DE3539476A1 - Novel pyridyl compounds and their N-oxides, process for their preparation, and their use in crop protection - Google Patents
Novel pyridyl compounds and their N-oxides, process for their preparation, and their use in crop protectionInfo
- Publication number
- DE3539476A1 DE3539476A1 DE19853539476 DE3539476A DE3539476A1 DE 3539476 A1 DE3539476 A1 DE 3539476A1 DE 19853539476 DE19853539476 DE 19853539476 DE 3539476 A DE3539476 A DE 3539476A DE 3539476 A1 DE3539476 A1 DE 3539476A1
- Authority
- DE
- Germany
- Prior art keywords
- alkyl
- compounds
- formula
- alkoxy
- substituted
- 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.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 125000004076 pyridyl group Chemical group 0.000 title claims abstract description 6
- 150000001204 N-oxides Chemical class 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims abstract description 72
- -1 (substituted) phenyl Chemical group 0.000 claims abstract description 33
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 6
- 239000004009 herbicide Substances 0.000 claims description 28
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 19
- 150000003839 salts Chemical class 0.000 claims description 16
- 230000002363 herbicidal effect Effects 0.000 claims description 13
- 230000000694 effects Effects 0.000 claims description 12
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Chemical class 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 125000005842 heteroatom Chemical group 0.000 claims description 8
- 150000002576 ketones Chemical class 0.000 claims description 8
- 125000000304 alkynyl group Chemical group 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 238000005956 quaternization reaction Methods 0.000 claims description 7
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 231100000208 phytotoxic Toxicity 0.000 claims description 6
- 230000000885 phytotoxic effect Effects 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000417 fungicide Substances 0.000 claims description 5
- 125000000623 heterocyclic group Chemical group 0.000 claims description 5
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 4
- 241000233866 Fungi Species 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 4
- 239000004476 plant protection product Substances 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- BADXJIPKFRBFOT-UHFFFAOYSA-N dimedone Chemical class CC1(C)CC(=O)CC(=O)C1 BADXJIPKFRBFOT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- FMPJHEINDXIEHS-UHFFFAOYSA-N (2-phenoxyphenyl) hydrogen carbonate Chemical class OC(=O)OC1=CC=CC=C1OC1=CC=CC=C1 FMPJHEINDXIEHS-UHFFFAOYSA-N 0.000 claims description 2
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 claims description 2
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 claims description 2
- 125000003601 C2-C6 alkynyl group Chemical group 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 150000004657 carbamic acid derivatives Chemical class 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 244000038559 crop plants Species 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000002883 imidazolyl group Chemical group 0.000 claims description 2
- 239000012038 nucleophile Substances 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims 1
- 239000011814 protection agent Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 19
- 230000000855 fungicidal effect Effects 0.000 abstract description 10
- 241000196324 Embryophyta Species 0.000 description 26
- 239000004480 active ingredient Substances 0.000 description 23
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- 206010061217 Infestation Diseases 0.000 description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 244000098338 Triticum aestivum Species 0.000 description 11
- 239000000047 product Substances 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 8
- 235000021307 Triticum Nutrition 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000009472 formulation Methods 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 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 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 240000005979 Hordeum vulgare Species 0.000 description 5
- 230000006378 damage Effects 0.000 description 5
- 239000004495 emulsifiable concentrate Substances 0.000 description 5
- 239000003995 emulsifying agent Substances 0.000 description 5
- 229920000151 polyglycol Polymers 0.000 description 5
- 239000010695 polyglycol Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 125000004201 2,4-dichlorophenyl group Chemical group [H]C1=C([H])C(*)=C(Cl)C([H])=C1Cl 0.000 description 4
- 235000007320 Avena fatua Nutrition 0.000 description 4
- 241000219310 Beta vulgaris subsp. vulgaris Species 0.000 description 4
- 240000008067 Cucumis sativus Species 0.000 description 4
- 235000007340 Hordeum vulgare Nutrition 0.000 description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000729 antidote Substances 0.000 description 4
- 235000013339 cereals Nutrition 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 238000001212 derivatisation Methods 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 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 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000005995 Aluminium silicate Substances 0.000 description 3
- 244000075850 Avena orientalis Species 0.000 description 3
- 241000221785 Erysiphales Species 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 206010039509 Scab Diseases 0.000 description 3
- 235000021536 Sugar beet Nutrition 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 235000012211 aluminium silicate Nutrition 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
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000011534 incubation Methods 0.000 description 3
- 238000011081 inoculation Methods 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000575 pesticide Substances 0.000 description 3
- 150000003222 pyridines Chemical class 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 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 description 3
- 239000004563 wettable powder Substances 0.000 description 3
- PIODTJOXJJOIIK-UHFFFAOYSA-N 2-(2,4-dichlorophenyl)-1-pyridin-3-ylethanone Chemical compound ClC1=CC(Cl)=CC=C1CC(=O)C1=CC=CN=C1 PIODTJOXJJOIIK-UHFFFAOYSA-N 0.000 description 2
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 2
- 241000209764 Avena fatua Species 0.000 description 2
- 235000007319 Avena orientalis Nutrition 0.000 description 2
- 241001480061 Blumeria graminis Species 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 2
- 241000530549 Cercospora beticola Species 0.000 description 2
- 235000010799 Cucumis sativus var sativus Nutrition 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 241000228452 Venturia inaequalis Species 0.000 description 2
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- 239000000853 adhesive Substances 0.000 description 2
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- MFSWTRQUCLNFOM-UHFFFAOYSA-N methyl 2-(4-{[3-chloro-5-(trifluoromethyl)pyridin-2-yl]oxy}phenoxy)propanoate Chemical compound C1=CC(OC(C)C(=O)OC)=CC=C1OC1=NC=C(C(F)(F)F)C=C1Cl MFSWTRQUCLNFOM-UHFFFAOYSA-N 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
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- 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
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- MMUWQHZQZQLGKK-UHFFFAOYSA-N 1,3-bis(2,4-dichlorophenyl)-1,3-dipyridin-3-ylpropan-2-one Chemical class ClC1=CC(Cl)=CC=C1C(C=1C=NC=CC=1)C(=O)C(C=1C(=CC(Cl)=CC=1)Cl)C1=CC=CN=C1 MMUWQHZQZQLGKK-UHFFFAOYSA-N 0.000 description 1
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- KOWHLENJKMKUSP-UHFFFAOYSA-N 2-(2,4-dichlorophenyl)-1-pyridin-3-ylprop-2-en-1-one Chemical compound ClC1=CC(Cl)=CC=C1C(=C)C(=O)C1=CC=CN=C1 KOWHLENJKMKUSP-UHFFFAOYSA-N 0.000 description 1
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- GVEQCFMNUYFHOE-UHFFFAOYSA-N 2-phenyl-1-pyridin-3-ylethanone Chemical class C=1C=CN=CC=1C(=O)CC1=CC=CC=C1 GVEQCFMNUYFHOE-UHFFFAOYSA-N 0.000 description 1
- FOGYNLXERPKEGN-UHFFFAOYSA-N 3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfopropyl)phenoxy]propane-1-sulfonic acid Chemical compound COC1=CC=CC(CC(CS(O)(=O)=O)OC=2C(=CC(CCCS(O)(=O)=O)=CC=2)OC)=C1O FOGYNLXERPKEGN-UHFFFAOYSA-N 0.000 description 1
- KHCXGFNZZRXOND-UHFFFAOYSA-N 3-(bromomethyl)pyridine Chemical compound BrCC1=CC=CN=C1 KHCXGFNZZRXOND-UHFFFAOYSA-N 0.000 description 1
- PTPIVUVKXKUXEA-UHFFFAOYSA-N 3-[di(propan-2-yl)amino]propane-1-thiol Chemical compound CC(C)N(C(C)C)CCCS PTPIVUVKXKUXEA-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- NNUHGJSXHBGPNM-UHFFFAOYSA-N 3-chloro-n,n-diethylbutan-1-amine Chemical compound CCN(CC)CCC(C)Cl NNUHGJSXHBGPNM-UHFFFAOYSA-N 0.000 description 1
- XYISTKLMNCHVRS-UHFFFAOYSA-N 4-(bromomethyl)pyridazine Chemical compound BrCc1ccnnc1 XYISTKLMNCHVRS-UHFFFAOYSA-N 0.000 description 1
- VTOWJTPBPWTSMK-UHFFFAOYSA-N 4-morpholin-4-ylbutane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCCN1CCOCC1 VTOWJTPBPWTSMK-UHFFFAOYSA-N 0.000 description 1
- 235000016068 Berberis vulgaris Nutrition 0.000 description 1
- 241000335053 Beta vulgaris Species 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/89—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members with hetero atoms directly attached to the ring nitrogen atom
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/34—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-halogen bonds; Phosphonium salts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
- C07D213/46—Oxygen atoms
- C07D213/50—Ketonic radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/55—Acids; Esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/57—Nitriles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
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- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
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Abstract
Description
Pyridinderivate sind bereits als wirksame Komponenten in fungiziden Mitteln bekannt: 3-Pyridyl-acetophenon-O- methyloxime aus EP-A 00 49 854 (= GB-A 20 85 007), 3- Pyridyl-2,4-dichlorbenzyl-ketone und deren 1,3-Dioxolanderivate aus EP-A 00 62 238 (= US-A 43 80 544), 3-Pyridyl- benzylcarbinole aus EP-A 00 69 330 (= US-A 44 31 812), Pyridyl- ethanonoxime aus Anna Babska et al. Pol. J. Pharmacol. Pharm., 1973, 25(2), 175 bis 180, aus den entsprechenden Ketonen hergestellt werden.Pyridine derivatives are already in use as effective components fungicidal agents known: 3-pyridyl-acetophenone-O- methyl oximes from EP-A 00 49 854 (= GB-A 20 85 007), 3- Pyridyl-2,4-dichlorobenzyl ketones and their 1,3-dioxolane derivatives from EP-A 00 62 238 (= US-A 43 80 544), 3-pyridyl benzylcarbinols from EP-A 00 69 330 (= US-A 44 31 812), pyridyl ethanonoxime from Anna Babska et al. Pole. J. Pharmacol. Pharm., 1973, 25 (2), 175 to 180, from the corresponding Ketones are made.
Die Wirkung dieser Pyridinderivate in fungiziden Mitteln ist jedoch insbesondere bei niedrigen Einsatzmengen nicht immer befriedigend.The effect of these pyridine derivatives in fungicidal agents is however not particularly with low amounts always satisfactory.
In den prioritätsälteren, nicht-veröffentlichten DE-A 33 26 456 und DE-A 33 42 671 werden u. a. Pyridinderivate beschrieben, die sich vom Pyridyl-(2-triazolyl-ethyl)- keton ableiten.In the older, unpublished ones DE-A 33 26 456 and DE-A 33 42 671 are u. a. Pyridine derivatives described, which is derived from pyridyl- (2-triazolyl-ethyl) - derive ketone.
Diese Verbindungen haben fungizide, herbizide und wachstumsregulierende Eigenschaften.These compounds have fungicidal, herbicidal and growth regulating Properties.
Ferner werden in der prioritätsälteren nicht vorveröffentlichten EP-A 1 29 507 derivatisierte Ketale von 3-Pyridylbenzylketonen beschrieben, welche mikrobizide Eigenschaften besitzen.Furthermore, the older ones are not pre-published EP-A 1 29 507 derivatized ketals of 3-pyridylbenzyl ketones described what microbicidal properties have.
Es wurde nunmehr gefunden, daß die neuen substituierten Pyridylverbindungen der nachfolgend definierten allgemeinen Formel (I) zum Teil erheblich bessere fungizide Wirksamkeit als die Verbindungen des Standes der Technik und ferner eine ausgeprägte Safener-Wirkung gegenüber Herbiziden besitzen.It has now been found that the new substituted Pyridyl compounds of the general defined below Formula (I) partly much better fungicidal Efficacy than the prior art compounds and also a pronounced safener effect Own herbicides.
Die vorliegende Erfindung betrifft somit die Pyridylverbindungen
der allgemeinen Formel I
worin die Symbole folgende Bedeutung haben:
X N oder N → O,
R Wasserstoff, (C1-C6)Alkyl,
p 0, 1 oder 2, wobei im Falle p ≦λτ 1 die Reste R auch
unterschiedlich sein können,
Ar Phenyl, das ein- oder mehrfach halogeniert sein
kann und/oder durch 1 bis 3 Reste aus der Gruppe
Halogen (C1-C5)alkyl mit 1 bis 7 Halogenatomen,
insbesondere Chlor- oder Fluoratomen, (C1-C6)Alkyl,
(C1-C6)Alkoxy, Halogen(C1-C4)alkoxy mit 1 bis 7
Halogenatomen, insbesondere Fluor- oder Chloratomen,
Phenyl oder Phenoxy, die beide jeweils durch
bis zu drei Halogenatome substituiert sein können,
substituiert sein kann,
Y Wasserstoff, (C1-C6)Alkyl, (C2-C6)Alkenyl, (C2-
C6)-Alkinyl, (C1-C4-Alkoxy)-(C1-C4)-alkyl, Di-
(C1-C4-alkoxy)-(C1-C4)alkyl, oder eine der folgenden
Gruppen:
wobei
R1 Wasserstoff, (C1-C6)Alkyl, (C3-C6)Cycloalkyl, (C3-C6)
Alkenyl, (C3-C6)Alkinyl, Phenyl-(C1-C6)alkyl oder
Phenoxy-(C1-C6)alkyl, die beide bis zu dreifach im
Phenylteil durch Halogen substituiert sein können,
Cyano(C1-C4)alkyl, Carbamoyl(C1-C4)-alkyl, (C1-C12-
Alkylmercapto)methyl oder
R2, R3 gleich oder verschieden sind und Wasserstoff, (C1-C6)-
Alkyl oder im Falle
zusammen mit dem
Stickstoffatom an das sie gebunden sind einen Imidazolring
bilden,
R4 (C1-C6)Alkyl, das halogeniert sein kann, (C3-C6)-
Cycloalkyl, (C3-C6)Alkenyl, (C3-C6)Alkinyl, (C1-
C6-Alkoxy)-(C1-C4)alkyl, (C1-C12)Alkoxy, Hydroxy,
Hydroxy(C2-C4)alkoxy, unsubstituiertes oder bis zu
dreifach durch Halogen substituiertes Phenyl,
R5, R6 bei gleicher oder verschiedener Bedeutung (C1-C6)-
Alkyl, Phenoxy(C1-C4)alkyl, wobei der Phenylrest bis
zu dreifach halogeniert sein kann, oder
beide Reste stehen zusammen mit dem Stickstoffatom,
an das sie gebunden sind, für einen unsubstituierten
oder einfach oder mehrfach, gleich oder verschieden
substituierten 5 bis 7-gliedrigen, gesättigten oder
ungesättigten Heterocyclus mit 1-3 gleichen oder
verschiedenen Heteroatomen, vorzugsweise mit den
Heteroatomen Stickstoff, Sauerstoff und/oder Schwefel
und dem Substituenten (C1-C4)Alkyl,
Me⁺ ein Alkalimetallkation oder ein Äquivalent
eines Erdalkalimetallkations,
q 0, 1, 2 oder 3
Z CH oder N
W Wasserstoff, (C1-C6)Alkoxy, oder (C1-C6)-
Alkyl, die beide durch bis zu zwei nicht an
dasselbe C-Atom gebundene Hydroxygruppen oder
durch bis zu drei Halogene substituiert sein
können, ein über C- oder ein Heteroatom gebundener
5- bis 7gliedriger, gesättigter oder ungesättigter
Heterocyclus mit 1 bis 3 gleichen
oder verschiedenen Heteroatomen, vorzugsweise
mit den Heteroatomen Stickstoff, Sauerstoff
und/oder Schwefel,
oder die Gruppe -NR5R6,
sowie deren Säureadditionssalze, Metallkomplexe und
Quarternisierungsprodukte,
wobei im Falle X = N Verbindungen, in denen
a) p = O, Y = H, (C1-C4)Alkyl, -CN, -CONH2oder -COR4
bei R4 = (C1-C6)Alkoxy,
oder
b) p = 1, R = H und
bedeuten, ausgenommen sind.
The present invention thus relates to the pyridyl compounds of the general formula I. where the symbols have the following meaning:
XN or N → O,
R is hydrogen, (C 1 -C 6 ) alkyl,
p 0, 1 or 2, where in the case p ≦ λτ 1 the radicals R can also be different,
Ar phenyl, which can be halogenated once or more and / or by 1 to 3 radicals from the group halogen (C 1 -C 5 ) alkyl having 1 to 7 halogen atoms, in particular chlorine or fluorine atoms, (C 1 -C 6 ) Alkyl, (C 1 -C 6 ) alkoxy, halogen (C 1 -C 4 ) alkoxy with 1 to 7 halogen atoms, in particular fluorine or chlorine atoms, phenyl or phenoxy, both of which can each be substituted by up to three halogen atoms can,
Y is hydrogen, (C 1 -C 6) alkyl, (C 2 -C 6) alkenyl, (C 2 - C 6) alkynyl, (C 1 -C 4 alkoxy) - (C 1 -C 4) -alkyl , Di- (C 1 -C 4 alkoxy) - (C 1 -C 4 ) alkyl, or one of the following groups: in which
R 1 is hydrogen, (C 1 -C 6 ) alkyl, (C 3 -C 6 ) cycloalkyl, (C 3 -C 6 ) alkenyl, (C 3 -C 6 ) alkynyl, phenyl- (C 1 -C 6 ) alkyl or phenoxy- (C 1 -C 6 ) alkyl, both of which can be substituted up to three times in the phenyl part by halogen, cyano (C 1 -C 4 ) alkyl, carbamoyl (C 1 -C 4 ) alkyl, (C 1 - C 12 - alkylmercapto) methyl or R 2 , R 3 are the same or different and are hydrogen, (C 1 -C 6 ) alkyl or in the case together with the nitrogen atom to which they are attached form an imidazole ring,
R 4 (C 1 -C 6 ) alkyl, which may be halogenated, (C 3 -C 6 ) cycloalkyl, (C 3 -C 6 ) alkenyl, (C 3 -C 6 ) alkynyl, (C 1 - C 6 Alkoxy) - (C 1 -C 4 ) alkyl, (C 1 -C 12 ) alkoxy, hydroxy, hydroxy (C 2 -C 4 ) alkoxy, unsubstituted or up to triple halogen-substituted phenyl,
R 5 , R 6 with the same or different meaning (C 1 -C 6 ) alkyl, phenoxy (C 1 -C 4 ) alkyl, where the phenyl radical can be halogenated up to three times, or
both radicals together with the nitrogen atom to which they are attached represent an unsubstituted or mono- or polysubstituted, identically or differently substituted 5 to 7-membered, saturated or unsaturated heterocycle with 1-3 identical or different heteroatoms, preferably with the heteroatoms nitrogen , Oxygen and / or sulfur and the substituent (C 1 -C 4 ) alkyl,
Measuring an alkali metal cation or an equivalent of an alkaline earth metal cation,
q 0, 1, 2 or 3
Z CH or N
W is hydrogen, (C 1 -C 6 ) alkoxy, or (C 1 -C 6 ) alkyl, both of which can be substituted by up to two hydroxyl groups not bonded to the same C atom or by up to three halogens, one via C 5 or 7-membered, saturated or unsaturated heterocycle with 1 to 3 identical or different heteroatoms, preferably with the heteroatoms nitrogen, oxygen and / or sulfur,
or the group -NR 5 R 6 ,
as well as their acid addition salts, metal complexes and quaternization products,
where X = N compounds in which
a) p = O, Y = H, (C 1 -C 4 ) alkyl, -CN, -CONH 2 or -COR 4 when R 4 = (C 1 -C 6 ) alkoxy,
or
b) p = 1, R = H and mean, are excluded.
Dabei können die bei der Definition der allgemeinen Formel (I), vorkommenden Alkyl-, Alkenyl- und Alkinylreste sowohl geradkettig als auch verzweigt sein; unter Halogen ist insbesondere F, Cl und Br zu verstehen.It can be used to define the general formula (I), occurring alkyl, alkenyl and alkynyl residues both straight chain as well as branched; is especially halogen To understand F, Cl and Br.
Für Ar ist halogeniertes Phenyl bevorzugt. Die Disclaimer a) und b) beziehen sich auf den eingangs dargestellten Stand der Technik.Halogenated phenyl is preferred for Ar. The disclaimer a) and b) relate to the above State of the art.
Als Heterocyclen für den Rest W kommen insbesondere der Morpholin-, Piperidin-, Pyrrolidin-, Triazol-, Imidazol- oder Pyrazolrest infrage.As heterocycles for the rest W come in particular the Morpholine, piperidine, pyrrolidine, triazole, imidazole or pyrazole residue in question.
Die Erfindung umfaßt alle unter die Formel I fallenden Steroisomeren und deren Gemische.The invention includes all those falling under the formula I. Steroisomers and their mixtures.
Erfindungsgemäß verwendbare Verbindungen sind - wie bereits vorstehend definiert - auch die Additionsprodukte von Säuren mit den Verbindungen der Formel (I), die Metallsalzkomplexe der Verbindungen der Formel (I), sowie die Quarternisierungsprodukte der Verbindungen der Formel (I).Compounds which can be used according to the invention are - as already defined above - also the addition products of acids with the compounds of formula (I), the metal salt complexes of the compounds of formula (I) and the quaternization products of the compounds of formula (I).
Zur Herstellung der Säureadditionssalze der Verbindungen der Formel (I) kommen folgende Säuren in Frage: Halogenwasserstoffsäuren wie Chlorwasserstoffsäure oder Bromwasserstoffsäure, ferner Phosphorsäure, Salpetersäure, Schwefelsäure, mono- und bifunktionelle Carbonsäuren und Hydroxycarbonsäuren wie Essigsäure, Maleinsäure, Bernsteinsäure, Fumarsäure, Weinsäure, Citronensäure, Salicylsäure, Sorbinsäure oder Milchsäure, sowie Sulfonsäuren wie p-Toluolsulfonsäure oder 1,5-Naphthalindisulfonsäure. Die Säureadditionssalze der Verbindungen der Formel (I) können in einfacher Weise nach üblichen Salzbildungsmethoden, z. B. durch Lösen einer Verbindung der Formel (I) in einem geeigneten organischen Lösemittel und Hinzufügen der Säure erhalten werden und in bekannter Weise, z. B. durch Abfiltrieren, isoliert und gegebenenfalls durch Waschen mit einem inerten organischen Lösemittel gereinigt werden. Zur Herstellung von Metallsalzkomplexen der Verbindungen der Formel (I) kommen vorzugsweise Salze von Metallen der II. bis IV. Haupt- und der I. und II. sowie IV. bis VIII. Nebengruppe des Periodensystems der Elemente in Frage, wobei Kupfer, Zink, Mangan, Magnesium, Zinn, Eisen und Nikkel beispielhaft genannt seien. Die Herstellung der Metallsalzkomplexe von Verbindungen der Formel (I) folgt üblichen Methoden.For the preparation of the acid addition salts of the compounds of the formula (I), the following acids are suitable: hydrohalic acids such as hydrochloric acid or hydrobromic acid, also phosphoric acid, nitric acid, Sulfuric acid, mono- and bifunctional carboxylic acids and Hydroxycarboxylic acids such as acetic acid, maleic acid, succinic acid, Fumaric acid, tartaric acid, citric acid, salicylic acid, Sorbic acid or lactic acid, as well as sulfonic acids such as p-toluenesulfonic acid or 1,5-naphthalenedisulfonic acid. The Acid addition salts of the compounds of formula (I) can in a simple manner using conventional salt formation methods, e.g. B. by dissolving a compound of formula (I) in a suitable one obtained organic solvents and adding the acid be and in a known manner, for. B. by filtering, isolated and optionally by washing with a inert organic solvents can be cleaned. For the production of metal salt complexes of the compounds of the formula (I) are preferably salts of metals II. To IV. Main and I. and II. As well as IV. To VIII. Subgroup of the periodic table of the elements in question, whereby copper, zinc, manganese, magnesium, tin, iron and Nikkel may be mentioned as an example. The manufacture of the Metal salt complexes of compounds of formula (I) follows usual methods.
Zur Herstellung von Quarternisierungsprodukten verwendet man Alkyl-, Alkylthioalkyl-, Alkoxyalkyl-, insbesondere (C1-C6)- Alkyl- und gegebenenfalls im Phenylrest substituierte, insbesondere halogenierte Phenacylhalogenide. Die Herstellung dieser Derivate erfolgt nach den allgemein üblichen Methoden.To produce quaternization products, alkyl, alkylthioalkyl, alkoxyalkyl, in particular (C 1 -C 6 ) alkyl and optionally substituted, in particular halogenated, phenacyl halides are used. These derivatives are prepared by the generally customary methods.
Ein weiterer Gegenstand der Erfindung sind Verfahren zur Herstellung der neuen Verbindungen der allgemeinen Formel (I) sowie ihrer Salze, Metallsalzkomplexe und Quarternisierungsprodukte.The invention further relates to methods for Preparation of the new compounds of the general formula (I) and their salts, metal salt complexes and quaternization products.
Verfahren zur Herstellung der Verbindungen der Formel I
sind dadurch gekennzeichnet, daß man
a) Ketone der Formel (II) mit Verbindungen der Formel III,
worin Z1 eine nucleofuge Abgangsgruppe bedeutet, umsetzt
oder
b) zur Herstellung von Verbindungen der Formel I, in denen
p = 1 und R = H bedeutet, Verbindungen der Formel IV mit
Nucleophilen,
der Formel V umsetzt und die erhaltenen Verbindungen
der Formel I gegebenenfalls in ihre Säureadditionssalze,
Metallsalzkomplexe oder Quarternisierungsprodukte umwandelt.Processes for the preparation of the compounds of the formula I are characterized in that
a) reacting ketones of the formula (II) with compounds of the formula III in which Z 1 is a nucleofugic leaving group or
b) for the preparation of compounds of the formula I in which p = 1 and R = H, compounds of the formula IV with nucleophiles, of the formula V and, if appropriate, converting the compounds of the formula I obtained into their acid addition salts, metal salt complexes or quaternization products.
Die Verbindungen der Formel II mit X = N sind zum Teil bekannt oder lassen sich nach bekannten Verfahren herstellen (s. J. Am. Chem. Soc. 72 1990 (1950), US-A 37 17 647, EP-A 62 238).Some of the compounds of formula II with X = N are known or can be prepared by known methods (see J. Am. Chem. Soc. 72 1990 (1950), US-A 37 17 647, EP-A 62 238).
Die Verbindungen der Formel II mit X = N → O werden durch Oxidation der Verbindungen der Formel II mit X = N nach üblichen Methoden erhalten. Als Oxidationsmittel verwendet man beispielsweise H2O2 in Essigsäure (s. J. Org. Chem. 18 (1953), s. 534-51).The compounds of formula II with X = N → O are obtained by oxidation of the compounds of formula II with X = N by conventional methods. The oxidizing agent used is, for example, H 2 O 2 in acetic acid (see J. Org. Chem. 18 (1953), see 534-51).
Die Verbindungen der Formel (III) in der Verfahrensvariante a) stehen für bekannte Alkylierungsmittel mit einer nucleofugen Abgangsgruppe Z1, die insbesondere ein Halogenid wie Chlorid, Bormid oder Jodid, Tosylat oder Mesylat sein kann. Genannt seien beispielsweise: 1- Chlor-3-(N,N-diethylamino)-1-methylpropan, 3-Morpholino- prop-1-ylmesylat, 1-Chlorpropandiol(2,3), 2-Brom-1-(4- Chlor-phenylmercapto)-butan, N-Benzyl-N-methyl-brom- acetamid, 3-(2,4-Dichlorphenoxy)-2-methyl-prop-1-yl- tosylat, 3-Brommethyl-pyridin, 4-Brommethylpyridazin, 2-(2,4,5-Trichlorphenoxy)-ethyltosylat, Hexahydroazepin- 1-ylmethyljodid. Die Umsetzung zu Ketonen der allgemeinen Formel (I) wird zweckmäßigerweise in Anwesenheit von Basen wie Alkalicarbonaten, Alkalihydriden oder auch Lithiumdialkylamiden - genannt sein beispielhaft Lithiumdiisopropylamid -, gegebenenfalls unter vorheriger Salzbildung der Verbindungen der Formel (II), in einem Verdünnungsmittel, vorzugsweise einem aprotischen organischen Lösemittel wie Tetrahydrofuran, Dioxan, Dimethoxyethan, Diethylether oder Dimethylformamid, Reaktionstemperaturen zwischen -78°C und +50°C durchgeführt.The compounds of formula (III) in process variant a) stand for known alkylating agents with a nucleofugic leaving group Z 1 , which can in particular be a halide such as chloride, bormide or iodide, tosylate or mesylate. Examples include: 1- chloro-3- (N, N-diethylamino) -1-methylpropane, 3-morpholino-prop-1-ylmesylate, 1-chloropropanediol (2,3), 2-bromo-1- (4- Chlorophenylmercapto) butane, N-benzyl-N-methyl-bromoacetamide, 3- (2,4-dichlorophenoxy) -2-methyl-prop-1-yl-tosylate, 3-bromomethyl-pyridine, 4-bromomethyl-pyridazine , 2- (2,4,5-trichlorophenoxy) ethyl tosylate, hexahydroazepin-1-ylmethyl iodide. The conversion to ketones of the general formula (I) is advantageously carried out in the presence of bases such as alkali metal carbonates, alkali metal hydrides or also lithium dialkylamides - lithium diisopropylamide may be mentioned by way of example - optionally with prior salt formation of the compounds of the formula (II), in a diluent, preferably an aprotic organic one Solvents such as tetrahydrofuran, dioxane, dimethoxyethane, diethyl ether or dimethylformamide, reaction temperatures between -78 ° C and + 50 ° C.
Bei dieser Umsetzung wird neben der C-Alkylierung in Abhängigkeit vom Keton (II), dem Alkylierungsmittel (III), der verwendeten Base und dem Lösemittel ein wechselnder, gegebenenfalls bis zu 100% betragender Anteil an O-Alkylierungsprodukten der allgemeinen Formel (VI) beobachtet: In this reaction, in addition to the C-alkylation, depending on the ketone (II), the alkylating agent (III), the base used and the solvent, an alternating proportion, optionally up to 100%, of O-alkylation products of the general formula (VI) is observed :
Die für die Verfahrensvariante b) geeigneten Verbindungen (V) sind allgemein bekannt; genannt seien beispielsweise 3-(N,N-Diisopropylamino)-prop-1-ylmercaptan, 2-(N-Benzyl-N-methylamino)-prop-1-ylmercaptan, 2-Morpholino- ethylmercaptan, β-Diethylaminoethanol, N-[2- (2,4,5-Trichlorphenoxy)-ethyl]-propylamin, N-[3-(4- Chlorphenylmercapto)-propyl]-benzylamin, N-Methyl-1- ethinyl-1-cyclohexylamin, N-Methyl-β-alaninethylester, 2-(4-Methoxyphenyl)ethyl-mercaptan, Benzylhydrylmercaptan. Die Verbindungen der Formel (IV) erhält man beispielsweise in einer modifizierten Mannich-Reaktion durch α-Methenylierung der Ketone der Formel (II).The compounds suitable for process variant b) (V) are generally known; be mentioned for example 3- (N, N-diisopropylamino) prop-1-yl mercaptan, 2- (N-benzyl-N-methylamino) prop-1-yl mercaptan, 2-morpholino ethyl mercaptan, β-diethylaminoethanol, N- [2- (2,4,5-trichlorophenoxy) ethyl] propylamine, N- [3- (4- Chlorophenylmercapto) propyl] benzylamine, N-methyl-1- ethynyl-1-cyclohexylamine, N-methyl-β-alanine ethyl ester, 2- (4-methoxyphenyl) ethyl mercaptan, benzylhydryl mercaptan. The compounds of formula (IV) are obtained, for example in a modified Mannich reaction by α-methenylation of the ketones of the formula (II).
Dabei werden die Ketone der Formel (II) in prinzipiell bekannter Weise (z. B. in der eingangs zitierten DE-A 33 26 456 und 33 42 671) in einem polaren organischen Lösemittel wie Dimethylformamid, Ethylenglykol oder Methanol zusammen mit einem 2- bis 5-fachen molaren Überschuß an wäßriger Formaldehydlösung nach Zusatz von katalytischen Mengen eines tertiären Amins (genannt sei beispielsweise Piperidin) während 4 bis 20 h bei Temperaturen zwischen 40 und 150°C, bevorzugt 60 bis 100°C, behandelt. Die teils zunächst in Form ihrer Dimeren anfallenden Propenone der Formel IV werden bei der Destillation im Hochvakuum monomerisiert.The ketones of formula (II) are in principle known manner (e.g. in DE-A 33 26 456 and 33 42 671) in a polar organic Solvents such as dimethylformamide, ethylene glycol or methanol together with a 2- to 5-fold molar excess in aqueous formaldehyde solution after adding catalytic Amounts of a tertiary amine (may be mentioned for example piperidine) for 4 to 20 h at temperatures between 40 and 150 ° C, preferably 60 to 100 ° C, treated. Some of these are initially obtained in the form of their dimers Propenones of formula IV are used in the distillation Monomerized in a high vacuum.
Die erfindungsgemäßen Verbindungen der Formel (I) zeigen eine hervorragende, zum Teil auch curative fungizide Wirkung gegen Phytopathogene Pilze und eignen sich daher sehr gut als Pflanzenbehandlungsmittel. Die Verbindungen erfassen z. B. Plasmopora viticola und Piricularia oryzae, insbesondere aber Venturia inaequalis, Cercospora beticola, echte Mehltaupilze und Rostpilze. Damit können Pilze an den verschiedensten Kulturpflanzen wie Mais, Reis, Getreide, Zuckerrüben, Gemüse, Obst, Gurkengewächsen, Regen, Hopfen, Tabak, Citrus- und Paprikaarten, Zierpflanzen, Kakao, Bananen und Kautschuk bekämpft bzw. gehemmt oder ihr Auftreten an diesen Pflanzen vollständig verhindert werden. Die beanspruchten Verbindungen weisen teilweise auch systemische Wirkung auf. Sie lassen sich auch als Beizmittel zur Bekämpfung von samenbürtigen Pilzen an Saatgut oder zur Bekämpfung der im Erdboden auftretenden phytopathogenen Pilze einsetzen.The compounds of formula (I) according to the invention show an excellent, sometimes curative fungicide Effect against phytopathogenic fungi and are suitable therefore very good as a plant treatment agent. The connections capture z. B. Plasmopora viticola and Piricularia oryzae, but especially Venturia inaequalis, Cercospora beticola, powdery mildew and rust fungi. So that can Mushrooms on various crops such as corn, Rice, cereals, sugar beets, vegetables, fruit, cucumber plants, Rain, hops, tobacco, citrus and pepper types, ornamental plants, Combat or inhibit cocoa, bananas and rubber or their appearance completely on these plants be prevented. The claimed compounds point sometimes also systemic effects. You let yourself be also as a mordant to control seed-bearing fungi on seeds or to combat those occurring in the soil use phytopathogenic mushrooms.
Die erfindungsgemäßen Verbindungen eignen sich daneben auch für den Einsatz in technischen Bereichen, beispielsweise als Holzschutzmittel, als Konservierungsmittel in Anstrichfarben, in Kühlschmiermitteln für die Metallbearbeitung oder als Konservierungsmittel in Bohr- und Schneidölen.The compounds of the invention are also suitable for use in technical areas, for example as a wood preservative, as a preservative in paints, in cooling lubricants for metalworking or as a preservative in drilling and cutting oils.
Überraschenderweise wurde gefunden, daß Verbindungen der Formel I auch die Eigenschaften haben, phytotoxische Nebenwirkungen von Pflanzenschutzmitteln, insbesondere von Herbiziden, beim Einsatz in Nutzpflanzenkulturen zu vermindern oder ganz auszuschalten. Die erfindungsgemäßen Mittel können in Verbindung mit anderen Herbiziden ausgebracht werden und sind dann in der Lage, schädliche Nebenwirkungen dieser Herbizide zu antagonisieren und völlig aufzuheben, ohne die Wirksamkeit dieser Herbizide gegen Schadpflanzen zu beeinträchtigen. Solche Verbindungen, die die Eigenschaften besitzen, Kulturpflanzen gegen phytotoxische Schäden durch Herbizide zu schützen, werden "Antidote" oder "Safener" genannt.Surprisingly, it was found that compounds of Formula I also have the properties of phytotoxic side effects of pesticides, especially of Reduce herbicides when used in crops or switch off completely. The invention Agents can be applied in conjunction with other herbicides are and are then able to have harmful side effects to antagonize these herbicides and totally repeal without affecting the effectiveness of these herbicides Affect harmful plants. Such connections that possess the properties, crop plants against phytotoxic Protecting herbicide damage will become "antidotes" or called "safener".
Mit Hilfe der erfindungsgemäßen Verbindungen kann das Einsatzgebiet herkömmlicher Pflanzenschutzmittel ganz erheblich vergrößert werden. Gegenstand der vorliegenden Erfindung ist daher auch ein Verfahren zum Schutz von Kulturpflanzen gegen phytotoxische Nebenwirkungen von Pflanzenschutzmitteln, insbesondere Herbiziden, das dadurch gekennzeichnet ist, daß man die Pflanzen, Pflanzensamen oder Anbauflächen mit einer Verbindung der Formel I vor, nach oder vorzugsweise gleichzeitig mit dem Pflanzenschutzmittel behandelt.With the aid of the compounds according to the invention, the field of application can conventional pesticides quite considerably be enlarged. Subject of the present invention is therefore also a process for protecting crops against phytotoxic side effects of pesticides, in particular herbicides, which is characterized is that the plants, plant seeds or Cultivated areas with a compound of formula I before, after or preferably at the same time as the plant protection product treated.
Herbizide, deren phytotoxische Nebenwirkungen mittels Verbindungen der Formel I herabgesetzt werden können, sind z. B. Carbamate, Thiolcarbamate, Halogenacetanilide, substituierte Phenoxy-, Naphthoxy- und Phenoxyphenoxycarbonsäurederivate sowie Heteroaryloxyphenoxycarbonsäurederivate wie Chinolyloxy-, Chinoxaloxy, Pyridyloxy-, Benzoxazolyloxy-, Benzthiazolyloxy-phenoxycarbonsäureester und ferner Dimedonabkömmlinge. Bevorzugt hierin sind Phenoxyphenoxy- und Heteroarlyoxyphenoxycarbonsäureester. Als Ester kommen hierbei insbesondere niedere Alkyl-, Alkenyl- und Alkinylester in Frage.Herbicides, their phytotoxic side effects by means of compounds of the formula I can be reduced e.g. B. carbamates, thiol carbamates, haloacetanilides Phenoxy, naphthoxy and phenoxyphenoxycarboxylic acid derivatives as well as heteroaryloxyphenoxycarboxylic acid derivatives such as quinolyloxy, quinoxaloxy, pyridyloxy, benzoxazolyloxy, Benzthiazolyloxy-phenoxycarboxylic acid esters and further Dimedon descendants. Preferred herein are phenoxyphenoxy and heteroarlyoxyphenoxycarboxylic acid esters. Come as an ester in particular lower alkyl, alkenyl and alkynyl esters in question.
Beispiele seien, ohne daß dadurch eine Beschränkung erfolgen soll, folgende Herbizide genannt:Examples are, without being restricted the following herbicides:
A) Herbizide vom Typ der Phenoxyphenoxy- und Heteroaryloxy-
phenoxycarbonsäure-(C1-C4)alkyl-, (C2-C4)alkenyl- und (C3-C4)
alkinylester wie
2-(2,4-Dichlorphenoxy)-phenoxy)-propionsäuremethylester,
2-(4-(4-Brom-2-chlorphenoxy)-phenoxy)-propionsäuremethylester,
2-(4-(4-Trifluormethylphenoxy)-phenoxy)-propionsäuremethylester,
2-(4-(2-Chlor-4-trifluormethylphenoxy)-phenoxy)-propionsäuremethyles-ter,
2-(4-(2,4-Dichlorbenzyl)-phenoxy)-propionsäuremethylester,
4-(4-(4-Trifluormethylphenoxy)-phenoxy)-pent-2-en-säure-
ethylester,
2-(4-(3,5-Dichlorpyridyl-2-oxy)-phenoxy)-propionsäureethylester,
2-(4-(3,5-Dichlorpyridyl-2-oxy)-phenoxy)-propionsäurepropargylester,-
2-(4-(6-Chlorbenzoxazol-2-yl-oxy)-phenoxy)-propionsäureethylester,
2-(4-(6-Chlorbenzthiazol-2-yl-oxy)-phenoxy)-propionsäureethylester,
2-(4-(3-Chlor-5-trifluormethyl-2-pyridyloxy)-phenoxy)-
propionsäuremethylester,
2-(4-(3-Chlor-5-trifluormethyl-2-pyridyloxy)-phenoxy)-
propionsäuremethylester,
2-(4-(5-Trifluormethyl-2-pyridyloxy)-phenoxy)-propionsäurebutylester-,
2-(4-(6-Chlor-2-chinoxalyloxy)-phenoxy)-propionsäureethylester,
2-(4-(6-Fluor-2-chinoxalyloxy)-phenoxy)-propionsäureethylester,
2-(4-(6-Chlor-2-chinolyloxy)-phenoxy)-propionsäureethylester,
sowie deren optische Isomeren und Isomerengemische,A) herbicides of the phenoxyphenoxy and heteroaryloxyphenoxycarboxylic acid (C 1 -C 4 ) alkyl, (C 2 -C 4 ) alkenyl and (C 3 -C 4 ) alkynyl esters such as
Methyl 2- (2,4-dichlorophenoxy) phenoxy) propionate,
Methyl 2- (4- (4-bromo-2-chlorophenoxy) phenoxy) propionate,
Methyl 2- (4- (4-trifluoromethylphenoxy) phenoxy) propionate,
Methyl 2- (4- (2-chloro-4-trifluoromethylphenoxy) phenoxy) propionate,
Methyl 2- (4- (2,4-dichlorobenzyl) phenoxy) propionate,
Ethyl 4- (4- (4-trifluoromethylphenoxy) phenoxy) pent-2-ene,
Ethyl 2- (4- (3,5-dichloropyridyl-2-oxy) phenoxy) propionate,
2- (4- (3,5-dichloropyridyl-2-oxy) phenoxy) propionic acid propargyl ester,
Ethyl 2- (4- (6-chlorobenzoxazol-2-yl-oxy) phenoxy) propionate,
Ethyl 2- (4- (6-chlorobenzthiazol-2-yl-oxy) phenoxy) propionate,
Methyl 2- (4- (3-chloro-5-trifluoromethyl-2-pyridyloxy) phenoxy) propionate,
Methyl 2- (4- (3-chloro-5-trifluoromethyl-2-pyridyloxy) phenoxy) propionate,
2- (4- (5-trifluoromethyl-2-pyridyloxy) phenoxy) propionic acid butyl ester,
Ethyl 2- (4- (6-chloro-2-quinoxalyloxy) phenoxy) propionate,
Ethyl 2- (4- (6-fluoro-2-quinoxalyloxy) phenoxy) propionate,
Ethyl 2- (4- (6-chloro-2-quinolyloxy) phenoxy) propionate,
as well as their optical isomers and isomer mixtures,
B) Chloracetanilid-Herbizide wie
N-Methoxymethyl-2,6-diethyl-chloracetanilid,
N-(3′-Methoxyprop-2′-yl)-methyl-6-ethyl-chloracetanilid,
N-(3-Methyl-1,2,4-oxidazol-5-yl-methyl)-chloressigsäure-
2,6-dimethylanilid,B) chloroacetanilide herbicides such as
N-methoxymethyl-2,6-diethylchloroacetanilide,
N- (3'-methoxyprop-2'-yl) methyl-6-ethylchloroacetanilide,
N- (3-methyl-1,2,4-oxidazol-5-yl-methyl) -chloroacetic acid-2,6-dimethylanilide,
C) Thiolcarbamate wie
S-Ethyl-N,N-dipropylthiocarbamat oder
S-Ethyl-N,N-diisobutylthiocarbamatC) thiol carbamates such as
S-ethyl-N, N-dipropylthiocarbamate or
S-ethyl-N, N-diisobutylthiocarbamate
D) Dimedon-Derivate wie
2-(N-Ethoxybutyrimidoyl-5-(2-ethylthiopropyl)-3-hydroxy-2-
cyclohexen-1-on,
2-(N-Ethoxybutyrimidoyl)-5-(2-phenylthiopropyl)-3-hydroxy-
2-cyclohexen-1-on oder
2-(1-Allyloxyiminobutyl)-4-methoxycarbonyl-5,5-dimethyl-3-
oxocyclohexenol.D) Dimedon derivatives such as
2- (N-ethoxybutyrimidoyl-5- (2-ethylthiopropyl) -3-hydroxy-2-cyclohexen-1-one,
2- (N-ethoxybutyrimidoyl) -5- (2-phenylthiopropyl) -3-hydroxy-2-cyclohexen-1-one or
2- (1-allyloxyiminobutyl) -4-methoxycarbonyl-5,5-dimethyl-3-oxocyclohexenol.
Das Mengenverhältnis Antidot : Herbizid kann innerhalb weiter Grenzen im Bereich zwischen 1 : 10 und 10 : 1, insbesondere zwischen 2 : 1 und 1 : 10, schwanken. Die jeweils optimalen Mengen an Herbizid und Antidot sind abhängig vom Typ des verwendeten Herbizids oder vom verwendeten Antidot sowie von der Art des zu behandelnden Pflanzenbestandes und lassen sich von Fall zu Fall durch entsprechende Versuche ermitteln. The quantitative ratio of antidote: herbicide can continue within Limits in the range between 1:10 and 10: 1, in particular fluctuate between 2: 1 and 1:10. The each optimal amounts of herbicide and antidote depend on Type of herbicide or antidote used and the type of crop to be treated and can be tested on a case by case basis determine.
Haupteinsatzgebiete für die Anwendung der Safener sind vor allem Getreidekulturen (Weizen, Roggen, Gerste, Hafer), Reis, Mais, Sorghum, aber auch Baumwolle, Zuckerrüben, Zuckerrohr und Sojabohne.The main areas of application for the application of safeners are all cereal crops (wheat, rye, barley, oats), Rice, corn, sorghum, but also cotton, sugar beet, sugar cane and soybean.
Die Safener der Formel I können je nach ihren Eigenschaften zur Vorbehandlung des Saatgutes der Kulturpflanze (Beizung der Samen) verwendet werden oder vor der Saat in die Saatfurchen eingebracht werden oder zusammen mit dem Herbizid vor oder nach dem Auflaufen der Pflanzen angewendet werden. Vorauflaufbehandlungen schließt sowohl die Behandlung der Anbaufläche vor der Aussaat als auch die Behandlung der angesäten, aber noch nicht bewachsenen Anbauflächen ein. Bevorzugt ist die gemeinsame Anwendung mit dem Herbizid. Hierzu können Tankmischungen oder Fertigformulierungen eingesetzt werden, wobei die nachstehend genannten Formulierungshilfsmittel verwendet werden können.The safeners of the formula I can, depending on their properties for the pretreatment of the seed of the crop (dressing the seed) or before sowing into the furrows be introduced or together with the herbicide be applied before or after emergence of the plants. Pre-emergence treatment includes both the treatment of the acreage before sowing as well as treating the sown, but not yet overgrown areas. Prefers is the common application with the herbicide. Tank mixes or finished formulations can be used for this be, the formulation aids mentioned below can be used.
Die erfindungsgemäßen Verbindungen der allgemeinen Formel (I) können als Spritzpulver, emulgierbare Konzentrate, versprühbare Lösungen, Stäubemittel, Beizmittel, Dispersionen, Granulate oder Mikrogranulate in den üblichen Zubereitungen angewendet werden.The compounds of the general formula according to the invention (I) can be used as wettable powder, emulsifiable concentrates, sprayable Solutions, dusts, mordants, dispersions, Granules or microgranules in the usual preparations be applied.
Gegenstand der vorliegenden Erfindung sind daher auch Mittel, welche die Verbindungen der allgemeinen Formel (I) neben geeigneten Formulierungshilfsmitteln enthalten.The present invention therefore also relates to means which the compounds of the general formula (I) in addition to suitable formulation aids.
Spritzpulver sind in Wasser gleichmäßig dispergierbare Präparate, die neben dem Wirkstoff außer gegebenenfalls einem Verdünnungs- oder Inertstoff noch Netzmittel wie polyoxethylierte Fettalkohole, Alkyl- oder Alkylphenylsulfonate und/oder Dispergierhilfsmittel wie ligninsulfonsaures Natrium, 2,2′-dinaphthylmethan-6,6′-disulfonsaures Natrium, dibutylnaphthalinsulfonsaures Natrium oder auch oleoylmethyltaurinsaures Natrium enthalten. Die Herstellung erfolgt in üblicher Weise, z. B. durch Mahlen und Vermischen der Komponenten.Spray powders are preparations that are evenly dispersible in water, which in addition to the active ingredient, if necessary, one Diluent or inert or wetting agents such as polyoxethylated Fatty alcohols, alkyl or alkylphenyl sulfonates and / or dispersing aids such as lignosulfonic acid Sodium, 2,2′-dinaphthylmethane-6,6′-disulfonic acid sodium, dibutylnaphthalenesulfonic acid sodium or oleoylmethyltauric acid Contain sodium. The production takes place in usual way, e.g. B. by grinding and mixing the components.
Emulgierbare Konzentrate können z. B. durch Auflösen des Wikstoffes in einem inerten organischen Lösemittel wie Butanol, Cyclohexanon, Dimethylformamid, Xylo, oder auch höhersiedenden Aromaten oder aliphatischen oder cycyloaliphatischen Kohlenwasserstoffen unter Zusatz von einem oder mehreren Emulgatoren hergestellt werden. Bei flüssigen Wirkstoffen kann der Lösemittelanteil auch ganz oder teilweise entfallen. Als Emulgatoren können beispielsweise verwendet werden: Alkyl-arylsulfonsaure Calciumsalze wie Ca-dodecylbenzolsulfonat oder nichtionische Emulgatoren wie Fettsäurepolyglykolester, Alkylarylpolyglykolether, Fettalkoholpolyglykolether, Propylenoxid-Ethylenoxid-Kondensationsprodukte, Fettalkohol-Propylenoxid-Kondensationsprodukte, Alkylpolyglykolether, Sorbitanfettsäureester, Polyoxethylensorbitanfettsäureester oder Polyoxethylensorbitester.Emulsifiable concentrates can e.g. B. by dissolving the In an inert organic solvent such as Butanol, cyclohexanone, dimethylformamide, xylo, or also higher-boiling aromatics or aliphatic or cycyloaliphatic Hydrocarbons with the addition of one or several emulsifiers can be produced. With liquid active ingredients can also partially or completely omitted. For example, emulsifiers can be used are: Alkyl-arylsulfonic acid calcium salts such as Ca-dodecylbenzenesulfonate or nonionic emulsifiers such as fatty acid polyglycol esters, Alkylaryl polyglycol ether, fatty alcohol polyglycol ether, Propylene oxide-ethylene oxide condensation products, Fatty alcohol propylene oxide condensation products, Alkyl polyglycol ethers, sorbitan fatty acid esters, polyoxethylene sorbitan fatty acid esters or polyoxethylene sorbitol ester.
Stäubemittel kann man durch Vermahlen des Wirkstoffes mit feinverteilten, festen Stoffen, z. B. Talkum, natürlichen Tonen wie Kaolin, Bentonit, Pyrophillit oder Diatomeenerde erhalten. Granulate können entweder durch Verdüsen des Wirkstoffes auf adsorptionsfähiges, granuliertes Inertmaterial hergestellt werden oder durch Aufbringen von Wirkstoffkonzentrationen mittels Bindemitteln, z. B. Polyvinylalkohol, polyacrylsaurem Natrium oder auch Mineralölen auf die Oberfläche von Trägerstoffen wie Sand, Kaolinite oder von granuliertem Inertmaterial. Auch können geeignete Wirkstoffe in der für die Herstellung von Düngemittelgranulaten üblichen Weise - gewünschtenfalls in Mischung mit Düngemitteln - granuliert werden. In Spritzpulver beträgt die Wirkstoffkonzentration etwa 10 bis 90 Gew.-%, der Rest zu 100 Gew.-% besteht aus üblichen Formulierungsbestandteilen. Bei emulgierbaren Konzentraten kann die Wirkstoffkonzentration etwa 10 bis 80 Gew.-% betragen. Staubförmige Formulierungen enthalten meistens 5 bis 20 Gew.-% an Wirkstoff, versprühbare Lösungen etwa 2 bis 20 Gew.-%. Bei Granulaten hängt der Wirkstoffgehalt zum Teil davon ab, ob die wirksame Verbindung flüssig oder fest vorliegt und welche Granulierhilfsmittel, Füllstoffe usw. verwendet werden. Daneben enthalten die genannten Wirkstofformulierungen gegebenenfalls die jeweils übliche Haft-, Netz-, Dispergier-, Emulgier-, Penetrations-, Lösemittel, Füll- oder Trägerstoffe.Dusts can be obtained by grinding the active ingredient with finely divided, solid substances, e.g. B. talc, natural Clays such as kaolin, bentonite, pyrophillite or diatomaceous earth receive. Granules can either by spraying the active ingredient on adsorbable, granulated inert material be produced or by applying drug concentrations by means of binders, e.g. B. polyvinyl alcohol, polyacrylic acid sodium or mineral oils on the surface of carriers such as sand, kaolinite or granulated Inert material. Suitable active ingredients can also the usual for the production of fertilizer granules Way - if desired in a mixture with fertilizers - be granulated. The active ingredient concentration in wettable powder is about 10 to 90% by weight, the rest 100% by weight consists of common formulation components. With emulsifiable Concentrates can be the active ingredient concentration 10 to 80 wt .-%. Contain dusty formulations usually 5 to 20 wt .-% of active ingredient, sprayable Solutions about 2 to 20 wt .-%. With granules it depends Active ingredient content depends in part on whether the active compound is in liquid or solid form and which granulation aids, Fillers, etc. are used. Also included the active ingredient formulations mentioned, if appropriate the usual adhesive, wetting, dispersing, Emulsifiers, penetrants, solvents, fillers or carriers.
Zur Anwendung werden die in handelsüblicher Form vorliegenden Konzentrate gegebenenfalls in üblicher Weise verdünnt, z. B. bei Spritzpulvern, emulgierbaren Konzentraten, Dispersionen und teilweise auch bei Mikrogranulaten mittels Wasser. Staubförmige und granulierte Zubereitungen sowie versprühbare Lösungen werden vor der Anwendung üblicherweise nicht mehr mit weiteren inerten Stoffen verdünnt.Those available in the commercial form are used If necessary, concentrates diluted in the usual way, e.g. B. with wettable powders, emulsifiable concentrates, Dispersions and sometimes also with microgranules by means of water. Dusty and granular preparations as well as sprayable solutions are common before use no longer diluted with other inert substances.
Die Anwendungskonzentrationen der erfindungsgemäßen Verbindungen der allgemeinen Formel (I) bei Verwendung als Fungizide betragen in der fertigen Spritzbrühe im allgemeinen zwischen 1 mg und 500 mg Wirkstoff pro Liter Spritzbrühe (entsprechend 1 bis 500 g a. i./ha). Die Pflanzen werden bei der Anwendung tropfnaß gespritzt. In den nachfolgenden Beispielen verhalten sich Gew.-Teile (GT) zu Vol.-Teilen (VT) wie kg zu dm3 (1) und %-Angaben beziehen sich - falls nicht anders angegeben ist - auf das Gewicht.The use concentrations of the compounds of the general formula (I) according to the invention when used as fungicides in the finished spray mixture are generally between 1 mg and 500 mg of active compound per liter of spray mixture (corresponding to 1 to 500 g ai / ha). The plants are sprayed until dripping wet. In the following examples, parts by weight (parts by weight) to parts by volume (parts by weight) such as kg to dm 3 (1) and percentages relate to the weight, unless stated otherwise.
Die benötigten Aufwandmengen der Verbindungen der Formel I beim Einsatz als Safener können je nach Indikation und verwendetem Herbizid innerhalb weiter Grenzen schwanken und variieren zwischen 0,01 und 10 kg Wirkstoff pro ha. The application rates required for the compounds of the formula I when used as a safener, depending on the indication and used Herbicide fluctuate within wide limits and vary between 0.01 and 10 kg of active ingredient per ha.
Ein Stäubemittel wird erhalten, indem man a) 10 GT Wirkstoff und 90 GT Talkum oder einem anderen Inertstoff mischt und in einer Schlagmühle zerkleinert, oder indem man b) 60 GT Wirkstoff, 35 GT Talkum und 5 GT Haftmittel (z. B. ein Polysaccharid wie ®Rhodopol der Rhone-Poulence S. A.) in der gleichen Weise homogenisiert.A dusts are obtained by a) 10 pbw of active ingredient and 90 pbw of talc or another inert substance and crushed in a hammer mill, or by b) 60 pbw of active ingredient, 35 pbw of talc and 5 pbw of adhesive (e.g. a polysaccharide such as ®Rhodopol from Rhone-Poulence S. A.) homogenized in the same way.
Ein in Wasser leicht dispergierbares, benetzbares Pulver wird erhalten, indem man 25 GT Wirkstoff, 64 GT kaolinhaltigen Quarz als Inertstoff, 10 GT ligninsulfonsaures Kalium und 1 GT oleoylmethyltaurinsaures Natrium als Netz- und Dispergierhilfsmittel mischt und in einer Stiftmühle mahlt. Eine Formulierung mit 5% Wirkstoffgehalt kann wie folgt zusammengesetzt sein: 5% Wirkstoff, 6% eines sulfonierten Naphthalinformaldehydkondensats (z. B. ®Dispersogen A der HOECHST AG), 2% eines Na-Salzes einer Alkylnaphthalinsulfonsäure (z. B. ®Leonil DB der HOECHST AG), 5% eines Gemisches aus Polypropylenglykol und SiO2 (z. B. ®Acrotin 341 der HOECHST AG), 25% eines SiO2 (z. B. ®Sipernat der Degussa AG) und 57% Kaolin Typ 1777.A wettable powder which is readily dispersible in water is obtained by mixing 25 pbw of active ingredient, 64 pbw of kaolin-containing quartz as the inert substance, 10 pbw of potassium lignosulfonate and 1 pbw of sodium oleoylmethyl taurine as wetting and dispersing aid and grinding in a pin mill. A formulation with a 5% active ingredient content can be composed as follows: 5% active ingredient, 6% of a sulfonated naphthalene formaldehyde condensate (e.g. ®Dispersogen A from HOECHST AG), 2% of a sodium salt of an alkylnaphthalenesulfonic acid (e.g. ®Leonil DB from HOECHST AG), 5% of a mixture of polypropylene glycol and SiO 2 (e.g. ®Acrotin 341 from HOECHST AG), 25% of SiO 2 (e.g. ®Sipernat from Degussa AG) and 57% kaolin type 1777.
Ein in Wasser leicht dispergierbares Dispersionskonzentrat wird erhalten indem man 20 GT Wirkstoff mit 6 GT eines Alkylphenolpolyglykolethers (z. B. ®Triton X 207 von Rohm and Haas Co.), 3 GT Isotridecanolpolyglykolether (8 EO- Einheiten) und 71 GT paraffinischem Mineralöl (Siedebereich ca. 255 bis über 377°C) mischt und in einer Reibkugelmühle auf eine Feinheit von unter 5 µm vermahlt. A dispersion concentrate that is easily dispersible in water is obtained by adding 20 pb of active ingredient with 6 pbw of a Alkylphenol polyglycol ether (e.g. ®Triton X 207 from Rohm and Haas Co.), 3 pbw isotridecanol polyglycol ether (8 EO- Units) and 71 pbw of paraffinic mineral oil (boiling range approx. 255 to over 377 ° C) and mixes in a friction ball mill ground to a fineness of less than 5 µm.
Ein emulgierbares Konzentrat wird erhalten aus 15 GT Wirkstoff, 75 GT Cyclohexanon als Lösemittel und 10 GT oxethyliertem Nonylphenol (10 EO-Einheiten) als Emulgator.An emulsifiable concentrate is obtained from 15 pbw of active ingredient, 75 pbw of cyclohexanone as solvent and 10 pbw of oxyethylated Nonylphenol (10 EO units) as an emulsifier.
Ethyl-3-(2,4-dichlorphenyl)-4-oxo-4-(3-pyridyl)-butanoatEthyl 3- (2,4-dichlorophenyl) -4-oxo-4- (3-pyridyl) butanoate
26,6 g (0,10 mol) 3-Pyridyl-(2,4-dichlorbenzyl)-keton werden in 400 ml abs. Dimethylformamid gelöst und bei 0-10°C unter Kühlung portionsweise mit 3,00 g (0,10 mol) 80%igem Natriumhydrid versetzt. Die anfangs heftige Wassserstoffentwicklung wird durch Nachrühren bei Raumtemperatur vervollständigt. Zur homogenen Lösung tropft man ohne weitere Kühlung 16,7 g (0,10 mol) Bromessigsäureethylester, wobei die Reaktionstemperatur um ca. 20°C ansteigt. Nach beendeter Umsetzung gießt man auf Eis und extrahiert mit Diethylether. Die Etherphasen werden über Na2SO4 getrocknet, einrotiert und schließlich im Hochvakuum von Lösemittelresten befreit.26.6 g (0.10 mol) of 3-pyridyl- (2,4-dichlorobenzyl) ketone in 400 ml of abs. Dissolved dimethylformamide and mixed with 3.00 g (0.10 mol) of 80% sodium hydride in portions at 0-10 ° C with cooling. The initially violent evolution of hydrogen is completed by stirring at room temperature. 16.7 g (0.10 mol) of ethyl bromoacetate are added dropwise to the homogeneous solution without further cooling, the reaction temperature rising by about 20.degree. When the reaction has ended, the mixture is poured onto ice and extracted with diethyl ether. The ether phases are dried over Na 2 SO 4 , evaporated and finally freed from solvent residues in a high vacuum.
Man erhält 31,0 g (88% d. Theorie) Ethyl-3-(2,4-dichlorphenyl)- 4-oxo-4-(3-pyridoyl)-butanoat als Sirup. Die Strukturzuordnung erfolgt durch 1H-NMR.31.0 g (88% of theory) of ethyl 3- (2,4-dichlorophenyl) -4-oxo-4- (3-pyridoyl) butanoate are obtained as a syrup. The structure is assigned by 1 H NMR.
5-(2,4-Dichlorphenyl)-5-(3-pyridoyl)-3-tiavaleriansäuremethylesterMethyl 5- (2,4-dichlorophenyl) -5- (3-pyridoyl) -3-tiavalerate
13,1 g (0,047 mol) 2-(2,4-Dichlorphenyl)-1-(3-pyridyl)- prop-2-en-1-on werden in 100 ml abs. Toluol gelöst und bei Raumtemperatur mit 5,70 g (0,052 mol) Thioglykolsäuremethylester versetzt. Nach Zugabe einiger Tropfen 1,8-Diazabicyclo (5. 4. 0)undec-7-en tritt eine exotherme Reaktion ein. Zur Vervollständigung der Umsetzung wird 1 h bei ca. 50°C nachgerührt. Nach der üblichen Aufarbeitung erhält man 15,6 g (86% d. Theorie) 5-(2,4-Dichlorphenyl)-5-(3-pyridoyl) -3-tiavaleriansäuremethylester als Sirup. Die Strukturzuordnung erfolgt durch 1H-NMR.13.1 g (0.047 mol) of 2- (2,4-dichlorophenyl) -1- (3-pyridyl) prop-2-en-1-one are dissolved in 100 ml of abs. Toluene dissolved and mixed with 5.70 g (0.052 mol) of thioglycolic acid methyl ester at room temperature. After adding a few drops of 1,8-diazabicyclo (5. 4. 0) undec-7-ene, an exothermic reaction occurs. To complete the reaction, the mixture is stirred at about 50 ° C. for 1 h. After the usual work-up, 15.6 g (86% of theory) of methyl 5- (2,4-dichlorophenyl) -5- (3-pyridoyl) -3-tiavalerate are obtained as a syrup. The structure is assigned by 1 H NMR.
3-(2,4-Dichlorphenylacetyl)pyridin-N-oxyd3- (2,4-dichlorophenylacetyl) pyridine-N-oxide
30.0 g (0.11 Mol) 3-(2,4-Dichlorphenylacetyl)pyridin werden in 90 ml Eisessig aufgenommen und mit 18 mol 30%igem H2O2 für ca. 12 h, auf 70°C erhitzt. Nach Entfernung der bis 100°C bei 12 mbar flüchtigen Anteile versetzt man mit 35 ml Wasser und entfernt erneut die flüchtigen Anteile wie oben. Nach Anreiben mit Essigester kristallisieren 26.0 g (42% d. Theorie) 3-(2,4-Dichlorphenylacetyl)pyridin-N-oxyd vom Fp. 174-8°C aus.30.0 g (0.11 mol) of 3- (2,4-dichlorophenylacetyl) pyridine are taken up in 90 ml of glacial acetic acid and heated to 70 ° C. with 18 mol of 30% H 2 O 2 for about 12 h. After removal of the volatile components up to 100 ° C. at 12 mbar, 35 ml of water are added and the volatile components are removed again as above. After rubbing with ethyl acetate, 26.0 g (42% of theory) of 3- (2,4-dichlorophenylacetyl) pyridine-N-oxide crystallize from mp. 174-8 ° C.
In analoger Weise, beziehungsweise durch literaturbekannte Derivatisierung der Verbindungen dieser Beispiele, werden die in der nachstehenden Tabelle 1 aufgelisteten Verbindungen hergestellt.In an analogous manner, or by means known from the literature Derivatization of the compounds of these examples the compounds listed in Table 1 below produced.
Das Zeichen * in Spalte 7 der Tabelle 1 gibt an, daß zur Herstellung der betreffenden Verbindung eine literaturbekannte Derivatisierung des Produktes des entsprechenden Beispiels durchgeführt wird.The symbol * in column 7 of Table 1 indicates that a literature derivatization of the product of the corresponding example is carried out to prepare the compound in question.
In analoger Weise, beziehungsweise durch literaturbekannte Derivatisierung der Verbindungen dieser Beispiele, werden die in der nachstehenden Tabelle 1 aufgelisteten Verbindungen hergestellt.In an analogous manner, or by means known from the literature Derivatization of the compounds of these examples the compounds listed in Table 1 below produced.
Das Zeichen * in Spalte 7 der Tabelle 1 gibt an, daß zur Herstellung der betreffenden Verbindung eine literaturbekannte Derivatisierung des Produktes des entsprechenden Beispiels durchgeführt wird. The symbol * in column 7 of Table 1 indicates that a literature derivatization of the product of the corresponding example is carried out to prepare the compound in question.
Weizenpflanzen wurden im 3-Blattstadium mit Konidien des Weizenmehltaus (Erysiphe graminis) stark inokuliert und in einem Gewächshaus bei 20°C und einer relativen Luftfeuchte von 90-95% aufgestellt. 3 Tage nach Inokulation wurden die Pflanzen mit den zu prüfenden Verbindungen in den Wirkstoffkonzentrationen von 500, 250 und 125 mg/Liter Spritzbrühe tropfnaß gespritzt. Nach der Inkubationszeit von 10 Tagen untersuchte man die Pflanzen auf Befall mit Weizenmehltau.Wheat plants were in the 3-leaf stage with conidia of Wheat mildew (Erysiphe graminis) heavily inoculated and in a greenhouse at 20 ° C and a relative humidity set up by 90-95%. 3 days after inoculation the plants with the compounds to be tested in the active ingredient concentrations of 500, 250 and 125 mg / liter spray liquor sprayed soaking wet. After the incubation period of 10 days the plants were examined for infestation with powdery mildew.
Der Befallsgrad wird ausgedrückt in % befallener Blattfläche, bezogen auf unbehandelte, infizierte Kontrollpflanzen (= 100% Befall). Die Ergebnisse zeigt die nachstehende Tabelle 2. The degree of infestation is expressed in% infested leaf area, based on untreated, infected control plants (= 100% Infestation). The results are shown in Table 2 below.
Gerstenpflanzen wurdem im 3-Blattstadium mit Konidien des Gerstenmehltaus (Erysiphe graminis sp. hordei) stark inokuliert und in einem Gewächshaus bei 20°C und einer relativen Luftfeuchtigkeit von 90 bis 95% aufgestellt. 3 Tage nach Inokulation wurden die Pflanzen mit den zu prüfenden Verbindungen in den Wirkstoffkonzentrationen von 500, 250 und 125 mg/Liter Spritzbrühe tropfnaß gespritzt. Nach einer Inkubationszeit von 10 Tagen wurde der Befall mit Gerstentaumehl untersucht.Barley plants were in the 3-leaf stage with conidia of barley mildew (Erysiphe graminis sp. Hordei) heavily inoculated and in a greenhouse at 20 ° C and a relative humidity from 90 to 95%. 3 days after inoculation Plants with the compounds to be tested in the active ingredient concentrations of 500, 250 and 125 mg / liter spray liquor dripping wet sprayed. After an incubation period of 10 days, the infestation became examined with barley dew.
Der Befallgrad wird ausgedürckt in % befallener Blattfläche, bezogen auf unbehandelte, infizierte Kontrollpflanzen (= 100% Befall). Die Ergebnisse zeigt Tabelle 3: The degree of infestation is expressed in% infested leaf area, based on untreated, infected control plants (= 100% Infestation). The results are shown in Table 3:
Gurkenpflanzen (Sorte Delikateß) wurden im 2-Blattstadium mit einer Konidiensuspension von Gurkenmehltau (Erysiphe cichora- cearum) stark inokuliert. Nach einer Antrocknungszeit der Sporensuspension von 30 Minuten wurden die Pflanzen in einem Gewächshaus bei 22°C und 90% relativer Luftfeuchte aufgestellt. 3 Tage nach Infektion wurde mit den zu prüfenden Verbindungen in den in Tabelle 4 angegebenen Wirkstoffkonzentrationen tropfnaß gespritzt. Nach 10 Tagen erfolgte die Bonitur.Cucumber plants (variety delicacy) were in the 2-leaf stage a conidia suspension of cucumber mildew (Erysiphe cichora- cearum) heavily inoculated. After a drying time of the spore suspension of 30 minutes, the plants were in a greenhouse set up at 22 ° C and 90% relative humidity. 3 days after infection with the compounds to be tested in the Active substance concentrations given in Table 4 are sprayed to runoff. The assessment was made after 10 days.
Der Befallgrad wird ausgedrückt in % befallener Blattfläche, bezogen auf unbehandelte, infizierte Kontrollpflanzen (= 100% Befall). Tabelle 4 zeigt die Ergebnisse:The degree of infestation is expressed in% infested leaf area, based on untreated, infected control plants (= 100% Infestation). Table 4 shows the results:
Weizenpflanzen wurden mit den erfindungsgemäßen Verbindungen in den in Tabelle 4 genannten Anwendungskonzentrationen gleichmäßig behandelt. Nach dem Antrocknen des Wirkstoffbelages wurden die mit Sporen des Weizenbraunrosts (Puccinia triticina) inokuliert und tropfnaß in eine Klimakammer mit 20°C und 100% relativer Luftfeuchte gestellt. 24 Stunden später kamen die Pflanzen in ein Gewächshaus zurück und wurden hier 14 Tage nach Inokulation auf Befall mit Weizenbraunrost untersucht.Wheat plants were made with the compounds of the invention even in the application concentrations listed in Table 4 treated. After the active ingredient covering has dried on those with spores of the wheat brown rust (Puccinia triticina) inoculated and dripping wet in a climate chamber at 20 ° C and 100% relative humidity. They came 24 hours later Plants back in a greenhouse and were there for 14 days after inoculation examined for infestation with wheat brown rust.
Der Befallsgrad wurde ausgedrückt in % befallener Blattfläche, bezogen auf unbehandelte, infizierte Kontrollpflanzen (= 100% Befall). Aus Tabelle 5 ist die gute Wirkung ersichtlich.The degree of infestation was expressed in% infested leaf area, based on untreated, infected control plants (= 100% Infestation). Table 5 shows the good effect.
Apfelunterlagen (EM IX) wurden im 4-Blattstadium mit den erfindungsgemäßen Verbindungen in den in Tabelle 5 angegebenen Anwendungskonzentrationen gleichmäßig behandelt. Nach Antrocknen des Wirkstoffbelages wurden die Pflanzen mit Konidien des Apfelschorfs (Venturia inaequalis) stark inokuliert und tropfnaß in eine Klimakammer gestellt, deren Temperatur 22°C und deren relative Luftfeuchte 100% betrug. Nach einer Infektionszeit von 48 Stunden kamen sie in ein Gewächshaus mit 18°C und einer relativen Luftfeuchte von 95 bis 100°C.Apple rootstocks (EM IX) were in the 4-leaf stage with the inventive Compounds in those given in Table 5 Application concentrations treated evenly. After drying the plants with conidia of the active ingredient coating of apple scab (Venturia inaequalis) heavily inoculated and placed dripping wet in a climatic chamber, the temperature of which is 22 ° C and their relative humidity was 100%. After an infection period of 48 hours they came with them to a greenhouse 18 ° C and a relative humidity of 95 to 100 ° C.
Nach einer Inkubationszeit von 14 Tagen wurden die Pflanzen auf Befall mit Apfelschorf untersucht. Die Beurteilung des Befalls erfolgte wie üblich nach Augenschein. Der Befallsgrad wurde in % befallener Blattfläche, bezogen auf unbehandelte, infizierte Pflanzen, ausgedrückt und ist in Tabelle 6 ersichtlich.After an incubation period of 14 days, the plants examined for infestation with apple scab. The assessment of the Infestation took place as usual after inspection. The degree of infestation was in% affected leaf area, based on untreated, infected plants, expressed and can be seen in Table 6.
Zuckerrübenpflanzen wurden im 6-Blattstadium mit den zu prüfenden Verbindungen in den in Tabelle 6 angegebenen Aufwandmengen gleichmäßig behandelt.Sugar beet plants were in the 6-leaf stage with the ones to be tested Compounds in the application rates given in Table 6 treated evenly.
Nach Antrocknen des Wirkstoffbelages wurden die Pflanzen mit Konidien des Erregers der Blattfleckenkrankheit der Rübe (Cercospora beticola) stark inkuliert und tropfnaß in eine Klimakammer mit ca. 100% relativer Luftfeucht und 25°C gestellt. 48 Stunden später kamen sie in ein Gewächshaus zurück. 14 tage später wurde auf Befall mit der Blattfleckenkrankheit untersucht. Der Befallsgrad ist in % befallener Blattfläche, bezogen auf unbehandelte, infizierte Kontrollpflanzen (= 100% Befall), ausgedrückt, und in Tabelle 7 verzeichnet. After the active ingredient coating had dried on, the plants were removed Conidia of the pathogen of leaf spot disease of the beet (Cercospora beticola) heavily incubated and dripping wet in one Climatic chamber with approx. 100% relative humidity and 25 ° C. They came back to a greenhouse 48 hours later. 14 days later was diagnosed with leaf spot disease examined. The degree of infestation is in% affected leaf area, based on untreated, infected control plants (= 100% Infestation), expressed, and listed in Table 7.
Weizen wurde im Gewächshaus in Plastiktöpfen von 9 cm Durchmesser bis zum 3-4-Blattstadium herangezogen und dann gleichzeitig mit den erfindungsgemäßen Verbindungen und den getesteten Herbiziden im Nachauflaufverfahren behandelt. Herbizide und die Verbindungen der Formel I wurden dabei in Form wässriger Suspensionen bzw. Emulsionen mit einer Wassermenge von umgerechnet 800 l/ha ausgebracht. 3-4 Wochen nach der Behandlung wurden die Pflanzen visuell auf jede Art von Schädigung durch die ausgebrachten Herbizide bonitiert, wobei insbesondere das Ausmaß der anhaltenden Wachstumshemmung berücksichtigt wurde.Wheat was grown in the greenhouse in 9 cm diameter plastic pots pulled up to the 3-4 leaf stage and then simultaneously with the compounds of the invention and those tested Post-emergence herbicides treated. Herbicides and the compounds of formula I became more aqueous in the form Suspensions or emulsions with a water volume of equivalent to 800 l / ha applied. 3-4 weeks after treatment the plants were visually exposed to any type of damage rated by the applied herbicides, in particular takes into account the extent of the continued growth retardation has been.
Die Ergebnisse aus Tabelle 8 veranschaulichen, daß die erfindungsgemäßen Verbindungen starke Herbizidschäden an Kulturpflanzen effektiv reduzieren können.The results from Table 8 illustrate that the inventive Compounds severe herbicide damage to crops can effectively reduce.
Selbst bei starken Überdosierungen des Herbizids H werden bei den Kulturpflanzen auftretenden schwere Schädigungen stark reduziert, geringere Schadsymptome völlig aufgehoben. Even when the herbicide H is overdosed, severe damage to crops reduced, less harmful symptoms completely eliminated.
Mischungen aus Herbiziden und erfindungsgemäßen Verbindungen eignen sich deshalb in ausgezeichneter Weise zur selektiven Unkrautbekämpfung in Kulturpflanzen.Mixtures of herbicides and compounds according to the invention are therefore excellent for selective Weed control in crops.
Getreide und das Schadgras Avena fatua wurden in Plastiktöpfen von 9 cm Durchmesser in lehmigem Sandboden ausgesät, unter optimalen Wuchsbedingungen im Gewächshaus bis zum 3-4-Blattstadium angezogen und mit Mischungen aus den erfindungsgemäßen Verbindungen und Herbiziden behandelt. Die Präparate wurden dabei in Form wässriger Suspension bzw. Emulsion mit einer Wasseraufwandmenge von umgerechnet 300-600 l/ha ausgebracht.Grain and the harmful grass Avena fatua were in plastic pots 9 cm in diameter sown in loamy sandy soil, under optimal growing conditions in the greenhouse up to the 3-4 leaf stage attracted and with mixtures of the invention Compounds and herbicides treated. The preparations were thereby in the form of an aqueous suspension or emulsion with a Water application rate equivalent to 300-600 l / ha applied.
3-4 Wochen nach Applikation wurden die die Versuchspflanzen auf Wachstumsveränderungen und Schädigung im Vergleich zu unbehandelten und mit den Herbiziden alleine behandelten Kontrollen visuell bonitiert. 3-4 weeks after application, the test plants were on growth changes and damage compared to untreated and controls treated with the herbicides alone visually rated.
Die Ergebnisse aus Tabelle 9 zeigen, daß die erfindungsgemäßen Verbindungen sehr gute Safenereigenschaften bei Kulturpflanzen aufweisen und Herbizidschäden, die an Kulturpflanzen wie z. B. Getreide entstehen, wirkungsvoll verhindern können, ohne die eigentliche herbizide Wirkung gegen Schadgräser zu beeinträchtigen.The results from Table 9 show that the inventive Compounds very good safener properties in crops have and herbicide damage to crops such. B. Cereals arise, can effectively prevent without affect actual herbicidal activity against harmful grass.
Mischungen aus Herbiziden und erfindungsgemäßen Verbindungen können somit zur selektiven Unkrautbekämpfung eingesetzt werden.Mixtures of herbicides and compounds according to the invention can thus be used for selective weed control.
Claims (7)
X N oder N → O
R Wasserstoff, (C1-C6)Alkyl,
p 0, 1 oder 3, wobei im Falle p ≦λτ 1 die Reste R auch unterschiedlich sein können,
Ar Phenyl, das ein oder mehrfach halogeniert sein kann, und/oder durch 1 bis 3 Reste aus der Gruppe Halogen- (C1-C5)alkyl mit 1 bis 7 Halogenatomen, insbesondere Chlor- oder Fluoratomen, (C1-C6)Alkyl, (C1-C6)Alkoxy, Halogen (C1-C4)alkoxy mit 1 bis 7 Halogenatomen, insbesondere Fluor oder Chloratomen, Phenyl oder Phenoxy, die beide jeweils durch bis zu drei Halogenatome substituiert sein können, substituiert sein kann,
Y Wasserstoff (C1-C6)Alkyl, (C2-C6)Alkenyl, (C2-C6)Alkinyl, (C1-C4)Alkoxy)-(C1-C4)alkyl, Di-(C1-C4- alkoxy)-(C1-C4)alkyl oder eine der drei folgenden Gruppen: wobei
R1 Wasserstoff, (C1-C6)Alkyl, (C3-C6)Cycloalkyl, (C3-C6) Alkenyl, (C3-C6)Alkinyl, Phenyl-(C1-C6)alkyl oder Phenoxy-(C1-C6)alkyl, die beide bis zu dreifach im Phenylteil durch Halogen substituiert sein können, Cyano(C1-C4)alkyl, Carbamoyl(C1-C4)-alkyl, (C1-C12- Alkylmercapto)methyl oder R2, R3 gleich oder verschieden sind und Wasserstoff, (C1-C6) Alkyl oder im Falle zusammen mit dem Stickstoffatom, an das sie gebunden sind einen Imidazolring bilden,
R4 (C1-C6)Alkyl, das halogeniert sein kann, (C3-C6)- Cycloalkyl, (C3-C6)Alkenyl, (C3-C6)Alkinyl, C1- C6-Alkoxy)-(C1-C4)alkyl, (C1-C12)Alkoxy, Hydroxy, Hydroxy(C2-C4)alkoxy, unsubstituiertes oder bis zu dreifach durch Halogen substituiertes Phenyl,
R5, R6 bei gleicher oder verschiedener Bedeutung (C1-C6)- Alkyl, Phenoxy(C1-C4)alkyl, wobei der Phenylrest bis zu dreifach halogeniert sein kann, oder
beide Reste stehen zusammen mit dem Stickstoffatom, an das sie gebunden sind, für einen unsubstituierten oder einfach oder mehrfach, gleich oder verschieden substituierten 5 bis 7-gliedrigen, gesättigten oder ungesättigten Heterocyclus mit 1-3 gleichen oder verschiedenen Heteroatomen, vorzugsweise mit den Heteroatomen Stickstoff, Sauerstoff und/oder Schwefel und dem Substituenten (C1-C4)Alkyl,
Me⁺ ein Alkalimetallkation oder ein Äquivalent eines Erdalkalimetallkations,
q 0, 1, 2 oder 3
Z CH oder N
W Wasserstoff, (C1-C6)Alkoxy, oder (C1-C6)- Alkyl, die beide durch bis zu zwei nicht an dasselbe C-Atom gebundene Hydroxygruppen oder durch bis zu drei Halogene substituiert sein können, ein über C- oder ein Heteroatom gebundener 5- bis 7gliedriger, gesättigter oder ungesättigter Heterocyclus mit 1 bis 3 gleichen oder verschiedenen Heteroatomen, vorzugsweise mit den Heteroatomen Stickstoff, Sauerstoff und/oder Schwefel,
oder die Gruppe -NR5R6,
sowie deren Säureadditionssalze, Metallkomplexe und Quaternisierungsprodukte,
wobei im Falle X = N Verbindungen, in denen
a) p = O, Y = H, (C1-C4)Alkyl, -CN, -CONH2 oder -COR4 bei R4 = (C1-C6)Alkoxy, oder
b) p = 1, R = H und bedeuten, ausgenommen sind.1. pyridyl compounds of the general formula (I) where the symbols have the following meaning.
XN or N → O
R is hydrogen, (C 1 -C 6 ) alkyl,
p 0, 1 or 3, where in the case p ≦ λτ 1 the radicals R can also be different,
Ar phenyl, which can be halogenated one or more times, and / or by 1 to 3 radicals from the group halogen (C 1 -C 5 ) alkyl having 1 to 7 halogen atoms, in particular chlorine or fluorine atoms, (C 1 -C 6 ) Alkyl, (C 1 -C 6 ) alkoxy, halogen (C 1 -C 4 ) alkoxy with 1 to 7 halogen atoms, in particular fluorine or chlorine atoms, phenyl or phenoxy, both of which can each be substituted by up to three halogen atoms can,
Y hydrogen (C 1 -C 6 ) alkyl, (C 2 -C 6 ) alkenyl, (C 2 -C 6 ) alkynyl, (C 1 -C 4 ) alkoxy) - (C 1 -C 4 ) alkyl, di- (C 1 -C 4 alkoxy) - (C 1 -C 4 ) alkyl or one of the following three groups: in which
R 1 is hydrogen, (C 1 -C 6 ) alkyl, (C 3 -C 6 ) cycloalkyl, (C 3 -C 6 ) alkenyl, (C 3 -C 6 ) alkynyl, phenyl- (C 1 -C 6 ) alkyl or phenoxy- (C 1 -C 6 ) alkyl, both of which can be substituted up to three times in the phenyl part by halogen, cyano (C 1 -C 4 ) alkyl, carbamoyl (C 1 -C 4 ) alkyl, (C 1 - C 12 - alkylmercapto) methyl or R 2 , R 3 are the same or different and are hydrogen, (C 1 -C 6 ) alkyl or in the case together with the nitrogen atom to which they are attached form an imidazole ring,
R 4 (C 1 -C 6 ) alkyl, which can be halogenated, (C 3 -C 6 ) - cycloalkyl, (C 3 -C 6 ) alkenyl, (C 3 -C 6 ) alkynyl, C 1 - C 6 - Alkoxy) - (C 1 -C 4 ) alkyl, (C 1 -C 12 ) alkoxy, hydroxy, hydroxy (C 2 -C 4 ) alkoxy, unsubstituted or up to triple halogen-substituted phenyl,
R 5 , R 6 with the same or different meaning (C 1 -C 6 ) alkyl, phenoxy (C 1 -C 4 ) alkyl, where the phenyl radical can be halogenated up to three times, or
Both radicals together with the nitrogen atom to which they are attached represent an unsubstituted or mono- or polysubstituted, identically or differently substituted, 5 to 7-membered, saturated or unsaturated heterocycle with 1-3 identical or different heteroatoms, preferably with the heteroatoms nitrogen , Oxygen and / or sulfur and the substituent (C 1 -C 4 ) alkyl,
Measuring an alkali metal cation or an equivalent of an alkaline earth metal cation,
q 0, 1, 2 or 3
Z CH or N
W is hydrogen, (C 1 -C 6 ) alkoxy, or (C 1 -C 6 ) alkyl, both of which can be substituted by up to two hydroxyl groups not bound to the same C atom or by up to three halogens, one via C 5 or 7-membered, saturated or unsaturated heterocycle with 1 to 3 identical or different heteroatoms, preferably with the heteroatoms nitrogen, oxygen and / or sulfur,
or the group -NR 5 R 6 ,
as well as their acid addition salts, metal complexes and quaternization products,
where X = N compounds in which
a) p = O, Y = H, (C 1 -C 4 ) alkyl, -CN, -CONH 2 or -COR 4 when R 4 = (C 1 -C 6 ) alkoxy, or
b) p = 1, R = H and mean, are excluded.
a) Ketone der Formel (II) mit Verbindungen der Formel III, worin Z1 eine nucleofuge Abgangsgruppe bedeutet, umsetzt oder
b) zur Herstellung von Verbindungen der Formel I, in denen p = 1 und R = H bedeutet, Verbindungen der Formel IV mit Nucleophilen der Formel V umsetzt und die erhaltenen Verbindungen der Formel I gegebenenfalls in ihre Säureadditionssalze, Metallsalzkomplexe oder Quarternisierungsprodukte umwandelt.2. A process for the preparation of the compounds of claim 1, characterized in that
a) reacting ketones of the formula (II) with compounds of the formula III in which Z 1 is a nucleofugic leaving group or
b) for the preparation of compounds of the formula I in which p = 1 and R = H, compounds of the formula IV with nucleophiles of the formula V and, if appropriate, converting the compounds of the formula I obtained into their acid addition salts, metal salt complexes or quaternization products.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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DE19853539476 DE3539476A1 (en) | 1985-11-07 | 1985-11-07 | Novel pyridyl compounds and their N-oxides, process for their preparation, and their use in crop protection |
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Application Number | Priority Date | Filing Date | Title |
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DE19853539476 DE3539476A1 (en) | 1985-11-07 | 1985-11-07 | Novel pyridyl compounds and their N-oxides, process for their preparation, and their use in crop protection |
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DE3539476A1 true DE3539476A1 (en) | 1987-05-14 |
Family
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DE19853539476 Withdrawn DE3539476A1 (en) | 1985-11-07 | 1985-11-07 | Novel pyridyl compounds and their N-oxides, process for their preparation, and their use in crop protection |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1989000568A1 (en) * | 1987-07-10 | 1989-01-26 | Rhone Poulenc Agrochimie | Fungicidal compositions based on nicotine derivatives, new nicotine derivatives, and their preparation |
EP0317881A2 (en) * | 1987-11-25 | 1989-05-31 | Hoechst Aktiengesellschaft | Pyridyl- and pyrazinyl compounds, process for their preparation, composition containing them and their use as fungicides |
DE19652961A1 (en) * | 1996-12-19 | 1998-06-25 | Hoechst Schering Agrevo Gmbh | New 2-fluoroacrylic acid derivatives, new mixtures of herbicides and antidots and their use |
US6124240A (en) * | 1996-09-19 | 2000-09-26 | Hoechst Agrevo Gmbh | Combinations of sulfonylurea herbicides and safeners |
WO2003001913A1 (en) * | 2001-06-26 | 2003-01-09 | Bayer Chemicals Ag | Thiazines and thiazoles for use as material protective agents |
-
1985
- 1985-11-07 DE DE19853539476 patent/DE3539476A1/en not_active Withdrawn
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1989000568A1 (en) * | 1987-07-10 | 1989-01-26 | Rhone Poulenc Agrochimie | Fungicidal compositions based on nicotine derivatives, new nicotine derivatives, and their preparation |
GR880100452A (en) * | 1987-07-10 | 1989-04-12 | Rhone Poulenc Agrochimie | Fungicide compositions on the basis of nicotine derivatives new nicotine derivatives and preparation therefor |
US4908375A (en) * | 1987-07-10 | 1990-03-13 | Rhone-Poulenc Agrochimie | Fungicidal compositions based on nicotinic derivatives |
EP0317881A2 (en) * | 1987-11-25 | 1989-05-31 | Hoechst Aktiengesellschaft | Pyridyl- and pyrazinyl compounds, process for their preparation, composition containing them and their use as fungicides |
EP0317881A3 (en) * | 1987-11-25 | 1990-05-23 | Hoechst Aktiengesellschaft | Pyridyl- and pyrazinyl compounds, process for their preparation, composition containing them and their use as fungicides |
US6124240A (en) * | 1996-09-19 | 2000-09-26 | Hoechst Agrevo Gmbh | Combinations of sulfonylurea herbicides and safeners |
DE19652961A1 (en) * | 1996-12-19 | 1998-06-25 | Hoechst Schering Agrevo Gmbh | New 2-fluoroacrylic acid derivatives, new mixtures of herbicides and antidots and their use |
WO2003001913A1 (en) * | 2001-06-26 | 2003-01-09 | Bayer Chemicals Ag | Thiazines and thiazoles for use as material protective agents |
US7084137B2 (en) | 2001-06-26 | 2006-08-01 | Bayer Aktiengesellschaft | Thiazines and thiazoles as agents for protecting materials |
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