CA2114699A1 - Selective herbicides based on n-azinyl-n'-(2-ethylthio- phenylsulphonyl)-ureas - Google Patents
Selective herbicides based on n-azinyl-n'-(2-ethylthio- phenylsulphonyl)-ureasInfo
- Publication number
- CA2114699A1 CA2114699A1 CA 2114699 CA2114699A CA2114699A1 CA 2114699 A1 CA2114699 A1 CA 2114699A1 CA 2114699 CA2114699 CA 2114699 CA 2114699 A CA2114699 A CA 2114699A CA 2114699 A1 CA2114699 A1 CA 2114699A1
- Authority
- CA
- Canada
- Prior art keywords
- methoxy
- ethylthio
- chlorine
- phenylsulphonyl
- fluorine
- 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.)
- Abandoned
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D521/00—Heterocyclic compounds containing unspecified hetero rings
-
- 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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
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- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Dentistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Selective herbicides based on N-azinyl-N'-(2-ethylthio-phenylsulphonyl)-ureas A b s t r a c t The invention relates to selective herbicides based on N-azinyl-N'-(2-ethylthio-phenylsulphonyl)-ureas of the general formula (I)
Description
211 ~3 The present invention relates to the use of N-azinyl-N'-(2-ethylthio-phenylsulphonyl)-ureas, some of which are known, as selective herbicides and to certain new N-azinyl-N'-(2-ethylthio-phenylsulphonyl)-ureas.
Various N-pyrimidinyl- and N-triazinyl-N'-(2-alkylthio-phenylsulphonyl)-ureas have been disclosed as potential herbicides, but have not acquired importance in practice as agents for selectively combating weeds (cf.
US-P 4127405, US-P 4169719, EP-A 35893 and JP-A 61060667 - cited in Chem. Abstracts 105:172513x).
It has now been found that N-azinyl-N'-(2-ethylthio-phenylsulphonyl)-ureas of the general formula (I) ~S~ X
N--~
~SO~-~OO-I;I~/ ~`Z
N
in which X represents hydrogen, halogen, C1-C3-alkyl (which is optionally substituted by fluorine, chlorine, ; methoxy or ethoxy), Cl-C3-alkoxy (which is optionally substituted by ~luorine, chlorine, methoxy or ethoxy), Cl-C3-alkylthio, C,-C3-alkylamino or di-(C,-C2-alkyl)-amino, Le A 29 573 211~9~
Y represents halogen, C,-C3-alkyl (which is optionally substituted by fluorine, chlorine, methoxy or ethoxy)~ C~-C3-alkoxy (which is optionally substitu-ted by fluorine, chlorine, methoxy or ethoxy), Cl-C,-alkylthio, Cl-C3-alkylamino or di-(C,-C2-alkyl)-amino, and Z represents nitrogen or the grouping C-Z', where Zl represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, methoxy or ethoxy, are particularly suitable for selectively combating weed in crop plants.
Formula (I) provides a general definition of the N-azinyl-N'-(2-ethylthio-phenylsulphonyl)-ureas to be used according to the invention. Preferably, in formula (I), X represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, methylthio, ethylthio, methylamino, ethylamino or dimethylamino, 0 Y represents fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoro-methoxy, methylthio, ethylthio, methylamino, ethyl-amino or dimethylamino, and Le A 29 573 - 2 ~
211~
Z represents nitrogen or the grouping C-Z1, where Z1 represents hydrogen, fluorine or chlorine.
A particularly preferred group of compounds of the formula (I) to be used according to the invention com-prises those in which X represents chlorine, methyl or methoxy, Y represents methyl or methoxy, and Z represents a C~ grouping.
Another particularly preferred group of compounds of the formula (I) to be used according to the invention com-prises those in which X represents methyl or methoxy, Y represents methyl or methoxy and ~ -Z represents nitrogen.
Examples of the compounds of the formula (I) to be used according to the invention are listed in the following ~-Table 1.
' ' ' ,~ ~ , Le A 29 573 - 3 ~
.~
211~3~) ,~s C,~ ~ ' ~SO2-N~C~ Z
Table 1: Examples of the compounds of the formula ( I ) ~- . _ Ex. No. X Y Z Melting point ( C) _ _ _ 4 CH3C~3 CH 187 _ _ ...... _ . 6 Cl OCH3 CH 16 2 With the exception of N- ( 4, 6-dimethoxy-s-triazin-2-yl ) -N ' - ( 2 -ethylthio-phenyl sulphonyl ) -urea ( cf .
JP-A 61060667 - cited in Chem. Abstracts 105:172513x~, the N-azinyl-N ' - ( 2-ethylthio-phenylsulphonyl ) -ureas of the f ormula ( I ) are not yet known f rom the literature and, as new substances, they form the subject matter of : -the present application. - -In particular the compounds listed in Table l as Examples :
2, 3, 4, 5 and 6 are claimed as new substances.
Le A ? 9 5 7 3 - 4 - ; `
: .
,-, ' , , ., . ~ ' 211 ~39 The following compounds o~ the formula (I) may be men-tioned as particularly preferred new substances:
N-(4,6-dimethoxy-pyrimidin-2-yl)-N'-(2-ethylthio-phenyl-sulphonyl)-urea, N-(4,6-dimethyl-pyrimidin-2-yl)-N'-(2-ethylthio-phenylsulphonyl)-urea, N-(4-methoxy-6-methyl-pyrimidin-2-yl)-N'-(2-ethylthio-phenylsul-phonyl)-urea and N-(4-chloro-6-methoxy-pyrimidin-2-yl)-N'-(2-ethylthio-phenylsulphonyl)-urea.
The N-azinyl-N'-(2-ethylthio-phenylsulphonyl)-ureas of the formula (I) are obtained by a process in which ~ a) 2-ethylthio-benzenesulphonamide of the formula (II) ~S C2~
., I (Il) SO2~
is reacted with a chloroformic acid ester of the general formula (III) C1-CO-O-R (III) in which R represents alkyl (in particular methyl or ethyl), aralkyl (in particular benzyl) or aryl (in particular phenyl), Le A 29 573 - 5 -211~9 if appropriate in the presence of an acid acceptor, such as, for example, triethylamine or pyridine, and if appropriate in the presence of a diluent, such as, for example, acetonitrile, at temperatures between 0C and 100C and the sulphonylurethanes (sulphonylcarbamates) formed in this reaction, of the general formula (IV) ~S C2~
~I T ~
~ S~-NHK3~R
in which R has the abovementioned meaning, are reacted - in ~itu or after intermediate isolation -with an aminoazine of the general formula (V) _~,X
~/ Z ~
in which .
X, Y and Z have the abovementioned meaning, and with an acid, such as, for example, Le A 29 573 - 6 ----` 2 1 1 ~ 5 ~ 9 methanesulphonic acid, if appropriate in the presence of a diluent, such as, for example, acetonitrile, at temperatures between 0C and 100C
(cf. the Preparation Examples), or by a procedure in which (b~ 2-ethylthio-phenylsulphonyl isocyanate of the formula (VI) .-~S~
Il ~ ~`S4-N~C~O
is reacted with an aminoazine of the general formula (V) ~N~J Z
in which X, Y and Z have the abovementioned meaning, if appropriate in the presence of a diluent, such as, for example, acetonitrile, at temperatures between 20C and 120C (cf. the Preparation . ~xamples~.
The starting substances of the formulae (II), (III), (V) ~ :-and (VI) are known and/or can he prepared by processes Le A 29 5?3 ,. ~'` -~ ' . ;`
2114~
which are known per se (cf. JP-A 61060667 - cited in Chem. Abstracts 105:172513x; Preparation Examples).
The active compounds according to the invention can be used as defoliants, desiccants, agents for destroying broad-leaved plants and, especially, as weed-killers. By weeds, in the broadest sense, there are to be understood all plants which grow in locations where they are undesired. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.
The active compounds according to the invention can be used, for example, in connection with the following plants:
Dicotyledon weeds of the aenera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchu~, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus and Taraxacum.
Dicotvledon cultures of the qenera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.
Le A 29 573 - 8 -2114~9 Monocotyledon weeds of the qenera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleu~ine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and Apera.
Monocotvledon cultures of the qenera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium.
However, the use of the active compounds according to the invention is in no way restricted to these genera, but also extends in the same manner to other plants.
The compounds are suitable, depending on the concentra-tion, for the total combating of weeds, for example on industrial terrain and rail tracks, and on paths and squares with or without trees planted. Equally, the compounds can be employed for combating weeds in peren-nial cultures, for example forests, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hopfields, on decorative lawns and sporting turf, on meadowland, and ; fcr the selective combating of weeds in annual cultures.
The compounds of the formula (I) according to the inven-tion are particularly suitable for selectively combating Le A 29 573 - 9 ~
:, .
. -211~
monocotyledon and dicotyledon weeds in monocotyledon crops both by the pre-emergence and by the post-emergence method.
The active compounds can be converted into the customary formulations, such as solutions, emulqions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspension-emulsion concentra-tes, natural and synthetic materials impregnated with active compound, and very fine capsules in polymeric substances.
These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is liquid solvents and/or solid carrier~, optionally with the use of surface-active agents, that is emulsify-ing agents and/or dispersing agents and/or foam-forming agents. : -:
In the case of the use of water as an extender, organic iolvents can, for example, also be used as auxiliary solvents. As liquid solvents, there are suitable in the main: aromaticsi, such as xylene, toluene or alkyl-naphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloro-ethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl Le A 29 573 - 10 -211~
isobutyl ketone or cyclohexanone, strongly polar sol-vents, such as dimethylformamide and dimethyl sulphoxide, as well as water.
As solid carriers there are suitable:
S for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly disperse silica, alumina and silicates, as solid carriers for granules there are suitable: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; as emulsifying andtor foam-forming agents there are suitable: for example non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates as well as albumen hydrolysis products; as dispersing agents there are suitable: for example lignin-sulphite waste liquors and methylcellulose.
Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latexes, such as gum arabic~ polyvinyl alcohol and polyvinyl acetatej as well as natural phospholipids, such Le A 29 573 211~39 as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Further additive~ can be mineral and vegetable oils.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dye-stuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.
For controlling weeds, the active compounds according to the invention, as such or in the form of their for-mulations, can also be used as mixtures with knownherbicides, finished formulations or tank mixes being possible.
.
Suitable herbicides for the mixture~ are known herbi-cides, for example anilides such as, for example, diflu-fenican and propanil; arylcarboxylic acids such as, forexample, dichloropicolinic acid, dicamba and picloram;
aryloxyalkanoic acids such as, for example, 2,4 D, 2,4 DB, 2,4 DP, fluroxypyr, MCPA, MCPP and triclopyr; aryl-oxy-phenoxy-alkanoic esters such as, for example, diclo-fop-methyl, fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl and quizalofop-ethyl; azinones such as, for Le A 29 573 - 12 -211~
example, chloridazon and norflurazon; carbamates such as, for example, chlorpropham, desmedipham, phenmedipham and propham; chloroacetanilides such as, for example, ala-chlor, acetochlor, butachlor, metazachlor, metolachlor, pretilachlor and propachlor; dinitroanilines such as, for example, oryzalin, pendimethalin and trifluralin; di-phenyl ethers such as, for example, acifluorfen, bifenox, fluoroglycofen, fomesafen, halosaen, lactofen and oxyfluorfen; ureas such as, for example, chlortoluron, diuron, fluometuron, isoproturon, linuron and methabenz-thiazuron; hydroxylamines such as, for example, alloxy-dim, clethodim, cycloxydim, sethoxydim and tralkoxydim;
imidazolinones such as, for example, imazethapyr, imaza-methabenz, imazapyr and imazaquin; nitriles such as, for 15 example, bromoxynil, dichlobenil and ioxynil; oxyacet-amides such as, for example, mefenacet; sulphonylureas such as, for example, amidosulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, metsulfuron-methyl, nicosulfuron, primisulfuron, pyrazo-sulfuron-ethyl, thifensulfuron-methyl, triasulfuran and tribenuron-methyl; thiocarbamates such as, for example, butylate, cycloate, di-allate, EPTC, esprocarb, molinate, prosulfocarb, thiobencarb and tri-allate; triazines such as, for example, atrazine, cyanazine, simazine, sime-tryne, terbutryne and terbutylazine; triazinones such as, for example, hexazinone, metamitron and metribuzin;
others such as, for example, aminotriazole, benfuresate, bentazone, cinmethylin, clomazone, clopyralid, difenzo-quat, dithiopyr, ethofumesate, fluorochloridone, glufo-sinate, glyphosate, isoxaben, pyridate, quinchloraç, Le A 29 573 - 13 -2114~9~
quinmerac, sulphosate and tridiphane.
Mixtures with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellents, plant nutrients and agents which improve soil structure, are also possible.
The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules.
They are used in the customary manner, for example by watering, spraying, atomizing or scattering.
The active compounds according to the invention can be applied either before or after emergence of the plants.
They can also be incorporated into the soil before sowing.
The amount of active compound used can vary within a substantial range. It depends essentially on the nature of the desired effect. In general, the amounts used are between 5 g and 250 g of active compound per hectare of soil surface, preferably between 15 g and 150 g per ha.
The preparation and use of the active compounds according to the invention can be seen from the following examples.
Le A 29 573 - 14 -,j A . ~ : ' , ~ ' ' ' 2ll~u3 Use ExamDles:
Example A
Pre-emergence test Solvent: 5 parts by weight of acetone Emulsifier: l part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, l part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
Seeds of the test plants are sown in normal soil and, after 24 hours, watered with the preparation of the active compound. It is expedient to keep constant the amount of water per unit area. The concentration of the active compound in the preparation is of no importance, only the amount of active compound applied per unit area being decisive. After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control. The figures denote:
0~ - no action (like untreated control) 100% = total destruction In this test, for example, the compounds of Example numbers 2 and 3 in ~able 1 exhibit a clear superiority in Le A 29 573 - 15 -211~3~
activity compared with the prior art, coupled with a very good crop plant selectivity, in particular with respect to wheat.
Le A 29 573 - 16 211~39 o o t~
P~ , , Id ~ o , - -~q ,., ~ o~ o ~, ~ ,.
o . ::
I:n ~ , ~
~ ~ _ -- -- -, -. -.co .,~
0 a-~ Y ~U ~ ~
.. ~r 0 ~ ~ ~
Z ~ Z; ' 14 P~ ~ ~ ~ g. o~
Le A 29 573 - 17 - ~ ~
2114~9 ~q 'a~
C ~ o U~
o o Ct~ o ,~ o .~
o o :~
,c ~ ~ ~o o o ~
~ , Ii ,~ ~ ~ C
a~
Y
Le A 29 573 - 18 - -2 ~ 9 Ex~mple ~
Post-emergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
Test plants which have a height of 5-15 cm are sprayed with the preparation of the active compound in such a way as to apply the particular amounts of active compound desired per unit area. The concentration of the spray liquor is so chosen that the particular amounts of active compound desired are applied in 2,000 l of water/ha.
After three weeks, the degree of damage to the plants is rated in % damage in compari60n to the development of the untreated control. The figures denote:
0% = no action (like untreated control) 100% z total destruction In this test, for example, the compounds of Example number~ 1, 2, 3, 4 and 5 in Table 1 show a clear superiority in activity compared with the prior art, Le A 29 573 - 19 ~
: ':
- '. ' ~ ~ . :
2 ~ 9 ~
coupled with a very good crop plant selectivity, in particular with respect to wheat.
Le A 29 573 - 20 - :-21~ 4~39 E
o~ o æ O
U~ 0 æ ~ ~
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8 o _ ., C~
o o 3~
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~ o ~ q~
Le A 29 573 - 21 -.. , ~ . .. . . .
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O~ O
tq , ' O C:~ -O
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~ e ~ e Le A 29 573 - 25 ~
- 211~
Preparation Examples:
Preparation of the compound listed as Example 5 in Table 1 :
~ S~ 0~
~SO2 N~CO ~/~
16 g (O.1 mol) of phenyl chloroformate are added to a mixture of 21.8 g (0.1 mol) of 2-ethylthio-benzene-sulphonamide, 22 g of triethylamine and 200 ml of aceto-nitrile at 20C to 35C, while stirring, and the mixture is stirred for 30 minutes. 13.9 g tO.l mol) of 2-amino-4-methoxy-6-methylpyrimidine and 10 g of methanesulphonic acid are then added in succession. ~he reaction mixture is stirred at 20C to 30C for 60 minutes and then diluted slowly to about twice the volume with water, and the crystalline product i8 isolated by filtration with suction.
24.1 g (63% of theory) of N-(4-methoxy-6-methyl-pyrimidin-2-yl)-N~-(2-ethylthio-phenylsulphonyl)-urea of melting point 190C are obtained.
Preparation of the compound listed as ExamPle 2 in Table 1:
Le A 29 573 - 26 -,' :
21~639 S~
N ~
~ ~SO~h~ ~ ~ / N
A mixture of 14 g (0.1 mol) of 2-amino-4-methcxy-6-methyl-s-triazine, 40 g (0.16 mol) of 2-ethylthio-phenylsulphonyl isocyanate and 200 ml of acetonitrile is stirred at 80C for 3 hours. After cooling to room temperature (about 20C), the product obtained as crystals is isolated by filtration with suction.
28.8 g (75% of theory) of N-(4-methoxy-6-methyl-s-triazin-2-yl)-N~-(2-ethylthio-phenylsulphonyl)-urea of melting point 169C are obtained.
Preparation of 2-ethylthio-phenylsulphonyl isocyanate: -~S~, ~SO2-N~O
50 ml of chlorosulphonyl isocyanate are added to a mixture of 87 g (0.4 mol) of 2-ethylthio-benzenesulphonamide and 300 ml of chlorobenzene at 90C, while stirring, and the entire mixture is then stirred at 110C for 3 hours. After cooling, the mixture is filtered and the filtrate is concentrated carefully under reduced pressure. -~ -Le A 29 573 - 27 -- ~ 2 ~
77.8 g (80% of theory) of 2-ethylthio-phenylsulphonyl-isocyanate are obtained (crude product, which can be employed directly for the reaction according to Example 2, but can also be purified by distillation).
~oiling point: 147C (at 0.8 mbar).
Le A 29 573 - 28 ~
'~'' '~
Various N-pyrimidinyl- and N-triazinyl-N'-(2-alkylthio-phenylsulphonyl)-ureas have been disclosed as potential herbicides, but have not acquired importance in practice as agents for selectively combating weeds (cf.
US-P 4127405, US-P 4169719, EP-A 35893 and JP-A 61060667 - cited in Chem. Abstracts 105:172513x).
It has now been found that N-azinyl-N'-(2-ethylthio-phenylsulphonyl)-ureas of the general formula (I) ~S~ X
N--~
~SO~-~OO-I;I~/ ~`Z
N
in which X represents hydrogen, halogen, C1-C3-alkyl (which is optionally substituted by fluorine, chlorine, ; methoxy or ethoxy), Cl-C3-alkoxy (which is optionally substituted by ~luorine, chlorine, methoxy or ethoxy), Cl-C3-alkylthio, C,-C3-alkylamino or di-(C,-C2-alkyl)-amino, Le A 29 573 211~9~
Y represents halogen, C,-C3-alkyl (which is optionally substituted by fluorine, chlorine, methoxy or ethoxy)~ C~-C3-alkoxy (which is optionally substitu-ted by fluorine, chlorine, methoxy or ethoxy), Cl-C,-alkylthio, Cl-C3-alkylamino or di-(C,-C2-alkyl)-amino, and Z represents nitrogen or the grouping C-Z', where Zl represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, methoxy or ethoxy, are particularly suitable for selectively combating weed in crop plants.
Formula (I) provides a general definition of the N-azinyl-N'-(2-ethylthio-phenylsulphonyl)-ureas to be used according to the invention. Preferably, in formula (I), X represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, methylthio, ethylthio, methylamino, ethylamino or dimethylamino, 0 Y represents fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoro-methoxy, methylthio, ethylthio, methylamino, ethyl-amino or dimethylamino, and Le A 29 573 - 2 ~
211~
Z represents nitrogen or the grouping C-Z1, where Z1 represents hydrogen, fluorine or chlorine.
A particularly preferred group of compounds of the formula (I) to be used according to the invention com-prises those in which X represents chlorine, methyl or methoxy, Y represents methyl or methoxy, and Z represents a C~ grouping.
Another particularly preferred group of compounds of the formula (I) to be used according to the invention com-prises those in which X represents methyl or methoxy, Y represents methyl or methoxy and ~ -Z represents nitrogen.
Examples of the compounds of the formula (I) to be used according to the invention are listed in the following ~-Table 1.
' ' ' ,~ ~ , Le A 29 573 - 3 ~
.~
211~3~) ,~s C,~ ~ ' ~SO2-N~C~ Z
Table 1: Examples of the compounds of the formula ( I ) ~- . _ Ex. No. X Y Z Melting point ( C) _ _ _ 4 CH3C~3 CH 187 _ _ ...... _ . 6 Cl OCH3 CH 16 2 With the exception of N- ( 4, 6-dimethoxy-s-triazin-2-yl ) -N ' - ( 2 -ethylthio-phenyl sulphonyl ) -urea ( cf .
JP-A 61060667 - cited in Chem. Abstracts 105:172513x~, the N-azinyl-N ' - ( 2-ethylthio-phenylsulphonyl ) -ureas of the f ormula ( I ) are not yet known f rom the literature and, as new substances, they form the subject matter of : -the present application. - -In particular the compounds listed in Table l as Examples :
2, 3, 4, 5 and 6 are claimed as new substances.
Le A ? 9 5 7 3 - 4 - ; `
: .
,-, ' , , ., . ~ ' 211 ~39 The following compounds o~ the formula (I) may be men-tioned as particularly preferred new substances:
N-(4,6-dimethoxy-pyrimidin-2-yl)-N'-(2-ethylthio-phenyl-sulphonyl)-urea, N-(4,6-dimethyl-pyrimidin-2-yl)-N'-(2-ethylthio-phenylsulphonyl)-urea, N-(4-methoxy-6-methyl-pyrimidin-2-yl)-N'-(2-ethylthio-phenylsul-phonyl)-urea and N-(4-chloro-6-methoxy-pyrimidin-2-yl)-N'-(2-ethylthio-phenylsulphonyl)-urea.
The N-azinyl-N'-(2-ethylthio-phenylsulphonyl)-ureas of the formula (I) are obtained by a process in which ~ a) 2-ethylthio-benzenesulphonamide of the formula (II) ~S C2~
., I (Il) SO2~
is reacted with a chloroformic acid ester of the general formula (III) C1-CO-O-R (III) in which R represents alkyl (in particular methyl or ethyl), aralkyl (in particular benzyl) or aryl (in particular phenyl), Le A 29 573 - 5 -211~9 if appropriate in the presence of an acid acceptor, such as, for example, triethylamine or pyridine, and if appropriate in the presence of a diluent, such as, for example, acetonitrile, at temperatures between 0C and 100C and the sulphonylurethanes (sulphonylcarbamates) formed in this reaction, of the general formula (IV) ~S C2~
~I T ~
~ S~-NHK3~R
in which R has the abovementioned meaning, are reacted - in ~itu or after intermediate isolation -with an aminoazine of the general formula (V) _~,X
~/ Z ~
in which .
X, Y and Z have the abovementioned meaning, and with an acid, such as, for example, Le A 29 573 - 6 ----` 2 1 1 ~ 5 ~ 9 methanesulphonic acid, if appropriate in the presence of a diluent, such as, for example, acetonitrile, at temperatures between 0C and 100C
(cf. the Preparation Examples), or by a procedure in which (b~ 2-ethylthio-phenylsulphonyl isocyanate of the formula (VI) .-~S~
Il ~ ~`S4-N~C~O
is reacted with an aminoazine of the general formula (V) ~N~J Z
in which X, Y and Z have the abovementioned meaning, if appropriate in the presence of a diluent, such as, for example, acetonitrile, at temperatures between 20C and 120C (cf. the Preparation . ~xamples~.
The starting substances of the formulae (II), (III), (V) ~ :-and (VI) are known and/or can he prepared by processes Le A 29 5?3 ,. ~'` -~ ' . ;`
2114~
which are known per se (cf. JP-A 61060667 - cited in Chem. Abstracts 105:172513x; Preparation Examples).
The active compounds according to the invention can be used as defoliants, desiccants, agents for destroying broad-leaved plants and, especially, as weed-killers. By weeds, in the broadest sense, there are to be understood all plants which grow in locations where they are undesired. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.
The active compounds according to the invention can be used, for example, in connection with the following plants:
Dicotyledon weeds of the aenera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchu~, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus and Taraxacum.
Dicotvledon cultures of the qenera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.
Le A 29 573 - 8 -2114~9 Monocotyledon weeds of the qenera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleu~ine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and Apera.
Monocotvledon cultures of the qenera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium.
However, the use of the active compounds according to the invention is in no way restricted to these genera, but also extends in the same manner to other plants.
The compounds are suitable, depending on the concentra-tion, for the total combating of weeds, for example on industrial terrain and rail tracks, and on paths and squares with or without trees planted. Equally, the compounds can be employed for combating weeds in peren-nial cultures, for example forests, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hopfields, on decorative lawns and sporting turf, on meadowland, and ; fcr the selective combating of weeds in annual cultures.
The compounds of the formula (I) according to the inven-tion are particularly suitable for selectively combating Le A 29 573 - 9 ~
:, .
. -211~
monocotyledon and dicotyledon weeds in monocotyledon crops both by the pre-emergence and by the post-emergence method.
The active compounds can be converted into the customary formulations, such as solutions, emulqions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspension-emulsion concentra-tes, natural and synthetic materials impregnated with active compound, and very fine capsules in polymeric substances.
These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is liquid solvents and/or solid carrier~, optionally with the use of surface-active agents, that is emulsify-ing agents and/or dispersing agents and/or foam-forming agents. : -:
In the case of the use of water as an extender, organic iolvents can, for example, also be used as auxiliary solvents. As liquid solvents, there are suitable in the main: aromaticsi, such as xylene, toluene or alkyl-naphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloro-ethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl Le A 29 573 - 10 -211~
isobutyl ketone or cyclohexanone, strongly polar sol-vents, such as dimethylformamide and dimethyl sulphoxide, as well as water.
As solid carriers there are suitable:
S for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly disperse silica, alumina and silicates, as solid carriers for granules there are suitable: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; as emulsifying andtor foam-forming agents there are suitable: for example non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates as well as albumen hydrolysis products; as dispersing agents there are suitable: for example lignin-sulphite waste liquors and methylcellulose.
Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latexes, such as gum arabic~ polyvinyl alcohol and polyvinyl acetatej as well as natural phospholipids, such Le A 29 573 211~39 as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Further additive~ can be mineral and vegetable oils.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dye-stuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.
For controlling weeds, the active compounds according to the invention, as such or in the form of their for-mulations, can also be used as mixtures with knownherbicides, finished formulations or tank mixes being possible.
.
Suitable herbicides for the mixture~ are known herbi-cides, for example anilides such as, for example, diflu-fenican and propanil; arylcarboxylic acids such as, forexample, dichloropicolinic acid, dicamba and picloram;
aryloxyalkanoic acids such as, for example, 2,4 D, 2,4 DB, 2,4 DP, fluroxypyr, MCPA, MCPP and triclopyr; aryl-oxy-phenoxy-alkanoic esters such as, for example, diclo-fop-methyl, fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl and quizalofop-ethyl; azinones such as, for Le A 29 573 - 12 -211~
example, chloridazon and norflurazon; carbamates such as, for example, chlorpropham, desmedipham, phenmedipham and propham; chloroacetanilides such as, for example, ala-chlor, acetochlor, butachlor, metazachlor, metolachlor, pretilachlor and propachlor; dinitroanilines such as, for example, oryzalin, pendimethalin and trifluralin; di-phenyl ethers such as, for example, acifluorfen, bifenox, fluoroglycofen, fomesafen, halosaen, lactofen and oxyfluorfen; ureas such as, for example, chlortoluron, diuron, fluometuron, isoproturon, linuron and methabenz-thiazuron; hydroxylamines such as, for example, alloxy-dim, clethodim, cycloxydim, sethoxydim and tralkoxydim;
imidazolinones such as, for example, imazethapyr, imaza-methabenz, imazapyr and imazaquin; nitriles such as, for 15 example, bromoxynil, dichlobenil and ioxynil; oxyacet-amides such as, for example, mefenacet; sulphonylureas such as, for example, amidosulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, metsulfuron-methyl, nicosulfuron, primisulfuron, pyrazo-sulfuron-ethyl, thifensulfuron-methyl, triasulfuran and tribenuron-methyl; thiocarbamates such as, for example, butylate, cycloate, di-allate, EPTC, esprocarb, molinate, prosulfocarb, thiobencarb and tri-allate; triazines such as, for example, atrazine, cyanazine, simazine, sime-tryne, terbutryne and terbutylazine; triazinones such as, for example, hexazinone, metamitron and metribuzin;
others such as, for example, aminotriazole, benfuresate, bentazone, cinmethylin, clomazone, clopyralid, difenzo-quat, dithiopyr, ethofumesate, fluorochloridone, glufo-sinate, glyphosate, isoxaben, pyridate, quinchloraç, Le A 29 573 - 13 -2114~9~
quinmerac, sulphosate and tridiphane.
Mixtures with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellents, plant nutrients and agents which improve soil structure, are also possible.
The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules.
They are used in the customary manner, for example by watering, spraying, atomizing or scattering.
The active compounds according to the invention can be applied either before or after emergence of the plants.
They can also be incorporated into the soil before sowing.
The amount of active compound used can vary within a substantial range. It depends essentially on the nature of the desired effect. In general, the amounts used are between 5 g and 250 g of active compound per hectare of soil surface, preferably between 15 g and 150 g per ha.
The preparation and use of the active compounds according to the invention can be seen from the following examples.
Le A 29 573 - 14 -,j A . ~ : ' , ~ ' ' ' 2ll~u3 Use ExamDles:
Example A
Pre-emergence test Solvent: 5 parts by weight of acetone Emulsifier: l part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, l part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
Seeds of the test plants are sown in normal soil and, after 24 hours, watered with the preparation of the active compound. It is expedient to keep constant the amount of water per unit area. The concentration of the active compound in the preparation is of no importance, only the amount of active compound applied per unit area being decisive. After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control. The figures denote:
0~ - no action (like untreated control) 100% = total destruction In this test, for example, the compounds of Example numbers 2 and 3 in ~able 1 exhibit a clear superiority in Le A 29 573 - 15 -211~3~
activity compared with the prior art, coupled with a very good crop plant selectivity, in particular with respect to wheat.
Le A 29 573 - 16 211~39 o o t~
P~ , , Id ~ o , - -~q ,., ~ o~ o ~, ~ ,.
o . ::
I:n ~ , ~
~ ~ _ -- -- -, -. -.co .,~
0 a-~ Y ~U ~ ~
.. ~r 0 ~ ~ ~
Z ~ Z; ' 14 P~ ~ ~ ~ g. o~
Le A 29 573 - 17 - ~ ~
2114~9 ~q 'a~
C ~ o U~
o o Ct~ o ,~ o .~
o o :~
,c ~ ~ ~o o o ~
~ , Ii ,~ ~ ~ C
a~
Y
Le A 29 573 - 18 - -2 ~ 9 Ex~mple ~
Post-emergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
Test plants which have a height of 5-15 cm are sprayed with the preparation of the active compound in such a way as to apply the particular amounts of active compound desired per unit area. The concentration of the spray liquor is so chosen that the particular amounts of active compound desired are applied in 2,000 l of water/ha.
After three weeks, the degree of damage to the plants is rated in % damage in compari60n to the development of the untreated control. The figures denote:
0% = no action (like untreated control) 100% z total destruction In this test, for example, the compounds of Example number~ 1, 2, 3, 4 and 5 in Table 1 show a clear superiority in activity compared with the prior art, Le A 29 573 - 19 ~
: ':
- '. ' ~ ~ . :
2 ~ 9 ~
coupled with a very good crop plant selectivity, in particular with respect to wheat.
Le A 29 573 - 20 - :-21~ 4~39 E
o~ o æ O
U~ 0 æ ~ ~
~ ~ ~ O
~ O ~
U~
8 o _ ., C~
o o 3~
0 .C
O
,~, o ,: -rl h _I
Q
D~
U
~ o ~ q~
Le A 29 573 - 21 -.. , ~ . .. . . .
. . , ~ .
2 ~ 3 9 Q) Cq æ O
O
O
O~ O
tq , ' O C:~ -O
o 00 Q) 5~ _ .
_ _ ~ Q~
a) _, ~ D. . -, la ~ ~u ~ 3 o o , ~:
Le A 29 573 - 22 ~
21~39 o o o U~ "
,1 C~ o o o a o , -~'-,'~
e ~ v~
~CO 'O - - ::
e~ rl : ~:
_I
11~ ~ - ' ':
7~
31 Y I ~ ~w~ y Le A 29 573 - 23 -211~
U~ o U~
X~
~, o~ o C
,, ~ ~ o ~ o o~ ~
U~
o~
a .~ o o ;~ ::
o .:
æ
..
o 3 ~
~ -~o . . ~ ~ ô
Z~Z ~Z ~D
O O R ~: :
Le A 29 573 - 24 - -- ~ , .,: ; ., ., - , 2 1 ~
E
~1 s o o ~ O ~D
x o~ o "
U~ : ~ `
o . , ~,.
. : ~ ~
o ' :-'-' ~ --U~~ ~ o O Q~ ~
~ ~ ~:
a ~ . .
.' ~u ~ ~' ,~
Z~Z Z~Z
W ~ Z ~ Z ~
~ e ~ e Le A 29 573 - 25 ~
- 211~
Preparation Examples:
Preparation of the compound listed as Example 5 in Table 1 :
~ S~ 0~
~SO2 N~CO ~/~
16 g (O.1 mol) of phenyl chloroformate are added to a mixture of 21.8 g (0.1 mol) of 2-ethylthio-benzene-sulphonamide, 22 g of triethylamine and 200 ml of aceto-nitrile at 20C to 35C, while stirring, and the mixture is stirred for 30 minutes. 13.9 g tO.l mol) of 2-amino-4-methoxy-6-methylpyrimidine and 10 g of methanesulphonic acid are then added in succession. ~he reaction mixture is stirred at 20C to 30C for 60 minutes and then diluted slowly to about twice the volume with water, and the crystalline product i8 isolated by filtration with suction.
24.1 g (63% of theory) of N-(4-methoxy-6-methyl-pyrimidin-2-yl)-N~-(2-ethylthio-phenylsulphonyl)-urea of melting point 190C are obtained.
Preparation of the compound listed as ExamPle 2 in Table 1:
Le A 29 573 - 26 -,' :
21~639 S~
N ~
~ ~SO~h~ ~ ~ / N
A mixture of 14 g (0.1 mol) of 2-amino-4-methcxy-6-methyl-s-triazine, 40 g (0.16 mol) of 2-ethylthio-phenylsulphonyl isocyanate and 200 ml of acetonitrile is stirred at 80C for 3 hours. After cooling to room temperature (about 20C), the product obtained as crystals is isolated by filtration with suction.
28.8 g (75% of theory) of N-(4-methoxy-6-methyl-s-triazin-2-yl)-N~-(2-ethylthio-phenylsulphonyl)-urea of melting point 169C are obtained.
Preparation of 2-ethylthio-phenylsulphonyl isocyanate: -~S~, ~SO2-N~O
50 ml of chlorosulphonyl isocyanate are added to a mixture of 87 g (0.4 mol) of 2-ethylthio-benzenesulphonamide and 300 ml of chlorobenzene at 90C, while stirring, and the entire mixture is then stirred at 110C for 3 hours. After cooling, the mixture is filtered and the filtrate is concentrated carefully under reduced pressure. -~ -Le A 29 573 - 27 -- ~ 2 ~
77.8 g (80% of theory) of 2-ethylthio-phenylsulphonyl-isocyanate are obtained (crude product, which can be employed directly for the reaction according to Example 2, but can also be purified by distillation).
~oiling point: 147C (at 0.8 mbar).
Le A 29 573 - 28 ~
'~'' '~
Claims (23)
1. A herbicidal composition comprising at least one N-azinyl-N'-(2-ethylthio-phenylsulphonyl)-urea of the formula (I) (I) in which X represents hydrogen, halogen, C1-C3-alkyl (which is optionally substituted by fluorine, chlorine, methoxy or ethoxy), C1-C3-alkoxy (which is optionally substituted by fluorine, chlorine, methoxy or ethoxy), C1-C3-alkylthlo, C1-C3-alkylamino or di-(C1-C2-alkyl)-amino, Y represents halogen, C1-C3-alkyl (which is optionally substituted by fluorine, chlorine, methoxy or ethoxy), C1-C3-alkoxy (which is optionally substituted by fluorine, chlorine, methoxy or ethoxy),C1-C3-alkylthio, C1-C3-alkylamino or di-(C1-C2-alkyl)-amino, and Z represents nitrogen or the grouping C-Z1, where Z1 represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, methoxy or in admixture with a suitable diluent or carrier.
2. A composition according to Claim 1, comprising an N-azinyl-N'-(2-ethylthio-phenylsulphonyl)-urea of the formula (I) in which X represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, methylthio, ethylthio, methylamino, ethylamino or dimethylamino, Y represents fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, methylthio, ethylthio, methylamino, ethylamino or dimethylamino, and Z represents nitrogen or the grouping C-Z1, where Z1 represents hydrogen, fluorine or chlorine.
3. A composition according to Claim 1, comprising an N-azinyl-N'-(2-ethylthio-phenylsulphonyl)-urea of the formula (I) in which X represents chlorine, methyl or methoxy, Y represents methyl or methoxy, and Z represents a CH grouping.
4. A composition according to Claim 1, comprising an N-azinyl-N'-(2-ethylthio-phenylsulphonyl)-urea of the formula (I) in which X represents methyl or methoxy, Y represents methyl or methoxy and Z represents nitrogen.
5. A method of combating weeds in crop plants, which comprises applying to the crop plants a composition according to any one of Claims 1 to 4.
6. A use of a composition according to any one of Claims 1 to 4 for selectively combating weeds in crop plants.
7. A process for preparing a herbicidal composition comprising admixing an N-azinyl-N'-(2-ethylthio-phenylsulphonyl)-urea of the formula (I) as defined in any one of Claims 1 to 4 with an extender or surface-active agent.
8. An N-azinyl-N'-(2-ethylthio-phenylsulphonyl)-urea of the general formula (I) (I) in which X represents hydrogen, halogen, C1-C3-alkyl (which is optionally substituted by fluorine, chlorine, methoxy or ethoxy), C1-C3-alkoxy (which is optionally substituted by fluorine, chlorine, methoxy or ethoxy), C1-C3-alkylthio, C1-C3-alkylamino or di-(C1-C2-alkyl)-amino, Y represents halogen, C1-C3-alkyl (which is optionally substituted by fluorine, chlorine, methoxy or ethoxy), C1-C3-alkoxy (which is optionally substituted by fluorine, chlorine, methoxy or ethoxy), C1-C3-alkylthio, C1-C3 alkylamino or di-(C1-C2-alkyl)-amino, and Z represents nitrogen or the grouping C-Z1, where Z1 represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, methoxy or ethoxy, with the exception of the compound N-(4,6-dimethoxy-s-triazin-2-yl)-N'-(2-ethylthio-phenylsulphonyl)-urea.
9. The compound N-(4,6-dimethoxy-pyrimidin-2-yl)-N'-(2-ethylthio-phenylsulphonyl)-urea.
10. The compound N-(4,6-dimethyl-pyrimidin-2-yl)-N'-(2-ethylthio-phenylsulphonyl)-urea.
11. The compound N-(4-methoxy-6-methyl-pyrimidin-2-yl)-N'-(2-ethylthio-phenylsulphonyl)-urea.
12. The compound N-(4-chloro-6-methoxy-pyrimidin-2-yl)-N'-(2-ethylthio-phenylsulphonyl)-urea.
13. A herbicidal composition comprising a herbicidally effective amount of a compound according to any one of Claims 9 to 12 in admixture with a suitable carrier or diluent.
14. A herbicidal composition comprising a herbicidally effective amount of a compound according to any one of Claims 9 to 12 in admixture with a solid diluent or carrier, a liquified normally gaseous diluent or carrier, or a liquid diluent or carrier containing a surface active agent.
15. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a compound according to any one of Claims 9 to 12.
16. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a composition containing a compound according to any one of Claims 9 to 12 in admixture with a suitable carrier or diluent.
17. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a composition containing between 0.1 and 95 % by weight of a compound according to any one of Claims 8 to 12 in admixture with a suitable carrier or diluent.
18. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a composition containing between 0.5 and 90 % by weight of a compound according to any one of Claims 8 to 12 in admixture with a suitable carrier or diluent.
19. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a compound according to any one of Claims 8 to 12 wherein the compound is applied as a pre-emergence herbicide.
20. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a compound according to any one of Claims 8 to 12 wherein the compound is applied as a post-emergence herbicide.
21. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a compound according to any one of Claims 8 to 12 wherein the compound is applied to an area of cultivation at a rate of between 5 and 250 g/ha.
22. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a compound according to any one of Claims 8 to 12 wherein the compound is applied to an area of cultivation at a rate of between 15 and 150 g/ha.
23. A process for preparing an N-azinyl-N'-(2-ethylthio-phenylsulphonyl)-urea of the formula (I) as defined in Claim 8, which process comprises (a) reacting a 2-ethylthio-benzenesulphonamide of the formula (II) (II) with a chloroformic acid ester of the general formula (III) C1-CO-O-R (III) in which R represents alkyl, aralkyl or aryl, at temperatures between 0°C and 100°C and reacting the sulphonylurethane of the general formula (IV) so obtained (IV) in which R has the abovementioned meaning, with an aminoazine of the general formula (V) (V) in which X, Y and Z are as defined in Claim 8, and with an acid, at a temperature between 0°C and 100°C or (b) reacting a 2-ethylthio-phenylsulphonyl isocyanate of the formula (VI) (VI) with an aminoazine of the general formula (V) (V) in which X, Y and Z have the abovementioned meaning, at a temperature between 20°C and 120°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4303130.7 | 1993-02-04 | ||
| DE19934303130 DE4303130A1 (en) | 1993-02-04 | 1993-02-04 | Selective herbicides based on N-azinyl-N '- (2-ethylthiophenylsulfonyl) ureas |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2114699A1 true CA2114699A1 (en) | 1994-08-05 |
Family
ID=6479585
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2114699 Abandoned CA2114699A1 (en) | 1993-02-04 | 1994-02-01 | Selective herbicides based on n-azinyl-n'-(2-ethylthio- phenylsulphonyl)-ureas |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0609733A3 (en) |
| JP (1) | JPH06247940A (en) |
| CA (1) | CA2114699A1 (en) |
| DE (1) | DE4303130A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4206146A1 (en) * | 1992-02-28 | 1993-09-02 | Basf Ag | HERBICIDES N - ((1,3,5-TRIAZIN-2-YL) AMINOCARBONYL) BENZOLSULFONAMIDE |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL7703809A (en) * | 1976-04-07 | 1977-10-11 | Du Pont | HERBICIDE SULFONAMIDES. |
| AU543161B2 (en) * | 1980-03-07 | 1985-04-04 | E.I. Du Pont De Nemours And Company | Pyrimidine or s.triazine derivatives |
| US4543120A (en) * | 1982-08-12 | 1985-09-24 | E. I. Du Pont De Nemours And Company | Alkyl sulfonyl sulfonamides |
| CA1229086A (en) * | 1984-05-09 | 1987-11-10 | Hugh M. Brown | Herbicidal halopyrimidines |
| US5270288A (en) * | 1991-08-09 | 1993-12-14 | Bayer Aktiengesellschaft | Herbicidal N-azinyl-N'-(2-ethylsulphinyl-phenylsulphonyl)-ureas |
-
1993
- 1993-02-04 DE DE19934303130 patent/DE4303130A1/en not_active Withdrawn
-
1994
- 1994-01-24 EP EP9494100937A patent/EP0609733A3/en not_active Withdrawn
- 1994-01-28 JP JP2630694A patent/JPH06247940A/en active Pending
- 1994-02-01 CA CA 2114699 patent/CA2114699A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| EP0609733A2 (en) | 1994-08-10 |
| JPH06247940A (en) | 1994-09-06 |
| DE4303130A1 (en) | 1994-08-11 |
| EP0609733A3 (en) | 1994-10-19 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Dead |