USH168H - Herbicidal sulfonamides - Google Patents

Herbicidal sulfonamides Download PDF

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Publication number
USH168H
USH168H US06/449,547 US44954782A USH168H US H168 H USH168 H US H168H US 44954782 A US44954782 A US 44954782A US H168 H USH168 H US H168H
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sub
och
compound
benzenesulfonamide
compounds
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US06/449,547
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Michael Conner
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D521/00—Heterocyclic compounds containing unspecified hetero rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof

Definitions

  • This invention relates to N-[(heterocyclic)(alkyl)aminocarbonyl]benzenesulfonamides useful as agricultural chemicals.
  • R is CHF 2 , CF 3 , CH 2 CF 3 or CF 2 CHFG, where G is F, Cl, CF 3 or Br;
  • A is O or S(O) n , where n is 0, 1 or 2;
  • R 1 is H, F, Cl, Br or CH 3 ;
  • X is CH 3 or OCH 3 ;
  • Y is CH 3 , OCH 3 , OCH 2 CH 3 , (CH 2 ) m OCH 3 (where m is 1 or 2), OCH 2 CH 2 OCH 3 , or OCHR 2 CO 2 R 3 , where R 2 is H or CH 3 and R 3 is CH 3 or C 2 H 5 ; and
  • E is CH or N.
  • R 2 is H or alkyl of one to three carbon atoms
  • R 3 is ##STR3##
  • R 4 and R 7 are independently hydrogen, fluorine, chlorine, bromine, alkyl of 1-4 carbon atoms, alkoxy of 1-4 carbon atoms, nitro, CF 3 , CH 3 S-- or CH 3 CH 2 S--;
  • R 5 , R 6 and R 8 are independently hydrogen, fluorine, chlorine, bromine or methyl
  • X is Cl, CH 3 , --CH 2 CH 3 , alkoxy of one to three carbons, CF 3 , CH 3 S--, CH 3 OCH 2 -- or CH 3 OCH 2 CH 2 O--;
  • Y is CH 3 or OCH 3 ;
  • Z is CH or N
  • R 1 and R 2 may not simultaneously be hydrogen
  • herbicides A wide variety of materials useful for killing or inhibiting (controlling) the growth of undesired vegetation is available; such materials are commonly referred to as herbicides. The need exists, however, for still more effective herbicides that destroy or retard weeds without causing significant damage to useful crops.
  • This invention relates to novel compounds of Formula I, agriculturally suitable compositions containing them and their method-of-use as preemergent or postemergent herbicides or plant growth regulants.
  • the invention also includes the use of certain compounds of Formula I as selective herbicides, particularly on wheat and corn. ##STR5## wherein A is O or S(O) n ;
  • R is C 1 -C 4 alkyl substituted with 1-6 halogen atoms selected from 1-6 F, 0-3 Cl or 0-1 Br;
  • R 1 is H, F, Cl, Br, CH 3 , CF 3 or OCH 3 ;
  • n 0, 1 or 2;
  • X is CH 3 or OCH 3 ;
  • Y is CH 3 , OCH 3 , OCH 2 CH 3 , CH 2 CH 3 , CH 2 OCH 3 or CH 2 CH 2 OCH 3 ;
  • Z is CH or N
  • the compounds of Formula I wherein n is 0 or 2 can be prepared by the reaction of an appropriately substituted sulfonyl isocyanate of Formula II with an appropriately substituted 2-methylaminopyrimidine or 2-methylamino-1,3,5-triazine of Formula III, A, R, R 1 , X, Y and Z being as previously defined.
  • reaction is best carried out in inert aprotic organic solvents such as methylene chloride, tetrahydrofuran or acetonitrile, at ambient pressure and temperature.
  • aprotic organic solvents such as methylene chloride, tetrahydrofuran or acetonitrile.
  • the mode of addition is not critical; however, it is often convenient to add the sulfonyl isocyanate II to a stirred suspension of amine III. Since such isocyanates are usually liquids, their addition can be easily controlled.
  • the reaction is generally exothermic.
  • the desired product is insoluble in the warm reaction medium and crystallizes from it in pure form.
  • Products soluble in the reaction medium are isolated by evaporation of the solvent, trituration of the solid residue with solvents such as 1-chlorobutane or ethyl ether, and filtration.
  • the intermediate sulfonyl isocyanates of Formula II wherein n is 0 or 2 can be prepared as shown in Equation 2 by the reaction of the corresponding sulfonamides of Formula IV with phosgene in the presence of n-butyl isocyanate at reflux in a solvent such as xylene, according to the procedure of H. Ulrich and A. A. Y. Sayigh, Newer Methods of Preparative Organic Chemistry, Vol. VI, p. 223-241, Academic Press, New York and London, W. Foerst Ed.
  • a tertiary amine base such as 1,4-diaza-[2.2.2.]-bicyclooctane may catalyze the preceeding phosgenations.
  • Sulfonyl isocyanates can also be made by the method of Ulrich et al. [J. Org. Chem., 34, 3200 (1969)]: ##STR8##
  • the sulfonamide is boiled under reflux with an excess of thionyl chloride until the sulfonamide protons are undetectable by proton resonance spectrum. An overnight reaction period (about 16 hours) is generally sufficient. After evaporation of the thionyl chloride, the residue is dissolved in an inert solvent, such as toluene, benzene or xylene, and a catalytic amount of pyridine. The mixture is heated to about 60°-140° (80°-100° preferred) with at least one equivalent of phosgene to yield the desired isocyanate, usually with 3 hours.
  • an inert solvent such as toluene, benzene or xylene
  • the mixture containing the sulfonyl isocyanate can be used directly for the synthesis of sulfonylureas or the sulfonyl isocyanate can be purified by filtration and evaporation of the filtrate, followed by vacuum distillation.
  • Equation 2a Conversion of sulfonyl chlorides to sulfonamides, as shown in Equation 2a, is well known (e.g., L. Fieser and M. Fieser, op. cit., 699). It is convenient to dissolve the sulfonyl chloride in an inert solvent, e.g. toluene, ethyl acetate, tetrahydrofuran, etc., and pass in gaseous ammonia. Temperature is not critical and can range from about -20° to the boiling point of the solvent. For convenience, ambient temperatures are preferred.
  • the product can be isolated from the reaction mixture by the addition of water, evaporation of the solvent and filtration of the solid sulfonamide. If the product is soluble in the reaction mixture and the solvent is water-miscible, the product can be precipitated by addition of water and isolated by filtration.
  • Trifluoroethoxybenzene derivatives can be made by reaction of trifluoroethanol with an activated aromatic halide, e.g.:
  • Equation 3 sodium hydride and trifluoroethanol are mixed in an aprotic solvent, such as dimethylformamide (DMF), dioxane or tetrahydrofuran (THF), with 2-(fluoro or chloro)-1-nitrobenzene.
  • an aprotic solvent such as dimethylformamide (DMF), dioxane or tetrahydrofuran (THF)
  • 2-(fluoro or chloro)-1-nitrobenzene 2-(fluoro or chloro)-1-nitrobenzene.
  • the reaction proceeds to completion at ambient temperature. Heat may be applied (e.g., with a steam bath) if desired to speed the reaction to completion.
  • the product is isolated by diluting the reaction mixture with water, extracting with an organic water-immiscible solvent and evaporation of the solvent. This reaction is similar to that described in Japanese Pat. No. 5 2057-320.
  • Chlorosulfonation of aromatic substrates is well known (e.g., L. F. Fieser and M. Fieser, "Advanced Organic Chemistry", 696-698, Reinhold, New York, 1961).
  • the chlorosulfonation (Equation 4) can be accomplished by addition of the trifluoroalkoxy compound to the chlorosulfonic acid or vice versa, optionally in the presence of a cosolvent, such as an alkane or chlorinated alkane (e.g., hexane, 1-chlorobutane, methylene chloride, etc.).
  • the reaction temperature is not critical, with a range of about -5° to 50° C. operable and ambient temperature (e.g.
  • the aromatic sulfonyl chloride is conveniently isolated from the reaction mixture by pouring the mixture into ice-water, followed by extraction with a water-immiscible organic solvent in which the aromatic sulfonyl chloride is soluble.
  • solvents include 1-chlorobutane, methylene chloride, 1,2-dichloroethane, ethyl acetate, toluene and diethyl ether.
  • the solution of the sulfonyl chloride can be dried and evaporated to provide the sulfonyl chloride, which can be further purified by distillation, preferably in vacuum to suppress any thermally dependent decomposition.
  • the solution of the sulfonyl chloride can be used directly in reaction with ammonia in the next step, preparation of the sulfonamide.
  • Chlorosulfonation can produce isomeric mixtures.
  • Such isomeric mixtures can be separated by conventional routes (e.g., fractional distillation, chromatography) or used without separation. In the latter case, isomeric mixtures of sulfonamides, sulfonyl isocyanates and sulfonylureas are formed in the subsequent reactions.
  • the isomeric mixtures of intermediates formed further in the synthesis sequence can be separated or used as isomeric mixtures; isomeric mixtures of product sulfonyl(ureas and thioureas) can be used as herbicides or separated and used as individual compounds.
  • Aniline derivatives where R is CF 3 , tetrahaloethyl, HCF 2 or hexafluoropropyl can be produced by methods described by Sheppard (op. cit.), England (op. cit.) and Yagupolskii (op. cit.).
  • the aniline compound is diazotized according to methods well known in the art, [c.f. H. L. Yale and F. Sowinski, J. Org. Chem., 25, 1824 (1960)].
  • the sulfonyl chloride generally an oil
  • an organic solvent such as 1-chlorobutane, diethyl ether, toluene or ethyl acetate
  • the organic extract dried and evaporated to yield the sulfonyl chloride or the solution can be used directly to prepare the desired sulfonamide.
  • isomeric mixtures can be separated by conventional means (e.g., fractional distillation or chromatography) or used as such; in the latter case isomeric mixtures of the aniline VII, sulfonyl chloride, sulfonamide, sulfonyl isocyanate and sulfonylures are found in the reactions which follow.
  • isomeric mixtures of intermediates further in the synthesis sequence can be separated or used as the isomeric mixtures.
  • Haloalkylthio, haloalkylsulfinyl and haloalkylsulfonyl)benzene derivatives VIIIa and VIIIb below which are used as starting materials for preparation of Ib, can be made by known methods [e.g., Chem. Abstr., 70, 96324c (1969); Chem. Abstr., 72, 66651f (1970); England, loc. cit.; Yagupolskii, loc. cit.],
  • the (trifluoroethylthio)benzenes can be made by reaction of the appropriate thiophenol with a trifluoroethylating agent, such as trifluoroethyl iodide or trifluoroethyl trichloromethanesulfonate.
  • a trifluoroethylating agent such as trifluoroethyl iodide or trifluoroethyl trichloromethanesulfonate.
  • the thiophenol compound is reacted with powdered potassium hydroxide and trifluoroethyl iodide in an aprotic solvent such as DMF, dioxane or THF.
  • the reaction proceeds to completion at ambient temperature.
  • Heat e.g., with a steam bath
  • the product is isolated as described in Equation 3 above.
  • Chlorosulfonation of VIIIa proceeds in the same manner as described for the oxygen analog and is shown in Equation 6.
  • the nitration is conveniently carried out by slow addition of slightly more than 1 equivalent of 90% nitric acid to a stirred, cooled (10°-30°) mixture of the sulfide VIIIb in sulfuric acid, stirring for an additional 10-45 minutes, pouring the reaction mixture into ice-water, extracting the nitro compound into a water-immiscible organic solvent (e.g., 1-chlorobutane or methylene chloride), and evaporating the solution to leave residual nitro compound, which may be further purified by vacuum distillation.
  • a water-immiscible organic solvent e.g., 1-chlorobutane or methylene chloride
  • the reaction is a simple mononitration of a substituted benzene ring, a reaction well known in the art.
  • the sulfide X is oxidized to the sulfoxide (e.g., with 20-30% H 2 O 2 in acetic acid, 1-2 hours at 90°-100°); or the sulfide X is oxidized to the Sulfone [e.g., with chromium trioxide in acetic acid at 90°-110° during 1/2-2 hours]. See Chem. Abstr., 70, 96324c (1969). If no oxidizing agent is used, n remains at zero and X is equal to XI.
  • nitrobenzene derivatives Reduction of nitrobenzene derivatives to nitroaniline derivatives is well known in the art [e.g., W. J. Hickinbottom, "Reactions of Organic Compounds," 452-459, Longmans, London, 1959].
  • aniline derivative XII is diazotized and converted to the sulfonyl chloride, sulfonamide, sulfonyl isocyanate and sulfonylurea as described for reactions 1, 2, 2a and 5.
  • the sulfide VIIIb is oxidized with hydrogen peroxide as described above, XIII, followed by nitration to the nitrosulfone XIa.
  • Nitration is accomplished with 90% nitric acid in 20% oleum at 90°-100°, the nitro group joining the ring meta to the haloalkylsulfonyl group [Chem. Abstr., 53, 21766a (1959)].
  • the nitrosulfone XIa is converted to the sulfonylurea as already described.
  • 2-Methylaminopyridimides are readily prepared by the reaction of methylamine with the appropriately substituted 2-chloropyrimidine as shown in Equation 13.
  • Equation 13 can also be carried out, for example according to references in Smolin and Rapaport, op. cit., p. 220-221.
  • the method of O. Kemal and C. B. Reese, J. Chem. Soc. Perkin I, 1981, 1569-1573 can also be used for the preparation of N-methylaminopyrimidines and triazines used as intermediates for this invention.
  • Useful formulations of the compounds of Formula I can be prepared in conventional ways. They include dusts, granules, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates and the like. Many of these may be applied directly. Sprayable formulations can be extended in suitable media and used at spray volumes of from a few liters to several hundred liters per hectare. High strength compositions are primarily used as intermediates for further formulation.
  • the formulations broadly, contain about 0.1% to 99% by weight of active ingredient(s) and at least one of (a) about 0.1% to 20% surfactant(s) and (b) about 1% to 99.9% solid or liquid inert diluent(s). More specifically, they will contain these ingredients in the following approximate proportions:
  • Typical solid diluents are described in Watkins, et al., "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books, Caldwell, N.J., but other solids, either mined or manufactured, may be used. The more absorptive diluents are preferred for wettable powders and the denser ones for dusts.
  • Typical liquid diluents and solvents are described in Marsden, “Solvents Guide,” 2nd Ed., Interscience, New York 1950. Solubility under 0.1% is preferred for suspension concentrates; solution concentrates are preferably stable against phase separation at 0° C.
  • compositions are well known. Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer or fluid energy mill. Suspensions are prepared by wet milling (see, for example, Littler, U.S. Pat. No. 3,060,084). Granules and pellets may be made by spraying the active material upon preformed granular carriers or by agglomeration techniques as demonstrated in J. E. Browning, "agglomeration”, Chemical Engineering, Dec. 4, 1967, pp. 147ff, and "Perry's Chemical Engineer's Handbook", 5th Ed., McGraw-Hill, New York, 1973, pp. 8-57ff.
  • the ingredients are blended, hammer-milled until all the solids are essentially under 50 microns, reblended, and packaged.
  • the ingredients are blended, coarsely hammer-milled and then air-milled to produce particles essentially all below 10 microns in diameter.
  • the product is reblended before packaging.
  • a slurry of wettable powder containing ⁇ 25% solids is sprayed on the surface of attapulgite granules in a double-cone blender. The granules are dried and packaged.
  • the ingredients are blended, hammer-milled and then moistened with about 12% water.
  • the mixture is extruded as cylinders about 3 mm diameter which are cut to produce pellets about 3 mm long. These may be used directly after drying, or the dried pellets may be crushed to pass a U.S.S. No 20 sieve (0.84 mm openings).
  • the granules held on a U.S.S. No. 40 sieve (0.42 mm openings) may be packaged for use and the fines recycle
  • the ingredients are ground together in a sand mill until the solid particles have been reduced to under about 5 microns.
  • the resulting thick suspension may be applied directly, but preferably after being extended with oils or emulsified in water.
  • the ingredients are thoroughly blended. After grinding in a hammer-mill to produce particles essentially all below 100 microns, the material is reblended and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) and packaged.
  • the active ingredient is dissolved in the solvent and the solution is sprayed upon dedusted granules in a double cone blender. After spraying of the solution has been completed, the blender is allowed to run for a short period and then the granules are packaged.
  • the ingredients are blended and ground together in a sand mill to produce particles essentially all under 5 microns in size.
  • the salt is added directly to the water with stirring to produce the solution, which may then be packaged for use.
  • the active ingredient is dissolved in a solvent and the solution is sprayed upon dedusted granules in a double-cone blender. After spraying of the solution has been completed, the material is warmed to evaporate the solvent. The material is allowed to cool and then packaged.
  • the ingredients are blended and milled to pass through a 100 mesh screen.
  • This material is then added to a fluid bed granulator, the air flow is adjusted to gently fluidize the material, and a fine spray of water is sprayed onto the fluidized material.
  • the fluidization and spraying are continued until granules of the desired size range are made.
  • the spraying is stopped, but fluidization is continued, optionally with heat, until the water content is reduced to the desired level, generally less than 1%.
  • the material is then discharged, screened to the desired size range, generally 14-100 mesh (1410-149 microns), and packaged for use.
  • the ingredients are blended and ground in a hammer-mill to produce a material essentially all passing a U.S.S. No. 50 screen (0.3 mm opening).
  • the concentrate may be formulated further if necessary.
  • the ingredients are blended and ground in a hammer-mill to produce particles essentially all below 100 microns.
  • the material is sifted through a U.S.S. No. 50 screen and then packaged.
  • the ingredients are thoroughly blended, coarsely hammer-milled and then air-milled to produce particles essentially all below 10 microns in size.
  • the material is reblended and then packaged.
  • the ingredients are combined and ground together in a sand mill to produce particles essentially all below 5 microns.
  • the product can be used directly, extended with oils, or emulsified in water.
  • the active ingredient is blended with attapulgite and then passed through a hammer-mill to produce particles substantially all below 200 microns.
  • the ground concentrate is then blended with powdered pyrophyllite until homogeneous.
  • the compounds of the present invention are active herbicides. They have utility for broadspectrum pre- and/or post-emergence weed control in areas where complete control of all vegetation is desired, such as around fuel storage tanks, ammunition depots, industrial storage areas, parking lots, drivein theaters, around billboards, highway and railroad structures. Alternatively, the subject compounds are useful to beneficially modify plant growth.
  • the rates of application for the compounds of the invention are determined by a number of factors, including their use as herbicides, or plant growth modifiers, the types of weeds to be controlled, weather and climate, formulations selected, mode of application, amount of foliage present, etc.
  • the subject compounds should be applied at levels of around 0.004 to 5 kg/ha, the lower rates being suggested for use on lighter soils and/or those having a low organic matter content, for plant growth modification or for situations where only short-term persistence is required.
  • the compounds of the invention may be used in combination with any other commercial herbicide examples of which are those of the triazine, triazole, uracil, urea, amide, diphenylether, carbamate and bipyridylium types.
  • Two plastic bulb pans were filled with fertilized and limed Woodstown sandy loam soil.
  • One pan was planted with corn, sorghum, Kentucky bluegrass and several grass weeds.
  • the other pan was planted with cotton, soybeans, purple nutsedge (Cyperus rotundus), and several broadleaf weeds.
  • the following grass and broadleaf weeds were planted: crabgrass (Digitaria sanguinalis), barnyardgrass (Echinochloa crusgalli), wild oats (Avena fatua), johnsongrass (Sorghum halepense), dallisgrass (Paspalum dilatatum), giant foxtail (Setaria faberii), cheatgrass (Bromus secalinus), mustard (Brassica arvensis), cocklebur (Xanthium pensylvanicum), morningglory (Ipomoea hederacea), sicklepod (Cassia obtusifolia), teaweed (Sida spinosa), velvetleaf (Abutilon theophrasti), and jimsonweed (Datura stramonium).
  • a 12.5 cm diameter plastic pot was also filled with prepared soil and planted with rice and wheat. Another 12.5 cm pot was planted with sugar beets. The above four containers were treated pre-emergence with one of the test compounds within
  • test chemical dissolved in a non-phytotoxic solvent
  • the test chemical was applied in an overall spray to the foliage and surrounding soil of selected plant species.
  • plants were checked for rapid burn injury.
  • Approximately fourteen days after treatment all species were visually compared to untreated controls and rated for response to treatment.
  • the rating system was as described previously for Test A. The data are presented in Table C.
  • Two plastic pans lined with polyethylene liners were filled with prepared Woodstown sandy loam soil.
  • One pan was planted with seeds of wheat (Triticum aestivum), barley (Hordeum vulgare), wild oats (Avena fatua), cheatgrass (Bromus secalinus), blackgrass (Alopecurus myosuroides), annual bluegrass (Poa annua), green foxtail (Setaria viridis), Italian ryegrass (Lolium multiflorum) and rapeseed (Brassica napus).
  • the other pan was planted with seeds of Russian thistle (Salsola kali), cleavers (Galium aparine), speedwell (Veronica persica), kochia (Kochia scoparia), shepherd's purse (Capsella bursa -pastoris), Matricaria inodora, black nightshade (Solanum nigrum), wild buckwheat (Polygonum convolvulus) and sugar beets (Beta vulgaris).
  • Russian thistle Salsola kali
  • cleavers Ga aparine
  • speedwell Veronica persica
  • kochia Kera scoparia
  • shepherd's purse Capsella bursa -pastoris
  • Matricaria inodora black nightshade
  • Solanum nigrum Solanum nigrum
  • wild buckwheat Polygonum convolvulus
  • sugar beets Beta vulgaris
  • the compound applied was diluted with a non-phytotoxic solvent and sprayed over-the-top of the pans.
  • An untreated control and a solvent alone control were included for comparison. All treatments were maintained in the greenhouse for 19-22 days at which time the treatments were compared to the controls and the effects visually rated. The recorded data are presented in Table D.

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  • Chemical & Material Sciences (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
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Abstract

This invention relates to novel N-[(heterocyclic)(alkyl)aminocarbonyl]benzenesulfonamides and their use as agricultural chemicals.

Description

BACKGROUND OF THE INVENTION
This invention relates to N-[(heterocyclic)(alkyl)aminocarbonyl]benzenesulfonamides useful as agricultural chemicals.
In EPO Publication 0023422, published Feb. 4, 1981, the following compounds are taught to be herbicides, especially useful for controlling weeds in wheat. ##STR1## wherein W is O or S;
R is CHF2, CF3, CH2 CF3 or CF2 CHFG, where G is F, Cl, CF3 or Br;
A is O or S(O)n, where n is 0, 1 or 2;
R1 is H, F, Cl, Br or CH3 ;
X is CH3 or OCH3 ;
Y is CH3, OCH3, OCH2 CH3, (CH2)m OCH3 (where m is 1 or 2), OCH2 CH2 OCH3, or OCHR2 CO2 R3, where R2 is H or CH3 and R3 is CH3 or C2 H5 ; and
E is CH or N.
In U.S. Pat. No. 4,257,802, issued Mar. 24, 1981, the following compounds are taught to be herbicides and plant-growth-regulants. ##STR2## wherein R1 is H, alkyl of one to three carbon atoms or --OCH3 ;
R2 is H or alkyl of one to three carbon atoms;
R3 is ##STR3## R4 and R7 are independently hydrogen, fluorine, chlorine, bromine, alkyl of 1-4 carbon atoms, alkoxy of 1-4 carbon atoms, nitro, CF3, CH3 S-- or CH3 CH2 S--;
R5, R6 and R8 are independently hydrogen, fluorine, chlorine, bromine or methyl;
X is Cl, CH3, --CH2 CH3, alkoxy of one to three carbons, CF3, CH3 S--, CH3 OCH2 -- or CH3 OCH2 CH2 O--;
Y is CH3 or OCH3 ; and
Z is CH or N;
and their agriculturally suitable salts; provided that:
(a) R1 and R2 may not simultaneously be hydrogen;
(b) when R4 and R8 are both hydrogen, at least one of R5, R6 or R7 must be hydrogen;
(c) when R6 is other than H, at least one of R4, R5, R7 and R8 is other than H and at least two of R4, R5, R7 and R8 must be hydrogen; and
(d) when R6 is H and all of R4, R5, R7 and R8 are other than H, then all of R4, R5, R7 and R8 must be either Cl or CH3.
Compounds of Formula (ii), and their use as antidiabetic agents, are reported in J. Drug. Res. 6, 123 (1974): ##STR4##
The presence of undesired vegetation causes substantial damage to useful crops, especially agricultural products that satisfy man's basic food needs, such as soybeans, wheat and the like. The current population explosion and concomitant world food shortage demand improvements in the efficiency of producing these crops. Prevention or minimizing the loss of a portion of such valuable crops by killing, or inhibiting the growth of undesired vegetation is one way of improving this efficiency.
A wide variety of materials useful for killing or inhibiting (controlling) the growth of undesired vegetation is available; such materials are commonly referred to as herbicides. The need exists, however, for still more effective herbicides that destroy or retard weeds without causing significant damage to useful crops.
SUMMARY OF THE INVENTION
This invention relates to novel compounds of Formula I, agriculturally suitable compositions containing them and their method-of-use as preemergent or postemergent herbicides or plant growth regulants. The invention also includes the use of certain compounds of Formula I as selective herbicides, particularly on wheat and corn. ##STR5## wherein A is O or S(O)n ;
R is C1 -C4 alkyl substituted with 1-6 halogen atoms selected from 1-6 F, 0-3 Cl or 0-1 Br;
R1 is H, F, Cl, Br, CH3, CF3 or OCH3 ;
n is 0, 1 or 2;
X is CH3 or OCH3 ;
Y is CH3, OCH3, OCH2 CH3, CH2 CH3, CH2 OCH3 or CH2 CH2 OCH3 ; and
Z is CH or N; and
their agriculturally suitable salts.
Preferred for reasons of their higher herbicidal activity and/or more favorable ease of synthesis are:
(1) Compounds of Formula I where R is CHF2, CF3, CH2 CF3, CF2 CF2 H, CF2 CFHCl, CF2 CFHBr, CF2 CF3 or CF2 CHFCF3.
(2) Compounds of Preferred 1 where R1 is H.
(3) Compounds of Preferred 2 where R is CF3, CHF2, CH2 CF3 or CF2 CF2 H.
(4) Compounds of Preferred 3 where A is O or S and Y is CH3 or OCH3.
Specifically preferred for reasons of their highest herbicidal activity and/or most favorable ease of synthesis are:
• N-[N-(4-methoxy-6-methylpyrimidin-2-yl)-N-methylaminocarbonyl]-2-(difluoromethoxy)benzenesulfonamide;
• N-[N-(4,6-dimethoxypyrimidin-2-yl)-N-methylaminocarbonyl]-2-(difluoromethoxy)benzenesulfonamide;
• N-[N-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-N-methylaminocarbonyl]-2-(difluoromethoxy)benzenesulfonamide;
• N-[N-(4,6-dimethoxy-1,3,5-triazin-2-yl)-N-methylaminocarbonyl]-2-(difluoromethoxy)benzenesulfonamide;
• N-[N-(4-methoxy-6-methylpyrimidin-2-yl)-N-methylaminocarbonyl]-2-(difluoromethylthio)benzenesulfonamide;
• N-[N-(4,6-dimethoxypyrimidin-2-yl)-N-methylaminocarbonyl]-2-(difluoromethylthio)benzenesulfonamide;
• N-[N-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-N-methylaminocarbonyl]-2-(difluoromethylthio)benzenesulfonamide;
• N-[N-(4,6-dimethoxy-1,3,5-triazin-2-yl)-N-methylaminocarbonyl]-2-(difluoromethylthio)benzenesulfonamide; and
• N-[N-(4,6-dimethoxy-1,3,5-triazin-2-yl)-N-methylaminocarbonyl]-2-(trifluoromethylthio)benzenesulfonamide.
Synthesis
As shown in Equation 1, the compounds of Formula I, wherein n is 0 or 2 can be prepared by the reaction of an appropriately substituted sulfonyl isocyanate of Formula II with an appropriately substituted 2-methylaminopyrimidine or 2-methylamino-1,3,5-triazine of Formula III, A, R, R1, X, Y and Z being as previously defined.
Equation 1 ##STR6##
The reaction is best carried out in inert aprotic organic solvents such as methylene chloride, tetrahydrofuran or acetonitrile, at ambient pressure and temperature. The mode of addition is not critical; however, it is often convenient to add the sulfonyl isocyanate II to a stirred suspension of amine III. Since such isocyanates are usually liquids, their addition can be easily controlled.
The reaction is generally exothermic. In some cases, the desired product is insoluble in the warm reaction medium and crystallizes from it in pure form. Products soluble in the reaction medium are isolated by evaporation of the solvent, trituration of the solid residue with solvents such as 1-chlorobutane or ethyl ether, and filtration.
The intermediate sulfonyl isocyanates of Formula II wherein n is 0 or 2 can be prepared as shown in Equation 2 by the reaction of the corresponding sulfonamides of Formula IV with phosgene in the presence of n-butyl isocyanate at reflux in a solvent such as xylene, according to the procedure of H. Ulrich and A. A. Y. Sayigh, Newer Methods of Preparative Organic Chemistry, Vol. VI, p. 223-241, Academic Press, New York and London, W. Foerst Ed. In cases where formation of the desired sulfonyl isocyanate is difficult by the above procedure, the sulfonylurea formed by the reaction of butyl isocyanate with the appropriate sulfonamide is reacted with phosgene according to the above reference.
Equation 2 ##STR7##
Alternatively, the addition of a tertiary amine base such as 1,4-diaza-[2.2.2.]-bicyclooctane may catalyze the preceeding phosgenations.
Sulfonyl isocyanates can also be made by the method of Ulrich et al. [J. Org. Chem., 34, 3200 (1969)]: ##STR8##
The sulfonamide is boiled under reflux with an excess of thionyl chloride until the sulfonamide protons are undetectable by proton resonance spectrum. An overnight reaction period (about 16 hours) is generally sufficient. After evaporation of the thionyl chloride, the residue is dissolved in an inert solvent, such as toluene, benzene or xylene, and a catalytic amount of pyridine. The mixture is heated to about 60°-140° (80°-100° preferred) with at least one equivalent of phosgene to yield the desired isocyanate, usually with 3 hours. The mixture containing the sulfonyl isocyanate can be used directly for the synthesis of sulfonylureas or the sulfonyl isocyanate can be purified by filtration and evaporation of the filtrate, followed by vacuum distillation.
Conversion of sulfonyl chlorides to sulfonamides, as shown in Equation 2a, is well known (e.g., L. Fieser and M. Fieser, op. cit., 699). It is convenient to dissolve the sulfonyl chloride in an inert solvent, e.g. toluene, ethyl acetate, tetrahydrofuran, etc., and pass in gaseous ammonia. Temperature is not critical and can range from about -20° to the boiling point of the solvent. For convenience, ambient temperatures are preferred.
The product can be isolated from the reaction mixture by the addition of water, evaporation of the solvent and filtration of the solid sulfonamide. If the product is soluble in the reaction mixture and the solvent is water-miscible, the product can be precipitated by addition of water and isolated by filtration.
Equation 2a ##STR9##
(Haloalkoxy)benzene derivatives can be made by methods well known in the art.
(Trifluoromethoxy)benzene derivatives can be made by the method of Sheppard [J. Org. Chem., 29, 1 (1964)], e.g.: ##STR10##
(Tetrahaloethoxy)benzene derivatives can be made by the method of England et al. [J. Am. Chem. Soc., 82, 5116 (1960)], which also applies to the hexafluoropropoxy compounds, e.g.: ##STR11##
(Trifluoroethoxy)benzene derivatives can be made by reaction of trifluoroethanol with an activated aromatic halide, e.g.:
Equation 3 ##STR12##
In Equation 3, sodium hydride and trifluoroethanol are mixed in an aprotic solvent, such as dimethylformamide (DMF), dioxane or tetrahydrofuran (THF), with 2-(fluoro or chloro)-1-nitrobenzene. The reaction proceeds to completion at ambient temperature. Heat may be applied (e.g., with a steam bath) if desired to speed the reaction to completion. The product is isolated by diluting the reaction mixture with water, extracting with an organic water-immiscible solvent and evaporation of the solvent. This reaction is similar to that described in Japanese Pat. No. 5 2057-320.
(Difluoromethoxy)benzene derivatives can be made by the method of Yagupolskii et al. [Chem. Abstr., 70, 96318d (1969)]e.g.: ##STR13##
Chlorosulfonation of aromatic substrates is well known (e.g., L. F. Fieser and M. Fieser, "Advanced Organic Chemistry", 696-698, Reinhold, New York, 1961). The chlorosulfonation (Equation 4) can be accomplished by addition of the trifluoroalkoxy compound to the chlorosulfonic acid or vice versa, optionally in the presence of a cosolvent, such as an alkane or chlorinated alkane (e.g., hexane, 1-chlorobutane, methylene chloride, etc.). The reaction temperature is not critical, with a range of about -5° to 50° C. operable and ambient temperature (e.g. 20° to 30°) preferred, for convenience. At ambient temperature some hydrolysis of the trifluoromethoxy group occurs. At lower temperatures, chlorosulfonation occurs more slowly with less of the hydrolysis, while at higher temperatures, chlorosulfonation occurs more rapidly with more accompanying hydrolysis. Reaction time at ambient temperature is about 1 to 24 hours, depending on the exact substrate being chlorosulfonated, with an overnight period (about 16 hours) satisfactory. Chlorosulfonation of the tetrahaloethoxy, hexafluoropropoxy and difluoromethoxy compounds is more difficult to control without hydrolysis of the haloalkoxy group than is chlorosulfonation of the trifluoromethoxy or trifluoroethoxy compounds.
Equation 4 ##STR14##
The aromatic sulfonyl chloride is conveniently isolated from the reaction mixture by pouring the mixture into ice-water, followed by extraction with a water-immiscible organic solvent in which the aromatic sulfonyl chloride is soluble. Such solvents include 1-chlorobutane, methylene chloride, 1,2-dichloroethane, ethyl acetate, toluene and diethyl ether. The solution of the sulfonyl chloride can be dried and evaporated to provide the sulfonyl chloride, which can be further purified by distillation, preferably in vacuum to suppress any thermally dependent decomposition. Alternatively, the solution of the sulfonyl chloride can be used directly in reaction with ammonia in the next step, preparation of the sulfonamide.
Chlorosulfonation can produce isomeric mixtures. Such isomeric mixtures can be separated by conventional routes (e.g., fractional distillation, chromatography) or used without separation. In the latter case, isomeric mixtures of sulfonamides, sulfonyl isocyanates and sulfonylureas are formed in the subsequent reactions. Similarly, the isomeric mixtures of intermediates formed further in the synthesis sequence can be separated or used as isomeric mixtures; isomeric mixtures of product sulfonyl(ureas and thioureas) can be used as herbicides or separated and used as individual compounds.
Sulfonyl chlorides can also be prepared, as shown in Equation 5, from aniline derivatives by diazotization, followed by reaction with sulfur dioxide and cuprous chloride. It should be emphasized that whereas chlorosulfonation is applicable to compounds where R=CF3 or CF3 CH2 (trifluoromethoxy or trifluoroethoxy compounds), the diazotization route (Equation 5) is of more general applicability.
Equation 5 ##STR15##
Aniline derivatives where R is CF3, tetrahaloethyl, HCF2 or hexafluoropropyl can be produced by methods described by Sheppard (op. cit.), England (op. cit.) and Yagupolskii (op. cit.). The aniline compound is diazotized according to methods well known in the art, [c.f. H. L. Yale and F. Sowinski, J. Org. Chem., 25, 1824 (1960)]. The sulfonyl chloride, generally an oil, is extracted into an organic solvent, such as 1-chlorobutane, diethyl ether, toluene or ethyl acetate, the organic extract dried and evaporated to yield the sulfonyl chloride or the solution can be used directly to prepare the desired sulfonamide.
When a nitration reaction is used to make the precursor to VII, in some cases isomeric mixtures are formed, e.g.: ##STR16##
These isomeric mixtures can be separated by conventional means (e.g., fractional distillation or chromatography) or used as such; in the latter case isomeric mixtures of the aniline VII, sulfonyl chloride, sulfonamide, sulfonyl isocyanate and sulfonylures are found in the reactions which follow. Likewise, the isomeric mixtures of intermediates further in the synthesis sequence can be separated or used as the isomeric mixtures.
(Haloalkylthio, haloalkylsulfinyl and haloalkylsulfonyl)benzenesulfonylureas ##STR17## wherein the substituents are defined as for compound (I).
(Haloalkylthio, haloalkylsulfinyl and haloalkylsulfonyl)benzene derivatives VIIIa and VIIIb below which are used as starting materials for preparation of Ib, can be made by known methods [e.g., Chem. Abstr., 70, 96324c (1969); Chem. Abstr., 72, 66651f (1970); England, loc. cit.; Yagupolskii, loc. cit.],
The (trifluoroethylthio)benzenes can be made by reaction of the appropriate thiophenol with a trifluoroethylating agent, such as trifluoroethyl iodide or trifluoroethyl trichloromethanesulfonate. The thiophenol compound is reacted with powdered potassium hydroxide and trifluoroethyl iodide in an aprotic solvent such as DMF, dioxane or THF. The reaction proceeds to completion at ambient temperature. Heat (e.g., with a steam bath) may be applied to increase the reaction rate. The product is isolated as described in Equation 3 above.
Equation 6 ##STR18##
Chlorosulfonation of VIIIa proceeds in the same manner as described for the oxygen analog and is shown in Equation 6.
Equation 7 ##STR19##
Conversion of the sulfonyl chloride sequentially to the amide, isocyanate, and the sulfonylurea proceeds as described for the oxygen analogs in reactions 2, 2a and 1, as shown in Equation 7.
Equation 8 ##STR20##
The nitration is conveniently carried out by slow addition of slightly more than 1 equivalent of 90% nitric acid to a stirred, cooled (10°-30°) mixture of the sulfide VIIIb in sulfuric acid, stirring for an additional 10-45 minutes, pouring the reaction mixture into ice-water, extracting the nitro compound into a water-immiscible organic solvent (e.g., 1-chlorobutane or methylene chloride), and evaporating the solution to leave residual nitro compound, which may be further purified by vacuum distillation. Thus, the reaction is a simple mononitration of a substituted benzene ring, a reaction well known in the art.
As mentioned for the oxygen analog, nitration of VIIIb can lead to isomeric nitro compounds which, likewise, can be separated or used as such.
Equation 5 ##STR21##
The sulfide X is oxidized to the sulfoxide (e.g., with 20-30% H2 O2 in acetic acid, 1-2 hours at 90°-100°); or the sulfide X is oxidized to the Sulfone [e.g., with chromium trioxide in acetic acid at 90°-110° during 1/2-2 hours]. See Chem. Abstr., 70, 96324c (1969). If no oxidizing agent is used, n remains at zero and X is equal to XI.
Equation 10 ##STR22##
Reduction of nitrobenzene derivatives to nitroaniline derivatives is well known in the art [e.g., W. J. Hickinbottom, "Reactions of Organic Compounds," 452-459, Longmans, London, 1959]. For example, the reduction can be accomplished by the portionwise addition of powdered iron to a mixture of the nitro compound in aqueous acetic acid at 60°-110°; followed by dilution of the reaction mixture with water and filtering off, extracting or, when n=0, steam-distilling the aniline product. Aminothiophenols can be directly tetrahaloethylated or hexafluoropropylated on the sulfur with tetrahaloethylene or hexafluoropropene to provide directly compounds XII with n=0 (England et al., loc. cit.; Chem. Abst., 75, 36584q). Also, compound XIIa is commercially available (Aldrich Chemical Co., Milwaukee, Wisc.): ##STR23## Equation 11 ##STR24##
The aniline derivative XII is diazotized and converted to the sulfonyl chloride, sulfonamide, sulfonyl isocyanate and sulfonylurea as described for reactions 1, 2, 2a and 5.
Equation 12 ##STR25##
As an alternate method for preparation of the intermediate nitrosulfone XIa, the sulfide VIIIb is oxidized with hydrogen peroxide as described above, XIII, followed by nitration to the nitrosulfone XIa. Nitration is accomplished with 90% nitric acid in 20% oleum at 90°-100°, the nitro group joining the ring meta to the haloalkylsulfonyl group [Chem. Abstr., 53, 21766a (1959)]. The nitrosulfone XIa is converted to the sulfonylurea as already described.
Exemplary compounds within structure (I) that can be made by one or more of the described method are listed in Table I.
The synthesis of heterocyclic amine derivatives has been reviewed in "The Chemistry of Heterocyclic Compounds," a series published by interscience Pub., New York and London. 2-Methylaminopyrimidines are described by D. J. Brown in "The Pyridimidines", Vol. XVI and Vol. XVI Supplement I of the above series. 2-Amino-1,3,5-triazines can be synthesized according to the methods described by E. M. Smolin and L. Rapaport in "s-Triazines and Derivatives," Vol. XIII of the same series.
2-Methylaminopyridimides are readily prepared by the reaction of methylamine with the appropriately substituted 2-chloropyrimidine as shown in Equation 13.
Equation 13 ##STR26## wherein X and Y are previously defined; and
Z is CH;
(c.f. Brown, op. cit., Supplement I, p. 131).
Similarly, with Z=N, the reaction of Equation 13 can also be carried out, for example according to references in Smolin and Rapaport, op. cit., p. 220-221. Optionally, the method of O. Kemal and C. B. Reese, J. Chem. Soc. Perkin I, 1981, 1569-1573 can also be used for the preparation of N-methylaminopyrimidines and triazines used as intermediates for this invention.
In the examples which follow, all parts and percentages are by weight and all temperatures in degrees centigrade unless specified otherwise. The examples are not to be considered as limiting, but merely to exemplify the methods which can be used to prepared the compounds of this invention.
EXAMPLE 1 2-Difluoromethylthio-N-[N-( 4,6-dimethoxy-1,3,3-triazin-2-yl)-N-methylaminocarbonyl]benzenesulfonamide
To 0.80 g of 4,6-dimethoxy-2-methylamino-1,3,5-triazine in 25 ml of dry methylene chloride was added at ambient temperature 1.33 g of 2-difluoromethylthiobenzenesulfonyl isocyanate in 15 ml of methylene chloride. The reaction mixture was stirred for 16 hours and the resultant precipitate removed by filtration. It melted at 158°-164°, showed absorption peaks by Nuclear Magnetic Resonance (60MC) at:
3.22s, N-CH3 ;
4.08S, (OCH3)2 ;
6.56s, CF2 H; and
7.2-8.2 mult., aryl;
and showed peaks by infrared absorption spectroscopy at 1710, 1590 and 1560 cm-1. These physical properties were all consistent for the desired structure.
EXAMPLE 2 2-Difluoromethyl-N-[N-(4,6-dimethoxy-1,3,5-triazin-2-yl)-N-methylaminocarbonyl]benzenesulfonamide
To 1.7 g of 4,6-dimethoxy- 2-methylamino-1,3,5-triazine in 25 ml of dry methylene chloride was added with stirring at ambient temperature 2.5 g of 2-difluoromethoxybenzenesulfonyl isocyanate. The mixture was stirred, at ambient temperature, for sixteen hours and the precipitate thus formed was removed by filtration to yield the desired product melting at 164°-170°. This product showed peaks by infrared absorption spectroscopy at 1730, 1580 and 1560 cm-1, consistent for the desired structure.
Using the procedures of Examples 1 and 2, the following compounds of Table I can readily be prepared by one skilled in the art.
                                  TABLE I                                 
__________________________________________________________________________
 ##STR27##                                                                
RA          R.sub.1                                                       
                 Z  X   Y        m.p. (°C.)                        
__________________________________________________________________________
CF.sub.3 S  H    N  OCH.sub.3                                             
                        OCH.sub.3                                         
                                 158-160°                          
CF.sub.3 O  5-Cl CH CH.sub.3                                              
                        CH.sub.3                                          
HCF.sub.2 CF.sub.2 O                                                      
            5-Cl CH CH.sub.3                                              
                        CH.sub.3                                          
HCFClCF.sub.2 O                                                           
            5-Cl CH CH.sub.3                                              
                        CH.sub.3                                          
HCFBrCF.sub.2 O                                                           
            5-Cl CH CH.sub.3                                              
                        CH.sub.3                                          
CF.sub.3 CH.sub.2 O                                                       
            5-Cl CH CH.sub.3                                              
                        CH.sub.3                                          
CF.sub.3 O  5-Br CH CH.sub.3                                              
                        CH.sub.3                                          
CF.sub.3 O  5-F  CH CH.sub.3                                              
                        CH.sub.3                                          
HCF.sub.2 CF.sub.2 O                                                      
            5-CH.sub.3                                                    
                 CH CH.sub.3                                              
                        CH.sub.3                                          
CF.sub.3 O  5-Cl CH CH.sub.3                                              
                        CH.sub.3                                          
CF.sub.3 O  5-Cl N  OCH.sub.3                                             
                        OCH.sub.3                                         
CF.sub.3 O  H    CH CH.sub.3                                              
                        CH.sub.3                                          
CF.sub.2 HCF.sub.2 O                                                      
            H    CH CH.sub.3                                              
                        CH.sub.3 190-193°                          
CF.sub.2 HCF.sub.2 O                                                      
            H    N  OCH.sub.3                                             
                        CH.sub.3 180-183°                          
CF.sub.2 HCF.sub.2 O                                                      
            H    CH OCH.sub.3                                             
                        OCH.sub.3                                         
                                 172-175°                          
CF.sub.3 O  5-Cl CH CH.sub.3                                              
                        OCH.sub.3                                         
CF.sub.3 O  5-Cl CH OCH.sub.3                                             
                        OCH.sub.3                                         
CF.sub.3 O  5-Cl CH OCH.sub.3                                             
                        CH.sub.2 OCH.sub.3                                
CF.sub.3 O  5-Cl CH OCH.sub.3                                             
                        CH.sub.2 CH.sub.2 OCH.sub.3                       
CF.sub.3 O  5-Cl CH CH.sub.3                                              
                        CH.sub.2 CH.sub.2 OCH.sub.3                       
CF.sub.3 O  5-Cl CH CH.sub.3                                              
                        OC.sub.2 H.sub.5                                  
CF.sub.3 O  5-Cl N  CH.sub.3                                              
                        CH.sub.3                                          
CF.sub.3 O  5-Cl N  CH.sub.3                                              
                        OCH.sub.3                                         
CF.sub.3 O  5-Cl N  OCH.sub.3                                             
                        OCH.sub.3                                         
CF.sub.3 O  5-Cl N  OCH.sub.3                                             
                        CH.sub.2 OCH.sub.3                                
CF.sub.3 O  5-Cl N  OCH.sub.3                                             
                        CH.sub.2 CH.sub.2 OCH.sub.3                       
CF.sub.3 CH.sub.2 O                                                       
            H    CH CH.sub. 3                                             
                        CH.sub.3                                          
HCFClCF.sub.2 O                                                           
            H    CH CH.sub.3                                              
                        CH.sub.3                                          
HCFBrCF.sub.2 O                                                           
            H    CH CH.sub.3                                              
                        CH.sub.3                                          
CF.sub.3 O  2-Cl N  OCH.sub.3                                             
                        CH.sub.2 CH.sub.2 OCH.sub.3                       
CF.sub.3 O  5-Cl N  CH.sub.3                                              
                        OC.sub.2 H.sub.5                                  
CF.sub.3 S  5-Cl CH CH.sub.3                                              
                        CH.sub.3                                          
 ##STR28##  5-Cl CH CH.sub.3                                              
                        CH.sub.3                                          
CF.sub.3 SO.sub.2                                                         
            H    CH CH.sub.3                                              
                        CH.sub.3                                          
 ##STR29##  H    CH CH.sub.3                                              
                        CH.sub.3                                          
CF.sub.3 SO.sub.2                                                         
            H    CH CH.sub.3                                              
                        CH.sub.3                                          
CF.sub.3 S  H    CH CH.sub.3                                              
                        CH.sub.3                                          
CF.sub.2 HCF.sub.2 S                                                      
            H    CH CH.sub.3                                              
                        CH.sub.3                                          
CFClHCF.sub.2 S                                                           
            H    CH CH.sub.3                                              
                        CH.sub.3                                          
CFBrHCF.sub.2 S                                                           
            H    CH CH.sub.3                                              
                        CH.sub.3                                          
 ##STR30##  H    CH CH.sub.3                                              
                        CH.sub.3                                          
CF.sub.2 HCF.sub.2 SO.sub.2                                               
            H    CH CH.sub.3                                              
                        CH.sub.3                                          
HCF.sub.2 O H    CH CH.sub.3                                              
                        CH.sub.3                                          
CF.sub.3 CHFCF.sub.2 O                                                    
            H    CH CH.sub.3                                              
                        CH.sub.3                                          
CF.sub.3 CHFCF.sub.2 O                                                    
            H    N  OCH.sub.3                                             
                        CH.sub.3                                          
CF.sub.3 CHFCF.sub.2 O                                                    
            H    CH OCH.sub.3                                             
                        OCH.sub.3                                         
CF.sub.3 CHFCF.sub.2 O                                                    
            H    CH OCH.sub.3                                             
                        CH.sub.3                                          
HCFBrCF.sub.2 O                                                           
            5-Br CH CH.sub.3                                              
                        CH.sub.3                                          
CF.sub.2 HCF.sub.2 S                                                      
            5-Cl CH CH.sub.3                                              
                        CH.sub.3                                          
CF.sub.2 HCF.sub.2 O                                                      
            6-CH.sub.3                                                    
                 CH CH.sub.3                                              
                        CH.sub.3                                          
CHF.sub.2 S H    CH CH.sub.3                                              
                        CH.sub.3                                          
 ##STR31##  H    CH CH.sub.3                                              
                        CH.sub.3                                          
CHF.sub.2 SO.sub.2                                                        
            H    CH CH.sub.3                                              
                        CH.sub.3                                          
CF.sub.3 CHFCF.sub.2 S                                                    
            H    CH CH.sub.3                                              
                        CH.sub.3                                          
 ##STR32##  H    CH CH.sub.3                                              
                        CH.sub.3                                          
CF.sub.3 CHFCF.sub.2 SO.sub.2                                             
            H    CH CH.sub.3                                              
                        CH.sub.3                                          
HCF.sub.2 O H    CH OCH.sub.3                                             
                        OCH.sub.3                                         
                                 140-148° C.                       
HCF.sub.2 S 5-OCH.sub.3                                                   
                 CH OCH.sub.3                                             
                        OCH.sub.3                                         
HCF.sub.2 S 6-OCH.sub.3                                                   
                 CH OCH.sub.3                                             
                        OCH.sub.3                                         
HCF.sub.2 S 5-OCH.sub.3                                                   
                 N  CH.sub.3                                              
                        OCH.sub.3                                         
HCF.sub.2 S 6-OCH.sub.3                                                   
                 N  CH.sub.3                                              
                        OCH.sub.3                                         
HCF.sub.2 S 5-CF.sub.3                                                    
                 CH OCH.sub.3                                             
                        OCH.sub.3                                         
HCF.sub. 2 S                                                              
            5-CF.sub.3                                                    
                 N  CH.sub.3                                              
                        OCH.sub.3                                         
HCF.sub.2 S 5-F  CH OCH.sub.3                                             
                        OCH.sub.3                                         
HCF.sub.2 S 5-F  N  CH.sub.3                                              
                        OCH.sub.3                                         
HCF.sub.2 S 6-F  N  CH.sub.3                                              
                        OCH.sub.3                                         
HCF.sub.2 O 5-OCH.sub.3                                                   
                 CH OCH.sub.3                                             
                        OCH.sub.3                                         
HCF.sub.2 O 6-OCH.sub.3                                                   
                 CH OCH.sub.3                                             
                        OCH.sub.3                                         
HCF.sub.2 O 5-OCH.sub.3                                                   
                 N  CH.sub.3                                              
                        OCH.sub.3                                         
HCF.sub.2 O 6-OCH.sub.3                                                   
                 N  CH.sub.3                                              
                        OCH.sub.3                                         
HCF.sub.2 O 5-CF.sub.3                                                    
                 CH OCH.sub.3                                             
                        OCH.sub.3                                         
HCF.sub.2 O 5-CF.sub.3                                                    
                 N  CH.sub.3                                              
                        OCH.sub.3                                         
HCF.sub.2 O 5-F  CH OCH.sub.3                                             
                        OCH.sub.3                                         
HCF.sub.2 O 5-F  N  CH.sub.3                                              
                        OCH.sub.3                                         
HCF.sub.2 O 6-F  N  CH.sub.3                                              
                        OCH.sub.3                                         
 ##STR33##  H    CH CH.sub.3                                              
                        OCH.sub.3                                         
 ##STR34##  H    N  CH.sub.3                                              
                        OCH.sub.3                                         
 ##STR35##  H    CH OCH.sub.3                                             
                        OCH.sub.3                                         
 ##STR36##  H    N  OCH.sub.3                                             
                        OCH.sub.3                                         
CF.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 O                                     
            H    CH CH.sub.3                                              
                        OCH.sub.3                                         
CF.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 O                                     
            H    N  CH.sub.3                                              
                        OCH.sub.3                                         
CF.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 O                                     
            H    CH OCH.sub.3                                             
                        OCH.sub.3                                         
CF.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 O                                     
            H    N  OCH.sub.3                                             
                        OCH.sub.3                                         
 ##STR37##  H    CH CH.sub.3                                              
                        OCH.sub.3                                         
 ##STR38##  H    N  CH.sub.3                                              
                        OCH.sub.3                                         
 ##STR39##  H    CH OCH.sub.3                                             
                        OCH.sub.3                                         
 ##STR40##  H    N  OCH.sub.3                                             
                        OCH.sub.3                                         
CF.sub.3 CFClCF.sub.2 O                                                   
            H    CH CH.sub.3                                              
                        OCH.sub.3                                         
CF.sub.3 CFClCF.sub.2 O                                                   
            H    N  CH.sub.3                                              
                        OCH.sub.3                                         
CF.sub.3 CFClCF.sub.2 O                                                   
            H    CH OCH.sub.3                                             
                        OCH.sub.3                                         
CF.sub.3 CFClCF.sub.2 O                                                   
            H    N  OCH.sub.3                                             
                        OCH.sub.3                                         
CF.sub.3 CF.sub.2 O                                                       
            H    CH CH.sub.3                                              
                        OCH.sub.3                                         
CF.sub.3 CF.sub.2 O                                                       
            H    N  CH.sub.3                                              
                        OCH.sub.3                                         
CF.sub.3 CF.sub.2 O                                                       
            H    CH OCH.sub.3                                             
                        OCH.sub.3                                         
CF.sub.3 CF.sub.2 O                                                       
            H    N  OCH.sub.3                                             
                        OCH.sub.3                                         
CF.sub.3 CF.sub.2 S                                                       
            H    CH CH.sub.3                                              
                        OCH.sub.3                                         
CF.sub.3 CF.sub.2 S                                                       
            H    N  CH.sub.3                                              
                        OCH.sub.3                                         
CF.sub.3 CF.sub.2 S                                                       
            H    CH OCH.sub.3                                             
                        OCH.sub.3                                         
CF.sub.3 CF.sub.2 S                                                       
            H    N  OCH.sub.3                                             
                        OCH.sub.3                                         
CF.sub.3 CHFCF.sub.2 S                                                    
            H    CH CH.sub.3                                              
                        OCH.sub.3                                         
CF.sub.3 CHFCF.sub.2 S                                                    
            H    N  CH.sub.3                                              
                        OCH.sub.3                                         
CF.sub.3 CHFCF.sub.2 S                                                    
            H    CH OCH.sub.3                                             
                        OCH.sub.3                                         
CF.sub.3 CHFCF.sub.2 S                                                    
            H    N  OCH.sub.3                                             
                        OCH.sub.3                                         
CF.sub.3 CHClCF.sub.2 O                                                   
            H    CH CH.sub.3                                              
                        OCH.sub.3                                         
CF.sub.3 CHClCF.sub.2 O                                                   
            H    N  CH.sub.3                                              
                        OCH.sub.3                                         
CF.sub.3 CHClCF.sub.2 O                                                   
            H    CH OCH.sub.3                                             
                        OCH.sub.3                                         
CF.sub.3 CHClCF.sub.2 O                                                   
            H    N  OCH.sub.3                                             
                        OCH.sub.3                                         
CH.sub.3 CH.sub.2 CH.sub.2 CHFO                                           
            H    CH CH.sub.3                                              
                        OCH.sub.3                                         
CH.sub.3 CH.sub.2 CH.sub.2 CHFO                                           
            H    N  CH.sub.3                                              
                        OCH.sub.3                                         
CH.sub.3 CH.sub.2 CHFCHFO                                                 
            H    CH CH.sub.3                                              
                        OCH.sub.3                                         
CH.sub.3 CH.sub.2 CHFCHFO                                                 
            H    N  CH.sub.3                                              
                        OCH.sub.3                                         
CF.sub.3 CH.sub.2 CH.sub.2 CHFO                                           
            H    CH CH.sub.3                                              
                        OCH.sub.3                                         
CF.sub.3 CH.sub.2 CH.sub.2 CHFO                                           
            H    N  CH.sub.3                                              
                        OCH.sub.3                                         
FCl.sub.2 CCH.sub.2 O                                                     
            H    CH CH.sub.3                                              
                        OCH.sub.3                                         
FCl.sub.2 CCH.sub.2 O                                                     
            H    N  CH.sub.3                                              
                        OCH.sub.3                                         
CF.sub.2 HO H    CH CH.sub.3                                              
                        OCH.sub.3                                         
                                 100-107°                          
CF.sub.2 HO H    N  CH.sub.3                                              
                        OCH.sub.3                                         
                                 141-148°                          
CF.sub.2 HO H    N  OCH.sub.3                                             
                        C.sub.2 H.sub.5                                   
CF.sub.2 HO H    N  CH.sub.3                                              
                        OC.sub.2 H.sub.5                                  
CF.sub.2 HO H    N  OCH.sub.3                                             
                        OC.sub.2 H.sub.5                                  
CF.sub.2 HO H    N  CH.sub.3                                              
                        CH.sub.2 OCH.sub.3                                
CF.sub.2 HS H    CH CH.sub.3                                              
                        CH.sub.3                                          
CF.sub.2 HS H    CH CH.sub.3                                              
                        OCH.sub.3                                         
                                 187-193°                          
CF.sub.2 HS H    CH OCH.sub.3                                             
                        OCH.sub.3                                         
                                 173-176°                          
CF.sub.2 HS H    CH CH.sub.3                                              
                        CH.sub.2 OCH.sub.3                                
CF.sub.2 HS H    CH CH.sub.3                                              
                        CH.sub.2 CH.sub.2 OCH.sub.3                       
CF.sub.2 HS H    CH OCH.sub.3                                             
                        OC.sub.2 H.sub.5                                  
CF.sub.2 HS H    CH OCH.sub.3                                             
                        C.sub.2 H.sub.5                                   
CF.sub.2 HS H    N  CH.sub.3                                              
                        CH.sub.3                                          
CF.sub.2 HS H    N  CH.sub.3                                              
                        OCH.sub.3                                         
                                 184-186°                          
CF.sub.2 HS H    N  CH.sub.3                                              
                        CH.sub.2 OCH.sub.3                                
CF.sub.2 HS H    N  OCH.sub.3                                             
                        CH.sub.2 OCH.sub.3                                
CF.sub.2 HS H    N  CH.sub.3                                              
                        OC.sub.2 H.sub.5                                  
CF.sub.2 HS H    N  OCH.sub.3                                             
                        CH.sub.2 CH.sub.2 OCH.sub.3                       
__________________________________________________________________________
Formulations
Useful formulations of the compounds of Formula I can be prepared in conventional ways. They include dusts, granules, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates and the like. Many of these may be applied directly. Sprayable formulations can be extended in suitable media and used at spray volumes of from a few liters to several hundred liters per hectare. High strength compositions are primarily used as intermediates for further formulation. The formulations, broadly, contain about 0.1% to 99% by weight of active ingredient(s) and at least one of (a) about 0.1% to 20% surfactant(s) and (b) about 1% to 99.9% solid or liquid inert diluent(s). More specifically, they will contain these ingredients in the following approximate proportions:
              TABLE 2                                                     
______________________________________                                    
            Active  Weight Percent*                                       
            Ingredient                                                    
                    Diluent(s)                                            
                              Surfactant(s)                               
______________________________________                                    
Wettable Powders                                                          
              20-90      0-74     1-10                                    
Oil Suspensions,                                                          
               3-50     40-95     0-15                                    
Emulsions, Solutions,                                                     
(including Emulsifiable                                                   
Concentrates)                                                             
Aqueous Suspension                                                        
              10-50     40-84     1-20                                    
Dusts          1-25     70-99     0-5                                     
Granules and Pellets                                                      
              0.1-95      5-99.9  0-15                                    
High Strength 90-99      0-10     0-2                                     
Compositions                                                              
______________________________________                                    
 *Active ingredient plus at least one of a Surfactant or a Diluent equals 
 100 weight percent.
Lower or higher levels of active ingredient can, of course, be present depending on the intended use and the physical properties of the compound. Higher ratios of surfactant to active ingredient are sometimes desirable, and are achieved by incorporation into the formulation or by tank mixing.
Typical solid diluents are described in Watkins, et al., "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books, Caldwell, N.J., but other solids, either mined or manufactured, may be used. The more absorptive diluents are preferred for wettable powders and the denser ones for dusts. Typical liquid diluents and solvents are described in Marsden, "Solvents Guide," 2nd Ed., Interscience, New York 1950. Solubility under 0.1% is preferred for suspension concentrates; solution concentrates are preferably stable against phase separation at 0° C. "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood, N.J., as well as Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foaming, caking, corrosion, microbiological growth, etc.
The methods of making such compositions are well known. Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer or fluid energy mill. Suspensions are prepared by wet milling (see, for example, Littler, U.S. Pat. No. 3,060,084). Granules and pellets may be made by spraying the active material upon preformed granular carriers or by agglomeration techniques as demonstrated in J. E. Browning, "agglomeration", Chemical Engineering, Dec. 4, 1967, pp. 147ff, and "Perry's Chemical Engineer's Handbook", 5th Ed., McGraw-Hill, New York, 1973, pp. 8-57ff.
For further information regarding the art of formulation, see for example:
H. M, Loux, U.S. Pat. No. 3,235,361, Feb. 15, 1966, Col. 6, line 16 through Col. 7, line 19 and Examples 10 through 41;
R. W. Luckenbaugh, U.S. Pat. No. 3,309,192, Mar. 14, 1967, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182;
H. Gysin and E. Knusli, U.S. Pat. No. 2,891,855, June 23, 1959, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4;
G. C. Klingman, "Weed Control as a Science", John Wiley and Sons, Inc., New York, 1961, pp 81-96; and
J. D. Fryer and S. A. Evans, "Weed Control Handbook", 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pp. 101-103.
In the following examples, all parts are by weight unless otherwise indicated.
EXAMPLE 3
Wettable Powder
______________________________________                                    
N--[N--(4,6-dimethoxy-1,3,5-triazin-2-yl)-N--methylamino-                 
                              80%                                         
carbonyl]-2-(difluoromethylthio)benzenesulfonamide                        
sodium alkylnaphthalenesulfonate                                          
                               2%                                         
sodium ligninsulfonate         2%                                         
synthetic amorphous silica     3%                                         
kaolinite                     13%                                         
______________________________________
The ingredients are blended, hammer-milled until all the solids are essentially under 50 microns, reblended, and packaged.
EXAMPLE 4
Wettable Powder
______________________________________                                    
N--[N--(4,6-dimethoxy-1,3,5-triazin-2-yl)-N--methylamino-                 
                              50%                                         
carbonyl]-2-(trifluoromethylthio)benzenesulfonamide                       
sodium alkylnaphthalenesulfonate                                          
                               2%                                         
low viscosity methyl cellulose                                            
                               2%                                         
diatomaceous earth            46%                                         
______________________________________
The ingredients are blended, coarsely hammer-milled and then air-milled to produce particles essentially all below 10 microns in diameter. The product is reblended before packaging.
EXAMPLE 5
Granule
______________________________________                                    
Wettable Powder of Example 4                                              
                        5%                                                
attapulgite granules   95%                                                
(U.S.S. 20-40 mesh; 0.84-0.42 mm)                                         
______________________________________
A slurry of wettable powder containing ≈25% solids is sprayed on the surface of attapulgite granules in a double-cone blender. The granules are dried and packaged.
EXAMPLE 6
Extruded Pellet
______________________________________                                    
N--[N--(4-methoxy-6-methylpyrimidin-2-yl)-N--                             
                           25%                                            
methylaminocarbonyl]-2-(difluoromethylthio)-                              
benzenesulfonamide                                                        
anhydrous sodium sulfate   10%                                            
crude calcium ligninsulfonate                                             
                            5%                                            
sodium alkylnaphthalenesulfonate                                          
                            1%                                            
calcium/magnesium bentonite                                               
                           59%                                            
______________________________________
The ingredients are blended, hammer-milled and then moistened with about 12% water. The mixture is extruded as cylinders about 3 mm diameter which are cut to produce pellets about 3 mm long. These may be used directly after drying, or the dried pellets may be crushed to pass a U.S.S. No 20 sieve (0.84 mm openings). The granules held on a U.S.S. No. 40 sieve (0.42 mm openings) may be packaged for use and the fines recycle
EXAMPLE 7
Oil Suspension
______________________________________                                    
N--[N--(4,6-dimethoxy-1,3,5-triazin-2-yl)-N--methyl-                      
                             25%                                          
aminocarbonyl]-2-(difluoromethoxy)benzenesulfonamide                      
polyoxyethylene sorbitol hexaoleate                                       
                              5%                                          
highly aliphatic hydrocarbon oil                                          
                             70%                                          
______________________________________
The ingredients are ground together in a sand mill until the solid particles have been reduced to under about 5 microns. The resulting thick suspension may be applied directly, but preferably after being extended with oils or emulsified in water.
EXAMPLE 8
Wettable Powder
______________________________________                                    
N--[N--(4,6-dimethoxypyrimidin-2-yl)-N--methylamino-                      
                             20%                                          
carbonyl]-2-(difluoromethoxy)benzenesulfonamide                           
sodium alkylnaphthalenesulfonate                                          
                              4%                                          
sodium ligninsulfonate        4%                                          
low viscosity methyl cellulose                                            
                              3%                                          
attapulgite                  69%                                          
______________________________________
The ingredients are thoroughly blended. After grinding in a hammer-mill to produce particles essentially all below 100 microns, the material is reblended and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) and packaged.
EXAMPLE 9
Low Strength Granule
______________________________________                                    
N--[N--(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-N--methyl-                 
                               1%                                         
aminocarbonyl]-2-(difluoromethoxy)benzenesulfonamide                      
N,N--dimethylformamide         9%                                         
attapulgite granules          90%                                         
(U.S.S. 20-40 sieve)                                                      
______________________________________
The active ingredient is dissolved in the solvent and the solution is sprayed upon dedusted granules in a double cone blender. After spraying of the solution has been completed, the blender is allowed to run for a short period and then the granules are packaged.
EXAMPLE 10
Aqueous Suspension
______________________________________                                    
N--[N--(4,6-dimethoxy-1,3,5-triazin-2-yl)-N--                             
                           40%                                            
methylaminocarbonyl]-2-(difluoromethylthio)-                              
benzenesulfonamide                                                        
polyacrylic acid thickener                                                
                          0.3%                                            
dodecylphenol polyethylene glycol ether                                   
                          0.5%                                            
disodium phosphate          1%                                            
monosodium phosphate      0.5%                                            
polyvinyl alcohol         1.0%                                            
water                     56.7%                                           
______________________________________
The ingredients are blended and ground together in a sand mill to produce particles essentially all under 5 microns in size.
EXAMPLE 11
Solution
______________________________________                                    
N--[N--(4-methoxy-6-methylpyrimidin-2-yl)-N--                             
                            5%                                            
methylaminocarbonyl]-2-(difluoromethylthio)-                              
benzenesulfonamide, sodium salt                                           
water                      95%                                            
______________________________________
The salt is added directly to the water with stirring to produce the solution, which may then be packaged for use.
EXAMPLE 12
Low Srength Granule
______________________________________                                    
N--[N--(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-N--                        
                            0.1%                                          
methylaminocarbonyl]-2-(difluoromethylthio)-                              
benzenesulfonamide                                                        
attapulgite granules       99.9%                                          
(U.S.S. 20-40 mesh)                                                       
______________________________________
The active ingredient is dissolved in a solvent and the solution is sprayed upon dedusted granules in a double-cone blender. After spraying of the solution has been completed, the material is warmed to evaporate the solvent. The material is allowed to cool and then packaged.
Example 13
Granule
______________________________________                                    
N--[N--(4,6-dimethoxy-1,3,5-triazin-2-yl)-N--methylamino-                 
                              80%                                         
carbonyl]-2-(trifluoromethylthio)benzenesulfonamide                       
wetting agent                  1%                                         
crude ligninsulfonate salt (containing                                    
                              10%                                         
5-20% of the natural sugars)                                              
attapulgite clay               9%                                         
______________________________________
The ingredients are blended and milled to pass through a 100 mesh screen. This material is then added to a fluid bed granulator, the air flow is adjusted to gently fluidize the material, and a fine spray of water is sprayed onto the fluidized material. The fluidization and spraying are continued until granules of the desired size range are made. The spraying is stopped, but fluidization is continued, optionally with heat, until the water content is reduced to the desired level, generally less than 1%. The material is then discharged, screened to the desired size range, generally 14-100 mesh (1410-149 microns), and packaged for use.
EXAMPLE 14
High Strength Concentrate
______________________________________                                    
N--[N--(4,6-dimethoxy-1,3,5-triazin-2-yl)-N--methyl-                      
                              99%                                         
aminocarbonyl]-2-(difluoromethoxy)benzenesulfonamide                      
silica aerogel               0.5%                                         
synthetic amorphous silica   0.5%                                         
______________________________________
The ingredients are blended and ground in a hammer-mill to produce a material essentially all passing a U.S.S. No. 50 screen (0.3 mm opening). The concentrate may be formulated further if necessary.
EXAMPLE 15
Wettable Powder
______________________________________                                    
N--[N--(4,6-dimethoxy-1,3,5-triazin-2-yl)-N--methylamino-                 
                               90%                                        
carbonyl]-2-(difluoromethylthio)benzenesulfonamide                        
dioctyl sodium sulfosuccinate 0.1%                                        
synthetic fine silica         9.9%                                        
______________________________________
The ingredients are blended and ground in a hammer-mill to produce particles essentially all below 100 microns. The material is sifted through a U.S.S. No. 50 screen and then packaged.
EXAMPLE 16
Wettable Powder
______________________________________                                    
N--[N--(4,6-dimethoxy-1,3,5-triazin-2-yl)-N--methylamino-                 
                              40%                                         
carbonyl]-2-(trifluoromethylthio)benzenesulfonamide                       
sodium ligninsulfonate        20%                                         
montmorillonite clay          40%                                         
______________________________________
The ingredients are thoroughly blended, coarsely hammer-milled and then air-milled to produce particles essentially all below 10 microns in size. The material is reblended and then packaged.
EXAMPLE 17
Oil Suspension
______________________________________                                    
N--[N--(4,6-dimethoxy-1,3,5-triazin-2-yl)-N--methyl-                      
                             35%                                          
aminocarbonyl]-2-(difluoromethoxy)benzenesulfonamide                      
blend of polyalcohol carboxylic                                           
                              6%                                          
esters and oil soluble petroleum                                          
sulfonates                                                                
xylene                       59%                                          
______________________________________
The ingredients are combined and ground together in a sand mill to produce particles essentially all below 5 microns. The product can be used directly, extended with oils, or emulsified in water.
EXAMPLE 18
Dust
______________________________________                                    
N--[N--(4,6-dimethoxypyrimidin-2-yl)-N--methylamino-                      
                             10%                                          
carbonyl]-2-(difluoromethylthio)benzenesulfonamide                        
attapulgite                  10%                                          
Pyrophyllite                 80%                                          
______________________________________
The active ingredient is blended with attapulgite and then passed through a hammer-mill to produce particles substantially all below 200 microns. The ground concentrate is then blended with powdered pyrophyllite until homogeneous.
Utility
The compounds of the present invention are active herbicides. They have utility for broadspectrum pre- and/or post-emergence weed control in areas where complete control of all vegetation is desired, such as around fuel storage tanks, ammunition depots, industrial storage areas, parking lots, drivein theaters, around billboards, highway and railroad structures. Alternatively, the subject compounds are useful to beneficially modify plant growth.
The rates of application for the compounds of the invention are determined by a number of factors, including their use as herbicides, or plant growth modifiers, the types of weeds to be controlled, weather and climate, formulations selected, mode of application, amount of foliage present, etc. In general terms, the subject compounds should be applied at levels of around 0.004 to 5 kg/ha, the lower rates being suggested for use on lighter soils and/or those having a low organic matter content, for plant growth modification or for situations where only short-term persistence is required.
The compounds of the invention may be used in combination with any other commercial herbicide examples of which are those of the triazine, triazole, uracil, urea, amide, diphenylether, carbamate and bipyridylium types.
The herbicidal and growth modifying properties of the subject compounds were discovered in a number of greenhouse tests. The test procedures and results follow.
Test A
Seeds of crabgrass (Digitaria sp.), barnyardgrass (Echinochloa crusgalli), wild oats (Avena fatua), sicklepod (Cassia obtusifolia), morningglory (Ipomoea sp.), cocklebur (Xanthium sp.), sorghum, corn, soybean, sugar beet, rice, wheat and purple nutsedge tubers (Cyperus rotundus) tubers were planted and treated pre-emergence with the test chemicals dissolved in a non-phytotoxic solvent. At the same time, these crop and weed species, along with cotton and bush bean, were treated with a soil/foliage application. At the time of treatment, the plants ranged in height from 2 to 18 cm. Treated plants and controls were maintained in a greenhouse for sixteen days, after which all species were compared to controls and visually rated for response to treatment. The ratings, summarized in Table A, are based on a numerical scale extending from 0=no injury, to 10=complete kill. The accompanying descriptive symbols have the following meanings:
C=Chlorosis or necrosis;
E=emergence inhibition;
G=growth retardation; and
H=formative effects.
It will be seen that the compounds tested possess herbicidal and growth retarding properties. ##STR41##
              TABLE A                                                     
______________________________________                                    
               Cmpd. 1   Cmpd. 2   Cmpd. 3                                
Rate kg/ha     0.05      0.05      0.05                                   
______________________________________                                    
POST-EMERGENCE                                                            
Bush bean      2C,2H     0         0                                      
Cotton         4C,9G     3C,7H     2C,2H                                  
Morningglory   5C,9G     5C,9G     4C,8H                                  
Cocklebur      5C,9G     4C,9G     4C,9H                                  
Sicklepod      4C,9G     5C,9G     3C,8G                                  
Nutsedge       0         0         8G                                     
Crabgrass      0         0         0                                      
Barnyardgrass  0         2H        0                                      
Wild Oats      0         0         0                                      
Wheat          0         0         0                                      
Corn           1H        2C,8H     0                                      
Soybean        4C,9G     3C,9G     2C,9G                                  
Rice           0         4G        0                                      
Sorghum        0         2C        0                                      
Sugar beet     9C        5C,9G     9C                                     
PRE-EMERGENCE                                                             
Morningglory   2C,5H     9G        4C,5G                                  
Cocklebur      5H        8H        9H                                     
Sicklepod      0         2C        0                                      
Nutsedge       0         0         0                                      
Crabgrass      0         0         0                                      
Barnyardgrass  0         2C        0                                      
Wild Oats      0         0         0                                      
Wheat          0         0         0                                      
Corn           0         2G        0                                      
Soybean        0         0         1H                                     
Rice           0         3G        0                                      
Sorghum        0         0         0                                      
Sugar beet     2C,9G     10E       10E                                    
______________________________________                                    
 Test B
Two plastic bulb pans were filled with fertilized and limed Woodstown sandy loam soil. One pan was planted with corn, sorghum, Kentucky bluegrass and several grass weeds. The other pan was planted with cotton, soybeans, purple nutsedge (Cyperus rotundus), and several broadleaf weeds. The following grass and broadleaf weeds were planted: crabgrass (Digitaria sanguinalis), barnyardgrass (Echinochloa crusgalli), wild oats (Avena fatua), johnsongrass (Sorghum halepense), dallisgrass (Paspalum dilatatum), giant foxtail (Setaria faberii), cheatgrass (Bromus secalinus), mustard (Brassica arvensis), cocklebur (Xanthium pensylvanicum), morningglory (Ipomoea hederacea), sicklepod (Cassia obtusifolia), teaweed (Sida spinosa), velvetleaf (Abutilon theophrasti), and jimsonweed (Datura stramonium). A 12.5 cm diameter plastic pot was also filled with prepared soil and planted with rice and wheat. Another 12.5 cm pot was planted with sugar beets. The above four containers were treated pre-emergence with one of the test compounds within the scope of the invention.
Twenty-eight days after treatment, the plants were evaluated and visually rated for response to the chemical treatments utilizing the rating system described previously for Test A. The data are summarized in Table B.
              TABLE B                                                     
______________________________________                                    
PRE-EMERGENCE ON                                                          
WOODSTOWN SANDY LOAM                                                      
                 Compound 3                                               
Rate kg/ha         0.06       0.25                                        
______________________________________                                    
Crabgrass          4G         4G                                          
Barnyardgrass      4G         4G                                          
Sorghum            4G         2G                                          
Wild Oats          3G         2G                                          
Johnsongrass       2G         2G                                          
Dallisgrass        0          0                                           
Giant foxtail      0          2G                                          
Ky. bluegrass      0          2G                                          
Cheatgrass         0          2G                                          
Sugar beets        8G         9G                                          
Corn               3G         3G                                          
Mustard            9G         9G                                          
Cocklebur          3G         3G                                          
Pigweed            --         --                                          
Nutsedge           2G         4G                                          
Cotton             4G         4G                                          
Morningglory       5G         8G                                          
Sicklepod          0          2G                                          
Teaweed            2G         2G                                          
Velvetleaf         4G         7G                                          
Jimsonweed         2G         4G                                          
Soybean            4G         5G                                          
Rice               0          2G                                          
Wheat              0          2G                                          
______________________________________
Test C
The test chemical, dissolved in a non-phytotoxic solvent, was applied in an overall spray to the foliage and surrounding soil of selected plant species. One day after treatment, plants were checked for rapid burn injury. Approximately fourteen days after treatment, all species were visually compared to untreated controls and rated for response to treatment. The rating system was as described previously for Test A. The data are presented in Table C.
All plant species were seeded in Woodstown sandy loam soil and grown in a greenhouse. The following species were grown in soil contained in plastic pots (25 cm diameter by 13 cm deep): soybeans, cotton, alfalfa, corn, rice, wheat, sorghum, velvetleaf (Abutilon theophrasti), sesbania (Sesbania exaltata), sicklepod (Cassia obtusifolia), morningglory (Ipomoea hederacea), jimsonweed (Datura stramonium), cocklebur (Xanthium pensylvanicum), crabgrass (Digitaria sp.), nutsedge (Cyperus rotundus), barnyardgrass (Echinochloa crusgalli), giant foxtail (Setaria faberii) and wild oats (Avena fatua). The following species were grown in soil in a paper cup (12 cm diameter by 13 cm deep): sunflower, sugar beets, and rape. All plants were sprayed approximately 14 days after planting. Additional plant species such as johnsongrass and bindweed are sometimes added to this standard test in order to evaluate unusual selectivity.
              TABLE C                                                     
______________________________________                                    
Over-the-Top Soil/Foliage Treatment                                       
              Compound 3                                                  
Rate kg/ha      0.004    0.015     0.06                                   
______________________________________                                    
Soybeans        4G,3C    7G,9C     10C                                    
Velvetleaf      6G       4C,7G     9G                                     
Sesbania        8G       9G        9G                                     
Sicklepod       4G       1C,8G     3C,6G                                  
Cotton          4G       7G        7G                                     
Morningglory    2G       3G,3C     4G,3C                                  
Alfalfa         4G       3G        1G                                     
Jimsonweed      8G       9G        9G                                     
Cocklebur       2G       3G        6G                                     
Corn            2G       2G        0                                      
Crabgrass       6G       7G        6G                                     
Rice            3G       0         2G                                     
Nutsedge        0        0         0                                      
Barnyardgrass   0        0         0                                      
Wheat           0        0         0                                      
Giant foxtail   0        0         0                                      
Wild Oats       0        0         0                                      
Sorghum         0        0         0                                      
Sunflower       6G,4C    10C       10C                                    
Rape            7G       9G        9G                                     
Johnsongrass    0        0         0                                      
Sugar beet      9G       10C       10C                                    
Bindweed        0        0         0                                      
______________________________________
Test D
Two plastic pans lined with polyethylene liners were filled with prepared Woodstown sandy loam soil. One pan was planted with seeds of wheat (Triticum aestivum), barley (Hordeum vulgare), wild oats (Avena fatua), cheatgrass (Bromus secalinus), blackgrass (Alopecurus myosuroides), annual bluegrass (Poa annua), green foxtail (Setaria viridis), Italian ryegrass (Lolium multiflorum) and rapeseed (Brassica napus). The other pan was planted with seeds of Russian thistle (Salsola kali), cleavers (Galium aparine), speedwell (Veronica persica), kochia (Kochia scoparia), shepherd's purse (Capsella bursa -pastoris), Matricaria inodora, black nightshade (Solanum nigrum), wild buckwheat (Polygonum convolvulus) and sugar beets (Beta vulgaris). The above two pans were treated pre-emergence. At the same time two pans in which the above plant species were already growing were treated post-emergence. Plant heights at the time of treatment ranged from 1-20 cm depending on plant species.
The compound applied was diluted with a non-phytotoxic solvent and sprayed over-the-top of the pans. An untreated control and a solvent alone control were included for comparison. All treatments were maintained in the greenhouse for 19-22 days at which time the treatments were compared to the controls and the effects visually rated. The recorded data are presented in Table D.
              TABLE D                                                     
______________________________________                                    
              Compound 2                                                  
Rate g/ha       1        4        15                                      
______________________________________                                    
Pre-Emergence                                                             
wheat           0        0        0                                       
barley          0        0        0                                       
wild oats       0        0        0                                       
cheatgrass      0        2G       0                                       
blackgrass      2G       3G       5G                                      
annual bluegrass                                                          
                3G       4G       4G                                      
green foxtail   2G       3G       3G                                      
Italian ryegrass                                                          
                2G       2G       2G                                      
rapeseed        0        5G       8G                                      
Matricaria inodora                                                        
                0        0        8G                                      
Galium aparine  0        2G       7G                                      
Russian thistle 0        0        0                                       
shepherd's purse                                                          
                0        4G       8G                                      
kochia          0        0        0                                       
black nightshade                                                          
                0        2G       5G                                      
speedwell       0        2G       5G                                      
wild buckwheat  0        1G       4G                                      
sugar beets     0        5G       9G,9C                                   
Post-emergence                                                            
wheat           0        0        0                                       
barley          0        0        0                                       
wild oats       0        0        0                                       
cheatgrass      0        0        0                                       
blackgrass      0        0        0                                       
annual bluegrass                                                          
                0        0        0                                       
green foxtail   0        0        0                                       
Italian ryegrass                                                          
                0        0        0                                       
rapeseed        8G       8G       10C                                     
Matricaria inodora                                                        
                --       --       --                                      
Galium aparine  --       --       --                                      
Russian thistle 0        0        0                                       
shepherd's purse                                                          
                6G       8G       3C,9G                                   
kochia          0        0        0                                       
black nightshade                                                          
                0        0        6G                                      
speedwell       3G       2G       3G                                      
wild buckwheat  0        3G       8G                                      
sugar beets     4G       6G       5G                                      
______________________________________

Claims (17)

What is claimed is:
1. A compound of the formula ##STR42## wherein A is O or S(O)n ;
R is CHF2, CF3, CH2 CF3, CF2 CF2 H, CF2 CFHCl, CF2 CFHBr, or CF2 CHFCF3 ;
R1 is H, F, Cl, Br, CH3, CF3 or OCH3 ;
n is 0, 1 or 2;
X is CH3 or OCH3 ;
Y is CH3, OCH3, OCH2 CH3, CH2 CH3, CH2 OCH3 or CH2 CH2 OCH3 ; and
Z is CH or N; and
their agriculturally suitable salts.
2. Compounds of claim 1 where R1 is H.
3. Compounds of claim 2 where R is CF3, CHF2, CH2 CH3 or CF2 CF2 H.
4. Compounds of claim 3 where A is O or S and Y is CH3 or OCH3.
5. The compound of claim 1 which is N-[N-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-N-methylaminocarbonyl]-2-(difluoromethoxy)benzenesulfonamide.
6. The compound of claim 1 which is N-[N-(4,6-dimethoxy-1,3,5-triazin-2-yl)-N-methylaminocarbonyl]-2-(difluoromethoxy)benzenesulfonamide.
7. The compound of claim 1 which is N-[N-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-N-methylaminocarbonyl]-2-(difluoromethylthio)benzenesulfonamide.
8. The compound of claim 1 which is N-[N-(4,6-dimethoxy-1,3,5-triazin-2-yl)-N-methylaminocarbonyl]-2-(difluoromethylthio)benzenesulfonamide.
9. The compound of claim 1 which is N-[N-(4,6-dimethoxy-1,3,5-triazin-2-yl)-N-methylaminocarbonyl]-2-(trifluoromethylthio)benzenesulfonamide.
10. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of claim 1 and at least one of the following: surfactant, solid or liquid diluent.
11. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of claim 2 and at least one of the following: surfactant, solid or liquid diluent.
12. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of claim 3 and at least one of the following: surfactant, solid or liquid diluent.
13. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of claim 4 and at least one of the following: surfactant, solid or liquid diluent.
14. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of claim 1.
15. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of claim 2.
16. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of claim 3.
17. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of claim 4.
US06/449,547 1982-12-13 1982-12-13 Herbicidal sulfonamides Abandoned USH168H (en)

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US4780126A (en) 1984-08-30 1988-10-25 Bayer Aktiengesellschaft 3-substituted 1-(2-halogenoalkoxy-benzenesulphonyl)-3-heteroaryl-(thio)ureas

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US4257802A (en) 1977-10-06 1981-03-24 E. I. Du Pont De Nemours And Company Herbicidal sulfonamides
US4310346A (en) 1980-03-14 1982-01-12 E. I. Du Pont De Nemours And Company N(Substituted phenylsulfonyl) N'(substituted cyumidin-2-yl) ureas
US4378991A (en) 1980-07-11 1983-04-05 E. I. Du Pont De Nemours And Company Herbicidal o-aryl or alkarylsulfonylureas
US4420325A (en) 1981-09-29 1983-12-13 E. I. Du Pont De Nemours & Company Herbicidal sulfonamides
EP0023422B1 (en) 1979-07-26 1984-02-22 E.I. Du Pont De Nemours And Company Herbicidal sulfonamides, preparation and use thereof, and compositions containing them
US4515620A (en) 1982-01-12 1985-05-07 Ciba Geigy Corporation Triaza compounds
US4537619A (en) 1980-07-17 1985-08-27 Ciba Geigy Corporation N-Phenylsulfonyl-N'-triazinylureas

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US4257802A (en) 1977-10-06 1981-03-24 E. I. Du Pont De Nemours And Company Herbicidal sulfonamides
EP0023422B1 (en) 1979-07-26 1984-02-22 E.I. Du Pont De Nemours And Company Herbicidal sulfonamides, preparation and use thereof, and compositions containing them
US4452628A (en) 1979-07-26 1984-06-05 E. I. Du Pont De Nemours And Company Herbicidal sulfonamides
US4310346A (en) 1980-03-14 1982-01-12 E. I. Du Pont De Nemours And Company N(Substituted phenylsulfonyl) N'(substituted cyumidin-2-yl) ureas
US4378991A (en) 1980-07-11 1983-04-05 E. I. Du Pont De Nemours And Company Herbicidal o-aryl or alkarylsulfonylureas
US4537619A (en) 1980-07-17 1985-08-27 Ciba Geigy Corporation N-Phenylsulfonyl-N'-triazinylureas
US4420325A (en) 1981-09-29 1983-12-13 E. I. Du Pont De Nemours & Company Herbicidal sulfonamides
US4515620A (en) 1982-01-12 1985-05-07 Ciba Geigy Corporation Triaza compounds

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4780126A (en) 1984-08-30 1988-10-25 Bayer Aktiengesellschaft 3-substituted 1-(2-halogenoalkoxy-benzenesulphonyl)-3-heteroaryl-(thio)ureas

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