DE1568138B2 - DIURETHANES AND HERBICIDALS CONTAINING THEM - Google Patents
DIURETHANES AND HERBICIDALS CONTAINING THEMInfo
- Publication number
- DE1568138B2 DE1568138B2 DE1966B0087883 DEB0087883A DE1568138B2 DE 1568138 B2 DE1568138 B2 DE 1568138B2 DE 1966B0087883 DE1966B0087883 DE 1966B0087883 DE B0087883 A DEB0087883 A DE B0087883A DE 1568138 B2 DE1568138 B2 DE 1568138B2
- Authority
- DE
- Germany
- Prior art keywords
- radical
- diurethanes
- spp
- group
- damage
- 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
- 150000001875 compounds Chemical group 0.000 claims description 15
- -1 methoxyl group Chemical group 0.000 claims description 14
- 230000002363 herbicidal effect Effects 0.000 claims description 11
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- SLRMQYXOBQWXCR-UHFFFAOYSA-N 2154-56-5 Chemical compound [CH2]C1=CC=CC=C1 SLRMQYXOBQWXCR-UHFFFAOYSA-N 0.000 claims description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- NQOJWOIPQBVKKX-UHFFFAOYSA-N cyclooctane Chemical compound [CH]1CCCCCCC1 NQOJWOIPQBVKKX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical group [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims 1
- 230000006378 damage Effects 0.000 description 14
- 241000196324 Embryophyta Species 0.000 description 13
- 244000042664 Matricaria chamomilla Species 0.000 description 8
- 235000007232 Matricaria chamomilla Nutrition 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 240000008042 Zea mays Species 0.000 description 7
- 239000012948 isocyanate Substances 0.000 description 7
- 150000002513 isocyanates Chemical class 0.000 description 7
- 244000024671 Brassica kaber Species 0.000 description 6
- 240000006694 Stellaria media Species 0.000 description 6
- 235000009108 Urtica dioica Nutrition 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000006467 substitution reaction Methods 0.000 description 6
- 241000520028 Lamium Species 0.000 description 5
- 244000274883 Urtica dioica Species 0.000 description 5
- 239000004480 active ingredient Substances 0.000 description 5
- 150000001714 carbamic acid halides Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 5
- 235000008427 Brassica arvensis Nutrition 0.000 description 4
- 235000004977 Brassica sinapistrum Nutrition 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 4
- 244000292693 Poa annua Species 0.000 description 4
- 235000007244 Zea mays Nutrition 0.000 description 4
- 229940112021 centrally acting muscle relaxants carbamic acid ester Drugs 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 210000001699 lower leg Anatomy 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- DSVGFKBFFICWLZ-UHFFFAOYSA-N 1-fluoro-4-isocyanatobenzene Chemical compound FC1=CC=C(N=C=O)C=C1 DSVGFKBFFICWLZ-UHFFFAOYSA-N 0.000 description 3
- 241000335053 Beta vulgaris Species 0.000 description 3
- 235000007866 Chamaemelum nobile Nutrition 0.000 description 3
- 241000219312 Chenopodium Species 0.000 description 3
- 240000006122 Chenopodium album Species 0.000 description 3
- ULBXWWGWDPVHAO-UHFFFAOYSA-N Chlorbufam Chemical compound C#CC(C)OC(=O)NC1=CC=CC(Cl)=C1 ULBXWWGWDPVHAO-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- HPNSNYBUADCFDR-UHFFFAOYSA-N chromafenozide Chemical compound CC1=CC(C)=CC(C(=O)N(NC(=O)C=2C(=C3CCCOC3=CC=2)C)C(C)(C)C)=C1 HPNSNYBUADCFDR-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- LCEYJTJDZROKOK-UHFFFAOYSA-N (3-hydroxyphenyl)carbamic acid Chemical compound OC(=O)NC1=CC=CC(O)=C1 LCEYJTJDZROKOK-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 2
- 235000016068 Berberis vulgaris Nutrition 0.000 description 2
- 235000005637 Brassica campestris Nutrition 0.000 description 2
- 235000014750 Brassica kaber Nutrition 0.000 description 2
- 235000010149 Brassica rapa subsp chinensis Nutrition 0.000 description 2
- 235000010570 Brassica rapa var. rapa Nutrition 0.000 description 2
- 102100028637 CLOCK-interacting pacemaker Human genes 0.000 description 2
- 235000009344 Chenopodium album Nutrition 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- 241000208175 Daucus Species 0.000 description 2
- 244000000626 Daucus carota Species 0.000 description 2
- 241000221079 Euphorbia <genus> Species 0.000 description 2
- 239000004471 Glycine Substances 0.000 description 2
- 235000010469 Glycine max Nutrition 0.000 description 2
- 244000068988 Glycine max Species 0.000 description 2
- 241000219146 Gossypium Species 0.000 description 2
- 101000766839 Homo sapiens CLOCK-interacting pacemaker Proteins 0.000 description 2
- 240000006503 Lamium purpureum Species 0.000 description 2
- 235000002594 Solanum nigrum Nutrition 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 244000152045 Themeda triandra Species 0.000 description 2
- 240000005592 Veronica officinalis Species 0.000 description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 description 2
- GTCAXTIRRLKXRU-UHFFFAOYSA-N carbamic acid methyl ester Natural products COC(N)=O GTCAXTIRRLKXRU-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- CWJSHJJYOPWUGX-UHFFFAOYSA-N chlorpropham Chemical compound CC(C)OC(=O)NC1=CC=CC(Cl)=C1 CWJSHJJYOPWUGX-UHFFFAOYSA-N 0.000 description 2
- 235000005822 corn Nutrition 0.000 description 2
- 239000004009 herbicide Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000006188 syrup Substances 0.000 description 2
- 235000020357 syrup Nutrition 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BIHORWRPXKVBIH-UHFFFAOYSA-N (2-hydroxyphenyl) carbamate Chemical compound NC(=O)OC1=CC=CC=C1O BIHORWRPXKVBIH-UHFFFAOYSA-N 0.000 description 1
- UVMTZTPUIFOAGM-UHFFFAOYSA-N (3-chlorophenyl)carbamic acid Chemical compound OC(=O)NC1=CC=CC(Cl)=C1 UVMTZTPUIFOAGM-UHFFFAOYSA-N 0.000 description 1
- NBJZEUQTGLSUOB-UHFFFAOYSA-N 1-chloro-4-isocyanato-2-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC(N=C=O)=CC=C1Cl NBJZEUQTGLSUOB-UHFFFAOYSA-N 0.000 description 1
- 229940018563 3-aminophenol Drugs 0.000 description 1
- 235000006760 Acer pensylvanicum Nutrition 0.000 description 1
- 241000219318 Amaranthus Species 0.000 description 1
- 235000009328 Amaranthus caudatus Nutrition 0.000 description 1
- 240000001592 Amaranthus caudatus Species 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 235000011498 Chenopodium album var missouriense Nutrition 0.000 description 1
- 235000013328 Chenopodium album var. album Nutrition 0.000 description 1
- 235000014052 Chenopodium album var. microphyllum Nutrition 0.000 description 1
- 235000014050 Chenopodium album var. stevensii Nutrition 0.000 description 1
- 235000013012 Chenopodium album var. striatum Nutrition 0.000 description 1
- 235000002767 Daucus carota Nutrition 0.000 description 1
- 241000192043 Echinochloa Species 0.000 description 1
- 235000012043 Euphorbia helioscopia Nutrition 0.000 description 1
- 241000287828 Gallus gallus Species 0.000 description 1
- 241000208818 Helianthus Species 0.000 description 1
- 235000003222 Helianthus annuus Nutrition 0.000 description 1
- 244000020551 Helianthus annuus Species 0.000 description 1
- 241001456088 Hesperocnide Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 235000021506 Ipomoea Nutrition 0.000 description 1
- 241000207783 Ipomoea Species 0.000 description 1
- 240000001549 Ipomoea eriocarpa Species 0.000 description 1
- 235000012587 Lamium purpureum var. incisum Nutrition 0.000 description 1
- 235000017945 Matricaria Nutrition 0.000 description 1
- CNFGKOUTOFNRTQ-UHFFFAOYSA-N OC(NCC1=CC(OC(NC(C=C2)=CC(C(F)(F)F)=C2Cl)=O)=CC=C1)=O Chemical compound OC(NCC1=CC(OC(NC(C=C2)=CC(C(F)(F)F)=C2Cl)=O)=CC=C1)=O CNFGKOUTOFNRTQ-UHFFFAOYSA-N 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- 244000061457 Solanum nigrum Species 0.000 description 1
- 240000002307 Solanum ptychanthum Species 0.000 description 1
- 244000062793 Sorghum vulgare Species 0.000 description 1
- 235000005545 Veronica americana Nutrition 0.000 description 1
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 1
- GVCGZJIBRCRXPW-UHFFFAOYSA-N [3-[(4-fluorophenyl)carbamoyloxy]phenyl]-methylcarbamic acid Chemical compound OC(=O)N(C)C1=CC=CC(OC(=O)NC=2C=CC(F)=CC=2)=C1 GVCGZJIBRCRXPW-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Chemical group 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 235000011655 cotton Nutrition 0.000 description 1
- 244000038559 crop plants Species 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000035784 germination Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 235000009973 maize Nutrition 0.000 description 1
- HAMGRBXTJNITHG-UHFFFAOYSA-N methyl isocyanate Chemical compound CN=C=O HAMGRBXTJNITHG-UHFFFAOYSA-N 0.000 description 1
- FFQQCJGNKKIRMD-UHFFFAOYSA-N methyl n-(3-hydroxyphenyl)carbamate Chemical compound COC(=O)NC1=CC=CC(O)=C1 FFQQCJGNKKIRMD-UHFFFAOYSA-N 0.000 description 1
- 235000019713 millet Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- VXPLXMJHHKHSOA-UHFFFAOYSA-N propham Chemical compound CC(C)OC(=O)NC1=CC=CC=C1 VXPLXMJHHKHSOA-UHFFFAOYSA-N 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000009331 sowing Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
- C07C271/40—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of six-membered aromatic rings
- C07C271/58—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of six-membered aromatic rings with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
- C07C271/40—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of six-membered aromatic rings
- C07C271/42—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of six-membered aromatic rings with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C271/44—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of six-membered aromatic rings with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
- C07C271/40—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of six-membered aromatic rings
- C07C271/42—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of six-membered aromatic rings with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C271/46—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of six-membered aromatic rings with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by halogen atoms or by nitro or nitroso groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
- C07C271/40—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of six-membered aromatic rings
- C07C271/56—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of six-membered aromatic rings with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a ring other than a six-membered aromatic ring
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
N —CO —ON —CO —O
IlIl
NH-C —OR1 NH-C-OR 1
HOHO
O NH-C-OR1 O NH-C-OR 1
N —CO —YN -CO -Y
in der Y Chlor oder Brom bedeutet und R die obengenannten Bedeutungen hat, in an sich bekannter Weise umsetzt, wobei die Umsetzung mit dem Carbaminsäurehalogenid in Gegenwart eines säurebindenden Mittels erfolgt.in which Y is chlorine or bromine and R has the abovementioned meanings, in more known per se Way, the reaction with the carbamic acid halide in the presence of an acid-binding agent Means done.
Diese Verbindungen sind meist gut kristallisierende Produkte, die eine gute herbizide Wirkung haben.
Sie sind wirksam sowohl zur selektiven als auch zur totalen Pflanzenbekämpfung. Durch Mischung
der Wirkstoffe mit üblichen festen oder flüssigen Trägerstoffen erhält man herbizide Mittel.
Das Verfahren zur Herstellung der neuen Verbindungen verläuft nach den allgemeinen Reaktionsgleichungen
a oder b.These compounds are mostly products that crystallize well and have a good herbicidal effect. They are effective for both selective and total crop control. Mixing the active ingredients with customary solid or liquid carriers gives herbicidal compositions.
The process for the preparation of the new compounds proceeds according to the general reaction equations a or b.
R-N=C=O + HOR-N = C = O + HO
Die vorliegende Erfindung betrifft wertvolle Diurethane mit guter herbizider Wirkung und Herbizide, die diese Verbindungen enthalten.The present invention relates to valuable diurethanes with good herbicidal action and herbicides, which contain these compounds.
Es ist bekannt, Isocyanate bzw. Carbaminsäurehalogenide mit Alkoholen zu Urethanen umzusetzen. Hydroxylgruppen mit saurem Charakter, wie die der Phenole, reagieren erst bei höherer Temperatur mit Isocyanaten, ζ. B. bei der Umsetzung von «-Naphthol mit Methylisocyanat.It is known to convert isocyanates or carbamic acid halides with alcohols to give urethanes. Hydroxyl groups with an acidic character, like those of the phenols, only react at higher temperatures Isocyanates, ζ. B. in the implementation of «-naphthol with methyl isocyanate.
Es wurde gefunden, daß wertvolle Diurethane der allgemeinen FormelIt has been found that valuable diurethanes of the general formula
R—NH-CR-NH-C
C-OR1 C-OR 1
NH-C—OR1 NH-C-OR 1
R—NH-C-R — NH-C-
-γ+ho—<\~y -γ + ho- <\ ~ y
NH-C—OR1 NH-C-OR 1
-HY-HY
in der R1 eine Methylgruppe oder eine Butin-(l'-yl-(3)-gruppe und R einen durch ein Fluoratom oder zwei Methylgruppen oder ein Chloratom und eine Trifluormethylgruppe oder eine Methoxylgruppe oder ein Jodatom substituierten Phenylrest oder den a-Naphthylrest oder den 2-Methylcyclohexylrest oder den 2-Äthylhexylrest oder den Cyclooctylrest oder den Benzylrest oder den Tetrahydrodicyclopentadienylrest bedeutet, eine gute herbizide Wirkung haben. Diese Verbindungen werden erhalten, wenn man ein Hydroxyphenylcarbamat der Formelin which R 1 is a methyl group or a butyn- (l'-yl- (3) group and R is a phenyl group or a-naphthyl group substituted by a fluorine atom or two methyl groups or a chlorine atom and a trifluoromethyl group or a methoxyl group or an iodine atom or the 2-methylcyclohexyl radical or the 2-ethylhexyl radical or the cyclooctyl radical or the benzyl radical or the tetrahydrodicyclopentadienyl radical have a good herbicidal action These compounds are obtained when a hydroxyphenyl carbamate of the formula
45 R—NH-C—O 45 R-NH-C-O
in der R1 die obengenannten Bedeutungen hat, mit einem Isocyanat oder Carbaminsäurehalogenid der Formelin which R 1 has the abovementioned meanings with an isocyanate or carbamic acid halide of the formula
R-N=C=OR-N = C = O
NH
O = C
OR1 NH
O = C
OR 1
wobei R und R1 die obengenannten Bedeutungen haben.
Als Ausgangsprodukte für das erfindungsgemäße Herstellungsverfahren kommen z. B. m-Hydroxyphenylcarbamate
in Betracht, die Umsetzungsprodukte von Chloikohlensäuremethyl-, oder butin-(l)-yl-(3)-ester,
mit m-Aminophenol sind. Ihre Herstellung kann in Gegenwart von Chlorwasserstoffbindemitteln,
z. B. tertiären Aminen oder Alkalicarbonaten, durchgeführt werden.where R and R 1 have the meanings given above.
As starting products for the manufacturing process according to the invention, for. B. m-Hydroxyphenylcarbamate into consideration, the reaction products of Chloikohlensäuremethyl-, or butyn- (1) -yl (3) ester, with m-aminophenol. Their preparation can be carried out in the presence of hydrogen chloride binders, e.g. B. tertiary amines or alkali metal carbonates.
Als Isocyanate, die als Ausgangsprodukte für das erfindungsgemäße Herstellungsverfahren in Frage kommen, sind Cycloociyl-, Anisidyl-, m,p-Fluor-As isocyanates, which can be used as starting materials for the production process according to the invention come, are cycloociyl, anisidyl, m, p-fluoro
phenyl-, p-Jodphenyl-, ^Chlor-j-trirluormethylphenyl-, Isocyanat zu nennen. Es können ferner die den Isocyanaten entsprechenden Carbaminsäurehalogenide verwendet werden.phenyl-, p-iodophenyl-, ^ chloro-j-trirluormethylphenyl-, Mention isocyanate. The carbamic acid halides corresponding to the isocyanates can also be used be used.
Die erfindungsgemäßen Umsetzungen der beiden Ausgangsprodukte erfolgten in Lösung, und zwar werden indifferente Lösungsmittel, z. B. Dioxan, Tetrahydrofuran, Äther, Kohlenwasserstoffe, Chlorbenzol, verwendet. Die Umsetzung wird ausgeführt bei Temperaturen von 15 bis 15O0C, vorteilhaft zwischen 30 und 80° C. Es werden etwa äquivalente Mengen der Ausgangsprodukte für die Umsetzung verwendet. Die Umsetzung mit dem Carbaminsäurehalogenid erfolgt in Gegenwart eines säurebindenden Mittels, z. B. eines tertiären Amins, Aminoalkohole, Alkalialkoholats, Alkalicarbonats oder Alkalihydroxyds.The inventive reactions of the two starting materials took place in solution, namely inert solvents such. B. dioxane, tetrahydrofuran, ether, hydrocarbons, chlorobenzene, are used. The reaction is carried out at temperatures of 15 to 15O 0 C, preferably between 30 and 80 ° C. There approximately equivalent amounts of the starting materials are used for the reaction. The reaction with the carbamic acid halide is carried out in the presence of an acid-binding agent, e.g. B. a tertiary amine, amino alcohols, alkali metal alcoholate, alkali metal carbonate or alkali metal hydroxide.
Die folgenden Beispiele sollen die Herstellung der erfindungsgemäßen Verbindungen erläutern.The following examples are intended to explain the preparation of the compounds according to the invention.
Zu 16,7 Gwtln. N-m-Hydroxyphenylcarbaminsäuremethylester, gelöst in 50 Volumteilen Dioxan und einer Spur Natriummethlat werden unter Rühren bei 30 bis 4O0C 13,7 Gwtle. p-Fluorphenylisocyanat zugetropft, wobei die Umsetzung teilweise stattfindet. Zur Vervollständigung der Umsetzung wird das Gemisch einige Stunden auf 60 bis 70° C erwärmt. Ein Teil des Lösungsmittels wird im Vakuum abdestilliert, und durch Zugabe von Petroläther wird das 3-(4'-Fluorphenylcarbamoyl)-oxyphenyl-methylcarbamat kristallin erhalten. Die Ausbeute beträgt 29 Gewichtsteile. Die Substanz hat den Fp. 161 bis 1630C.At 16.7 Gwtln. Nm Hydroxyphenylcarbaminsäuremethylester dissolved in 50 parts by volume of dioxane and a track Natriummethlat with stirring at 30 to 4O 0 C 13.7 Gwtle. p-Fluorophenyl isocyanate was added dropwise, the reaction partially taking place. To complete the reaction, the mixture is heated to 60 to 70 ° C. for a few hours. Some of the solvent is distilled off in vacuo, and the 3- (4'-fluorophenylcarbamoyl) oxyphenyl methylcarbamate is obtained in crystalline form by adding petroleum ether. The yield is 29 parts by weight. The substance has a melting point of 161 to 163 ° C.
B eisp i el 2Example 2
Wird beim Verfahren gemäß Beispiel 1 an Stelle von p-Fluorphenylisocyanat das 4-Chlor-3-trifluormethylphenylisocyanat angewandt, so erhält man das 3-(4'-Chlor-3'-trifluormethyl-phenylcarbamoyl)-oxyphenylmethylcarbamat mit dem Fp. 184 bis 186,5° C.In the process according to Example 1, 4-chloro-3-trifluoromethylphenyl isocyanate is used instead of p-fluorophenyl isocyanate applied, the 3- (4'-chloro-3'-trifluoromethyl-phenylcarbamoyl) -oxyphenylmethylcarbamate is obtained with a melting point of 184 to 186.5 ° C.
Verwendet man bei sonst gleicher Arbeitsweise anstatt p-Fluorphenylisocyanat das m-Anisidylisocyanat und anstatt N-m-Hydroxyphenylcarbaminsäuremethylester den m-Hydroxyphenylcarbaminsäurebutin-(l)-yl-(3)-ester, so erhält man 3-(3'-Anisidylcarbamoyl)-oxyphenyl-isobutin-(l)-yl-(3)-carbamat mit dem Fp. 135 bis 138° C.If the procedure is otherwise identical, m-anisidyl isocyanate is used instead of p-fluorophenyl isocyanate and instead of N-m-hydroxyphenylcarbamic acid methyl ester, m-hydroxyphenylcarbamic acid butyn- (1) -yl- (3) -ester, 3- (3'-anisidylcarbamoyl) -oxyphenyl-isobutyn- (1) -yl- (3) -carbamate is obtained with the Mp. 135 to 138 ° C.
Nachfolgend sind einige der neuen Verbindungen aufgeführt und durch Schmelzpunkte charakterisiert, wobei R und R1 die verschiedenen Substituenten dieser Verbindungen bedeuten:Some of the new compounds are listed below and characterized by melting points, where R and R 1 mean the various substituents of these compounds:
Die folgenden Versuche beweisen die gute Wirkung der erfindungsgemäßen Verbindungen.The following tests demonstrate the good action of the compounds according to the invention.
Versuch 1Attempt 1
Im Gewächshaus wurden die Pflanzen Beta vulgaris (Rüben), Stellaria media (Vogelmiere), Chenopodium album (weißer Gänsefuß), Urtica urens (kleine Brennnessel), Matricaria chamomilla (Kamille), Sinapis arvensis (Ackersenf), Poa annua (einj. Rispengras) bei einer Wuchshöhe von 2 bis 10 cm im Nachauflaufverfahren und Gossypium sp. (Baumwolle), Zea mays (Mais) im Unterblattverfahren mit 2 kg 3-(4'-Fluorphenyl-carbamoyl)-oxyphenyl-methylcarbamat (I) je ha, dispergiert in 500 Liter Wasser behandelt. Nach 1 bis 2 Wochen konnte man feststellen, daß die Unkräuter Stellaria media, Chenopodium albu, Urtica urens, Matricaria chamomilla, Sinapis arvensis und Poa annua fast vollkommen abgestorben waren, während die Rüben, Baumwolle und Mais ohne Schaden weiterwuchsen.The plants Beta vulgaris (beets), Stellaria media (chickweed) and Chenopodium were grown in the greenhouse album (white goose foot), Urtica urens (small nettle), Matricaria chamomilla (chamomile), Sinapis arvensis (field mustard), Poa annua (aj. bluegrass) at a height of 2 to 10 cm in the post-emergence method and Gossypium sp. (Cotton), Zea mays (maize) in the undersheet method with 2 kg of 3- (4'-fluorophenyl-carbamoyl) -oxyphenyl-methylcarbamate (I) per hectare, dispersed in 500 liters of water treated. After 1 to 2 weeks you could see that the weeds Stellaria media, Chenopodium albu, Urtica urens, Matricaria chamomilla, Sinapis arvensis and Poa annua were almost completely dead, while the beets, cotton and corn without Damage continued to grow.
Versuch 2Attempt 2
Eine landwirtschaftliche Nutzfläche, die mit Stellaria media (Vogelmiere), Chenopodium album (weißer Gänsefuß), Urtica urens (kleine Brennessel), Matricaria chamomilla (Kamille), Sinapis arvensis (Ackersenf) und Poa annua (einj. Rispengras) bewachsen war, wurde bei einer Wuchshöhe der Unkräuter von 3 bis 7 cm mit 3-(4'-Fluorphenylcarbamoyl)-oxyphenyl-methylcarbamat (I) in einer Aufwandmenge von 5 kg Wirkstoff je ha dispergiert in 500 Liter Wasser gespritzt. Nach 5 bis 8 Tagen konnte man feststellen, daß die Unkräuter Stellaria media, Chenopodium album, Urtica urens, Matricaria chamomilla, Sinapis arvensis und Poa annua fast vollkommen abgestorben waren. Anschließend kann das Feld ohne Schaden für die Pflanzen neu bestellt werden.An agricultural area covered with Stellaria media (chickweed), Chenopodium album (whiter Goose foot), Urtica urens (small stinging nettle), Matricaria chamomilla (chamomile), Sinapis arvensis (field mustard) and Poa annua (aj. bluegrass) was overgrown, became at a stature height of the weeds from 3 to 7 cm with 3- (4'-fluorophenylcarbamoyl) oxyphenyl methylcarbamate (I) in one application rate of 5 kg of active ingredient per hectare dispersed in 500 liters of water. After 5 to 8 days you could see that the weeds Stellaria media, Chenopodium album, Urtica urens, Matricaria chamomilla, Sinapis arvensis and Poa annua were almost completely dead. Then the field can be used without Damage to the plants to be reordered.
Biologisch gleich wirksam wie I in Versuch 1 und 2 sind: 3-(3'-Anisidyl-carbamoyl)-oxyphenyl-isobutin-(l)-yl-(3)-carbamat, 3-(Tetrahydrodicyclopentadienyl-carbamoyl)-oxyphenyl-methylcarbamat. Biologically just as effective as I in experiments 1 and 2 are: 3- (3'-anisidyl-carbamoyl) -oxyphenyl-isobutyn- (l) -yl- (3) -carbamate, 3- (Tetrahydrodicyclopentadienyl-carbamoyl) -oxyphenyl-methylcarbamate.
bisuntil
until
184° C157 ° C
184 ° C
4'-J3'-CH 3
4'-J
1 2
1
-CH3 -CH 3
-CH 3
183155
183
«-Naphthyl«-Naphthyl
2-Methylcyclohexyl2-methylcyclohexyl
2-Äthylhexyl2-ethylhexyl
CyclooctylCyclooctyl
BenzylBenzyl
Tetrahydrodicyclo-Tetrahydrodicyclo-
pentadienylpentadienyl
-CH3 170bisl71°C-CH 3 170 to 71 ° C
-CH3 166 bis 167° C-CH 3 166 to 167 ° C
-CH3 Sirup-CH 3 syrup
-CH3 98 bis 100°C-CH 3 98 to 100 ° C
-CH3 132,5 bis 134° C-CH 3 132.5-134 ° C
-CH3 Sirup-CH 3 syrup
Versuch 3Attempt 3
Beim Vergleich der herbiziden Wirkung von neuen substituierten Diurethanen mit bekannten Herbiziden sind Verbindungen vom Typ der Carbaminsäureester heranzuziehen. Als wichtige Vertreter sind N-Phenyl-carbaminsäure-isopropylester (IPC, DT-PS 8 83 274), N-S-Chlorphenyl-carbaminsäure-isopropylester (CIPC, US-PS 26 95 225) und N-3-Chlorphenylcarbaminsäure-butin-l-yl-3-ester (BIPC, DT-PS 10 34912) zu nennen. Sie fanden als Einzelprodukte oder in Mischungen mit anderen herbiziden Komponenten limitierten Eingang in der landwirtschaftlichen und gärtnerischen Praxis. Die genannten Carbaminsäureester haben einerseits nur ein sehr enges Wirkungsspektrum und andererseits nur eine fragwürdige Selektivität bei den für diese Substanzen in Frage kommenden Kulturpflanzen. Die Präparate zeichnen sich aus durch ihre Residualwirkung bei Anwendung über den Boden (Vorauflaufanwendung). Sie besitzen ferner bei einigen Pflanzen eine herbizide Wirkung bei Blattbehandlung. Letztere ist jedoch auf Einzelfälle beschränkt. Die Vorteile der neuen Verbindungen werden in dem folgenden Versuch dargestellt. When comparing the herbicidal effect of new substituted diurethanes with known herbicides compounds of the carbamic acid ester type are to be used. As important representatives are N-phenyl-carbamic acid isopropyl ester (IPC, DT-PS 8 83 274), N-S-chlorophenyl carbamic acid isopropyl ester (CIPC, US Pat. No. 2,695,225) and N-3-chlorophenylcarbamic acid butyn-1-yl-3-ester (BIPC, DT-PS 10 34912). They found as individual products or in mixtures with other herbicidal components limited input in agricultural and horticultural practice. The carbamic acid esters mentioned on the one hand only have a very narrow spectrum of activity and on the other hand only a questionable one Selectivity in the crop plants coming into question for these substances. The preparations are characterized by their residual effect when applied above the ground (pre-emergence application). They also have a herbicidal effect on leaf treatment on some plants. The latter, however, is on Limited individual cases. The advantages of the new compounds are shown in the following experiment.
Die verwendeten Substanzen gehen aus den beigefügten Tabellen 1 und 2 hervor. Dasselbe gilt für die Aufwaridmengen in Aktivsubstanz je Hektar. Die Ausbringung erfolgte durch feinverteilende Spritzdüsen mit Dimethylformamid als Trägerstoff, worin die Substanzen jeweils emulgiert oder suspendiert waren. Als Versuchsgefäße dienten paraffmierte Pappbecher von 170 cm3 Inhalt. In diese wurde lehmiger Sand als Erdsubstrat gefüllt. .The substances used are shown in Tables 1 and 2 attached. The same applies to the amount of active ingredient added per hectare. It was applied through finely distributing spray nozzles with dimethylformamide as a carrier, in which the substances were each emulsified or suspended. Paraffinized paper cups with a capacity of 170 cm 3 were used as test vessels. Loamy sand was filled into this as a soil substrate. .
Die Einsaat der Testpflanzen erfolgte nach Arten getrennt flach. Die Vorauflaufbehandlung wurde sofort nach dem Säen getätigt. Die Blattspritzungen (Nachauflaufbehandlung) erfolgten bei Wuchshöhen von 3 bis 10 cm je nach Wuchsform der einzelnen Pflanzen.The test plants were sown flat, separated by species. The pre-emergence treatment was immediate made after sowing. The leaf spraying (post-emergence treatment) took place at heights of 3 to 10 cm depending on the habit of the individual plants.
Folgende Testpflanzen fanden Verwendung:The following test plants were used:
Lat. NameLat. Surname
Abkürzung
in Tab.abbreviation
in tab.
Deutscher NameGerman name
Solanum
nigrum
Veronica spp.
Zea maysSolanum
nigrum
Veronica spp.
Zea mays
Solan, nigr.Solan, nigr.
Veron. spp.
Zea maysVeron. spp.
Zea mays
Schwarzer
Nachtschatten
Ehrenpreisarten
MaisBlack
Nightshade
Speedwell types
Corn
ίο Die Versuchsdauer währte 4 Wochen. In dieser Zeit wurden die Töpfe gut feuchtgehalten. Sie standen in den kühlen und warmen Sektionen des Gewächshauses mit Temperaturbereichen von 10 bis 20° C und 18 bis 26° C. Die Bewertung wurde visuell nach dem Schema 0 bis 100 vorgenommen. Dabei bedeutete 0 = keine Schädigung, 100 = völlige Zerstörung der Pflanzen.ίο The experiment lasted 4 weeks. In this Time the pots were kept well moist. They stood in the cool and warm sections of the greenhouse with temperature ranges from 10 to 20 ° C and 18 to 26 ° C. The assessment was made visually the scheme 0 to 100 made. Here 0 = no damage, 100 = complete destruction of the plants.
ErgebnisResult
Die neuen Verbindungen unterscheiden sich herbologisch von den bekannten Carbaminsäureestern in folgenden Punkten:The new compounds differ herbologically from the known carbamic acid esters in following points:
1. Eine herbizide Wirkung der neuen Diurethane über den Boden existiert nicht oder ist so gering,1. A herbicidal effect of the new diurethanes via the soil does not exist or is so small that
daß für Kulturen, welche in vorher behandelte Flächen eingesät werden, keinerlei Beeinträchtigung der Keimung oder des Wuchses zu erwarten ist (Tabelle 1).that for crops which are sown in previously treated areas, no impairment whatsoever germination or growth is to be expected (Table 1).
2. Die herbizide Wirkung der neuen Verbindungen bei Blattbehandlung (Nachauflaufverfahren) gegenüber unerwünschtem Pflanzenwuchs ist intensiver pro Einheit Aktivsubstanz und breiter im erfaßbaren Artenspektrum als die der bekannten Substanzen (Tabelle 2). Besonders zu erwähnen sind hierbei die neuen Verbindungen Methylm-tetrahydrodicyclopentadienyl-carbamoyl-oxy-N-phenylcarbamat und Methyl-m-benzylcarbamoyl-oxy-N-phenylcarbamat. 2. The herbicidal effect of the new compounds in foliar treatment (post-emergence method) unwanted vegetation is more intense per unit of active ingredient and broader in the detectable spectrum of species than that of the known substances (Table 2). Particularly worth mentioning The new compounds are methylm-tetrahydrodicyclopentadienyl-carbamoyl-oxy-N-phenylcarbamate and methyl m-benzylcarbamoyl-oxy-N-phenylcarbamate.
Die neuen Verbindungen sind den bekannten Wirkstoffen überall da überlegen, wo eine Abtötung von bereits etablierten Unkräutern erfolgen soll und eine Residualwirkung entweder nicht verlangt oder gar abträglich ist.The new compounds are superior to the known active ingredients wherever they kill already established weeds should take place and a residual effect is either not required or at all is detrimental.
Vorauflaufwirkung bekannter Carbaminsäureester im Vergleich zu neuen DiurethanenPre-emergence effect of known carbamic acid esters compared to new diurethanes
Grundkörper der Diurethane <f \— NH — C — O—R1 Basic structure of the diurethanes <f \ - NH - C - O - R 1
O —CO —NH-R2 O —CO —NH-R 2
Substitutionen
R1 R2 Substitutions
R 1 R 2
-CH3 -CH 3
-CH,-CH,
Fortsetzung SubstitutionenContinued substitutions
CH3 CH 3
-CH,-CH,
R2 R 2
C2H5 C 2 H 5
-CH2-^A-CH 2 - ^ A
Substitutionen R1 R2 Substitutions R 1 R 2
Aufwand- Testpflanzen und Schädigung,
mengeEffort - test plants and damage,
lot
a.S.kg / ha
as
carotaDaucus
carota
maxGlycine
Max
anth.
annuusHeli
anth.
annuus
maysZea
mays
retr.Amar.
retr.
genic.Euph.
genic.
nigr.Solan,
nigr.
spp.Veron
spp.
4,02.0
4.0
105
10
3020th
30th
155
15th
9592.5
95
4535
45
8545
85
4025th
40
8060
80
4,02.0
4.0
77,550
77.5
47,540
47.5
1510
15th
92,590
92.5
9090
90
82,572.5
82.5
9595
95
9090
90
4,02.0
4.0
7550
75
1010
10
155
15th
9587.5
95
9090
90
9077.5
90
9082.5
90
9090
90
IPC (bekannt) CI PC (bekannt) BIPC (bekannt)IPC (known) CI PC (known) BIPC (known)
0 = Keine Schädigung. 100 = Totale Schädigung.0 = no damage. 100 = total damage.
Herbizide Wirksamkeit einiger neuer Diurethane im Vergleich zu bekannten Carbaminsäureestern BlattbehandlungHerbicidal effectiveness of some new diurethanes compared to known carbamic acid esters Leaf treatment
Grundkörper der DiurethaneBasic body of the diurethane
O
[ —C —O —R1 O
[—C —O —R 1
0 —CO —NH-R2 0 —CO —NH-R 2
SubstitutionenSubstitutions
R1 R2 R 1 R 2
Aufwand- % Schädigung der Testpflanzen mengeEffort-% damage to the test plants amount
IPC (bekannt)IPC (known)
Fortsetzungcontinuation
Substitutionen R1 Substitutions R 1
CIPC (bekannt)CIPC (known)
BIPC (bekannt)BIPC (known)
-CH,-CH,
-CH3 -CH 3
CH,CH,
CH,CH,
-CH,-CH,
Aufwand- % Schädigung der Testpflanzen mengeEffort-% damage to the test plants amount
hei.Euph.
hey
spp.Lamium
spp.
cham.Matric.
cham.
exalt.Sesb. .
exalt.
nigr.Solan,
nigr.
crus g.Echin.
crus g.
spp.I pom.
spp.
R1 R2 kg/ha
a.S.lot
R 1 R 2 kg / ha
as
2010
20th
4040
40
4040
40
9595
95
100
10
2020th
20th
8565
85
2,0 C 2 H 5 '. °
2.0
0 = Keine Schädigung. — = Keine Werte. 100 = Totale Schädigung.0 = no damage. - = No values. 100 = total damage.
Claims (2)
Priority Applications (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1966B0087883 DE1568138B2 (en) | 1966-07-06 | 1966-07-06 | DIURETHANES AND HERBICIDALS CONTAINING THEM |
| IL2821267A IL28212A (en) | 1966-07-06 | 1967-06-27 | Carbamoyloxyphenyl carbamates and their use as herbicides |
| GB3031167A GB1197788A (en) | 1966-07-06 | 1967-06-30 | Biscarbamates and Herbicides containing them |
| NL6709361A NL139521B (en) | 1966-07-06 | 1967-07-05 | PROCEDURE FOR PREPARING BISCARBAMATES, PROCEDURE FOR PREPARING HERBICIDE EFFECTIVENESS PREPARATIONS CONTAINING THESE BISCARBAMATES AS WELL AS MOLDED PREPARATIONS OBTAINED UNDER THIS PROCESS. |
| FR113222A FR1531794A (en) | 1966-07-06 | 1967-07-05 | Process for preparing dicarbamates |
| BE700942D BE700942A (en) | 1966-07-06 | 1967-07-05 | |
| SE10342/67A SE318557B (en) | 1966-07-06 | 1967-07-05 | |
| BR19108867A BR6791088D0 (en) | 1966-07-06 | 1967-07-06 | HERBICIDIC COMPOSITES PROCESS FOR MANUFACTURING THESE COMPOSITES AND THE BICARBAMATES THEREINABLE IN THEM |
| AT632267A AT277654B (en) | 1966-07-06 | 1967-07-06 | Herbicidal Mixture |
| ES342712A ES342712A1 (en) | 1966-07-06 | 1967-07-06 | Biscarbamates and Herbicides containing them |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1966B0087883 DE1568138B2 (en) | 1966-07-06 | 1966-07-06 | DIURETHANES AND HERBICIDALS CONTAINING THEM |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| DE1568138A1 DE1568138A1 (en) | 1970-01-08 |
| DE1568138B2 true DE1568138B2 (en) | 1976-07-01 |
Family
ID=6984001
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE1966B0087883 Granted DE1568138B2 (en) | 1966-07-06 | 1966-07-06 | DIURETHANES AND HERBICIDALS CONTAINING THEM |
Country Status (9)
| Country | Link |
|---|---|
| AT (1) | AT277654B (en) |
| BE (1) | BE700942A (en) |
| BR (1) | BR6791088D0 (en) |
| DE (1) | DE1568138B2 (en) |
| ES (1) | ES342712A1 (en) |
| GB (1) | GB1197788A (en) |
| IL (1) | IL28212A (en) |
| NL (1) | NL139521B (en) |
| SE (1) | SE318557B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1567164C2 (en) * | 1966-09-10 | 1985-03-07 | Schering AG, 1000 Berlin und 4709 Bergkamen | Herbicidal agents based on N-carbamoyloxyphenyl carbamates |
| DE2413933A1 (en) * | 1974-03-20 | 1975-09-25 | Schering Ag | DIURETHANE WITH SELECTIVE HERBICIDAL EFFECT |
| YU45662B (en) * | 1983-09-20 | 1992-07-20 | Berol Nobel (Suisse) S.A. | PROCEDURE FOR OBTAINING FENMEDIFAM OR DESMEDIFAM |
-
1966
- 1966-07-06 DE DE1966B0087883 patent/DE1568138B2/en active Granted
-
1967
- 1967-06-27 IL IL2821267A patent/IL28212A/en unknown
- 1967-06-30 GB GB3031167A patent/GB1197788A/en not_active Expired
- 1967-07-05 SE SE10342/67A patent/SE318557B/xx unknown
- 1967-07-05 BE BE700942D patent/BE700942A/xx unknown
- 1967-07-05 NL NL6709361A patent/NL139521B/en unknown
- 1967-07-06 AT AT632267A patent/AT277654B/en not_active IP Right Cessation
- 1967-07-06 ES ES342712A patent/ES342712A1/en not_active Expired
- 1967-07-06 BR BR19108867A patent/BR6791088D0/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| AT277654B (en) | 1970-01-12 |
| DE1568138A1 (en) | 1970-01-08 |
| IL28212A (en) | 1971-10-20 |
| BE700942A (en) | 1968-01-05 |
| GB1197788A (en) | 1970-07-08 |
| NL139521B (en) | 1973-08-15 |
| ES342712A1 (en) | 1969-01-01 |
| SE318557B (en) | 1969-12-15 |
| NL6709361A (en) | 1968-01-08 |
| BR6791088D0 (en) | 1973-12-26 |
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