EP0000377A1 - Process for the preparation of chromone derivatives, new chromone derivatives and their use as plant-protecting agents - Google Patents
Process for the preparation of chromone derivatives, new chromone derivatives and their use as plant-protecting agents Download PDFInfo
- Publication number
- EP0000377A1 EP0000377A1 EP78100318A EP78100318A EP0000377A1 EP 0000377 A1 EP0000377 A1 EP 0000377A1 EP 78100318 A EP78100318 A EP 78100318A EP 78100318 A EP78100318 A EP 78100318A EP 0000377 A1 EP0000377 A1 EP 0000377A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- chromon
- carboxy
- carboxymethyl
- carbo
- hydroxyacetophenone
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims description 14
- 238000002360 preparation method Methods 0.000 title claims description 9
- 150000004777 chromones Chemical class 0.000 title claims description 8
- 239000003223 protective agent Substances 0.000 title 1
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 19
- JECYUBVRTQDVAT-UHFFFAOYSA-N 2-acetylphenol Chemical class CC(=O)C1=CC=CC=C1O JECYUBVRTQDVAT-UHFFFAOYSA-N 0.000 claims abstract description 18
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical class OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 11
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 11
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 11
- 125000000392 cycloalkenyl group Chemical group 0.000 claims abstract description 10
- 150000002148 esters Chemical class 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 125000004663 dialkyl amino group Chemical group 0.000 claims abstract description 8
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 7
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims abstract description 7
- 125000000547 substituted alkyl group Chemical group 0.000 claims abstract description 7
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 6
- 150000002367 halogens Chemical class 0.000 claims abstract description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 6
- 125000004104 aryloxy group Chemical group 0.000 claims abstract description 5
- 150000007514 bases Chemical class 0.000 claims abstract description 5
- 125000002837 carbocyclic group Chemical group 0.000 claims abstract description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 4
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract 4
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 150000001768 cations Chemical class 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 150000003335 secondary amines Chemical class 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 23
- 239000013543 active substance Substances 0.000 abstract description 9
- 238000011161 development Methods 0.000 abstract description 8
- 241000238421 Arthropoda Species 0.000 abstract description 5
- 239000004480 active ingredient Substances 0.000 abstract description 5
- 241000233866 Fungi Species 0.000 abstract description 4
- 239000011814 protection agent Substances 0.000 abstract description 4
- 241000221785 Erysiphales Species 0.000 abstract description 3
- 230000002464 fungitoxic effect Effects 0.000 abstract description 3
- -1 aliphatic aldehydes Chemical class 0.000 description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 13
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 10
- 241000196324 Embryophyta Species 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
- 230000018109 developmental process Effects 0.000 description 7
- 239000003995 emulsifying agent Substances 0.000 description 7
- 229950009263 methylchromone Drugs 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- PXPNSQMWVPLERM-UHFFFAOYSA-N 2-methylchromen-4-one Chemical compound C1=CC=C2OC(C)=CC(=O)C2=C1 PXPNSQMWVPLERM-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Natural products CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- AIUUQDBBEGDNLH-UHFFFAOYSA-N 3-(carboxymethyl)-4-oxochromene-2-carboxylic acid Chemical compound C1=CC=C2C(=O)C(CC(=O)O)=C(C(O)=O)OC2=C1 AIUUQDBBEGDNLH-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 238000005554 pickling Methods 0.000 description 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 206010061217 Infestation Diseases 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- 241001465754 Metazoa Species 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000004606 Fillers/Extenders Substances 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 3
- 125000002877 alkyl aryl group Chemical group 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- ABJKIHHNDMEBNA-UHFFFAOYSA-N methylchromone Chemical compound C1=CC=C2C(=O)C(C)=COC2=C1 ABJKIHHNDMEBNA-UHFFFAOYSA-N 0.000 description 3
- 229920000151 polyglycol Polymers 0.000 description 3
- 239000010695 polyglycol Substances 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- SULYEHHGGXARJS-UHFFFAOYSA-N 2',4'-dihydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1O SULYEHHGGXARJS-UHFFFAOYSA-N 0.000 description 2
- SHJXSYJQBXYBGA-UHFFFAOYSA-N 2-cyclohexyl-2-hydroxy-1-phenylethanone Chemical compound C=1C=CC=CC=1C(=O)C(O)C1CCCCC1 SHJXSYJQBXYBGA-UHFFFAOYSA-N 0.000 description 2
- GBNGEWROXPPBOJ-UHFFFAOYSA-N 6-methoxy-2,2-dimethylchromene Chemical compound O1C(C)(C)C=CC2=CC(OC)=CC=C21 GBNGEWROXPPBOJ-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 241000209219 Hordeum Species 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 230000000855 fungicidal effect Effects 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 208000015181 infectious disease Diseases 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- ZDTXZMPNQXBHOH-UHFFFAOYSA-N methyl 6,8-dichloro-3-(2-methoxy-2-oxoethyl)-5-methyl-4-oxochromene-2-carboxylate Chemical compound C1=C(Cl)C(C)=C2C(=O)C(CC(=O)OC)=C(C(=O)OC)OC2=C1Cl ZDTXZMPNQXBHOH-UHFFFAOYSA-N 0.000 description 2
- KLGADKVDMJEVFO-UHFFFAOYSA-N methyl 6-methoxy-3-(2-methoxy-2-oxoethyl)-4-oxochromene-2-carboxylate Chemical compound C1=C(OC)C=C2C(=O)C(CC(=O)OC)=C(C(=O)OC)OC2=C1 KLGADKVDMJEVFO-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 239000006072 paste Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 239000004476 plant protection product Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
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- 230000001681 protective effect Effects 0.000 description 2
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- 0 *C1=C(*=C)Oc(cc(C2C=C*CC2)cc2)c2N1 Chemical compound *C1=C(*=C)Oc(cc(C2C=C*CC2)cc2)c2N1 0.000 description 1
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 1
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- AGQNLHOTLJFJCG-UHFFFAOYSA-N 1-(2-hydroxy-4-phenylmethoxyphenyl)ethanone Chemical compound C1=C(O)C(C(=O)C)=CC=C1OCC1=CC=CC=C1 AGQNLHOTLJFJCG-UHFFFAOYSA-N 0.000 description 1
- MLIBGOFSXXWRIY-UHFFFAOYSA-N 1-(2-hydroxy-5-methoxyphenyl)ethanone Chemical compound COC1=CC=C(O)C(C(C)=O)=C1 MLIBGOFSXXWRIY-UHFFFAOYSA-N 0.000 description 1
- CJFYGRLJDKWMDI-UHFFFAOYSA-N 1-(3,5-dichloro-2-hydroxyphenyl)ethanone Chemical compound CC(=O)C1=CC(Cl)=CC(Cl)=C1O CJFYGRLJDKWMDI-UHFFFAOYSA-N 0.000 description 1
- MTAVHKCZHOJIRE-UHFFFAOYSA-N 1-(3-chlorophenyl)-2-hydroxyethanone Chemical compound OCC(=O)C1=CC=CC(Cl)=C1 MTAVHKCZHOJIRE-UHFFFAOYSA-N 0.000 description 1
- BAYUSCHCCGXLAY-UHFFFAOYSA-N 1-(3-methoxyphenyl)ethanone Chemical compound COC1=CC=CC(C(C)=O)=C1 BAYUSCHCCGXLAY-UHFFFAOYSA-N 0.000 description 1
- XTGCUDZCCIRWHL-UHFFFAOYSA-N 1-(5-chloro-2-hydroxyphenyl)ethanone Chemical compound CC(=O)C1=CC(Cl)=CC=C1O XTGCUDZCCIRWHL-UHFFFAOYSA-N 0.000 description 1
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- HEJLFBLJYFSKCE-UHFFFAOYSA-N 2',3'-Dihydroxyacetophenone Chemical compound CC(=O)C1=CC=CC(O)=C1O HEJLFBLJYFSKCE-UHFFFAOYSA-N 0.000 description 1
- XLEYFDVVXLMULC-UHFFFAOYSA-N 2',4',6'-trihydroxyacetophenone Chemical compound CC(=O)C1=C(O)C=C(O)C=C1O XLEYFDVVXLMULC-UHFFFAOYSA-N 0.000 description 1
- WLDWSGZHNBANIO-UHFFFAOYSA-N 2',5'-Dihydroxyacetophenone Chemical compound CC(=O)C1=CC(O)=CC=C1O WLDWSGZHNBANIO-UHFFFAOYSA-N 0.000 description 1
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- KPACBFJTZSMBKD-OAQYLSRUSA-N 2-[2-[(4-carbamimidoylphenyl)carbamoyl]-6-methoxypyridin-3-yl]-5-[[(2s)-1-hydroxy-3,3-dimethylbutan-2-yl]carbamoyl]benzoic acid Chemical compound C=1C=C(C(N)=N)C=CC=1NC(=O)C1=NC(OC)=CC=C1C1=CC=C(C(=O)N[C@H](CO)C(C)(C)C)C=C1C(O)=O KPACBFJTZSMBKD-OAQYLSRUSA-N 0.000 description 1
- GWFBKWHPRHMWGH-UHFFFAOYSA-N 2-hydroxy-1-(2-nitrophenyl)ethanone Chemical compound OCC(=O)C1=CC=CC=C1[N+]([O-])=O GWFBKWHPRHMWGH-UHFFFAOYSA-N 0.000 description 1
- FPRVEQAYURPPAI-UHFFFAOYSA-N 2-hydroxy-1-(3-methoxyphenyl)ethanone Chemical compound COC1=CC=CC(C(=O)CO)=C1 FPRVEQAYURPPAI-UHFFFAOYSA-N 0.000 description 1
- VRURKJLCRYVJSK-UHFFFAOYSA-N 2-hydroxy-3-oxo-3-phenylpropanoic acid Chemical compound OC(=O)C(O)C(=O)C1=CC=CC=C1 VRURKJLCRYVJSK-UHFFFAOYSA-N 0.000 description 1
- MGADZUXDNSDTHW-UHFFFAOYSA-N 2H-pyran Chemical compound C1OC=CC=C1 MGADZUXDNSDTHW-UHFFFAOYSA-N 0.000 description 1
- WVOHFUDPKVOUBC-UHFFFAOYSA-N 3-(carboxymethyl)-4-oxo-7-phenylchromene-2-carboxylic acid Chemical compound C=1C=C2C(=O)C(CC(=O)O)=C(C(O)=O)OC2=CC=1C1=CC=CC=C1 WVOHFUDPKVOUBC-UHFFFAOYSA-N 0.000 description 1
- AMHJPOYNLKNLGG-UHFFFAOYSA-N 3-(carboxymethyl)-5,6,7-trimethyl-4-oxochromene-2-carboxylic acid Chemical compound O1C(C(O)=O)=C(CC(O)=O)C(=O)C2=C1C=C(C)C(C)=C2C AMHJPOYNLKNLGG-UHFFFAOYSA-N 0.000 description 1
- MSTDXOZUKAQDRL-UHFFFAOYSA-N 4-Chromanone Chemical class C1=CC=C2C(=O)CCOC2=C1 MSTDXOZUKAQDRL-UHFFFAOYSA-N 0.000 description 1
- OUYLDJXFDLBCTQ-UHFFFAOYSA-N 4-[hydroxy-(4-hydroxynaphthalen-1-yl)-phenylmethyl]naphthalen-1-ol Chemical compound C12=CC=CC=C2C(O)=CC=C1C(O)(C=1C2=CC=CC=C2C(O)=CC=1)C1=CC=CC=C1 OUYLDJXFDLBCTQ-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000235349 Ascomycota Species 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 241001480061 Blumeria graminis Species 0.000 description 1
- 240000007124 Brassica oleracea Species 0.000 description 1
- 241000760356 Chytridiomycetes Species 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 1
- BUDQDWGNQVEFAC-UHFFFAOYSA-N Dihydropyran Chemical compound C1COC=CC1 BUDQDWGNQVEFAC-UHFFFAOYSA-N 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- 206010017533 Fungal infection Diseases 0.000 description 1
- 235000007340 Hordeum vulgare Nutrition 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 241000233654 Oomycetes Species 0.000 description 1
- 241001608567 Phaedon cochleariae Species 0.000 description 1
- 241001503460 Plasmodiophorida Species 0.000 description 1
- 241000500437 Plutella xylostella Species 0.000 description 1
- 206010037888 Rash pustular Diseases 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 241000287436 Turdus merula Species 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000005078 alkoxycarbonylalkyl group Chemical group 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- WWVJLWGVZUOOIW-UHFFFAOYSA-N benzyl 4-oxo-3-(2-oxo-2-phenylmethoxyethyl)chromene-2-carboxylate Chemical compound C=1C=CC=CC=1COC(=O)CC(C(C1=CC=CC=C1O1)=O)=C1C(=O)OCC1=CC=CC=C1 WWVJLWGVZUOOIW-UHFFFAOYSA-N 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000008422 chlorobenzenes Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 230000002538 fungal effect Effects 0.000 description 1
- 208000024386 fungal infectious disease Diseases 0.000 description 1
- 231100000162 fungitoxic Toxicity 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000005928 isopropyloxycarbonyl group Chemical group [H]C([H])([H])C([H])(OC(*)=O)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 230000029052 metamorphosis Effects 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- ATYFVROFDUMHSM-UHFFFAOYSA-N methyl 3-(2-methoxy-2-oxoethyl)-4-oxochromene-2-carboxylate Chemical compound C1=CC=C2C(=O)C(CC(=O)OC)=C(C(=O)OC)OC2=C1 ATYFVROFDUMHSM-UHFFFAOYSA-N 0.000 description 1
- HOEWPEBUCOKQAW-UHFFFAOYSA-N methyl 6,8-dichloro-3-(2-methoxy-2-oxoethyl)-4-oxochromene-2-carboxylate Chemical compound C1=C(Cl)C=C2C(=O)C(CC(=O)OC)=C(C(=O)OC)OC2=C1Cl HOEWPEBUCOKQAW-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 230000004660 morphological change Effects 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004998 naphthylethyl group Chemical group C1(=CC=CC2=CC=CC=C12)CC* 0.000 description 1
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- KLAKIAVEMQMVBT-UHFFFAOYSA-N p-hydroxy-phenacyl alcohol Natural products OCC(=O)C1=CC=C(O)C=C1 KLAKIAVEMQMVBT-UHFFFAOYSA-N 0.000 description 1
- UILPJVPSNHJFIK-UHFFFAOYSA-N p-methoxy-o-hydroxyacetophenone Natural products COC1=CC=C(C(C)=O)C(O)=C1 UILPJVPSNHJFIK-UHFFFAOYSA-N 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- 244000052769 pathogen Species 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 125000004742 propyloxycarbonyl group Chemical group 0.000 description 1
- 239000003531 protein hydrolysate Substances 0.000 description 1
- 208000029561 pustule Diseases 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- SOEVVANXSDKPIY-UHFFFAOYSA-M sodium glyoxylate Chemical compound [Na+].[O-]C(=O)C=O SOEVVANXSDKPIY-UHFFFAOYSA-M 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000005346 substituted cycloalkyl group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/22—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4
- C07D311/24—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
Definitions
- the present invention relates to a new, chemically peculiar process for the production of new chromone derivatives and their use as crop protection agents.
- chromones can also be prepared from o-acylphenols and carboxylic acid derivatives in a ratio of 1: 1 (cf. P. Karrer, "Textbook of Organic Chemistry”. 13th edition, page 584, Georg Thieme Verlag, Stuttgart (1959)).
- zinc ethylenebis-dithiocarbamidate is known as a standard preparation with worldwide distribution (from R. Wegler, "Chemistry of Plant Protection Products and Pest Control", Volume 4, page 139, Springer-Verlag, Berlin / Heidelberg / New York (1977)). At low application rates, however, the effect is not always satisfactory.
- the new compounds of formula (I) have fungicidal properties; they also inhibit the development of arthropods. They are therefore of interest as pesticides.
- R , R 2 also represent optionally substituted cycloalkyl and cycloalkenyl radicals having 3 to 8, preferably having 4 to 6, carbon atoms, such as, for example, cyclobutyl and in particular cyclopentyl and cyclohexyl.
- Aryl radicals which may be substituted may be those having 6 to 10 carbon atoms, such as phenyl and naphthyl, preferably phenyl.
- Suitable substituted aralkyl radicals are those having 7 to 18 carbon atoms, the aliphatic part of which contains 1 to 8, preferably 1 to 4, carbons and the aromatic part of which represents a carbocyclic radical having 6 to 10 carbon atoms.
- the following aralkyl radicals may be mentioned by way of example: benzyl, phenylethyl, phenylpropyl, phenylbutyl, naphthylmethyl and naphthylethyl, preferably benzyl.
- Preferred alkoxy groups are those with up to 4 carbon atoms, such as methoxy, xthoxy, propoxy, isopropoxy, butoxy, isobutoxy and tert-butoxy.
- Preferred aryloxy groups are those with 6 or 10 carbon atoms, such as phenoxy and naphthoxy.
- Preferred aralkoxy groups are those having 7 to 10 carbon atoms, such as benzyloxy, phenylethoxy, phenylpropoxy, phenylisopropoxy, phenylbutoxy, phenylisobutoxy and phenyl tert-butoxy.
- Preferred alkoxycarbonyl groups are those with up to 4 carbon atoms in the alkyl radical, such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl.
- Preferred dialkylamino groups are those with up to 3 carbon atoms in the alkyl radical, such as dimethylamino, diethylamino, and diisopropylamino, called. It is also possible for the two alkyl radicals of the dialkylamino group to be closed to form a ring, such as, for example, pyrrolidinyl, piperidinyl.
- Halogens are fluorine, chlorine, bromine and iodine, preferably chlorine and bromine.
- the radicals R and R 1 can in particular form a carbocyclic or heterocyclic five- or six-membered ring, such as, for example, a cyclopentene, cyclohexene, benzene, furan, dihydrofuran, thiophene, with the two carbon atoms of the benzene ring on which they are seated -, Dihydrothiophene, pyran, dihydropyran, pyridine or dioxole ring.
- a carbocyclic or heterocyclic five- or six-membered ring such as, for example, a cyclopentene, cyclohexene, benzene, furan, dihydrofuran, thiophene, with the two carbon atoms of the benzene ring on which they are seated -, Dihydrothiophene, pyran, dihydropyran, pyridine or dioxole ring.
- Substituents which do not change under the reaction conditions are suitable as substituents of the alkyl, cycloalkyl, aryl, aralkyl, alkoxy, aralkoxy, alkoxycarbonyl and dialkylamino groups of the radicals R to R 2 .
- substituents of the alkyl, cycloalkyl, aryl, aralkyl, alkoxy, aralkoxy, alkoxycarbonyl and dialkylamino groups of the radicals R to R 2 examples include the halogens, such as fluorine, chlorine, bromine and iodine and the cyano group, furthermore the alkoxy and alkoxycarbonyl group with up to 4 and - if the substituents on ring systems are concerned - the alkyl and alkoxycarbonylalkyl groups. Group with up to 4 carbon atoms.
- dialkylamino group with a total of up to 6, preferably up to 2, carbon atoms, then
- the glyoxylic acid derivatives of the formula (III) are also required as starting compounds.
- Z is preferably monovalent or divalent cations of alkali and alkaline earth metals, and ONO for the ammonium cation and M, di- and Trialkylamnonium cations.
- the alkyl radicals preferably contain up to 2 carbon atoms.
- Secondary amines are preferred as such, in particular cyclic amines such as pyrrolidine, also piperidine, N-methylpiperazine, morpholine, but also open-chain amines such as dimethylamine and diethylamine.
- Secondary amines are preferred as such, in particular cyclic amines such as pyrrolidine, also piperidine, N-methylpiperazine, morpholine, but also open-chain amines such as dimethylamine and diethylamine.
- the compounds mentioned are generally known.
- the inventive process may at a temperature of -30 to + 150 ° C, preferably from 20 to 80 o C, to be performed.
- the o-hydroxycarbonyl compounds and the salt of glyoxylic acid in stoichiometric amounts ie in a ratio of 1: 2.
- a small excess of a component, in particular the glyoxylic acid salt is used (for example up to a molar ratio of 1: 2.5).
- the amount of the amine used is not critical. In general, 0.05 to 1.5, preferably 0.1 to 1 mol of the amine, based on 1 mol of the o-hydroxycarbonyl compound, is used. If the o-hydroxyacetophenones are substituted by acidic groups such as carboxy groups, it may be expedient to neutralize the acidic groups with an excess of the amine.
- the esterification of the dicarboxylic acids obtained can be carried out, for example, in a customary manner by stirring the dicarboxylic acid in 4 to 100, preferably 10 to 50 times the molar amount of alcohol of the formula R 3 --OH, with an acid such as conc. Added sulfuric acid or saturated with hydrogen chloride gas and warmed to temperatures from 60 to 120 ° C for a few hours.
- the mixture of the dicarboxylic acid with the alcohol can also be mixed with at least twice the molar amount, based on the dicarboxylic acid, of a dehydrating agent, such as inorganic acid halides, for example thionyl chloride or phosphorus oxychloride.
- salts of the dicarboxylic acids can also be reacted with at least twice the molar amount of an alkyl halide in a solvent such as dimethyl sulfoxide or dimethylformamide.
- the active compounds according to the invention have a good fungitoxic effect. They do not damage crops in the concentrations necessary to control fungi. For these reasons, they are suitable for use as crop protection agents for combating fungi. Fungitoxic agents are used in crop protection to combat Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Bsidiomycetes, Deuteromycetes.
- the active compounds according to the invention can be used against parasitic fungi and bacteria which attack above-ground parts of plants or attack the plants from the ground, and against seed-borne pathogens.
- the good tolerance to plants allows use against fungal plant diseases by treating the standing crop or individual parts of it or the seed or the crop soil.
- the active. substances are particularly effective against powdery mildew.
- the active compounds according to the invention can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, pastes and granules. These are manufactured in a known manner, e.g. B. by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents.
- extenders that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents.
- organic solvents can also be used as auxiliary solvents.
- liquid solvents aromatics, such as xylene, toluene, benzene or alkylnaphthalenes, chlorinated aroses or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, Chloroethylene or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. B.
- Liquefied gaseous extenders or carriers mean those liquids which are gaseous at normal temperature and pressure, e.g. B.
- aerosol propellants such as dichlorodifluoromethane or trichlorofluoromethane; as solid carriers: natural rock flour, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock meals, such as highly disperse silica, aluminum oxide and silicates; as an emulsifier; nonionic and anionic emulsifiers, such as polyoxyethylene photo acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ether, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; as a dispersant: e.g. B. lignin sulfite and methyl cellulose.
- natural rock flour such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic
- the formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.
- the active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules. They are used in the usual way, e.g. by spraying, spraying, misting, scattering, dusting, pouring, dry pickling, slurry pickling (slurry pickling), wet pickling and wet pickling.
- the active substance content of the use forms prepared from the commercially available formulations can vary within wide ranges.
- the active substance concentration of the use forms can be from 0.0000001 to 100% by weight of active substance, preferably between 0.01 and 10% by weight.
- active compound 10 mg to 10 g, preferably 100 mg to 3 q, are generally used per kilogram of seed.
- active substance concentrations of 1 to 1000 g of active substance per m 3 of soil, preferably 10 to 200 g per m 3 , are required at the location of the expected action.
- the compounds according to the invention inhibit the development of arthropods (arthrophodes).
- active compound 2 parts by weight of active compound are mixed with the stated amount of solvent, emulsifier and enough water to form a 1% mixture which is diluted with water to the desired concentration.
- test animals are such that an amount of active ingredient is obtained in ppm ( "parts p ro million") on the leaves, fed with leaves of the feed plants, which are provided with a uniform spray coating of the active ingredient mixture of the chosen concentration, to the development of the imago.
- active compound 0.25 part by weight of active compound is taken up in 25 parts by weight of dimethylformamide and 0.06 part by weight of emulsifier (alkyl aryl polyglycol ether), and 975 parts by weight of water are added.
- emulsifier alkyl aryl polyglycol ether
- the single-leafed barley young plants of the Amsel variety are sprayed with the preparation of active compound as dewy. After drying, the barley plants are dusted with spores from Erysiphe graminis var. Hordei.
- the stocking of the plants with mildew pustules is evaluated.
- the degree of infestation is expressed as a percentage of the infestation of the untreated control plants. O% means no infection and 100% means the same degree of infection as in the untreated control. The lower the mildew infestation, the more effective the active ingredient.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pyrane Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
Die Verbindungen der Formel <IMAGE> in welcher R, R¹ und R² gleich oder verschieden, für Wasserstoff, gegebenenfalls substituiertes Alkyl, Alkenyl, Cycloalkyl, Cycloalkenyl, Aralkyl, Aryl, ferner für Halogen, Hydroxy, Alkoxy, Aryloxy, Aralkoxy, Alkoxycarbonyl, Cyan und/oder Dialkylamino stehen, und weiterhin zwei Reste R und R¹ zusammen mit zwei Kohlenstoffatomen des Benzolringsystems einen carbocyclischen oder heterocyclischen 5- oder 6-Ring bilden können, und R³ für Wasserstoff, gegebenenfalls substituiertes Alkyl, Alkenyl, Cycloalkyl, Cycloalkenyl oder Aralkyl steht, werden erhalten, wenn man o-Hydroxy-acetophenone mit Glyoxylsäure-Derivaten in Gegenwart von basischen Verbindungen umsetzt, und noch gegebenenfalls die dabei erhaltenen Carbonsäuren in an sich bekannter Weise in die entsprechenden Ester überführt. Die erfindungsgemässen Wirkstoffe weisen eine fungitoxische Wirkung auf. Aus diesen Gründen sind sie für den Gebrauch als Pflanzenschutzmittel zur Bekämpfung von Pilzen geeignet. Die Wirkstoffe sind besonders wirksam gegen Getreidemehltau und hemmen ferner die Entwicklung von Gliederfüsslern (Arthrophoden).The compounds of the formula <IMAGE> in which R, R¹ and R² are the same or different, for hydrogen, optionally substituted alkyl, alkenyl, cycloalkyl, cycloalkenyl, aralkyl, aryl, furthermore for halogen, hydroxy, alkoxy, aryloxy, aralkoxy, alkoxycarbonyl, cyan and / or dialkylamino, and furthermore two radicals R and R¹ together with two carbon atoms of the benzene ring system can form a carbocyclic or heterocyclic 5- or 6-ring, and R³ represents hydrogen, optionally substituted alkyl, alkenyl, cycloalkyl, cycloalkenyl or aralkyl, are obtained if o-hydroxy-acetophenones are reacted with glyoxylic acid derivatives in the presence of basic compounds, and, if appropriate, the carboxylic acids obtained are converted into the corresponding esters in a manner known per se. The active substances according to the invention have a fungitoxic effect. For these reasons, they are suitable for use as crop protection agents for combating fungi. The active ingredients are particularly effective against powdery mildew and also inhibit the development of arthropods (arthrophodes).
Description
Die vorliegende Erfindung betrifft ein neues, chemisch eigenartiges Verfahren zur Herstellung von neuen Chromon-Derivaten sowie ihre Verwendung als Pflanzenschutzmittel.The present invention relates to a new, chemically peculiar process for the production of new chromone derivatives and their use as crop protection agents.
Es ist bereits bekannt, daß aromatische Aldehyde in Gegenwart von Natronlauge mit o-Hydroxyacetophenonen zu 2-Phenyl-chromanonen reagieren (Elderfield, "Heterocyclic Compounds", Vol. 2, Seite 347), ferner ist noch bekannt, daß man auch aliphatische Aldehyde mit o-Hydroxyacetophenonen zu den entsprechenden 2-Alkylehromanonen umsetzen kann (vgl. DT-OS 2 535 338 LLe A 16 634]). In beiden Fällen reagieren o-Hydroxyacetophenon und Aldehyd im Molverhältnis 1:1. Weiterhin ist noch bekannt, daß man aus o-Acylphenolen und Carbonsaure-Derivaten ebenfalls im Verhältnis 1:1 Chromone herstellen kann (vgl. P. Karrer, "Lehrbuch der Organischen Chemie". 13. Auflage, Seite 584, Georg Thieme Verlag, Stuttgart (1959)).It is already known that aromatic aldehydes react with o-hydroxyacetophenones to give 2-phenyl-chromanones in the presence of sodium hydroxide solution (Elderfield, "Heterocyclic Compounds", Vol. 2, page 347). It is also known that aliphatic aldehydes are also used can convert o-hydroxyacetophenones to the corresponding 2-alkylhromanones (cf. DT-OS 2 535 338 LLe A 16 634]). In both cases, o-hydroxyacetophenone and aldehyde react in a molar ratio of 1: 1. Furthermore, it is also known that chromones can also be prepared from o-acylphenols and carboxylic acid derivatives in a ratio of 1: 1 (cf. P. Karrer, "Textbook of Organic Chemistry". 13th edition, page 584, Georg Thieme Verlag, Stuttgart (1959)).
Als Pflanzenschutzmittel mit fungizider Wirkung ist als Standard-Präparat mit weltweiter Verbreitung Zink-äthylenbis-dithiocarbamidat bekannt (vql. R. Wegler, "Chemie der Pflanzenschutz- und Schädlingsbekämpfungsmittel", Band 4, Seite 139, Springer-Verlag, Berlin/Heidelberg/New York (1977)). Bei niedrigen Aufwandmengen ist die Wirkung jedoch nicht immer befriedigend.As a plant protection product with a fungicidal action, zinc ethylenebis-dithiocarbamidate is known as a standard preparation with worldwide distribution (from R. Wegler, "Chemistry of Plant Protection Products and Pest Control", Volume 4, page 139, Springer-Verlag, Berlin / Heidelberg / New York (1977)). At low application rates, however, the effect is not always satisfactory.
Wirkstoffe, die die Metamorphose von Arthropoden hemmen, sind erst seit jüngerer Zeit im Pflanzenschutz von Interesse. Zu nennen ist hier z.B. das 2,2-Dimethyl-6-methoxy- benzopyran (Chem. Eng. News 54, 19 - 20 (1976)).Active substances that inhibit the metamorphosis of arthropods have only recently been of interest in crop protection. To be mentioned here is e.g. 2,2-dimethyl-6-methoxybenzopyran (Chem. Eng. News 54, 19-20 (1976)).
Es wurde gefunden, daß man die neuen Chromon-Derivate der allgemeinen Formel
- R, R 1 und R2 gleich oder verschieden sein können und für Wasserstoff, gegebenenfalls substituiertes Alkyl, Alkenyl, Cycloalkyl, Cycloalkenyl, Aralkyl, Aryl, ferner für Halogen, Hydroxyl, Alkoxy, Aryloxy, Aralkoxy, Alkoxycarbonyl, Cyan und/oder Dialkylamino stehen, und weiterhin zwei Reste
- R und R1 zusammen mit zwei Kohlenstoffatomen des Benzolringsystems einen carbocyclisehen oder heterocyclischen 5- oder 6-Ring bilden können, und
- R 3 für Wasserstoff, gegebenenfalls substituiertes Alkyl, Alkenyl, Cycloalkyl, Cycloalkenyl oder Aralkyl steht, in einfacher Weise erhält, wenn man o-Hydroxyacetophenone der allgemeinen Formel
- R, R1 und R2 die oben angegebene Bedeutung haben, mit Glyoxylsäure-Derivaten der allgemeinen Formel
- Z für ein Kation steht, in Gegenwart von basischen Verbindungen umsetzt, und noch gegebenenfalls die dabei erhaltenen Carbonsäuren (Verbindungen der Formel (I), wobei R3 für Wasserstoff steht) in an sich bekannter Weise in die entsprechenden Ester überführt (Verbindungen der Formel (I), wobei R für gegebenenfalls substituiertes Alkyl, Alkenyl, Cycloalkyl, Cycloalkenyl oder Aralkyl steht).
- R , R 1 and R 2 may be the same or different and represent hydrogen, optionally substituted alkyl, alkenyl, cycloalkyl, cycloalkenyl, aralkyl, aryl, furthermore halogen, hydroxyl, alkoxy, aryloxy, aralkoxy, alkoxycarbonyl, cyano and / or dialkylamino , and two remains
- R and R 1 together with two carbon atoms of the benzene ring system can form a carbocyclic or heterocyclic 5- or 6-ring, and
- R 3 represents hydrogen, optionally substituted alkyl, alkenyl, cycloalkyl, cycloalkenyl or aralkyl, is obtained in a simple manner if o-hydroxyacetophenones of the general formula are obtained
- R, R 1 and R 2 have the meaning given above, with glyoxylic acid derivatives of the general formula
- Z stands for a cation, in the presence of basic compounds, and optionally also the carboxylic acids obtained in this way (compounds of the formula (I), where R 3 stands for hydrogen) in converted into the corresponding esters in a manner known per se (compounds of the formula (I), where R represents optionally substituted alkyl, alkenyl, cycloalkyl, cycloalkenyl or aralkyl).
Die neuen Verbindungen der Formel (I) besitzen fungizide Eigenschaften; ferner hemmen sie die Entwicklung von Arthropoden. Sie sind daher als Pflanzenschutzmittel von Interesse.The new compounds of formula (I) have fungicidal properties; they also inhibit the development of arthropods. They are therefore of interest as pesticides.
Es ist als ausgesprochen überraschend zu bezeichnen, daß die o-Hydroxyacetophenone der Formel (II) mit den Glyoxylsäure-Derivaten der Formel (III) in einer einfachen und überschaubaren Reaktion die Chromon-Derivate der Formel (I) ergeben und keine Chromanon-Verbindungen entstehend Das Auffinden der neuen Reaktion stellt eine Bereicherung der Technik dar. Von praktischem Interesse ist, daß die neuen Verbindungen als Pflanzenschutzmittel verwendet werden können.It can be described as extremely surprising that the o-hydroxyacetophenones of the formula (II) with the glyoxylic acid derivatives of the formula (III) give the chromone derivatives of the formula (I) in a simple and manageable reaction and no chromanone compounds are formed Finding the new reaction is an enrichment of the technology. It is of practical interest that the new compounds can be used as crop protection agents.
Setzt man o-Hydroxyacetophenon mit dem Natriumsalz der Glyoxylsäure in Gegenwart von Pyrrolidin um und verestert die dabei erhaltene Dicarbonsäure anschließend mit Methanol, so kann der Reaktionsablauf durch das folgende Reaktionsschema wiedergegeben werden:
In der Formel (II) stehen R, R1 und R2 vorzugsweise für Wasserstoff und für gegebenenfalls substituiertes, geradkettiges oder verzweigtes Alkyl mit bis zu 8, bevorzugt bis zu 2 Kohlenstoffatomen, ferner für geradkettiges oder verzweigtes Alkenyl mit einer oder mehreren Doppelbindungen und bis zu 8 Kohlenstoffatomen, vorzugsweise bis zu 3 Kohlenstoffatomen und einer Doppelbindung. Als Alkyl- bzw. Alkenyl-Reste seien beispielsweise genannt:
- Methyl, Äthyl, Propyl, Isopropyl, Butyl, Isobutyl, tert.-Butyl, Hexyl, Buten-(3)-yl und 4-Methyl-penten-(3)-yl.
- Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, hexyl, butene- (3) -yl and 4-methyl-penten- (3) -yl.
R, Rund R2 stehen weiterhin für gegebenenfalls substituierte Cycloalkyl- und Cycloalkenyl-Reste mit 3 bis 8, bevorzugt mit 4 bis 6 Kohlenstoffatomen, wie beispielsweise Cyclobutyl und insbesondere Cyclopentyl und Cyclohexyl. R , R 2 also represent optionally substituted cycloalkyl and cycloalkenyl radicals having 3 to 8, preferably having 4 to 6, carbon atoms, such as, for example, cyclobutyl and in particular cyclopentyl and cyclohexyl.
Als gegebenenfalls substituierte Arylreste seien solche mit 6 bis 10 Kohlenstoffatomen genannt, wie Phenyl und Naphthyl, bevorzugt Phenyl.Aryl radicals which may be substituted may be those having 6 to 10 carbon atoms, such as phenyl and naphthyl, preferably phenyl.
Als gegebenenfalls substituierte Aralkylreste kommen beispielsweise solche mit 7 bis 18 Kohlenstoffatomen, deren aliphatischer Teil 1 bis 8, bevorzugt 1 bis 4, Kohlenstoffe enthält und deren aromatischer Teil einen carbocyclischen Rest mit 6 bis 10 Kohlenstoffatomen darstellt, in Frage. Beispielhaft seien die folgenden Aralkylreste genannt: Benzyl, Phenyläthyl, Phenylpropyl, Phenylbutyl, Naphthylmethyl und Naphthyläthyl, bevorzugt Benzyl.Examples of suitable substituted aralkyl radicals are those having 7 to 18 carbon atoms, the aliphatic part of which contains 1 to 8, preferably 1 to 4, carbons and the aromatic part of which represents a carbocyclic radical having 6 to 10 carbon atoms. The following aralkyl radicals may be mentioned by way of example: benzyl, phenylethyl, phenylpropyl, phenylbutyl, naphthylmethyl and naphthylethyl, preferably benzyl.
Als bevorzugte Alkoxygruppen seien solche mit bis zu 4 Kohlenstoffatomen, wie Methoxy, Xthoxy, Propoxy, Isopropoxy, Butoxy, Isobutoxy und tert.-Butoxy,genannt.Preferred alkoxy groups are those with up to 4 carbon atoms, such as methoxy, xthoxy, propoxy, isopropoxy, butoxy, isobutoxy and tert-butoxy.
Als bevorzugte Aryloxygruppen seien solche mit 6 oder 10 Kohlenstoffatomen, wie Phenoxy und Naphthoxy, genannt.Preferred aryloxy groups are those with 6 or 10 carbon atoms, such as phenoxy and naphthoxy.
Als bevorzugte Aralkoxygruppen seien solche mit 7 bis 10 Kohlenstoffatomen, wie Benzyloxy, Phenyläthoxy, Phenylpropoxy, Phenylisopropoxy, Phenylbutoxy, Phenylisobutoxy und Phenyl-tert.-butoxy, genannt.Preferred aralkoxy groups are those having 7 to 10 carbon atoms, such as benzyloxy, phenylethoxy, phenylpropoxy, phenylisopropoxy, phenylbutoxy, phenylisobutoxy and phenyl tert-butoxy.
Als bevorzugte Alkoxycarbonylgruppen seien solche mit bis zu 4 Kohlenstoffatomen im Alkylrest, wie Methoxycarbonyl, Äthoxycarbonyl, Propoxycarbonyl, Isopropoxycarbonyl, genannt.Preferred alkoxycarbonyl groups are those with up to 4 carbon atoms in the alkyl radical, such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl.
Als bevorzugte Dialkylaminogruppan seien solche mit bis zu 3 Kohlenstoffatomen im Alkylrest, wie Dimethylamino, Diäthylamino, und Diisopropylamino, qenannt. Es ist auch möglich, daß die beiden Alkylreste der Dialkylaminogruppe zu einem Ring geschlossen sind, wie beispielsweise Pyrrolidinyl, Piperidinyl.Preferred dialkylamino groups are those with up to 3 carbon atoms in the alkyl radical, such as dimethylamino, diethylamino, and diisopropylamino, called. It is also possible for the two alkyl radicals of the dialkylamino group to be closed to form a ring, such as, for example, pyrrolidinyl, piperidinyl.
Als Halogene seien Fluor, Chlor, Brom und Jod, bevorzugt Chlor und Brom genannt.Halogens are fluorine, chlorine, bromine and iodine, preferably chlorine and bromine.
Die Reste R und R1 können insbesondere mit den beiden Kohlenstoffatomen des Benzolrings, an dem sie sitzen, einen carbocyclischen oder heterocyclischen fünf- oder sechsgliedrigen Ring bilden, wie z.B. einen Cyclopenten-, Cyclohexen-, Benzol-, Furan-, Dihydrofuran-, Thiophen-, Dihydrothiophen-, Pyran-, Dihydropyran-, Pyridin-oder Dioxolen-Ring.The radicals R and R 1 can in particular form a carbocyclic or heterocyclic five- or six-membered ring, such as, for example, a cyclopentene, cyclohexene, benzene, furan, dihydrofuran, thiophene, with the two carbon atoms of the benzene ring on which they are seated -, Dihydrothiophene, pyran, dihydropyran, pyridine or dioxole ring.
Als Substituenten der Alkyl-, Cycloalkyl-, Aryl-, Aralkyl-, Alkoxy-, Aralkoxy-, Alkoxycarbonyl- und Dialkylamino-Gruppen der Reste R bis R2 kommen Substituenten in Frage, die unter den Reaktionsbedingungen nicht verändert werden. Beispielsweise seien die Halogene, wie Fluor, Chlor, Brom und Jod und die Cyangruppe genannt, ferner die Alkoxy- und Alkoxycarbonyl-Gruppe mit bis zu 4, und - sofern es sich um Substituenten an Ringsystemen handelt - noch die Alkyl- und die Alkoxycarbonylalkyl-Gruppe mit bis zu 4 Kohlenstoffatomen. Ferner sind als weitere Zweitsubstituenten noch die Dialkylamino-Gruppe mit insgesamt bis zu 6, vorzugsweise bis zu 2 Kohlenstoffatomen zu nennen, sodann die Carboxyl-Gruppe und der Phenyl-Rest.Substituents which do not change under the reaction conditions are suitable as substituents of the alkyl, cycloalkyl, aryl, aralkyl, alkoxy, aralkoxy, alkoxycarbonyl and dialkylamino groups of the radicals R to R 2 . Examples include the halogens, such as fluorine, chlorine, bromine and iodine and the cyano group, furthermore the alkoxy and alkoxycarbonyl group with up to 4 and - if the substituents on ring systems are concerned - the alkyl and alkoxycarbonylalkyl groups. Group with up to 4 carbon atoms. Also to be mentioned as further second substituents are the dialkylamino group with a total of up to 6, preferably up to 2, carbon atoms, then the carboxyl group and the phenyl radical.
Die o-Hydroxy-aryl-carbonylverbindungen, die für das erfindungsgemäße Verfahren Verwendung finden können, sind bekannt (vgl. Beilstein, Handbuch der Organischen Chemie, H8, Seite 85 ff.). Beispielsweise sieen genannt:
- o-Hydroxyacetophenon 3-Chlor-2-hydroxyacetophenon 5-Chlor-2-hydroxyacetophenon 3,5-Dichlor-2-hydroxyacetophenon 3-Methyl-5-chlor-2-hydroxyacetophenon 2,4-Dihydroxyacetophenon 2,5-Dihydroxyacetophenon 2,6-Dihydroxyacetophenon 2,3-Dihydroxyacetophenon 2,4,6-Trihydroxyacetophenon 4-Pentyl-2,6-dihydroxyacetophenon 4-Heptyl-2,6-dihydroxyacetophenon 4-(1',1'-Dimethylpentyl)-2,6-dihydroxyacetophenon 3,4-Dimethoxy-6-methyl-2-hydroxyacetophenon 3,4,6-Trimethyl-2-hydroxyacetophenon 3-Methoxy-2-hydroxyacetophenon 4-Methoxy-2-hydroxyacetophenon 5-Methoxy-2-hydroxyacetophenon 6-Methoxy-2-hydroxyacetophenon 4-Benzyloxy-2-hydroxyacetophenon 5-Benzyloxy-2-hydroxyacetophenon 4-Phenoxy-2-hydroxyacetophenon 4-Cyclohexyl-2-hydroxyacetophenon 5-Phenyl-2-hydroxyacetophenon 3-β-Phenyläthyl-2-hydroxyacetophenon 5- -Phenylbutyl-2-hydroxyacetophenon 3,5-Dibrom-2-hydroxyacetophenon 4-Äthoxy-2-hydroxyacetophenon 5-Äthoxycarbonyl-äthoxy-2-hydroxyacetophenon 4-Methoxycarbonylmethoxy-2-hydroxyacetophenon 4-Carboxymethyl-2-hydroxyacetophenon 5-Nitro-2-hydroxyacetophenon 3-Cyan-2-hydroxyacetophenon 4-Trifluormethyl-2-hydroxyacetophenon 5-Trifluormethyl-2-hydroxyacetophenon 3-Trifluormethyl-2-hydroxyacetophenon 3-Methoxycarbonyl-2-hydroxyacetophenon 5-Carboxy-2-hydroxyacetophenon 5-Dimethylamino-2-hydroxyacetophenon 4-N-Piperidinyl-2-hydroxyacetophenon 3-rhenoxy-2-hydroxyacetophenon 4-p-Chlorphenoxy-2-hydroxyacetophenon 5-p-Tolyl-2-hydroxyacetophenon 1-Hydroxy-2-acetylnaphthalin 2-Hydroxy-1-acetylnaphthalin
- o-Hydroxyacetophenone 3-chloro-2-hydroxyacetophenone 5-chloro-2-hydroxyacetophenone 3,5-dichloro-2-hydroxyacetophenone 3-methyl-5-chloro-2-hydroxyacetophenone 2,4-dihydroxyacetophenone 2,5-dihydroxyacetophenone 2.6 -Dihydroxyacetophenone 2,3-dihydroxyacetophenone 2,4,6-trihydroxyacetophenone 4-pentyl-2,6-dihydroxyacetophenone 4-heptyl-2,6-dihydroxyacetophenone 4- (1 ', 1'-dimethylpentyl) -2,6-dihydroxyacetophenone 3 , 4-Dimethoxy-6-methyl-2-hydroxyacetophenone 3,4,6-trimethyl-2-hydroxyacetophenone 3-methoxy-2-hydroxyacetophenone 4-methoxy-2-hydroxyacetophenone 5-methoxy-2-hydroxyacetophenone 6-methoxy-2- hydroxyacetophenone 4-benzyloxy-2-hydroxyacetophenone 5-benzyloxy-2-hydroxyacetophenone 4-phenoxy-2-hydroxyacetophenone 4-cyclohexyl-2-hydroxyacetophenone 5-phenyl-2-hydroxyacetophenone 3-β-phenylethyl-2-hydroxyacetophenone 5- -phenylbutyl-2-hydroxyacetophenone 3,5-dibromo-2-hydroxyacetophenone 4-ethoxy-2-hydroxyacetophenone 5-ethoxycarbonyl-ethoxy-2-hydroxyacetophenone 4-methoxycarbonylmethoxy-2-hydroxyacetophenone -Carboxymethyl-2-hydroxyacetophenone 5-nitro-2-hydroxyacetophenone 3-cyano-2-hydroxyacetophenone 4-trifluoromethyl-2-hydroxyacetophenone 5-trifluoromethyl-2-hydroxyacetophenone 3-trifluoromethyl-2-hydroxyacetophenone 3-methoxyacetophenone 5-methoxycarbonylophenone Carboxy-2-hydroxyacetophenone 5-dimethylamino-2-hydroxyacetophenone 4-N-piperidinyl-2-hydroxyacetophenone 3-rhenoxy-2-hydroxyacetophenone 4-p-chlorophenoxy-2-hydroxyacetophenone 5-p-tolyl-2-hydroxyacetophenone 1-hydroxy- 2-acetylnaphthalene 2-hydroxy-1-acetylnaphthalene
Weiterhin werden als Ausgangsverbindungen noch die Glyoxylsäure-Derivate der Formel (III) benötigt. In der Formel (III) steht Z bevorzugt für ein- oder zweiwertige Kationen von Alkali- und Erdalkali-Metallen, sowie für das AmmoniumKation und die Mono-, Di- und Trialkylamnonium-Kationen. In den drei letztgenannten Fällen enthalten die Alkylreste vorzugsweise bis zu 2 Kohlenstoffatome.The glyoxylic acid derivatives of the formula (III) are also required as starting compounds. In the formula (III) Z is preferably monovalent or divalent cations of alkali and alkaline earth metals, and ONO for the ammonium cation and M, di- and Trialkylamnonium cations. In the latter three cases, the alkyl radicals preferably contain up to 2 carbon atoms.
Die Synthese wird in Gegenwart von basischen Verbindungen durchgeführt. Als solche kommen bevorzugt sekundäre Amine in Frage, insbesondere cyclische Amine wie Pyrrolidin, ferner Piperidin, N-Methyl-piperazin, Morpholin, aber auch offenkettige Amine wie Dimethylamin und Diäthylamin. Die genannten Verbindungen sind allgemein bekannt.The synthesis is carried out in the presence of basic compounds. Secondary amines are preferred as such, in particular cyclic amines such as pyrrolidine, also piperidine, N-methylpiperazine, morpholine, but also open-chain amines such as dimethylamine and diethylamine. The compounds mentioned are generally known.
Das erfindungsgemäße Verfahren kann mit oder ohne Lösungsmittel durchgeführt werden. Zur Durchführung des Verfahrens kommen alle Lösungsmittel in Betracht, die gegenüber den Ausgangskomponenten und dem Endprodukt inert sind. Als Lösungsmittel seien beispielsweise genannt:
- Aliphatische oder aromatische Kohlenwasserstoffe, wie Petroläther, Benzol, Toluol oder Xylol, aliphatische oder aromatische Halogenkohlenwasserstoffe, wie Tetrachlorkohlenstoff, Chlorbenzol oder Dichlorbenzol, Äther, wie Diäthyläther, Tetrahydrofuran, Dioxan oder Glykoldimethyläther, sodann Amide, wie Dimethylformamid, Dimethylacetamid und N-Methylpyrrolidon, ferner Ester wie Essigsäureäthylester, Nitrile, wie Acetonitril, Propionnitril, und Alkohole, wie Methanol, Äthanol und Glykolmonomethyläther, und schließlich Wasser.
- Aliphatic or aromatic hydrocarbons, such as petroleum ether, benzene, toluene or xylene, aliphatic or aromatic halohydrocarbons such as carbon tetrachloride, chlorobenzene or dichlorobenzene, ethers such as diethyl ether, tetrahydrofuran, dioxane or Glykoldimethyläther, then amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, and Esters such as ethyl acetate, nitriles such as acetonitrile, propionitrile, and alcohols such as methanol, ethanol and glycol monomethyl ether, and finally water.
Das erfindungsgemäße Verfahren kann bei einer Temperatur von -30 bis +150°C, bevorzugt von 20 bis 80oC, durchgeführt werden.The inventive process may at a temperature of -30 to + 150 ° C, preferably from 20 to 80 o C, to be performed.
Zur Durchführung des erfindungsgemäßen Verfahrens werden im allgemeinen die o-Hydroxycarbonyl-Verbindungen und das Salz der Glyoxylsäure in stöchiometrischen Mengen, also im Verhältnis 1:2, eingesetzt. Für die Durchführung des erfindungsgemäßen Verfahrens ist es jedoch ohne Bedeutung, wenn ein kleiner Überschuß einer Komponente, insbesondere des Glyoxylsäuresalzes, eingesetzt wird (z.B. bis zum Molverhältnis 1:2,5). Die Menge des eingesetzten Amins ist nicht kritisch. Im allgemeinen verwendet man 0,05 bis 1,5, bevorzugt 0,1 bis 1 Mol des Amins, bezogen auf 1 Mol der o-Hydroxycarbonyl-Verbindung. Falls die o-Hydroxyacetophenone durch sauer reagierende Gruppen wie z.B. Carboxygruppen, substituiert sind, kann es zweckmäßig sein, durch einen Uberschuß des Amins die sauren Gruppen zu neutralisieren.To carry out the process according to the invention, the o-hydroxycarbonyl compounds and the salt of glyoxylic acid in stoichiometric amounts, ie in a ratio of 1: 2. For the implementation of the process according to the invention, however, it is of no importance if a small excess of a component, in particular the glyoxylic acid salt, is used (for example up to a molar ratio of 1: 2.5). The amount of the amine used is not critical. In general, 0.05 to 1.5, preferably 0.1 to 1 mol of the amine, based on 1 mol of the o-hydroxycarbonyl compound, is used. If the o-hydroxyacetophenones are substituted by acidic groups such as carboxy groups, it may be expedient to neutralize the acidic groups with an excess of the amine.
Im allgemeinen wird das erfindungsgemäße Verfahren wie folgt ausgeführt:
- Die Ausgangsverbindungen werden bei der gewählten Reaktionstemperatur, gegebenenfalls in einem Lösungsmittel, gelöst und mit dem Amin versetzt. Durch die exotherme Reaktion steigt die Reaktionstemperatur im allgemeinen an, so daß eine weitere Erwärmung nicht notwendig ist. Man läßt dann das Reaktionsgemisch bis zur Beendigung der Reaktion ohne weitere Erwärmung stehen, kann jedoch auch die Reaktionszeit durch äußeres Erwärmen abkürzen. Nach Beendigung der Reaktion isoliert man die Chromon-Derivate, indem man die entstandenen Salze in Wasser löst und diese Lösungen ansäuert, beispielsweise mit Mineralsäuren wie Salz-, Schwefel- oder Phosphorsäure. Man erhält dann die Dicarbonsäure-Verbindungen der Formel (I), wobei R3 für Wasserstoff steht.
- The starting compounds are dissolved at the selected reaction temperature, if appropriate in a solvent, and the amine is added. The reaction temperature generally rises due to the exothermic reaction, so that further heating is not necessary. The reaction mixture is then left to stand without further heating until the reaction has ended, but the reaction time can also be shortened by external heating. After the reaction has ended, the chromone derivatives are isolated by dissolving the salts formed in water and acidifying these solutions, for example using mineral acids such as hydrochloric, sulfuric or phosphoric acid. The dicarboxylic acid compounds of the formula (I) are then obtained, where R 3 is hydrogen.
Die Veresterung der erhaltenen Dicarbonsäuren kann beispielsweise in üblicher Weise dadurch erfolgen, daß man die Dicarbonsäure in der 4- bis 100-, vorzugsweise 10- bis 50-fachen molaren Menge Alkohol der Formel R3-OH verrührt, mit einer Säure wie konz. Schwefelsäure versetzt oder mit Chlorwasserstoff-Gas sättigt und einige Stunden auf Temperaturen von 60 bis 120°C erwärmt. Man kann das Gemisch der Dicarbonsäure mit dem Alkohol auch mit der mindestens doppelten molaren Menge, bezogen auf die Dicarbonsäure, eines Dehydratisierungsmittels, wie anorganischen Säurehalogeniden, z.B. Thionylchlorid oder Phosphoroxychlorid, versetzen. Schließlich kann man auch Salze der Dicarbonsäuren mit mindestens der doppelten molaren Menge eines Alkylhalogenids in einem Lösungsmittel wie Dimethylsulfoxid oder Dimethylformamid zur Reaktion bringen.The esterification of the dicarboxylic acids obtained can be carried out, for example, in a customary manner by stirring the dicarboxylic acid in 4 to 100, preferably 10 to 50 times the molar amount of alcohol of the formula R 3 --OH, with an acid such as conc. Added sulfuric acid or saturated with hydrogen chloride gas and warmed to temperatures from 60 to 120 ° C for a few hours. The mixture of the dicarboxylic acid with the alcohol can also be mixed with at least twice the molar amount, based on the dicarboxylic acid, of a dehydrating agent, such as inorganic acid halides, for example thionyl chloride or phosphorus oxychloride. Finally, salts of the dicarboxylic acids can also be reacted with at least twice the molar amount of an alkyl halide in a solvent such as dimethyl sulfoxide or dimethylformamide.
Als neue Chromondicarbonsäuren und deren Ester seien beispielsweise genannt:
- 2-Carboxy-3-carboxymethyl-6-chlor-chromon 2-Carboxy-3-carboxymethyl-7-chlor-chromon 2-Carboxy-3-carboxymethyl-8-chlor-chromon 2-Carboxy-3-carboxymethyl-6,8-dichlor-chromon 2-Carboxy-3-carboxymethyl-6-methyl-chromon 2-Carboxy-3-carboxymethyl-7-methyl-chromon 2-Carboxy-3-carboxymethyl-6-isobutyl-chromon 2-Carboxy-3-carboxymethyl-7-äthyl-chromon 2-Carboxy-3-carboxymethyl-6-sek.-butyl-chromon 2-Carboxy-3-carboxymethyl-6-benzyl-chromon 2-Carboxy-3-carboxymethyl-7-phenyl-chromon 2-Carboxy-3-carboxymethyl-5-methoxy-chromon 2-Carboxy-3-carboxymethyl-6-methoxy-chromon 2-Carboxy-3-carboxymethyl-7-methoxy-chromon 2-Carboxy-3-carboxymethyl-8-methoxy-chromon 2-Carboxy-3-carboxymethyl-6-chlor-8-methyl-chromon 2-Carboxy-3-carboxymethyl-6-pyrrolidinyl-chromon 2-Carboxy-3-carboxymethyl-6-dimethylamino-chromon 2-Carboxy-3-carboxymethyl-7,8-dimethoxy-chromon 2-Carboxy-3-carboxymethyl-6,7-dimethoxy-chromon 2-Carboxy-3-carboxymethyl-6-methoxycarbonyl-chromon 2-Carboxy-3-carboxymethyl-8-carboxy-chromon 2-Carboxy-3-carboxymethyl-7-cyan-chromon 2-Carboxy-3-carboxymethyl-6-cyan-chromon 2-Carboxy-3-carboxymethyl-5,6,7-trimethyl-chromon 2-Carboxy-3-carboxymethyl-5,6-benzo-chromon 2-Carboxy-3-carboxymethyl-5,6-trimethylen-chromon 2-Carboxy-3-carboxymethyl-5-methyl-6,8-dichlor-chromon 2-Carbomethoxy-3-carbomethoxymethyl-6-chlor-chromon 2-Carbomethoxy-3-carbomethoxymethyl-7-chlor-chromon 2-Carbomethoxy-3-carbomethoxymethyl-6,8-dichlor-chromon 2-Carbomethoxy-3-carbomethoxymethyl-6-methyl-chromon 2-Carbomethoxy-3-carbomethoxymethyl-7-methyl-chromon 2-Carbomethoxy-3-carbomethoxymethyl-6-isobutyl-chromon 2-Carbomethoxy-3-carbomethoxymethyl-6-cyclopentyl-chromon 2-Carbanethoxy-3-carbomethoxymethyl-7-phenyl-chromon 2-Carbomethoxy-3-carbomethoxymethyl-S-methoxy-chramon 2-Carbomethoxy-3-carbomethoxymethyl-6-methoxy-chromon 2-Carboenethoxy-3-carbomethoxymethyl-7-methoxy-chromon 2-Carbomethoxy-3-carbomethoxymethyl-8-methoxy-chrason 2-Carbomethoxy-3-carbomethoxymethyl-6-chlor-8-methyl-chromon 2-Carbomethoxy-3-carbomethoxymethyl-7,8-dimethoxy-chromon 2-Carbomethoxy-3-carbomethoxymethyl-6,7-dimethoxy-chromon 2-Carbomethoxy-3-carbomethoxymethyl-8-carboxy-chromon 2-Carbomethoxy-3-carbomethoxymethyl-6-cyan-chromon 2-Carbomethoxy-3-carbomethoxymethyl-5,6-benzo-chromon 2-Carbomethoxy-3-carbomethoxymethyl-5-methyl-6,8-dichlor-chromon 2-Carbo-äthoxy-3-carbo-äthoxy methylchromon 2-Carbo-propoxy-3-carbo-propoxy methylchromon 2-Carbo-isopropoxy-3-carbo-isopropoxy methylchromon 2-Carbo-butoxy-3-carbo-butoxy methylchromon 2-Carbo-sek.-butoxy-3-carbo-sek. butoxy methylchromon 2-Carbo-iso-butoxy-3-carbo-iso-butoxy methylchromon 2-Carbo-tert.-butoxy-3-carbo-tert.-butoxy methylchromon 2-Carbo-benzyloxy-3-carbo-benzyloxy methylchromon 2-Carbo-phenäthoxy-3-carbo-phenäthoxy methylchromon 2-Carbo-cyclopentyloxy-3-carbo-cyclopentyloxy methylchromon 2-Carbo-cyclohexyloxy-3-carbo-cyclohexyloxy methylchromon 2-Carbo-allyloxy-3-carbo-allyloxy methylchromon 2-Carbo-p-chlorbenzyloxy-3-carbo-p-Chlorbenzyloxy methylchromon 2-Carbo-2'-methoxyäthoxy-3-carbo-2'-methoxyäthoxy methylchromon 2-Carbo-2'-bromäthoxy-3-carbo-2'-bromätboxy methylchromon
- 2-carboxy-3-carboxymethyl-6-chloro-chromon 2-carboxy-3-carboxymethyl-7-chloro-chromon 2-carboxy-3-carboxymethyl-8-chloro-chromon 2-carboxy-3-carboxymethyl-6.8 -dichloro-chromon 2-carboxy-3-carboxymethyl-6-methyl-chromon 2-carboxy-3-carboxymethyl-7-methyl-chromon 2-carboxy-3-carboxymethyl-6-isobutyl-chromon 2-carboxy-3-carboxymethyl -7-ethyl-chromon 2-carboxy-3-carboxymethyl-6-sec-butyl-chromon 2-carboxy-3-carboxymethyl-6-benzyl-chromon 2-carboxy-3-carboxymethyl-7-phenyl-chromon 2-carboxy-3-carboxymethyl-5-methoxy-chromon 2-carboxy-3-carboxymethyl-6-methoxy-chromon 2-carboxy-3-carboxymethyl-7-methoxy-chromon 2-carboxy-3-carboxymethyl-8-methoxy -chromon 2-carboxy-3-carboxymethyl-6-chloro-8-methyl-chromon 2-carboxy-3-carboxymethyl-6-pyrrolidinyl-chromon 2-carboxy-3-carboxymethyl-6-dimethylamino-chromon 2-carboxy-3 -carboxymethyl-7,8-dimethoxy-chromon 2-carboxy-3-carboxymethyl-6,7-dimethoxy-chromon 2-carboxy-3-carboxymethyl-6-methoxycarbonyl-chromon 2-carboxy-3-carboxymethyl-8-carboxy- chromon 2-carboxy-3-carboxymethyl-7-cyan-chromon 2-carboxy-3-carboxymethyl-6-cyan-chromon 2-carboxy-3-carboxymethyl-5,6,7-trimethyl-chromon 2-carboxy-3- carboxymethyl-5,6-benzo-chromon 2-carboxy-3-carboxymethyl-5,6-trimethylene-chromon 2-carboxy-3-carboxymethyl-5-methyl-6,8-dichloro-chromon 2-carbomethoxy-3-carbomethoxymethyl -6-chloro-chromon 2-carbomethoxy-3-carbomethoxymethyl-7-chloro-chromon 2-carbomethoxy-3-carbomethoxymethyl-6,8-dichloro-chromon 2-carbomethoxy-3-carbomethoxymethyl-6-met hyl-chromon 2-carbomethoxy-3-carbomethoxymethyl-7-methyl-chromon 2-carbomethoxy-3-carbomethoxymethyl-6-isobutyl-chromon 2-carbomethoxy-3-carbomethoxymethyl-6-cyclopentyl-chromon 2-carbanethoxy-3-carbomethoxymethyl- 7-phenyl-chromon 2-carbomethoxy-3-carbomethoxymethyl-S-methoxy-chramon 2-carbomethoxy-3-carbomethoxymethyl-6-methoxy-chromon 2-carboenethoxy-3-carbomethoxymethyl-7-methoxy-chromon 2-carbomethoxy-3- carbomethoxymethyl-8-methoxy-chrasone 2-carbomethoxy-3-carbomethoxymethyl-6-chloro-8-methyl-chromon 2-carbomethoxy-3-carbomethoxymethyl-7,8-dimethoxy-chromon 2-carbomethoxy-3-carbomethoxymethyl-6,7-dimethoxy-chromon 2-carbomethoxy -3-carbomethoxymethyl-8-carboxy-chromon 2-carbomethoxy-3-carbomethoxymethyl-6-cyan-chromon 2-carbomethoxy-3-carbomethoxymethyl-5,6-benzo-chromon 2-carbomethoxy-3-carbomethoxymethyl-5-methyl- 6,8-dichloro-chromon 2-carbo-ethoxy-3-carbo-ethoxy methylchromone 2-carbo-propoxy-3-carbo-propoxy methylchromone 2-carbo-isopropoxy-3-carbo-isopropoxy methylchromone 2-carbo-butoxy-3 -carbo-butoxy methylchromon 2-carbo-sec.-butoxy-3-carbo-sec. butoxy methylchromone 2-carbo-iso-butoxy-3-carbo-iso-butoxy methylchromone 2-carbo-tert-butoxy-3-carbo-tert-butoxy methylchromone 2-carbo-benzyloxy-3-carbo-benzyloxy methylchromone 2- Carbo-phenethoxy-3-carbo-phenethoxy methylchromon 2-carbo-cyclopentyloxy-3-carbo-cyclopentyloxy methylchromon 2-carbo-cyclohexyloxy-3-carbo-cyclohexyloxy methylchromon 2-carbo-allyloxy-3-carbo-allyloxy methylchromon 2-carbo p-chlorobenzyloxy-3-carbo-p-chlorobenzyloxy methylchromone 2-carbo-2'-methoxyethoxy-3-carbo-2'-methoxyethoxy methylchromone 2-carbo-2'-bromoethoxy-3-carbo-2'-bromoetboxy methylchromone
Die erfindungsgemäßen Wirkstoffe weisen eine gute fungitoxische Wirkung auf. Sie schädigen Kulturpflanzen in den zur Bekämpfung von Pilzen notwendigen Konzentrationen nicht. Aus diesen Gründen sind sie für den Gebrauch als Pflanzenschutzmittel zur Bekämpfung von Pilzen geeignet. Fungitoxische Mittel im Pflanzenschutz werden eingesetzt zur Bekämpfung von Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Bsidiomycetes, Deuteromycetes.The active compounds according to the invention have a good fungitoxic effect. They do not damage crops in the concentrations necessary to control fungi. For these reasons, they are suitable for use as crop protection agents for combating fungi. Fungitoxic agents are used in crop protection to combat Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Bsidiomycetes, Deuteromycetes.
Die erfindungsgemäßen Wirkstoffe können angewandt werden gegen parasitäre Pilze und Bakterien, die oberirdische Pflanzenteile befallen oder die Pflanzen vom Boden her angreifen, sowie gegen samenübertragbare Krankheitserreger.The active compounds according to the invention can be used against parasitic fungi and bacteria which attack above-ground parts of plants or attack the plants from the ground, and against seed-borne pathogens.
Die gute Pflanzenverträglichkeit erlaubt eine Anwendung gegen pilzliche Pflanzenkrankheiten durch Behandlung der stehenden Kulturpflanze oder einzelner Teile von ihr oder des Saatgutes oder auch des Kulturbodens. Die Wirk-. stoffe sind besonders Wirksam gegen Getreidemehltau.The good tolerance to plants allows use against fungal plant diseases by treating the standing crop or individual parts of it or the seed or the crop soil. The active. substances are particularly effective against powdery mildew.
Die erfindungsgemäßen Wirkstoffe können in die Üblichen Formulierungen übergeführt werden, wie Lösungen, Emulsionen, Suspensionen, Pulver, Pasten und Granulate. Diese werden in bekannter Weise hergestellt, z. B. durch Vermischen der Wirkstoffe mit Streckmitteln, also flüssigen Lösungsmitteln, unter Druck stehenden verflüssigten Gasen und/oder festen Trägerstoffen, gegebenenfalls unter Verwendung von oberflächenaktiven Mitteln, also Emulgiermitteln und/oder Dispergiermitteln und/oder schaumerzeugenden Mitteln. Im Falle der Benutzung von Wasser als Streckmittel können z. B. auch organische Lösuncsmittel als Hilfslösungsmittel verwendet werden. Als flüssige Lösungsmittel kommen im wesentlichen in Frage: Aromaten, wie Xylol, Toluol, Benzol oder Alkylnaphthaline, chlorierte Arossten oder chlorierte aliphatische Kohlenwasserstoffe, wie Chlorbenzole, Chloräthylene oder Methylenchlorid, aliphatische Kohlenwasserstoffe, wie Cyclohexan oder Paraffine, z. B. Erdölfraktionen, Alkohole, wie Butanol oder Glycol sowie deren Äther und Ester, Ketone, wie Aceton, Methyläthylketon, Methylisobutylketon oder Cyclohexanon, stark polare Lösungsmittel, wie Dimethylformamid und Dimethylsulfoxid, sowie Wasser; mit verflüssigten gasförmigen Streckmitteln oder Trägerstoffen sind solche Flüssigkeiten gemeint, welche bei normaler Temperatur und unter Normaldruck gasförmig sind, z. B. Aerosol-Treibgase, wie Dichlordifluormethan oder Trichlorfluormethan; als feste Trägerstoffe: naturliche Gesteinsmehle, wie Kaoline, Tonerden, Talkum, Kreide, Quarz, Attapulgit, Montmorillonit oder Diatomeenerde und synthetische Gesteinsmehle, wie hochdisperse Kieselsäure, Aluminiumoxid und Silikate; als Emulgiermittel; nichtionogene und anionische Emulgatoren, wie Polyoxyäthylen-Fottsäure-Ester,Polyoxy- äthylen-Fettalkohol-Äther, z.B. Alkylaryl-polyglycol-Äther, Alkylsulfonate, Alkylsulfate, Arylsulfonate sowie Eiweißhydrolysate; als Dispergiermittel: z. B. Lignin-Sulfitablaugen und Methylcellulose.The active compounds according to the invention can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, pastes and granules. These are manufactured in a known manner, e.g. B. by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. In the case of the use of water as an extender, e.g. B. organic solvents can also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene, benzene or alkylnaphthalenes, chlorinated aroses or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, Chloroethylene or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. B. petroleum fractions, alcohols, such as butanol or glycol and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water; Liquefied gaseous extenders or carriers mean those liquids which are gaseous at normal temperature and pressure, e.g. B. aerosol propellants such as dichlorodifluoromethane or trichlorofluoromethane; as solid carriers: natural rock flour, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock meals, such as highly disperse silica, aluminum oxide and silicates; as an emulsifier; nonionic and anionic emulsifiers, such as polyoxyethylene photo acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ether, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; as a dispersant: e.g. B. lignin sulfite and methyl cellulose.
Die Formulierungen enthalten im allgemeinen zwischen 0,1 und 95 Gewichtsprozent Wirkstoff, vorzugsweise zwischen O,5 und 90 %.The formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.
Die Wirkstoffe können als solche, in Form ihrer Formulierungen oder der daraus bereiteten Anwendungsformen, wie gebrauchsfertige Lösungen, Emulsionen, Suspensionen, Pulver, Pasten und Granulate angewendet werden. Die Anwendung geschieht in üblicher Weise, z.B. durch Spritzen, Sprühen, Nebeln, Streuen, Stäuben, Gießen, Trockenbeizen, Schlämmbeizen (Slurrybeizen), Feuchtbeizen und Naßbeizen.The active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules. They are used in the usual way, e.g. by spraying, spraying, misting, scattering, dusting, pouring, dry pickling, slurry pickling (slurry pickling), wet pickling and wet pickling.
Der Wirkstoffgehalt der aus den handelsüblichen Formulierungen bereiteten Anwendungsformen kann in weiten Bereichen variieren. Die Wirkstoffkonzentration der Anwendungsformen kann von 0,0000001 bis zu 100 Gew.-% Wirkstoff, vorzugsweise zwischen 0,01 und 10 Gew.-% liegen.The active substance content of the use forms prepared from the commercially available formulations can vary within wide ranges. The active substance concentration of the use forms can be from 0.0000001 to 100% by weight of active substance, preferably between 0.01 and 10% by weight.
Bei der Beizung kommen im allgemeinen je Kilogramm Saatgut Wirkstoffmengen von 10 mg bis 10 g, vorzugsweise 100 mg bis 3 q zur Anwendung. Bei der Bodenhandlung, die ganzflächig, streifenförmig oder punktförmig durchgeführt werden kann, werden am Ort der erwarteten Wirkung Wirkstoffkonzentrationen von 1 bis 1000 g Wirkstoff je m3 Boden benötigt, vorzugsweise 10 bis 200 g pro m3.In the case of dressing, amounts of active compound of 10 mg to 10 g, preferably 100 mg to 3 q, are generally used per kilogram of seed. In the soil handling, which can be carried out over the whole area, in strips or in punctiform form, active substance concentrations of 1 to 1000 g of active substance per m 3 of soil, preferably 10 to 200 g per m 3 , are required at the location of the expected action.
Wie schon erwähnt, hemmen die erfindungsgemäßen Verbindungen die Entwicklung von Gliederfüßlern (Arthrophoden).As already mentioned, the compounds according to the invention inhibit the development of arthropods (arthrophodes).
Durch den im folgenden angegebenen Versuche wird die arthropodenmethamorphosehemmende Wirkung der erfindungsgemäßen Verbindungen gezeigt, ohne eine Beschränkung hinsichtlich der Wirkungsbreite dieser Verbindungen vornehmen zu wollen. Dabei werden während der gesamten angegebenen Entwicklung der Testtiere die morphologischen Veränderungen, wie zur Hälfte verpuppte Tiere, unvollständig geschlüpfte Larven oder Raupen, defekte Flügel, puppale Kutikula bei Imagines sowie das Absterben bewertet. Die Summe der morphologischen Mißbildungen und der Abtötung während der Entwicklung werden bonitiert.The tests given below show the arthropod methamorphosis-inhibiting activity of the compounds according to the invention, without wishing to carry out any restriction with regard to the range of action of these compounds. During the entire development of the test animals, the morphological changes, such as half pupated animals, incompletely hatched larvae or caterpillars, defective wings, puppal cuticles in adults as well as the death are assessed. The sum of the morphological M ißbildungen and killing during development are scored.
Entwicklungshemmende Wirkung / Fraßtest Testtiere: Plutella maculipennis (Raupen im 4. Entwicklungsstadium) 20 Stück Phaedon cochleariae (Larven im 4. Entwicklungsstadium) 20 Stück Futterpflanzen: Kohlpflanzen (Brasica oleracea) Lösungsmittel: 4 Gew.-Teile Aceton Emulgator: 1 Gew.-Teil AlkylarylpolyglykolätherDevelopmental inhibiting effect / feeding test Test animals: Plutella maculipennis (caterpillars in the 4th stage of development) 20 pieces of Phaedon cochleariae (larvae in the 4th stage of development) 20 pieces of fodder plants: Cabbage plants (Brasica oleracea) Solvent: 4 parts by weight of acetone emulsifier: 1 part by weight Alkylaryl polyglycol ether
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 2 Gewichtsteile Wirkstoff mit der angegebenen Menge Lösungsmittel, Emulgator und soviel Wasser, daß eine 1 %ige Mischung entsteht, die mit Wasser auf die gewünschte Konzentration verdünnt wird.To produce a suitable preparation of active compound, 2 parts by weight of active compound are mixed with the stated amount of solvent, emulsifier and enough water to form a 1% mixture which is diluted with water to the desired concentration.
Die Testtiere werden mit Blättern der Futterpflanzen, die mit einem gleichmäßigen Spritzbelag der Wirkstoffmischung der gewählten Konzentration versehen sind, so daß eine Wirkstoffmenge in ppm ("parts pro million") auf den Blättern erhalten wird, bis zur Entwicklung der Imago gefüttert.The test animals are such that an amount of active ingredient is obtained in ppm ( "parts p ro million") on the leaves, fed with leaves of the feed plants, which are provided with a uniform spray coating of the active ingredient mixture of the chosen concentration, to the development of the imago.
Zur Kontrolle werden nur mit Lösungsmittel und Emulgator der angegebenen Konzentration versehene Blätter verfüttert.As a control, only leaves provided with solvent and emulsifier of the specified concentration are fed.
Die Versuchsauswertung ergab, daß insbesondere die folgenden erfindungsgemäßen Verbindungen einem bekannten Vergleichspräparat (2,2-Dimethyl-6-methoxy-benzopyran) überlegen sind:
- Verbindungen gemäß Herstellungsbeispielen 3, 5 und 10.
- Compounds according to Preparation Examples 3, 5 and 10.
Sproßbehandlunqs-Test / Getreidemehltau / protektiv (blattzerstörende Mykose)Shoot treatment test / powdery mildew / protective (leaf-destroying mycosis)
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung nimmt man 0,25 Gewichtsteile Wirkstoff in 25 Gewichtsteilen Dimethylformamid und 0,06 Gewichtsteilen Emulgator (Alkyl-aryl-polyglkyoläther) auf und gibt 975 Gewichtsteile Wasser hinzu. Das Konzentrat verdünnt man mit Waser auf die gewünschte Endkonzentration der Spritzbrühe.To prepare a suitable preparation of active compound, 0.25 part by weight of active compound is taken up in 25 parts by weight of dimethylformamide and 0.06 part by weight of emulsifier (alkyl aryl polyglycol ether), and 975 parts by weight of water are added. The concentrate is diluted with water to the desired final concentration of the spray mixture.
Zur Prüfung auf protektive Wirksamkeit besprüht man die einblättrigen Gerstenjungpflanzen der Sorte Amsel mit der Wirkstoffzubereitung taufeucht. Nach Antrocknen bestäubt man die Gerstenpflanzen mit Sporen von Erysiphe graminis var. hordei.To test for protective activity, the single-leafed barley young plants of the Amsel variety are sprayed with the preparation of active compound as dewy. After drying, the barley plants are dusted with spores from Erysiphe graminis var. Hordei.
Nach 6 Tagen Verweilzeit der Pflanzen bei einer Temperatur von 21 bis 22°C und einer Luftfeuchtigkeit von 80 bis 90 % wertet man den Besatz der Pflanzen mit Mehltaupusteln aus. Der Befallsgrad wird in Prozenten des Befalls der unbehandelten Kontrollpflanzen ausgedrückt. Dabei bedeutet O % keinen Befall und 100 % den gleichen Befallsgrad wie bei der unbehandelten Kontrolle. Der Wirkstoff ist umso wirksamer, je geringer der Mehltaubefall ist.After 6 days of dwell time of the plants at a temperature of 21 to 22 ° C and a humidity of 80 to 90%, the stocking of the plants with mildew pustules is evaluated. The degree of infestation is expressed as a percentage of the infestation of the untreated control plants. O% means no infection and 100% means the same degree of infection as in the untreated control. The lower the mildew infestation, the more effective the active ingredient.
Wirkstoffe, Wirkstoffkonzentrationen in der Spritzbrühe .und Befallsgrade gehen aus der nachfolgenden Tabelle hervor:
Man arbeitet wie in Beispiel 1 angegeben, erwärmt aber nach dem Zusammengeben der Ausgangstoffe während 30 Minuten auf 950C. Die Aufarbeitung ergibt 112 g 2-Carboxy-3-carboxymethyl-chromon, das sind 82 % der Theorie.The procedure is as indicated in example 1, but heated after mixing the starting materials for 30 minutes at 95 0 C. The work-up gives 112 g of 2-carboxy-3-carboxymethyl-chromone, which are 82% of theory.
(Veresterungs-Reaktion)
Man verrührt 15 g 2-Carboxy-3-carboxymethyl-chromon in 60 ml Methanol und versetzt in ca. 10 Minuten mit 15 ml Thionylchlorid, wobei man die Temperatur unter 35°C hält. Anschließend heizt man während 2 Stunden auf 60°C, läßt abkühlen und saugt ab. Man erhält 13,5 g des gleichen Produktes wie in Beispiel 3 angegeben.15 g of 2-carboxy-3-carboxymethyl-chromone are stirred in 60 ml of methanol, and 15 ml are added in about 10 minutes Thionyl chloride, keeping the temperature below 35 ° C. The mixture is then heated to 60 ° C. for 2 hours, allowed to cool and suction filtered. 13.5 g of the same product as given in Example 3 are obtained.
In ähnlicher Weise wie in den Beispielen 1 bis 4 beschrieben, lassen sich die folgenden Verbindungen der allgemeinen Formel
Claims (4)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2731566 | 1977-07-13 | ||
| DE19772731566 DE2731566A1 (en) | 1977-07-13 | 1977-07-13 | PROCESS FOR PRODUCING NEW CHROMONE DERIVATIVES AND THEIR USE AS PLANT PROTECTIVE PRODUCTS |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0000377A1 true EP0000377A1 (en) | 1979-01-24 |
| EP0000377B1 EP0000377B1 (en) | 1981-01-21 |
Family
ID=6013786
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP78100318A Expired EP0000377B1 (en) | 1977-07-13 | 1978-07-06 | Process for the preparation of chromone derivatives, new chromone derivatives and their use as plant-protecting agents |
Country Status (8)
| Country | Link |
|---|---|
| US (3) | US4189498A (en) |
| EP (1) | EP0000377B1 (en) |
| JP (1) | JPS5419981A (en) |
| BR (1) | BR7804502A (en) |
| DE (2) | DE2731566A1 (en) |
| DK (1) | DK314078A (en) |
| IL (1) | IL55112A (en) |
| IT (1) | IT7825578A0 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0241003A3 (en) * | 1986-04-11 | 1988-10-12 | Hoechst Aktiengesellschaft | 4h-1-benzopyran-4-one derivatives, process for their preparation and their use as medicaments |
| WO1998027080A1 (en) * | 1996-12-19 | 1998-06-25 | Agrevo Uk Limited | Chromones useful as fungicides |
| US6812225B2 (en) | 2001-01-16 | 2004-11-02 | Astrazeneca Ab | Therapeutic heterocyclic compounds |
| US7026314B2 (en) | 2001-01-16 | 2006-04-11 | Astrazeneca Ab | Therapeutic chromone compounds |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE0103646D0 (en) * | 2001-11-01 | 2001-11-01 | Astrazeneca Ab | Therapeutic chroman compounds |
| SE0103647D0 (en) * | 2001-11-01 | 2001-11-01 | Astrazeneca Ab | Therapeutic chromone compounds |
| JP4561245B2 (en) * | 2004-08-31 | 2010-10-13 | 住友化学株式会社 | Chromone compounds and uses thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3879427A (en) * | 1972-11-24 | 1975-04-22 | Warner Lambert Co | Derivatives of polycyclic gamma-pyrones |
| US3862143A (en) * | 1972-12-04 | 1975-01-21 | Warner Lambert Co | Substituted chromone-3-carbonitriles, carboxamides and carboxylic acids |
-
1977
- 1977-07-13 DE DE19772731566 patent/DE2731566A1/en not_active Withdrawn
-
1978
- 1978-06-22 US US05/918,129 patent/US4189498A/en not_active Expired - Lifetime
- 1978-07-06 EP EP78100318A patent/EP0000377B1/en not_active Expired
- 1978-07-06 DE DE7878100318T patent/DE2860356D1/en not_active Expired
- 1978-07-10 IL IL55112A patent/IL55112A/en unknown
- 1978-07-11 IT IT7825578A patent/IT7825578A0/en unknown
- 1978-07-11 JP JP8364878A patent/JPS5419981A/en active Pending
- 1978-07-12 DK DK783140A patent/DK314078A/en unknown
- 1978-07-12 BR BR7804502A patent/BR7804502A/en unknown
-
1979
- 1979-12-17 US US06/104,223 patent/US4285965A/en not_active Expired - Lifetime
-
1980
- 1980-07-14 US US06/167,880 patent/US4307020A/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| JOURNAL OF THE CHEMICAL SOCIETY Perkin Transactions I (22) 1974, Seiten 2570-2574, Benzopyrones, Part XI Some 3-substituted 4-oxochromen-2-carboxilic acid derivates by Gwynn P. Ellis and Idris L. Thomas. * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0241003A3 (en) * | 1986-04-11 | 1988-10-12 | Hoechst Aktiengesellschaft | 4h-1-benzopyran-4-one derivatives, process for their preparation and their use as medicaments |
| WO1998027080A1 (en) * | 1996-12-19 | 1998-06-25 | Agrevo Uk Limited | Chromones useful as fungicides |
| US6812225B2 (en) | 2001-01-16 | 2004-11-02 | Astrazeneca Ab | Therapeutic heterocyclic compounds |
| US7026314B2 (en) | 2001-01-16 | 2006-04-11 | Astrazeneca Ab | Therapeutic chromone compounds |
| US7045514B2 (en) | 2001-01-16 | 2006-05-16 | Astrazeneca Ab | Therapeutic heterocyclic compounds |
| US7285662B2 (en) | 2001-01-16 | 2007-10-23 | Astrazeneca Ab | Therapeutic heterocyclic compounds |
Also Published As
| Publication number | Publication date |
|---|---|
| US4285965A (en) | 1981-08-25 |
| US4307020A (en) | 1981-12-22 |
| DK314078A (en) | 1979-01-14 |
| IT7825578A0 (en) | 1978-07-11 |
| DE2731566A1 (en) | 1979-02-01 |
| US4189498A (en) | 1980-02-19 |
| BR7804502A (en) | 1979-03-20 |
| IL55112A0 (en) | 1978-09-29 |
| EP0000377B1 (en) | 1981-01-21 |
| DE2860356D1 (en) | 1981-03-12 |
| JPS5419981A (en) | 1979-02-15 |
| IL55112A (en) | 1983-02-23 |
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