CA1229608A - Herbicidally active substituted phenyl-sulfamoyl pyridyl or triazinyl ureas - Google Patents

Abstract

Abstract Of The Disclosure The invention relates to herbicidally active sulfamoyl urea derivatives, including herbicidal formulations and uses thereof to control the growth of noxious plants, i.e., weeds.

Description

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Field Of The Invention This invention relates to herbicidally active sulfamoyl urea derivatives, including herbicidal formulations uses thereof to control the growth of noxious plants, i.e., weeds.

Description Of The Invention This invention concerns sulfamoyl urea derivatives represented by the Formula I:
It Al \ US

wherein: Z is N or OH;
R and R are thy same or different and represent halogen or Of to C4 alkyd, or alkoxy;
R3 and R4 are the same or different and represent hydrogen, Of to C4 alkyd, alkoxyalkyl, haloalkyl, or up to C3 alkenyl or alkynyl;

go R5 is:

wherein:
R6 is hydrogen or halogen;
R7 is R8 R9 Roll O - OH - R12 or (Sheehan wherein R8 is Of to C3 alkyd;
R9 and R are Of to C6 alkyd;
R is Of to C3 alkyd;
R12 and R13 are hydrogen or Of to C3 alkyd; and n is 0, 1 or 2.
It is, of course, to be understood what àgronomically suitable cat ionic salts of the Formula I compounds are within the scope of this invention.
The Formula I compounds may conveniently be prepared by reacting a suitably substituted amino pyrimidine or amino treason of the Formula II:
II. Al H
R

6~3 wherein R1, R2, R3 and Z are as previously defined, with a halosulfonyl isocyanate of the formula OCN-SO2-Hal, wherein Hal is halogen, e.g., chlorine, fluorine or bromide to form the corresponding halosulfonyl urea of the Formula III:
III.

- NH - SO - Hal I, The Formula III compound is then reacted in the presence of an acid accepting agent with at least a stoichiometric amount of a suitably substituted amine of the Formula IV:

IV.
, / R4 H -\ R5 wherein R4 and R5 are as previously defined, to form a Formula I
compound of the invention.
Preferred compounds of the invention are those wherein R3, R4 and R6 are hydrogen and Z is N. Preparation of particularly preferred compounds of the invention are illustrated by the following Examples:
Example I

Preparation of: 1-[2-(1,1-dimethoxyethyl)phenyl-sulfamoyl]-3-(4-methyl,6-methoxy-1,3,5-tria~in-2-yyowler (a) To a flask was charged 6.0 grams of ortho-I

nitroacetophenone, 6.0 grams of trimethylorthoformate 0.25 gram of p-Tulane sulfonic cold and 50 milliliters of methanol. The stirred mixture was then heated to 60C. under a nitrogen blanket. After about 3 days at 60C., HP~C indicated the reaction was over 90 percent complete.
The mixture was cooled, poured into aqueous sodium carbonate solution, stripped of solvent and extracted with ethylene chloride. The organic layer was dried over sodium carbonate and again stripped of solvent. The residue was dissolved in an aqueous solution of methanol containing 0.5 gram of sodium carbonate, transferred to a Parr shaker flask and reduced over 5% palladium on charcoal. The hydrogenated mixture was then filtered to remove catalyst. Most of the methanol was evaporated and the residue was extracted with ethylene chloride. After phase separation, the organic layer was dried over an hydrous sodium carbonate and stripped of solvent affording a clear oil which was identified by NOR analysis as

2-(1,1-dimethoxyethyl)aniline.
(b) To 50 milliliters of ethylene chloride maintained at 0-5C., via an ice bath was added 1.38 grams of 4-methyl-6-methoxy-2-amino-1,3,5-tr$azine and 1.60 grams of chlorosulfonyl isocyanate. Thy mixture was stirred at ice temperature for about 3 hours after which a ethylene chloride solution containing 1.10 grams of triethylamine and 1.70 grams of the amine prepared in part (a) of this Example was added. The mixture was permitted to rise to ambient temperature and washed with three portions of ice cold water and dried over an hydrous sodium sulfate. Filtration, followed by evaporation of solvent, afforded a pasty material which was dissolved in 80 milliliters of diethylether. The ether insoluble residue was discarded and the ether was evaporated, affording a resinous solid that was taken-up in pontoon Z96~

and filtered. Vacuum drying afforded 1.3 grams of yellow crystalline solid identified by NOR analysis as the desired product, 1-[2-(1,1-dimethoxyethyl)phenylsulfamoyl]-3-(4-methyl-66-methoxy-1,3,5-triazin-2-yl)urea.
Example II

Preparation of: 1-[2-(1,3-dioxolan-2yl-methyl~phenyl-sulfamoyl]-3-(4-methyl,6-methoxy-1,3?5-tri_zln-2-yyowler (a) To a round bottom flask was charged 10 grams of ortho-nitroacetophenone, 40 milliliters of ethylene glycol and 0.5 gram of p-Tulane sulfonic acid. The stirred mixture was then heated to 140C.
with a nitrogen purge to remove water. After about 36 hours, HPLC
Indicated the reaction was over 90 percent complete. The mixture was cooled and suction filtered and the solid product was washed with aqueous sodium carbonate solution and suction dried affording 8 grams of white crystalline solid. The solid was taken up in a solution of methanol and aqueous sodium carbonate, transferred to a Parr shaker flask and 0.5 gram of palladium on charcoal was added. the mixture was hydrogenated at 50 psi for 2 hours, hydrogen uptake being complete at this point. The hydrogenated mixture was then filtered to remove catalyst and stripped of solvent on a rotary evaporator. The residue was then extracted with a mixture of water and msthylene chloride. After phase separation, the organic phase was dried over an hydrous sodium sulfate and stripped on a rotary evaporator affording 7.0 grams of clear oil (which solidified on standing) which was identified by NOR analysis as 2-(1,3 dioxolan-2yl-methyl aniline tub) To 150 milliliters of ethylene chloride maintained at 0-5C. via an ice bath was added 1.41 grams (0.01 mole) of 4-methyl-~;~29~i~8 6-methoxy-2-amino-1,3,5-tria~ine and 1.54 grams of chlorosulfonyl isocyanate. The mixture was stirred at ice temperature until all of the solid had dissolved and for an additional one-half hour after which a ethylene chloride solution containing 0.01 mole of triethylamine and 0.01 mole of the amine prepared in part (a) of this Example were added drops, the mixture maintained at ice temperature throughout the addition. The mixture was permitted to rise to ambient temperature, retooled in the ice bath and poured into ice cold 2% aqueous hydrochloric acid where it was shaken and rapidly separated. The organic phase was washed with three portions of ice cold water and dried over an hydrous sodium sulfate. Evaporation of solvent afforded a pasty material that crystallized Iron addition of a small amount of diethylether. Suction filtration afforded 2.6 grams of material identified by NOR analysis a the desired product 1-[2-(1,3-dioxolan-2yl-methyl)phenylsulfamoyl]-3-(4 methyl-6-methoxy-1,3,$-triazin-2-yl)ureaO
Although the invention has been illustrated by the foregoing Examples with regard to the preparation of specific compounds within the scope of Formula It it is to be understood that other compounds within the scope of Formula I may readily be prepared by those skilled in the art simply by varying the choice of starting materials and using the same or similar techniques.
Weed control in accordance with this invention is effected by applying to the soil prior to emergence of weeds therefrom or to the plant surfaces subsequent to emergence from the soil, a herbicidally effective amount of a compound of this invention. It is, of course, to be understood that the term "a compound of this invention" also includes mixtures of such compounds or a formulation containing a compound or mixture of compounds of this invention ~2:~6~3 The term "herbicidally effective amount" is amount of a compound of this invention required to so injure or damage weeds such that the weeds are incapable of recovering following application, while not causing any substantial damage to any valuable crop amongst which the weeds might be growing. The quantity of a compound of this invention applied in order to exhibit such satisfactory herbicidal effect may vary over a wide range and depends on a variety of factors, such as, for example, hardiness of a particular weed species, extent of weed infestation, climatic conditions, soil conditions, method of application, and the like. Typically, as little as one or less pound per acre of a compound of this invention would be expected to provide satisfactory weed control, although in some instances application rates in excess of one pound per acre; e.g., up to 5 or more pounds per acre might be required.
Of course, the efficacy of a particular compound against a particular weed species may readily be determined by routine laboratory or field testing in a manner well known to the art. It is expected that satisfactory weed control can be had at a rate of application in the range of 0.01 to 2.0 pounds per acre.
Of course, a compound of this invention can be formulated according to routine methods with any of several known and commonly used herbicidal delineates, adjutants and carriers. The formulations can contain liquid carriers and adjutants such as organic solvents, as well as emulsifiers, stabilizers, dispPrsants, suspending agents, spreaders, penetrants, wetting agents and the like. Typical carriers utilized in dry formulations include clay, talc, diatomaceous earth, silica and the like. Preferred formulations are those in the form of wettable powders, flowables, dispersible granulates or aqueous emulsifiable concentrates I

which can be diluted with water at the site of application. Also, dry formulations such as granules, dusts, and the like, may be used.
When desired, a compound of this invention can be applied in combination with other herbic~dal agents in an effort to achieve even broader vegetative control. Typical herbicides which can be conveniently combined with Formula I compound include atrazlne, hexazinone, metribuzin, ametryn, Swenson, cyprazine, prometon, prometryn, propazine, Samson, terbutryn, prop ham, alachlor, acifluorfen, bentazon, metolachlor and N,N-dialkyl thiocarbamates such as EPIC, butylate or vernolate. These, as well as other herbicides described, for example, in the Herbicide Handbook of the Weed Science Society of America, may be used in combination with a compound or compounds of the invention. Typic Cole such formulations will contain from about 5 to about 95 percent by weight of a compound of this invention.
The herbicidal formulations contemplated herein can be applied by any of several method known to the art. Generally, the formulation will be surface applied as an aqueous spray. Such application can be carried out by conventional ground equipment, or if desired, the sprays can be aerially applied. Soil incorporation of such surface applied her-besides is accomplished by natural leaching, and is of course facilitated by natural rainfall and melting snow. If desired, however, the herbicides can be incorporated into the soil by conventional village means.
Compounds of this invention are believed effective for reemergence or post emergence control of a wide variety of broadleaf and grassy weeds. Typical of the. various species of vegetative growth that may be controlled, combated, or eliminated are, for example, annuals such ~29~
as pugged, lambs quarters, foxtail, crabgrass, wild mustard, field pancreas, rigors, goose grass, chickweed, wild oats, velvet leaf, porcelain, barnyard grass, smarted, nutted, cocklebur couch, medic, ragweed, hemp nettle, surrey, pounded, carpeted, morning glory, duck salad, cheat grass, fall panicum, jimsonweed, witch grass, water grass, wild turnip, and similar annual grasses and weeds. Biennials that may be controlled include wild barley, champion, burdock, bull thistle, round leaved mallow, purple star thistle, and the like. Also controlled by the compounds of this invention are perennials such as quack grass, Johnson grass, Canada thistle, curly dock, field chickweed, dandelion, Russian nipped aster, hairstyle, ironed, sesbania, cattail, winter cress, horizontal, nut sedge, milkweed, cyclopedia, and the like.
More particularly, by way of example, the compounds prepared in the Examples were each tested for reemergence and postemergenc~
herbicidal activity by spraying a solvent solution of same on a variety of common broadleaf and grassy weed species under controlled laboratory conditions of light, temperature and humidity. The extent of herbicidal injury was evaluated, periodically after application, and a Numerical Injury Rating tNIR) assigned on a scale of from O (no injury) to 10 (all plants dead). The following Table gives the NOR assigned to each weed specie (identified by common name) 21 days after reemergence and post emergence application of the compound of Example I at a rate of 0.5 pound per acre:

_ g _ 5q:)~

WEED SPECIESPREEMERGENCE POST EMERGENCE
Seaweed 9 5 Jimsonweed 9 10 Wild mustard 9 10 Yellow nut sedge 10 6 Yellow foxtail 10 8 Large crabgrass 9 Johnson grass 9 8 Coughed 9 8 Velvet leaf 9 8 Tall morning glory 9 3 Wild oats 8 3 Barnyard grass 9 4 The following Table gives the NOR assigned to each weed species (identified by common name) 22 days after reemergence and post emergence application of the compound of Example II at rates of 0.5 and 1.0 per acre:
WEED SPECIESPREEMERGENCE POST EMERGENCE
0.5 1.0 0.5 1.0 Seaweed 6 6 5 5 Jimsonweed 5 6 8 8 Wild mustard 8 8 8 10 Yellow nut sedge 10 10 6 7 Yellow foxtail 7 8 6 7 Large crabgrass 7 8 - -Johnson grass 7 8 6 6 Coughed 3 6 6 6 ~%~

Velvstleaf 5 5 8 8 Tall morning glory 4 5 5 6 Wild oats 8 7 2 Barnyard grass 8 8 3 5 Although the invention has been described in considerable detail by the foregoing, it is to be understood that many variations may be made therein by those skilled in the art without departing from the spirit and scope thereof as defined by the appended claims.

Claims (4)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY OR PRIVILEGE
IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A compound represented by the formula:

wherein: Z is a N or CH;
R1 and R2 are the same or different and represent halogen or C1 to C4 alkyl or alkoxy;
R3 and R4 are the same or different and represent hydrogen, C1 to C4 alkyl, C1 to C4 alkoxyalkyl, C1 to C4 haloalkyl, or up to C3 alkenyl or alkynyl;
R5 is wherein:
R6 is hydrogen or halogen;
R7 is wherein: R is C1 to C3 alkyl;
R9 and R10 are C1 to C6 alkyl;

R11 is C1 to C3 alkyl;

R12 and R13 are hydrogen or C1 to C3 alkyl; and n is 0, 1 or 2.

2. A compound of Claim 1 wherein Z is N and R3, R4 and R6 are hydrogen.

3. A compound of Claim 2 that is 1-[2-(1,1-dimethoxyethyl)phenylsufamoyl) -3-(methyl-6-methoxy-1,3,5-triazin-2yl)urea or 1-[2-(1,3-dioxolan-2yl-methyl) phenylsulfamoyl]-3-(4-methyl-6-methoxy-1,3,5-triazin-2yl)urea.

4. In a method of controlling weeds wherein a herbicidally effective amount of herbicide is applied to a growth medium prior to emergence of weeds therefrom or to the weeds subsequent to their emergence from the growth medium, the improvement residing in using as the herbicide a compound or mixture of compounds defined in Claim 1.