CN103113318A - New etoxazole compounds, and preparation method and acarid killing activities thereof - Google Patents
New etoxazole compounds, and preparation method and acarid killing activities thereof Download PDFInfo
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- CN103113318A CN103113318A CN201310059306XA CN201310059306A CN103113318A CN 103113318 A CN103113318 A CN 103113318A CN 201310059306X A CN201310059306X A CN 201310059306XA CN 201310059306 A CN201310059306 A CN 201310059306A CN 103113318 A CN103113318 A CN 103113318A
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- 238000002360 preparation method Methods 0.000 title claims description 7
- IXSZQYVWNJNRAL-UHFFFAOYSA-N etoxazole Chemical class CCOC1=CC(C(C)(C)C)=CC=C1C1N=C(C=2C(=CC=CC=2F)F)OC1 IXSZQYVWNJNRAL-UHFFFAOYSA-N 0.000 title abstract description 4
- 230000002147 killing effect Effects 0.000 title abstract 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 31
- CRZJPEIBPQWDGJ-UHFFFAOYSA-N 2-chloro-1,1-dimethoxyethane Chemical compound COC(CCl)OC CRZJPEIBPQWDGJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000004076 pyridyl group Chemical group 0.000 claims abstract description 6
- ONOTYLMNTZNAQZ-UHFFFAOYSA-N 2,6-difluorobenzoic acid Chemical compound OC(=O)C1=C(F)C=CC=C1F ONOTYLMNTZNAQZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 26
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 11
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 230000000895 acaricidal effect Effects 0.000 claims description 7
- 239000002585 base Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 6
- 150000003851 azoles Chemical group 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 claims description 5
- KOPFEFZSAMLEHK-UHFFFAOYSA-N 1h-pyrazole-5-carboxylic acid Chemical class OC(=O)C=1C=CNN=1 KOPFEFZSAMLEHK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000642 acaricide Substances 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000006482 condensation reaction Methods 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- 241000607479 Yersinia pestis Species 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 3
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 3
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 238000007171 acid catalysis Methods 0.000 claims description 2
- 239000003377 acid catalyst Substances 0.000 claims description 2
- 150000001263 acyl chlorides Chemical class 0.000 claims description 2
- 239000002671 adjuvant Substances 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 238000005815 base catalysis Methods 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- SSVFMICWXDVRQN-UHFFFAOYSA-N ethanol;sodium Chemical compound [Na].CCO SSVFMICWXDVRQN-UHFFFAOYSA-N 0.000 claims description 2
- 150000008282 halocarbons Chemical class 0.000 claims description 2
- 230000002140 halogenating effect Effects 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 235000010755 mineral Nutrition 0.000 claims description 2
- 150000007530 organic bases Chemical class 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 239000012453 solvate Substances 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 8
- 241000344246 Tetranychus cinnabarinus Species 0.000 abstract description 4
- 235000013601 eggs Nutrition 0.000 abstract description 4
- 230000004071 biological effect Effects 0.000 abstract description 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 abstract 2
- OMGDPSKWKSSNHI-UHFFFAOYSA-N 1-tert-butyl-3-[2-[2-(3-tert-butylphenyl)ethoxy]ethyl]benzene Chemical compound CC(C)(C)C1=CC=CC(CCOCCC=2C=C(C=CC=2)C(C)(C)C)=C1 OMGDPSKWKSSNHI-UHFFFAOYSA-N 0.000 abstract 1
- KEHFXHBLTNJADN-UHFFFAOYSA-N 3-[4-(4-tert-butyl-2-methoxyphenyl)-4,5-dihydro-1,3-oxazol-2-yl]-2,4-difluoroaniline Chemical compound NC=1C(=C(C(=CC1)F)C=1OCC(N1)C1=C(C=C(C=C1)C(C)(C)C)OC)F KEHFXHBLTNJADN-UHFFFAOYSA-N 0.000 abstract 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 abstract 1
- 238000006069 Suzuki reaction reaction Methods 0.000 abstract 1
- 230000010933 acylation Effects 0.000 abstract 1
- 238000005917 acylation reaction Methods 0.000 abstract 1
- 150000001408 amides Chemical group 0.000 abstract 1
- 238000005915 ammonolysis reaction Methods 0.000 abstract 1
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 abstract 1
- 238000009833 condensation Methods 0.000 abstract 1
- 230000005494 condensation Effects 0.000 abstract 1
- 230000026030 halogenation Effects 0.000 abstract 1
- 238000005658 halogenation reaction Methods 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- 238000010189 synthetic method Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 102000002322 Egg Proteins Human genes 0.000 description 4
- 108010000912 Egg Proteins Proteins 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- 239000004327 boric acid Substances 0.000 description 4
- 210000004681 ovum Anatomy 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000005897 Etoxazole Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 229920000136 polysorbate Polymers 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- DTQJMAHDNUWGFH-UHFFFAOYSA-N 2,4-diphenyl-4,5-dihydro-1,3-oxazole Chemical class C1OC(C=2C=CC=CC=2)=NC1C1=CC=CC=C1 DTQJMAHDNUWGFH-UHFFFAOYSA-N 0.000 description 1
- MXIUWSYTQJLIKE-UHFFFAOYSA-N 2-(trifluoromethyl)benzoyl chloride Chemical compound FC(F)(F)C1=CC=CC=C1C(Cl)=O MXIUWSYTQJLIKE-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 241000238876 Acari Species 0.000 description 1
- 241000256844 Apis mellifera Species 0.000 description 1
- 241000239290 Araneae Species 0.000 description 1
- IEGLIYXDCJXANV-UHFFFAOYSA-N CCOc1c(C2N=C(c(c(F)c(cc3)I)c3F)OC2)ccc(C)c1 Chemical compound CCOc1c(C2N=C(c(c(F)c(cc3)I)c3F)OC2)ccc(C)c1 IEGLIYXDCJXANV-UHFFFAOYSA-N 0.000 description 1
- 0 CCOc1cc([*-])ccc1C1N=C(c(c(*2)c(cc3)-c4c2c(F)ncc4)c3F)OC1 Chemical compound CCOc1cc([*-])ccc1C1N=C(c(c(*2)c(cc3)-c4c2c(F)ncc4)c3F)OC1 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 description 1
- 241001672694 Citrus reticulata Species 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 241000220324 Pyrus Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 241001454294 Tetranychus Species 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- 235000010749 Vicia faba Nutrition 0.000 description 1
- 240000006677 Vicia faba Species 0.000 description 1
- 235000002098 Vicia faba var. major Nutrition 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000008431 aliphatic amides Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000008430 aromatic amides Chemical class 0.000 description 1
- 150000007980 azole derivatives Chemical class 0.000 description 1
- 230000003570 biosynthesizing effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000003810 ethyl acetate extraction Methods 0.000 description 1
- GFAUNYMRSKVDJL-UHFFFAOYSA-N formyl chloride Chemical compound ClC=O GFAUNYMRSKVDJL-UHFFFAOYSA-N 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 230000012447 hatching Effects 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 230000000974 larvacidal effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 210000001161 mammalian embryo Anatomy 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- 230000001537 neural effect Effects 0.000 description 1
- 231100000194 ovacidal Toxicity 0.000 description 1
- 230000003151 ovacidal effect Effects 0.000 description 1
- 235000021017 pears Nutrition 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 1
- IBBMAWULFFBRKK-UHFFFAOYSA-N picolinamide Chemical compound NC(=O)C1=CC=CC=N1 IBBMAWULFFBRKK-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
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- 238000010992 reflux Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 238000003107 structure activity relationship analysis Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
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- Plural Heterocyclic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention relates to new etoxazole compounds of the same category and a synthetic method and biological activities thereof. The structure of the compounds provided by the invention is shown in a structural formula I in the specification. The compound containing an amide fragment takes 2-(3-amino-2,6-difluorophenyl)-4-(2-methoxy-4-tert-butylphenyl) oxazoline as a key intermediate and other derivatives are prepared by taking 2,6-difluorobenzoic acid as a starting material and carrying out halogenation, acylation, ammonolysis, condensation with chloroacetaldehyde dimethyl acetal, Friedel-Crafts reaction with 3-tert-butylphenylethylether, cyclization and Suzuki coupling reaction with organic boronic acid. With eggs of tetranychus cinnabarinus as tested targets, the biological activities of the related compounds are tested and the results show that most of the compounds have good egg killing activities. In the formula I, R is substituted phenyl, substituted pyridyl and R1CONH-; and R1 is substituted phenyl, substituted pyridyl, C1-6 alkyl and halogenated C1-6 alkyl.
Description
Technical field
The present invention relates to the chemistry of pesticide field, relate to specifically a class and carry out the second mite azole derivative of structure of modification, the method for preparing these compounds and their acaricidal activity on 2 phenyl.
Technical background
Second mite azoles is the miticide (WO93/22297) of a kind of tool special construction of SUMITOMO CHEMICAL KCC research and development, Universal Chinese character is called second mite azoles, English general etoxazole by name, chemistry (the RS)-5-tertiary butyl-2-[2-(2 by name, the 6-difluorophenyl)-4,5-dihydro-1,3-oxazole-4-yl] phenetole.Second mite azoles has very high ovicidal, larvicidal activity to various tetranychids such as vegetables tetranychid, citrus reticulata leaf spiders, apple tetranychus, pears tetranychids.This medicament quick-acting is poor, but long-lasting is long, to the people, animal low toxicity, and to honeybee and natural enemies security, can be mixed with multiple Insecticidal and acaricidal agent.
Nauen etc. have reported the mode of action (Nauen R, Smagghe G.Mode of action of etoxazole.Pest Manag.Sci.2006,62, the 379-382 of second mite azoles in 2006; Dekeyser M.A.Acaricide mode of action.Pest Manag.Sci.2005,67,103-110), the mechanism of action of second mite azoles is the chitinous biosynthesizing that suppresses in insect body, with embryo's formation and the process of casting off a skin from young mite to the one-tenth mite of controlling the mite ovum, be different from traditional acaricidal respiration inhibition and neural poison fully and wait binding mode, therefore developing this type of miticide will have broad application prospects.
The inventor is on the basis of previous work (CN201210162589.6), make two kinds of suppositions by the structure activity relationship analysis: import on 2 phenyl ring of (1) 2,4-diphenyl oxazoline compounds amide group may make the LogP of compound surpassed just when and unfavorable to activity; Importing the picolinamide base on 2 phenyl ring of (2) 2,4-diphenyl oxazoline compounds may be unfavorable to activity because pyridine rolls into a ball as strong electron-withdrawing group.Upper analysis according to this, the inventor has designed on 2 phenyl ring and directly to have imported phenyl ring or the pyridine ring with structure rigidity and hydrophobic character, and on 2 phenyl ring with aromatic amides base, aliphatic amide base or based on the new compound of the pyrazole heterocycle amide group of principle of hybridization.
Summary of the invention
First purpose of the present invention is to provide a kind of second mite azole new compound with following general structural formula.Second purpose of the present invention is to provide a kind of method for preparing above-claimed cpd; The 3rd purpose of the present invention is the acaricidal activity of open above-claimed cpd.
The R=substituted-phenyl, substituted pyridinyl, R
1CONH-
R
1=substituted-phenyl, substituted pyrazolecarboxylic base, C
1-6Alkyl, halo C
1-6Alkyl
Structural formula I
Compound involved in the present invention can be take following particular compound as example.
Have general structure I in compound involved in the present invention, wherein, the preparation method of the compound of R=substituted-phenyl, substituted pyridinyl is as follows:
Halogenating reaction occurs and obtains intermediate A in (1) 2,6-difluoro-benzoic acid and halogen simple substance in acetate solvate, said halogen simple substance is bromine or iodine, and the mol ratio of 2,6-difluoro-benzoic acid and halogen simple substance is 1: 0.9～3;
Intermediate A and sulfur oxychloride obtain intermediate B at organic solvent or without the solvent reacting by heating, said solvent is a kind of in benzene, toluene, methylene dichloride, ethylene dichloride, suitable temperature of reaction is 20～120 ℃, and the mol ratio of intermediate A and sulfur oxychloride is 1: 1.1～5;
Pass into ammonia gas react in the solution of intermediate B and obtain intermediate C, said solvent is a kind of in benzene, toluene, methylene dichloride, chloroform, tetrahydrofuran (THF), ammonia with for the mol ratio of B is 0.8～2: 1, suitable temperature of reaction is-20～10 ℃;
Condensation reaction occurs and obtains D in C and monochloroacetaldehyde dimethyl acetal under acid catalysis, said catalyzer is a kind of in trifluoromethanesulfonic acid, tosic acid, the vitriol oil, the mol ratio of C and monochloroacetaldehyde dimethyl acetal and acid catalyst is 1: 0.9～3.0: 0.75～1.5, and suitable temperature of reaction is 10～80 ℃;
(2) in the mixture of D and a kind of solvent, add successively aluminum chloride and between the tert.-butylbenzene diethyl ether solution, obtain E, said solvent is a kind of in methylene dichloride, ethylene dichloride, chloroform, tetracol phenixin, the mol ratio of D and aluminum chloride, a tert.-butylbenzene ether is 1: 0.9～2.0: 0.9: 2.0, and suitable temperature of reaction is 0～50 ℃;
(3) ring closure reaction occurs and obtains F in E under base catalysis, and said alkaline catalysts is solid sodium ethanol, solid sodium hydroxide or triethylamine, and the mol ratio of E and catalyzer is 1: 0.9～2, and suitable temperature of reaction is 0～70 ℃;
(4) the Suzuki linked reaction occurs in F and organic boronic under Pd catalyzer and promoter effect, obtain target product I-1～I-10, said catalyzer is a kind of in tetra-triphenylphosphine palladium, palladium, catalyst adjuvant is triethylamine, the mol ratio of F and organic boronic and catalyzer is 1: 0.9～2.0: 0.001～0.1, and solvent is DMF, water or mixture that both are mixed to get according to arbitrary proportion.
Have general structure I in compound involved in the present invention, wherein, R=R
1CONH-, R
1=substituted-phenyl, substituted pyrazolecarboxylic base, C
1-6Alkyl, halo C
1-6The preparation method of the compound of alkyl is as follows:
2-(3-amino-2,6-difluorophenyl)-4-(2-methoxyl group-4-tert-butyl-phenyl) oxazoline and a kind of acyl chlorides (R
1COCl) carry out in a kind of solvent, and used a kind of alkali as acid binding agent generation condensation reaction, said acid binding agent is a kind of in organic bases triethylamine, tri-n-butylamine, pyridine or mineral alkali sodium carbonate, salt of wormwood, sodium bicarbonate, saleratus; The solvent that uses is halogenated hydrocarbon solvent, aromatic hydrocarbon solvent.
Embodiment
Further illustrate preparation method and the biological activity of compound involved in the present invention below by specific examples.
Embodiment 1
Intermediate D's is synthetic:
Add 0.1mol2 in the Glacial acetic acid of 100mL, 6-difluoro-benzoic acid and iodine 0.1mol, stirring at room 24h in reactant impouring water, filter to collect filter cake, uses the methanol-water recrystallization, obtains A, yield 70%, mp:134～139 ℃.
To 0.1mol3-iodo-2, add the sulfur oxychloride of 0.3mol in the 6-difluoro-benzoic acid, under agitation temperature rising reflux 5h, reduce pressure and slough excessive sulfur oxychloride, obtains crude product 2, and 6-difluoro benzoyl chloride (B) need not be made with extra care, and adds wherein tetrahydrofuran (THF) 25mL.Mixture is cooled to-5 ℃, slowly passes into dry ammonia, to there being a large amount of crystal to separate out, stop ventilation, be cooled to-20 ℃, keep 1h, filter, collect filter cake, drying obtains C, yield: 81%, mp:162～165 ℃.
With 0.1mol3-iodo-2, the 6-difluorobenzamide mixes with 0.3mol monochloroacetaldehyde dimethyl acetal, add wherein tosic acid 0.15mol, be warming up to 60～70 ℃ of reaction 19h, be cooled to room temperature, add entry 100mL, filter and collect filter cake, appropriate methanol rinse obtains D, yield: 82%, mp:112～115 ℃.
Embodiment 2
Intermediate F's is synthetic:
Intermediate 0.1mol D with the dissolving of 100mL methylene dichloride, is cooled to 0 ℃, adds wherein the 0.15mol aluminum chloride, then drip tert.-butylbenzene ether between 0.1mol, dropwise, rise to room temperature, stopped reaction after stirring 10h, slowly add wherein trash ice 200g, tell organic layer, washing twice, anhydrous sodium sulfate drying, slough solvent and obtain vitreous state crude product (intermediate E), content＞90%.
The intermediate E that after folding hundred is 0.1mol is dissolved with the 70mL anhydrous isopropyl alcohol, add sodium hydrate solid 0.2mol, backflow 5h, after being cooled to room temperature, add 200mL water, ethyl acetate extraction, after ethyl acetate is removed in decompression, column chromatography obtains intermediate F, yield: 88%, mp:74～78 ℃.
Embodiment 3
Synthesizing of Compound I-1:
Add 30mL DMF and 30mL water and catalyzer 0.05mmol Pd (PPh in the mixture of 5mmol intermediate C and 5mmol phenylo boric acid
3)
4, be warming up to 40 ℃ of reaction 8h under stirring, add 60mL water and 60mL ethyl acetate, tell organic layer, wash with 10% sodium hydroxide, anhydrous sodium sulfate drying is sloughed after solvent residuum and is used column chromatography and obtain I-1, productive rate: 70%.
Embodiment 4
Compound I-2 synthetic: with reference to embodiment 4, take to fluorobenzoic boric acid as coupling reagent, palladium is catalyzer, makes I-2, productive rate 45%.
Embodiment 5
Compound I-4 are synthetic: with reference to embodiment 4, be coupling reagent with 2,3-difluoro pyridine-4-boric acid, at Pd (PPh
3)
4For catalyzer makes I-4, productive rate 35%.
Embodiment 6
Synthesizing of Compound I-7:
With reference to embodiment 4, take 2-fluoro-3-chloro-pyridine-4-boric acid as coupling reagent, at Pd (PPh
3)
4For catalyzer makes I-7, productive rate 40%.
Embodiment 7
Synthesizing of Compound I-13: add 1.87g compd A (0.6mmol) in the 50mL there-necked flask, 1.26g triethylamine and 20mL methylene dichloride are cooled to 0 ℃.O-trifluoromethyl Benzoyl chloride (0.66mmol) is dissolved in the methylene dichloride of 5mL, slowly splashes in four-hole boiling flask.Dropwise, TLC follows the tracks of reaction.Reaction removes by filter organic salt after finishing, and with the reaction solution precipitation, residuum separates with column chromatography (silica gel 200-300 order), productive rate: 65%.
Embodiment 8
Synthesizing of Compound I-14: with reference to embodiment 7, take the 2-thiophene chloride as acylting agent, tri-n-butylamine is acid binding agent, and ethylene dichloride makes I-14 as solvent, productive rate: 75%.
Embodiment 9
Synthesizing of Compound I-15: with reference to embodiment 7, take 3-tetrahydrofuran (THF) formyl chloride as acylting agent, pyridine is acid binding agent, and toluene is as solvent, and temperature of reaction is controlled at 10 ℃, makes I-15, productive rate: 75%.
Embodiment 10
Synthesizing of Compound I-16: with reference to embodiment 7, so that 3-bromo-1-(3-chloropyridine-2-yl)-1H-pyrazoles-5-formyl chloride is as acylting agent, anhydrous sodium carbonate is acid binding agent; methylene dichloride is as solvent; temperature of reaction is controlled at 30 ℃, makes I-16, productive rate: 85%.
Embodiment 11
Synthesizing of Compound I-18: with reference to embodiment 7, so that the N-methyl-4-chloro-5-ethyl pyrazoles-the 3-formyl chloride is as acylting agent, saleratus is acid binding agent, and ethylene dichloride is as solvent, and temperature of reaction is controlled at 20 ℃, makes I-18, productive rate: 90%.
Embodiment 12
Synthesizing of Compound I-20: with reference to embodiment 7, take chloroacetyl chloride as acylting agent, sodium bicarbonate is acid binding agent, and toluene is as solvent, and temperature of reaction is controlled at 35 ℃, makes I-20, productive rate: 93%.
Embodiment 13
(active testing to the mite ovum of carmine spider mite of I-1～I-20): take the former medicinal acetone solution of 10mg, tween water is mixed with the mother liquor of 100mg/L to part of compounds involved in the present invention.Mother liquor namely obtains the desired concn liquid with 0.05% tween water dilution.Each is processed 3 and repeats, and establishes blank.
Connect carmine spider mite and become 5 of mites on the leaf of Broadbean dish, remove into mite after the 24h of laying eggs.There is the leaf dish of mite ovum to flood 10s in liquid product, takes out and be placed in moisturizing cultivation under constant temperature, put 3 leaf dish in each culture dish.Periodic investigation blank egg hatching rate records and carries out statistical study.Experimental temperature: 25 ± 1 ℃.
Compound I-1～I-20 sees the following form to the inhibition of carmine spider mite mite ovum.
Numbering and the physicochemical constant of part of compounds involved in the present invention see the following form.
Claims (4)
1. novel 2 as shown in structural formula I of a class, 4-diphenyl oxazoline compounds is introduced again other active groups when it is characterized in that having kept miticide second mite azoles structure.
The R=substituted-phenyl, substituted pyridinyl, R
1CONH-
R
1=substituted-phenyl, substituted pyrazolecarboxylic base, C
1-6Alkyl, halo C
1-6Alkyl.
2. the new compound preparation method with general structure I (wherein, R=substituted-phenyl, substituted pyridinyl) as claimed in claim 1 is characterized in that adopting following reactions steps:
Halogenating reaction occurs and obtains intermediate A in (1) 2,6-difluoro-benzoic acid and halogen simple substance in acetate solvate, said halogen simple substance is bromine or iodine, and the mol ratio of 2,6-difluoro-benzoic acid and halogen simple substance is 1: 0.9～3;
Intermediate A and sulfur oxychloride obtain intermediate B at organic solvent or without the solvent reacting by heating, said solvent is a kind of in benzene, toluene, methylene dichloride, ethylene dichloride, suitable temperature of reaction is 20～120 ℃, and the mol ratio of intermediate A and sulfur oxychloride is 1: 1.1～5;
Pass into ammonia gas react in the solution of intermediate B and obtain intermediate C, said solvent is a kind of in benzene, toluene, methylene dichloride, chloroform, tetrahydrofuran (THF), ammonia with for the mol ratio of B is 0.8～2: 1, suitable temperature of reaction is-20～10 ℃;
Condensation reaction occurs and obtains D in C and monochloroacetaldehyde dimethyl acetal under acid catalysis, said catalyzer is a kind of in trifluoromethanesulfonic acid, tosic acid, the vitriol oil, the mol ratio of C and monochloroacetaldehyde dimethyl acetal and acid catalyst is 1: 0.9～3.0: 0.75～1.5, and suitable temperature of reaction is 10～80 ℃;
(2) in the mixture of D and a kind of solvent, the mixed solution that adds aluminum chloride and a tert.-butylbenzene ether, obtain E, said solvent is a kind of in methylene dichloride, ethylene dichloride, chloroform, tetracol phenixin, the mol ratio of D and aluminum chloride, a tert.-butylbenzene ether is 1: 0.9～2.0: 0.9: 2.0, and suitable temperature of reaction is 0～50 ℃;
(3) ring closure reaction occurs and obtains F in E under base catalysis, and said alkaline catalysts is solid sodium ethanol, solid sodium hydroxide or triethylamine, and the mol ratio of E and catalyzer is 1: 0.9～2, and suitable temperature of reaction is 0～70 ℃;
(4) the Suzuki linked reaction is occuring in F and organic boronic in a kind of solvent under Pd catalyzer and promoter effect, said catalyzer is a kind of in tetra-triphenylphosphine palladium, palladium, catalyst adjuvant is triethylamine, the mol ratio of F and organic boronic and catalyzer is 1: 0.9～2.0: 0.001～0.1, and solvent is DMF, water or mixture that both are mixed to get according to arbitrary proportion.
3. as claimed in claim 1 have general structure I (wherein a, R=R
1CONH-, R
1=substituted-phenyl, substituted pyrazolecarboxylic base, C
1-6Alkyl, halo C
1-6The preparation method of compound alkyl) is characterized in that adopting following reaction to carry out:
In the situation that used a kind of alkali as acid binding agent, 2-(3-amino-2,6-difluorophenyl)-4-(2-methoxyl group-4-tert-butyl-phenyl) oxazoline and a kind of acyl chlorides (R
1COCI) in a kind of solvent, condensation reaction occurs, said acid binding agent is a kind of in organic bases triethylamine, tri-n-butylamine, pyridine or mineral alkali sodium carbonate, salt of wormwood, sodium bicarbonate, saleratus; The solvent that uses is halogenated hydrocarbon solvent, aromatic hydrocarbon solvent.
4. have as claimed in claim 1 the acaricidal activity of the compound of general structure I, it is characterized in that can be used for preventing and treating the mite pest of damage to crops under certain concentration.
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Cited By (3)
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| CN104016962A (en) * | 2014-06-16 | 2014-09-03 | 商丘凯瑞达化工有限公司 | Process for synthetizing 2-thiopheneacetyl chloride |
| CN107556260A (en) * | 2017-10-20 | 2018-01-09 | 南通泰禾化工股份有限公司 | A kind of etoxazole preparation method |
| CN110128470A (en) * | 2018-02-08 | 2019-08-16 | 青县科瑞希医药技术有限公司 | A method of preparing formyl methylene triphenyl phosphine |
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| CN104016962A (en) * | 2014-06-16 | 2014-09-03 | 商丘凯瑞达化工有限公司 | Process for synthetizing 2-thiopheneacetyl chloride |
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