JPH0136828B2 - - Google Patents
Info
- Publication number
- JPH0136828B2 JPH0136828B2 JP56160857A JP16085781A JPH0136828B2 JP H0136828 B2 JPH0136828 B2 JP H0136828B2 JP 56160857 A JP56160857 A JP 56160857A JP 16085781 A JP16085781 A JP 16085781A JP H0136828 B2 JPH0136828 B2 JP H0136828B2
- Authority
- JP
- Japan
- Prior art keywords
- acetophenone
- pyrazinyl
- dichloro
- pyridyl
- methyloxime
- 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
Links
- 150000001875 compounds Chemical class 0.000 claims description 51
- 239000000203 mixture Substances 0.000 claims description 37
- 150000003839 salts Chemical class 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 19
- 230000000855 fungicidal effect Effects 0.000 claims description 15
- KUZOAJKWVPACQX-UHFFFAOYSA-N 1-(2,4-dichlorophenyl)-2-pyrazin-2-ylethanone Chemical compound ClC1=CC(Cl)=CC=C1C(=O)CC1=CN=CC=N1 KUZOAJKWVPACQX-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 7
- KBCBKIPUEHCLJB-UHFFFAOYSA-N 1-(4-chlorophenyl)-2-pyrazin-2-ylethanone Chemical compound C1=CC(Cl)=CC=C1C(=O)CC1=CN=CC=N1 KBCBKIPUEHCLJB-UHFFFAOYSA-N 0.000 claims description 7
- -1 2',4'-dichloro-2-(3-pyridyl)-acetophenone O-propargyloxime Compound Chemical class 0.000 claims description 7
- CGZQCZNRBCLEOH-UHFFFAOYSA-N 1-(2,4-dichlorophenyl)-2-pyridin-3-ylethanone Chemical compound ClC1=CC(Cl)=CC=C1C(=O)CC1=CC=CN=C1 CGZQCZNRBCLEOH-UHFFFAOYSA-N 0.000 claims description 6
- 239000012876 carrier material Substances 0.000 claims description 6
- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 125000001475 halogen functional group Chemical group 0.000 claims description 5
- 125000004307 pyrazin-2-yl group Chemical group [H]C1=C([H])N=C(*)C([H])=N1 0.000 claims description 5
- CKPCAYZTYMHQEX-JXAWBTAJSA-N (z)-1-(2,4-dichlorophenyl)-n-methoxy-2-pyridin-3-ylethanimine Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(=N/OC)\CC1=CC=CN=C1 CKPCAYZTYMHQEX-JXAWBTAJSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- PVPPSYNNEIDORF-UHFFFAOYSA-N 1-(2,4-dichlorophenyl)-n-ethoxy-2-pyridin-3-ylethanimine Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(=NOCC)CC1=CC=CN=C1 PVPPSYNNEIDORF-UHFFFAOYSA-N 0.000 claims description 2
- KAUVMPWDSMAISH-UHFFFAOYSA-N 1-(2,4-dichlorophenyl)-n-methoxy-2-pyrazin-2-ylpropan-1-imine Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(=NOC)C(C)C1=CN=CC=N1 KAUVMPWDSMAISH-UHFFFAOYSA-N 0.000 claims description 2
- NVKWOGAKCQFEHR-UHFFFAOYSA-N 1-(2,4-dichlorophenyl)-n-prop-2-ynoxy-2-pyrazin-2-ylethanimine Chemical compound ClC1=CC(Cl)=CC=C1C(=NOCC#C)CC1=CN=CC=N1 NVKWOGAKCQFEHR-UHFFFAOYSA-N 0.000 claims description 2
- CCIFCWHNVQXPTI-UHFFFAOYSA-N 1-(2-chlorophenyl)-n-methoxy-2-pyrazin-2-ylethanimine Chemical compound C=1C=CC=C(Cl)C=1C(=NOC)CC1=CN=CC=N1 CCIFCWHNVQXPTI-UHFFFAOYSA-N 0.000 claims description 2
- ACWFIYYVDCWFPR-UHFFFAOYSA-N 1-(4-bromophenyl)-n-methoxy-2-pyrazin-2-ylethanimine Chemical compound C=1C=C(Br)C=CC=1C(=NOC)CC1=CN=CC=N1 ACWFIYYVDCWFPR-UHFFFAOYSA-N 0.000 claims description 2
- USGFTVNSUJEMMH-UHFFFAOYSA-N 1-(4-chlorophenyl)-n-methoxy-2-pyrazin-2-ylethanimine Chemical compound C=1C=C(Cl)C=CC=1C(=NOC)CC1=CN=CC=N1 USGFTVNSUJEMMH-UHFFFAOYSA-N 0.000 claims description 2
- GDANOLXKBFVBJB-UHFFFAOYSA-N 1-(4-chlorophenyl)-n-methoxy-2-pyrazin-2-ylpropan-1-imine Chemical compound C=1C=C(Cl)C=CC=1C(=NOC)C(C)C1=CN=CC=N1 GDANOLXKBFVBJB-UHFFFAOYSA-N 0.000 claims description 2
- JOUGEUWUSSLCLD-UHFFFAOYSA-N 1-(4-chlorophenyl)-n-methoxy-2-pyridin-3-ylethanimine Chemical compound C=1C=C(Cl)C=CC=1C(=NOC)CC1=CC=CN=C1 JOUGEUWUSSLCLD-UHFFFAOYSA-N 0.000 claims description 2
- HVRJPFMZBBOCJF-UHFFFAOYSA-N 1-(4-fluorophenyl)-n-methoxy-2-pyrazin-2-ylethanimine Chemical compound C=1C=C(F)C=CC=1C(=NOC)CC1=CN=CC=N1 HVRJPFMZBBOCJF-UHFFFAOYSA-N 0.000 claims description 2
- 125000004201 2,4-dichlorophenyl group Chemical group [H]C1=C([H])C(*)=C(Cl)C([H])=C1Cl 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- 125000005526 alkyl sulfate group Chemical group 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 claims description 2
- MJUZRRQGMFPACE-UHFFFAOYSA-N 1-(2,4-dichlorophenyl)-n-ethoxy-2-pyrazin-2-ylethanimine Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(=NOCC)CC1=CN=CC=N1 MJUZRRQGMFPACE-UHFFFAOYSA-N 0.000 claims 1
- UDJHGZNLDNVICL-UHFFFAOYSA-N 1-(2,4-dichlorophenyl)-n-methoxy-2-pyrazin-2-ylethanimine Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(=NOC)CC1=CN=CC=N1 UDJHGZNLDNVICL-UHFFFAOYSA-N 0.000 claims 1
- DDUCWCUOGZLMTN-UHFFFAOYSA-N 1-(4-chlorophenyl)-n-prop-2-ynoxy-2-pyrazin-2-ylethanimine Chemical compound C1=CC(Cl)=CC=C1C(=NOCC#C)CC1=CN=CC=N1 DDUCWCUOGZLMTN-UHFFFAOYSA-N 0.000 claims 1
- 125000000753 cycloalkyl group Chemical group 0.000 claims 1
- 239000013543 active substance Substances 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 239000003921 oil Substances 0.000 description 15
- 241000196324 Embryophyta Species 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- XNXVOSBNFZWHBV-UHFFFAOYSA-N hydron;o-methylhydroxylamine;chloride Chemical compound Cl.CON XNXVOSBNFZWHBV-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- CAWHJQAVHZEVTJ-UHFFFAOYSA-N methylpyrazine Chemical compound CC1=CN=CC=N1 CAWHJQAVHZEVTJ-UHFFFAOYSA-N 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- 241000220225 Malus Species 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- 241000221785 Erysiphales Species 0.000 description 5
- 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 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 description 5
- 235000011152 sodium sulphate Nutrition 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 240000008067 Cucumis sativus Species 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- KVFIJIWMDBAGDP-UHFFFAOYSA-N ethylpyrazine Chemical compound CCC1=CN=CC=N1 KVFIJIWMDBAGDP-UHFFFAOYSA-N 0.000 description 4
- 208000015181 infectious disease Diseases 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- BVUNKIYUJIIEEX-UHFFFAOYSA-N n-[1-(2,4-dichlorophenyl)-2-pyridin-3-ylethylidene]hydroxylamine Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(=NO)CC1=CC=CN=C1 BVUNKIYUJIIEEX-UHFFFAOYSA-N 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- 241000896246 Golovinomyces cichoracearum Species 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 241000228452 Venturia inaequalis Species 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000003898 horticulture Methods 0.000 description 3
- XIQUJVRFXPBMHS-UHFFFAOYSA-N hydron;o-prop-2-enylhydroxylamine;chloride Chemical compound Cl.NOCC=C XIQUJVRFXPBMHS-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 150000002923 oximes Chemical class 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- YORCIIVHUBAYBQ-UHFFFAOYSA-N propargyl bromide Chemical compound BrCC#C YORCIIVHUBAYBQ-UHFFFAOYSA-N 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000012312 sodium hydride Substances 0.000 description 3
- 229910000104 sodium hydride Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- YHPUJWQWBMOWSZ-UHFFFAOYSA-N 1-(2-chlorophenyl)-2-pyrazin-2-ylethanone Chemical compound ClC1=CC=CC=C1C(=O)CC1=CN=CC=N1 YHPUJWQWBMOWSZ-UHFFFAOYSA-N 0.000 description 2
- YQBAOXWHMUDREK-UHFFFAOYSA-N 1-(4-bromophenyl)-2-pyrazin-2-ylethanone Chemical compound C1=CC(Br)=CC=C1C(=O)CC1=CN=CC=N1 YQBAOXWHMUDREK-UHFFFAOYSA-N 0.000 description 2
- DHIYWPQTECHUNX-UHFFFAOYSA-N 1-(4-chlorophenyl)-2-pyrazin-2-ylpropan-1-one Chemical compound C=1N=CC=NC=1C(C)C(=O)C1=CC=C(Cl)C=C1 DHIYWPQTECHUNX-UHFFFAOYSA-N 0.000 description 2
- KYAATGSGTLPBHN-UHFFFAOYSA-N 2,4-dichloro-3-methylbenzoic acid Chemical compound CC1=C(Cl)C=CC(C(O)=O)=C1Cl KYAATGSGTLPBHN-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 235000009849 Cucumis sativus Nutrition 0.000 description 2
- 241000221787 Erysiphe Species 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 241001181537 Hemileia Species 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 241001123561 Puccinia coronata Species 0.000 description 2
- 206010039509 Scab Diseases 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 241000221577 Uromyces appendiculatus Species 0.000 description 2
- 241000317942 Venturia <ichneumonid wasp> Species 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000000417 fungicide Substances 0.000 description 2
- 229940093915 gynecological organic acid Drugs 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- CUKYGXFNZUNZLN-UHFFFAOYSA-N n-[1-(2,4-dichlorophenyl)-2-pyrazin-2-ylethylidene]hydroxylamine Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(=NO)CC1=CN=CC=N1 CUKYGXFNZUNZLN-UHFFFAOYSA-N 0.000 description 2
- IOUXLAZQWNNGRA-UHFFFAOYSA-N n-[1-(4-chlorophenyl)-2-pyrazin-2-ylethylidene]hydroxylamine Chemical compound C=1C=C(Cl)C=CC=1C(=NO)CC1=CN=CC=N1 IOUXLAZQWNNGRA-UHFFFAOYSA-N 0.000 description 2
- XTEGVFVZDVNBPF-UHFFFAOYSA-N naphthalene-1,5-disulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1S(O)(=O)=O XTEGVFVZDVNBPF-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 244000000003 plant pathogen Species 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- 230000009885 systemic effect Effects 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- XHDPNHNJYMVCCO-UHFFFAOYSA-N 1-(2,4-dichlorophenyl)-n-prop-2-ynoxy-2-pyridin-3-ylethanimine Chemical compound ClC1=CC(Cl)=CC=C1C(=NOCC#C)CC1=CC=CN=C1 XHDPNHNJYMVCCO-UHFFFAOYSA-N 0.000 description 1
- BSBDMMWCKABSKX-UHFFFAOYSA-N 1-(2,4-dichlorophenyl)-n-propan-2-yloxy-2-pyrazin-2-ylethanimine Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(=NOC(C)C)CC1=CN=CC=N1 BSBDMMWCKABSKX-UHFFFAOYSA-N 0.000 description 1
- RMGGNVKRVNWVCV-UHFFFAOYSA-N 1-(2,4-dichlorophenyl)-n-propan-2-yloxy-2-pyridin-3-ylethanimine Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(=NOC(C)C)CC1=CC=CN=C1 RMGGNVKRVNWVCV-UHFFFAOYSA-N 0.000 description 1
- XPSQHYPYPLUYAC-UHFFFAOYSA-N 1-(4-chlorophenyl)-2-pyridin-3-ylethanone Chemical compound C1=CC(Cl)=CC=C1C(=O)CC1=CC=CN=C1 XPSQHYPYPLUYAC-UHFFFAOYSA-N 0.000 description 1
- BDJBVPOPIPGRSP-UHFFFAOYSA-N 1-(4-chlorophenyl)-n-ethoxy-2-pyrazin-2-ylethanimine Chemical compound C=1C=C(Cl)C=CC=1C(=NOCC)CC1=CN=CC=N1 BDJBVPOPIPGRSP-UHFFFAOYSA-N 0.000 description 1
- XZOODJULVBPISP-UHFFFAOYSA-N 1-(4-fluorophenyl)-2-pyrazin-2-ylethanone Chemical compound C1=CC(F)=CC=C1C(=O)CC1=CN=CC=N1 XZOODJULVBPISP-UHFFFAOYSA-N 0.000 description 1
- MASZWWSKALDSJQ-UHFFFAOYSA-N 2,4-dichloro-3-ethylbenzoic acid Chemical compound CCC1=C(Cl)C=CC(C(O)=O)=C1Cl MASZWWSKALDSJQ-UHFFFAOYSA-N 0.000 description 1
- SXAMGRAIZSSWIH-UHFFFAOYSA-N 2-[3-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,2,4-oxadiazol-5-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NOC(=N1)CC(=O)N1CC2=C(CC1)NN=N2 SXAMGRAIZSSWIH-UHFFFAOYSA-N 0.000 description 1
- NAMYKGVDVNBCFQ-UHFFFAOYSA-N 2-bromopropane Chemical compound CC(C)Br NAMYKGVDVNBCFQ-UHFFFAOYSA-N 0.000 description 1
- LWOKLXMNGXXORN-UHFFFAOYSA-N 2-chloro-3-methylbenzoic acid Chemical compound CC1=CC=CC(C(O)=O)=C1Cl LWOKLXMNGXXORN-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- RVCJOGNLYVNRDN-UHFFFAOYSA-N 4-bromo-2-methylbenzoic acid Chemical compound CC1=CC(Br)=CC=C1C(O)=O RVCJOGNLYVNRDN-UHFFFAOYSA-N 0.000 description 1
- XXFKOBGFMUIWDH-UHFFFAOYSA-N 4-chloro-2-methylbenzoic acid Chemical compound CC1=CC(Cl)=CC=C1C(O)=O XXFKOBGFMUIWDH-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 241001480061 Blumeria graminis Species 0.000 description 1
- 241001157813 Cercospora Species 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241001600095 Coniophora puteana Species 0.000 description 1
- 241001529717 Corticium <basidiomycota> Species 0.000 description 1
- 235000010799 Cucumis sativus var sativus Nutrition 0.000 description 1
- 241000371644 Curvularia ravenelii Species 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 241001313288 Labia Species 0.000 description 1
- 241000222634 Lenzites Species 0.000 description 1
- 241001337928 Podosphaera leucotricha Species 0.000 description 1
- 241000896203 Podosphaera pannosa Species 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 241000221300 Puccinia Species 0.000 description 1
- 241001123569 Puccinia recondita Species 0.000 description 1
- 241000221535 Pucciniales Species 0.000 description 1
- 241001361634 Rhizoctonia Species 0.000 description 1
- 235000004789 Rosa xanthina Nutrition 0.000 description 1
- 241000109329 Rosa xanthina Species 0.000 description 1
- 241001533598 Septoria Species 0.000 description 1
- 241000270295 Serpentes Species 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 241000722133 Tilletia Species 0.000 description 1
- 241000221576 Uromyces Species 0.000 description 1
- 241000221566 Ustilago Species 0.000 description 1
- 241000589652 Xanthomonas oryzae Species 0.000 description 1
- 230000000895 acaricidal effect Effects 0.000 description 1
- 239000000642 acaricide Substances 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 1
- 150000008046 alkali metal hydrides Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 235000021016 apples Nutrition 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- OOCMUZJPDXYRFD-UHFFFAOYSA-L calcium;2-dodecylbenzenesulfonate Chemical compound [Ca+2].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O.CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O OOCMUZJPDXYRFD-UHFFFAOYSA-L 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229960004106 citric acid Drugs 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000008029 eradication Effects 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- RPWXYCRIAGBAGY-UHFFFAOYSA-N ethyl 2-pyridin-3-ylacetate Chemical compound CCOC(=O)CC1=CC=CN=C1 RPWXYCRIAGBAGY-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 229960002598 fumaric acid Drugs 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 125000002346 iodo group Chemical group I* 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 229960000448 lactic acid Drugs 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229940098895 maleic acid Drugs 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- MSEBQGULDWDIRW-UHFFFAOYSA-N methyl 4-fluorobenzoate Chemical compound COC(=O)C1=CC=C(F)C=C1 MSEBQGULDWDIRW-UHFFFAOYSA-N 0.000 description 1
- LWMALPSZHLPXRM-UHFFFAOYSA-N n-(1-phenyl-2-pyrazin-2-ylethylidene)hydroxylamine Chemical compound C=1C=CC=CC=1C(=NO)CC1=CN=CC=N1 LWMALPSZHLPXRM-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- NUXCOKIYARRTDC-UHFFFAOYSA-N o-ethylhydroxylamine;hydron;chloride Chemical compound Cl.CCON NUXCOKIYARRTDC-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 230000003032 phytopathogenic effect Effects 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 239000005648 plant growth regulator Substances 0.000 description 1
- 229920000417 polynaphthalene Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- 229920005552 sodium lignosulfonate Polymers 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 229960001367 tartaric acid Drugs 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Landscapes
- Pyridine Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
本発明は一般式
(式中R1は2−ハロ−、4−ハロ−又は2,4
−ジハロ−フエニルを表わし、
R2は3−ピリジル又は2−ピラジニルを表わ
し、
R3は水素又は直鎖状C1-4−アルキルを表わし、
そして、
R4はC1-6−アルキル、C3-6−シクロアルキル、
C3-6−アルケニル又はC3-6−アルキニルを表わ
す)
なる化合物およびこれら化合物の酸付加塩に関す
る。
式なる化合物およびそれらの酸付加塩は殺カ
ビ特性を有し、また殺カビ活性物質として、特に
農業および園芸での使用に適している。
本発明はさらに式なる化合物およびそれらの
酸付加塩の製造方法、殺カビ活性物質としての式
なる化合物およびその酸付加塩、式なる化合
物又はその酸付加塩を活性物質として含有する殺
カビ組成物、ならびに前記化合物、酸付加塩およ
び組成物の農業および園芸におけるカビ防除への
使用に関する。
式の定義中の「ハロ」という術語はフルオ
ロ、クロロ、ブロモおよびヨードを含むが、クロ
ロが好ましい。
R1によつて示される2,4−ジハロ−フエニ
ル基中のハロゲン原子は同一でも異つていてもよ
い。
「C1-6−アルキル」、「C3-6−アルケニル」、お
よび「C3-6−アルキニル」という術語は直鎖状の
みならず分枝状炭化水素基を含む。アルキルに関
しては、明記された炭素原子の数により理解すれ
ばよく、たとえば次の基;メチル、エチル、n−
プロピル、イソプロピル、n−ブチル、tert−ブ
チル、イソアミルおよびn−ヘキシルが考えられ
る。
もしもR4がC1-6−アルキル、C3-6−アルケニ
ル又はC3-6−アルキニルを表わすならば、その時
にはこの基はC1-4−アルキル、C3もしくは4−ア
ルケニル又はC3もしくは 4−アルキニルが好まし
い。アリル基はアルケニル基が特に好ましく、ま
たプロパルギル基はアルキニル基が特に好まし
い。
R1は4−クロロフエニル又は2,4−ジクロ
ロフエニルを表わすのが好ましいが、特に後者の
基を表わすのが好ましい。
R3は水素、メチル又はエチルを表わすのが好
ましいが、特に水素を表わすのが好ましい。
式なる化合物で特に好ましいものは2′,4′−
ジクロロ−2−(3−ピリジル)−アセトフエノン
O−メチルオキシムである。
代表的な式なる化合物は
4′−クロロ−2−(3−ビリジル)−アセトフエ
ノンO−アリルオキシムおよび
2′,4′−ジクロロ−2−(2−ピラジニル)−ア
セトフエノンO−イソプロピルオキシム
である。
式なる化合物中にC=Nの二重結合が存在す
る結果として幾何異性体が生ずる。さらに不斉炭
素原子が存在し得るため、化合物は光学対掌体と
して存在し得る。式は従つてすべてのこれら可
能な異性体を包含することを意味する。
式なる化合物の酸付加塩としては生理学上相
容れる塩を考える。
これらの塩としては無機又は有機酸たとえば塩
酸、硝酸、リン酸、一もしくは二官能カルボル酸
およびヒドロキシカルボン酸(たとえば酢酸、マ
レイン酸、コハク酸、フマール酸、酒石酸、クエ
ン酸、サリチル酸、ソルビン酸および乳酸)なら
びにスルホン酸(たとえば1,5−ナフタレン−
ジスルホン酸)との式なる化合物の塩が好まし
い。
式なる化合物およびそれらの塩を製造する本
発明の方法は、
(a) 式
(式中R1、R2およびR3は上記の意味を有する)
なるオキシムを、式
R4U
{式中R4は上記の意味を有し、Uは離れる基
(たとえば塩素、臭素、ヨウ素、メシルオキシ、
トシルオキシ又はアルキルスルフエート基)を
表わす}
なる化合物と反応させるか、又は
(b) 式
(式中R1、R2およびR3は上記の意味を有する)
なるケトンを、式
R41ONH2
(式中R41はC1-6−アルキル、C3-6−シクロア
ルキル又はC3-6−アルケニルを表わす)
なるO−置換ヒドロキシルアミンと反応させ、
かつ、所望ならば、得られた式なる化合物を
酸付加塩に変換することからなる。
変法(a)は式なる出発物質を式なる化合物
で、便宜には塩基の存在下に、有機溶媒中で0℃
と反応混合物の還流温度との間の温度範囲内にて
処理することによつて行われ得る。溶媒はプロト
ン性でも非−プロトン性でもよい。プロトン性溶
媒たとえばアルコール、特にメタノール又はエタ
ノール、を用いる場合には、水酸化アルカリ金属
(たとえば水酸化ナトリウム又はカリウム)又は
アルカリ金属アルコラートを塩基として用いるの
が好ましい。非−プロトン性溶媒たとえばエーテ
ル又はエーテル様溶媒、特にテトラヒドロフラン
もしくはジメトキシエタン、およびジアルキルア
ミド、特にジメチルホルムアミド、を用いた場合
には、水素化金属アルカリ(たとえば水素化ナト
リウム)を塩基として用いるのが好ましい。
変法(a)の好ましい態様では、水素化ナトリウム
を塩基として用い、またエーテルもしくはエーテ
ル様化合物、特にテトラヒドロフランもしくはジ
メトキシエタン、又はジアルキルアミド、特にジ
メチルホルムアミド、を溶媒として用いる。
R4がC1-6−アルキル、C3-6−シクロアルキル
もしくはC3-6−アルケニルを表わす式なる化合
物が得られる変法(b)では、反応を有機溶媒、たと
えばアルコールたとえばメタノールもしくはエタ
ノール、ジアルキルアミドたとえばジメチルホル
ムアミド又はtert−アミンたとえばピリジン、中
にて行うのが便宜である。本反応は室温と反応混
合物の還流温度との間の温度範囲内で行われるの
が好ましい。式なる出発物質は酸付加塩(たと
えば塩酸塩又は硫酸塩)の形態で用いられるのが
好ましいため、塩基たとえば炭酸ナトリウムもし
くはカリウム、トリエチルアミン又はピリジンを
反応混合物へ添加するのが便宜である。
酸付加塩の製造には、式なる化合物を、所望
ならば、無機もしくは有機酸たとえば塩酸、硝
酸、リン酸、一、および二官能カルボン酸および
ヒドロキシカルボン酸又はスルホン酸と反応させ
る。
こうして製造された式なる化合物およびそれ
らの酸付加塩の単離および精製は、それ自体知ら
れている方法によつて行われる。
出発物質として用いられる式、、および
なる化合物は知られているか、又はそれ自体知
られている方法によつて製造され得る。たとえば
式なるオキシムは相当する式なるケトンから
ヒドロキシルアミンとの反応によつて製造するこ
とができ、ケトンそれ自体はDOS2221546、
DOS2800010および英国特許明細書第2015524号
に記載された方法により製造され得る。
本発明による化合物(すなわち式なる化合物
およびそれらの酸付加塩)は殺カビ活性を有し、
従つて農業および園芸におけるカビの防除に用い
られ得る。これらは特に植物の部分(たとえば
葉、幹、根、鬼茎、実又は花)および種子の、な
らびに土壤中の植物病原菌を根絶又は防除するの
に適しており、また特にうどんこ病菌たとえばエ
リシフエグラミニス(Erysiphe graminis(穀粒
のうどん粉病)、エリシフエシチヨラシ−ラム
(Erysiphe cichoracearum)(キユウリのうどん
粉菌)、ポドスフエラリユウコトリチヤ
(Podosphaera leucotricha)(リンゴのうどん粉
病)およびスフエロテカパンノーサ
(Sphaerotheca pannosa)(バラのうどん粉病)
の;ベントウリアイネクアリス(Venturia
inaequalis)(リンゴ黒星病)の、さび菌たとえ
ばプチニア、ウロミセスおよびヘミレイア属のさ
び菌、特にプチニアコロナタ(Puccinia
coronata)(オート麦の冠さび病)、プチニアレ
コンジタ(Puccinia recondita)(穀粒の赤さび
病)、ウロミセスアペンジキユラタス
(Uromyces appendiculatus)(豆さび病)およ
びヘミリアバスタトリクス(Hemileia
vastatrix)(コーヒーさび病)の防除に有効であ
る。
さらに、本発明の種々の化合物はまた次の属の
植物病原菌に対して活性を有する:ヘルミントス
ポリウム(Helminthosporium)、リゾクトニア
(Rhizoctonia)、セプトリア(Septoria)、サー
コスポラ(Cercospora)、コーチシウム
(Corticium)、チレツチア(Tilletia)およびウ
ステイラゴ(Ustilago)。
さらに本発明の個々の化合物は木材破壊菌たと
えばコニオフオラプテアナ(Coniophora
puteana)およびレンジテストラビア(Lenzites
trabea)に対して顕著な活性を有する。さらに各
化合物はまた植物病原細菌たとえばキサントモナ
マオリザエ(Xanthomonas oryzae)に対して
も活性を有する。
本発明の化合物は系統活性(systemic
activity)ならびに良好な植物の耐容性の点で顕
著である。
本発明の化合物は温室状態下で噴霧液体の当
り5mgないし500mgの活性物質濃度でさえも活性
である。野外では、ヘクタール当り50gないし
1000gの式なる活性物質濃度と処理が施用に有
利である。たとえば、リンゴうどん粉病およびリ
ンゴさび病の有効な防除には、ヘクタール当り50
gないし400gの式なる活性物質濃度を用いて
処理する。消毒過程における種子につくカビの防
除には、種子のKg当り0.1gないし2.5gの式な
る活性物質を用いるのが有利である。
本発明の化合物を製剤化して種々の組成物を与
えることができる(たとえば噴霧液、水性懸濁
液、乳濁液、乳化濃縮液および粉状製剤)。本発
明の殺カビ組成物は有効量の少くとも1種類の上
記定義の如き一般式なる化合物又はかかる化合
物の酸付加塩ならびに不活性担体物質を含有す
る。
組成物は一般的に、その型にもよるが、0.0001
と95との間の重量%の本発明の化合物を活性物質
として含有する。
種々の不活性粉状担体物質たとえばカオリン、
ベントナイト、タルク、白亜、炭酸マグネシウム
およびケイ質土は粉状殺カビ組成物の製造に用い
られ得る。活性成分はかかる担体物質と混合(た
とえば一緒に粉砕することにより)するか、又は
不活性担体物質を活性成分の溶液と含浸させてか
ら溶媒を蒸発、加熱又は減圧下で吸引ろ取するこ
とによつて除去する。かかる粉状組成物は保護し
ようとする植物へ通常の撤布装置を用いて撤布組
成物として施用され得る。湿潤および(又は)分
散剤を添加することによつて、かかる粉状組成物
を容易に水で湿潤し得るようにできるため、これ
らを噴霧組成物として水性懸濁液の形態で用いる
こともできる。
乳化濃縮液を製造するには、活性物質を、たと
えば、乳化剤と混合するか又は不活性溶媒中に溶
かして乳化剤と混合する。かかる濃縮液を水で希
釈することにより、すぐに使用出来る乳濁液が得
られる。かかる濃縮液は5ないし95重量%の、特
に25ないし75重量%の活性物質を含む。
本発明の殺カビ組成物は、式なる活性物質に
加えて、他の活性物質(たとえば他の殺カビ剤、
殺虫および殺ダニ剤、他の殺菌剤、植物成長調整
剤および肥料)を含有し得る。かかる併用組成物
は活性スペクトルを広げるのに又は特定的な植物
成長に影響を及ぼすのに適している。
本発明の化合物は植物保護に又は農業で一般的
な施用方法により用いられ得る。本発明によるカ
ビの防除方法は、保護しようとする品物(たとえ
ば植物、植物又は種子の部分)を有効量の本発明
の化合物又は本発明の組成物で処理することを特
徴とする。
次例は本発明を例証するものである。すべての
温度は℃を示す。
活性物質の製造
例 1
40mlのエタノール中に13.3gの2′,4′−ジクロ
ロ−2−(3−ピリジル)−アセトフエノンを有す
る溶液を、10gの炭酸ナトリウムおよび8.3gの
O−メチルヒドロキシルアミン塩酸塩で処理し、
混合物を次に還流温度で撹拌下に加熱する。4時
間後、この混合物を氷上に注ぎ、酢酸エチルで抽
出する。有機層を洗滌し、硫酸ナトリウム上で乾
燥させ、減圧下に濃縮する。2′,4′−ジクロロ−
2−(3−ピリジル)−アセトフエノンO−メチル
オキシムをE,Z−異性体混合物として黄色油状
物の形態で得る。シリカゲル上でn−ヘキサン/
酢酸エチル(4:1)を用いてクロマトグラフイ
ー分離を行い、まずE−異性体(n20 D=1.5845)
を、次いでZ−異性体(n20 D=1.5745)を溶出す
る。
同様にして、
4′−クロロ−2−(3−ピラジル)−アセトフエ
ノンとO−メチル−ヒドロキシルアミン塩酸塩か
ら4′−クロロ−2−(3−ピリジル)−アセトフエ
ノンO−メチルオキシム、m.p.55−58゜を得;
4′−クロロ−2−(2−ピラジニル)−アセトフ
エノンとO−メチルヒドロキシルアミン塩酸塩か
ら4′−クロロ−2−(2−ピラジニル)−アセトフ
エノンO−メチルオキシム、m.p.53−58℃、を
得;
4′−クロロ−2−(2−ピラジニル)−アセトフ
エノンとO−エチルヒドロキシルアミン塩酸塩か
ら4′−クロロ−2−(2−ピラジニル)−アセトフ
エノンO−エチルオキシム、m.p.44−46゜、を
得;
4′−クロロ−2−(2−ピラジニル)−アセトフ
エノンとO−アリルヒドロキシルアミン塩酸塩か
ら4′−クロロ−2−(2−ピラジニル)−アセトフ
エノンO−アリルオキシムを黄色油状物として
得;
2′,4′−ジクロロ−2−(3−ピリジル)−アセ
トフエノンとO−アリルヒドロキシルアミン塩酸
塩から2′,4′−ジクロロ−2−(3−ピリジル)−
アセトフエノンO−アリルオキシムを無色油状物
として得る。
例 2
3gの2′−クロロ−2−(2−ピラジニル)−ア
セトフエノンと0.8gのO−メチルヒドロキシル
アミン塩酸塩を10mlのピリジン中に溶かし、この
混合物80℃で30分間加熱する。ピリジンを次に減
圧下で除去し、水を粗生成物へ添加する。そこで
直ちに、本混合物を酢酸エチルで抽出し、有機層
を硫酸ナトリウムで乾燥させ、かつ濃縮する。
2′−クロロ−2−(2−ピラジニル)−アセトフエ
ノンO−メチルオキシムを油状物として得る。
同様にして、
4′−フルオロ−2−(2−ピラジニル)−アセト
フエノンとO−メチルヒドロキシルアミン塩酸塩
から4′−フルオロ−2−(2−ピラジニル)−アセ
トフエノンO−メチルオキシム、m.p.52−54゜、
を得;
4′−ブロモ−2−(2−ピラジニル)−アセトフ
エノンとO−メチルヒドロキシルアミン塩酸塩か
ら4′−ブロモ−2−(2−ピラジニル)−アセトフ
エノンO−メチルオキシム、m.p.81−84゜、を
得;
4′−クロロ−2−(2−ピラジニル)−プロピオ
フエノンとO−メチルヒドロキシルアミン塩酸塩
から4′−クロロ−2−(2−ピラジニル)−プロピ
オフエノンO−メチルオキシムを油状物として
得;
2′,4′−ジクロロ−2−(2−ピラジニル)−ア
セトフエノンとO−メチルヒドロキシルアミン塩
酸塩から2′,4′−ジクロロ−2−(2−ピラジニ
ル)−アセトフエノンO−メチルオキシムを油状
物として得;
2′,4′−ジクロロ−2−(2−ピラジニル)−ア
セトフエノンとO−メチルヒドロキシルアミン塩
酸塩から2′,4′−ジクロロ−2−(2−ピラジニ
ル)−アセトフエノンO−エチルオキシムを油状
物として得;
2′,4′−ジクロロ−2−(2−ピラジニル)−ア
セトフエノンとO−アリルヒドロキシルアミン塩
酸塩から2′,4′−ジクロロ−2−(2−ピラジニ
ル)−アセトフエノンO−アリルオキシムを油状
物として得;
2′,4′−ジクロロ−2−(2−ピラジニル)−プ
ロピオ−フエノンとO−メチルヒドロキシルアミ
ン塩酸塩から2′,4′−ジクロロ−2−(2−ピラ
ジニル)−プロピオフエノンO−メチルオキシム
を油状物として得る。
例 3
25mlのジメトキシエタン中の3gの2′,4′−ジ
クロロ−2−(3−ピリジル)−アセトフエノンオ
キシムの溶液を、0.51gの水素化ナトリウム分散
液(油中55%)で少しづつ処理し、この混合物を
室温で30分間撹拌する。次に、2.0gのヨウ化エ
チルを添加し、混合物を還流温度で加熱する。4
時間後、混合物を氷上に注ぎ、酢酸エチルで抽出
し、有機層を硫酸ナトリウムで乾燥させ、かつ減
圧下に濃縮する。粗生成物をシリカゲル上クロマ
トグラフイーによつて精製する。2′,4′−ジクロ
ロ−2−(3−ピリジル)−アセトフエノンO−エ
チルオキシムを黄色油状物として得る。
同様にして、
2′,4′−ジクロロ−2−(3−ピリジル)−アセ
トフエノンオキシムと臭化イソプロピルから2′,
4′−ジクロロ−2−(3−ピリジル)−アセトフエ
ノンO−イソプロピルオキシムを黄色油状物とし
て得;
2′,4′−ジクロロ−2−(3−ピリジル)−アセ
トフエノンオキシムと臭化プロパルギルから2′,
4′−ジクロロ−2−(3−ピリジル)−アセトフエ
ノンO−プロパルギルオキシム、m.p.60−62゜、
を得;
4′−クロロ−2−(2−ピラジニル)−アセトフ
エノンオキシムと臭化プロパルギルから4′−クロ
ロ−2−(2−ピラジニル)−アセトフエノンO−
プロパルギルオキシム、m.p.76−77゜、を得;
2′,4′−ジクロロ−2−(2−ピラジニル)−ア
セトフエノンオキシムと臭化プロパルギルから
2′,4′−ジ−クロロ−2−(2−ピラジニル)−ア
セトフエノンO−プロパルギルオキシムを油状物
として得る。
出発物質の製造
例 4
例1で出発物質として必要な2′,4′−ジクロロ
−2−(3−ピリジル)−アセトフエノンは次の如
く構成され得る:
27.6gのエチル2,4−ジクロロ安息香酸と
20.81gのエチル3−ピリジルアセテートの混合
物を20−25゜で10.59gのナトリウムメトキシドで
少しづつ処理する。この混合物を次に65−70゜で
加熱し、得られた揮発性の高い生成物を乾燥窒素
で吹きとばす(blow off)。20時間後、この混合
物を40mlの濃塩酸で処理し、還流温度で18時間加
熱する。混合物をジエチルエーテルで洗浄し、水
性層を濃アンモニアの添加によつて塩基性とし、
塩化メチレンで抽出する。有機層を濃縮し、粗生
成物をシリカゲル上で塩化メチレン/メタノール
(98:2)を用いてクロマトグラフイーにかける。
精生成物、2′,4′−ジクロロ−2−(3−ピリジ
ル)−アセトフエノン、をジエチルエーテル/n
−ペンタンから再結晶させる。m.p.55−56゜。
例 5
例2で出発物質として必要な2′,4′−ジクロロ
−2−(2−ピラジニル)−アセトフエノンは次の
如く製造される;
20gの2−メチルピラジンを液体アンモニア中
のナトリウムアミドの懸濁液(200mlのアンモニ
アと4.83gのナトリウムから)へ−30゜で滴下添
加し、この混合物を30分間撹拌する。20.5gのメ
チル2,4−ジクロロ安息香酸を次にゆつくりと
滴下添加し、この混合物を−30゜で1時間反応さ
せる。次に混合物を塩化アンモニウムで処理し、
アンモニアを除去し、そしてジエチルエーテルを
添加する。有機層を水洗し、硫酸ナトリウムで乾
燥させ、かつ濃縮する。少量のエタノールで処理
すると、2′,4′−ジクロロ−2−(2−ピラジニ
ル)−アセトフエノンが粗反応生成物から晶出す
る。生成物は96−98゜で融解する。
同様の方法で、
2−メチルピラジンとメチル2−クロロ安息香
酸から2′−クロロ−2−(2−ピラジニル)−アセ
トフエノンを油状物として得;
2−メチルピラジンとメチル4−フルオロ安息
香酸から4′−フルオロ−2−(2−ピラジニル)−
アセトフエノン、m.p.100−103゜、を得;
2−メチルピラジンとメチル4−ブロモ安息香
酸から4′−ブロモ−2−(2−ピラジニル)−アセ
トフエノン、m.p.121−122゜、を得;
2−エチルピラジンとメチル4−クロロ安息香
酸から4′−クロロ−2−(2−ピラジニル)−プロ
ピオフエノン、m.p.85゜、を得;
2−エチルピラジンとメチル2,4−ジクロロ
安息香酸から2′,4′ジクロロ−2−(2−ピラジ
ニル)−プロピオフエノンを油状物として得る。
例 6
例3で出発物質として必要な4′−クロロ−2−
(2−ピラジニル)−アセトフエノンオキシムは次
の如く製造され得る;
10gの4′−クロロ−2−(2−ピラジニル)−ア
セトフエノン、10gのヒドロキシルアミン塩酸塩
および12gの無水炭酸ナトリウムを60゜で100mlの
エタノール中にて2時間撹拌する。次にこの混合
物を水で処理し、酢酸エチルで抽出し、有機層を
硫酸ナトリウムで乾燥させ、次に濃縮する。残留
物をアセトン/n−ヘキサンから再結晶させる。
4′−クロロ−2−(2−ピラジニル)−アセトフエ
ノンオキシム、m.p.134゜、を得る。
同様の方法で、
2′,4′−ジクロロ−2−(2−ピラジニル)−ア
セトフエノンとヒドロキシルアミン塩酸塩から
2′,4′−ジクロロ−2−(2−ピラジニル)−アセ
トフエノンオキシムを粘性油状物として得;
2′,4′−ジクロロ−2−(3−ピリジル)−アセ
トフエノンとヒドロキシルアミン塩酸塩から2′,
4′−ジクロロ−2−(3−ピリジル)−アセトフエ
ノンオキシム、m.p.134−136゜、を得る。
製剤例
例 7
1 噴霧粉末剤(液体であるか又は75゜以下で融
解する活性物質に対する)
重量部
式なる活性物質 50
水和ケイ酸 37
カオリン 5
アルキルフエノールエトキシレート 4
ナトリウムポリナフタレンスルホネート 4
100
液体又は融解活性物質をケイ酸に吸収させ、
残りの成分を混和し、この混合物を適当なミル
中で細かく粉砕する。
2 噴霧粉末剤(75゜以上で融解する固体活性物
質に対する)
重量部
式なる活性物質 50
水和ケイ酸 5
カオリン 42
ナトリウムウラリルサルフエート 1
ナトリウムリグノスルホネート 2
100
各成分をお互いに混合し、この混合物を適当
なミル中で細かく粉砕する。
例 8
乳化濃厚液剤(20−25゜で液体である活性物質
に対して)
重量部
式なる活性物質 500
カスターオイルエトキシレート 100
カルシウムドデシルベンゼンスルホネート 25
C10−アルキルベンゼンの混合物
加えて1000容量部
各成分をお互いに清澄な溶液が得られるまで混
合する。
殺カビ活性の評価
試験:キユウリのウドンコ病(Erysiphe
cichorracearum)に対する活性「チヤイニ
ーズスネーク」(Chinese Snake)種の二葉
段階のキユウリ植物物2本のそれぞれに、被
験化合物(噴霧用粉末ととして常法により製
造されたもの)の水分分散液を全方向から充
分に噴霧し、その後温室内で栽培した。この
処置の24時間後に、植物の第一葉に
Erysiphe cichoracearumの胞子をふりかけ
ることにより、感染させた。さらに7〜9日
後に、被験化合物により付与された防護の程
度を、被験植物の葉の表面上に見い出される
感染と被験化合物で処置せずに、Erysiphe
cichoracearumを感染せた対照植物の葉の表
面上に見い出される感染とを比較することに
より評価した。
試験:リンゴ黒星病(Venturia inaequalis)
に対する活性
「ゴールデン デリシヤス」(Golden
Delicious)種のリンゴの苗木3本に
Venturia inaequalisの胞子の懸濁液を噴霧
し、次いで18℃で、露点条件の下でインキユ
ベートした。24時間後に、植物に被験化合物
(噴霧用粉末として常法で製造したもの)の
水性分散液を全方向から充分に噴霧した。こ
のように処置したリンゴ苗木を温室内でさら
に栽培した。9〜10日後に、被験化合物によ
り付与された防護の程度を、被験植物の葉の
表面上に見い出される感染とVenturia
inaequalisを同様に感染させたが、被験化合
物で処置されていない対照植物の葉の表面上
に見い出される感染とを比較することにより
評価した。
これらの被験化合物に対する2つの両方の
試験の活性パーセントとして表わし、次表に
示す:
The present invention is based on the general formula (In the formula, R 1 is 2-halo-, 4-halo- or 2,4
-dihalo-phenyl, R2 represents 3-pyridyl or 2-pyrazinyl, R3 represents hydrogen or linear C1-4 -alkyl,
and R 4 is C 1-6 -alkyl, C 3-6 -cycloalkyl,
C 3-6 -alkenyl or C 3-6 -alkynyl) and acid addition salts of these compounds. The compounds of the formula and their acid addition salts have fungicidal properties and are suitable as fungicidal active substances, in particular for use in agriculture and horticulture. The present invention further provides a process for producing compounds of the formula and their acid addition salts, compounds of the formula and their acid addition salts as fungicidal active substances, and fungicidal compositions containing the compounds of the formula or their acid addition salts as active substances. , and the use of said compounds, acid addition salts and compositions for mold control in agriculture and horticulture. The term "halo" in the formula definitions includes fluoro, chloro, bromo and iodo, with chloro being preferred. The halogen atoms in the 2,4-dihalo-phenyl group represented by R 1 may be the same or different. The terms " C1-6 -alkyl", " C3-6 -alkenyl" and " C3-6 -alkynyl" include straight-chain as well as branched hydrocarbon groups. Alkyl may be understood by the specified number of carbon atoms, such as the following groups: methyl, ethyl, n-
Propyl, isopropyl, n-butyl, tert-butyl, isoamyl and n-hexyl come into consideration. If R 4 represents C 1-6 -alkyl, C 3-6 -alkenyl or C 3-6 -alkynyl, then this radical is C 1-4 -alkyl, C 3 or 4-alkenyl or C 3 Or 4 -alkynyl is preferred. The allyl group is particularly preferably an alkenyl group, and the propargyl group is particularly preferably an alkynyl group. R 1 preferably represents 4-chlorophenyl or 2,4-dichlorophenyl, particularly preferably the latter group. R 3 preferably represents hydrogen, methyl or ethyl, particularly preferably hydrogen. Particularly preferred compounds of the formula are 2′,4′-
Dichloro-2-(3-pyridyl)-acetophenone O-methyloxime. Representative compounds of the formula are 4'-chloro-2-(3-biridyl)-acetophenone O-allyloxime and 2',4'-dichloro-2-(2-pyrazinyl)-acetophenone O-isopropyloxime. Geometric isomers result from the presence of a C=N double bond in the compound of formula. Additionally, asymmetric carbon atoms may be present, so that the compounds may exist as optical antipodes. The formula is therefore meant to include all these possible isomers. Physiologically compatible salts are considered as acid addition salts of the compound of formula. These salts include inorganic or organic acids such as hydrochloric acid, nitric acid, phosphoric acid, mono- or difunctional carboxylic acids and hydroxycarboxylic acids such as acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid) as well as sulfonic acids (e.g. 1,5-naphthalene-
Disulfonic acid) is preferred. The method of the present invention for producing compounds of formula (a) and their salts comprises: (a) (In the formula, R 1 , R 2 and R 3 have the above meanings)
An oxime of the formula R 4 U {where R 4 has the above meaning and U represents a leaving group (e.g. chlorine, bromine, iodine, mesyloxy,
tosyloxy or alkyl sulfate group), or (b) (In the formula, R 1 , R 2 and R 3 have the above meanings)
reacting a ketone of the formula R 41 ONH 2 with an O-substituted hydroxylamine of the formula R 41 ONH 2 , in which R 41 represents C 1-6 -alkyl, C 3-6 -cycloalkyl or C 3-6 -alkenyl;
and, if desired, converting the obtained compound of formula into an acid addition salt. Variant (a) comprises starting with a compound of the formula, conveniently in the presence of a base, in an organic solvent at 0°C.
and the reflux temperature of the reaction mixture. The solvent may be protic or aprotic. If protic solvents such as alcohols, especially methanol or ethanol, are used, preference is given to using alkali metal hydroxides (eg sodium or potassium hydroxide) or alkali metal alcoholates as bases. When using aprotic solvents such as ethers or ether-like solvents, especially tetrahydrofuran or dimethoxyethane, and dialkylamides, especially dimethylformamide, preference is given to using alkali metal hydrides (e.g. sodium hydride) as the base. . In a preferred embodiment of variant (a), sodium hydride is used as base and an ether or ether-like compound, especially tetrahydrofuran or dimethoxyethane, or a dialkylamide, especially dimethylformamide, is used as solvent. In variant (b), which gives compounds of the formula in which R 4 represents C 1-6 -alkyl, C 3-6 -cycloalkyl or C 3-6 -alkenyl, the reaction is carried out in an organic solvent, such as an alcohol such as methanol or ethanol. , a dialkylamide such as dimethylformamide or a tertiary amine such as pyridine. Preferably, the reaction is carried out within a temperature range between room temperature and the reflux temperature of the reaction mixture. Since the starting materials of the formula are preferably used in the form of acid addition salts (for example hydrochlorides or sulphates), it is expedient to add a base such as sodium or potassium carbonate, triethylamine or pyridine to the reaction mixture. For the preparation of acid addition salts, compounds of the formula are reacted, if desired, with inorganic or organic acids such as hydrochloric acid, nitric acid, phosphoric acid, mono- and difunctional carboxylic acids and hydroxycarboxylic acids or sulfonic acids. Isolation and purification of the compounds of the formula and their acid addition salts thus prepared are carried out by methods known per se. The formulas and compounds used as starting materials are known or can be prepared by methods known per se. For example, oximes of the formula can be prepared from the corresponding ketones of the formula by reaction with hydroxylamine;
It can be manufactured by the method described in DOS2800010 and British Patent Specification No. 2015524. The compounds according to the invention (i.e. the compounds of formula and their acid addition salts) have fungicidal activity;
Therefore, it can be used for controlling mold in agriculture and horticulture. They are particularly suitable for eradicating or controlling plant pathogens on plant parts (e.g. leaves, stems, roots, stems, fruits or flowers) and seeds, and in soil, and in particular for the eradication or control of powdery mildews, e.g. Erysiphe graminis (powdery mildew of grains), Erysiphe cichoracearum (mildew of cucumbers), Podosphaera leucotricha (mildew of apples) and Erysiphe cichoracearum (mildew of cucumbers) Sphaerotheca pannosa (powdery mildew of roses)
Venturia ainequaris (Venturia
inaequalis (apple scab), rust fungi such as Puccinia, Uromyces and Hemileia, especially Puccinia coronata
coronata (crown rust of oats), Puccinia recondita (red rust of grains), Uromyces appendiculatus (bean rust) and Hemileia
It is effective in controlling coffee rust (coffee rust). Additionally, various compounds of the invention also have activity against plant pathogens of the following genera: Helminthosporium, Rhizoctonia, Septoria, Cercospora, Corticium. , Tilletia and Ustilago. Furthermore, the individual compounds of the invention may be used in wood-destroying fungi such as Coniophora
puteana) and range test labia (Lenzites)
trabea). Furthermore, each compound also has activity against phytopathogenic bacteria such as Xanthomonas oryzae. The compounds of the invention have systemic activity (systemic activity).
activity) as well as good plant tolerance. The compounds of the invention are active under greenhouse conditions even at concentrations of active substance from 5 mg to 500 mg per spray liquid. In the field, 50g per hectare
Active substance concentrations and treatments of the formula 1000 g are advantageous for application. For example, effective control of apple powdery mildew and apple rust requires a
Active substance concentrations of formulas from g to 400 g are used. For controlling mold on seeds during disinfection processes, it is advantageous to use from 0.1 to 2.5 g of active substance per kg of seeds. The compounds of the invention can be formulated to provide a variety of compositions, such as spray solutions, aqueous suspensions, emulsions, emulsion concentrates, and powder formulations. The fungicidal compositions of the present invention contain an effective amount of at least one compound of the general formula as defined above or an acid addition salt of such a compound and an inert carrier material. The composition is generally 0.0001 depending on its type.
and 95% by weight of the compound of the invention as active substance. Various inert powder carrier materials such as kaolin,
Bentonite, talc, chalk, magnesium carbonate and siliceous earth can be used to make powdered fungicidal compositions. The active ingredient can be mixed with such a carrier material (e.g. by grinding together) or an inert carrier material can be impregnated with a solution of the active ingredient and the solvent can be evaporated, heated or filtered off with suction under reduced pressure. Twist and remove. Such a powder composition can be applied as a wiping composition to the plants to be protected using conventional wiping equipment. By adding wetting and/or dispersing agents, such pulverulent compositions can be made easily wettable with water, so that they can also be used in the form of aqueous suspensions as spray compositions. . To produce emulsified concentrates, the active substance is mixed with an emulsifier, for example, or dissolved in an inert solvent and mixed with an emulsifier. By diluting such a concentrate with water, a ready-to-use emulsion is obtained. Such concentrates contain 5 to 95% by weight of active substance, in particular 25 to 75% by weight. The fungicidal compositions of the present invention contain, in addition to the active substance of the formula, other active substances such as other fungicides,
(insecticides and acaricides, other fungicides, plant growth regulators and fertilizers). Such combination compositions are suitable for broadening the spectrum of activity or for influencing specific plant growth. The compounds of the invention can be used in plant protection or in agriculture by conventional application methods. The method for controlling mold according to the invention is characterized in that the article to be protected (for example a plant, a part of a plant or a seed) is treated with an effective amount of a compound according to the invention or a composition according to the invention. The following examples illustrate the invention. All temperatures are in °C. Example of Preparation of Active Substances 1 A solution of 13.3 g of 2',4'-dichloro-2-(3-pyridyl)-acetophenone in 40 ml of ethanol is mixed with 10 g of sodium carbonate and 8.3 g of O-methylhydroxylamine hydrochloride. treated with salt,
The mixture is then heated to reflux temperature with stirring. After 4 hours, the mixture is poured onto ice and extracted with ethyl acetate. Wash the organic layer, dry over sodium sulfate and concentrate under reduced pressure. 2′,4′-dichloro-
2-(3-Pyridyl)-acetophenone O-methyloxime is obtained as an E,Z-isomer mixture in the form of a yellow oil. n-hexane/on silica gel
Chromatographic separation was performed using ethyl acetate (4:1) to first separate the E-isomer (n 20 D = 1.5845).
and then the Z-isomer (n 20 D =1.5745). Similarly, 4'-chloro-2-(3-pyridyl)-acetophenone O-methyloxime, mp55-58, was prepared from 4'-chloro-2-(3-pyridyl)-acetophenone and O-methyl-hydroxylamine hydrochloride. 4'-chloro-2-(2-pyrazinyl)-acetophenone O-methyloxime from 4'-chloro-2-(2-pyrazinyl)-acetophenone and O-methylhydroxylamine hydrochloride, mp53-58℃ , obtained from 4'-chloro-2-(2-pyrazinyl)-acetophenone and O-ethylhydroxylamine hydrochloride, 4'-chloro-2-(2-pyrazinyl)-acetophenone O-ethyloxime, mp44-46° obtained; 4'-chloro-2-(2-pyrazinyl)-acetophenone O-allyl oxime as a yellow oil from 4'-chloro-2-(2-pyrazinyl)-acetophenone and O-allylhydroxylamine hydrochloride. Obtained; 2',4'-dichloro-2-(3-pyridyl)- from 2',4'-dichloro-2-(3-pyridyl)-acetophenone and O-allylhydroxylamine hydrochloride.
Acetophenone O-allyl oxime is obtained as a colorless oil. Example 2 3 g of 2'-chloro-2-(2-pyrazinyl)-acetophenone and 0.8 g of O-methylhydroxylamine hydrochloride are dissolved in 10 ml of pyridine and the mixture is heated at 80 DEG C. for 30 minutes. The pyridine is then removed under reduced pressure and water is added to the crude product. Thereupon, the mixture is extracted with ethyl acetate, the organic layer is dried over sodium sulfate and concentrated.
2'-chloro-2-(2-pyrazinyl)-acetophenone O-methyloxime is obtained as an oil. Similarly, 4'-fluoro-2-(2-pyrazinyl)-acetophenone O-methyloxime, mp52-54°, was prepared from 4'-fluoro-2-(2-pyrazinyl)-acetophenone and O-methylhydroxylamine hydrochloride. ,
4'-bromo-2-(2-pyrazinyl)-acetophenone O-methyloxime, mp81-84°, from 4'-bromo-2-(2-pyrazinyl)-acetophenone and O-methylhydroxylamine hydrochloride; 4'-Chloro-2-(2-pyrazinyl)-propiophenone O-methyloxime was obtained as an oil from 4'-chloro-2-(2-pyrazinyl)-propiophenone and O-methylhydroxylamine hydrochloride. Obtained as a product; 2',4'-dichloro-2-(2-pyrazinyl)-acetophenone O-methyl from 2',4'-dichloro-2-(2-pyrazinyl)-acetophenone and O-methylhydroxylamine hydrochloride The oxime was obtained as an oil; 2',4'-dichloro-2-(2-pyrazinyl)-acetophenone from 2',4'-dichloro-2-(2-pyrazinyl)-acetophenone and O-methylhydroxylamine hydrochloride. O-ethyloxime was obtained as an oil; 2',4'-dichloro-2-(2-pyrazinyl) was obtained from 2',4'-dichloro-2-(2-pyrazinyl)-acetophenone and O-allylhydroxylamine hydrochloride. )-acetophenone O-allyloxime obtained as an oil; 2',4'-dichloro-2-(2-pyrazinyl)-propio-phenone and O-methylhydroxylamine hydrochloride to obtain 2',4'-dichloro-2 -(2-pyrazinyl)-propiophenone O-methyloxime is obtained as an oil. Example 3 A solution of 3 g of 2',4'-dichloro-2-(3-pyridyl)-acetophenone oxime in 25 ml of dimethoxyethane is diluted with 0.51 g of a sodium hydride dispersion (55% in oil). The mixture is stirred for 30 minutes at room temperature. Then 2.0 g of ethyl iodide are added and the mixture is heated to reflux temperature. 4
After some time, the mixture is poured onto ice, extracted with ethyl acetate, the organic layer is dried over sodium sulfate and concentrated under reduced pressure. The crude product is purified by chromatography on silica gel. 2',4'-dichloro-2-(3-pyridyl)-acetophenone O-ethyloxime is obtained as a yellow oil. Similarly, from 2',4'-dichloro-2-(3-pyridyl)-acetophenone oxime and isopropyl bromide, 2',
4'-Dichloro-2-(3-pyridyl)-acetophenone O-isopropyloxime obtained as a yellow oil; from 2',4'-dichloro-2-(3-pyridyl)-acetophenone oxime and propargyl bromide. 2′,
4'-dichloro-2-(3-pyridyl)-acetophenone O-propargyloxime, mp60-62°,
obtained; 4'-chloro-2-(2-pyrazinyl)-acetophenone O- from 4'-chloro-2-(2-pyrazinyl)-acetophenone oxime and propargyl bromide.
Propargyl oxime, mp76−77°, was obtained from 2′,4′-dichloro-2-(2-pyrazinyl)-acetophenone oxime and propargyl bromide.
2',4'-di-chloro-2-(2-pyrazinyl)-acetophenone O-propargyloxime is obtained as an oil. Preparation of Starting Materials Example 4 The 2',4'-dichloro-2-(3-pyridyl)-acetophenone required as starting material in Example 1 may be constituted as follows: 27.6 g of ethyl 2,4-dichlorobenzoic acid and
A mixture of 20.81 g of ethyl 3-pyridyl acetate is treated in portions at 20-25° with 10.59 g of sodium methoxide. The mixture is then heated to 65-70° and the resulting highly volatile product is blown off with dry nitrogen. After 20 hours, the mixture is treated with 40 ml of concentrated hydrochloric acid and heated at reflux temperature for 18 hours. The mixture was washed with diethyl ether, the aqueous layer made basic by addition of concentrated ammonia,
Extract with methylene chloride. The organic layer is concentrated and the crude product is chromatographed on silica gel with methylene chloride/methanol (98:2).
The purified product, 2',4'-dichloro-2-(3-pyridyl)-acetophenone, was dissolved in diethyl ether/n
- Recrystallization from pentane. mp55−56°. Example 5 The 2',4'-dichloro-2-(2-pyrazinyl)-acetophenone required as starting material in Example 2 is prepared as follows; 20 g of 2-methylpyrazine is added to the suspension of sodium amide in liquid ammonia. Add dropwise to the suspension (from 200 ml of ammonia and 4.83 g of sodium) at -30° and stir the mixture for 30 minutes. 20.5 g of methyl 2,4-dichlorobenzoic acid are then slowly added dropwise and the mixture is allowed to react for 1 hour at -30°. The mixture was then treated with ammonium chloride,
Remove ammonia and add diethyl ether. The organic layer is washed with water, dried over sodium sulfate, and concentrated. Upon treatment with a small amount of ethanol, 2',4'-dichloro-2-(2-pyrazinyl)-acetophenone crystallizes from the crude reaction product. The product melts at 96-98°. In a similar manner, 2'-chloro-2-(2-pyrazinyl)-acetophenone was obtained as an oil from 2-methylpyrazine and methyl 2-chlorobenzoic acid; 4 from 2-methylpyrazine and methyl 4-fluorobenzoic acid. '-Fluoro-2-(2-pyrazinyl)-
Acetophenone, mp100-103°, was obtained; 2-methylpyrazine and methyl 4-bromobenzoic acid gave 4'-bromo-2-(2-pyrazinyl)-acetophenone, mp121-122°; 2-ethylpyrazine and 4'-chloro-2-(2-pyrazinyl)-propiophenone, mp85°, is obtained from methyl 4-chlorobenzoic acid; 2',4' dichloro is obtained from 2-ethylpyrazine and methyl 2,4-dichlorobenzoic acid. -2-(2-pyrazinyl)-propiophenone is obtained as an oil. Example 6 4'-Chloro-2- required as starting material in Example 3
(2-pyrazinyl)-acetophenone oxime may be prepared as follows; 10 g of 4'-chloro-2-(2-pyrazinyl)-acetophenone, 10 g of hydroxylamine hydrochloride and 12 g of anhydrous sodium carbonate at 60° Stir in 100 ml of ethanol for 2 hours. The mixture is then treated with water, extracted with ethyl acetate, and the organic layer is dried over sodium sulfate and then concentrated. The residue is recrystallized from acetone/n-hexane.
4'-chloro-2-(2-pyrazinyl)-acetophenone oxime, mp 134°, is obtained. In a similar manner, 2',4'-dichloro-2-(2-pyrazinyl)-acetophenone and hydroxylamine hydrochloride were prepared.
2',4'-dichloro-2-(2-pyrazinyl)-acetophenone oxime obtained as a viscous oil; from 2',4'-dichloro-2-(3-pyridyl)-acetophenone and hydroxylamine hydrochloride. 2′,
4'-dichloro-2-(3-pyridyl)-acetophenone oxime, mp 134-136°, is obtained. EXAMPLE 7 FORMULATION EXAMPLE 7 1 Spray Powder (for active substance that is liquid or melts below 75°) Parts by weight of active substance 50 Hydrated silicic acid 37 Kaolin 5 Alkylphenol ethoxylate 4 Sodium polynaphthalene sulfonate 4 100 Liquid or absorbing the molten active substance into silicic acid;
Mix the remaining ingredients and finely grind the mixture in a suitable mill. 2 Spray powder (based on solid active substances melting above 75°) Parts by weight of active substance 50 Hydrated silicic acid 5 Kaolin 42 Sodium uralyl sulfate 1 Sodium lignosulfonate 2 100 The components are mixed together and this The mixture is finely ground in a suitable mill. Example 8 Emulsified concentrate (for active substance liquid at 20-25°) Parts by weight Active substance of the formula 500 Castor oil ethoxylate 100 Calcium dodecylbenzene sulfonate 25 C 10 -Mixture of alkylbenzenes
Add 1000 parts by volume of each component to each other and mix until a clear solution is obtained. Evaluation of fungicidal activity Test: Powdery mildew of cucumber (Erysiphe
Aqueous dispersion of the test compound (prepared in a conventional manner as a powder for spraying) was thoroughly applied to each of two cucumber plants at the two-leaf stage of the Chinese Snake species. The plants were thoroughly sprayed from all directions and then cultivated in a greenhouse. 24 hours after this treatment, on the first leaf of the plant
Infection was achieved by sprinkling with spores of Erysiphe cichoracearum. After a further 7-9 days, the degree of protection conferred by the test compound was determined by comparing the infections found on the leaf surface of the test plants with Erysiphe, without treatment with the test compound.
It was evaluated by comparing the infection found on the leaf surface of control plants infected with Cichoracearum. Test: Apple scab (Venturia inaequalis)
Activity against “Golden Delicious”
Delicious) 3 seedlings of apple seeds
A suspension of Venturia inaequalis spores was sprayed and then incubated at 18° C. under dew point conditions. After 24 hours, the plants were thoroughly sprayed from all directions with an aqueous dispersion of the test compound (prepared in a conventional manner as a powder for spraying). The apple seedlings thus treated were further cultivated in a greenhouse. After 9 to 10 days, the degree of protection conferred by the test compound was determined by the amount of infection and Venturia found on the leaf surface of the test plants.
inaequalis similarly infected, but not treated with the test compound. The activity of both tests for these test compounds, expressed as percent activity, is shown in the following table:
【表】【table】
【表】
上記2つの各試験において、本発明の代表的化
合物は16mg/および5mg/の低い施用量にお
いてさえも、僅かの例外はあるとしても殺カビ活
性を示した。160mg/の最高施用量における活
性はほとんどの場合が100%であつた。これらの
優れた結果に反して、従来技術の化合物、すなわ
ち特開昭55−19288号公報(ヨーロツパ特許出願
公報第7679号)の例1の9番目および10番目の化
合物は160mg/の最高施用量でも、一段と低い
殺カビ活性を示し、さらに低い施用量では、ほと
んど活性をしめさないか、または全く活性を示さ
ない。
上記試験結果にもとづき、本発明の化合物は優
れた殺カビ活性を有することが証明され、他方従
来技術の化合物はこれらの試験結果にもとづき、
殺カビ活性を僅かしか有しないか、または全く有
していないことが証明された。Table: In each of the two tests above, representative compounds of the invention showed fungicidal activity, with few exceptions, even at low application rates of 16 mg/ and 5 mg/. The activity at the highest application rate of 160 mg/was 100% in most cases. Contrary to these excellent results, the compounds of the prior art, i.e. the 9th and 10th compounds of Example 1 of JP-A-55-19288 (European Patent Application Publication No. 7679), have a maximum application rate of 160 mg/ However, it shows even lower fungicidal activity, and at even lower application rates it shows little or no activity. Based on the above test results, the compounds of the present invention were proved to have excellent fungicidal activity, whereas the compounds of the prior art were shown to have excellent fungicidal activity based on these test results.
It was demonstrated that they had little or no fungicidal activity.
Claims (1)
−ジハロ−フエニルを表わし、 R2は3−ピリジル又は2−ピラジニルを表わ
し、 R3は水素又は駄鎖状C1-4−アルキルを表わし、
そして R4はC1-6−アルキル、C3-6−シクロアルキル、
C3-6−アルケニル又はC3-6−アルキニルを表わ
す) なる化合物およびこれら化合物の酸付加塩。 2 R1が4−クロロフエニル又は2,4−ジク
ロロフエニルを表わす特許請求の範囲第1項の化
合物。 3 R3が水素を表わす特許請求の範囲第1項又
は第2項のいずれか1つの化合物。 4 2′,4′−ジクロロ−2−(3−ピリジル)−ア
セトフエノンO−メチルオキシムである特許請求
の範囲第1項の化合物。 5 4′−クロロ−2−(3−ピリジル)−アセトフ
エノンO−メチルオキシム、 4′−クロロ−2−(2−ピラジニル)−アセトフ
エノンO−メチルオキシム、 4′−クロロ−2−(2−ピラジニル)−アセトフ
エノンO−エチルオキシム、 4′−クロロ−2−(2−ピラジニル)−アセトフ
エノンO−アリルオキシム、 2′,4′−ジクロロ−2−(3−ピリジル)−アセ
トフエノンO−エチルオキシム、 2′,4′−ジクロロ−2−(3−ピリジル)−アセ
トフエノンO−イソプロピルオキシムおよび 2′,4′−ジクロロ−2−(3−ピリジル)−アセ
トフエノンO−プロパルギルオキシム から選択される特許請求の範囲第1項の化合物。 6 2′,4′−ジクロロ−2−(3−ピリジル)−ア
セトフエノンO−アリルオキシム、 2′−クロロ−2−(2−ピラジニル)−アセトフ
エノンO−メチルオキシム、 4′−フルオロ−2−(2−ピラジニル)−アセト
フエノンO−メチルオキシム、 4′−ブロモ−2−(2−ピラジニル)−アセトフ
エノンO−メチルオキシム、 4′−クロロ−2−(2−ピラジニル)−プロピオ
フエノンO−メチルオキシム、 2′,4′−ジクロロ−2−(2−ピラジニル)−ア
セトフエノンO−メチルオキシム、 2′,4′−ジクロロ−2−(2−ピラジニル)−ア
セトフエノンO−エチルオキシム、 2′,4′−ジクロロ−2−(2−ピラジニル)−ア
セトフエノンO−アリルオキシム、 2′,4′−ジクロロ−2−(2−ピラジニル)−プ
ロピオフエノンO−メチルオキシム、 4′−クロロ−2−(2−ピラジニル)−アセトフ
エノンO−プロパルギルオキシムおよび 2′,4′−ジクロロ−2−(2−ピラジニル)−ア
セトフエノンO−プロパルギルオキシム から選択される特許請求の範囲第1項の化合物。 7 有効量の少くとも1種類の一般式 (式中R1は2−ハロ−、4−ハロ−又は2,4
−ジハロ−フエニルを表わし、 R2は3−ピリジル又は2−ピラジニルを表わ
し、 R3は水素又は直鎖状C1-4−アルキルを表わし、
そして R4はC1-6−アルキル、C3-6−シクロアルキル、
C3-6−アルケニル又はC3-6−アルキニルを表わ
す) なる化合物又はかかる化合物の酸付加塩ならびに
不活性担体物質を含有する殺カビ組成物。 8 有効量の2′,4′−ジクロロ−2−(3ピリジ
ル)−アセトフエノンO−メチルオキシムおよび
不活性担体物質を含有する特許請求の範囲第8項
の殺カビ組成物。 9 一般式 (R1は2−ハロ−、4−ハロ−又は2,4−ジ
ハロ−フエニルを表わし、 R2は3−ピリジル又は2−ピラジニルを表わ
し、 R3は水素又は直鎖状C1-4−アルキルを表わし、
そして R4はC1-6−アルキル、C3-6−シクロアルキル、
C3-6−アルケニル又はC3-6−アルキニルを表わ
す) なる化合物およびそれらの酸付加塩の製造方法で
あつて 式 (式中R1、R2およびR3は前記の定義と同じであ
る) なるオキシム化合物を、式 R4U (式中R4は定義と同じであり、そしてUは塩素、
臭素、ヨウ素、メシルオキシ、トシルオキシまた
はアルキルスルフエート基を表わす) なる化合物と反応させ、そして所望ならば、得ら
れた式なる化合物を酸付加塩に変換することか
らなるその製造方法。 10 一般式1 (R1は2−ハロ−、4−ハロ−又は2,4−ジ
ハロ−フエニルを表わし、 R2は3−ピリジル又は2−ピラジニルを表わ
し、 R3は水素又は直鎖状C1-4−アルキルを表わし、
そして R4はC1-6−アルキル、C3-6−シクロアルキル、
C3-6−アルケニル又はC3-6−アルキニルを表わ
す) なる化合物およびそれらの酸付加塩の製造方法で
あつて、 式 (式中R1、R2およびR3は前記の定義と同じであ
る) なるケトン化合物物を、式 R41ONH2 () (式中R41はC1-6−アルキル、C3-6−シクロアル
キル又はC3-6−アルケニルを表わす) なるO−置換ヒドロキシルアミン化合物と反応さ
せ、そして所望ならば、得られた式なる化合物
を酸付加塩に変換することからなるその製造方
法。[Claims] 1. General formula (In the formula, R 1 is 2-halo-, 4-halo- or 2,4
-dihalo-phenyl, R 2 represents 3-pyridyl or 2-pyrazinyl, R 3 represents hydrogen or chain-like C 1-4 -alkyl,
and R 4 is C 1-6 -alkyl, C 3-6 -cycloalkyl,
C3-6 -alkenyl or C3-6 -alkynyl) and acid addition salts of these compounds. 2. A compound according to claim 1, wherein R 1 represents 4-chlorophenyl or 2,4-dichlorophenyl. 3. A compound according to claim 1 or claim 2, wherein R 3 represents hydrogen. 4. The compound of claim 1 which is 2',4'-dichloro-2-(3-pyridyl)-acetophenone O-methyloxime. 5 4'-chloro-2-(3-pyridyl)-acetophenone O-methyloxime, 4'-chloro-2-(2-pyrazinyl)-acetophenone O-methyloxime, 4'-chloro-2-(2-pyrazinyl) )-acetophenone O-ethyloxime, 4'-chloro-2-(2-pyrazinyl)-acetophenone O-allyloxime, 2',4'-dichloro-2-(3-pyridyl)-acetophenone O-ethyloxime, 2 Claims selected from ',4'-dichloro-2-(3-pyridyl)-acetophenone O-isopropyloxime and 2',4'-dichloro-2-(3-pyridyl)-acetophenone O-propargyloxime Compound of item 1. 6 2',4'-dichloro-2-(3-pyridyl)-acetophenone O-allyloxime, 2'-chloro-2-(2-pyrazinyl)-acetophenone O-methyloxime, 4'-fluoro-2-( 2-pyrazinyl)-acetophenone O-methyloxime, 4'-bromo-2-(2-pyrazinyl)-acetophenone O-methyloxime, 4'-chloro-2-(2-pyrazinyl)-propiophenone O-methyloxime , 2',4'-dichloro-2-(2-pyrazinyl)-acetophenone O-methyloxime, 2',4'-dichloro-2-(2-pyrazinyl)-acetophenone O-ethyloxime, 2',4' -dichloro-2-(2-pyrazinyl)-acetophenone O-allyloxime, 2',4'-dichloro-2-(2-pyrazinyl)-propiophenone O-methyloxime, 4'-chloro-2-(2 -Pyrazinyl)-acetophenone O-propargyl oxime and 2',4'-dichloro-2-(2-pyrazinyl)-acetophenone O-propargyl oxime. 7. At least one general formula for effective amounts (In the formula, R 1 is 2-halo-, 4-halo- or 2,4
-dihalo-phenyl, R2 represents 3-pyridyl or 2-pyrazinyl, R3 represents hydrogen or linear C1-4 -alkyl,
and R 4 is C 1-6 -alkyl, C 3-6 -cycloalkyl,
C3-6 -alkenyl or C3-6 -alkynyl) or an acid addition salt of such a compound and an inert carrier material. 8. The fungicidal composition of claim 8 containing an effective amount of 2',4'-dichloro-2-(3pyridyl)-acetophenone O-methyloxime and an inert carrier material. 9 General formula (R 1 represents 2-halo-, 4-halo- or 2,4-dihalo-phenyl, R 2 represents 3-pyridyl or 2-pyrazinyl, R 3 is hydrogen or linear C 1-4 - represents alkyl,
and R 4 is C 1-6 -alkyl, C 3-6 -cycloalkyl,
C 3-6 -alkenyl or C 3-6 -alkynyl) and an acid addition salt thereof (wherein R 1 , R 2 and R 3 are as defined above), an oxime compound of the formula R 4 U (wherein R 4 is as defined above and U is chlorine,
bromine, iodine, mesyloxy, tosyloxy or an alkylsulfate group and, if desired, converting the resulting compound of the formula into an acid addition salt. 10 General formula 1 (R 1 represents 2-halo-, 4-halo- or 2,4-dihalo-phenyl, R 2 represents 3-pyridyl or 2-pyrazinyl, R 3 is hydrogen or linear C 1-4 - represents alkyl,
and R 4 is C 1-6 -alkyl, C 3-6 -cycloalkyl,
C 3-6 -alkenyl or C 3-6 -alkynyl) and acid addition salts thereof, the method comprising: (wherein R 1 , R 2 and R 3 are the same as defined above), a ketone compound having the formula R 41 ONH 2 () (wherein R 41 is C 1-6 -alkyl, C 3-6 -representing cycloalkyl or C3-6 -alkenyl) and, if desired, converting the obtained compound of the formula into an acid addition salt.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH758480 | 1980-10-10 |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5793903A JPS5793903A (en) | 1982-06-11 |
JPH0136828B2 true JPH0136828B2 (en) | 1989-08-02 |
Family
ID=4327425
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP16085781A Granted JPS5793903A (en) | 1980-10-10 | 1981-10-08 | Fungicide |
Country Status (2)
Country | Link |
---|---|
JP (1) | JPS5793903A (en) |
ZA (1) | ZA816850B (en) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5519288A (en) * | 1978-07-25 | 1980-02-09 | Acf Chemiefarma Nv | Tumorrcontrol active drug composition*novel oxime ether derivative for its use and its manufacture |
-
1981
- 1981-10-02 ZA ZA816850A patent/ZA816850B/en unknown
- 1981-10-08 JP JP16085781A patent/JPS5793903A/en active Granted
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5519288A (en) * | 1978-07-25 | 1980-02-09 | Acf Chemiefarma Nv | Tumorrcontrol active drug composition*novel oxime ether derivative for its use and its manufacture |
Also Published As
Publication number | Publication date |
---|---|
JPS5793903A (en) | 1982-06-11 |
ZA816850B (en) | 1982-09-29 |
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