CA1222753A - Sulfonyl(thio)ureas, processes for producing them, and their use as herbicides and/or as growth regulators - Google Patents
Sulfonyl(thio)ureas, processes for producing them, and their use as herbicides and/or as growth regulatorsInfo
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Abstract
Case 5-13937/=
Novel sulfonyl(thio)ureas, processes for producing them, and their use as herbicides and/or as growth regulators Abstract There are described novel sulfonylureas of the formula I defined herein (I) wherein R1 is hydrogen or C1-C5-alkyl, R2 and R3 indepen-dently of one another are each hydrogen, C1-C5-alkyl, C1-C5-alkoxy, C1-C5-alkylthio, C1-C5-haloalkyl, halogen, C1-C5-haloalkoxy, C1-C5-haloalkylthio, C1-C4,-alkylamino, di-C1-C4-alkylamino, or an alkoxyalkyl group or alkoxy-alkoxy group each having a maximum of 6 carbon atoms, Z is oxygen or sulfur, E is -CH= or -N=, and Q is an unsubstituted or substituted, five-membered, heterocyclic radical which is bound by way of a carbon atom, and which contains 2 or 3 identical or different hetero atoms;
including also the salts of these compounds; as well as the production and use thereof. The active substances of the formula I can be incorporated into compositions which can be used in agriculture for controlling weeds and/or for specifically influencing plant growth.
Novel sulfonyl(thio)ureas, processes for producing them, and their use as herbicides and/or as growth regulators Abstract There are described novel sulfonylureas of the formula I defined herein (I) wherein R1 is hydrogen or C1-C5-alkyl, R2 and R3 indepen-dently of one another are each hydrogen, C1-C5-alkyl, C1-C5-alkoxy, C1-C5-alkylthio, C1-C5-haloalkyl, halogen, C1-C5-haloalkoxy, C1-C5-haloalkylthio, C1-C4,-alkylamino, di-C1-C4-alkylamino, or an alkoxyalkyl group or alkoxy-alkoxy group each having a maximum of 6 carbon atoms, Z is oxygen or sulfur, E is -CH= or -N=, and Q is an unsubstituted or substituted, five-membered, heterocyclic radical which is bound by way of a carbon atom, and which contains 2 or 3 identical or different hetero atoms;
including also the salts of these compounds; as well as the production and use thereof. The active substances of the formula I can be incorporated into compositions which can be used in agriculture for controlling weeds and/or for specifically influencing plant growth.
Description
75i3 Case 5-13937/=
Novel sul~onyl~hio2ur as, processes for producin~ them, and their use as herbicides and/or as ~rowth re~ulators The present invention embraces a group of novel sulfonyl(thio)ureas which have valuable properties of regulating plant growth, and which are suitable for specifically influencing plant growth, for the control of weeds, for example in crops of useful plants, and/or for the affecting of the phytotoxic properties of other herbicidal substances. It embraces also the production of these sulfonyl(thio)ureas, and also the agricultural preparations containing these substances as active ingredients.
The invention relates to compounds of the formula I
Q-s02-Nu-c-N-~/ ~E (I) wherein R~l is hydrogen or Cl C5-alkyl, R2 and R3 independently of one another are each hydrogen, Cl-C5-alkyl, Cl-C5-alkoxy, Cl-C5-alkylthio, Cl-C5-haloalkyl, halogen, Cl-C5-haloalkoxy, Cl-C5-halo-alkylthio, Cl-C5-alkylamino, di-Cl-C4-alkylamino, or ~ an alkoxyalkyl group or alkoxyalkoxy group each having a maximum of 6 carbon atoms, " , Z is oxygen or sulfur, E is -CH= or -N=, and ~, is an unsubstituted or substituted, five-membered, heterocyclic radical which is bound by ~ay of a carbon atom, and which contains 2 or 3 identical or different hetero atoms 9 and ~he invention embraces also the salts of these compounds.
Hetero atoms within the scope o the present invention are nitrogen, oxygen and sulfur.
By alkyl, or alkyl constituent of another substituent, are meant, depending on the given number of carbon atoms, for example the following groups: methyl, ethyl, propyl, butyl or pentyl, as well as isomers thereof, such as isopropyl, isobutyl, tert-butyl, isopentyl, and so forth;
haloalkyl is an alkyl group mono- or polysubstituted by halogen, for example: CF3, CH2Cl, CC13, CHF2, CH2J, C2H4Cl, C2H4Br, CH2Br, and so rorth; halogen denotes here and in the following: fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine. The salts applicable in the agricultural field are Eor example those which the compounds of the formula I form with amines or alkali metal and alkaline-earth metal bases, or with quaternary ammonium bases. Alkali metal bases or alkaline-earth metal bases are in this case particularly the hydroxides of lithium~ sodium, potassium, magnesium or calcium.
~ xamples of amines suitable for forming salts are primary, secondary and tertiary aliphatic and aromatic amines, such as: methylamine, ethylamine, propylamine~
i-propylamine, the four isomeric butylamines, dimethylamine, diethylamine, diethanolamine, dipropylamine, diisopropyl-amine, di-n-butylamine, pyrrolidine, piperidine, morpholine, trimethylamine, triethylamine, tripropylamine, quinuclidine, pyridine, quinoline and i quinoline, especially however ethyl- 3 propyl- 9 diethyl- or triethylaminej in particular iso-propylamine and diethanolamine.
Examples of quaternary ammonium bases are in general the cations of halogen ammonium salts, for example the tetramethylammonium cation, the trimethylbenzylammonium cation, the triethylbenzylammonium cation, the tetraethyl-ammonium cation, the trimethylethylammonium cation, and also the ammonium cation.
Typical substituents for the molecule part Q in the formula I of the present invention are: halogen, pseudohalogen, nitro, alkyl, hydroxyl, haloalkyl, alkoxy, alkylthio, haloalkoxy, haloalkylthio, amino, alkylamino, dialkylamino, alkylcarbonylamino, alkylcarbonyl, alkoxy-carbonyl, alkoxyalkyl, alkylthiocarbonyl, carbamoyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkylsulfinyl, alkylsulfonyl, alkenyloxy or alkynyloxy; and groups such as phenyl, phenoxy or phenylthio, which are unsubstituted or substituted by halogen, nitro, cyano, alkyl, alkoxy, haloalkyl, alkylcarbonyl, alkoxycarbonyl or haloalkoxy;
and also benzyl unsubstituted or substituted by halogen and/or alkyl. Preferred substituents are those of which the aliphatic constituent has a maximum of 6, preferably a maximum of 4, carbon atoms~
And typical five-membered, heterocyclic radicals Q, within the scope of the present invention, are: pyrazole, imidazole, 1,2,4-triazole, 1,2,3-triazole, oxazole, thiazole, isooxazole, isothiazole, furazan, 1,2,4-oxadiazole, 1,3,4-oxadiazole, 1~2,3-thiadiazole, 1,2,4-thiadiazole and 1,3,4-thiadiazole~
~ ~3 The heterocyclic radical Q can be unsubstituted, or mono- or polysubstituted.
The compounds of the formula I are, at room tempera-ture, stable/biological active oilsg resins or solids, which are distinguished by very valuable properties for regulating plant growth, particularly for inhibi~ing growth. They can therefore be used in the agricultural field, or in related fields of application, for the specific reduction of the growth of monocotyledonous or dicotyledonous plants, whereby, depending on the type of application and on the applied amount, they bring into effect selectively herbicidal to total-herbicidal properties.
A preferred group of compounds of the formula I
embrac~s those wherein Z is oxygen, and Rl is hydrogen.
In addition, a preferred group of active substances is that composed of compounds of the formula I wherein Rl is hydrogen, R2 and R3 are Cl-C4-alkyl or Cl-C4-alkoxy, Q is any one of the following unsubstituted or substituted azolyl groups -* W ~ W , ~ . or ~ ~
in which Y is in each case oxygen, sulfur or nitrogen, and Z and E are as defined under the formula I.
A particularly preferred group of active substances comprises compounds of the formula I wherein Rl is hydrogen, R2 and R3 are each Cl-C3-alkyl or Cl-C3-alkoxy, Z is oxygen, E is nitrogen or CH, and Q is a hetero-cyclic radical defined under the formula I, which is unsubstituted or substituted by chlorine, bromine, fluorine, nitro, cyano, Cl-C4-alkylcarbonyl, Cl-C4-alkoxycarbonyl, ~ 27~3 Cl-C3-alkoxy, Cl-C3-alkylthio, c2-C6-alko~yalkyl, Cl-C3-alkylsulfinyl, Cl-C3-alkylsulfonyl, Cl-C4-alkyl, trifluoromethyl, trichloromethyl, cyano-Cl-C4-alkyl, C2~C~-alkenyloxy, C3-C~-alkynyloxy or N-Cl-C4-alkyl-carboilylamino .
The following indlvidual substance is especiallypreferred:
N-[1-(3-methoxy-1-propyl)-imidazol-2-ylsulfonyl]-N'-(4 methoxy-6-methyl-pyrimidin-2-yl) urea.
The active substances of the formula I can be produced, in a manner known per se, in an organic solvent or solvent mixture each inert to the reactants.
The procedure can be carried out in particular as follows, and compounds of the formula I are obtained in accordance with equation [1]
~R2 Q-s02w ~ [1~, ~ 3 (II) (III) by reacting a phenylsulfonyl derivative II with a compound of the formula III, in which X and W are the groups -NH2, -N=CaZ or -NRl-CZ-OR; the substituents Rl, R2, R3, Q, Z and E have the meanings defined under the formula I, R is an aliphatic or aromatic radical, preferably Cl-C4-alkyl, phenyl or benzyl; with the proviso that the reactants of the formulae II and III are in all cases selected so that an amino function is reacted either with an isocyanato or isothiocyanato function, or with the [-NRl-CZ-OR] group.
The process is advantageously performed in the presence of a base. It can be of advantage in some cases if the 7~ii3 reaction is carried out in a protective gas atmosphere, for example in a nitrogen atmosphere.
The production processes described herein form part of the subject mat~er of the present invEntion The resulting products of the formula I can if desired be converted, by reaction with amines, alkali metal or alkaline-earth metal hydroxides or quaternary ammonium bases, into basic addition salts usable in agric~lture. This is effected for example by reaction with the equimolar amount of a base, and subsequent removal of the solvent by evaporation. Such reactions, and also the production of individual starting materials of the formula III are known, and are described for example in the U.S. Patent Specifications Nos. 3,384,757 and 3,410,887.
The starting compounds of the formula III, and those of the formula II wherein W is NH2 or -N=C=0, are known, and are produced by methods known per se.
The starting compounds of the formula II in which W is -NRl-CZ-OR are novel, and have been specially developed for the synthesis of compounds of ~he formula I.
They therefore form a further aspect of the present invention. They are produced by methods known per se.
The azolyl-sulfonamides of the formula II are thus produced by reaction of the corresponding sulfonyl chlorides with ammonia or ammonium hydroxide solutions:
cp. Gazz. chim. ital. 70, 1 (1940); U.S. Patent Specifi-cation No. 2,603,649; G.B. Patent Specification No.
710,614; J. org. Chem. 19, 894 (1954~; Arch. Pharm. 278, 437 (1940); and French Patent Specification No. 1,002,201.
The isocyanates of the formulae II and III can be obtained by reaction of the basic amino compounds with ~z~
~'7~i3 phosgene in the presence of butylisocyanate, at the reflux temperature, ln a chlorinated hydrocarbon as solvent (cp. in this connection "Neuere Methoden der prapa.rativen orga.nischen Chemie", Vol ~l, 211-229~ Ver~ag Chemie, Weinheim, 1970. With the use of thiophosgene are obtained, in an analogous manner, isothiocyanates II and III
The isothiocyanates of the formula II are in addi~ion obtained by treatment of the sulfonamides II with carbon disulfide and potassium hydroxide, and subsequent reaction of the dipotassium salt with phosgene (cp.
Arch. Pharm. 299, 174 (1966)).
Compounds of the formulae II and III wherein W and X
are each the group -NRl-CZ-OR can be produced from the basic amino compounds by reaction with a halo(thio)-formic acid ester of the formula IV
z Hal - C - OR (IV), or with a (thio)carbonic acid diester of the formula V
z RO - C OR (V);
wherein Hal is halogen, preferably chlorine or bromine, Z is oxygen or sulfur, and R is an aliphatic or aromatic radical, preferably Cl-C4-alkyl, phenyl or benzyl. This reaction is performed preferably in the presence of a base.
The amines used as starting compounds of the formula III are known, or they can be produced by methods known per se for the synthesis of heterocyclic amines. Refer-ence is made in this respect to the following publication:
"The Chemistry of Heterocyclic Compounds", Vol. XVI, Interscience Publishers, New York~ London, wherein there are to be found syntheses both for 2-aminopyrimidines and for 2~amino-l,2,5-triazines.
These reactions are advantageously performed in aprotic, inert organic solvents, such as methylene chloride, tetrahydrofuran, acetonitrile, dioxane and ~oluene~
The reaction temperatures are preferably between -20 and -~120C. The reactions proceed in general slighcly exothermically~ and can be performed at room temperature. For the purpose of shortening the reaction time or initiating the reaction, heating is advantageously applied for a short time until the boiling point of the reaction mixture is reached. The reaction times can be shortened also by the addition of a few drops of a base or isocyanate as a reaction catalyst.
The active substances of the formula I are stable compounds, and they are negligibly toxic for warm-blooded animals.
In the production of the compounds of the formula I
according to equation [1], it is possible in certain cases, by an addition reaction of a compound of the formula II with a ring nitrogen atom of a compound of the formula III, for isomeric reaction products of the formulae Ia and Ib, respectively, to be isolated:
-s02-NH~ R2 (Ia) Q-S02-NH~-~ E,~-R3 (Ib).
7~3 Y 1~ R2, R3, Q, Z and E in -these formulae are as defined u~der the formula I. Also the isomeric products Ia and Ib influence the growth of plants. The present in~7ention hence embraces all products and mixtures of products which are formed on reaction of the compounds of the formula II with III, and which are usable in agricultural chemistry. Sulfonylureas having two or three hetero atoms in the molecule part Q have not been known hitherto.
~ he novel active substances of the formula I have selective-herbicidal properties, and are therefore suitable for application on cultivated crops of productive plants, particularly cereals, soya-bean and cotton.
Some compounds of the formula I have properties which render them capable of being translocated, that is to say, they are taken up at the treated location of the plant (leaf, stalk, root, etc.), and are transported to other locations, where they produce the desired effect. The compounds are translocated not only from the roots to the leaves of the plant, in the direction in which the nu-trient is transported, but, conversely, also from the leaves to the roots. By virtue of this property of compounds of the formula I of being translocatable, it is possible for example by surface treatment of perenniaL weeds to destroy the weeds at their roots. Furthermore, the novel active substances of the formula I are effective in applied amounts which are very small compared with the amounts required to obtain the same effect using conven-tional herbicides.
Compounds of the formula I can moreover intensify the phytotoxic activity of other herbicidal substances against harmful plants, and and lessen it against useful plants. This property can lead to a reduction in the total 7~i~
amount of herbicidal active substances and thus to less environmental contamination.
When the applied amounts of the active substances according ~o ~he inventls~n a~e further decreased, the growth regulatlng properties in particular become of greater importance in that the compounds of the formuia I
specifically influence the metabolism of the plants, and effect especially a reduction of vegetative growth, frequently in favour of generative growth. This specific influencing of the physiological processes of plant development render the active substances of the formula I
applicable for various purposes, particularly for those in connection with the saving of labour in the management of cultivatecl crops, or with the attainment of higher yields.
Compounds of the formula I clisclosed herein can be used as herbicides and/or as growth regulators. According to previous experience, a factor to be considered with regard to the applicati.on of growth regulators is that the active substances can bring about one or more varying effects on the plants. These different effects depend essentially on the time of application, that is to say, on the stage of development of the seed or of the plant, on the manner of application, and also in particular on the concentration applied. These effects differ however according to the species of plant. The application of compounds of the formula I thus opens up the possibility of influencing the growth of plants in a desired manner.
The vegetative plant growth is suppressed with use of the novel active substances of the formula I or with the novel compositions containing them. As a result of this influencing of growth, the active substances used according to the invention greatly increase the crop yield of plants.
~Z~2753 Thus, soya-bean plants and other leguminosae, such as beans, peas or lentils, undergo a reduction of their vegetative growth in favour of generative growth, in consequence of which an imrnediate increase in crop yleld is obtained Also in the case of other species of plants, for example grape vine, varieties o-f c~reals, grasses and ornamental plants, the vegetative growth is reduced in the desired manner Furthermore, a distinct strengthening of the supporting tissues is observed.
An important mode of in1uencing plants is based on the particular property of the compounds of the formula I to bring about, in the case of certain plants, especially cultivated cereals, a specific reduction in growth, which, with an unchanged crop yield, greatly increases the plant's resistance to bending and snapping.
This provides an economical and very interesting method of protecting crops of plants from the danger of becoming flattened as a result of storm or bad weather. In addition, a specific reduction of vegetative growth in the case of many cultivated plants renders possible a denser planting of crops; the result of this is that, with the same level of frui~ setting and the same area under cultivation, there is achieved a marked increase in crop yield. The use of growth inhibitors results also in a more effective utilisation of the nutrients, which to an increased extent are available now for the benefit of the blossom and of fruit formation. Higher crop yields can be attained in this manner with at the same time a smaller proportion of waste of vegetative plant residues [for example straw, potato foliage, beet leaves, and so forth] occurring.
To be emphasised also is the possibility of achieving with the substances and compositions according to the invention, in the case of various species of plants, especially tobacco plants, a reduction in the amount of undesirable side shoots when the leading shoot has been cut off, shortly before flowering, for the purpose o. ob~inlng the increase in growth aimed at, The invention hence relates to a herbicidal and/or growth-regulating application of the compounds of the formula I. Included also is a method for the pre- and post-emergence controlling of weeds; for the reduction of plant growth of monocotyledonous and dicotyledonous plants, ~specially grasses, varieties of cereals and side shoots of tobacco plants; and also for the increasing of crop yields, particularly in the case of leguminosae.
~22~;i3 The compounds of the formula I are used either in an unmodified form or preferably in composltions, together with auxiliaries customarily employed in for~ulation practice, and are thus processed, in a known manner, for 5 example into the form of emulsion concentrates, directly sprayable or dilutable solutions, diluted emulsions, wettable powders, soluble powders, dusts or granulates, and also encapsulations in for example polymeric substances.
The application processes, such as spraying, atomising, 10 dusting, scattering or pouring, and likewise the type of composition, are selected to suit the objects to be achieved and the given conditions.
The formulations, that is to say, the compositions or preparations containing the active ingredient of the 15 formula I and optionally a solid or liquid additive, are produced in a known manner, for example by the intimate mixing and/or grinding of the active ingredients with extenders, such as with solvents, solid carriers and optionally surface-active compounds (tensides~.
Suitable solvents are: aromatic hydrocarbons, prefer-ably the fractions C8 to C12, such as xylene mixtures or substituted naphthalenes, phthalic esters, such as dibutyl-or dioctylphthalate, aliphatic hydrocarbons, s~ch as cyclohexane or paraffins, alcohols and glycols, as well as 25 ethers and esters thereof, such as ethanol, ethylene glycol, ethylene glycol monomethyl or -ethyl ethers, ketones, such as cyclohexanone, strongly polar solvents, such as N-methyl-2-pyrrolidone, dimethylsulfoxide or dimethyl-~2~ 3 formamide, as well as optionally epoxidised vegetable oils, such as epoxidised coconut oil or soybean oili or water.
The solid carriers used, for example for dusts and 5 dispersible powders, are as a rule natural mineral fillers, such as calcite, talcum, kaolin, montmorillonite or attapulgite. In order to improve the physical properties, it is also possible to add highly dispersed ~~
silicic acid or highly dispersed absorbent polymers.
lO Suitable granulated adsorptive carriers are porous types, for example pumice, ground brick, sepiolite or bentonite;
and suitable nonsorbent carriers are materials such as calcite or sand. There can also be used a great number of pre~granulated materials of inorganic or organic 15 nature, such as in particular dolomite or ground plant residues.
Suitable surface-active compounds are, depending on the nature of the active substance of the formula I to be formulated, nonionic, cationic and/or anionic tensides 20 having good emulsifying, dispersing and wetting properties.
; By 'tensides' are also meant mixtures of tensides~
Suitable anionic tensides are both so-called water-soluble soaps as well as water-soluble, synthetic, surface-active compounds.
Soaps which are applicable are the alkali metal, alkaline-earth metal or optionally substituted ammonium salts of higher fatty acids ~C~0-C22), for example the Na or K salts of oleic or stearic acid, or of natural fatty acid mixtures, which can be obtained for example 30 from coconut oil or tallow oil. Also to be mentioned are ~ 3 the fatty acid-methyl-taurine salts.
So-called synthetic tensides are however more frequently used, particularly fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or 5 alkylarylsulfonates. The fatty sulfonates or sulfates are as a rule in the form of alkali metal, alkaline-earth metal or optionally substituted ammonium salts, and contain an alkyi group having 8 to 22 C atoms, 'alkyl' including also the alkyl moiety of acyl groups, for 10 example the Na or Ca salt of ligninsulfonic acid, of dodecylsulfuric acid ester or of a fatty alcohol sulfate mixture produced from natural fatty acids. Included among these are also the salts of sulfuric acid esters and sulfonic acids or fatty alcohol ethylene oxide adducts.
15 The sulfonated benzimidazole derivatives preferably contain
Novel sul~onyl~hio2ur as, processes for producin~ them, and their use as herbicides and/or as ~rowth re~ulators The present invention embraces a group of novel sulfonyl(thio)ureas which have valuable properties of regulating plant growth, and which are suitable for specifically influencing plant growth, for the control of weeds, for example in crops of useful plants, and/or for the affecting of the phytotoxic properties of other herbicidal substances. It embraces also the production of these sulfonyl(thio)ureas, and also the agricultural preparations containing these substances as active ingredients.
The invention relates to compounds of the formula I
Q-s02-Nu-c-N-~/ ~E (I) wherein R~l is hydrogen or Cl C5-alkyl, R2 and R3 independently of one another are each hydrogen, Cl-C5-alkyl, Cl-C5-alkoxy, Cl-C5-alkylthio, Cl-C5-haloalkyl, halogen, Cl-C5-haloalkoxy, Cl-C5-halo-alkylthio, Cl-C5-alkylamino, di-Cl-C4-alkylamino, or ~ an alkoxyalkyl group or alkoxyalkoxy group each having a maximum of 6 carbon atoms, " , Z is oxygen or sulfur, E is -CH= or -N=, and ~, is an unsubstituted or substituted, five-membered, heterocyclic radical which is bound by ~ay of a carbon atom, and which contains 2 or 3 identical or different hetero atoms 9 and ~he invention embraces also the salts of these compounds.
Hetero atoms within the scope o the present invention are nitrogen, oxygen and sulfur.
By alkyl, or alkyl constituent of another substituent, are meant, depending on the given number of carbon atoms, for example the following groups: methyl, ethyl, propyl, butyl or pentyl, as well as isomers thereof, such as isopropyl, isobutyl, tert-butyl, isopentyl, and so forth;
haloalkyl is an alkyl group mono- or polysubstituted by halogen, for example: CF3, CH2Cl, CC13, CHF2, CH2J, C2H4Cl, C2H4Br, CH2Br, and so rorth; halogen denotes here and in the following: fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine. The salts applicable in the agricultural field are Eor example those which the compounds of the formula I form with amines or alkali metal and alkaline-earth metal bases, or with quaternary ammonium bases. Alkali metal bases or alkaline-earth metal bases are in this case particularly the hydroxides of lithium~ sodium, potassium, magnesium or calcium.
~ xamples of amines suitable for forming salts are primary, secondary and tertiary aliphatic and aromatic amines, such as: methylamine, ethylamine, propylamine~
i-propylamine, the four isomeric butylamines, dimethylamine, diethylamine, diethanolamine, dipropylamine, diisopropyl-amine, di-n-butylamine, pyrrolidine, piperidine, morpholine, trimethylamine, triethylamine, tripropylamine, quinuclidine, pyridine, quinoline and i quinoline, especially however ethyl- 3 propyl- 9 diethyl- or triethylaminej in particular iso-propylamine and diethanolamine.
Examples of quaternary ammonium bases are in general the cations of halogen ammonium salts, for example the tetramethylammonium cation, the trimethylbenzylammonium cation, the triethylbenzylammonium cation, the tetraethyl-ammonium cation, the trimethylethylammonium cation, and also the ammonium cation.
Typical substituents for the molecule part Q in the formula I of the present invention are: halogen, pseudohalogen, nitro, alkyl, hydroxyl, haloalkyl, alkoxy, alkylthio, haloalkoxy, haloalkylthio, amino, alkylamino, dialkylamino, alkylcarbonylamino, alkylcarbonyl, alkoxy-carbonyl, alkoxyalkyl, alkylthiocarbonyl, carbamoyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkylsulfinyl, alkylsulfonyl, alkenyloxy or alkynyloxy; and groups such as phenyl, phenoxy or phenylthio, which are unsubstituted or substituted by halogen, nitro, cyano, alkyl, alkoxy, haloalkyl, alkylcarbonyl, alkoxycarbonyl or haloalkoxy;
and also benzyl unsubstituted or substituted by halogen and/or alkyl. Preferred substituents are those of which the aliphatic constituent has a maximum of 6, preferably a maximum of 4, carbon atoms~
And typical five-membered, heterocyclic radicals Q, within the scope of the present invention, are: pyrazole, imidazole, 1,2,4-triazole, 1,2,3-triazole, oxazole, thiazole, isooxazole, isothiazole, furazan, 1,2,4-oxadiazole, 1,3,4-oxadiazole, 1~2,3-thiadiazole, 1,2,4-thiadiazole and 1,3,4-thiadiazole~
~ ~3 The heterocyclic radical Q can be unsubstituted, or mono- or polysubstituted.
The compounds of the formula I are, at room tempera-ture, stable/biological active oilsg resins or solids, which are distinguished by very valuable properties for regulating plant growth, particularly for inhibi~ing growth. They can therefore be used in the agricultural field, or in related fields of application, for the specific reduction of the growth of monocotyledonous or dicotyledonous plants, whereby, depending on the type of application and on the applied amount, they bring into effect selectively herbicidal to total-herbicidal properties.
A preferred group of compounds of the formula I
embrac~s those wherein Z is oxygen, and Rl is hydrogen.
In addition, a preferred group of active substances is that composed of compounds of the formula I wherein Rl is hydrogen, R2 and R3 are Cl-C4-alkyl or Cl-C4-alkoxy, Q is any one of the following unsubstituted or substituted azolyl groups -* W ~ W , ~ . or ~ ~
in which Y is in each case oxygen, sulfur or nitrogen, and Z and E are as defined under the formula I.
A particularly preferred group of active substances comprises compounds of the formula I wherein Rl is hydrogen, R2 and R3 are each Cl-C3-alkyl or Cl-C3-alkoxy, Z is oxygen, E is nitrogen or CH, and Q is a hetero-cyclic radical defined under the formula I, which is unsubstituted or substituted by chlorine, bromine, fluorine, nitro, cyano, Cl-C4-alkylcarbonyl, Cl-C4-alkoxycarbonyl, ~ 27~3 Cl-C3-alkoxy, Cl-C3-alkylthio, c2-C6-alko~yalkyl, Cl-C3-alkylsulfinyl, Cl-C3-alkylsulfonyl, Cl-C4-alkyl, trifluoromethyl, trichloromethyl, cyano-Cl-C4-alkyl, C2~C~-alkenyloxy, C3-C~-alkynyloxy or N-Cl-C4-alkyl-carboilylamino .
The following indlvidual substance is especiallypreferred:
N-[1-(3-methoxy-1-propyl)-imidazol-2-ylsulfonyl]-N'-(4 methoxy-6-methyl-pyrimidin-2-yl) urea.
The active substances of the formula I can be produced, in a manner known per se, in an organic solvent or solvent mixture each inert to the reactants.
The procedure can be carried out in particular as follows, and compounds of the formula I are obtained in accordance with equation [1]
~R2 Q-s02w ~ [1~, ~ 3 (II) (III) by reacting a phenylsulfonyl derivative II with a compound of the formula III, in which X and W are the groups -NH2, -N=CaZ or -NRl-CZ-OR; the substituents Rl, R2, R3, Q, Z and E have the meanings defined under the formula I, R is an aliphatic or aromatic radical, preferably Cl-C4-alkyl, phenyl or benzyl; with the proviso that the reactants of the formulae II and III are in all cases selected so that an amino function is reacted either with an isocyanato or isothiocyanato function, or with the [-NRl-CZ-OR] group.
The process is advantageously performed in the presence of a base. It can be of advantage in some cases if the 7~ii3 reaction is carried out in a protective gas atmosphere, for example in a nitrogen atmosphere.
The production processes described herein form part of the subject mat~er of the present invEntion The resulting products of the formula I can if desired be converted, by reaction with amines, alkali metal or alkaline-earth metal hydroxides or quaternary ammonium bases, into basic addition salts usable in agric~lture. This is effected for example by reaction with the equimolar amount of a base, and subsequent removal of the solvent by evaporation. Such reactions, and also the production of individual starting materials of the formula III are known, and are described for example in the U.S. Patent Specifications Nos. 3,384,757 and 3,410,887.
The starting compounds of the formula III, and those of the formula II wherein W is NH2 or -N=C=0, are known, and are produced by methods known per se.
The starting compounds of the formula II in which W is -NRl-CZ-OR are novel, and have been specially developed for the synthesis of compounds of ~he formula I.
They therefore form a further aspect of the present invention. They are produced by methods known per se.
The azolyl-sulfonamides of the formula II are thus produced by reaction of the corresponding sulfonyl chlorides with ammonia or ammonium hydroxide solutions:
cp. Gazz. chim. ital. 70, 1 (1940); U.S. Patent Specifi-cation No. 2,603,649; G.B. Patent Specification No.
710,614; J. org. Chem. 19, 894 (1954~; Arch. Pharm. 278, 437 (1940); and French Patent Specification No. 1,002,201.
The isocyanates of the formulae II and III can be obtained by reaction of the basic amino compounds with ~z~
~'7~i3 phosgene in the presence of butylisocyanate, at the reflux temperature, ln a chlorinated hydrocarbon as solvent (cp. in this connection "Neuere Methoden der prapa.rativen orga.nischen Chemie", Vol ~l, 211-229~ Ver~ag Chemie, Weinheim, 1970. With the use of thiophosgene are obtained, in an analogous manner, isothiocyanates II and III
The isothiocyanates of the formula II are in addi~ion obtained by treatment of the sulfonamides II with carbon disulfide and potassium hydroxide, and subsequent reaction of the dipotassium salt with phosgene (cp.
Arch. Pharm. 299, 174 (1966)).
Compounds of the formulae II and III wherein W and X
are each the group -NRl-CZ-OR can be produced from the basic amino compounds by reaction with a halo(thio)-formic acid ester of the formula IV
z Hal - C - OR (IV), or with a (thio)carbonic acid diester of the formula V
z RO - C OR (V);
wherein Hal is halogen, preferably chlorine or bromine, Z is oxygen or sulfur, and R is an aliphatic or aromatic radical, preferably Cl-C4-alkyl, phenyl or benzyl. This reaction is performed preferably in the presence of a base.
The amines used as starting compounds of the formula III are known, or they can be produced by methods known per se for the synthesis of heterocyclic amines. Refer-ence is made in this respect to the following publication:
"The Chemistry of Heterocyclic Compounds", Vol. XVI, Interscience Publishers, New York~ London, wherein there are to be found syntheses both for 2-aminopyrimidines and for 2~amino-l,2,5-triazines.
These reactions are advantageously performed in aprotic, inert organic solvents, such as methylene chloride, tetrahydrofuran, acetonitrile, dioxane and ~oluene~
The reaction temperatures are preferably between -20 and -~120C. The reactions proceed in general slighcly exothermically~ and can be performed at room temperature. For the purpose of shortening the reaction time or initiating the reaction, heating is advantageously applied for a short time until the boiling point of the reaction mixture is reached. The reaction times can be shortened also by the addition of a few drops of a base or isocyanate as a reaction catalyst.
The active substances of the formula I are stable compounds, and they are negligibly toxic for warm-blooded animals.
In the production of the compounds of the formula I
according to equation [1], it is possible in certain cases, by an addition reaction of a compound of the formula II with a ring nitrogen atom of a compound of the formula III, for isomeric reaction products of the formulae Ia and Ib, respectively, to be isolated:
-s02-NH~ R2 (Ia) Q-S02-NH~-~ E,~-R3 (Ib).
7~3 Y 1~ R2, R3, Q, Z and E in -these formulae are as defined u~der the formula I. Also the isomeric products Ia and Ib influence the growth of plants. The present in~7ention hence embraces all products and mixtures of products which are formed on reaction of the compounds of the formula II with III, and which are usable in agricultural chemistry. Sulfonylureas having two or three hetero atoms in the molecule part Q have not been known hitherto.
~ he novel active substances of the formula I have selective-herbicidal properties, and are therefore suitable for application on cultivated crops of productive plants, particularly cereals, soya-bean and cotton.
Some compounds of the formula I have properties which render them capable of being translocated, that is to say, they are taken up at the treated location of the plant (leaf, stalk, root, etc.), and are transported to other locations, where they produce the desired effect. The compounds are translocated not only from the roots to the leaves of the plant, in the direction in which the nu-trient is transported, but, conversely, also from the leaves to the roots. By virtue of this property of compounds of the formula I of being translocatable, it is possible for example by surface treatment of perenniaL weeds to destroy the weeds at their roots. Furthermore, the novel active substances of the formula I are effective in applied amounts which are very small compared with the amounts required to obtain the same effect using conven-tional herbicides.
Compounds of the formula I can moreover intensify the phytotoxic activity of other herbicidal substances against harmful plants, and and lessen it against useful plants. This property can lead to a reduction in the total 7~i~
amount of herbicidal active substances and thus to less environmental contamination.
When the applied amounts of the active substances according ~o ~he inventls~n a~e further decreased, the growth regulatlng properties in particular become of greater importance in that the compounds of the formuia I
specifically influence the metabolism of the plants, and effect especially a reduction of vegetative growth, frequently in favour of generative growth. This specific influencing of the physiological processes of plant development render the active substances of the formula I
applicable for various purposes, particularly for those in connection with the saving of labour in the management of cultivatecl crops, or with the attainment of higher yields.
Compounds of the formula I clisclosed herein can be used as herbicides and/or as growth regulators. According to previous experience, a factor to be considered with regard to the applicati.on of growth regulators is that the active substances can bring about one or more varying effects on the plants. These different effects depend essentially on the time of application, that is to say, on the stage of development of the seed or of the plant, on the manner of application, and also in particular on the concentration applied. These effects differ however according to the species of plant. The application of compounds of the formula I thus opens up the possibility of influencing the growth of plants in a desired manner.
The vegetative plant growth is suppressed with use of the novel active substances of the formula I or with the novel compositions containing them. As a result of this influencing of growth, the active substances used according to the invention greatly increase the crop yield of plants.
~Z~2753 Thus, soya-bean plants and other leguminosae, such as beans, peas or lentils, undergo a reduction of their vegetative growth in favour of generative growth, in consequence of which an imrnediate increase in crop yleld is obtained Also in the case of other species of plants, for example grape vine, varieties o-f c~reals, grasses and ornamental plants, the vegetative growth is reduced in the desired manner Furthermore, a distinct strengthening of the supporting tissues is observed.
An important mode of in1uencing plants is based on the particular property of the compounds of the formula I to bring about, in the case of certain plants, especially cultivated cereals, a specific reduction in growth, which, with an unchanged crop yield, greatly increases the plant's resistance to bending and snapping.
This provides an economical and very interesting method of protecting crops of plants from the danger of becoming flattened as a result of storm or bad weather. In addition, a specific reduction of vegetative growth in the case of many cultivated plants renders possible a denser planting of crops; the result of this is that, with the same level of frui~ setting and the same area under cultivation, there is achieved a marked increase in crop yield. The use of growth inhibitors results also in a more effective utilisation of the nutrients, which to an increased extent are available now for the benefit of the blossom and of fruit formation. Higher crop yields can be attained in this manner with at the same time a smaller proportion of waste of vegetative plant residues [for example straw, potato foliage, beet leaves, and so forth] occurring.
To be emphasised also is the possibility of achieving with the substances and compositions according to the invention, in the case of various species of plants, especially tobacco plants, a reduction in the amount of undesirable side shoots when the leading shoot has been cut off, shortly before flowering, for the purpose o. ob~inlng the increase in growth aimed at, The invention hence relates to a herbicidal and/or growth-regulating application of the compounds of the formula I. Included also is a method for the pre- and post-emergence controlling of weeds; for the reduction of plant growth of monocotyledonous and dicotyledonous plants, ~specially grasses, varieties of cereals and side shoots of tobacco plants; and also for the increasing of crop yields, particularly in the case of leguminosae.
~22~;i3 The compounds of the formula I are used either in an unmodified form or preferably in composltions, together with auxiliaries customarily employed in for~ulation practice, and are thus processed, in a known manner, for 5 example into the form of emulsion concentrates, directly sprayable or dilutable solutions, diluted emulsions, wettable powders, soluble powders, dusts or granulates, and also encapsulations in for example polymeric substances.
The application processes, such as spraying, atomising, 10 dusting, scattering or pouring, and likewise the type of composition, are selected to suit the objects to be achieved and the given conditions.
The formulations, that is to say, the compositions or preparations containing the active ingredient of the 15 formula I and optionally a solid or liquid additive, are produced in a known manner, for example by the intimate mixing and/or grinding of the active ingredients with extenders, such as with solvents, solid carriers and optionally surface-active compounds (tensides~.
Suitable solvents are: aromatic hydrocarbons, prefer-ably the fractions C8 to C12, such as xylene mixtures or substituted naphthalenes, phthalic esters, such as dibutyl-or dioctylphthalate, aliphatic hydrocarbons, s~ch as cyclohexane or paraffins, alcohols and glycols, as well as 25 ethers and esters thereof, such as ethanol, ethylene glycol, ethylene glycol monomethyl or -ethyl ethers, ketones, such as cyclohexanone, strongly polar solvents, such as N-methyl-2-pyrrolidone, dimethylsulfoxide or dimethyl-~2~ 3 formamide, as well as optionally epoxidised vegetable oils, such as epoxidised coconut oil or soybean oili or water.
The solid carriers used, for example for dusts and 5 dispersible powders, are as a rule natural mineral fillers, such as calcite, talcum, kaolin, montmorillonite or attapulgite. In order to improve the physical properties, it is also possible to add highly dispersed ~~
silicic acid or highly dispersed absorbent polymers.
lO Suitable granulated adsorptive carriers are porous types, for example pumice, ground brick, sepiolite or bentonite;
and suitable nonsorbent carriers are materials such as calcite or sand. There can also be used a great number of pre~granulated materials of inorganic or organic 15 nature, such as in particular dolomite or ground plant residues.
Suitable surface-active compounds are, depending on the nature of the active substance of the formula I to be formulated, nonionic, cationic and/or anionic tensides 20 having good emulsifying, dispersing and wetting properties.
; By 'tensides' are also meant mixtures of tensides~
Suitable anionic tensides are both so-called water-soluble soaps as well as water-soluble, synthetic, surface-active compounds.
Soaps which are applicable are the alkali metal, alkaline-earth metal or optionally substituted ammonium salts of higher fatty acids ~C~0-C22), for example the Na or K salts of oleic or stearic acid, or of natural fatty acid mixtures, which can be obtained for example 30 from coconut oil or tallow oil. Also to be mentioned are ~ 3 the fatty acid-methyl-taurine salts.
So-called synthetic tensides are however more frequently used, particularly fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or 5 alkylarylsulfonates. The fatty sulfonates or sulfates are as a rule in the form of alkali metal, alkaline-earth metal or optionally substituted ammonium salts, and contain an alkyi group having 8 to 22 C atoms, 'alkyl' including also the alkyl moiety of acyl groups, for 10 example the Na or Ca salt of ligninsulfonic acid, of dodecylsulfuric acid ester or of a fatty alcohol sulfate mixture produced from natural fatty acids. Included among these are also the salts of sulfuric acid esters and sulfonic acids or fatty alcohol ethylene oxide adducts.
15 The sulfonated benzimidazole derivatives preferably contain
2 sulfonic acid groups and a fatty acid group having 8 - 22 C atoms. Alkylarylsulfonates are for example the Na, Ca or triethanolamine salts of dodecylbenzenesulfonic acid~ of dibutylnaphthalenesulfonic acid or of a 20 naphthalenesulfonic acid-~ormaldehyde condensation product.
Also suitable are corresponding phosphates, for example salts of the phosphoric ester of a p-nonylphenol-(4-14)-ethylene oxide adduct~ or phospholipidesO
Suitable nonionic tensides are in particular polyylycol 25 ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, which can contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.
Further suitable nonionic tensides are the water-soluble polyethylene oxide adducts, which contain 20 to 250 ethylene glycol ether groups and lO to 100 propylene glycol ether groups, with polypropylene glycol, ethylene-diaminopolypropylene glycol and alkylpolypropylene glycol having 1 to 10 carbon atoms in the alkyl chain. The compounds mentioned usually contain 1 to 5 ethylene glycol units per propylene glycol unit. Examples of nonionic tensides which ma~ be mentioned are: nonylphenol~
polyetho~yethanols5 cas~or oil polyglycol ethers~
polypropyiene/polyethyleneoxy adducts~ tributylphenoxy polyethoxyethanol, polyethylene glycol and octylpheno~y-polyethoxyethanol. Suitable also are fatty acid esters of polyoxyethylenesorbitan, such as polyoxyethylene-sorbitan-trioleate.
In the case of the cationic tensides, they are in particular quaternary ammonium salts which contain as N-substituents at least one alkyl group having 8 to 22 C atoms and, as further substituents, lower, optionally halogenated alkyl, benzyl or lower hydroxyalkyl groups.
The salts are preferably in the form of halides, methyl sulfates or ethyl sulfates, for exa~ple stearyltrimethyl-ammonium chloride or benzyldi(2-chloroethyl)ethyla~monium bromide.
The tensides customarily used in formulation practice are described, inter alia, in the following publications:
"Mc Cutcheon's Detergents and Emulsifiers Annual"
MC Publishing Corp., Ridgewood, New Jersey, 1979; and Sisley and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co., Inc. New York, 1964.
The agrochemical preparations contain as a rule 0.1 to 95%, especially 0.1 to 800/D~ of active ingredient of the formula I, 1 to g9.9% of a solid or liquid additive, and 0 to 25%, particularly 0.1 to 25V/o~ of a tenside.
Preferred formulations are made up in particular as follows (% = per cent by weight):
2 ~ ~ ~ ~
o~ 3 Emulsifiable concentrates active ingredient: 1 to 20%, preferably 5 to 10%
surface active agent: 5 to 30%, preferably 10 to 20%
'i~uid carrie~ 50 to 9/~%, preferably 70 to ~S% .
~usts .__ active ingredient- 0.1 to 10%, preferably Ool to 1%
solid carrier: 99.9 to 90% preferably 99.9 to 99% .
Suspension concentrates active ingredient: 5 to 75%, preferably 10 to 50%
water: 9~ to 25%, preferably 90 to 30%
surface-active agent: 1 to 40%, preferably 2 to 30% .
Wettable powders active ingredient: 0.5 to 90%, preferably 1 to 80%
surface-active agent: 0.5 to 20%, preferably 1 to 15%
solid carrier: 5 to 95%, preferably 15 to 90% .
Granulates active ingredient: 0.5 to 30%, preferably 3 to 15%
solid carrier: 99.5 to 70%, preferably 97 to 85% .
Whereas commercial products are preferably in the form of concentrated compositions, the compositions employed by the end-user are as a rule diluted. The preparations can for application be diluted down to 0.001% of active ingredient. The applied amounts are usually 0.01 to 10 kg, preferably 0.025 to 5 kg, of active substance per hectare.
The compositions can also contain additi.ves such as stabilisers, antifoaming agents, viscosity regulators, binders and adhesives, as well as fertilisers or ot'rer active substances for obtaining special effects.
2~53 The invention relates also to such compositions which are usable in agriculture and which contain, as at least one active ingredient, a compound of the formula I.
The present invention embraces also the produc~ion of the said compositions, whereby the active ingredient is intimately mixed with one or more substances or groups of substances described herein. Likewise included is a method for treating plants, which method comprises the application of the compounds of the formula I or of the novel compositions containing them.
Temperatures in the following Examples are given in degrees Centigrade, and percentages and parts are by weight.
Production Examples Example 1: a) Production of the intermediate I
\S02-~TH-C-0--~ ~, N-(4-Imidazolylsulfonyl)-phenylcarbamate 2.18 g of a 55% sodium hydride dispersion in oil are added portionwise at room temperature in the course of 15 minutes, in a nitrogen atmosphere, to a solution of 7.35 g of 4-imidazolylsulfonamide in 100 ml of dimethyl-formamide; and the mixture is allowed to react for a further 20 minutes. To the resulting solution are added dropwise during 30 minutes, at room temperature, 11.24 g of diphenylcarbonate dissolved in 40 ml of dimethyl-formamide. The reaction mixture is stirred for a further 30 minutes, and is then poured into a mixture of 400 ml ~.22~$3 of ice and 50 ml of 2N HCl; the formed precipitate is subsequently taken up in 300 ml of ethyl acetate, extracted twice with ethyl acetate and ice water, dried, and concentrated by evaporation. The carbamate desired is obtained in quantitative yield: m.p. ]98-200C.
b) Production of the final product ~ S02-NH- C-NH- ~
=--N-(4-Imidazolylsulfonyl~-N'-(4-methyl-6-methoxy-1,3,5-triazin-2-yl)-urea A suspension of 13.35 g of N-(4-imidazolylsulfonyl)~
phenylcarbamate and 7 g of 2-amino-4-methyl-6-methoxy-1,3,5-triazine in 140 ml of absolute dioxane is stirred for 75 minutes at reflux temperature. The reaction mixture is filtered hot, and 8.4 ml of isopropylamine are added to the cooled filtrate; the solvent is subsequently decanted, and the semicrystalline isopropylammonium salt is washed three times with ethyl acetate. The salt is dissolved cold in 200 ml of water; the solution is filtered, the filtrate is adjusted to pH 1 with 2N hydrochloric acid, and then filtered. The filter residue is washed with cold water and dried. The yield is 5.6 g of the desired sulfonylurea; m.p. from 147C, with decomposition.
Example 2- a) Production of the starting product -T~ T~ o ._.
C 2H5 S S 02-~H-C-O ~ ,, IL~53 N-~5-Eth~1-1,3,4-thiadiazol~1~2-sulfonyl2-~henylcarbamate 2.2 g of sodium hydride are added portionwise at room temperature in a nitrogen atmosphere, with stirring, to a solution of 9 7 g of 5-~ethyl~ 3~4 thiadiazcLe-2 sulfonamide in 100 ml of absolute dîmethylfoxma~ide.
After lS minutes' stirring, a solution of 31.2 g of dipherlylcarbonate in 30 ml of dimethylformamide is added dropwise. The whole is stirred for a further three hours, and then treated with 50 ml of HCl 2N/500 ml of waterO
After filtration with suction, the precipitated crystals are washed with water and dried. The yield is 12.8 g of a substance of the above formula having the melting point of 142Co b) Production of the final product 1`1 W N_-~CH3 C H / \S/ \SO -NH-C-NH--~ ~N
N-(5-Ethyl-1,3,4-thiadiazolyl-2-sulfonyl)-N'-(4-methyl-6-methoxy-1,3,5-triazin-2-yl)-urea A mixture of 12.8 g of the product described under a) and 5.8 g of 2-amino-4-methoxy-6-methyl-1,3,5-triazine in 100 ml of absolute dioxane is refluxed for 1 hour.
The mixture is concentrated by evaporation, and hexane is added to the residue. The yield is 2.9 g of a white substance of the above formula, m.p. 60C.
Example 3:
~\ ~- -so2NH-c-NH- .~ ~.
'753 N-(l-Methylimidazol-2-ylsulfonyl)-N'-(4,6-dimethoxy-pyrimidin-2-yl)-urea .. .. . _ . _ 2.4 g of methylimidazol-2-yl-sulfonamide are dissolved in SQ ml of absolute dioxane., and 2.25 g of 1.8-~laza-bicyclo[5.4 0]undec 7-ene are addedO Ther.e are :hen added porti.onwise at 20-25C~ within 30 minutes~ 4~2 g of 4,6 d:i.methoxy-2-phenoxycarbonylaminopyrimidine. After 4 hours, the reaction mixture is taken up with ice water and acidified with 2N HCl, whereupon a precipitate is formed.
50 ml of ethyl acetate are addedj and filtration is carried out~ the precipitate is subsequently washed with water and ethyl acetate and then dried. The yield is 4.0 g (78%) of a colourless, crystalline product, m.pD 189C
(decomposition).
~22275i3 The intermediates and final products listed in the following Tables can be produced in an analogous manner.
The heterocycles Q defined in Table 1 appear in the other Tables wi-.h the same abbreviated meaning~
Table 1:
Q-S02~ H2 No. _ Abbrevi- ¦ Physical data _ ation 1.1 ~ Ql 1.2 n~ Q2 1.3 W,-~ Q3 1. 4 ' H C W ~ Q4 1.5 H3C-N~o~il Q5 1. 6 H C- --'-- Q6 .. __.. ._____....... .__ -~Z2;~53 Table 1 (continuation) __ _ .
ll o . a t ion Phy s i ca l data lo7H C--CO-N-II ~ - Q7 1. 8 \S/ Q8 1. 9 ~NI Qg . loH3C-IIb 1-- Qlo 1~ llI; 11 Qll 1. 12 \s Ql2 .13 ~I; Ql3 .14 ll ll_ Ql4 1 ~15Cl- .~I! Q15 , I _ ~_ 22~S3 Table 1 (continuation) ~ ..
No. Q Abbrevi- Physical data ation _ ..... ... . - . . _ ___ l.16 11 ~ol _ Q16 n,p.142-145c C~13 1.17 ; --N Q17 1.18 I; I!N Q18 Y
1 19 'I-li Ql9 1.20H3C- ~U; - Q20 1.21 N ~ . _ Q21 1.22 ~ --N Q22 D
H
1.23 . N Q23 ~ \S;- _ ' .
.
,~7~i3 Table 1 (contlnuation) .
No, Q Abbrevi- Physical data _ _ _ . _ _ ation _ ___ _ _ _ l.2l, N-- Q2~
''\/
1.25 \o/ Q25 1.26 S Q26 1.27 - N\ / Q27 1.. 8 H3C~II\s~l~ _ Q28 1.29 _ Q29 1.30 I; I!_ Q30 m.p.l68-169C
\NI /6H5 1.31 I; 11_ Q31 m.p. 99C
(CH2) 2-OCH3 1.32 Ij l! Q32 m.p.114C
. CH -C H I
7~3 Table 1 (continuation) _. , , . _ . , .
No. ¦ Q ! Abbrevi- Physical data ' _l ation 1.33 ~ - N ¦ Q33 1.34 ~ Q34 m.p. 179~C
1.35 ~ N_ Q35 m.p. 92C
y Q36 m . p . 182 ~C
~. Q37 m,p, 152~C
1.38 HO-- N Q m.p. 183~C
Also suitable are corresponding phosphates, for example salts of the phosphoric ester of a p-nonylphenol-(4-14)-ethylene oxide adduct~ or phospholipidesO
Suitable nonionic tensides are in particular polyylycol 25 ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, which can contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.
Further suitable nonionic tensides are the water-soluble polyethylene oxide adducts, which contain 20 to 250 ethylene glycol ether groups and lO to 100 propylene glycol ether groups, with polypropylene glycol, ethylene-diaminopolypropylene glycol and alkylpolypropylene glycol having 1 to 10 carbon atoms in the alkyl chain. The compounds mentioned usually contain 1 to 5 ethylene glycol units per propylene glycol unit. Examples of nonionic tensides which ma~ be mentioned are: nonylphenol~
polyetho~yethanols5 cas~or oil polyglycol ethers~
polypropyiene/polyethyleneoxy adducts~ tributylphenoxy polyethoxyethanol, polyethylene glycol and octylpheno~y-polyethoxyethanol. Suitable also are fatty acid esters of polyoxyethylenesorbitan, such as polyoxyethylene-sorbitan-trioleate.
In the case of the cationic tensides, they are in particular quaternary ammonium salts which contain as N-substituents at least one alkyl group having 8 to 22 C atoms and, as further substituents, lower, optionally halogenated alkyl, benzyl or lower hydroxyalkyl groups.
The salts are preferably in the form of halides, methyl sulfates or ethyl sulfates, for exa~ple stearyltrimethyl-ammonium chloride or benzyldi(2-chloroethyl)ethyla~monium bromide.
The tensides customarily used in formulation practice are described, inter alia, in the following publications:
"Mc Cutcheon's Detergents and Emulsifiers Annual"
MC Publishing Corp., Ridgewood, New Jersey, 1979; and Sisley and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co., Inc. New York, 1964.
The agrochemical preparations contain as a rule 0.1 to 95%, especially 0.1 to 800/D~ of active ingredient of the formula I, 1 to g9.9% of a solid or liquid additive, and 0 to 25%, particularly 0.1 to 25V/o~ of a tenside.
Preferred formulations are made up in particular as follows (% = per cent by weight):
2 ~ ~ ~ ~
o~ 3 Emulsifiable concentrates active ingredient: 1 to 20%, preferably 5 to 10%
surface active agent: 5 to 30%, preferably 10 to 20%
'i~uid carrie~ 50 to 9/~%, preferably 70 to ~S% .
~usts .__ active ingredient- 0.1 to 10%, preferably Ool to 1%
solid carrier: 99.9 to 90% preferably 99.9 to 99% .
Suspension concentrates active ingredient: 5 to 75%, preferably 10 to 50%
water: 9~ to 25%, preferably 90 to 30%
surface-active agent: 1 to 40%, preferably 2 to 30% .
Wettable powders active ingredient: 0.5 to 90%, preferably 1 to 80%
surface-active agent: 0.5 to 20%, preferably 1 to 15%
solid carrier: 5 to 95%, preferably 15 to 90% .
Granulates active ingredient: 0.5 to 30%, preferably 3 to 15%
solid carrier: 99.5 to 70%, preferably 97 to 85% .
Whereas commercial products are preferably in the form of concentrated compositions, the compositions employed by the end-user are as a rule diluted. The preparations can for application be diluted down to 0.001% of active ingredient. The applied amounts are usually 0.01 to 10 kg, preferably 0.025 to 5 kg, of active substance per hectare.
The compositions can also contain additi.ves such as stabilisers, antifoaming agents, viscosity regulators, binders and adhesives, as well as fertilisers or ot'rer active substances for obtaining special effects.
2~53 The invention relates also to such compositions which are usable in agriculture and which contain, as at least one active ingredient, a compound of the formula I.
The present invention embraces also the produc~ion of the said compositions, whereby the active ingredient is intimately mixed with one or more substances or groups of substances described herein. Likewise included is a method for treating plants, which method comprises the application of the compounds of the formula I or of the novel compositions containing them.
Temperatures in the following Examples are given in degrees Centigrade, and percentages and parts are by weight.
Production Examples Example 1: a) Production of the intermediate I
\S02-~TH-C-0--~ ~, N-(4-Imidazolylsulfonyl)-phenylcarbamate 2.18 g of a 55% sodium hydride dispersion in oil are added portionwise at room temperature in the course of 15 minutes, in a nitrogen atmosphere, to a solution of 7.35 g of 4-imidazolylsulfonamide in 100 ml of dimethyl-formamide; and the mixture is allowed to react for a further 20 minutes. To the resulting solution are added dropwise during 30 minutes, at room temperature, 11.24 g of diphenylcarbonate dissolved in 40 ml of dimethyl-formamide. The reaction mixture is stirred for a further 30 minutes, and is then poured into a mixture of 400 ml ~.22~$3 of ice and 50 ml of 2N HCl; the formed precipitate is subsequently taken up in 300 ml of ethyl acetate, extracted twice with ethyl acetate and ice water, dried, and concentrated by evaporation. The carbamate desired is obtained in quantitative yield: m.p. ]98-200C.
b) Production of the final product ~ S02-NH- C-NH- ~
=--N-(4-Imidazolylsulfonyl~-N'-(4-methyl-6-methoxy-1,3,5-triazin-2-yl)-urea A suspension of 13.35 g of N-(4-imidazolylsulfonyl)~
phenylcarbamate and 7 g of 2-amino-4-methyl-6-methoxy-1,3,5-triazine in 140 ml of absolute dioxane is stirred for 75 minutes at reflux temperature. The reaction mixture is filtered hot, and 8.4 ml of isopropylamine are added to the cooled filtrate; the solvent is subsequently decanted, and the semicrystalline isopropylammonium salt is washed three times with ethyl acetate. The salt is dissolved cold in 200 ml of water; the solution is filtered, the filtrate is adjusted to pH 1 with 2N hydrochloric acid, and then filtered. The filter residue is washed with cold water and dried. The yield is 5.6 g of the desired sulfonylurea; m.p. from 147C, with decomposition.
Example 2- a) Production of the starting product -T~ T~ o ._.
C 2H5 S S 02-~H-C-O ~ ,, IL~53 N-~5-Eth~1-1,3,4-thiadiazol~1~2-sulfonyl2-~henylcarbamate 2.2 g of sodium hydride are added portionwise at room temperature in a nitrogen atmosphere, with stirring, to a solution of 9 7 g of 5-~ethyl~ 3~4 thiadiazcLe-2 sulfonamide in 100 ml of absolute dîmethylfoxma~ide.
After lS minutes' stirring, a solution of 31.2 g of dipherlylcarbonate in 30 ml of dimethylformamide is added dropwise. The whole is stirred for a further three hours, and then treated with 50 ml of HCl 2N/500 ml of waterO
After filtration with suction, the precipitated crystals are washed with water and dried. The yield is 12.8 g of a substance of the above formula having the melting point of 142Co b) Production of the final product 1`1 W N_-~CH3 C H / \S/ \SO -NH-C-NH--~ ~N
N-(5-Ethyl-1,3,4-thiadiazolyl-2-sulfonyl)-N'-(4-methyl-6-methoxy-1,3,5-triazin-2-yl)-urea A mixture of 12.8 g of the product described under a) and 5.8 g of 2-amino-4-methoxy-6-methyl-1,3,5-triazine in 100 ml of absolute dioxane is refluxed for 1 hour.
The mixture is concentrated by evaporation, and hexane is added to the residue. The yield is 2.9 g of a white substance of the above formula, m.p. 60C.
Example 3:
~\ ~- -so2NH-c-NH- .~ ~.
'753 N-(l-Methylimidazol-2-ylsulfonyl)-N'-(4,6-dimethoxy-pyrimidin-2-yl)-urea .. .. . _ . _ 2.4 g of methylimidazol-2-yl-sulfonamide are dissolved in SQ ml of absolute dioxane., and 2.25 g of 1.8-~laza-bicyclo[5.4 0]undec 7-ene are addedO Ther.e are :hen added porti.onwise at 20-25C~ within 30 minutes~ 4~2 g of 4,6 d:i.methoxy-2-phenoxycarbonylaminopyrimidine. After 4 hours, the reaction mixture is taken up with ice water and acidified with 2N HCl, whereupon a precipitate is formed.
50 ml of ethyl acetate are addedj and filtration is carried out~ the precipitate is subsequently washed with water and ethyl acetate and then dried. The yield is 4.0 g (78%) of a colourless, crystalline product, m.pD 189C
(decomposition).
~22275i3 The intermediates and final products listed in the following Tables can be produced in an analogous manner.
The heterocycles Q defined in Table 1 appear in the other Tables wi-.h the same abbreviated meaning~
Table 1:
Q-S02~ H2 No. _ Abbrevi- ¦ Physical data _ ation 1.1 ~ Ql 1.2 n~ Q2 1.3 W,-~ Q3 1. 4 ' H C W ~ Q4 1.5 H3C-N~o~il Q5 1. 6 H C- --'-- Q6 .. __.. ._____....... .__ -~Z2;~53 Table 1 (continuation) __ _ .
ll o . a t ion Phy s i ca l data lo7H C--CO-N-II ~ - Q7 1. 8 \S/ Q8 1. 9 ~NI Qg . loH3C-IIb 1-- Qlo 1~ llI; 11 Qll 1. 12 \s Ql2 .13 ~I; Ql3 .14 ll ll_ Ql4 1 ~15Cl- .~I! Q15 , I _ ~_ 22~S3 Table 1 (continuation) ~ ..
No. Q Abbrevi- Physical data ation _ ..... ... . - . . _ ___ l.16 11 ~ol _ Q16 n,p.142-145c C~13 1.17 ; --N Q17 1.18 I; I!N Q18 Y
1 19 'I-li Ql9 1.20H3C- ~U; - Q20 1.21 N ~ . _ Q21 1.22 ~ --N Q22 D
H
1.23 . N Q23 ~ \S;- _ ' .
.
,~7~i3 Table 1 (contlnuation) .
No, Q Abbrevi- Physical data _ _ _ . _ _ ation _ ___ _ _ _ l.2l, N-- Q2~
''\/
1.25 \o/ Q25 1.26 S Q26 1.27 - N\ / Q27 1.. 8 H3C~II\s~l~ _ Q28 1.29 _ Q29 1.30 I; I!_ Q30 m.p.l68-169C
\NI /6H5 1.31 I; 11_ Q31 m.p. 99C
(CH2) 2-OCH3 1.32 Ij l! Q32 m.p.114C
. CH -C H I
7~3 Table 1 (continuation) _. , , . _ . , .
No. ¦ Q ! Abbrevi- Physical data ' _l ation 1.33 ~ - N ¦ Q33 1.34 ~ Q34 m.p. 179~C
1.35 ~ N_ Q35 m.p. 92C
y Q36 m . p . 182 ~C
~. Q37 m,p, 152~C
1.38 HO-- N Q m.p. 183~C
3 ~ lecOmp~) Table (continuation) . .
¦ No. ¦ Q Abbrevi- Physical data I . .. . ... _.
~ 1I ll _ Q39 m.pO223-225c ~ o/il- ~ ~
I.40 C3~17-i 1.41 -I; -~ N! Q41 C5H l l -n 1.42 I; ~I! . Q42 H C-C-C H -n 1.43 - ~ Q43 ~ . .
Table 1 (continuation) r -~
¦ No. Q Abbrevi- ¦ Physical data _ . _ ation . _ ~ _ ~ ~. ! "~5 1.~7 .~ Q47 ~ I
¦1.43 ~ nl ~ Q43 ~ ~
~ CO-CH
1.49 ; Ij C~lH37 _ ' Q49 1.50 ~ Q50 _ (CH2)3-OCH3 ~L~Z2~i3 Table 1 (continuation) j . .. ~ .
No. ¦ Q Abbrevi- Physical data I ation .. _ .. . . __ il ~1 H C-~ - N Q51 1.52 I; 11 _ Q52 2)3 3 lc53 ' ~ ,i-COOCH3 Q53 1.54 N---. Q54 !W!-COOC2H5 1.55 N-----COOCH3 o~55 W
1.56 N - -COOC2H5 Q56 ~.
H
, ~ ~ ~v Table 1 (continuation) No. Q I Abbrevi- Physical data . . , .
1.58H3~- . Q58 N\~C~;-CH3 1059. ~ I! Q59 1.60C~H5 Q60 ~
1.62H3C I! ~ I. Q62 1.63t-C H ~ l Q63 ^o-~(CH3)2 _ .
~Z2;~7~i3 Table 2 ?-so2-NH-co-oR
. . ~
No. Q ¦ R Physical data . .. 1_ ._ ¦ 2.1 Ql ¦ 6 5 m.p~ 198-200C
2.2 Q2 C6~15 ¦ 2.3 Q3 C6H5 2.4 Q4 C6H5 2.5 Q5 C6H5 2.6 Q6 C6H5 2.7 Q7 C6H5 2.8 Q8 C6H5 2 . 9 Q9 C6H5 2. lo Qlo C6H5 2.11 Qll C6H5 2.12 Q12 C6H5 m.p. 142C
2.13 Q13 C6H5 2.14 Q14 C6H5 2.15 Q15 C6H
2.16 Q16 C6H
2.17 Q17 C6H
2.18 Q18 C6H
2.19 Ql9 C6H
2.20 Q20 C6H
2. 21 Q21 C6H
~ ~" C6U5 ~ .
~L~22~3 Table 2 ~continuation) . . _ No. Q R Physical data _ 2.23 Q22 C~15 24 Q2~; 1 C6~15 2.25 Q25 C6H5 2.26 Q26 C6H5 2.27 Q27 C61-15 2.28 Q28 C6H5 2.29 Q29 C6H5 2.30 Q30 C6H5 2.31 Q31 C6H5 2.32 Q32 C6H5 2.34 Q34 C6H5 2.35 Q35 C6H5 2.36 Q36 C6H5 2.37 Q37 C6H5 2.38 Q38 C6H5 2.39 Q39 C6H5 2.40 Q40 C6H5 2.41 Q41 C6H5 2.42 Q42 C6H5 2.43 Q43 C6H5 ^ 4: Q44 C6H5 ~ ~9~
Table 2 (continuation) ~ .
No. ¦ Q R Physical data I Q45 C6~i5 ~46 Q4~ C6~15 2.47 Q47 C6FI5 2.48 Q48 C6H5 2.49 Q49 C6H5 2~50 Q50 C6H5 2~51 Q51 C6H5 2.52 Q52 C6H5 2.53 Q53 C6H5 2.55 Q55 C6H5 2.56 Q56 C6H5 2.57 Q57 C6H5 2.58 Q58 C6H5 2.59 Q59 C6H5 2.60 Q60 C6H5 ¦2.61 Q61 C6H5 2.62 Q62 C6H5 2.63 Q63 C6H5 2.64 Ql CH3 2.65 Q2 CH3 . .6 ~ CH3 .
Table 2 (continuation) No. Q i R Phy s i ca ï data ._ _ 2.67 Q4 CE13 ~.68 Q5 ~13 2.69 Q6 C113 2.70 Q7 CH3 2.71 Q8 CH3 2.72 Q9 CH3 2.73 Qlo CH3 2.74 Qll CH3 ?.75 Q12 CH3 2.76 Q13 CH3 2.77 Q14 CH3 2.78 Q15 CH3 2.79 Q16 CH3 2.80 Q17 CH3 2.81 Q18 CH3 2.82 Q19 CH3 2.83 Q20 CH3 2.84 Q21 CH3 2.85 Q22 CH3 2.86 Q23 CH3 2.87 Q24 CH3 . ~ ~.~ C~13 _ _ ~2~ 53 Table 2 (continuation) .
..
No. Q R Physical data . _ .. ._ ~ ._ 2.89 Q26 CH3 ~o90 Q27 C113 2~91 Q28 CH3 2~92 Q29 CH3 2.93 Q30 CH3 2.94 Q31 CH3 2.95 Q32 CH3 2.96 Q33 CH3 2.97 Q34 CH3 2.98 Q35 CH3 2.99 Q36 CH3 2.100 Q37 CH3 2.101 Q38 CH3 2.102 Q39 CH3 2.103 Q40 CH3 2.104 Q41 CH3 2.105 Q42 CH3 2.106 Q43 CH3 2.107 Q44 CH3 2.108 Q45 CH3 2.109 Q46 CH3 2.110 Q47 C~13 , ~ _ _ 2~5~
Table 2 (conti.nuation) No. . R ~ Physical da .. .. I
2.111 Q48 CH3 ~.112 Q~g ~ll3 2.l13 Q50 CH3 2.114 Q51 CH3 2.115 Q52 CH3 2.116 Q53 CH3 2.117 Q54 CH3 2.118 Q55 CH3 2.119 Q56 CH3 2.120 Q57 CH3 2.121 Q58 CH3 2.122 Q59 CH3 2.123 Q60 CH3 2.124 Q61 CH3 2.125 Q62 CH3 2.126 Q63 CH3 2.127 Ql C2H5 2.128 Q2 C2H5 2.129 Q3 C2H5 2.130 Q4 C2H5 2.131 Q5 C2H5 . ~ ~ C2~15 ~Z~ i3 Table 2 (continuation) ~. .. ~
No. Q R Physical data . _._ 2.133 Q7c2~s 2.134 Q8C2H5 2.135 Q9C2H5 2.136 QloC2H5 2.137 QllC2H5 2.138 Q12C2H5 2.139 Q13C2H5 2.140 Q14C2H5 2.141 Q15C2H5 2.142 Q16C2H5 2.143 Q17C2H5 2.144 Q18C2H5 2.145 Ql9C2H5 2.146 Q20C2H5 2.147 Q21C2H5 2.148 Q22C2H5 2.149 Q23C2H5 2.150 Q24C2H5 2.151 Q25C2H5 2.152 `26C2H5 2.153 Q27C2H5 ~ Q28__C ~15 -~L2~ ~ ~
Table 2 (continuation) No. Q ¦ R Physical data . _ ~
2.l55 Q29 C~H5 2.156 Q30 I C~ 5 20157 Q31 ~ C21-15 2.158 Q32 C2H5 2.159 Q33 C2H5 2.160 Q34 C2E5 2.161 Q35 C2H5 2.163 Q37 C2H5 2.l64 Q38 C2H5 2.165 Q39 C2H5 2.166 Q40 C2H5 2.167 Q41 C2H5 2.168 Q42 C2H5 2.169 Q43 C2H5 2.170 Q44 C2H5 2.171 Q45 C2H5 2.172 Q46 C2H5 2.173 ¦ Q47C2H5 2.174 Q48 C2H5 2.175 Qh9 C2H5 _ o~,, _ C2H5 , ~I.Z~2~i3 Table 2 (continuation) .
_ _ _ _ Q ¦ R Physical data - __ ~ _ 2.177 Q5, C2H5 2.178 Q52 C?H5 2.179 Q53 C2H5 2.180 Q54 C2H5 2.181 Q55 C2H5 2.182 Q59 C2H5 2.183 Q60 C2H5 2.184 Q61 C2H5 2.183 Q62 C2H5 2.184 Q63 C2H5 _ ~ ~,3 ~r O
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Formulation Examples E _ ele 4:
Formul~ion Exam~les for acti e~o~LJT~ ormula I
(~/0 = per cent by weight~
a) Wet~able powder a) b) c) active ingredient 20% 60% 0.5%
sodium lignin sulfonate 5% 5% 5%
sodium lauryl sulfate 3%
sodium diisobutylnaphthalene - 6% 6%
sulfonate octylphenolpolyethylene glycol - 2% 2%
ether (7-8 mols of ethylene oxide) highly dispersed silicic acid 5% 27% 27%
kaolin 67% - -sodium chloride - - 59.5%
The active ingredient is well mixed with the additives and ground in a suitable mill. There are obtained wettable powders which can be diluted with water to give suspensions of the concentratlon desired.
b) Emulsion concentrate a) b) active ingredient 10% 1%
octylphenolpolyethylene glycol ether 3% 3~/~
(4-5 mols of ethylene oxide) calcium dodecyl benzene sul~onate 3% 3%
castor oil polyglycol ether 4% 4%
(36 mols of ethylene oxide) cyclohexanone 30% 10%
xylene mixture 50% 79%
Emulsions of the concentration desired can be obtained from this concentrate by dilution with water.
5i3 c) Dust a) b) active ingredient 0.1% 1%
talcum 99.9%
haolln - 99%
~ -~sts ready for use are obtained by mixing the active-ingredient with the carriers, and grinding the mixture in a suitable mill.
d) Extruder granulate a) b) active ingredient 10% 1%
sodium lignin sulfonate 2% 2%
carboxymethylcellulose 1% 1%
kaolin 87% 96%
The active ingredient is mixed with the additives 3 and the mixture is then ground and moistened with water. It is extruded and subsequently dried in a stream of air.
e) Coated granulate active ingredient 3%
polyethylene glycol (MG 200) 3%
kaolin 94%
The finely ground active ingredient is uniformuly applied~ in a mixer, to the kaolin moistened with poiy-ethylene glycol. Non-dusty coated granulates are obtained in this manner.
f) Suspension concentrate a) b) active ingredient 40% 5%
ethylene glycol 10% 10%
nonylphenolpolyethylene glycol 6% 1%
ether (15 mols of ethylene oxide) sodium lignin sulfonate 10% 5%
carboxymethylcellulose 1% 1%
~2Z~753 - 54 - a) b) (cont.) 37% aqueous formaldehyde solution 0.2% 0.2%
silicone oil in the form of a 0.8% 0.8%
75% aqueous emulsîon water 32% 77%
rhe f:inely ground active ingredient is in~imately mixed with the additives. There is thus obtained a suspension concentrate from which can be produced, by dilution with water, suspensions of the concentration desired.
g) Salt solution active ingredient 5%
isopropylamine 1%
octylphenolpolyethylene glycol ether 3%
(78 mols of ethylene oxide) water 91%
Emulsions of the application concentration required can be obtained from such concentrates by dilution with water, and they are particularly suitable for leaf appli-cation. Furthermore, it is possible to produce further wettable powders having other mixture ratios or other carriers and additives common in formulation practice.
The active ingredients are intimately mixed, in suitable mixers, with the stated additives, and the mixture is ground in appropriate mills and rollers. There are obtained wettable powders having excellent wetting and suspension properties, which can be diluted with water to give suspensions of the required concentration and which can be used in particular for leaf application. Compositions of this type likewise form subject matter of the present invention.
Compositions which have been formulated in the manner described above, and which contain as active component one of the compounds shown in Table 1, can be used with a very high degree of success as plant~growth regulators and/or as herbic,ides.
Biological Examples xample 5: Herbicidal action before emergence of the plants Plastics pots are filled with expanded vermiculite (density: 0.135 g/cm3, water-absorption capacity:
0.565 1/1). After saturation of the non-adorptive vermiculite with an aqueous active-substance emulsion in deionised water, which contains the active-ingredient at a concentration of 70.8 ppm, seeds of the following plants are sown on the surface-: Nasturtium officinalis, Agrostis tenuis, Stellaria media and Digitaria sanguinalis. The test vessels are subsequently kept in a climatic chamber at 20~C, with an illumination of about 20 k lux and a relative humidity of 70%. During the germination phase of 4 to 5 days, the pots are covered over with light-permeable material in order to raise the local air humidity and watered with deionised water. After the 5th day, 0.5%
of a commercial liquid fertiliser ( ~ Greenzit) is added to the water. The test is evaluated 12 days after sowing, and the effect on the test plants assessed according to the following scale of ratings:
1 plants have not germinated or are totally destroyed 2-3 very strong action
¦ No. ¦ Q Abbrevi- Physical data I . .. . ... _.
~ 1I ll _ Q39 m.pO223-225c ~ o/il- ~ ~
I.40 C3~17-i 1.41 -I; -~ N! Q41 C5H l l -n 1.42 I; ~I! . Q42 H C-C-C H -n 1.43 - ~ Q43 ~ . .
Table 1 (continuation) r -~
¦ No. Q Abbrevi- ¦ Physical data _ . _ ation . _ ~ _ ~ ~. ! "~5 1.~7 .~ Q47 ~ I
¦1.43 ~ nl ~ Q43 ~ ~
~ CO-CH
1.49 ; Ij C~lH37 _ ' Q49 1.50 ~ Q50 _ (CH2)3-OCH3 ~L~Z2~i3 Table 1 (continuation) j . .. ~ .
No. ¦ Q Abbrevi- Physical data I ation .. _ .. . . __ il ~1 H C-~ - N Q51 1.52 I; 11 _ Q52 2)3 3 lc53 ' ~ ,i-COOCH3 Q53 1.54 N---. Q54 !W!-COOC2H5 1.55 N-----COOCH3 o~55 W
1.56 N - -COOC2H5 Q56 ~.
H
, ~ ~ ~v Table 1 (continuation) No. Q I Abbrevi- Physical data . . , .
1.58H3~- . Q58 N\~C~;-CH3 1059. ~ I! Q59 1.60C~H5 Q60 ~
1.62H3C I! ~ I. Q62 1.63t-C H ~ l Q63 ^o-~(CH3)2 _ .
~Z2;~7~i3 Table 2 ?-so2-NH-co-oR
. . ~
No. Q ¦ R Physical data . .. 1_ ._ ¦ 2.1 Ql ¦ 6 5 m.p~ 198-200C
2.2 Q2 C6~15 ¦ 2.3 Q3 C6H5 2.4 Q4 C6H5 2.5 Q5 C6H5 2.6 Q6 C6H5 2.7 Q7 C6H5 2.8 Q8 C6H5 2 . 9 Q9 C6H5 2. lo Qlo C6H5 2.11 Qll C6H5 2.12 Q12 C6H5 m.p. 142C
2.13 Q13 C6H5 2.14 Q14 C6H5 2.15 Q15 C6H
2.16 Q16 C6H
2.17 Q17 C6H
2.18 Q18 C6H
2.19 Ql9 C6H
2.20 Q20 C6H
2. 21 Q21 C6H
~ ~" C6U5 ~ .
~L~22~3 Table 2 ~continuation) . . _ No. Q R Physical data _ 2.23 Q22 C~15 24 Q2~; 1 C6~15 2.25 Q25 C6H5 2.26 Q26 C6H5 2.27 Q27 C61-15 2.28 Q28 C6H5 2.29 Q29 C6H5 2.30 Q30 C6H5 2.31 Q31 C6H5 2.32 Q32 C6H5 2.34 Q34 C6H5 2.35 Q35 C6H5 2.36 Q36 C6H5 2.37 Q37 C6H5 2.38 Q38 C6H5 2.39 Q39 C6H5 2.40 Q40 C6H5 2.41 Q41 C6H5 2.42 Q42 C6H5 2.43 Q43 C6H5 ^ 4: Q44 C6H5 ~ ~9~
Table 2 (continuation) ~ .
No. ¦ Q R Physical data I Q45 C6~i5 ~46 Q4~ C6~15 2.47 Q47 C6FI5 2.48 Q48 C6H5 2.49 Q49 C6H5 2~50 Q50 C6H5 2~51 Q51 C6H5 2.52 Q52 C6H5 2.53 Q53 C6H5 2.55 Q55 C6H5 2.56 Q56 C6H5 2.57 Q57 C6H5 2.58 Q58 C6H5 2.59 Q59 C6H5 2.60 Q60 C6H5 ¦2.61 Q61 C6H5 2.62 Q62 C6H5 2.63 Q63 C6H5 2.64 Ql CH3 2.65 Q2 CH3 . .6 ~ CH3 .
Table 2 (continuation) No. Q i R Phy s i ca ï data ._ _ 2.67 Q4 CE13 ~.68 Q5 ~13 2.69 Q6 C113 2.70 Q7 CH3 2.71 Q8 CH3 2.72 Q9 CH3 2.73 Qlo CH3 2.74 Qll CH3 ?.75 Q12 CH3 2.76 Q13 CH3 2.77 Q14 CH3 2.78 Q15 CH3 2.79 Q16 CH3 2.80 Q17 CH3 2.81 Q18 CH3 2.82 Q19 CH3 2.83 Q20 CH3 2.84 Q21 CH3 2.85 Q22 CH3 2.86 Q23 CH3 2.87 Q24 CH3 . ~ ~.~ C~13 _ _ ~2~ 53 Table 2 (continuation) .
..
No. Q R Physical data . _ .. ._ ~ ._ 2.89 Q26 CH3 ~o90 Q27 C113 2~91 Q28 CH3 2~92 Q29 CH3 2.93 Q30 CH3 2.94 Q31 CH3 2.95 Q32 CH3 2.96 Q33 CH3 2.97 Q34 CH3 2.98 Q35 CH3 2.99 Q36 CH3 2.100 Q37 CH3 2.101 Q38 CH3 2.102 Q39 CH3 2.103 Q40 CH3 2.104 Q41 CH3 2.105 Q42 CH3 2.106 Q43 CH3 2.107 Q44 CH3 2.108 Q45 CH3 2.109 Q46 CH3 2.110 Q47 C~13 , ~ _ _ 2~5~
Table 2 (conti.nuation) No. . R ~ Physical da .. .. I
2.111 Q48 CH3 ~.112 Q~g ~ll3 2.l13 Q50 CH3 2.114 Q51 CH3 2.115 Q52 CH3 2.116 Q53 CH3 2.117 Q54 CH3 2.118 Q55 CH3 2.119 Q56 CH3 2.120 Q57 CH3 2.121 Q58 CH3 2.122 Q59 CH3 2.123 Q60 CH3 2.124 Q61 CH3 2.125 Q62 CH3 2.126 Q63 CH3 2.127 Ql C2H5 2.128 Q2 C2H5 2.129 Q3 C2H5 2.130 Q4 C2H5 2.131 Q5 C2H5 . ~ ~ C2~15 ~Z~ i3 Table 2 (continuation) ~. .. ~
No. Q R Physical data . _._ 2.133 Q7c2~s 2.134 Q8C2H5 2.135 Q9C2H5 2.136 QloC2H5 2.137 QllC2H5 2.138 Q12C2H5 2.139 Q13C2H5 2.140 Q14C2H5 2.141 Q15C2H5 2.142 Q16C2H5 2.143 Q17C2H5 2.144 Q18C2H5 2.145 Ql9C2H5 2.146 Q20C2H5 2.147 Q21C2H5 2.148 Q22C2H5 2.149 Q23C2H5 2.150 Q24C2H5 2.151 Q25C2H5 2.152 `26C2H5 2.153 Q27C2H5 ~ Q28__C ~15 -~L2~ ~ ~
Table 2 (continuation) No. Q ¦ R Physical data . _ ~
2.l55 Q29 C~H5 2.156 Q30 I C~ 5 20157 Q31 ~ C21-15 2.158 Q32 C2H5 2.159 Q33 C2H5 2.160 Q34 C2E5 2.161 Q35 C2H5 2.163 Q37 C2H5 2.l64 Q38 C2H5 2.165 Q39 C2H5 2.166 Q40 C2H5 2.167 Q41 C2H5 2.168 Q42 C2H5 2.169 Q43 C2H5 2.170 Q44 C2H5 2.171 Q45 C2H5 2.172 Q46 C2H5 2.173 ¦ Q47C2H5 2.174 Q48 C2H5 2.175 Qh9 C2H5 _ o~,, _ C2H5 , ~I.Z~2~i3 Table 2 (continuation) .
_ _ _ _ Q ¦ R Physical data - __ ~ _ 2.177 Q5, C2H5 2.178 Q52 C?H5 2.179 Q53 C2H5 2.180 Q54 C2H5 2.181 Q55 C2H5 2.182 Q59 C2H5 2.183 Q60 C2H5 2.184 Q61 C2H5 2.183 Q62 C2H5 2.184 Q63 C2H5 _ ~ ~,3 ~r O
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Formulation Examples E _ ele 4:
Formul~ion Exam~les for acti e~o~LJT~ ormula I
(~/0 = per cent by weight~
a) Wet~able powder a) b) c) active ingredient 20% 60% 0.5%
sodium lignin sulfonate 5% 5% 5%
sodium lauryl sulfate 3%
sodium diisobutylnaphthalene - 6% 6%
sulfonate octylphenolpolyethylene glycol - 2% 2%
ether (7-8 mols of ethylene oxide) highly dispersed silicic acid 5% 27% 27%
kaolin 67% - -sodium chloride - - 59.5%
The active ingredient is well mixed with the additives and ground in a suitable mill. There are obtained wettable powders which can be diluted with water to give suspensions of the concentratlon desired.
b) Emulsion concentrate a) b) active ingredient 10% 1%
octylphenolpolyethylene glycol ether 3% 3~/~
(4-5 mols of ethylene oxide) calcium dodecyl benzene sul~onate 3% 3%
castor oil polyglycol ether 4% 4%
(36 mols of ethylene oxide) cyclohexanone 30% 10%
xylene mixture 50% 79%
Emulsions of the concentration desired can be obtained from this concentrate by dilution with water.
5i3 c) Dust a) b) active ingredient 0.1% 1%
talcum 99.9%
haolln - 99%
~ -~sts ready for use are obtained by mixing the active-ingredient with the carriers, and grinding the mixture in a suitable mill.
d) Extruder granulate a) b) active ingredient 10% 1%
sodium lignin sulfonate 2% 2%
carboxymethylcellulose 1% 1%
kaolin 87% 96%
The active ingredient is mixed with the additives 3 and the mixture is then ground and moistened with water. It is extruded and subsequently dried in a stream of air.
e) Coated granulate active ingredient 3%
polyethylene glycol (MG 200) 3%
kaolin 94%
The finely ground active ingredient is uniformuly applied~ in a mixer, to the kaolin moistened with poiy-ethylene glycol. Non-dusty coated granulates are obtained in this manner.
f) Suspension concentrate a) b) active ingredient 40% 5%
ethylene glycol 10% 10%
nonylphenolpolyethylene glycol 6% 1%
ether (15 mols of ethylene oxide) sodium lignin sulfonate 10% 5%
carboxymethylcellulose 1% 1%
~2Z~753 - 54 - a) b) (cont.) 37% aqueous formaldehyde solution 0.2% 0.2%
silicone oil in the form of a 0.8% 0.8%
75% aqueous emulsîon water 32% 77%
rhe f:inely ground active ingredient is in~imately mixed with the additives. There is thus obtained a suspension concentrate from which can be produced, by dilution with water, suspensions of the concentration desired.
g) Salt solution active ingredient 5%
isopropylamine 1%
octylphenolpolyethylene glycol ether 3%
(78 mols of ethylene oxide) water 91%
Emulsions of the application concentration required can be obtained from such concentrates by dilution with water, and they are particularly suitable for leaf appli-cation. Furthermore, it is possible to produce further wettable powders having other mixture ratios or other carriers and additives common in formulation practice.
The active ingredients are intimately mixed, in suitable mixers, with the stated additives, and the mixture is ground in appropriate mills and rollers. There are obtained wettable powders having excellent wetting and suspension properties, which can be diluted with water to give suspensions of the required concentration and which can be used in particular for leaf application. Compositions of this type likewise form subject matter of the present invention.
Compositions which have been formulated in the manner described above, and which contain as active component one of the compounds shown in Table 1, can be used with a very high degree of success as plant~growth regulators and/or as herbic,ides.
Biological Examples xample 5: Herbicidal action before emergence of the plants Plastics pots are filled with expanded vermiculite (density: 0.135 g/cm3, water-absorption capacity:
0.565 1/1). After saturation of the non-adorptive vermiculite with an aqueous active-substance emulsion in deionised water, which contains the active-ingredient at a concentration of 70.8 ppm, seeds of the following plants are sown on the surface-: Nasturtium officinalis, Agrostis tenuis, Stellaria media and Digitaria sanguinalis. The test vessels are subsequently kept in a climatic chamber at 20~C, with an illumination of about 20 k lux and a relative humidity of 70%. During the germination phase of 4 to 5 days, the pots are covered over with light-permeable material in order to raise the local air humidity and watered with deionised water. After the 5th day, 0.5%
of a commercial liquid fertiliser ( ~ Greenzit) is added to the water. The test is evaluated 12 days after sowing, and the effect on the test plants assessed according to the following scale of ratings:
1 plants have not germinated or are totally destroyed 2-3 very strong action
4-6 medium action 7-8 weak action 9 no action (as untreated control plants)
5~
Pre-emergence act _n:
Concentration of the active-ingredient emulsion: 70.8 ppm r.rest planr _, . . . _ Active in- Nasturtium Stellaria Agrostis Digitaria gredientNo.
. .
~L222~i3 Example 6: Verification of herbicidal action after emergence_of_the plants (contact action) A largish number of weeds and cultivated plants, both monocotyledonous and dicotyledonous, are sprayed after emergence, in the 4- to 6 leaf stage, with an aqueous active-ingredient dispersion in various dosages, and are Lhen kept at 24 to 26C with 45-60% relative humidity.
Fifteen days after the treatment, the compounds of the formula I exhibited a good herbicidal action.
Example_7: Reduction of ~rowth of cereals = _ The cereal varieties Hordeum vulgare (spring barley) and Secale (spring rye) are sown in plastics pots containing sterilised soil in a greenhouse, and watered as required. The young shoots are sprayed, about 21 days after sowing, with the aqueous spray liquor of an active ingredient of the formula I. After conversion, the amounts applied are 0.5 kg and 2.5 kg, respectively, of active ingredient per hectare, and 10 and 21 days after application, the growth of the cereals is assessed. It can be established that cereal plants which have been treated with active ingredients of the formula I show a high reduction in growth compared with that shown by the untreated control plants.
Example 8: Reduction of growth of grasses The grasses Lolium perenne, Poa pratensis, Festuca ovina and Cynodon dactylon are sown, in a greenhouse, in plastics dishes containing a soil/peat/sand mixture (6:3:1), and are watered as required. The emerged grasses are cut back weekly to a height of 4 cm, and are sprayed, about 50 days after sowing and one day after the final cutting, with the aqueous spray liquor of an active ingedient of the formula I. The amount of active ingredient corresponds, 2~
when converted, to 2.5 kg of active ingredient per hectare. The growth of the grasses is assessed 10 and 21 days after application. It is shown that the active ingredients from Table 3 according to the inv~ntion effect a marked reduction in growth.
Pre-emergence act _n:
Concentration of the active-ingredient emulsion: 70.8 ppm r.rest planr _, . . . _ Active in- Nasturtium Stellaria Agrostis Digitaria gredientNo.
. .
~L222~i3 Example 6: Verification of herbicidal action after emergence_of_the plants (contact action) A largish number of weeds and cultivated plants, both monocotyledonous and dicotyledonous, are sprayed after emergence, in the 4- to 6 leaf stage, with an aqueous active-ingredient dispersion in various dosages, and are Lhen kept at 24 to 26C with 45-60% relative humidity.
Fifteen days after the treatment, the compounds of the formula I exhibited a good herbicidal action.
Example_7: Reduction of ~rowth of cereals = _ The cereal varieties Hordeum vulgare (spring barley) and Secale (spring rye) are sown in plastics pots containing sterilised soil in a greenhouse, and watered as required. The young shoots are sprayed, about 21 days after sowing, with the aqueous spray liquor of an active ingredient of the formula I. After conversion, the amounts applied are 0.5 kg and 2.5 kg, respectively, of active ingredient per hectare, and 10 and 21 days after application, the growth of the cereals is assessed. It can be established that cereal plants which have been treated with active ingredients of the formula I show a high reduction in growth compared with that shown by the untreated control plants.
Example 8: Reduction of growth of grasses The grasses Lolium perenne, Poa pratensis, Festuca ovina and Cynodon dactylon are sown, in a greenhouse, in plastics dishes containing a soil/peat/sand mixture (6:3:1), and are watered as required. The emerged grasses are cut back weekly to a height of 4 cm, and are sprayed, about 50 days after sowing and one day after the final cutting, with the aqueous spray liquor of an active ingedient of the formula I. The amount of active ingredient corresponds, 2~
when converted, to 2.5 kg of active ingredient per hectare. The growth of the grasses is assessed 10 and 21 days after application. It is shown that the active ingredients from Table 3 according to the inv~ntion effect a marked reduction in growth.
Claims (15)
1. A compound of the formula I
(I) wherein R1 is hydrogen or C1-C5-alkyl, R2 and R3 independently of one another are each hydrogen, C1-C5-alkyl, C1-C5-alkoxy, C1-C5-alkylthio, C1-C5-haloalkyl, halogen, C1-C5-haloalkoxy, C1-C5-halo-alkylthio, C1-C5-alkylamino, di-C1-C4-alkylamino, or an alkoxyalkyl group or alkoxyalkoxy group each having a maximum of 6 carbon atoms, Z is oxygen or sulfur, E is -CH= or -N=, and Q is an unsubstituted or substituted, five-membered, heterocyclic radical selected from the group pyrazole, imidazole, 1,2,4-triazole, 1,2,3-triazole, oxazole, thiazole, isooxazole, isothiazole, furazan, 1,2,4-thiadiazole, 1,2,4-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole or 1,3,4-thiadiazole, which is bound by the way of a carbon atom wherein the optional substituents are selected from the group halogen, nitro, C1-C6-alkyl, C1-C6 haloalkyl, C1-C6-alkoxy, C1-C6-alkylthio, hydroxyl, C1-C6-haloalkoxy, C1-C6-haloalkylthio, amino, C1-C6-alkyl-amino,di-C1-C6-alkylamino, C1-C6-alkylcarbonylamino, C1-C6-alkylcaxbonyl, C1-C6-alkoxycarbonyl, C2-C8-alkoxyalkyl, C1-C6 alkylthiocarbonyl, carbamoyl, C1-C6-alkylaminocarbonyl, di-C1-C6,-alkylaminocarbonyl, C1-C6-alkylsulfinyl, C1-C6-alkylsulfonyl, C2-C6-alkenyloxy or C3-C6-alkynyloxy; or a phenyl, phenoxy or phenylthio group each unsubstituted or substituted by C1-C6-alkylcarbonyl, C1-C6-alkoxycarbonyl, halogen, nitro, cyano, C1-C6 alkyl, C1-C6-alkoxy, C1-C6-haloalkyl or C1-C6-haloalkoxy; or a benzyl group unsubsti-tuted or substituted by halogen and/or C1-C6-alkyl; inclu-ding the salts thereof.
(I) wherein R1 is hydrogen or C1-C5-alkyl, R2 and R3 independently of one another are each hydrogen, C1-C5-alkyl, C1-C5-alkoxy, C1-C5-alkylthio, C1-C5-haloalkyl, halogen, C1-C5-haloalkoxy, C1-C5-halo-alkylthio, C1-C5-alkylamino, di-C1-C4-alkylamino, or an alkoxyalkyl group or alkoxyalkoxy group each having a maximum of 6 carbon atoms, Z is oxygen or sulfur, E is -CH= or -N=, and Q is an unsubstituted or substituted, five-membered, heterocyclic radical selected from the group pyrazole, imidazole, 1,2,4-triazole, 1,2,3-triazole, oxazole, thiazole, isooxazole, isothiazole, furazan, 1,2,4-thiadiazole, 1,2,4-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole or 1,3,4-thiadiazole, which is bound by the way of a carbon atom wherein the optional substituents are selected from the group halogen, nitro, C1-C6-alkyl, C1-C6 haloalkyl, C1-C6-alkoxy, C1-C6-alkylthio, hydroxyl, C1-C6-haloalkoxy, C1-C6-haloalkylthio, amino, C1-C6-alkyl-amino,di-C1-C6-alkylamino, C1-C6-alkylcarbonylamino, C1-C6-alkylcaxbonyl, C1-C6-alkoxycarbonyl, C2-C8-alkoxyalkyl, C1-C6 alkylthiocarbonyl, carbamoyl, C1-C6-alkylaminocarbonyl, di-C1-C6,-alkylaminocarbonyl, C1-C6-alkylsulfinyl, C1-C6-alkylsulfonyl, C2-C6-alkenyloxy or C3-C6-alkynyloxy; or a phenyl, phenoxy or phenylthio group each unsubstituted or substituted by C1-C6-alkylcarbonyl, C1-C6-alkoxycarbonyl, halogen, nitro, cyano, C1-C6 alkyl, C1-C6-alkoxy, C1-C6-haloalkyl or C1-C6-haloalkoxy; or a benzyl group unsubsti-tuted or substituted by halogen and/or C1-C6-alkyl; inclu-ding the salts thereof.
2. A compound of the formula I according to Claim 1, wherein Z is oxygen, and R1 is hydrogen.
3. A compound embraced by the formula I according to Claim 1, wherein R1 is hydrogen, R2 and R3 are C1-C4-alkyl or C1-C4-a1koxy, and Q is any one of the following unsubstituted or substituted azolyl groups in which Y is in each case oxygen, sulfur or nitrogen, and Z and E are as defined under the formula I.
4. A compound of the formula I according to Claim 1, wherein R1 is hydrogen, R2 and R3 are each C1-C3-alkyl or C1-C3-alkoxy, Z is oxygen, E is nitrogen or CH, and Q is a heterocyclic radical defined under the formula I, which is unsubstituted or substituted by chlorine, bromine, fluorine, nitro, cyano, C1-C4-alkylcarbonyl, C1-C4-alkyloxycarbonyl, C1-C3-alkoxy, C1-C3-alkylthio, C1-C3-alkylsulfonyl, C2-C6-alkoxyalkyl, C1-C3-alkylsulfonyl, C1-C4-alkyl, trifluoromethyl, trichloromethyl, cyano-C1-C4-alkyl, C2-C4-alkenyloxy, C3-C4-alkynyloxy or N-C1-C4-alkylcarbonylamino.
5. N-[1-(3-Methoxy-1-propyl)-imidazol-2-ylsulfonyl]-N'-(4-methoxy-6-methyl-pyrimidin-2-yl) urea according to Claim 1.
6. A process for producing a compound of the formula I
according to Claim 1, which process comprises reacting a phenylsulfonyl derivative of the formula II
Q - S02W (II) with a compound of the formula III
(III) wherein X and W are each any one of the groups: -NH2, -N=C=Z or -NR1-CZ-OR; the substituents R1, R2, R3, Q, Z
and E have the meanings defined under the formula I, R is an aliphatic or aromatic radial; with the proviso that the reactants of the formulae II and III are in all cases selected so that an amino group is reacted either with an isocyanato or isothiocyanato group, or with an [-NR1-CZ-OR] group.
according to Claim 1, which process comprises reacting a phenylsulfonyl derivative of the formula II
Q - S02W (II) with a compound of the formula III
(III) wherein X and W are each any one of the groups: -NH2, -N=C=Z or -NR1-CZ-OR; the substituents R1, R2, R3, Q, Z
and E have the meanings defined under the formula I, R is an aliphatic or aromatic radial; with the proviso that the reactants of the formulae II and III are in all cases selected so that an amino group is reacted either with an isocyanato or isothiocyanato group, or with an [-NR1-CZ-OR] group.
7. A process according to Claim 6, wherein R is C1-C4-alkyl, phenyl or benzyl.
8. A process according to Claim 6, wherein the reaction is performed in the presence of a solvent or a solvent mixture inert to the reactants.
9. A process according to Claim 8, wherein the reaction is performed in the presence of a base.
10. A process according to Claim 8, wherein the reaction is performed at a temperature of between -20° and +120°C.
11. A method of controlling undesirable plant species in crops of cultivated plants and/or or regulating the growth of cultivated plants, which method comprises applying to the plants or to the locus thereof an effective amount of a compound of the formula I according to Claim 1.
12. A method according to Claim 11 for selectively controlling weeds.
13. A method according to Claim 11 for reducing plant growth.
14. A method for the pre- or post-emergence controlling of weeds and/or for the influencing of the growth of cultivated plants, which method comprises applying an effective amount of an active substance of the formula I
according to Claim I to the harmful plant or to the cultivated plant, to parts of these plants or to the locus thereof.
according to Claim I to the harmful plant or to the cultivated plant, to parts of these plants or to the locus thereof.
15. A herbicidal composition which contains as active ingredient a compound of formula I according to Claim 1, together with a carrier and/or inert adjuvants.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000428686A CA1222753A (en) | 1983-05-24 | 1983-05-24 | Sulfonyl(thio)ureas, processes for producing them, and their use as herbicides and/or as growth regulators |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000428686A CA1222753A (en) | 1983-05-24 | 1983-05-24 | Sulfonyl(thio)ureas, processes for producing them, and their use as herbicides and/or as growth regulators |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1222753A true CA1222753A (en) | 1987-06-09 |
Family
ID=4125306
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000428686A Expired CA1222753A (en) | 1983-05-24 | 1983-05-24 | Sulfonyl(thio)ureas, processes for producing them, and their use as herbicides and/or as growth regulators |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1222753A (en) |
-
1983
- 1983-05-24 CA CA000428686A patent/CA1222753A/en not_active Expired
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