyst. By the general formula (I)
The cyclohexane derivative represented by -1) or a salt thereof can be produced.
本反応で使用することができる不活性溶媒としては、
本反応の進行を著しく阻害しないものであれば良く、例
えばメタノール、エタノール、プロパノール、シクロヘ
キサノール等のアルコール類、ジクロロメタン、クロロ
ホルム、四塩化炭素等の塩素化炭化水素類、ベンゼン、
トルエン、キシレン等の芳香族炭化水素類、酢酸エチル
等のエステル類、アセトニトリル等のニトリル類、ジオ
キサン、テトラヒドロフラン等の環状エーテル類等を例
示することができる。Inert solvents that can be used in this reaction include:
As long as it does not significantly inhibit the progress of this reaction, for example, alcohols such as methanol, ethanol, propanol and cyclohexanol, dichloromethane, chloroform, chlorinated hydrocarbons such as carbon tetrachloride, benzene,
Examples include aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate, nitriles such as acetonitrile, and cyclic ethers such as dioxane and tetrahydrofuran.
本反応で使用できる触媒としては、例えば４−N,N−
ジメチルアミノピリジン、アセトンシアンヒドリン、KC
N、NaCN等の触媒を例示することができる。本反応の触
媒の使用量は、一般式（II）で表される化合物１モルに
対して0.01〜10倍モルの範囲から適宜選択して使用すれ
ば良く、好ましくは0.1〜１モルの範囲から選択すれば
良い。As a catalyst that can be used in this reaction, for example, 4-N, N-
Dimethylaminopyridine, acetone cyanohydrin, KC
Catalysts such as N and NaCN can be exemplified. The amount of the catalyst used in this reaction may be appropriately selected and used from the range of 0.01 to 10 moles per mole of the compound represented by the general formula (II), and preferably from the range of 0.1 to 1 mole. Just choose.
本反応の反応温度は室温乃至使用する不活性溶媒の沸
点域の範囲から適宜選択すれば良いが、好ましくは加熱
下に行うのが良い。反応時間は反応量及び反応温度等に
より一定しないが数分乃至48時間の範囲から選択すれば
良い。反応終了後、常法により、例えば酸でpHを調整
し、目的物を溶媒抽出等の操作により単離し、必要に応
じてカラムクロマトグラフィー法、再結晶法等の精製繰
作を行うことにより一般式（Ｉ−１）で表されるシクロ
へキサン誘導体を製造することができる。The reaction temperature of this reaction may be appropriately selected from the range of room temperature to the boiling point range of the inert solvent to be used, but is preferably carried out under heating. The reaction time is not fixed depending on the reaction amount and the reaction temperature, but may be selected from the range of several minutes to 48 hours. After the completion of the reaction, the pH is generally adjusted by an ordinary method, for example, by using an acid, the target substance is isolated by an operation such as solvent extraction, and, if necessary, a purification procedure such as a column chromatography method or a recrystallization method is performed. The cyclohexane derivative represented by the formula (I-1) can be produced.
（式中、R1，R2，R3，R4及びR6は前記に同じ。） 即ち、一般式（III）で表される化合物と一般式（I
V）で表される酸無水物とを不活性溶媒及び塩基の存在
下に反応させることにより、一般式（Ｉ−１）で表され
るシクロへキサン誘導体又はその塩類を製造することが
できる。 (In the formula, R 1 , R 2 , R 3 , R 4 and R 6 are the same as described above.) That is, the compound represented by the general formula (III) and the compound represented by the general formula (I
The cyclohexane derivative represented by the general formula (I-1) or a salt thereof can be produced by reacting the acid anhydride represented by V) with an inert solvent and a base.
本反応で使用できる不活性溶媒としては、例えば法
に例示の不活性溶媒を使用することができる他に、一般
式（IV）で表される酸無水物も溶媒として使用すること
ができる。As the inert solvent that can be used in this reaction, for example, in addition to the inert solvents exemplified in the method, an acid anhydride represented by the general formula (IV) can also be used as a solvent.
本反応で使用する塩基としては、無機塩基又は有機塩
基を使用することができ、無機塩基としては、例えばナ
トりウム、カリウム、マグネシウム又はカルシウム等の
アルカリ金属又はアルカリ土類金属の水酸化物、炭酸
塩、アルコラート等を上げることができ、有機塩基とし
ては、例えばトリエチルアミン等の第三級アミン、ピリ
ジン、DBU（1,8−ジアザビシクロ［5.4.0］−７−ウン
デセン）等を例示することができる。As the base used in this reaction, an inorganic base or an organic base can be used.Examples of the inorganic base include hydroxides of alkali metals or alkaline earth metals such as sodium, potassium, magnesium and calcium, Examples of the organic base include tertiary amines such as triethylamine, pyridine, and DBU (1,8-diazabicyclo [5.4.0] -7-undecene). it can.
本反応は一般式（III）で表される化合物及び一般式
（IV）で表される酸無水物を等モル使用すれば良いが、
一般式（IV）で表される酸無水物を過剰に使用すること
もできる。In this reaction, the compound represented by the general formula (III) and the acid anhydride represented by the general formula (IV) may be used in equimolar amounts.
The acid anhydride represented by the general formula (IV) can be used in excess.
又塩基の使用量は一般式（III）で表される化合物に
対して等モル乃至過剰モルの範囲から適宜選択して使用
すれば良い。The amount of the base used may be appropriately selected from the range of equimolar to excess molar with respect to the compound represented by formula (III).
反応温度は10℃乃至使用する不活性溶媒の沸点域の範
囲から選択すれば良い。The reaction temperature may be selected from the range of 10 ° C. to the boiling point range of the inert solvent used.
反応時間は反応量及び反応温度等により一定しないが
数分乃至48時間の範囲から適宜選択すれば良い。The reaction time is not fixed depending on the reaction amount and the reaction temperature, but may be appropriately selected from a range of several minutes to 48 hours.
反応終了後、反応液を常法により、例えば溶媒抽出の
操作により目的物を単離し、必要に応じてカラムクロマ
トグラフィー法、再結晶法等の精製操作を行うことによ
り一般式（Ｉ−１）で表されるシクロヘキサン誘導体を
製造することができる。After completion of the reaction, the reaction product is isolated by a conventional method, for example, a solvent extraction operation to isolate a target substance, and if necessary, a purification operation such as a column chromatography method or a recrystallization method, whereby the compound represented by the general formula (I-1) Can be produced.
（式中、R1，R2，R3，R4及びR6は前記に同じくし、R
11は炭素原子数２〜７のアルキル基、炭素原子数３〜６
のシクロアルキル基、フェニル基又は同一若しくは異な
っても良く、ハロゲン原子、炭素原子数１〜３のアルキ
ル基若しくは炭素原子数１〜３のアルコキシ基から選択
される１〜５個の置換基を有するフェニル基を示し、Ｚ
はハロゲン原子を示す。） 即ち、一般式（Ｉ−１）で表されるシクロヘキサン誘
導体と一般式（Ｖ）で表されるハライド類を不活性溶媒
及ビ塩基の存在下に反応させ、一般式（Ｉ−２）で表さ
れるシクロへキサン誘導体を製造することができる。 (Wherein R 1 , R 2 , R 3 , R 4 and R 6 are the same as above,
11 is an alkyl group having 2 to 7 carbon atoms, 3 to 6 carbon atoms
Having 1 to 5 substituents selected from a halogen atom, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, which may be the same or different, and Z represents a phenyl group;
Represents a halogen atom. That is, the cyclohexane derivative represented by the general formula (I-1) is reacted with a halide represented by the general formula (V) in the presence of an inert solvent and a bibase, and the compound represented by the general formula (I-2) The cyclohexane derivatives represented can be produced.
本反応は等モル反応であるので、一般式（Ｖ）で表さ
れるハライド類は一般式（Ｉ−１）で表されるシクロへ
キサン誘導体に対して等モル使用すれば良いが、過剰に
使用することもできる。Since this reaction is an equimolar reaction, the halides represented by the general formula (V) may be used in an equimolar amount to the cyclohexane derivative represented by the general formula (I-1). Can also be used.
本反応で使用することができる不活性溶媒としては、
本反応の進行を著しく阻害しないものであれば良く、例
えばジクロロメタン、クロロホルム、四塩化炭素等の塩
素化炭化水素類、ベンゼン、トルエン、キシレン等の芳
香族炭化水素類、酢酸エチル等のエステル類、アセトニ
トリル、ベンゾニトリル等のニトリル類、メチルセロソ
ルブ、ジエチルエーテル等の鎖状エーテル類、ジオキサ
ン、テトラヒドロフラン等の環状エーテル類、スルホラ
ン、ジメチルスルホン、ジメチルスルホキシド、水等を
例示することができ、これらの不活性溶媒は単独で若し
くは混合して使用することもできる。Inert solvents that can be used in this reaction include:
As long as it does not significantly inhibit the progress of this reaction, for example, dichloromethane, chloroform, chlorinated hydrocarbons such as carbon tetrachloride, benzene, toluene, aromatic hydrocarbons such as xylene, esters such as ethyl acetate, Examples thereof include nitriles such as acetonitrile and benzonitrile, chain ethers such as methyl cellosolve and diethyl ether, cyclic ethers such as dioxane and tetrahydrofuran, sulfolane, dimethyl sulfone, dimethyl sulfoxide, and water. The active solvents can be used alone or as a mixture.
本反応で使用できる塩基としては、例えばで使用す
る無機塩基若しくは有機塩基を使用することができる。As the base that can be used in this reaction, for example, the inorganic base or the organic base used in the above can be used.
又塩基の使用量は一般式（Ｉ−１）で表されるシクロ
ヘキサン誘導体に対して等モル乃至過剰モルの範囲から
適宜選択して使用すれば良い。The amount of the base used may be appropriately selected from the range of equimolar to excess molar with respect to the cyclohexane derivative represented by the general formula (I-1).
反応温度は０℃乃至使用する不活性溶媒の沸点域の範
囲から選択すれば良い。The reaction temperature may be selected from the range of 0 ° C. to the boiling point range of the inert solvent used.
反応時間は反応量及び反応温度等により一定しないが
数分乃至48時間の範囲から適宜選択すれば良い。The reaction time is not fixed depending on the reaction amount and the reaction temperature, but may be appropriately selected from a range of several minutes to 48 hours.
反応終了後、反応液を常法により、例えば溶媒抽出等
の操作により目的物を単離し、必要に応じてカラムクロ
マトグラフィー法、再結晶法等の精製繰作を行うことに
より一般式（Ｉ−２）で表されるシクロへキサン誘導体
を製造することができる。After completion of the reaction, the reaction solution is isolated from the reaction mixture by a conventional method, for example, by an operation such as solvent extraction, and, if necessary, is subjected to a purification procedure such as a column chromatography method or a recrystallization method to obtain a compound represented by the general formula (I- The cyclohexane derivative represented by 2) can be produced.
（式中、R1，R2，R3，R4，R6及びＺは前記に同じ。） 即ち、一般式（Ｉ−１）で表されるシクロへキサン誘
導体を不活性溶媒の存在下又は不存在下にハロゲン化剤
でハロゲン化することにより一般式（Ｉ−３）で表され
るシクロヘキサン誘導体を製造することができる。 (In the formula, R 1 , R 2 , R 3 , R 4 , R 6 and Z are the same as described above.) That is, the cyclohexane derivative represented by the general formula (I-1) is prepared in the presence of an inert solvent. Alternatively, the cyclohexane derivative represented by the general formula (I-3) can be produced by halogenation with a halogenating agent in the absence.
本反応で使用するハロゲン化剤としては、例えば三塩
化リン、五塩化リン、三臭化リン、塩化チオニル、オキ
ザリルクロリド等のハロゲン化剤を使用することがで
き、ハロゲン化剤の使用量は一般式（Ｉ−１）で表され
るシクロヘキサン誘導体に対して等モル乃至過剰モル使
用すれば良いが、好ましくは過剰に使用するのが良い。
又、ハロゲン化剤を大過剰に使用することにより、不活
性溶媒の不存在下に反応させることができる。As the halogenating agent used in this reaction, for example, a halogenating agent such as phosphorus trichloride, phosphorus pentachloride, phosphorus tribromide, thionyl chloride, oxalyl chloride can be used. The compound may be used in an equimolar amount or an excess amount with respect to the cyclohexane derivative represented by the general formula (I-1), but is preferably used in excess.
By using a large excess of the halogenating agent, the reaction can be carried out in the absence of an inert solvent.
本反応で使用することができる不活性溶媒としては、
本反応の進行を著しく阻害しないものであれば良く、例
えばジクロロメタン、クロロホルム、四塩化炭素等の塩
素化炭化水素類を使用することができる。Inert solvents that can be used in this reaction include:
Any chlorinated hydrocarbons such as dichloromethane, chloroform and carbon tetrachloride can be used as long as they do not significantly inhibit the progress of this reaction.
反応温度は室温乃至使用する不活性溶媒の沸点域の範
囲から選択すれば良い。The reaction temperature may be selected from the range of room temperature to the boiling point range of the inert solvent used.
反応時間は反応量及び反応温度等により一定しないが
数分乃至48時間の範囲から適宜選択すれば良い。The reaction time is not fixed depending on the reaction amount and the reaction temperature, but may be appropriately selected from a range of several minutes to 48 hours.
反応終了後、反応液を常法により、例えば溶媒留去、
溶媒抽出等の操作により日的物を単離し、必要に応じて
カラムクロマトグラフィー法、再結晶法等の精製操作を
行うことにより一般式（Ｉ−３）で表されるシクロへキ
サン誘導体を製造することができる。After completion of the reaction, the reaction solution is subjected to a conventional method, for example, solvent evaporation,
The cyclohexane derivative represented by the general formula (I-3) is produced by isolating a daily substance by an operation such as solvent extraction and performing a purification operation such as a column chromatography method and a recrystallization method as necessary. can do.
（式中、R1，R2，R3，R4，R6，R9，R10及びＺは前記
に同じくし、R12は炭素原子数１〜５のアルキル基、炭
素原子数１〜５のアルケニル基を示し、R13は炭素原子
数１〜５のアルキルチオ基炭素原子数１〜５のアルケニ
ルチオ基又は−Ｎ（R9）R10（式中、R9及びR10は前記に
同じ。）を示す。） 即ち、一般式（Ｉ−３）で表されるシクロヘキサン誘
導体と一般式（VI）で表されるチオール類又は一般式
（VII）で表されるアミン類とを不活性溶媒及び塩基の
存在下に反応させることにより一般式（Ｉ−４）で表さ
れるシクロヘキサン誘導体を製造することができる。 (Wherein, R 1 , R 2 , R 3 , R 4 , R 6 , R 9 , R 10 and Z are the same as described above, R 12 is an alkyl group having 1 to 5 carbon atoms, 1 to 5 carbon atoms) 5 represents an alkenyl group, wherein R 13 is an alkylthio group having 1 to 5 carbon atoms, an alkenylthio group having 1 to 5 carbon atoms, or —N (R 9 ) R 10 (wherein R 9 and R 10 are as defined above) In other words, the cyclohexane derivative represented by the general formula (I-3) is inactive with the thiols represented by the general formula (VI) or the amines represented by the general formula (VII). The cyclohexane derivative represented by the general formula (I-4) can be produced by reacting in the presence of a solvent and a base.
本反応はと同様にして反応させることにより、一般
式（Ｉ−４）で表されるシクロヘキサン誘導体を製造す
ることができる。This reaction is carried out in the same manner as in the above to produce a cyclohexane derivative represented by the general formula (I-4).
（式中、R2，R3，R4，R5及びR6は前記に同じくし、R
14は低級アルキル基、低級アルコキシカルボニル基、ベ
ンジル基、スルホニル基、アルコキシメチル基、アルケ
ニル基又はトリメチルシリル基を示す。） 即ち、一般式（II−１）で表されるシクロヘキサン類
のピラゾール環の１位の保護基を不活性溶媒の存在下に
脱保護剤と反応させることにより、一般式（Ｉ−５）で
表されるシクロヘキサン誘導体を製造することができ
る。 (Wherein R 2 , R 3 , R 4 , R 5 and R 6 are the same as above;
14 represents a lower alkyl group, a lower alkoxycarbonyl group, a benzyl group, a sulfonyl group, an alkoxymethyl group, an alkenyl group or a trimethylsilyl group. That is, by reacting the protecting group at the 1-position of the pyrazole ring of the cyclohexane represented by the general formula (II-1) with a deprotecting agent in the presence of an inert solvent, the compound represented by the general formula (I-5) The represented cyclohexane derivative can be produced.
本発明で使用できる脱保護剤としては、例えばH2／パ
ラジウムカーボン、亜鉛等の還元剤、酢酸、トリフルオ
ロ酢酸、パラトルエンスルホン酸、塩酸、臭化水素酸、
硫酸等の有機又は無機酸、アルカリ金属若しくはアルカ
リ土類金属の水酸化物若しくは炭酸塩等の無機塩基、ト
リエチルアミン、DBU等の有機塩基の他、フッ化カリウ
ム、テトラブチルアンモニウムフルオリド等を使用する
ことができる。Examples of the deprotecting agent that can be used in the present invention include reducing agents such as H 2 / palladium carbon, zinc, acetic acid, trifluoroacetic acid, paratoluenesulfonic acid, hydrochloric acid, hydrobromic acid,
Use of organic or inorganic acids such as sulfuric acid, inorganic bases such as alkali metal or alkaline earth metal hydroxides or carbonates, organic bases such as triethylamine and DBU, potassium fluoride, tetrabutylammonium fluoride, etc. be able to.
本反応で使用できる不活性溶媒としてはで使用でき
る不活性溶媒の他に水又は水とで使用できる不活性溶
媒との混合物も使用することができる。As the inert solvent that can be used in this reaction, water or a mixture with an inert solvent that can be used with water can be used in addition to the inert solvent that can be used.
反応温度は０℃乃至使用する不活性溶媒の沸点域から
選択すれば良い。The reaction temperature may be selected from the range of 0 ° C. to the boiling point of the inert solvent used.
反応時間は反応温度、反応規模等により一定しない
が、数分乃至48時間の範囲で行えば良い。The reaction time is not constant depending on the reaction temperature, the reaction scale and the like, but may be in the range of several minutes to 48 hours.
反応終了後、と同様にすることにより一般式（Ｉ−
５）で表されるシクロヘキサン誘導体を製造することが
できる。After completion of the reaction, the general formula (I-
The cyclohexane derivative represented by 5) can be produced.
又一般式（II−１）で表されるシクロヘキサン類は一
般式（II）で表されるシクロヘキサン類と同様にして製
造することができる。The cyclohexane represented by the general formula (II-1) can be produced in the same manner as the cyclohexane represented by the general formula (II).
（式中、R1，R2，R3，R4，R5，R6及びＺは前記に同
じ。） 即ち、一般式（Ｉ−５）で表されるシクロヘキサン誘
導体と一般式（VIII）で表されるハライド類を不活性溶
媒及び塩基の存在下に反応させることにより、一般式
（Ｉ）で表されるシクロヘキサン誘導体を製造すること
ができる。 (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and Z are the same as described above.) That is, the cyclohexane derivative represented by the general formula (I-5) and the general formula (VIII) Is reacted in the presence of an inert solvent and a base to produce a cyclohexane derivative represented by the general formula (I).
本反応はと同様に反応させることにより、一般式
（Ｉ−５）で表されるシクロヘキサン誘導体を製造する
ことができる。This reaction is carried out in the same manner as in the above to produce a cyclohexane derivative represented by the general formula (I-5).
（式中、R1，R2，R4，R5及びR6は前記に同じくし、R
15は炭素原子数１〜５のアルキル基又は炭素原子数１〜
５のハロアルキル基を示し、ｎは１〜２の整数を示
す。） 即ち、一般式（Ｉ−６）で表されるシクロヘキサン誘
導体を不活性溶媒の存在下に適当な酸化剤により酸化す
ることにより、一般式（Ｉ−７）で表されるシクロヘキ
サン誘導体を製造することができる。 (Wherein R 1 , R 2 , R 4 , R 5 and R 6 are the same as above;
15 is an alkyl group having 1 to 5 carbon atoms or 1 to 5 carbon atoms
5 represents a haloalkyl group, and n represents an integer of 1 to 2. That is, the cyclohexane derivative represented by the general formula (I-7) is produced by oxidizing the cyclohexane derivative represented by the general formula (I-6) with a suitable oxidizing agent in the presence of an inert solvent. be able to.
本反応で使用できる不活性溶媒としてはで使用でき
る不活性溶媒を使用することができる。As the inert solvent that can be used in this reaction, an inert solvent that can be used for the above can be used.
本反応で使用できる酸化剤としては、例えば硝酸、過
酸化水素、過安息香酸、メタクロロ過安息香酸、メタ過
沃素酸ナトリウム、ペルオキソ−硝酸カリウム等を例示
することができる。本反応は等モル反応であるので、酸
化剤を等モル使用すれば良いが、過剰に使用することも
できる。Examples of the oxidizing agent that can be used in this reaction include nitric acid, hydrogen peroxide, perbenzoic acid, metachloroperbenzoic acid, sodium metaperiodate, and peroxo-potassium nitrate. Since this reaction is an equimolar reaction, the oxidizing agent may be used in an equimolar amount, but may be used in excess.
反応温度は０℃乃至使用する不活性溶媒の沸点域の範
囲から選択すれば良く、好ましくは10℃乃至150℃の範
囲から選択すれば良い。The reaction temperature may be selected from the range of 0 ° C. to the boiling point range of the inert solvent used, and preferably from 10 ° C. to 150 ° C.
反応時間は反応規模、反応温度等により一定しない
が、数分乃至48時間の範囲から選択すれば良い。The reaction time is not fixed depending on the reaction scale, the reaction temperature and the like, but may be selected from a range of several minutes to 48 hours.
反応終了後、と同様にして、一般式（１−７）で表
されるシクロヘキサン誘導体を製造することができる。After the completion of the reaction, the cyclohexane derivative represented by the general formula (1-7) can be produced in the same manner as described above.
．塩類 乃至で製造されたシクロヘキサン誘導体を無機
酸、無機塩基、有機酸、有機塩基、アルカリ金属又は金
属塩等で処理することにより一般式（Ｉ）で表されるシ
クロヘキサン誘導体の塩類を製造することができる。. The salts of the cyclohexane derivative represented by the general formula (I) can be produced by treating the cyclohexane derivative prepared above with an inorganic acid, an inorganic base, an organic acid, an organic base, an alkali metal or a metal salt. it can.
一般式（IA）で表されるシクロヘキサン誘導体又はそ
の塩類は乃至の製造方法により製造することができ
る。The cyclohexane derivative represented by the general formula (IA) or a salt thereof can be produced by the following production methods.
以下に本発明の一般式（IA）又は（IB）で表されるシ
クロヘキサン誘導体又はその塩類の代表的な化合物を第
１表及び第２表に例示するが、本発明はこれらに限定さ
れるものではない。Representative compounds of the cyclohexane derivative represented by the general formula (IA) or (IB) of the present invention or salts thereof are shown in Tables 1 and 2 below, but the present invention is not limited thereto. is not.
又、第１表及び第２表中、物性が粘稠物、ガラス状物
である化合物のNMRデータを第３表に示す。 In Tables 1 and 2, NMR data of compounds having physical properties of viscous substances and glassy substances are shown in Table 3.
本発明の一般式（1A）又は（1B）で表されるシクロヘ
キサン誘導体又はその塩類を製造するための原料化合物
である一般式（II）及び一般式（III）で表される化合
物は、例えば以下に図示する製造方法により製造するこ
とができる。 The compounds represented by the general formulas (II) and (III), which are starting compounds for producing the cyclohexane derivative represented by the general formula (1A) or (1B) of the present invention or salts thereof, include, for example, Can be manufactured by the manufacturing method shown in FIG.
（式中、R1，R2，R3，R4，R6及びＺは前期に同じく
し、R16は低級アルキル基を示す。） 即ち、R4がアルキル基の場合、一般式（XIV）で表さ
れるピラゾール類と一般式（XIII）で表される酢酸エス
テル類とを反応させ、一般式（XII）で表されるピラゾ
ール類とし、該（XII）で表されるピラゾール類を一般
式（Ｘ）で表されるケトン類と反応させ、更に閉環反応
に付して一般式（III）で表される化合物を製造するこ
とができる。 (In the formula, R 1 , R 2 , R 3 , R 4 , R 6 and Z are the same as those described above, and R 16 represents a lower alkyl group.) When R 4 is an alkyl group, a compound represented by the general formula (XIV ) Is reacted with an acetic ester represented by the general formula (XIII) to give a pyrazole represented by the general formula (XII), and the pyrazole represented by the (XII) is generally The compound represented by the general formula (III) can be produced by reacting with a ketone represented by the formula (X) and further subject to a ring closure reaction.
次にR4が水素原子又はアルコキシカルボニル基の場
合、一般式（XIV）で表されるピラゾール類とアセトン
とを反応させ、一般式（XI）で表されるピラゾール類と
し、該（XI）で表されるピラゾール類を一般式（IX）で
表されるマロン酸エステル類と反応させ、更に閉環反応
に付して一般式（III−１）で表される化合物を製造す
ることができる。Next, when R 4 is a hydrogen atom or an alkoxycarbonyl group, a pyrazole represented by the general formula (XIV) is reacted with acetone to form a pyrazole represented by the general formula (XI). The compound represented by the general formula (III-1) can be produced by reacting the pyrazole represented by the malonic ester represented by the general formula (IX) and further subjecting it to a ring closure reaction.
次いで一般式（III−１）で表される化合物を加水分
解反応及び脱炭酸反応に付し、一般式（III−２）で表
される化合物を製造することができる。Next, the compound represented by the general formula (III-1) can be subjected to a hydrolysis reaction and a decarboxylation reaction to produce a compound represented by the general formula (III-2).
上記の方法によって一般式（III）で表される化合物
を製造することができる。The compound represented by the general formula (III) can be produced by the above method.
一般式（II）で表される化合物は一般式（III）で表
される化合物と一般式（Ｖ−１）で表されるアシルハラ
イド類とを反応させることにより製造することができ
る。The compound represented by the general formula (II) can be produced by reacting the compound represented by the general formula (III) with an acyl halide represented by the general formula (V-1).
以下に本発明の一般式（IA）又は（IB）で表されるシ
クロヘキサン誘導体又はその塩類の代表的な化合物の製
造例を例示する。Examples of the production of representative compounds of the cyclohexane derivative represented by the general formula (IA) or (IB) or salts thereof according to the present invention are shown below.
製造例1. ５−（1,3−ジメチル−1H−ピラゾール−４−イル）
−３−ヒドロキシ−２−プロピオニル−２−シクロヘキ
セン−１−オンの製造（化合物No.19） ブロピオン酸５−（1,3−ジメチル−1H−ピラゾール
−４−イル）−３−オキソ−１−シクロヘキセニル1.31
g（５ミリモル）及び４−N,N−ジメチルアミノピリジン
0.122g（１ミリモル）を乾燥させたテトラヒドロフラン
50mlに溶解し、窒素雰囲気下に８時間加熱還流し、反応
を行った。反応終了後、反応液を室温まで放冷し、反応
溶媒を減圧下に留去した。残渣に水50mlを加えた後に希
塩酸でpHを４に調整し、目的物を酢酸エチル（40ml×
３）で抽出し、抽出液を乾燥後、留去し、残渣をシリカ
ゲルカラムクロマトグラフィー（酢酸エチル:n−ヘキサ
ン）により精製し、目的物1.19gを得た。Production Example 1. 5- (1,3-dimethyl-1H-pyrazol-4-yl)
Production of -3-hydroxy-2-propionyl-2-cyclohexen-1-one (Compound No. 19) 5- (1,3-dimethyl-1H-pyrazol-4-yl) -3-oxo-1-cyclohexenyl propionate 1.31
g (5 mmol) and 4-N, N-dimethylaminopyridine
0.122 g (1 mmol) of dried tetrahydrofuran
It was dissolved in 50 ml and heated under reflux in a nitrogen atmosphere for 8 hours to carry out a reaction. After completion of the reaction, the reaction solution was allowed to cool to room temperature, and the reaction solvent was distilled off under reduced pressure. After adding 50 ml of water to the residue, the pH was adjusted to 4 with dilute hydrochloric acid, and the target substance was ethyl acetate (40 ml ×
The extract was extracted in 3), the extract was dried and evaporated, and the residue was purified by silica gel column chromatography (ethyl acetate: n-hexane) to obtain 1.19 g of the desired product.
物性m.p.90.0℃ 収率 91％ 製造例2. ５−（５−クロロ−1,3−ジメチル−1H−ピラゾール
−４−イル）−３−ヒドロキシ−２−プロピオニル−２
−シクロヘキセン−１−オンの製造（化合物No.22） プロピオン酸 ５−（５−クロロ−1,3−ジメチル−1
H−ピラゾール−４−イル）−３−オキソ−１−シクロ
ヘキセニル1.49g（５ミリモル）及び４−N,N−ジメチル
アミノピリジン0.122g（１ミリモル）を乾燥させたテト
ラヒドロフラン80mlに溶解し、窒素雰囲気下に８時間加
熱還流し、反応を行った。反応終了後、反応液を室温ま
で放冷し、反応溶媒を減圧下に留去した。残渣に水50ml
を加えた後に希塩酸でpHを４に調整し、目的物を酢酸エ
チル（40ml×３）で抽出し、抽出液を乾燥後、留去し、
残渣をシリカゲルカラムクロマトグラフィー（酢酸エチ
ル:n−ヘキサン）により精製し、目的物1.30gを得た。Properties mp 90.0 ° C Yield 91% Production Example 2. 5- (5-Chloro-1,3-dimethyl-1H-pyrazol-4-yl) -3-hydroxy-2-propionyl-2
Production of -cyclohexen-1-one (Compound No. 22) Propionic acid 5- (5-chloro-1,3-dimethyl-1
1.49 g (5 mmol) of H-pyrazol-4-yl) -3-oxo-1-cyclohexenyl and 0.122 g (1 mmol) of 4-N, N-dimethylaminopyridine were dissolved in 80 ml of dried tetrahydrofuran, and nitrogen was dissolved. The mixture was heated under reflux for 8 hours to carry out a reaction. After completion of the reaction, the reaction solution was allowed to cool to room temperature, and the reaction solvent was distilled off under reduced pressure. 50 ml of water in the residue
Was added, the pH was adjusted to 4 with dilute hydrochloric acid, the desired product was extracted with ethyl acetate (40 ml × 3), the extract was dried, and evaporated.
The residue was purified by silica gel column chromatography (ethyl acetate: n-hexane) to obtain 1.30 g of the desired product.
物性 nD 1.5462（25.1℃） 収率 87％ 製造例3. ２−イソブチリル−３−ヒドロキシ−５−（５−クロ
ロ−1,3−ジメチル−1H−ピラゾール−４−イル）−２
−シクロヘキセン−１−オンの製造（化合物No.25） イソ酪酸 ５−（５−クロロ−1,3−ジメチル−1H−
ピラゾール−４−イル）−３−オキソ−１−シクロヘキ
セニル1.56g（５ミリモル）を乾燥させたアセトニトリ
ル15mlに溶解し、アセトンシアンヒドリン0.085g（１ミ
リモル）及びトリエチルアミン1.01g（10ミリモル）を
加え１時間加熱還流し、反応を行った。反応終了後、反
応液を室温まで放冷し、反応溶媒を減圧下に留去した。
残渣に水20mlを加えた後に希塩酸でpHを４に調整し、目
的物をジエチルエーテル（50ml×３）で抽出し、抽出液
を乾燥後、留去し、残渣をシリカゲルカラムクロマトグ
ラフィー（酢酸エチル:n−ヘキサン）により精製し、目
的物1.13gを得た。Physical Properties nD 1.5462 (25.1 ° C) Yield 87% Production Example 3. 2-isobutyryl-3-hydroxy-5- (5-chloro-1,3-dimethyl-1H-pyrazol-4-yl) -2
Production of -cyclohexen-1-one (Compound No. 25) Isobutyric acid 5- (5-chloro-1,3-dimethyl-1H-
1.56 g (5 mmol) of pyrazol-4-yl) -3-oxo-1-cyclohexenyl were dissolved in 15 ml of dried acetonitrile, and 0.085 g (1 mmol) of acetone cyanohydrin and 1.01 g (10 mmol) of triethylamine were dissolved. The mixture was heated and refluxed for 1 hour to carry out a reaction. After completion of the reaction, the reaction solution was allowed to cool to room temperature, and the reaction solvent was distilled off under reduced pressure.
After adding 20 ml of water to the residue, the pH was adjusted to 4 with dilute hydrochloric acid, the desired product was extracted with diethyl ether (50 ml × 3), and the extract was dried and evaporated, and the residue was subjected to silica gel column chromatography (ethyl acetate). : n-hexane) to give 1.13 g of the desired product.
物性 m.p. 86.5℃ 収率 72％ 製造例4. ２−ブチリル−３−ヒドロキシ−５−（５−メトキシ
−1,3−ジメチル−1H−ピラゾール−４−イル）−２−
シクロヘキセン−１−オンの製造（化合物No.44） 酪酸 ５−（５−メトキシ−1,3−ジメチル−1H−ピ
ラゾール−４−イル）−３−オキソ−１−シクロヘキセ
ニル1.84g（５ミリモル）及び４−N,N−ジメチルアミノ
ピリジン0.122g（１ミリモル）を乾燥させたテトラヒド
ロフラン80mlに溶解し、窒素雰囲気下に８時間加熱還流
し、反応を行った。反応終了後、反応液を室温まで放冷
し、反応溶媒を減圧下に留去した。残渣に水50mlを加え
た後に希塩酸でpHを４に調整し、目的物を酢酸エチル
（40ml×３）で抽出し、抽出液を乾燥後、留去し、残渣
をシリカゲルカラムクロマトグラフィー（酢酸エチル:n
−ヘキサン）により精製し、目的物1.64gを得た。Physical properties mp 86.5 ° C Yield 72% Production Example 4. 2-butyryl-3-hydroxy-5- (5-methoxy-1,3-dimethyl-1H-pyrazol-4-yl) -2-
Production of cyclohexen-1-one (Compound No. 44) 1.84 g (5 mmol) of butyric acid 5- (5-methoxy-1,3-dimethyl-1H-pyrazol-4-yl) -3-oxo-1-cyclohexenyl and 0.122 g of 4-N, N-dimethylaminopyridine ( (1 mmol) was dissolved in 80 ml of dried tetrahydrofuran and heated to reflux for 8 hours under a nitrogen atmosphere to carry out a reaction. After completion of the reaction, the reaction solution was allowed to cool to room temperature, and the reaction solvent was distilled off under reduced pressure. After adding 50 ml of water to the residue, the pH was adjusted to 4 with dilute hydrochloric acid, the target substance was extracted with ethyl acetate (40 ml × 3), the extract was dried and evaporated, and the residue was subjected to silica gel column chromatography (ethyl acetate). : n
-Hexane) to give 1.64 g of the desired product.
物性 m.p. 73.2℃ 収率 89％ 製造例5. ５−（１−エチル−３−メチル−５−メチルチオ−1H
−ピラゾール−４−イル）−３−ヒドロキシ−２−シク
ロプロピカルボニル−２−シクロヘキセン−１−オンの
製造（化合物No.165） シクロプロパンカルボン酸 ５−（１−エチル−３−
メチル−５−メチルチオ−1H−ピラゾール−４−イル）
−３−オキソ−１−シクロヘキセニル12.3g（36.8ミリ
モル）を乾燥させたアセトニトリル100mlに溶解し、ア
セトンシアンヒドリン0.3g（3.7ミリモル）及びトリエ
チルアミン8.2g（81.2ミリモル）を加え、窒素雰囲気下
に８時間室温で反応を行った。Physical properties mp 73.2 ° C Yield 89% Production Example 5. 5- (1-ethyl-3-methyl-5-methylthio-1H
-Pyrazol-4-yl) -3-hydroxy-2-cyclopropycarbonyl-2-cyclohexen-1-one (Compound No. 165) Cyclopropanecarboxylic acid 5- (1-ethyl-3-
Methyl-5-methylthio-1H-pyrazol-4-yl)
Dissolve 12.3 g (36.8 mmol) of -3-oxo-1-cyclohexenyl in 100 ml of dried acetonitrile, add 0.3 g (3.7 mmol) of acetone cyanohydrin and 8.2 g (81.2 mmol) of triethylamine, and under a nitrogen atmosphere. The reaction was performed at room temperature for 8 hours.
反応終了後、反応溶媒を減圧下に留去した。得られた
残渣に水100mlを加えた後に希塩酸でpH4に調整し、目的
物を酢酸エチル（100ml×３）で抽出し、抽出液を乾燥
後、留去し、残渣をシリカゲルカラムクロマトグラフィ
ー（酢酸エチル:n−ヘキサン）により精製し、目的物1
1.2gを得た。After completion of the reaction, the reaction solvent was distilled off under reduced pressure. After adding 100 ml of water to the obtained residue, the pH was adjusted to 4 with dilute hydrochloric acid, the target substance was extracted with ethyl acetate (100 ml × 3), the extract was dried, and evaporated, and the residue was subjected to silica gel column chromatography (acetic acid). (Ethyl: n-hexane).
1.2 g were obtained.
物性 m.p. 93.1〜93.8℃ 収率 91.1％ 製造例6. ５−（１−エチル−３−メチル−５ピロリジノ−1H−
ピラゾール−４−イル）−３−ヒドロキシ−２−シクロ
プロピルカルボニル−２−シクロヘキセン−１−オンの
製造（化合物No.202） シクロプロパンカルボン酸 ５−（１−エチル−３−
メチル−５−ピロリジノ−1H−ピラゾール−４−イル）
−３−オキソ−１−シクロヘキセニル2.2g（6.2ミリモ
ル）を乾燥させたアセトニトリル50mlに溶解し、アセト
ンシアンヒドリン0.1g（1.2ミリモル）及びトリエチル
アミン1.4g（13.6ミリモル）を加え、窒素雰囲気下に８
時間室温で反応を行った。Physical properties mp 93.1 to 93.8 ° C. Yield 91.1% Production Example 6.5 5- (1-ethyl-3-methyl-5-pyrrolidino-1H-
Production of pyrazol-4-yl) -3-hydroxy-2-cyclopropylcarbonyl-2-cyclohexen-1-one (Compound No. 202) Cyclopropanecarboxylic acid 5- (1-ethyl-3-
Methyl-5-pyrrolidino-1H-pyrazol-4-yl)
Dissolve 2.2 g (6.2 mmol) of -3-oxo-1-cyclohexenyl in 50 ml of dried acetonitrile, add 0.1 g (1.2 mmol) of acetone cyanohydrin and 1.4 g (13.6 mmol) of triethylamine, and under nitrogen atmosphere. 8
The reaction was performed at room temperature for hours.
反応終了後、反応溶媒を減圧留去し、得られた残渣に
水50mlを加え、希塩酸でpHを４に調整し、目的物を酢酸
エチル（40ml×３）で抽出し、抽出液を乾燥後留去し、
残渣をシリカゲルカラムクロマトグラフィー（酢酸エチ
ル:n−ヘキサン）により精製し目的物を1.4g得た。After completion of the reaction, the reaction solvent was distilled off under reduced pressure, 50 ml of water was added to the obtained residue, the pH was adjusted to 4 with dilute hydrochloric acid, and the desired product was extracted with ethyl acetate (40 ml × 3). Distilled off,
The residue was purified by silica gel column chromatography (ethyl acetate: n-hexane) to obtain 1.4 g of the desired product.
m.p. 65.0−67.0℃ 収率 63.6％ 製造例7. ５−（3,5−ジメチル−１−ｎ−プロピル−1H−ピラ
ゾール−４−イル）−２−シクロプロピルカルボニル−
３−ヒドロキシ−２−シクロヘキセン−１−オンの製造
（化合物No.207） シクロプロパンカルボン酸 ５−（3,5−ジメチル−
１−ｎ−プロピル−1H−ピラゾール−４−イル）−３−
オキソ−１−シクロヘキセニル1.77g（5.6ミリモル）、
アセトンシアンヒドリン0.1g（1.1ミリモル）及びトリ
エチルアミン1.24g（12.3ミリモル）を乾燥させたアセ
トニトリル20mlに溶解し、窒素雰囲気下に８時間室温で
反応を行った。mp 65.0-67.0 ° C. Yield 63.6% Production Example 7. 5- (3,5-dimethyl-1-n-propyl-1H-pyrazol-4-yl) -2-cyclopropylcarbonyl-
Production of 3-hydroxy-2-cyclohexen-1-one (Compound No. 207) Cyclopropanecarboxylic acid 5- (3,5-dimethyl-
1-n-propyl-1H-pyrazol-4-yl) -3-
Oxo-1-cyclohexenyl 1.77 g (5.6 mmol),
0.1 g (1.1 mmol) of acetone cyanohydrin and 1.24 g (12.3 mmol) of triethylamine were dissolved in 20 ml of dried acetonitrile, and reacted at room temperature for 8 hours under a nitrogen atmosphere.
反応終了後、反応溶媒を減圧留去し、得られた残渣に
水50mlを加え、希塩酸でpHを４に調整し、目的物を酢酸
エチル（40ml×３）で抽出し、抽出液を乾燥後留去し、
残渣をシリカゲルカラムクロマトグラフィー（酢酸エチ
ル:n−ヘキサン）により精製し目的物を1.51g得た。After completion of the reaction, the reaction solvent was distilled off under reduced pressure, 50 ml of water was added to the obtained residue, the pH was adjusted to 4 with dilute hydrochloric acid, and the desired product was extracted with ethyl acetate (40 ml × 3). Distilled off,
The residue was purified by silica gel column chromatography (ethyl acetate: n-hexane) to obtain 1.51 g of the desired product.
nD 1.5432（15℃） 収率 85.3％ このものを更に精製することにより結晶物として1.48
g得た。nD 1.5432 (15 ° C.) Yield 85.3% The product was further purified to give 1.48 as a crystalline product.
g obtained.
製造例8. ５−（３−メチル−５−メチルスルフィニル−１−オ
クチル−1H−ピラゾール−４−イル）−２−シクロプロ
ピルカルボニル−３−ヒドロキシ−２−シクロヘキセン
−１−オンの製造（化合物No.260） シクロプロパンカルボン酸 ５−（３−メチル−５−
メチルスルフィニル−１−オクチル−1H−ピラゾール−
４−イル）−３−オキソ−１−シクロヘキセニル1.7g
（3.9ミリモル）を乾燥させたアセトニトリル20mlに溶
解し、アセトンシアンヒドリン0.1g（1.2ミリモル）及
びトリエチルアミン0.9g（8.6ミリモル）を加え、窒素
雰囲気下に８時間室温で反応を行った。Production Example 8. Production of 5- (3-methyl-5-methylsulfinyl-1-octyl-1H-pyrazol-4-yl) -2-cyclopropylcarbonyl-3-hydroxy-2-cyclohexen-1-one (compound No.260) Cyclopropanecarboxylic acid 5- (3-methyl-5-
Methylsulfinyl-1-octyl-1H-pyrazole-
4-yl) -3-oxo-1-cyclohexenyl 1.7 g
(3.9 mmol) was dissolved in 20 ml of dried acetonitrile, 0.1 g (1.2 mmol) of acetone cyanohydrin and 0.9 g (8.6 mmol) of triethylamine were added, and the reaction was carried out at room temperature for 8 hours under a nitrogen atmosphere.
反応終了後、反応溶媒を減圧留去し、得られた残渣に
水150mlを加え、希塩酸でpHを４に調整し、目的物を酢
酸エチル（40ml×３）で抽出し、抽出液を乾燥後留去
し、残渣をシリカゲルカラムクロマトグラフィー（酢酸
エチル:n−ヘキサン）により精製し目的物を1.6g得た。After completion of the reaction, the reaction solvent was distilled off under reduced pressure, 150 ml of water was added to the obtained residue, the pH was adjusted to 4 with dilute hydrochloric acid, the target substance was extracted with ethyl acetate (40 ml × 3), and the extract was dried. The residue was purified by silica gel column chromatography (ethyl acetate: n-hexane) to obtain 1.6 g of the desired product.
物性 nD 1.5435（21.1℃） 収率 94.1％ 製造例9. ５−（1,3−ジメチル−1H−ピラゾール−５−イル）
−２−プロピオニル−２−シクロヘキセン−１−オンの
製造（化合物No.320） プロピオン酸 ５−（1,3−ジメチル−1H−ピラゾー
ル−５−イル）−３−オキソ−１−シクロヘキセニル1
7.5g（66.7ミリモル）及び４−N,N−ジメチルアミノピ
リジン0.85g（7.0ミリモル）の混合物をテトラヒドロフ
ラン200mlに溶解し、２時間加熱還流し反応を行った。Physical Properties nD 1.5435 (21.1 ° C) Yield 94.1% Production Example 9. 5- (1,3-Dimethyl-1H-pyrazol-5-yl)
Production of -2-propionyl-2-cyclohexen-1-one (Compound No. 320) 5- (1,3-dimethyl-1H-pyrazol-5-yl) -3-oxo-1-cyclohexenyl propionate
A mixture of 7.5 g (66.7 mmol) and 0.85 g (7.0 mmol) of 4-N, N-dimethylaminopyridine was dissolved in 200 ml of tetrahydrofuran and heated to reflux for 2 hours to carry out a reaction.
反応終了後、反応液を冷却し、反応溶媒を減圧下に留
去し、得られた残渣をシリカゲルクロマトグラフィー
（酢酸エチル:n−ヘキサン）により精製し、目的物を1
6.40g得た。After completion of the reaction, the reaction solution was cooled, the reaction solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel chromatography (ethyl acetate: n-hexane) to obtain the desired product.
6.40 g were obtained.
物性 nD 1.5331（12.1℃） 収率 93.7％ 製造例10. 安息香酸 ５−（1,3−ジメチル−５−メチルスルフ
ィニル−1H−ピラゾール−４−イル）−３−オキソ−２
−シクロプロピルカルボニル−１−シクロヘキセニルの
製造（化合物No.110） ５−（1,3−ジメチル−５−メチルスルフィニル−1H
−ピラゾール−４−イル）−３−ヒドロキシ−２−シク
ロプロピカルボニル−２−シクロヘキセン−１−オン0.
6g（1.8ミリモル）と63％水素化ナトリウム0.082g（2.1
ミリモル）を乾燥テトラヒドロフラン30mlに加え、30分
間撹拌した。その後、該反応液に安息香酸クロリド0.30
g（2.1ミリモル）を加え、室温下に一夜攪拌した。反応
終了後、反応液に水を加え、目的物をエーテルにより抽
出した。抽出液を炭酸カリウム水溶液で洗浄し、水洗、
乾燥後、濃縮し、残渣をシリカゲルカラムクロマトグラ
フィー（酢酸エチル）により精製し、目的物0.20gを得
た。Physical Properties nD 1.5331 (12.1 ° C) Yield 93.7% Preparation Example 10. 5- (1,3-Dimethyl-5-methylsulfinyl-1H-pyrazol-4-yl) -3-oxo-2 benzoate
Production of -cyclopropylcarbonyl-1-cyclohexenyl (Compound No. 110) 5- (1,3-dimethyl-5-methylsulfinyl-1H
-Pyrazol-4-yl) -3-hydroxy-2-cyclopropycarbonyl-2-cyclohexen-1-one
6 g (1.8 mmol) and 63% sodium hydride 0.082 g (2.1
(Mmol) was added to 30 ml of dry tetrahydrofuran and stirred for 30 minutes. Then, benzoic acid chloride 0.30 was added to the reaction solution.
g (2.1 mmol) was added, and the mixture was stirred overnight at room temperature. After completion of the reaction, water was added to the reaction solution, and the desired product was extracted with ether. The extract is washed with an aqueous solution of potassium carbonate, washed with water,
After drying and concentration, the residue was purified by silica gel column chromatography (ethyl acetate) to obtain 0.20 g of the desired product.
物性 粘稠物 収率 25％ NMR（CDCl3/TMS δ値 ppm） 0.77−1.36（m,4H）,2.30（s,3H）,2.96（s,3H）,4.0
3（s,3H）,2.00−3.95（m,6H）,7.40−7.70（m,3H）,7.
87−8.17（m,2H）。Physical properties Viscous substance Yield 25% NMR (CDCl 3 / TMS δ value ppm) 0.77-1.36 (m, 4H), 2.30 (s, 3H), 2.96 (s, 3H), 4.0
3 (s, 3H), 2.00-3.95 (m, 6H), 7.40-7.70 (m, 3H), 7.
87-8.17 (m, 2H).
製造例11. ３−クロロ−５−（1,3−ジメチル−５−メチルチオ
−1H−ピラゾール−４−イル）−２−プロピオニル−２
−シクロヘキセン−１−オンの製造（化合物No.79） ３−ヒドロキシ−５−（1,3−ジメチル−５−メチル
チオ−1H−ピラゾール−４−イル）−２−プロピオニル
−２−シクロヘキセン−１−オン10g（32.5ミリモル）
をオキザリルクロリド29g（230ミリモル）に溶解し、室
温で１時間攪拌反応を行った。反応終了後、反応液を氷
水100ml中に注ぎ、1N水酸化ナトリウムでpH7に調整し、
酢酸エチル（100ml×３）で目的物を抽出し、抽出液を
乾燥後、溶媒を留去し、シリカゲルカラムクロマトグラ
フィー（酢酸エチル:n−ヘキサン）で精製して目的物9.
5gを得た。Production Example 11. 3-Chloro-5- (1,3-dimethyl-5-methylthio-1H-pyrazol-4-yl) -2-propionyl-2
Production of -cyclohexen-1-one (Compound No. 79) 10 g (32.5 mmol) of 3-hydroxy-5- (1,3-dimethyl-5-methylthio-1H-pyrazol-4-yl) -2-propionyl-2-cyclohexen-1-one
Was dissolved in 29 g (230 mmol) of oxalyl chloride, and the mixture was stirred and reacted at room temperature for 1 hour. After the completion of the reaction, the reaction solution was poured into 100 ml of ice water, adjusted to pH 7 with 1N sodium hydroxide,
The target product was extracted with ethyl acetate (100 ml × 3), the extract was dried, the solvent was distilled off, and the target product was purified by silica gel column chromatography (ethyl acetate: n-hexane).
5 g were obtained.
物性 m.p. 141.2〜142.3℃ 収率 89.5％ 製造例12. ３−ジエチルアミノ−５−（1,3−ジメチル−５−メ
チルチオ−1H−ピラゾール−４−イル）−２−プロピオ
ニル−２−シクロヘキセン−１−オンの製造（化合物N
o.84） ３−クロロ−５−（1,3−ジメチル−５−メチルチオ
−1H−ピラゾール−４−イル）−２−プロピオニル−２
−シクロヘキセン−１−オン0.6g（1.8ミリモル）及び
ジエチルアミン0.16g（2.2ミリモル）を乾燥させたテト
ラヒドロフラン30mlに溶解し、該溶液にトリエチルアミ
ン0.22g（2.2ミリモル）を加え、室温下４時間攪拌反応
を行った。反応終了後、反応溶媒を減圧留去し、得られ
た残渣に水50mlを加え、希塩酸でpH5に調整し、酢酸エ
チル（40ml×３）で抽出し、抽出液を乾燥後、溶媒を留
去し、残渣をシリカゲルクロマトグラフィー（酢酸エチ
ル:n−ヘキサン）で精製し、目的物0.4gを得た。Properties mp 141.2-142.3 ° C Yield 89.5% Production Example 12. 3-Diethylamino-5- (1,3-dimethyl-5-methylthio-1H-pyrazol-4-yl) -2-propionyl-2-cyclohexene-1- Preparation of (Compound N
o.84) 3-chloro-5- (1,3-dimethyl-5-methylthio-1H-pyrazol-4-yl) -2-propionyl-2
0.6 g (1.8 mmol) of -cyclohexen-1-one and 0.16 g (2.2 mmol) of diethylamine are dissolved in 30 ml of dried tetrahydrofuran, and 0.22 g (2.2 mmol) of triethylamine is added to the solution, followed by stirring at room temperature for 4 hours. went. After the completion of the reaction, the reaction solvent was distilled off under reduced pressure, 50 ml of water was added to the obtained residue, the pH was adjusted to 5 with dilute hydrochloric acid, extracted with ethyl acetate (40 ml × 3), the extract was dried, and the solvent was distilled off. The residue was purified by silica gel chromatography (ethyl acetate: n-hexane) to obtain 0.4 g of the desired product.
物性 nD 1.5729（20.1℃） 収率 61.2％ 製造例13. ５−（3,5−ジメチル−1H−ピラゾール−４−イル）
−３−ヒドロキシ−２−シクロプロピルカルボニル−２
−シクロヘキセン−１−オンの製造（化合物No.4） ５−（3,5−ジメチル−１−ビニル−1H−ピラゾール
−４−イル）−３−ヒドロキシ−２−シクロプロピルカ
ルボニル−２−シクロヘキセン−１−オン5.8g（19.3ミ
リモル）を1,4−ジオキサン50mlと水50mlの混合溶液に
溶解し、38％塩酸水溶液4.0g（41.6ミリモル）を滴下し
た。滴下終了後、３時間加熱還流し反応を行った。反応
終了後、反応液を室温まで放冷し、溶媒を減圧下に留去
した。得られた残渣に水100mlを加えた後、希水酸化ナ
トリウム水溶液でpHを４に調整し、酢酸エチル（100ml
×３）で目的物を抽出し、抽出液を乾燥後、減圧下に抽
出液を留去し、残渣をシリカゲルカラムクロマトグラフ
ィー（酢酸エチル）で精製し、目的物4.5gを得た。Physical Properties nD 1.5729 (20.1 ° C) Yield 61.2% Production Example 13. 5- (3,5-Dimethyl-1H-pyrazol-4-yl)
-3-Hydroxy-2-cyclopropylcarbonyl-2
Production of -cyclohexen-1-one (Compound No. 4) 5.8 g (19.3 mmol) of 5- (3,5-dimethyl-1-vinyl-1H-pyrazol-4-yl) -3-hydroxy-2-cyclopropylcarbonyl-2-cyclohexen-1-one in 1,4- It was dissolved in a mixed solution of 50 ml of dioxane and 50 ml of water, and 4.0 g (41.6 mmol) of a 38% hydrochloric acid aqueous solution was added dropwise. After the completion of the dropwise addition, the mixture was heated under reflux for 3 hours to carry out a reaction. After completion of the reaction, the reaction solution was allowed to cool to room temperature, and the solvent was distilled off under reduced pressure. After 100 ml of water was added to the obtained residue, the pH was adjusted to 4 with a dilute aqueous sodium hydroxide solution, and ethyl acetate (100 ml) was added.
The target product was extracted by × 3), the extract was dried, the extract was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (ethyl acetate) to obtain 4.5 g of the target product.
物性 m.p. 188.0〜191.3℃ 収率 85.1％ 製造例14. ５−（3,5−ジメチル−１−ｎ−プロピル−1H−ピラ
ゾール−４−イル）−２−シクロプロピルカルボニル−
３−ヒドロキシ−２−シクロヘキセン−１−オンの製造
（化合物No.207） ５−（3,5−ジメチル−1H−ピラゾール−４−イル）
−２−シクロプロピルカルボニル−３−ヒドロキシ−２
−シクロヘキセン−１−オン1.0g（3.7ミリモル）とカ
リウムtert−ブトキシド0.9g（8.0ミリモル）を乾燥さ
せたジメチルスルホキシド20mlに溶解し、ヨウ化ｎ−プ
ロピル0.8g（4.4ミリモル）を滴下した。滴下終了後、
室温で10時間反応を行った。Physical properties mp 188.0-191.3 ° C Yield 85.1% Production Example 14. 5- (3,5-Dimethyl-1-n-propyl-1H-pyrazol-4-yl) -2-cyclopropylcarbonyl-
Production of 3-hydroxy-2-cyclohexen-1-one (Compound No. 207) 5- (3,5-dimethyl-1H-pyrazol-4-yl)
-2-cyclopropylcarbonyl-3-hydroxy-2
1.0 g (3.7 mmol) of -cyclohexen-1-one and 0.9 g (8.0 mmol) of potassium tert-butoxide were dissolved in 20 ml of dried dimethyl sulfoxide, and 0.8 g (4.4 mmol) of n-propyl iodide was added dropwise. After dropping,
The reaction was performed at room temperature for 10 hours.
反応終了後、反応液に水100mlを加え、エーテル洗浄
（50ml×２）し、水層を希塩酸水溶液でpHを４に調整
し、目的物を酢酸エチル（100ml×３）で抽出し、抽出
液を乾燥後留去し、残渣をシリカゲルカラムクロマトグ
ラフィー（酢酸エチル:n−ヘキサン）により精製し目的
物を1.0g得た。After completion of the reaction, 100 ml of water was added to the reaction solution, washed with ether (50 ml × 2), the pH of the aqueous layer was adjusted to 4 with a dilute aqueous hydrochloric acid solution, and the desired product was extracted with ethyl acetate (100 ml × 3). The residue was purified by silica gel column chromatography (ethyl acetate: n-hexane) to obtain 1.0 g of the desired product.
物性 m.p. 79.7−79.9℃ 収率 85.5％ 製造例15. ５−（3,5−ジメチル−１−ｉ−プロピル−1H−ピラ
ゾール−４−イル）−２−シクロプロピルカルボニル−
３−ヒドロキシ−２−シクロヘキセン−１−オンの製造
（化合物No.232） ５−（3,5−ジメチル−1H−ピラゾール−４−イル）
−２−シクロプロピルカルボニル−３−ヒドロキシ−２
−シクロヘキセン−１−オン1.0g（3.7ミリモル）とカ
リウムtert−ブトキシド0.9g（8.0ミリモル）を乾燥さ
せたジメチルスルホキシド20mlに溶解し、ヨウ化イソプ
ロピル0.8g（4.4ミリモル）を滴下した。滴下終了後、
室温で９時間反応を行った。Physical properties mp 79.7-79.9 ° C. Yield 85.5% Production Example 15. 5- (3,5-Dimethyl-1-i-propyl-1H-pyrazol-4-yl) -2-cyclopropylcarbonyl-
Production of 3-hydroxy-2-cyclohexen-1-one (Compound No. 232) 5- (3,5-dimethyl-1H-pyrazol-4-yl)
-2-cyclopropylcarbonyl-3-hydroxy-2
1.0 g (3.7 mmol) of -cyclohexen-1-one and 0.9 g (8.0 mmol) of potassium tert-butoxide were dissolved in 20 ml of dried dimethyl sulfoxide, and 0.8 g (4.4 mmol) of isopropyl iodide was added dropwise. After dropping,
The reaction was performed at room temperature for 9 hours.
反応終了後、反応液に水100mlを加え、エーテル洗浄
（50ml×２）し、水層を希塩酸水溶液でpHを４に調整
し、目的物を酢酸エチル（100ml×３）で抽出し、抽出
液を乾燥後留去し、残渣をシリカゲルカラムクロマトグ
ラフィー（酢酸エチル:n−ヘキサン）により精製し目的
物を1.1g得た。After completion of the reaction, 100 ml of water was added to the reaction solution, washed with ether (50 ml × 2), the pH of the aqueous layer was adjusted to 4 with a dilute aqueous hydrochloric acid solution, and the desired product was extracted with ethyl acetate (100 ml × 3). The residue was purified by silica gel column chromatography (ethyl acetate: n-hexane) to obtain 1.1 g of the desired product.
物性 m.p. 97.2−99.6℃ 収率 95.3％ 製造例16. ５−（3,5−ジメチル−１−ｉ−ブチル−1H−ピラゾ
ール−４−イル）−２−シクロプロピルカルボニル−３
−ヒドロキシ−２−シクロヘキセン−１−オンの製造
（化合物No.248） ５−（3,5−ジメチル−1H−ピラゾール−４−イル）
−２−シクロプロピルカルボニル−３−ヒドロキシ−２
−シクロヘキセン−１−オン0.5g（1.8ミリモル）とカ
リウムtert−ブトキシド0.4g（3.8ミリモル）を乾燥さ
せたテトラヒドロフラン20mlに溶解し、ヨウ化イソブチ
ル0.4g（2.2ミリモル）を滴下した。滴下終了後、８時
間加熱還流し反応を行った。Physical properties mp 97.2-99.6 ° C Yield 95.3% Production Example 16. 5- (3,5-Dimethyl-1-i-butyl-1H-pyrazol-4-yl) -2-cyclopropylcarbonyl-3
Production of -Hydroxy-2-cyclohexen-1-one (Compound No. 248) 5- (3,5-dimethyl-1H-pyrazol-4-yl)
-2-cyclopropylcarbonyl-3-hydroxy-2
0.5 g (1.8 mmol) of cyclohexen-1-one and 0.4 g (3.8 mmol) of potassium tert-butoxide were dissolved in 20 ml of dried tetrahydrofuran, and 0.4 g (2.2 mmol) of isobutyl iodide was added dropwise. After completion of the dropwise addition, the mixture was heated under reflux for 8 hours to carry out a reaction.
反応終了後、反応液に水100mlを加え、エーテル洗浄
（50ml×２）し、水層を希塩酸水溶液でpHを４に調整
し、目的物を酢酸エチル（100ml×３）で抽出し、抽出
液を乾燥後留去し、残渣をシリカゲルカラムクロマトグ
ラフィー（酢酸エチル:n−ヘキサン）により精製し目的
物を0.2g得た。After completion of the reaction, 100 ml of water was added to the reaction solution, washed with ether (50 ml × 2), the pH of the aqueous layer was adjusted to 4 with a dilute aqueous hydrochloric acid solution, and the desired product was extracted with ethyl acetate (100 ml × 3). The residue was purified by silica gel column chromatography (ethyl acetate: n-hexane) to obtain 0.2 g of the desired product.
物性 nD 1.5485（27.0℃） 収率 33.3％ 製造例17. ５−（３−クロロ−１−エチル−５−メチルスルフィ
ニル−1H−ピラゾール−４−イル）−２−シクロプロピ
ルカルボニル−３−ヒドロキシ−２−シクロヘキセン−
１−オンの製造（化合物No.152） ５−（３−クロロ−１−エチル−５−メチルチオ−1H
−ピラゾール−４−イル）−２−シクロプロピルカルボ
ニル−３−ヒドロキシ−２−シクロヘキセン−１−オン
0.98g（2.8ミリモル）をエタノール10mlに溶解し、水5m
lに溶解したペルオキソ−硫酸カリウム1.02g（1.7ミリ
モル）を加えた後、室温にて10時間で反応を行った。Physical Properties nD 1.5485 (27.0 ° C) Yield 33.3% Production Example 17. 5- (3-Chloro-1-ethyl-5-methylsulfinyl-1H-pyrazol-4-yl) -2-cyclopropylcarbonyl-3-hydroxy- 2-cyclohexene-
Production of 1-one (Compound No. 152) 5- (3-chloro-1-ethyl-5-methylthio-1H
-Pyrazol-4-yl) -2-cyclopropylcarbonyl-3-hydroxy-2-cyclohexen-1-one
0.98 g (2.8 mmol) is dissolved in ethanol 10 ml, and water 5m
After adding 1.02 g (1.7 mmol) of potassium peroxo-sulfate dissolved in l, the reaction was carried out at room temperature for 10 hours.
反応終了後、反応溶媒を減圧留去し、得られた残渣か
ら塩化メチレンで目的物を抽出し、抽出液を乾燥後留去
し、残渣をシリカゲルカラムクロマトグラフィー（メタ
ノール：酢酸エチル）により精製し目的物を0.57g得
た。After completion of the reaction, the reaction solvent was distilled off under reduced pressure, the target substance was extracted from the obtained residue with methylene chloride, the extract was dried and evaporated, and the residue was purified by silica gel column chromatography (methanol: ethyl acetate). 0.57 g of the desired product was obtained.
物性 m.p. 140−141℃ 収率 56％ 製造例18. ５−（１−エチル−３−メチル−５−メチルスルフィ
ニル−1H−ピラゾール−４−イル）−３−ヒドロキシ−
２−シクロプロピルカルボニル−２−シクロヘキセン−
１−オンの製造（化合物No.176） ５−（１−エチル−３−メチル−５−メチルチオ−1H
−ピラゾール−４−イル）−３−ヒドロキシ−２−シク
ロプロピルカルボニル−２−シクロヘキセン−１−オン
9.3g（27.8ミリモル）をエタノール300mlに溶解し、水3
00mlに溶解したポタシウム パーオキシモノスルフェイ
ト9.4g（15.3ミリモル）を加えた後、室温下10時間反応
を行った。Physical properties mp 140-141 ° C Yield 56% Production Example 18. 5- (1-Ethyl-3-methyl-5-methylsulfinyl-1H-pyrazol-4-yl) -3-hydroxy-
2-cyclopropylcarbonyl-2-cyclohexene-
Production of 1-one (Compound No. 176) 5- (1-ethyl-3-methyl-5-methylthio-1H
-Pyrazol-4-yl) -3-hydroxy-2-cyclopropylcarbonyl-2-cyclohexen-1-one
Dissolve 9.3 g (27.8 mmol) in 300 ml of ethanol and add water 3
After adding 9.4 g (15.3 mmol) of potassium peroxymonosulfate dissolved in 00 ml, the reaction was carried out at room temperature for 10 hours.
反応終了後、反応溶媒を減圧下に留去した。目的物を
含む残渣から目的物を塩化メチレン（200ml×３）で抽
出し、抽出液を乾燥後、留去し、残渣をシリカゲルカラ
ムクロマトグラフィー（メタノール：酢酸エチル）によ
り精製し、目的物8.0gを得た。After completion of the reaction, the reaction solvent was distilled off under reduced pressure. The target substance was extracted from the residue containing the target substance with methylene chloride (200 ml × 3), the extract was dried and evaporated, and the residue was purified by silica gel column chromatography (methanol: ethyl acetate) to obtain 8.0 g of the target substance. I got
物性 m.p. 130.1〜131.1℃ 収率 82.1％ 製造例19. ５−（１−エチル−３−メチル−５−メチルスルフェ
ニル−1H−ピラゾール−４−イル）−３−ヒドロキシ−
２−シクロプロピルカルボニル−２−シクロヘキセン−
１−オンのナトリウム塩の製造（化合物No.177） 金属ナトリウム20mg（0.87ミリアトム）を乾燥エタノ
ール10mlに溶解し、該溶液に５−（１−エチル−３−メ
チル−５−メチルスルフィニル−1H−ピラゾール−４−
イル）−３−ヒドロキシ−２−シクロプロピルカルボニ
ル−２−シクロヘキセン−１−オン0.3g（0.86ミリモ
ル）を加え、１時間室温にて反応を行った。反応終了
後、溶媒を留去し、残渣を乾燥剤として塩化カルシウム
を用いて、減圧下約70℃に加熱し、乾燥させ、目的物0.
32gを得た。Physical properties mp 130.1 to 131.1 ° C. Yield 82.1% Production Example 19. 5- (1-ethyl-3-methyl-5-methylsulfenyl-1H-pyrazol-4-yl) -3-hydroxy-
2-cyclopropylcarbonyl-2-cyclohexene-
Preparation of 1-one sodium salt (Compound No. 177) 20 mg (0.87 milliatoms) of sodium metal was dissolved in 10 ml of dry ethanol, and 5- (1-ethyl-3-methyl-5-methylsulfinyl-1H-pyrazole-4- was added to the solution.
0.3 g (0.86 mmol) of yl) -3-hydroxy-2-cyclopropylcarbonyl-2-cyclohexen-1-one was added, and the reaction was carried out at room temperature for 1 hour. After completion of the reaction, the solvent was distilled off, and the residue was heated to about 70 ° C. under reduced pressure using calcium chloride as a desiccant, and dried to obtain the desired product.
32 g were obtained.
物性 ガラス状 NMR （D2/DSS,δ値,ppm） 0.90−1.00（m,4H）,1.35（t,3H）,2.44（s,3H）,2.2
5−2.49（m,3H）,2.65−2.85（m,2H）,3.11（s,3H）,3.
53−3.65（m,1H）,4.39（q,2H）。Properties glassy NMR (D 2 / DSS, δ value, ppm) 0.90-1.00 (m, 4H ), 1.35 (t, 3H), 2.44 (s, 3H), 2.2
5-2.49 (m, 3H), 2.65-2.85 (m, 2H), 3.11 (s, 3H), 3.
53-3.65 (m, 1H), 4.39 (q, 2H).
製造例20. ５−（3,5−ジメチル−1H−ピラゾール−４−イル）
−２−シクロプロピルカルボニル−３−ヒドロキシ−２
−シクロヘキセン−１−オン塩酸塩の製造（化合物No.
5） ５−（3,5−ジメチル−1H−ピラゾール−４−イル）
−２−シクロプロピルカルボニル−３−ヒドロキシ−２
−シクロヘキセン−１−オン0.5g（1.8ミリモル）と12
％塩酸1,4−ジオキサン溶液2g（6.6ミリモル）を1,4−
ジオキサン20mlに加え、10分間室温にて反応を行った。Production Example 20. 5- (3,5-dimethyl-1H-pyrazol-4-yl)
-2-cyclopropylcarbonyl-3-hydroxy-2
-Production of cyclohexen-1-one hydrochloride (Compound No.
Five) 5- (3,5-dimethyl-1H-pyrazol-4-yl)
-2-cyclopropylcarbonyl-3-hydroxy-2
0.5 g (1.8 mmol) of cyclohexen-1-one and 12
2 g (6.6 mmol) of a 1,4-dioxane solution in 1,4-dioxane
The mixture was added to 20 ml of dioxane and reacted at room temperature for 10 minutes.
反応終了後、析出した結晶を濾集し、エーテルで洗浄
し、減圧下に50℃で乾燥させ、目的物0.5g得た。After completion of the reaction, the precipitated crystals were collected by filtration, washed with ether, and dried at 50 ° C. under reduced pressure to obtain 0.5 g of the desired product.
物性 m.p. 280.9−288.2℃ 収率 89.5％ 本発明の一般式（IA）又は（IB）で表されるシクロヘ
キサン誘導体田又はその塩類を有効成分とする殺虫剤
は、特に半翅目害虫に対して顕著な効果を示し、そのう
ちでも果樹、作物等に寄生し、葉の退色、萎ちょうによ
る生成阻害を起こす吸汁害虫に対して有効で、例えば水
稲の代表的な有害害虫であるトビイロウンカ（Nila−pr
vata lugens）、セジロウンカ（Sogatella furcifer
a）、ヒメトビウンカ（Laodelphax striatellus）等の
ウンカ類、ナス、トマト、きゅうり、インゲン、大豆等
の野菜類、ワタ、桑、茶等の特用作物や、ミカン、ブド
ウ、ナシ、リンゴ、カキ等の果樹等に加害するオンシツ
コナジラミ（Trialeurodes vaporaiorum）、ミカンコナ
ジラミ（Dialeurodes citri）、ミカントゲコナジラミ
（Aleurocanthus spiniferus）、ブドウコナジラミ（Al
eurolobus taonabae）、タバココナジラミ（Bemisia ta
baci）、イチゴコナジラミ（Trialeurodes packardi）
等のコナジラミ類、ナシキジラミ（Psylla pyrisug
a）、クワキジラミ（Anomoneura mori）、キカンキジラ
ミ（Diaphorina citri）、リンゴキジラミ（Psylla mar
i）、等のキジラミ類、ツノロウカイガラムシ（Ceropla
stes pseudoceriferus）、ミカンワタカイガラムシ（Pu
lvinaria aurantii）、ミカンマルカイガラムシ（Pseud
aonidia duplex）、サンホーゼカイガラムシ（Quadrasp
idiotus perniciosus）、ヤノネカイガラムシ（Unaspis
yanonensis）等のカイガラムシ類、ナシグンバイ（Ste
phanitis nashi）、ツツジグンバイ（Stephanitis pyri
oides）等のグンバイムシ類に対して有効である。Physical properties mp 280.9-288.2 ° C. Yield 89.5% The insecticide containing the cyclohexane derivative represented by the general formula (IA) or (IB) of the present invention or a salt thereof as an active ingredient is particularly remarkable against Hemiptera pests. Among them, it is effective against sucking insect pests that infest fruit trees, crops, etc., and inhibit the formation of leaves due to fading and wilting. For example, Nila-pr.
vata lugens), stag beetle (Sogatella furcifer)
a), planthoppers such as brown planthopper (Laodelphax striatellus), eggplants, tomatoes, cucumbers, vegetables such as kidney beans and soybeans, special crops such as cotton, mulberry, tea, and tangerines, grapes, pears, apples and oysters Whiteflies (Trialeurodes vaporaiorum), orangeflies (Dialeurodes citri), orangeflies (Aleurocanthus spiniferus), grape whiteflies (Al
eurolobus taonabae, tobacco whitefly (Bemisia ta)
baci), Strawberry whitefly (Trialeurodes packardi)
Whiteflies such as Psylla pyrisug
a), winged lice (Anomoneura mori), citrus lice (Diaphorina citri), apple lice (Psylla mar)
i), lice such as lice, horned scale insects (Ceropla
stes pseudoceriferus), Citrus stinkbug (Pu)
lvinaria aurantii), orange scale insect (Pseud)
aonidia duplex), San Jose scale insect (Quadrasp
idiotus perniciosus)
scale insects such as yanonensis,
phanitis nashi), azalea gumbai (Stephanitis pyri)
oides).
本発明の殺虫剤は水田害虫であるウンカ類及び果樹、
野菜等の害虫であるコナジラミ類、キジラミ類に対し
て、特異的に殺虫効果を示し、その作用性は特に成虫に
対して効果的で、ウンカ類、コナジラミ類、キジラミ
類、カイガラムシ類、グンバイムシ類等の稲、果樹、野
菜等への吸汁行動を抑制し死に到らしめるものである。The insecticide of the present invention is a rice field pest, planthoppers and fruit trees,
It shows a pesticidal effect specifically on whiteflies and white lice, which are pests such as vegetables, and its action is particularly effective against adults, including planthoppers, whiteflies, white lice, scale insects, and brown bugs. It suppresses the sucking behavior of rice, fruit trees, vegetables, etc., and leads to death.
従って、水稲、果樹、野菜等の害虫類の発生が予測さ
れる時期に合わせて、害虫類の発生前又は発生が確認さ
れた時点で水稲、果樹、野菜等の水田水、茎葉又は土壌
等に処理することにより本発明の殺虫剤の所期の効果が
奏せられるものである。Therefore, according to the time when the occurrence of pests such as paddy rice, fruit trees, vegetables, etc. is predicted, before or when the occurrence of pests is confirmed, paddy water, foliage, soil, etc. of paddy rice, fruit trees, vegetables, etc. By the treatment, the desired effect of the insecticide of the present invention can be obtained.
しかし、本発明はこれらの態様のみに限定されるもの
ではない。However, the present invention is not limited to only these embodiments.
本発明の一般式（IA）又は（IB）で表されるシクロヘ
キサン誘導体又はその塩類を殺虫剤として使用する場
合、農業製剤上の常法に従い、使用上都合の良い形状に
製剤して使用するのが一般的である。即ち、本発明の一
般式（IA）又は（IB）で表されるシクロヘキサン誘導体
又はその塩類を適当な不活性担体に、又は必要に応じて
補助剤と一緒に、適当な割合に配合して溶解、分離、懸
濁、混合、含浸、吸着若しくは付着させ、適宜の剤形、
例えば懸濁剤、乳剤、液剤、水和剤、粒剤、粉剤錠剤等
に製剤して使用すれば良い。When the cyclohexane derivative represented by the general formula (IA) or (IB) of the present invention or a salt thereof is used as an insecticide, it may be used by formulating it into a convenient form according to a conventional agricultural formulation. Is common. That is, the cyclohexane derivative represented by the general formula (IA) or (IB) of the present invention or a salt thereof is dissolved in a suitable inert carrier or, if necessary, together with an auxiliary in a suitable ratio. , Separation, suspension, mixing, impregnation, adsorption or adhesion, appropriate dosage form,
For example, they may be formulated and used in suspensions, emulsions, solutions, wettable powders, granules, powder tablets and the like.
本発明で使用できる不活性担体としては固体又は液体
の何れであっても良く、固体の担体になりうる材料とし
ては、例えばダイズ粉、穀物粉、木粉、樹皮粉、鋸粉、
タバコ茎粉、クルミ殻粉、ふすま、繊維素粉末、植物エ
キス抽出後の残渣、粉砕合成樹脂等の合成重合体、粘土
類（例えばカオリン、ベントナイト、酸性白土等）、タ
ルク類（例えばタルク、ピロフィライト等）、シリカ類
（例えば珪藻土、珪砂、雲母、ホワイトカーボン〔含水
微粉珪素、含水珪酸ともいわれる合成高分散珪酸で、製
品により珪酸カルシウムを主成分として含むものもあ
る。〕）、活性炭、イオウ粉末、軽石、焼成珪藻土、レ
ンガ粉砕物、フライアッシュ、砂、炭酸カルシウム、燐
酸カルシウム等の無機鉱物性粉末、硫安、燐安、硝安、
尿素、塩安等の化学肥料、堆肥等を挙げることができ
る。これらは単独で若しくは二種以上の混合物の形で使
用される。The inert carrier that can be used in the present invention may be either solid or liquid. Examples of the material that can be a solid carrier include soybean flour, cereal flour, wood flour, bark flour, saw flour,
Tobacco stem flour, walnut shell flour, bran, fibrous powder, residue after extracting plant extract, synthetic polymer such as pulverized synthetic resin, clays (eg, kaolin, bentonite, acid clay), talcs (eg, talc, pyrophyllite) Etc.), silicas (for example, diatomaceous earth, silica sand, mica, white carbon [synthetic high-dispersion silicic acid also referred to as hydrous fine silicon powder and hydrous silicic acid, and depending on the product, containing calcium silicate as a main component]), activated carbon, sulfur powder , Pumice, calcined diatomaceous earth, brick crushed material, fly ash, sand, calcium carbonate, calcium phosphate and other inorganic mineral powders, ammonium sulfate, phosphorous ammonium, ammonium nitrate,
Examples include chemical fertilizers such as urea and salt and compost. These are used alone or in the form of a mixture of two or more.
液体の担体になりうる材料としては、それ自体溶媒能
を有するものの他、溶媒能を有さずとも補助剤の助けに
より有効成分化合物を分散させうることとなるものから
選択され、例えば代表例として次に挙げる担体を例示で
きるが、これらは単独で若しくは２種以上の混合物の形
で使用され、例えば水、アルコール類（例えばメタノー
ル、エタノール、イソプロパノール、ブタノール、エチ
レングリコール等）、ケトン類（例えばアセトン、メチ
ルエチルケトン、メチルイソブチルケトン、ジイソブチ
ルケトン、シクロヘキサノン等）、エーテル類（例えば
エチルエーテル、ジオキサン、セロソルブ、ジプロピル
エーテル、テトラヒドロフラン等）、脂肪族炭化水素類
（例えばガソリン、鉱油等）、芳香族炭化水素類（例え
ばベンゼン、トルエン、キシレン、ソルベントナフサ、
アルキルナフタレン等）、ハロゲン化炭化水素類（例え
ばジクロロエタン、クロロホルム、四塩化炭素、塩素化
ベンゼン等）、エステル類（例えば酢酸エチル、ジイソ
プロピルフタレート、ジブチルフタレート、ジオクチル
フタレート等）、アミド類（例えばジメチルホルムアミ
ド、ジエチルホルムアミド、ジメチルアセトアミド
等）、ニトリル類（例えばアセトニトリル等）、ジメチ
ルスルホキシド類等を挙げることができる。As a material that can be a liquid carrier, in addition to those having a solvent function per se, selected from those capable of dispersing the active ingredient compound with the aid of an auxiliary agent without having a solvent function, for example, as a representative example The following carriers can be exemplified, and these may be used alone or in the form of a mixture of two or more types. Examples thereof include water, alcohols (eg, methanol, ethanol, isopropanol, butanol, ethylene glycol, etc.) and ketones (eg, acetone). , Methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, etc.), ethers (eg, ethyl ether, dioxane, cellosolve, dipropyl ether, tetrahydrofuran, etc.), aliphatic hydrocarbons (eg, gasoline, mineral oil, etc.), aromatic hydrocarbons (Eg benzene, tolue , Xylene, solvent naphtha,
Alkylnaphthalene, etc.), halogenated hydrocarbons (eg, dichloroethane, chloroform, carbon tetrachloride, chlorinated benzene, etc.), esters (eg, ethyl acetate, diisopropyl phthalate, dibutyl phthalate, dioctyl phthalate, etc.), amides (eg, dimethylformamide) , Diethylformamide, dimethylacetamide, etc.), nitriles (eg, acetonitrile), dimethylsulfoxides and the like.
他の補助剤としては次に例示する代表的な補助剤をあ
げることができ、これらの補助剤は目的に応じて使用さ
れ、単独で、ある場合は二種以上の補助剤を併用し、又
ある場合には全く補助剤を使用しないことも可能であ
る。Examples of the other adjuvants include the following representative adjuvants. These adjuvants are used according to the purpose, and may be used alone or in combination of two or more kinds. In some cases, it is possible to use no auxiliaries at all.
有効成分化合物の乳化、分散、可溶化及び／又は湿潤
の目的のために界面活性剤が使用され、例えばポリオキ
シエチレンアルキルエーテル、ポリオキシエチレンアル
キルアリールエーテル、ポリオキシエチレン高級脂肪酸
エステル、ポリオキシエチレン樹脂酸エステル、ポリオ
キシエチレンソルビタンモノラウレート、ポリオキシエ
チレンソルビタンモノオレエート、アルキルアリールス
ルホン酸塩、ナフタレンスルホン酸縮合物、リグニンス
ルホン酸塩、高級アルコール硫酸エステル等の界面活性
剤を例示することができる。Surfactants are used for the purpose of emulsifying, dispersing, solubilizing and / or wetting the active ingredient compound, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene higher fatty acid ester, polyoxyethylene Examples of surfactants such as resin acid ester, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monooleate, alkyl aryl sulfonate, naphthalene sulfonic acid condensate, lignin sulfonate, higher alcohol sulfate, and the like. Can be.
又有効成分化合物の分散安定化、粘着及び／又は結合
の目的のために、次に例示する補助剤を使用することも
でき、例えばカゼイン、ゼラチン、澱粉、メチルセルロ
ース、カルボキシメチルセルロース、アラビアゴム、ポ
リビニルアルコール、松根油、糠油、ベントナイト、リ
グニンスルホン酸塩等の補助剤を使用することもでき
る。For the purpose of stabilizing the dispersion of the active ingredient compound, adhering and / or binding, the following auxiliaries can be used. For example, casein, gelatin, starch, methylcellulose, carboxymethylcellulose, gum arabic, polyvinyl alcohol Auxiliaries such as pine oil, bran oil, bentonite, and lignin sulfonate can also be used.
固体製品の流動性改良のために次に挙げる補助剤を使
用することもでき、例えばワックス、ステアリン酸塩、
燐酸アルキルエステル等の補助剤を使用できる。The following auxiliaries can also be used for improving the flowability of solid products, such as waxes, stearates,
Auxiliaries such as alkyl phosphates can be used.
懸濁性製品の解こう剤として、例えばナフタレンスル
ホン酸縮合物、縮合燐酸塩等の補助剤を使用することも
できる。As peptizers for suspension products, auxiliary agents such as, for example, naphthalenesulfonic acid condensates, condensed phosphates and the like can also be used.
消泡剤としては、例えばシリコーン油等の補助剤を使
用することもできる。As an antifoaming agent, for example, an auxiliary agent such as silicone oil can be used.
有効成分化合物の配合割合は必要に応じて加減するこ
とができ、例えば粉剤或いは粒剤とする場合は0.01〜50
重量％、又乳剤或いは水和剤とする場合も同様0.01〜50
重量％が適当である。The compounding ratio of the active ingredient compound can be adjusted as needed, for example, 0.01 to 50 when a powder or granules are used.
% By weight, or 0.01 to 50
% By weight is appropriate.
本発明の一般式（Ｉ）で表されるシクロヘキサン誘導
体又はその塩類を有効成分とする殺虫剤は、害虫類を防
除するために、そのまま、又は水等で適宜希釈し、若し
くは懸濁させた形で殺虫に有効な量を、当該害虫に、又
は当該害虫の発生若しくは生育が好ましくない場所にお
いて使用すれば良い。例えば水稲害虫であるウンカ類を
防除するには、本発明の殺虫剤を水稲の茎葉又は水稲が
植えられている水田土壌や水田水に処理しても良い。The insecticide containing the cyclohexane derivative represented by the general formula (I) of the present invention or a salt thereof as an active ingredient is used as it is, or is appropriately diluted or suspended with water or the like in order to control pests. In this case, an effective amount for insecticide may be used for the pest or at a place where the occurrence or growth of the pest is not preferable. For example, in order to control rice plant pests, planthoppers, the insecticide of the present invention may be applied to the foliage of paddy rice or paddy soil or paddy water in which paddy rice is planted.
本発明の一般式（IA）又は（IB）で表されるシクロヘ
キサン誘導体又はその塩類を有効成分とする殺虫剤の使
用量は種々の因子、例えば目的、対象害虫、作物の発生
／生育状況、害虫の発生傾向、天候、環境条件、剤型、
施用方法、施用場所又は施用時期等により変動するが、
有効成分化合物として10アール当たり1g〜3kgの範囲か
ら目的に応じて適宜選択すれば良い。The amount of the insecticide containing the cyclohexane derivative represented by the general formula (IA) or (IB) of the present invention or a salt thereof as an active ingredient depends on various factors such as the purpose, the target pest, the occurrence / growth status of the crop, and the pest. Trends, weather, environmental conditions, dosage forms,
It varies depending on the application method, application place or application time, etc.
The active ingredient compound may be appropriately selected from the range of 1 g to 3 kg per 10 ares according to the purpose.
本発明の一般式（IA）又は（IB）で表されるシクロヘ
キサン誘導体又はその塩類を有効成分とする殺虫剤を更
に防除対象害虫、防除適期の拡大のため、或いは薬量の
低減をはかる目的で他の殺虫剤又は殺菌剤と混合して使
用することも可能である。The insecticide containing the cyclohexane derivative represented by the general formula (IA) or (IB) of the present invention or a salt thereof as an active ingredient is further used for controlling pests to be controlled, extending a suitable period of control, or reducing the dose. It is also possible to use a mixture with other insecticides or fungicides.
以下に本発明の代表的な処方例及び試験例を示すが本
発明はこれらに限定されるものではない。Hereinafter, typical formulation examples and test examples of the present invention are shown, but the present invention is not limited thereto.
試験例1. トビイロウンカの殺虫試験 本発明化合物を有効成分とする薬剤の200ppmの濃度の
薬液に稲の実生（品種：金南風）を30秒間浸漬した。風
乾後にガラス試験管に入れ、トビイロウンカ（Nilaparv
ata lugens）３令を各10頭づつ接種した後、綿栓をし
た。接種８日後に生死虫数を調査し、下記の式により死
虫率を算出し、判定基準に従って判定した。 Test Example 1. Insecticidal test on brown planthopper Rice seedlings (variety: Kinnan style) were immersed for 30 seconds in a drug solution containing the compound of the present invention as an active ingredient at a concentration of 200 ppm. After air-drying, put in a glass test tube and place brown planthopper (Nilaparv
ata lugens) After inoculating 10 mice each with 3 instars, cotton plugs were added. Eight days after the inoculation, the number of live and dead insects was investigated, the mortality was calculated by the following formula, and the judgment was made according to the judgment criteria.
試験は25℃の恒温室内で行った。 The test was performed in a constant temperature room at 25 ° C.
判定基準 Ａ…死虫率90％以上。 Criteria A: Death rate of 90% or more.
Ｂ…死虫率70〜90％未満。 B: The mortality rate is less than 70 to 90%.
Ｃ…死虫率50〜70％未満。 C: Death rate is less than 50 to 70%.
Ｄ…死虫率50％未満。 D: Death rate is less than 50%.
結果を第４表に示す。 The results are shown in Table 4.
試験例2. オンシツコナジラミ殺虫試験。 Test Example 2. Test for insect lice on whitefly.
本発明化合物を有効成分とする薬剤の100ppmの濃度の
薬液にトマト小葉（品種：ポンテローザ）を30秒間浸漬
した。風乾後、葉柄部を湿潤させた脱脂綿でくるみ、ガ
ラス円筒（直径5cm×高さ20cm）に入れた。オンシツコ
ナジラミ（Trialeurodes vaporariorum）成虫を各10頭
放飼し、円筒上部をガーゼで蓋をした。放飼７日後に生
死を調査し、試験例１に準じて死虫率を算出し、判定を
行った。Tomato leaflets (variety: Ponterosa) were immersed in a drug solution having a concentration of 100 ppm of a drug containing the compound of the present invention as an active ingredient for 30 seconds. After air-drying, the petiole was wrapped with moist absorbent cotton and placed in a glass cylinder (5 cm in diameter × 20 cm in height). Ten adult whitefly (Trialeurodes vaporariorum) adults were released each, and the upper part of the cylinder was covered with gauze. Seven days after release, the animals were examined for life and death, and the mortality was calculated according to Test Example 1 to make a judgment.
試験は25℃の恒温室で行った。 The test was performed in a constant temperature room at 25 ° C.
結果を第５表に示す。 The results are shown in Table 5.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ０７Ｄ 231/18 Ｃ０７Ｄ 231/18 231/20 231/20 Ｚ 231/22 231/22 Ｚ 231/38 231/38 Ｚ 231/54 231/54 (72)発明者 西松 哲義 大阪府河内長野市南花台３―３―24― 502 (72)発明者 児玉 洋 大阪府河内長野市南花台３―３―21― 404 (56)参考文献 特開 平１−110674（ＪＰ，Ａ) 特開 昭63−253068（ＪＰ，Ａ) 特開 昭62−４（ＪＰ，Ａ) 米国特許4545806（ＵＳ，Ａ) 欧州公開162224（ＥＰ，Ａ１) (58)調査した分野(Int.Cl.6，ＤＢ名) C07D 231/12 - 231/54 A01N 43/56 ＣＡ（ＳＴＮ)──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification code FI C07D 231/18 C07D 231/18 231/20 231/20 Z 231/22 231/22 Z 231/38 231/38 Z 231/54 231/54 (72) Inventor Tetsuyoshi Nishimatsu 3-3-24-502 (72) Inventor Hiroshi Kodama 3-3-21- 404 (56) References Minamihanadai, Kawachinagano City, Osaka Prefecture JP-A 1-110674 (JP, A) JP-A 63-253068 (JP, A) JP-A 62-4 (JP, A) US Patent 4,545,806 (US, A) European Patent Publication 162224 (EP, A1) ( 58) Fields surveyed (Int.Cl. 6 , DB name) C07D 231/12-231/54 A01N 43/56 CA (STN)
Claims (11)
ｎ−ブチル基、ｉ−ブチル基、ｓ−ブチル基を示し、
R2′は水素原子、ハロゲン原子、炭素原子数１〜５のア
ルキル基を示し、R3′はハロゲン原子、炭素原子数１〜
５のアルキル基、炭素原子数１〜５のアルコキシ基炭素
原子数１〜５のアルキルチオ基、炭素原子数１〜５のア
ルキルスルフィニル基、炭素原子数１〜５のアルキルス
ルホニル基又は−Ｎ（R7′）R8′（式中、R7′及びR8′
は同一若しくは異なっても良く、水素原子又は炭素原子
数１〜３のアルキル基を示し、R7′及びR8′は４〜６の
メチレン基で結合されても良い。）を示し、R4′は水素
原子、炭素原子数１〜５のアルキル基又は炭素原子数２
〜５のアルコキシカルボニル基を示し、R5′は水酸基、
フェニルカルボニルオキシ基又は同一若しくは異なって
も良く、ハロゲン原子、炭素原子数１〜３のアルキル基
若しくは炭素原子数１〜３のアルコキシ基から選択され
る１〜５個の置換基をフェニル環上に有するフェニルカ
ルボニルオキシ基を示し、R6′は炭素原子数１〜５のア
ルキル基、炭素原子数３〜６のシクロアルキル基又は炭
素原子数１〜３のアルキル基により置換されたシクロア
ルキル基を示す。 但し、R1′がエチル基を、R2′がメチル基を、R3′がハ
ロゲン原子又はメチルチオ基を、R4′が水素原子を及び
R5′が水酸基を同時に示す場合、R6′はエチル基又はｎ
−プロピル基以外の置換基を示す。］ で表されるシクロへキサン誘導体又はその塩類。1. A compound of the general formula (IA) [Wherein R 1 ′ is a hydrogen atom, an ethyl group, an n-propyl group,
represents an n-butyl group, an i-butyl group, an s-butyl group,
R 2 ′ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 5 carbon atoms, and R 3 ′ represents a halogen atom, a 1 to 5 carbon atoms.
An alkyl group having 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkylthio group having 1 to 5 carbon atoms, an alkylsulfinyl group having 1 to 5 carbon atoms, an alkylsulfonyl group having 1 to 5 carbon atoms, or -N (R 7 ′) R 8 ′ (wherein, R 7 ′ and R 8 ′
May be the same or different and represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R 7 ′ and R 8 ′ may be bonded by a 4 to 6 methylene group. ) Wherein R 4 ′ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or 2 carbon atoms.
And R 5 ′ represents a hydroxyl group,
A phenylcarbonyloxy group or 1 to 5 substituents selected from a halogen atom, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms which may be the same or different, R 6 ′ represents an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms or a cycloalkyl group substituted by an alkyl group having 1 to 3 carbon atoms. Show. However, R 1 ′ is an ethyl group, R 2 ′ is a methyl group, R 3 ′ is a halogen atom or a methylthio group, R 4 ′ is a hydrogen atom and
When R 5 ′ simultaneously represents a hydroxyl group, R 6 ′ is an ethyl group or n
-Represents a substituent other than a propyl group. ] The cyclohexane derivative represented by these, or its salt.
し、R2′が水素原子、ハロゲン原子、炭素原子数１〜５
のアルキル基を示し、R3′が炭素原子数１〜５のアルキ
ル基、炭素原子数１〜５のアルキルチオ基、炭素原子数
１〜５のアルキルスルフィニル基、炭素原子数１〜５の
アルキルスルホニル基又は−Ｎ（R7′）R8′（式中、
R7′及びR8′は同一若しくは異なっても良く、水素原子
又は炭素原子数１〜３のアルキル基を示す。）を示し、
R4′が水素原子を示し、R5′が水酸基を示し、R6′が炭
素原子数１〜５のアルキル基、炭素原子数３〜６のシク
ロアルキル基又は炭素原子数１〜３のアルキル基により
置換されたシクロアルキル基を示すが、但し、R1′がエ
チル基を、R2′がメチル基を、R3′がメチルチオ基を、
R4′が水素原子を、R5′が水酸基を同時に示す場合、
R6′はエチル基又はｎ−プロピル基以外の置換基を示
す、請求項第１項記載のシクロヘキサン誘導体又はその
塩類。2. R 1 ′ represents an ethyl group or an n-propyl group, and R 2 ′ represents a hydrogen atom, a halogen atom or a C 1 to C 5 atom.
Wherein R 3 ′ is an alkyl group having 1 to 5 carbon atoms, an alkylthio group having 1 to 5 carbon atoms, an alkylsulfinyl group having 1 to 5 carbon atoms, and an alkylsulfonyl having 1 to 5 carbon atoms. A group or —N (R 7 ′) R 8 ′ (wherein
R 7 ′ and R 8 ′ may be the same or different and represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ),
R 4 ′ represents a hydrogen atom, R 5 ′ represents a hydroxyl group, and R 6 ′ represents an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms or an alkyl having 1 to 3 carbon atoms. A cycloalkyl group substituted by a group, provided that R 1 ′ represents an ethyl group, R 2 ′ represents a methyl group, R 3 ′ represents a methylthio group,
When R 4 ′ represents a hydrogen atom and R 5 ′ represents a hydroxyl group at the same time,
R 6 'represents a substituent other than an ethyl group or n- propyl group, claim cyclohexane derivative or its salt as set forth in claim 1, wherein.
ｎ−ブチル基、ｉ−ブチル基、ｓ−ブチル基を示し、
R2′は水素原子、ハロゲン原子、炭素原子数１〜５のア
ルキル基を示し、R3′はハロゲン原子、炭素原子数１〜
５のアルキル基、炭素原子数１〜５のアルコキシ基、炭
素原子数１〜５のアルキルチオ基、炭素原子数１〜５の
アルキルスルフィニル基、炭素原子数１〜５のアルキル
スルホニル基又は−Ｎ（R7′）R8′（式中、R7′及び
R8′は同一若しくは異なっても良く、水素原子又は炭素
原子数１〜３のアルキル基を示し、R7′及びR8′は４〜
６のメチレン基で結合されても良い。）を示し、R4′は
水素原子、炭素原子数１〜５のアルキル基又は炭素原子
数２〜５のアルコキシカルボニル基を示し、R6′は炭素
原子数１〜５のアルキル基、炭素原子数３〜６のシクロ
アルキル基又は炭素原子数１〜３のアルキル基により置
換されたシクロアルキル基を示す。 但し、R1′がエチル基を、R2′がメチル基を、R3′がハ
ロゲン原子又はメチルチオ基を及びR4′が水素原子を同
時に示す場合、R6′はエチル基又はｎ−プロピル基以外
の置換基を示す。］で表されるシクロへキサン類を触媒
の存在下に転位反応することを特徴とする一般式（I
A′） （式中、R1′、R2′、R3′、R4′及びR6′は前記に同
じ。） で表わされるシクロヘキサン誘導体又はその塩類の製造
方法。3. A compound of the general formula (IIA) [Wherein R 1 ′ is a hydrogen atom, an ethyl group, an n-propyl group,
represents an n-butyl group, an i-butyl group, an s-butyl group,
R 2 ′ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 5 carbon atoms, and R 3 ′ represents a halogen atom, a 1 to 5 carbon atoms.
5 alkyl groups, 1 to 5 carbon atom alkoxy groups, 1 to 5 carbon atom alkylthio groups, 1 to 5 carbon atom alkylsulfinyl groups, 1 to 5 carbon atom alkylsulfonyl groups, or -N ( R 7 ′) R 8 ′ (where R 7 ′ and
R 8 ′ may be the same or different and represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R 7 ′ and R 8 ′ are 4 to
And 6 may be linked by a methylene group. R 4 ′ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkoxycarbonyl group having 2 to 5 carbon atoms, and R 6 ′ represents an alkyl group having 1 to 5 carbon atoms, a carbon atom. And a cycloalkyl group substituted by a cycloalkyl group having 3 to 6 carbon atoms or an alkyl group having 1 to 3 carbon atoms. However, when R 1 ′ represents an ethyl group, R 2 ′ represents a methyl group, R 3 ′ represents a halogen atom or a methylthio group and R 4 ′ represents a hydrogen atom, R 6 ′ represents an ethyl group or n-propyl. A substituent other than a group. Wherein a cyclohexane represented by the general formula (I) is subjected to a rearrangement reaction in the presence of a catalyst.
A ') (Wherein R 1 ′, R 2 ′, R 3 ′, R 4 ′ and R 6 ′ are the same as described above) or a salt thereof.
基、炭素原子数１〜５のハロアルキル基、炭素原子数２
〜５のアルケニル基、炭素原子数２〜５のアルコキシア
ルキル基、フェニル基、同一若しくは異なっても良＜、
ハロゲン原子、炭素原子数１〜３のアルキル基若しくは
炭素原子数１〜３のアルコキシ基から選択される１〜５
個の置換基を有するフェニル基、ベンジル基又は同一若
しくは異なっても良く、ハロゲン原子、炭素原子数１〜
３のアルキル基若しくは炭素原子数１〜３のアルコキシ
基から選択される１〜５個の置換基を有するベンジル基
を示し、R2は水素原子、ハロゲン原子、炭素原子数１〜
５のアルキル基、炭素原子数１〜５のハロアルキル基、
フェニル基又は同一若しくは異なっても良く、ハロゲン
原子、炭素原子数１〜３のアルキル基若しくは炭素原子
数１〜３のアルコキシ基から選択される１〜５個の置換
基を有するフェニル基を示し、R3は水素原子、ハロゲン
原子、炭素原子数１〜５のアルキル基、炭素原子数１〜
５のハロアルキル基、炭素原子数１〜５のアルコキシ
基、炭素原子数１〜５のハロアルコキシ基、炭素原子数
１〜５のアルキルチオ基、炭素原子数１〜５のハロアル
キルチオ基、炭素原子数１〜５のアルキルスルフィニル
基、炭素原子数１〜５のハロアルキルスルフィニル基、
炭素原子数１〜５のアルキルスルホニル基、炭素原子数
１〜５のハロアルキルスルホニル基、フェノキシ基、同
一若しくは異なっても良く、ハロゲン原子、炭素原子数
１〜３のアルキル基若しくは炭素原子数１〜３のアルコ
キシ基から選択される１〜５個の置換基を有するフェノ
キシ基、フェニルチオ基、同一若しくは異なっても良
く、ハロゲン原子、炭素原子数１〜３のアルキル基若し
くは炭素原子数１〜３のアルコキシ基から選択される１
〜５個の置換基を有するフェニルチオ基、−Ｎ（R7）R8
（式中、R7及びR8は同一若しくは異なっても良く、水素
原子又は炭素原子数１〜３のアルキル基を示し、R7及び
R8は４〜６のメチレン基で結合されても良い。）又は炭
素原子数２〜５のアルキルカルボニルオキシ基を示し、
R2及びR3は一緒になって炭素原子数２〜５のメチレン基
を示すこともできる。R4は水素原子、炭素原子数１〜５
のアルキル基又は炭素原子数２〜５のアルコキシカルボ
ニル基を示し、R5は水酸基、ハロゲン原子、炭素原子数
１〜５のアルキルチオ基、炭素原子数１〜５のアルケニ
ルチオ基、−Ｎ（R9）R10（式中、R9及びR10は同一若し
くは異なっても良く、水素原子、炭素原子数１〜３のア
ルキル基又は炭素原子数１〜３のアルケニル基を示
す。）、炭素原子数２〜８のアルキルカルボニルオキシ
基、シクロアルキルの炭素原子数が３〜６のシクロアル
キルカルボニルオキシ基、フェニルカルボニルオキシ基
又は同一若しくは異なっても良く、ハロゲン原子、炭素
原子数１〜３のアルキル基若しくは炭素原子数１〜３の
アルコキシ基から選択される１〜５個の置換基をフェニ
ル環上に有するフェニルカルボニルオキシ基を示し、R6
は炭素原子数１〜18のアルキル基、炭素原子数３〜６の
シクロアルキル基、同一又は異なっても良く、ハロゲン
原子若しくは炭素原子数１〜３のアルキル基により置換
されたシクロアルキル基、炭素原子数２〜17のアルケニ
ル基、炭素原子数２〜８のアルコキシアルキル基、炭素
原子数２〜８のアルキルチオアルキル基、フェノキシア
ルキル基又は同一若しくは異なっても良く、ハロゲン原
子、炭素原子数１〜３のアルキル基若しくは炭素原子数
１〜３のアルコキシ基から選択される１〜５個の置換基
をフェニル環上に有するフェノキシアルキル基を示
す。］で表されるシクロへキサン誘導体又はその塩類を
有効成分として含有することを特徴とする殺虫剤。4. The formula (IB) [Wherein, R 1 represents a hydrogen atom, an alkyl group having 1 to 16 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms, and 2 carbon atoms.
5 to 5 alkenyl groups, C 2 to C 5 alkoxyalkyl groups, phenyl groups, which may be the same or different.
1 to 5 selected from a halogen atom, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms
Phenyl group having two substituents, a benzyl group or the same or different, a halogen atom, a carbon atom number of 1 to
A benzyl group having 1 to 5 substituents selected from an alkyl group of 3 or an alkoxy group of 1 to 3 carbon atoms, wherein R 2 is a hydrogen atom, a halogen atom,
5 alkyl groups, haloalkyl groups having 1 to 5 carbon atoms,
A phenyl group or a phenyl group having the same or different and having 1 to 5 substituents selected from a halogen atom, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, R 3 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms,
5 haloalkyl group, C1-5 alkoxy group, C1-5 haloalkoxy group, C1-5 alkylthio group, C1-5 haloalkylthio group, carbon atom number An alkylsulfinyl group having 1 to 5 carbon atoms, a haloalkylsulfinyl group having 1 to 5 carbon atoms,
An alkylsulfonyl group having 1 to 5 carbon atoms, a haloalkylsulfonyl group having 1 to 5 carbon atoms, a phenoxy group, which may be the same or different, a halogen atom, an alkyl group having 1 to 3 carbon atoms or 1 to carbon atoms. A phenoxy group having 1 to 5 substituents selected from 3 alkoxy groups, a phenylthio group, which may be the same or different, a halogen atom, an alkyl group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms. 1 selected from an alkoxy group
Phenylthio group having 5 substituents, -N (R 7) R 8
(Wherein, R 7 and R 8 may be the same or different, represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R 7 and
R 8 may be linked by 4 to 6 methylene groups. ) Or an alkylcarbonyloxy group having 2 to 5 carbon atoms,
R 2 and R 3 may together represent a methylene group having 2 to 5 carbon atoms. R 4 is a hydrogen atom, having 1 to 5 carbon atoms
R 5 is a hydroxyl group, a halogen atom, an alkylthio group having 1 to 5 carbon atoms, an alkenylthio group having 1 to 5 carbon atoms, -N (R 9 ) R 10 (wherein, R 9 and R 10 may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or an alkenyl group having 1 to 3 carbon atoms), a carbon atom An alkylcarbonyloxy group having 2 to 8 carbon atoms, a cycloalkylcarbonyloxy group having 3 to 6 carbon atoms of cycloalkyl, a phenylcarbonyloxy group, or a halogen atom, an alkyl having 1 to 3 carbon atoms which may be the same or different. the group or 1-5 substituents selected from alkoxy groups having 1 to 3 carbon atoms a phenyl carbonyl group having on the phenyl ring, R 6
Is an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a cycloalkyl group which may be the same or different and is substituted by a halogen atom or an alkyl group having 1 to 3 carbon atoms, An alkenyl group having 2 to 17 atoms, an alkoxyalkyl group having 2 to 8 carbon atoms, an alkylthioalkyl group having 2 to 8 carbon atoms, a phenoxyalkyl group or may be the same or different, a halogen atom, A phenoxyalkyl group having 1 to 5 substituents selected from an alkyl group of 3 or an alkoxy group having 1 to 3 carbon atoms on a phenyl ring. ] The insecticide which contains the cyclohexane derivative represented by these, or its salts as an active ingredient.
〜５のアルキル基、炭素原子数１〜５のハロアルキル基
又は炭素原子数２〜５のアルケニル基を示し、R2が水素
原子、ハロゲン原子、炭素原子数１〜５のアルキル基又
は炭素原子数１〜５のハロアルキル基を示し、R3が炭素
原子数１〜５のアルキル基、炭素原子数１〜５のアルコ
キシ基、炭素原子数１〜５のアルキルチオ基、炭素原子
数１〜５のハロアルキルチオ基、炭素原子数１〜５のア
ルキルスルフィニル基、炭素原子数１〜５のアルキルス
ルホニル基又は−Ｎ（R7）R8（式中、R7及びR8は同一若
しくは異なっても良く、水素原子又は炭素原子数１〜３
のアルキル基を示す。）を示し、R4が水素原子を示し、
R5が水酸基を示し、R6が炭素原子数１〜５のアルキル
基、炭素原子数３〜６のシクロアルキル基又は同一又は
異なっても良く、ハロゲン原子若しくは炭素原子数１〜
３のアルキル基により置換されたシクロアルキル基を示
すシクロへキサン誘導体又はその塩類を有効成分として
含有する請求項第４項記載の殺虫剤。5. In the general formula (I), R 1 has 1 carbon atom.
Represents an alkyl group having 1 to 5 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and R 2 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms or a carbon atom number. 1 to 5 haloalkyl groups, wherein R 3 is an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkylthio group having 1 to 5 carbon atoms, and a halo having 1 to 5 carbon atoms. An alkylthio group, an alkylsulfinyl group having 1 to 5 carbon atoms, an alkylsulfonyl group having 1 to 5 carbon atoms or —N (R 7 ) R 8 (wherein R 7 and R 8 may be the same or different, Hydrogen atom or carbon atom number 1-3
Represents an alkyl group. ), R 4 represents a hydrogen atom,
R 5 represents a hydroxyl group, R 6 is an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms or may be the same or different, and is a halogen atom or a carbon atom having 1 to 5 carbon atoms.
5. The insecticide according to claim 4, wherein the insecticide comprises a cyclohexane derivative or a salt thereof, which represents a cycloalkyl group substituted by the alkyl group of No. 3 as an active ingredient.
〜５のアルキル基を示し、R2が炭素原子数Ｉ〜５のアル
キル基を示し、R3が炭素原子数１〜５のアルキル基、炭
素原子数１〜５のアルキルチオ基、炭素原子数１〜５の
アルキルスルフィニル基又は−Ｎ（R7）R8（式中、R7及
びR8は同一若しくは異なっても良く、水素原子又は炭素
原子数１〜３のアルキル基又は炭素原子数１〜３のアル
ケニル基を示す。）を示し、R4が水素原子を示し、R5が
水酸基を示し、R6が、炭素原子数３〜６のシクロアルキ
ル基を示すシクロへキサン誘導体又はその塩類を有効成
分として含有する請求項第５項記載の殺虫剤。6. In the general formula (I), R 1 has 1 carbon atom.
Indicates 5 alkyl group, R 2 represents an alkyl group having a carbon number I~5, R 3 is an alkyl group having 1 to 5 carbon atoms, an alkylthio group having 1 to 5 carbon atoms, carbon atoms 1 To 5 alkylsulfinyl groups or —N (R 7 ) R 8 (wherein R 7 and R 8 may be the same or different, and are a hydrogen atom or an alkyl group having 1 to 3 carbon atoms or 1 to carbon atoms. R 4 represents a hydrogen atom, R 5 represents a hydroxyl group, and R 6 represents a cyclohexane derivative or a salt thereof which represents a cycloalkyl group having 3 to 6 carbon atoms. The insecticide according to claim 5, which is contained as an active ingredient.
及び６項のいずれか１項に記載の殺虫剤。7. The method according to claim 4, wherein the insecticide is for an insect of the order Hemiptera.
And the insecticide according to any one of 6.
基、炭素原子数１〜５のハロアルキル基、炭素原子数２
〜５のアルケニル基、炭素原子数２〜５のアルコキシア
ルキル基、フェニル基、同一若しくは異なっても良く、
ハロゲン原子、炭素原子数１〜３のアルキル基若しくは
炭素原子数１〜３のアルコキシ基から選択される１〜５
個の置換基を有するフェニル基、ベンジル基又は同一若
しくは異なっても良く、ハロゲン原子、炭素原子数１〜
３のアルキル基若しくは炭素原子数１〜３のアルコキシ
基から選択される１〜５個の置換基を有するベンジル基
を示し、R2は水素原子、ハロゲン原子、炭素原子数１〜
５のアルキル基、炭素原子数１〜５のハロアルキル基、
フェニル基又は同一若しくは異なっても良く、ハロゲン
原子、炭素原子数１〜３のアルキル基若しくは炭素原子
数１〜３のアルコキシ基から選択される１〜５個の置換
基を有するフェニル基を示し、R3は水素原子、ハロゲン
原子、炭素原子数１〜５のアルキル基、炭素原子数１〜
５のハロアルキル基、炭素原子数１〜５のアルコキシ
基、炭素原子数１〜５のハロアルコキシ基、炭素原子数
１〜５のアルキルチオ基、炭素原子数１〜５のハロアル
キルチオ基、炭素原子数１〜５のアルキルスルフィニル
基、炭素原子数１〜５のハロアルキルスルフィニル基、
炭素原子数１〜５のアルキルスルホニル基、炭素原子数
１〜５のハロアルキルスルホニル基、フェノキシ基、同
一若しくは異なっても良く、ハロゲン原子、炭素原子数
１〜３のアルキル基若しくは炭素原子数１〜３のアルコ
キシ基から選択される１〜５個の置換基を有するフェノ
キシ基、フェニルチオ基、同一若しくは異なっても良
く、ハロゲン原子、炭素原子数１〜３のアルキル基若し
くは炭素原子数１〜３のアルコキシ基から選択される１
〜５個の置換基を有するフェニルチオ基、−Ｎ（R7）R8
（式中、R7及びR8は同一若しくは異なっても良く、水素
原子又は炭素原子数１〜３のアルキル基を示し、R7及び
R8は４〜６のメチレン基で結合されても良い。）又は炭
素原子数２〜５のアルキルカルボニルオキシ基を示し、
R2及びR3は一緒になって炭素原子数２〜５のメチレン基
を示すこともできる。R4は水素原子、炭素原子数１〜５
のアルキル基又は炭素原子数２〜５のアルコキシカルボ
ニル基を示し、R5は水酸基、ハロゲン原子、炭素原子数
１〜５のアルキルチオ基、炭素原子数１〜５のアルケニ
ルチオ基、−Ｎ（R9）R10（式中、R9及びR10は同一若し
くは異なっても良く、水素原子、炭素原子数１〜３のア
ルキル基又は炭素原子数１〜３のアルケニル基を示
す。）、炭素原子数２〜８のアルキルカルボニルオキシ
基、シクロアルキルの炭素原子数が３〜６のシクロアル
キルカルボニルオキシ基、フェニルカルボニルオキシ基
又は同一若しくは異なっても良く、ハロゲン原子、炭素
原子数１〜３のアルキル基若しくは炭素原子数１〜３の
アルコキシ基から選択される１〜５個の置換基をフェニ
ル環上に有するフェニルカルボニルオキシ基を示し、R6
は炭素原子数１〜18のアルキル基、炭素原子数３〜６の
シクロアルキル基、同一又は異なっても良く、ハロゲン
原子若しくは炭素原子数１〜３のアルキル基により置換
されたシクロアルキル基、炭素原子数２〜17のアルケニ
ル基、炭素原子数２〜８のアルコキシアルキル基、炭素
原子数２〜８のアルキルチオアルキル基、フェノキシア
ルキル基又は同一若しくは異なっても良く、ハロゲン原
子、炭素原子数１〜３のアルキル基若しくは炭素原子数
１〜３のアルコキシ基から選択される１〜５個の置換基
をフェニル環上に有するフェノキシアルキル基を示
す。］で表されるシクロヘキサン誘導体又はその塩類を
有効成分として含有する殺虫剤を、植物に対する有害虫
が発生又は発生が予測される植物又はその周辺に10アー
ル当たり有効成分量として1g〜3kgの範囲で処理するこ
とを特徴とする殺虫方法。8. The formula (IB) [Wherein, R 1 represents a hydrogen atom, an alkyl group having 1 to 16 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms, and 2 carbon atoms.
5 to 5 alkenyl groups, an alkoxyalkyl group having 2 to 5 carbon atoms, a phenyl group, which may be the same or different,
1 to 5 selected from a halogen atom, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms
Phenyl group having two substituents, a benzyl group or the same or different, a halogen atom, a carbon atom number of 1 to
A benzyl group having 1 to 5 substituents selected from an alkyl group of 3 or an alkoxy group of 1 to 3 carbon atoms, wherein R 2 is a hydrogen atom, a halogen atom,
5 alkyl groups, haloalkyl groups having 1 to 5 carbon atoms,
A phenyl group or a phenyl group having the same or different and having 1 to 5 substituents selected from a halogen atom, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, R 3 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms,
5 haloalkyl group, C1-5 alkoxy group, C1-5 haloalkoxy group, C1-5 alkylthio group, C1-5 haloalkylthio group, carbon atom number An alkylsulfinyl group having 1 to 5 carbon atoms, a haloalkylsulfinyl group having 1 to 5 carbon atoms,
An alkylsulfonyl group having 1 to 5 carbon atoms, a haloalkylsulfonyl group having 1 to 5 carbon atoms, a phenoxy group, which may be the same or different, a halogen atom, an alkyl group having 1 to 3 carbon atoms or 1 to carbon atoms. A phenoxy group having 1 to 5 substituents selected from 3 alkoxy groups, a phenylthio group, which may be the same or different, a halogen atom, an alkyl group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms. 1 selected from an alkoxy group
Phenylthio group having 5 substituents, -N (R 7) R 8
(Wherein, R 7 and R 8 may be the same or different, represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R 7 and
R 8 may be linked by 4 to 6 methylene groups. ) Or an alkylcarbonyloxy group having 2 to 5 carbon atoms,
R 2 and R 3 may together represent a methylene group having 2 to 5 carbon atoms. R 4 is a hydrogen atom, having 1 to 5 carbon atoms
R 5 is a hydroxyl group, a halogen atom, an alkylthio group having 1 to 5 carbon atoms, an alkenylthio group having 1 to 5 carbon atoms, -N (R 9 ) R 10 (wherein, R 9 and R 10 may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or an alkenyl group having 1 to 3 carbon atoms), a carbon atom An alkylcarbonyloxy group having 2 to 8 carbon atoms, a cycloalkylcarbonyloxy group having 3 to 6 carbon atoms of cycloalkyl, a phenylcarbonyloxy group, or a halogen atom, an alkyl having 1 to 3 carbon atoms which may be the same or different. the group or 1-5 substituents selected from alkoxy groups having 1 to 3 carbon atoms a phenyl carbonyl group having on the phenyl ring, R 6
Is an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a cycloalkyl group which may be the same or different and is substituted by a halogen atom or an alkyl group having 1 to 3 carbon atoms, An alkenyl group having 2 to 17 atoms, an alkoxyalkyl group having 2 to 8 carbon atoms, an alkylthioalkyl group having 2 to 8 carbon atoms, a phenoxyalkyl group or may be the same or different, a halogen atom, A phenoxyalkyl group having 1 to 5 substituents selected from an alkyl group of 3 or an alkoxy group having 1 to 3 carbon atoms on a phenyl ring. An insecticide containing, as an active ingredient, a cyclohexane derivative represented by the formula (1), or a salt thereof, as an active ingredient in a range of 1 g to 3 kg as an active ingredient per 10 ares in or around a plant in which pests are generated or predicted to be generated. An insecticidal method characterized by treating.
〜５のアルキル基、炭素原子数１〜５のハロアルキル基
又は炭素原子数２〜５のアルケニル基を示し、R2が水素
原子、ハロゲン原子、炭素原子数１〜５のアルキル基又
は炭素原子数１〜５のハロアルキル基を示し、R3が炭素
原子数１〜５のアルキル基、炭素原子数１〜５のアルコ
キシ基、炭素原子数１〜５のアルキルチオ基、炭素原子
数１〜５のハロアルキルチオ基、炭素原子数１〜５のア
ルキルスルフィニル基、炭素原子数１〜５のアルキルス
ルホニル基又は−Ｎ（R7）R8（式中、R7及びR8は同一若
しくは異なっても良く、水素原子又は炭素原子数１〜３
のアルキル基を示す。）を示し、R4が水素原子を示し、
R5が水酸基を示し、R6が炭素原子数１〜５のアルキル
基、炭素原子数３〜６のシクロアルキル基又は同一又は
異なっても良く、ハロゲン原子若しくは炭素原子数１〜
３のアルキル基により置換されたシクロアルキル基を示
すシクロへキサン誘導体又はその塩類を有効成分として
含有する殺虫剤を植物に対する有害虫が発生又は発生が
予測される植物又はその周辺に10アール当たり有効成分
量として1g〜3kgの範囲で処理することを特徴とする請
求項第８項記載の殺虫方法。9. In the general formula (I), R 1 has 1 carbon atom
Represents an alkyl group having 1 to 5 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and R 2 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms or a carbon atom number. 1 to 5 haloalkyl groups, wherein R 3 is an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkylthio group having 1 to 5 carbon atoms, and a halo having 1 to 5 carbon atoms. An alkylthio group, an alkylsulfinyl group having 1 to 5 carbon atoms, an alkylsulfonyl group having 1 to 5 carbon atoms or —N (R 7 ) R 8 (wherein R 7 and R 8 may be the same or different, Hydrogen atom or carbon atom number 1-3
Represents an alkyl group. ), R 4 represents a hydrogen atom,
R 5 represents a hydroxyl group, R 6 is an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms or may be the same or different, and is a halogen atom or a carbon atom having 1 to 5 carbon atoms.
An insecticide containing, as an active ingredient, a cyclohexane derivative showing a cycloalkyl group substituted by an alkyl group of No. 3 or a salt thereof is effective per 10 ares on or around a plant in which pests are generated or predicted to be generated. 9. The insecticidal method according to claim 8, wherein the treatment is carried out in an amount of 1 g to 3 kg as an ingredient.
１〜５のアルキル基を示し、R2が炭素原子数１〜５のア
ルキル基を示し、R3が炭素原子数１〜５のアルキル基、
炭素原子数１〜５のアルキルチオ基、炭素原子数１〜５
のアルキルスルフィニル基又は−Ｎ（R7）R8（式中、R7
及びR8は同一若しくは異なっても良く、水素原子又は炭
素原子数１〜３のアルキル基を示す。）を示し、R4が水
素原子を示し、R5が水酸基を示し、R6が炭素原子数３〜
６のシクロアルキル基を示すシクロへキサン誘導体又は
その塩類を有効成分として含有する殺虫剤を植物に対す
る有害虫が発生又は発生が予測される植物又はその周辺
に10アール当たり有効成分量として1g〜3kgの範囲で処
理することを特徴とする請求項第９項記載の殺虫方法。10. In the general formula (I), R 1 represents an alkyl group having 1 to 5 carbon atoms, R 2 represents an alkyl group having 1 to 5 carbon atoms, and R 3 represents 1 to 5 carbon atoms. An alkyl group of 5,
Alkylthio group having 1 to 5 carbon atoms, 1 to 5 carbon atoms
An alkylsulfinyl group or —N (R 7 ) R 8 (wherein R 7
And R 8 may be the same or different and represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ), R 4 represents a hydrogen atom, R 5 represents a hydroxyl group, and R 6 represents 3 to 3 carbon atoms.
An insecticide containing, as an active ingredient, a cyclohexane derivative having a cycloalkyl group of 6 or a salt thereof, as an active ingredient, in an amount of 1 g to 3 kg as an active ingredient per 10 ares for a plant or its surroundings where pests are generated or predicted to be generated. The insecticidal method according to claim 9, wherein the treatment is performed within the range.
及び10項のいずれか１項記載の殺虫方法。11. The pest is a pest of the order Hemiptera.
11. The insecticidal method according to any one of items 10 and 10.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11182689 | 1989-04-28 | ||
| JP1-111826 | 1989-04-28 | ||
| JP2-93569 | 1990-04-09 | ||
| JP9356990 | 1990-04-09 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0418076A JPH0418076A (en) | 1992-01-22 |
| JP2935127B2 true JP2935127B2 (en) | 1999-08-16 |
Family
ID=26434902
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11253590A Expired - Lifetime JP2935127B2 (en) | 1989-04-28 | 1990-04-28 | Cyclohexane derivative or its salt, its production method, its use and its use |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2935127B2 (en) |
-
1990
- 1990-04-28 JP JP11253590A patent/JP2935127B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0418076A (en) | 1992-01-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR900002063B1 (en) | Pyrazole-oxime derivatives | |
| JP4136000B2 (en) | Insecticidal tetrahydrofuran compounds | |
| JP2704655B2 (en) | Tri-substituted phenylpyrazole derivatives or their salts and herbicides | |
| JP2704662B2 (en) | 3-Substituted phenylpyrazole derivatives or salts thereof and uses thereof | |
| JP4378855B2 (en) | 5- (1-Fluoroethyl) -1-methylpyrazole-4-carboxylic acid amide derivatives and pest control agents for agriculture and horticulture | |
| JP3258502B2 (en) | Insecticidal tetrahydrofuran derivative | |
| JPH08217777A (en) | 2-Pyrazolin-5-one derivatives, intermediates thereof and herbicides | |
| JP2905982B2 (en) | Heterocycle-containing phenylpyrazole derivatives or salts thereof, process for producing the same, and herbicides | |
| JPH0741471A (en) | Compounds having a basic structure of 3,4-diaryl- (5H) -furan-2-one having fungicidal activity | |
| JP2613651B2 (en) | Oxa or thiazoline compound and insecticide and acaricide containing the same | |
| JP2905981B2 (en) | 3-Substituted phenylpyrazole derivatives or salts thereof, process for producing the same, and herbicides | |
| KR20020035614A (en) | Insecticidal and acaricidal agents | |
| JP2690816B2 (en) | Quinolinyl oxadiazole herbicide | |
| JP2935127B2 (en) | Cyclohexane derivative or its salt, its production method, its use and its use | |
| EP0395422B1 (en) | Cyclohexane derivatives, its salts and uses as insecticides | |
| JP2887701B2 (en) | 3-Substituted phenylpyrazole derivatives or salts thereof and uses thereof | |
| JP3511729B2 (en) | 4- [2- (trifluoroalkoxy-substituted phenyl) ethylamino] pyrimidine derivative, its production method and pesticide for agricultural and horticultural use | |
| JPH045276A (en) | Cyclohexane derivatives or their salts and their uses | |
| US4863504A (en) | Cyclohexadione derivatives, selective herbicidal compositions as well as herbicidal method | |
| JP4038624B2 (en) | Fused heterocyclic derivatives and intermediates thereof, and pest control agents | |
| KR970002872B1 (en) | Cyclohexane derivatives, salts thereof, and preparation methods thereof | |
| JP4491913B2 (en) | 4- (1-Fluoroethyl) pyrimidine-5-carboxylic acid amide derivatives and agricultural and horticultural pest control agents | |
| JP3683004B2 (en) | Insecticidal (tetrahydro-3-furanyl) methyl derivatives | |
| JP4565286B2 (en) | 6-haloalkyl-3- (substituted amino) -1,2,4-triazin-5-one derivatives, agricultural chemicals containing this as an active ingredient, and production intermediates thereof | |
| JPH051060A (en) | 4-thienyl-oxa(thia)zoline derivative and insecticidal miticide containing the same |