Note: Descriptions are shown in the official language in which they were submitted.
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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
-- - NHS02-N
\ US
R2
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;
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go
R5 is:
R6
wherein:
R6 is hydrogen or halogen;
R7 is
R8 R9 Roll O - OH - R12
or (Sheehan
O R10 H - R13
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
R3
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,
R/2
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-
-- 3 --
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
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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
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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.
