EP0652883A1 - Derives heterocycliques de pyrimidinedione et leur utilisation comme herbicides - Google Patents
Derives heterocycliques de pyrimidinedione et leur utilisation comme herbicidesInfo
- Publication number
- EP0652883A1 EP0652883A1 EP93917695A EP93917695A EP0652883A1 EP 0652883 A1 EP0652883 A1 EP 0652883A1 EP 93917695 A EP93917695 A EP 93917695A EP 93917695 A EP93917695 A EP 93917695A EP 0652883 A1 EP0652883 A1 EP 0652883A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkyl
- haloalkyl
- halogen
- optionally substituted
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000004009 herbicide Substances 0.000 title claims abstract description 11
- -1 Heterocyclic pyrimidinedione derivatives Chemical class 0.000 title description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 49
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 17
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 17
- 150000002391 heterocyclic compounds Chemical class 0.000 claims abstract description 10
- 239000003085 diluting agent Substances 0.000 claims abstract description 7
- 230000002363 herbicidal effect Effects 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 59
- 239000001257 hydrogen Substances 0.000 claims description 59
- 229910052736 halogen Inorganic materials 0.000 claims description 56
- 150000002367 halogens Chemical class 0.000 claims description 56
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 39
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 39
- 125000006526 (C1-C2) alkyl group Chemical group 0.000 claims description 37
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 37
- 125000006583 (C1-C3) haloalkyl group Chemical group 0.000 claims description 30
- 125000003342 alkenyl group Chemical group 0.000 claims description 29
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 claims description 27
- 125000000304 alkynyl group Chemical group 0.000 claims description 23
- 125000001188 haloalkyl group Chemical group 0.000 claims description 23
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 22
- 239000000460 chlorine Substances 0.000 claims description 19
- 229910052801 chlorine Inorganic materials 0.000 claims description 19
- 150000002431 hydrogen Chemical class 0.000 claims description 19
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims description 17
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 17
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 17
- 125000004765 (C1-C4) haloalkyl group Chemical group 0.000 claims description 16
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical group FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 claims description 15
- 229910052731 fluorine Inorganic materials 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 239000011737 fluorine Substances 0.000 claims description 14
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 13
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 13
- 125000000262 haloalkenyl group Chemical group 0.000 claims description 12
- 125000005078 alkoxycarbonylalkyl group Chemical group 0.000 claims description 11
- 229910052794 bromium Inorganic materials 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 125000006536 (C1-C2)alkoxy group Chemical group 0.000 claims description 8
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 8
- 125000004966 cyanoalkyl group Chemical group 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- UUEVFMOUBSLVJW-UHFFFAOYSA-N oxo-[[1-[2-[2-[2-[4-(oxoazaniumylmethylidene)pyridin-1-yl]ethoxy]ethoxy]ethyl]pyridin-4-ylidene]methyl]azanium;dibromide Chemical compound [Br-].[Br-].C1=CC(=C[NH+]=O)C=CN1CCOCCOCCN1C=CC(=C[NH+]=O)C=C1 UUEVFMOUBSLVJW-UHFFFAOYSA-N 0.000 claims description 8
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 7
- 125000005081 alkoxyalkoxyalkyl group Chemical group 0.000 claims description 7
- 125000004448 alkyl carbonyl group Chemical group 0.000 claims description 7
- 125000004687 alkyl sulfinyl alkyl group Chemical group 0.000 claims description 7
- 125000004688 alkyl sulfonyl alkyl group Chemical group 0.000 claims description 7
- 125000006350 alkyl thio alkyl group Chemical group 0.000 claims description 7
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 claims description 7
- 125000004181 carboxyalkyl group Chemical group 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 125000004858 cycloalkoxyalkyl group Chemical group 0.000 claims description 7
- 125000001316 cycloalkyl alkyl group Chemical group 0.000 claims description 7
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 7
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 6
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 6
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 claims description 6
- 125000001153 fluoro group Chemical group F* 0.000 claims description 6
- 125000004994 halo alkoxy alkyl group Chemical group 0.000 claims description 6
- 125000000232 haloalkynyl group Chemical group 0.000 claims description 6
- 125000005347 halocycloalkyl group Chemical group 0.000 claims description 6
- 125000004076 pyridyl group Chemical group 0.000 claims description 6
- 125000006648 (C1-C8) haloalkyl group Chemical group 0.000 claims description 5
- 125000005082 alkoxyalkenyl group Chemical group 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 4
- 125000005452 alkenyloxyalkyl group Chemical group 0.000 claims description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 4
- 238000006798 ring closing metathesis reaction Methods 0.000 claims description 4
- 125000004767 (C1-C4) haloalkoxy group Chemical group 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims description 3
- 125000000171 (C1-C6) haloalkyl group Chemical group 0.000 claims description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 2
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical group BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 241000196324 Embryophyta Species 0.000 abstract description 14
- 238000002360 preparation method Methods 0.000 abstract description 10
- 239000007787 solid Substances 0.000 abstract description 9
- 239000004094 surface-active agent Substances 0.000 abstract description 6
- 239000013543 active substance Substances 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical class C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract 1
- 244000045561 useful plants Species 0.000 abstract 1
- 239000008187 granular material Substances 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000004615 ingredient Substances 0.000 description 12
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000004480 active ingredient Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 239000008188 pellet Substances 0.000 description 6
- 239000004563 wettable powder Substances 0.000 description 6
- 229960000892 attapulgite Drugs 0.000 description 5
- 229910052625 palygorskite Inorganic materials 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004495 emulsifiable concentrate Substances 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000005243 fluidization Methods 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052903 pyrophyllite Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229920005552 sodium lignosulfonate Polymers 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 229910002029 synthetic silica gel Inorganic materials 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- XYMMYXUTZLEDDA-UHFFFAOYSA-N 1,2,3,6,7,8,9,9a-octahydropyrido[1,2-a]pyrimidin-4-one Chemical compound C1CCCN2C(=O)CCNC21 XYMMYXUTZLEDDA-UHFFFAOYSA-N 0.000 description 1
- ADAKRBAJFHTIEW-UHFFFAOYSA-N 1-chloro-4-isocyanatobenzene Chemical compound ClC1=CC=C(N=C=O)C=C1 ADAKRBAJFHTIEW-UHFFFAOYSA-N 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- ODNYFOKFNAYLKH-UHFFFAOYSA-N 2,3,4,6,7,8,9,9a-octahydro-1h-pyrido[1,2-a]pyrimidine Chemical compound C1CCNC2CCCCN21 ODNYFOKFNAYLKH-UHFFFAOYSA-N 0.000 description 1
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 1
- PRNLNZMJMCUWNV-UHFFFAOYSA-N 2-piperidin-1-ium-2-ylacetate Chemical compound OC(=O)CC1CCCCN1 PRNLNZMJMCUWNV-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- CDOUZKKFHVEKRI-UHFFFAOYSA-N 3-bromo-n-[(prop-2-enoylamino)methyl]propanamide Chemical compound BrCCC(=O)NCNC(=O)C=C CDOUZKKFHVEKRI-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000000753 cycloalkyl 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
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 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
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000035784 germination Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 208000006278 hypochromic anemia Diseases 0.000 description 1
- AQYSYJUIMQTRMV-UHFFFAOYSA-N hypofluorous acid Chemical compound FO AQYSYJUIMQTRMV-UHFFFAOYSA-N 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- CYPPCCJJKNISFK-UHFFFAOYSA-J kaolinite Chemical compound [OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[O-][Si](=O)O[Si]([O-])=O CYPPCCJJKNISFK-UHFFFAOYSA-J 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 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
- 244000005700 microbiome Species 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 125000002757 morpholinyl group Chemical group 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000017074 necrotic cell death Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 231100001184 nonphytotoxic Toxicity 0.000 description 1
- 235000020030 perry Nutrition 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- YORCIIVHUBAYBQ-UHFFFAOYSA-N propargyl bromide Chemical compound BrCC#C YORCIIVHUBAYBQ-UHFFFAOYSA-N 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
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D498/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D498/10—Spiro-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
- C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
- C07D513/04—Ortho-condensed systems
Definitions
- the present invention relates to new types
- EP-Bl 0 070 389) can be used as herbicides.
- the object of the present invention therefore includes compounds of the formula I in which
- X represents O, S, CH 2 , CHF, CF 2 , CHCl, CHBr, CHOCH 2 F, CHOCF 3 or CHOCH 2 CF 3 ,
- n 1 or 2
- R 1 and R 2 independently of one another, for hydrogen, hydroxy, halogen, (C 1 - C 4 ) alkyl, (C 1 - C 4 ) alkoxy, (C 1 - C 4 ) haloalkyl or (C 1 - C 4 ) Haloalkoxy stand,
- R 3 and R 4 independently of one another, for hydrogen, hydroxy, halogen, cyano, (C 1 -C 4 ) alkyl,
- w O or S
- R 5 represents hydrogen or halogen
- R 7 represents hydrogen, (C 1 - C 8 ) alkyl
- CH CHCO 2 R 11
- CO 2 N CR 14 R 15 , NO 2 , CN, NHSO 2 R 16 or
- R 8 is hydrogen, (C 1 - C 3 ) alkyl
- R 9 represents hydrogen, (C 1 - C 3 ) alkyl
- R 10 for (C 1 -C 6 ) alkyl, (C 1 -C 6 ) haloalkyl
- Cycloalkylalkyl (C 2 - C 4 ) carboxyalkyl
- Halogen (C 1 -C 3 ) alkyl or (C 1 -C 3 ) haloalkyl;
- R 12 and R 14 independently of one another, represent hydrogen or (C 1 -C 4 ) alkyl
- R 13 and R 15 independently of one another, for
- R 12 and R 13 as - (CH 2 ) 5 -, - (CH 2 ) 4 - or
- -CH 2 CH 2 OCH 2 CH 2 - can be combined to form rings, it being possible for one or more H atoms in each ring to be optionally substituted by (C 1 - C 3 ) alkyl-, phenyl- or benzyl,
- R 14 and R 15 together with the carbon to which they are attached can form a (C 3 -C 8 ) cycloalkyl group
- R 16 represents (C 1 -C 4 ) alkyl or (C 1 -C 4 ) haloalkyl
- R 17 represents hydrogen or (C 1 - C 3 ) alkyl
- R 18 is (C 1 -C 6 ) alkyl, (C 3 -C 6 ) alkenyl or
- n 0, 1 or 2.
- alkyl alone or in the compound name such as “alkylthlo” or “haloalkyl”, includes a straight or branched chain, e.g. B. methyl,
- Alkoxy includes methoxy, ethoxy, n-propyloxy, isopropyloxy and the various
- Alkenyl includes straight or branched alkenes, e.g. B., 1-propenyl, 2-propenyl, 3-propenyl and the various butenyl isomers.
- Cycloalkyl includes cyclopropyl, cyclobutyl,
- Haloalkyl means fluorine, chlorine, bromine or iodine.
- alkyl when “haloalkyl” is used in the compound name, alkyl can be partially or completely substituted with halogen atoms, which in turn can be the same or different.
- haloalkyl examples include CH 2 CH 2 F, CF 2 CF 3 and CH 2 CHFCl.
- X represents O, S, CH 2 , CHF, CF 2 , CHCl, CHBr, CHOCHF 2 , CHOCF 3 or CHOCH, CF 3 ,
- R 1 and R 2 independently of one another, represent hydrogen, hydroxy, fluorine, chlorine, bromine, methyl or methoxy,
- R 3 and R 4 independently of one another, for hydrogen, hydroxyl, fluorine, chlorine, bromo, cyan,
- w 0 or S
- n 0, 1, 2
- R 6 represents halogen or CN
- R 7 is hydrogen, (C 1 - C 4 ) alkyl, (C 1
- CO 2 N CR 14 R 15 , NHSO 2 R 16 or NHSO 2 NHR 16 , R 8 represents hydrogen, (C 1 - C 3 ) alkyl or
- R 9 represents hydrogen, (C 1 - C 3 ) alkyl or
- R 1 0 (C 1 - C 4) alkyl, (C 1 - C 4) haloalkyl,
- R 11 is for (C 1 -C 4 ) alkyl, (C 3 -C 6 ) cycloalkyl,
- Halogen (C 1 - C 3 ) alkyl or (C 1 - C 3 ) haloalkyl, (C 4 - C 8 ) trialkylsiiylalkyl, (C 3 - C 4 ) cyanoalkyl, (C 3 - C 6 ) halocycloalkyl, (C 3 - C 6 ) haloalkenyl.
- R 14 and R 15 together with the carbon to which they are attached can form a (C 3 -C 6 ) cycloalkyl group
- R 16 represents (C 1 -C 4 ) alkyl or (C 1 -C 4 ) haloalkyl
- R 17 represents hydrogen or (C 1 -C 3 ) alkyl
- R 18 is (C 1 -C 4 ) alkyl, (C 3 -C 4 ) alkenyl or
- R 12 and R 13 When R 12 and R 13 are combined to form a ring, they form a pyrrolidinyl, piperidinyl or with the N atom to which they are attached
- n 1 or 2
- R 1 and R 2 represent hydrogen
- R 3 and R 4 represent hydrogen, Q means
- w O or S
- R 5 represents hydrogen, fluorine or chlorine
- R 6 represents chlorine, bromine or cyan
- R 8 and R 9 independently of one another, are hydrogen
- R 11 represents (C 1 -C 4 ) alkyl, (C 3 -C 6 ) cycloalkyl,
- R 12 represents hydrogen or (C 1 - C 2 ) alkyl
- R 12 and R 13 can be - (CH 2 ) 5 -, -CH 2 ) 4 - or
- -CH 2 CH 2 OCH 2 CH 2 - can be combined to form rings, where one or more H atoms in each ring can optionally be substituted by (C 1 - C 2 ) alkyl,
- R 17 represents hydrogen or (C 1 - C 2 ) alkyl
- R 18 is (C 1 -C 2 ) alkyl, (C 3 -C 4 ) alkenyl or
- X represents CH 2 , O or S
- n 1 or 2
- R 1 and R 2 represent hydrogen
- R 3 and R 4 represent hydrogen
- R 5 represents fluorine or chlorine
- R 6 represents chlorine
- R 11 is for (C 1 -C 4 ) alkyl, (C 3 -C 6 ) cycloalkyl,
- the invention relates both to the individual possible stereoisomers of the formula I and to mixtures of these isomers.
- novel heterocyclic compounds of general formula I are obtained according to the present invention when aryl isocyanates
- R represents hydrogen, (C 1 -C 4 ) alkyl or active ester, according to method A, optionally in the presence of an acid acceptor and optionally in the presence of a thinner
- Another object of the invention is
- Another object of the invention is method D for the preparation of compounds of formula I, which is explained below, wherein m, X, R 1 , R 2 , R 3 , R 4 and Q have the meaning given above and wherein a compound of Formula II with a compound of formula XI, optionally in the presence of a
- Acid acceptor and optionally in the presence of a diluent is brought to reaction and thereby
- halogenated hydrocarbon such as chloroform
- Organic bases are preferably used as bases, for example organic amines such as triethylamine or pyridine.
- R H
- the reaction is carried out in water as a solvent or, preferably, in a two-phase water / organic solvent system.
- an inorganic base for example an alkali metal or
- Hydrogen carbonate such as sodium hydroxide or also
- Potassium carbonate or together with an organic base such as, for example, an organic amine such as triethylamine, and then compounds of the formula II, dissolved in an inert solvent such as, for example, toluene, chlorobenzene or chloroform, are added.
- the reaction mixture is then kept at temperatures between -40 ° C. and + 50 ° C., preferably -10 ° C. and + 10 ° C., for several days, preferably between 3 and 50 hours.
- the aqueous phase is then adjusted to a pH between 1 and 3 using acid, preferably an inorganic acid such as aqueous hydrochloric or sulfuric acid.
- acid preferably an inorganic acid such as aqueous hydrochloric or sulfuric acid.
- Amines of the formula III are known and can be prepared analogously to the known methods; see, for example, M.Seklya et al., Chem. Pharm. Bull 31 (1) 94 (1983); J.M. Cassal, A. Mariest, W.
- heterocyclic compounds of general formula I have exceptional herbicidal properties.
- the invention therefore also relates to herbicides
- compositions containing an effective content of a compound of formula I and a carrier are advantageous
- the invention also relates to a method for
- Harmful plant control in which a herbicidally effective amount of a compound is applied to the harmful plants or their surroundings (before or after emergence)
- Sprayable preparations can be stretched with suitable media and sprayed in quantities between a few and a few hundred liters per hectare. Highly concentrated preparations are mainly used as intermediates for other formulations.
- the recipes contain, roughly speaking,
- active ingredient (s) between 0.1 and 99% by weight of active ingredient (s) and at least one representative of group a) 0.1 to 20% of surface-active substances and b) approximately 1 to 99.9% of solid or liquid diluents. More specifically,
- Active ingredient thinner active substances wetted powder 20 - 90 0 - 74 1 - 10
- Active ingredient Thinner Active substances Aqueous suspensions 10 - 50 40 - 84 1 - 20
- Active ingredients are sometimes desirable and are achieved by incorporating them into the recipe or by mixing in the container.
- Granules and pellets can be produced by spraying the active ingredient onto preformed granular carriers or by agglomerating. See J.E. Browning, "Agglomeration", Chemical
- the ingredients are mixed, roughly crushed in a hammer mill and then in a jet mill
- a slurry of wettable powder with 25% solids is converted into a double-cone
- the ingredients are mixed, ground in a hammer mill and then moistened with about 12% water.
- the mixture is extruded into cylinders about 3 mm in diameter, which are cut into pellets about 3 mm in length. These can be used directly after drying; however, the dried pellets can be crushed so that the USS No. Pass through the 2C sieve (openings 0.84 mm diameter).
- the on Granules remaining in the sieve USS No 40 (0.42 mm opening diameter) can be packaged for use while the fines are returned.
- the active ingredient is dissolved in the solvent and the solution is sprayed onto dedusted granules in a double cone mixer. After the solution has been sprayed, the mixer is left to run for a short time, after which the granules are packaged.
- Attapulgite clay 9% The ingredients are mixed and ground until they pass through a 100 mesh screen. This material is then fed to a fluid bed granulator, where the air flow is adjusted so that the material is easily whirled up and a fine jet of water is sprayed onto the whirled material. The fluidization and spraying are so long
- desired size range usually 14 to 100 mesh (1410 to 149 ⁇ m), after which for the
- the ingredients are mixed and ground together in a sand mill to create particles with
- the ingredients are mixed and mixed in one
- the ingredients are mixed and mixed in one
- Example J Hammer mill ground to obtain particles substantially below 100 microns. The material is sieved through a USS No. 50 sieve and then packaged. Example J
- the ingredients are mixed thoroughly, roughly ground in a hammer mill and then in one
- the material is then mixed and packed again.
- the ingredients are mixed and mixed in one
- Example L Sand mill ground to obtain particles substantially below 5 microns in size.
- the product can be used directly, stretched with oil or emulsified in water.
- the active ingredient is mixed with attapulgite and then passed through a hammer mill to obtain particles substantially less than 200 microns.
- the ground concentrate is then pulverized with the
- the ingredients are ground together in a sand mill until the size of the solid particles is below about 5 microns, resulting thick suspension can be used directly, but is preferably used after stretching with oils or after emulsifying in water.
- Biological examples
- selective weed control in crops such as rice, wheat, barley, corn, soybeans, sugar beet and cotton.
- the amount of the compounds according to the present invention to be applied depends on numerous factors, including the use as selective or universal herbicides, the particular crop, the type of weeds to be combated, the weather and climate, the selected recipe, the mode of application, the amount of leafy plants etc. In general, the compounds should be applied in amounts between 0.001 and 20 kg / ha, the lower amounts for lighter soils and / or soils
- the compounds of the present invention can be used in combination with any other commercial herbicide.
- the herbicidal properties of the compounds of the present invention have been found in a number of greenhouse experiments. The test methods and results are given below.
- Seeds from digitaria spp, echinochloa crus-galli, setaria feberii, avena fatua, bromus secalinus, abutilon theophrasti, ipomoea spp., Xanthium pensylvanicum and sorghum tubers were placed and treated with the test chemicals dissolved in a non-phytotoxic solvent before germination.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Plural Heterocyclic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
L'invention concerne des composés hétérocycliques. Les composés herbicides doivent agir à doses aussi faibles que possible en exerçant une haute sélectivité entre les plantes utiles et les mauvaises herbes. L'invention se propose de mettre au point de nouveaux composés chimiques pouvant être utilisés comme herbicides. Les nouveaux composés hétérocycliques ont la formule (I) dans laquelle X désigne O, S, CH2 ou CH2 substitué et Q désigne des benzols substitués. Ces composés peuvent être produits par exemple dans une formulation renfermant des substances tensioactives et des diluants solides ou liquides et utilisée afin de minimiser la croissance de végétation indésirable. L'invention concerne en outre des substances herbicides.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4225167 | 1992-07-30 | ||
| DE4225167 | 1992-07-30 | ||
| DE4225629 | 1992-08-03 | ||
| DE4225629A DE4225629A1 (de) | 1992-07-30 | 1992-08-03 | Heterocyclische Verbindungen |
| PCT/EP1993/002027 WO1994003459A1 (fr) | 1992-07-30 | 1993-07-29 | Composes heterocycliques et leur utilisation comme herbicides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0652883A1 true EP0652883A1 (fr) | 1995-05-17 |
Family
ID=25917054
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP93917695A Withdrawn EP0652883A1 (fr) | 1992-07-30 | 1993-07-29 | Derives heterocycliques de pyrimidinedione et leur utilisation comme herbicides |
Country Status (9)
| Country | Link |
|---|---|
| US (2) | US5661107A (fr) |
| EP (1) | EP0652883A1 (fr) |
| JP (1) | JPH07509474A (fr) |
| CN (1) | CN1085902A (fr) |
| AU (2) | AU671476B2 (fr) |
| CA (1) | CA2139585A1 (fr) |
| DE (1) | DE4225629A1 (fr) |
| RU (1) | RU95105602A (fr) |
| WO (1) | WO1994003459A1 (fr) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4225629A1 (de) * | 1992-07-30 | 1994-02-03 | Degussa | Heterocyclische Verbindungen |
| CN1202172A (zh) * | 1995-10-25 | 1998-12-16 | 纳幕尔杜邦公司 | 具有除草作用的磺酰胺 |
| CN108727367B (zh) * | 2017-04-18 | 2021-01-05 | 山东先达农化股份有限公司 | 含吡啶并嘧啶二酮的苯并噁嗪酮类化合物及其制备方法和应用和除草剂组合物 |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5888382A (ja) * | 1981-11-24 | 1983-05-26 | Ube Ind Ltd | イミダゾピリミジン類の製法 |
| US4725600A (en) * | 1984-07-13 | 1988-02-16 | Fujisawa Pharmaceutical Co., Ltd. | Pyrimidine compounds having activity as a cardiotonic anti-hypertensive cerebrovascular vasodilator and anti-platelet aggregation agent |
| DE3788737T2 (de) * | 1986-01-29 | 1994-05-05 | Sumitomo Chemical Co | Indazol-Verbindungen, Verfahren zu deren Herstellung, deren Anwendung und Zwischenprodukte. |
| EP0243734B1 (fr) * | 1986-04-19 | 1991-07-17 | MERCK PATENT GmbH | Hydantoine optiquement active |
| GB8620060D0 (en) * | 1986-08-18 | 1986-10-01 | Roussel Lab Ltd | Chemical compounds |
| DE3643748A1 (de) * | 1986-12-20 | 1988-06-30 | Hoechst Ag | Bicylische imide, verfahren zu ihrer herstellung sowie ihre verwendung im pflanzenschutz |
| DE3712782A1 (de) * | 1987-04-13 | 1988-11-03 | Schering Ag | Anellierte uracilderivate, verfahren zu ihrer herstellung und ihre verwendung als herbizide mittel |
| US4927451A (en) * | 1988-12-30 | 1990-05-22 | Uniroyal Chemical Company, Inc. | 3-aryldihydrouracils |
| US5270287A (en) * | 1989-10-31 | 1993-12-14 | Valent U.S.A. Corporation | Method for defoliating and desiccating cotton |
| DE4225629A1 (de) * | 1992-07-30 | 1994-02-03 | Degussa | Heterocyclische Verbindungen |
-
1992
- 1992-08-03 DE DE4225629A patent/DE4225629A1/de not_active Withdrawn
-
1993
- 1993-07-29 RU RU95105602/04A patent/RU95105602A/ru unknown
- 1993-07-29 CA CA002139585A patent/CA2139585A1/fr not_active Abandoned
- 1993-07-29 US US08/374,648 patent/US5661107A/en not_active Expired - Fee Related
- 1993-07-29 EP EP93917695A patent/EP0652883A1/fr not_active Withdrawn
- 1993-07-29 JP JP6504988A patent/JPH07509474A/ja active Pending
- 1993-07-29 AU AU47042/93A patent/AU671476B2/en not_active Ceased
- 1993-07-29 WO PCT/EP1993/002027 patent/WO1994003459A1/fr not_active Ceased
- 1993-07-29 AU AU47043/93A patent/AU671290B2/en not_active Ceased
- 1993-07-30 CN CN93117449.XA patent/CN1085902A/zh active Pending
-
1997
- 1997-06-12 US US08/873,797 patent/US5922647A/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| See references of WO9403459A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| US5922647A (en) | 1999-07-13 |
| AU671476B2 (en) | 1996-08-29 |
| CA2139585A1 (fr) | 1994-02-17 |
| WO1994003459A1 (fr) | 1994-02-17 |
| AU4704393A (en) | 1994-03-03 |
| JPH07509474A (ja) | 1995-10-19 |
| AU671290B2 (en) | 1996-08-22 |
| RU95105602A (ru) | 1997-05-10 |
| CN1085902A (zh) | 1994-04-27 |
| DE4225629A1 (de) | 1994-02-03 |
| AU4704293A (en) | 1994-03-03 |
| US5661107A (en) | 1997-08-26 |
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