CA1203534A - Herbicidal sulfonamides - Google Patents

Abstract

Abstract of the Disclosure Hydroxymethylbenzenesulfonamide derivatives have utility as agricultural chemicals and in particular as herbicides.

Description

lZV3S34 x 1 BA-8396-A
Title HERBICIDAL SULFONA~IIDES
Background of the Invention This invention relates to hydroxymethylbenzene-sulfonamide derivatives which are useful as agricul-tural chemicals and in particl~lar as general herbi-cides kaving both pre- and post-emergence activity.
Netherlands Patent 121,788, p~blished September 15, 1966, discloses the preparation of com-pounds of the following Formula and their use asgeneral or selective herbicides:
Cl l; R3 R2 wherein Rl and R2 may independently be alkyl of 1-4 carbon atoms; and R3 and R4 may independently be hydrogen, chlorine or alkyl of 1-4 carbon atoms.
U.S. Patent 3,637,366 discloses compounds having the formula:

RlHN~ SO~-N~IR2 wherein . Rl ~s hydrogen or lower saturated aliphatic acyl and R2 is hydrogen, 2-pyrimidinyl, pyridyl, amidino, acetyl or carbamoyl.
~he d$sclosed compounds are said to provide control of crabgrass, cress, endive, clover and Poa annua.

X , ~rench Patent No. 1,468,747 discloses the following ~ara-substituted phenylsulfonamides as being useful as antidiabetic agents:

~ ~ ~ N 3 wherein R ~ H, halogen, CF3 or alXyl.
~ogemann et al. Chem Ab., 53, 18052 g tl959), disc~ose a number of sulfonamides, including uracil derivatives and those having the formula:

H3C ~ S02N~CNHR
wherein , N
R is butyl, phenyl, or -~ ~ and Rl is hydrogen or methyl. -<~1 When tested for hypoglycemic effect in rats (oral doses of 25 mg/100 g), the compounds in which R is butyl and phenyl were most potent. The others were of low potency or inactive.
Wo~ciechowski, J. Acta. Polon. Pharm 19, p. 121-5 (1962) lChem. Ab., S9 1633 el describes the ~ynthesis of N-tt2,6-dimethoxypyrimidin-4-yl)amino-carbonyll-4-methylbenzenesu~fonamide:
oc~3 3 o CH3 ~3so2N~-c-N~N
oc~3 3~

x 3 Based upon similarity to a known comround, the author speculated that the foregoing compound might bave a hypoglycemic act~v~ty.
Subst~tuted-pyrimidinyl sulfonylureas of the 5 following formula, which are also ~ara-substituted on the phenyl ring, are disclosed in Farmco Ed. Sci., 12, 586 ~1957) lChem. Ab., 53, 18052 g (1959]:
c~3 1oCH3 ~ S02N~-C-NH ~/

whercin 15R ~ H or C~3.
The presence of undesired vegetation causes substantial damage to useful crops, especially agri-- cultural products that satisfy man's basic food and fiber needs, such as cotton, rice, corn, wheat, and the like. The current population explosion and con-20 comitant world food and fiber shortage demand improve-ments in the efficiency of producing these crops.
Preventing or minimizing loss of a portion of such valuable crops by ~illing, or inhibiting the growth of undesired vegetation is one way of improving this 25 efficiency. A wide variety of materials useful for kill-ing or inhibiting (controlling) the growth of unde-sired vegetation is available; such materials are commonly referred to as herbicides. The need still exists however, for more effective herbicides.

lZ03534 x 4 Summary of the Inventlon This invention relates to novel compounds of Formula I and their agriculturally suita~le salts, suitable agricultural compositions containing them, S and their method of use as general and selective pre-emergence and post-emergence herbicides and as plant-growth regulants.

R ~ O~-HCN-A

~I) where~ n L ~s OH, OC(O)Rll, OC(O)NHR12 or OC(O)OR13;
R is H, F, Cl, Br, NO2, CF3, Cl-C3 alkyl or Cl-C3 alkoxy;
Rl 1s H or Cl-C4 alkyl;
R2 is H or CH3;

R8 is H, CH3 or OCH3;
Rll is H, Cl-C5 alkyl, C2-C3 alkenyl, C2-C3 alkynyl, C3-C4 cycloalkyl, ~ 14 , Cl-C4 alkyl substi tuted with 1-4 substituents selected from 0-3 F, 0-3 Cl or 0-3 Br, or C2-C3 alkenyl substi tuted with 1-3 Cl;
R12 is H, Cl-C6 al kyl, C3-C4 alkenyl, C5-C6 cycloalkyl, ~ R17 ~ R17 or x 5 or C5-C6 cycloalkyl substituted w~th CH3;
R13 ls Cl-C6 alkyl or ~ R18 ;

R14 and R15 are independently H, N02, CH3, Cl or CH3;

R16 is H, F, Cl, Br, Cl-C3 alkyl, N02, CN, 502CH3, OCH3, SCH3 or CF3i R17 is H~ Cl or Cl-C3 alkyl;
R18 is H, CH3 or Cl;
A is ~ ~ ~ ~ or ~ is O or S;
X 1s H, Cl, 8r, CH3, CH2CH3, Cl-C3 alkoxy, CF3, SCH3 or CH20CH3;
Z ~s N, CH9 CCl, CBr, CCN, CCH3, CCH2CH3, CCH2CH2Cl or CCH2CH~CH2;
yl ~s H, CH3, OCH3 or OCH2CH3; and Q ~s O or CH2;
25 and their agriculturally su~table salts;
prov~ded that when W ~s S, then R8 1s H.

12(~353~
x 6 Preferred ~ompounds:
Preferred for their higher activity and/or more favorable ease of sytnthesis are:

5 (1) Compounds of the generic scope where Z ~s N, CH, CCl, CBr or CCH3, w is o and R8 is H or CH3

(2) Compounds of the generic scope where L is OH, R is H, Rl and R2 are CH3, R8 is H or CH3;

A is ~; Z ~s CH or N; X and Y are independently CH3 or OCH3; and W is O;

(3) Compounds of Preferred (1) where Z ~s CH or N; X
~s CH3 or OCH3; and Rl ~s H or CH3;

(4) Compounds of Preferred (3) where R and R8 are H, and A ~s ~N ~

(S) Compounds of Preferred (4) where Rll, R12 and Rl 3 are Cl -C3 alkrl;
(6) Compounds of Preferred (4I where L ~s OH.

Specifically preferred for their highest activity a~d/or most favorable ease of synthesis are:

12~3~34 x 7 N-r(4,6-Dimethoxypyrimid~n-2-yl)aminocarbonyl]-2-(hydroxymethyl)benzenesulfon3mide, ~p 149-151-;
N-~4,6-D~methoxy-1,3,~-triazin-2-yl)aminocarbonyl~-2-(hydrq~ymethyl)benzenesulfonamide, ~p 146-148-(d);

5 N-~(4,6-Dimethylpyrimidin-2-yl)aminocarbonyl3-2-(hydroxy-methyl)ben2enesulfonamide, N-t(4-methoxy-6-methylpyrimidin-2-yl~aminocarbonyl]-2-(hydroxymethyl)benzenesulfonamide;
N-t(4,6-Dimethy~-1,3,5-triazin-2-yl)aminocarbonyl3-2-thydroxy~ethyl)benzenesulfonamide; and N-~(4-Methoxy-6-me~hyl-1,3,5-triazin-2-yl)aminocarbonyl]-2-(hydroxymethyl)benzenesulfonamide.

Detailed Description of the Invention Synthesis Many of the compounds of Formula I may be pre-pared as shown in Equation 1 by reaction of an appro-priately substituted o-hydroxymethylbenzenesulfonyl-urea, II, with an appropriate acid chloride.
Equation 1 ~ C/ O R Rl R2 2S O + RlICCl --_~ O
SO2N~JC~.2~ So2NllcN-A

_ III
The reaction of Equation 1 is best carried out in inert aprotic solvents e.g. methylene chloride, tetrahydrofuran or acetonitrile at 0-80C. An excess of the acid chloride is used and at least one equiva-Xlent of a tertiary amine such as pyridine, triethyl-amine or 4-dimethylaminopyridine. Isolation 's achieved by evaporation of solvent and recrystalli-zation from suitable solvents such as l-chlorobutane, S ethyl acetate or ethyl ether or by column chroma-tography over silica gel.
Other compounds of Formula I may be prepared as shown in Equation 2 by reaction of an appropriately substituted o-hydroxymethylbenzenesulfonylurea, II, 0 with an appropriate isocyanate.
Equation 2 \C / , ~X c~o-cNHR l 2 15 ~ 12NCO----t O
SO2N~C~ A SO NUC

II TV
The reaction of Equation 2 is best carried out in inert aprotic solvents e.g. methylene chloride, tetrahydrofuran or acetonitrile at 0-80C. An excess of the isocyanate is used and a catalyst such as dibutyltindilaurate or 1,4-diazal2,2,2]bicyclo-octane (DABCO). Isolation is achieved by evaporation of solvent and recrystallization from 'suitable solvents such as l-chlorobutane, ethyl acetate or ethyl ether or by column chromatography over silica gel.
Other compounds of Formula I may be prepared as shown in Equation 3 by reaction of an appropriately substituted o-hydroxymethylbenzenesulfonylurea, II, with an appropriate chloroformate.

X g Equation 3 \C/ H O R Rl R2 5 ~ O + clCo-Rl3 ~ ~ O
S02N~ICN--A So2Nl~cN--A

II V

The reaction of Equation 3 is best carried out in inert aprotic solvents e.g. methylene chloride, tetrahydrofuran or acetonitrile at 0-80C. An excess of the chlorocarbonate is used and at least one equivalent of a tertiary amine e.g. pyridine, lS triethylamine or 4-dimethylaminopyxidine. Isolation is achieved by evaporation of solvent and recrystalli-zation from suitable solvents e.g. l-chlorobutane, ethyl acetate or diethyl ether or by column chroma-tography over silica gel.
The preparation of compounds of Formula II
where Rl=R2=H may be prepared as shown in Equation 4.
Equation 4 R

25~ C2~ O BH3.THF ~ CH2H
S02NHCN_A ) S02NHCN'--A-~8 VII 8 VI
The carboxylic acid, VI, may be converted to the alcohol by reduction with 4-5 equivalents OL borane-THF
reagent in TH~ at ambient pressure and temperature for 4 to 18 hours. Isolation is achieved by drowning in dilute acid followed by extraction of the product with a solvent e.g. methylene chloride, ethyl acetate or ethyl ether. Evaporation of solvent and crystalliztion or column chromatography on silica gel affords the pure alcohol, VII.

;

The carboxylic acids, VI, may be prepared by hydrolysis of the corresponding methyl esters as shown in Equation 5.
Equation 5 S02N}ICN--A ~ ~ 502N3CN-A

VIII VI
When A is a pyrimidine type structure, the methyl esters are best hydrolyzed by dissolving in a solution of 80 parts ethanol, 10 parts water and 10 parts potassium hydroxide. The mixture is stirred at ambient temperature for 18 hours followed by pouring into a large excess of water and acidifying to a pH of 2Ø The pure acid, VI, precipitates and is filtered and washed with water.
When A is a triazine and X or Y is alkoxy, the 2~ hydrolysis is best performed by dissolving the ester in a solution of potassium t-butoxide in dimethyl sulfoxide at ambient temperature for two hours. Addition of a large volume of water followed by acidification to a pH of 2.0 precipitates the acid, VI.
The preparation of esters of Formula VIII is described in European Patent Application 7687.
Compounds of Formula VIImay also be prepared by treatment of the carboxylic acids, VI, or the methyl esters, VIII, with lithium aluminum hydride - by the procedures described by R. ~. Nystrom and W. G. Brown, J. Am. Chem. Soc. 69, 2548 (1947) and R. B. Moffett, Or~anic Synthesis, Coll. Vol. 4, 834 12~3S34 o 11 (1963). Reduction of the esters with sodium bi5-(2-methoxyethQxy)aluminum hydride is described in . Fieser and L. E. Fieser, Reagents for Or~anic S~_thesis, John Wiley & Sons, New York, Vol. 5, 5p. 596 (1975~.
The preparation of compounds of Formula II
where Rl=H and R2=CH3 may be carried out as shown in Equation 6.
Equation 6 O C~3 "_~_, CCH3 ~ CHOH
O LiAlH4 ~ o S02NHCN--A ~ S02NHCN'--A
R~ R8 IX X
Compounds of Formula IX are treated with one - equivalent of li ~ um al~num hydride (IAH) in a sol~t e.g. ether, tetrahydrofuran or glyme at -20 to 2025C for 1 to 6 hours. Next there is a successive dropwise addition of an equivalent number of ml of water as grams of LAH followed by an equal number of ml of 15% sodium hydroxide followed by 3 times that number of ml of water. This produces a dry 25 granular precipitate of aluminum oxide which is easy to filter. The aqueous phase is then acidi-fied with dilute acid and the product extracted with solvent such as methylene chloride, ethyl acetate or ethyl ether. Evaporation of solvent 30 and crystallization or column chromatography on silica gel affords the pure alcohol, X.
Compounds of Formula IX are prepared by tne reaction, as shown in Equation 7, usinq an excess of methyl lithium with a carboxylic acid deriva-~ 35 tive of Formula VI.

x 1~
Equation 7 R

R SO2NHCN-ACU3Li SO2N~CN-A
~8 R8 Compounds of Formula VI are restricted to structures in which the substituents R, Z, X and Y contain no displaceable halogens, N~2 or CN.
An excess of methyl lithium in a suitable solvent such as diethyl ether, hexane, pentane or benzene is added to a solution or slurry of VI in a similar solvent at temperatures between -100 and 0C. The mixture is allowed to warm to room tempera-ture and stir for 30 minutes. Aqueous acid is then added and the compound IX is extracted into a suitable solvent to free it from salts,followed by evaporation of the solvent. Purification is by chromatography on silica gel.
Another procedure for ~he preparation of com-pounds of Formula X is the reaction of excess methyl lithium with the corresponding aldehyde XI as shown in Equation 8.
Equation 8 O C~ * ~ 5O2N~CN-A

~ZV3534 x 13 Compounds of Formula XI are restricted to structures in which the substituents R, Z, X and Y
contain no displaceable halogens; NO2 or CN.
An excess of methyl lithium in a suitable 5 solvent e.g. diethyl ether, hexane, pentane or benzene is adde~ to a solution or slurry of XI in a similar solvent at temperatures between -100 and 0C. The ~ixture is allowed to warm to room tempera-ture and stir for 30 minutes. Aqueous acid is then 10 added and the compound X is extracted into a suitable solvent to free it from salts followed by evaporation of the solvent. Purification is by chromatography on silica gel.
Aldehydes of Formula XI are prepared by the 15 procedure of Equation 9.
Equation 9 R C2CN3 NaAl(OcH2cH2oc~3)2(~J~

VIII
- R
~ ,CHO
~ O

XI

Following the procedure of R. Xanayawa and T. Tokoroyama, a solution of sodium bis(2-methoxy-ethoxy)aluminum hydride in THF is reacted with one equivalent of morpholine. To this solution at -40C
is added methyl ester of Formula VIII and the solu-tion is allowed to warm to 25C. The product is lZ03534 x 14 isolated by addition of aqueous acid and extraction into ether or methylene chloride. Evaporation of solvent and crystallization or column chromatography on silica gel affords the pure aldehyde, XI.
Aldehydes of Formula XI may also be prepared from the esters of Formula VIII by treatment with diisobutylaluminum hydride according to procedures of E. Winterfeldt, Synthesis, 617 (1975).
The preparation of compounds of Formula II
10 where Rl=R2=CH3 may be prepared as shown in Equation 10 .
Equatlon 10 R ~ R CH3 15 ~ CCH3 excess ~ 3 Q
SO2NHCN-A CH3Li SO2NHCNt-A
IX R8 . r~8 XII

Compounds of Formula XII are prepared by the reaction of an excess of methyl lithium with aceto-phenones of Formula IX.
Compounds of Formula IX are restricted to structures in which the substituents R, Z, X and Y
contain no displaceable halogens, NO2 or CN.
An excess of methyl lithium in a suitable solvent e.g. diethyl ether, hexane, pentane or benzene is added to a solution or slurry of IX in a similar solvent at temperatures between -100 and 0C. The mixture is allowed to warm to room tempera-ture and stir for 30 minutes. Aqueous acid is then added and the compound XII is extracted into a suitable solvent to free it from salts followed by evaporation of the solvent. Purification is by chromatography on silica gel.

~Z(~3534 Some of the compounds of Formula I, where Z is CH or N, can also be prepared by the method described in Equation 11.
Equation 11 s (lla) ~ C - L N ~ Cl + OCN ~ O z --~
t n S2NH2 Cl XIII , XIV

1~ / 2 R ~ C - L Cl ., N ~
S02N~ICNH--~ C Z
N~

XV

(llb) 30 8~ ~ SOz~Ch'll--( ~z XVI
XV ' 12~:13534 (llc) 1 ~ 2 1 / 2 ~C L ~C - L

5 R ~ " N ~ ~ " N ~
S02NHCNH ~ NO~Z S02N~ ~ O~z XVI XVII
wherein R, Rl and R2 are as described in Formula I, X is Cl-C3 alkoxy and L is not OH.
Reaction Step (lla) In Reaction Step (lla), an aromatic sulfon-amide of Formula XIII is contacted with a heterocyclicisocyanate of Formula XIV to yield an N-(halohetero-cyclicaminocarbonyl) aromatic sulfonamide of Formula XV.
The heterocyclic isocyanates used in Reaction (lla) may be prepared according to methods described in Swiss Patent 579,062, U.S. Patent 3,919,228, U.S. Patent 3,732,223 and Angew Chem. Int. Ed. 10, 402 (1976).
The aromatic sulfonamide and the heterocylic isocyanate are contacted in the presence of an inert organic solvent, for example, acetonitrile, tetrahydro-furan (THF), toluene, acetone or butanone. Optionally, a catalytic amount of a base, e.g. 1,4-diazabicyclo 12.2.2] octane (DABCO), potassium carbonate, sodium hydride or potassium tert-butoxide, may be added to the reaction mixture. The quantity of base constituting a catalytic amount would be obvious to one skilled in the art. The reaction mixture is preferably maintained at a temperature of about 25 x 17 to 110~, and the product can generally be recovered by cooling and filtering the reaction mixture. For reasons of efficiency and economy, the preferred solvents are acetonitrile and THF, and the preferred temperature range is about 60 to 85C.
Reaction Steps (llb) and (llc) In Reaction Steps (llb) and (llc), one or two of the halogen atoms on the heterocyclic ring of the compound of Pormula XV is displaced by a nucleophilic species. Generally, this may be done by contacting the compound of Formula XV either with alkanol or with alkoxide as described by X where X is ~1-3 alkox~.
Thus, in Reaction Step (llb), a compound of Formula XV, substituted with one displaceable group, can be contacted with at least one equiva-lent of alkanol. This reaction is sluggish, however, and it is preferred to contact the compound of ~ormula XV with at least two equivalents of alkoxide. The alkoxide can be provided in a - 20 number of ways.
(a) The compound of Formula XV can be suspended or dissolved in an alkanol solvent in the presence of at least two equivalents of alkoxide. The alkoxide can be added dixectly as alkali metal or alkaline earth metal alkoxide or can be generated by the addition to the alkanol solvent of at least two equivalents of a base capable of generating alkoxide from the solvent. Suitable bases include, but are not limited to, the alkali and alkaline earth metals, their hydrides and tert-butoxides. For example, when X is methoxy, the lZ03534 x 18 compound of Formula XV could be suspended or dissolved in methanol in the presence of two equivalents of sodium methoxide. Alternatively, S two equivalents of sodium hydride could be used in place of the sodium methoxide.
(b) The compound of Formula XV can be suspended or dissolved in an inert solvent in the presence of at least two equivalents of alkoxide. Suit-able inert solvents include, but are not limited to, acetonitrile, THF
and dimethylformamide. The alkoxide may be added directly as alkali metal or alkaline earth metal alkoxide or may be ger~erated from alkanol and a base as c.escribed in (a) above. ~or example, when X is methoxy, the com-pound of Formula XV could be suspended or diss-~lved in THF in the presence of two equivalents of sodium methoxide.
Alternatively, two equivalents each of methanol and sodium hydride could be used instead of sodium methoxide.
For reasons of economy and efficiency, proce-dure (a) is the more preierred method.
lt should be noted that two equivalents of alkoxide are required for Reaction Step (b) whereas only one equivalent of alkanol is needed for the same process. This difference is due to the reaction which is believed to occur between the alkoxide and the sulfonyl nitrogen of the sulfonamide of Formula XV. When alkoxide is used, the first equivalent of alkoxide removes a proton from the sulfonyl nitrogen, and is only the second e~uivalent which effects dis-x 19 placement of the halogen. As a result, two equiva-lents of alXoxide are re~uired. The resulting salt must be acidified, e.g., with sulfuric, hydrochloric or acetic acid, to yield a compound of Formula XVI.
5 Applicant, of course, does not intend to be bound by the mechanism described above.
In Reaction Step (llc) a compound of Formula XV~, is contacted with either one equivalent of methanol or with two equivalents of methoxide. When-10 methoxide is used, it may be provided in either ofthe methods described above in connection with Reaction Step (llb) and the resulting salt can be acidified to yield a compound of Formula XVII.
When X~XX3, Reaction Steps (llb) and (llc) 15 may be combined. Thus, a compound of Formula XV
may be contacted either with at least two equiva-lents of methanol or with at least three equivalents of methoxide.
For a compound of Formula XV, certain reaction conditions will favor displacement of only one of the chlorine gL~s. mese oonditions are thel-c~ of low tempera-tures and, when a~ide is used, the slcw addition of the stoi-chiometric amount of alkoxide or alkoxide-generating base to the medium containing the compound of Formula XV.
When alkoxide is used, both Reaction Steps (llb) and (llc) are preferably run at temperatures - within the range of about -10 to 80C, the range of about 0 to 25C being more preferred. Reaction 3C Steps (llb) and (llc) are more sluggish when alkanol is used instead of alkoxide, and more drastic condi-tions are required for the reaction to go to com-lZ~353~

x 20 pletion. Thus, higher temperatures, up to and in-cluding the boiling point of the alkanol itself, are required.
Depending on the nature of L in the compounds 5 of Formula XIII, the conversion to compounds of Formula XVII by the reactions described in Equation 11 is carried out without alteration of L. In other cases, the reactions result in the hydrolysis of the benzyl alcohol derivatives to give compounds of Formula XVIII wherein L is OH. Other compounds of Formula I may then be prepared by the methods previously described.
Thus, the reaction sequence described in Equation 12 shows a protected 2-hydroxymethylbenzene-lS sulfonamide converted to a useful herbicide via reaction with a heterocyclic isocyanate.
Equation 12 o R ~ 52~h2 OC~--< ON

XVIII XIX

"
~ CH20CCH3 Cl CH OH
R ~ --' XX

R ~ O N--~_~

As shown in Equation 13, compounds of Formula I wherein W is S are prepared by the reaction of an appropriately substituted benzene-sulfonamide with the appropriate triazine or pyrimidine isothiocyanate OL formula XXI.

~ L + SCN-A > R ~ \L S

The reaction of Equation 13 is best carried out by dissolving or suspending the sulfonamide and isothiocyanate in a polar solvent e-g. acetone, acetonitrile, ethyl acetate or methylethyl-ketone, adding an equivalent of a base e-g-potassium carbonate and stirring the mixture atambient temperature up to the reflux tem~erature for 1 to 24 hours. In some cases, the product precipitates from the reaction mixture and can be removed by filtration. The product is stirred in di7ute mineral acid, filtered and washed with cold water. If the product does not precipitate from the reaction mixture, it can be isolated by evaporation of the solvent, trituration of the residue with dilute mineral acid and filtering off the insoluble product.
The heterocyclic isothiocyanates which are used in the procedure of ~quation 13 are prepared, for example, according to the method of Japan patent Application Pub.: Kokai 51-143686, June 5, 1976, or that of W. Abraham and G. Barnikow,Tetrahedron, 29, 691-697 (1973).

lZV3534 x 22 From the above, it is seen that compounds of Formula XX are useful intermediates in the preparation of compounds of this invention.
Compounds of Formula XVIII can be prepared via a series of standard functional group transformations as (J. F. King, A. Hawson, B. L. Huston, L. J. Danks, and J. Romery, Can. J. Chem. 49, 943 (1971) for 2-(chloromethyl)benzenesulfonyl chloride.

~ NaBH4 ~ PC15 CHO ) ~ 2 POCl S03Na S03Na r So2cl Conversion of sulfonyl chlorides to sulfon-amides is well known, e.g., Crossley et al., J. Am.
Chem. Soc., 60, 2223 (1938).
For those examples containing reactive func-tionality on the position ortho to the sulfonamide moiety it is convenient to add the sulfonyl chloride to a measured quantity of ammonia in an inert sol-vent, e.g., tetrahydrofuran, ethyl acetate, etc.
at low temperatures (-78-0). Side reactions such as ring formation, elimination or condensa-tion are thereby substantially avoided.

2C ~~~~~~ ~ J2 2 12C~353~

x 2i The ~-haloalkylbenzenesulfonamide may be con-verted to other required intermediates for this in-vention by treatment with appropriate nucleop~iles, e.g., acetate ion as described in Example 4.

~ C - Cl KOA ~ C - OCCH3 XVIII

Thus, compounds of Formula XVIII are useful - intermediates in the preparation of compounds of this in~ention.
The synthesis of heterocyclic amines has been reviewed in ~The Chemistry of Heterocyclic Compounds"
a series published by Interscience Publ., New York and London. 2-Aminopyrimidines are described by D. J. Brown in The Pyrimidines, Vol. XVI of this series. The 2-amino-1,3,5-triazines are reviewed by K. R. Huffman and in The Triazines of this same series. The synthesis of triazines are also de-scribed by F. C. Schaefer, U.S. Patent No. 3,154,547 and by K. R. Huffman and F. C. Schaeffer, J. Org.
Chem. 28, 1816-1821 tl963).
The preparation of the aminoheterocycles de-scribed by the following formulae are prepared by methods described in unexamined European Patent 15683.

Y

~2N--( 0~ E12N

x 24 Agriculturally suitable salts of compounds of Formula I are also useful herbicides and can be pre-pared by a number of ways known to ~he art. For exam- .
ple, metal salts can be made by treating compounds of S Formula I with a so~ution of alkali or alkaline earth metal salt having a sufficiently basic anion (e.g., hydroxide, alkoxide, carbonate or hydride). Quaternary amine salts can be made by similar techniques.
Salts of compounds of Formula I can also be prepared by exchange of one cation to another.
Cationic exchange can be effected by direct treatment of an aqueous solution of a salt of a compound of Formula I (e.g., alkali metal or quaternary amine salt) with a solution containing the cation to be exchanged. This method is most effective when the desired salt containing the exchanged cation is in-soluble in water, e.g., a copper salt, and can be separated by filtration.
Exchange may also be effected by passing an aqueous solution of a salt of a compound of Formula I (e.g., an alXali metal or quaternary amine salt) through a column packed with a cation exchange resin containing the cation to be exchanged. In this method, the cation of the resin is exchanged for that of the original salt and the desired product is eluted from the column. This method is particularly useful when the desired salt is water soluble, e.g., a potassium, sodium or calcium salt.
Acid addition salts, useful in this invention, can be obtained by reacting a compound of Formula I
with a suitable acid, e.g., p-toluenesulfonic acid, trichloroacetic acid or the like.
The compounds of this invention and their pre-paration are further illustrated by the following examples wherein temperat~res are given in degrees centigrade and all parts are by weight unless other-wise indicated.

lZV3534 X ~s Example 1 N-1(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl]-2-carboxybenzenesulfonamide , A mixture containing 5 g of N-1(4,6-aimethoxy-pyrimidin-2-yl)aminocarbonyll-2-methoxycarbonylbenzene-sulfonamide, 20 ~1 of ethanol, 2.5 ml of water and 2.5 g of potassium hydroxide was stirred at ambient tempe~ature and pressure for 18 hours. The mixture was then diluted with 250 ml of water and 20 ml of concentrated hydrochloric acid was added with stirring.
The precipitate was filtered and washed with water and dried to yield 4.85 g of the desired product, melting at 161-2C. ~he infrared absorption peaks at 3500, 3400 and 1700 cm 1 are consistent with the desired lS structure and the nuclear magnetic resonance absorp-tion peaks at 3.95 ppm, S, 6H, OCH3 of pyrimidine;
5.8 ppm S, lH, pyrimidine proton at position 5; and 7.6-8.3 ppm, M, 4H, aromatic protons, are consistent with-the desired structure.
Example 2 N-[(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl]-2-(hydroxymethyl)benzenesulfonamide .
To a solution of 3.9 g of N-[(4,6-dimethoxy-pyrimidin-2-yl)aminocarbonyl]-2-carboxybenzenesul-fonamide in 100 ml of tetrahydrofuran was added 50 ml of a lM solution of borane, THF complex at 25C. The mixture was stirred at 25C for 18 hours followed by addition of water and HCl. The mixture was extracted with methylene chloride and the de-sired product crystallized from solution, 1.1 g 29% yield, m.p. 149-lS0C. The infrared absorption peaks at 3300 cm 1 and 1720 cm 1 are consistent with the desired structure and the nuclear magnetic resonance absorption peaks at 3.95 ppm, S, 6H, OCH3 of pyrimidine: 4.9 ppm, S, 2H, benzyl protons;

~2g:~534 \

5.9 ppm, S, lH, pyrimidine proton at position 5;
and 7.4-8.3 ppm, Multiplet, 4H, aromatic protons are consistent with the desired structure.
Example 3 N-l(4,5-Dimethoxypyrimidin-2-yl)aminocarbonyl~-2-methylcarbonylben~enesulfonamide A mixture containing 0.85 g of N-1(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-carboxybenzene-sulfonamide in 50 ml of anhydrous tetrahydrofuran was treated with 40 ml of 1.4 molar solution of methyl lithium (low halide, available from Aldrich Chemical Company) in ether at 25 under a nitrogen atmosphere. The mixture was stirred for 4 hours at 25 and was then poured into 500 ml of water containing 10 ml of concentrated hydrochloric acid. Thè precipitated oil was extracted into methylene chloride and the oil on evaporation of solvent was purified by preparative thin layer chromatography on silica gel (available from Analtec Inc, 2000 micron, 20 x 20 plates) by elution with ethyl acetate/hexane in a one to one ratio. The isolated product was recrystallized from a l-chlorobutane and hexane mixture to give 0.1 9, m.p. 126-8. The infrared absorption showed a broadened carbonyl peak at 1710 cm~l, and the absence of the 3500 and 3400 cm~l peaks of the starting material. The nuclear magnetic resonance spectrum showed peaks o at 2.6 ppm S, 3H, CH3CAr; 4.0 ppm, S, 6H, CH30 of pyrimidine; 5.7 ppm S, lH, pyrimidine proton at position S; and 7.3-7.7 ppm and 8.0 ppm M, 4H, aromatic, which are consistent with the desired structure.

t x 27 Example 4 N-~(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl]-2-(-hydr~ye~ l)benzenesulfonamide ~ mixture containing 1.0 g of N-[(4,6-dimethoxy-pyrimidin-2-yl)aminocarbonyl]-2-methylcarbonylbenzene-sulfonamide in 50 ml of anhydrous THF is treated with 0.1 g of lithium aluminum hydride at 25 under a nitrogen atmosphere. The mixture is stirred for 4 hours at 25 and is then poured into 500 ml of 1~ water containing 10 ml of concentrated hydrochloric acid. The precipitated oil is extracted into methylene chloride and the solid on evaporation is purified by column chromatography on silica gel.
Example 5 2-(Acetoxymethyl)benzenesulfonamide A mixture of 2-(chloromethyl)benzenesulfonamide (2.00 g), potassium acetate (6.0 g) and water (75 ml) was heated to reflux for 1.5 hour. The pH was ad-justed to ca. 5.0 by addition of hydrochloric acidand the chilled mixture was filtered to give 1.05 of of shiny white solid, m.p. 131-133. 'H ~ ~(CD3)2CO
8.00-7.83 (M), 7.60-7.25 (M), 6.55 (brd s), 5.47 (s), 2.97 (brd s), 2.10 (s), consistent with the assigned structure.

. --` ` 12~)3534 Example 6 2-~Acetoxymethyl)-N-[(4,6-dichloro-1,3,5-triazin-2-yl)aminocarbonyl]benzenesulfonamide A solution of 4,6-dichloro-1,3,5-triazin-2-yl isocyanate (0.87 g, 4.5 mmol) in acetonitrile (9 ml) was treated with 2-(acetoxymethyl)benzene-sulfonamide (1.04 g, 4.5 mmol) and stirred for 16 hours. Volatiles were removed under vacuum to give a residue whose 'H NMR showed ~(CD3)2CO, 8.05-7.80 (m, lH), 7.65-7.27 (m, 3H), 6.45 (brd s, lH), 5.50 (s, 2H), 2.10 (s, 3H), consistent with the assigned structure.
Example 7 2-(Hydroxymethyl)-N-1(4,6-dimethoxy-1,3,5-triazin-1; 2-yl)aminocarbonyl]benzenesulfonamide The crude 2-(acetoxymethyl)-N-[(4,6-dichloro-1,3,5-triazinyl)aminocarbonyl]benzenesulfonamide was treated with methanol (10 ml) and then with a solution of sodium methoxide (14 mmol) in methanol. The mixture was stirred at room temperature for 1.5 hour and evaported. The residue was taken up in water and filtered. The filtrate was acidified and filtered to give 0.45 g of gummy solid which was recrystallized from a chloroform/acetone mixture to give 115 mg of white solid, m.p. 146-148(dec.).
'H NMR ~ DMSO-d6 12.2(brd s, lH), 10.73 (s, lH), 8.00-7.15 (m,4H), 4.80 (s and ~4.9-4.2 (brd s), 3H) 3.90 (s, 6H), consistent with the assigned structure.
Using the procedures of Examples 1 to 7 and the proper reactants or the methods described herein, the compounds of Tables I-XII may be prepared.

lZQ35~

Table I
\ /

C -OH X

R ~ SO2NHCN ~ ~N

R Rl R2 W R8 X Y

6-F H H O H OCH3 OCH3 5-Cl H H O H CH3 OCH3 3-Cl H H O H OCH3 CH3 5-CH-(CH3)2 H H O H OCH3 CH3 ~2~3~

Table I (continued j R Rl ~2 W R8 X Y
_ H H H O H Cl Cl 5-CH3 H H O H Cl Br H CH3 H O H Cl Cl 5-OC2H5 H H O H Cl Cl 5-CH3 H H O H CH30CH2 Cl " ,CH3 H H H O H Br OCH3 ,CH3 H H CH3 O H CF3 Cl H H H O H OC2H5 Cl ~ j.

1203~;34 x 31 Table II

/
C - OH

R ~ SO2NHCN ~ ~ Z

y R ~ R2 W _ X Y Z m.p.(C) H HCH3 ~ O H CH3 CH3 CH

H CH3 CH3 o H CH3 CH3 CH
H CH3 CH3 o H CH3 OCH3 CH
H CH3 CH3 o H OCH3 OCH3 CH

5-Cl H H O H CH3 CH3 CH
6-Cl H H O H CH3 OCH3 CH
5-Cl H H O H OCH3 OCH3 CH

5-OCH3 a H O H CH3 CH3 CH
4-oCH3 H H O H CH3 OCH3 CH

H H H O H H CH3 CCl 3~ H H H O H CH3 CH3 C-CN

lZ03534 Table II (continued) R 1 2 W R8 X Y Z m.~.(C) H H H o H CH3 CH3 C CH3 S H . H H o H H CH3 C-CH3 H H H o H CH3 CH3 C-CH2CH3 H H H o H H CH3 C-CH2CH3 H H H . o H H CH3 C-CH2CH2Cl H H H O H CH3 CH3 C-CH2CH2Cl H H H o H CH3 CH3 C-CH2CH-CH2 H H H o H C~3 C CH2CH CH2 5-CH2CH2CH3 H H ' o H CH3 OCH3 CH
H~ CH3 H O H H CH3 C-C2H5 HCH3 CH3 O H H OCH3 C-Cl Table II (continued) R _ 2 W 8 X Y Z m.P.(C) 5-CH3 H H O H C~3 OCH3 CH

H H H O H Cl Cl CH
H CH3 H O H Cl Cl CH
5-OC2H5 H H O H Cl Cl CH
~ CH3 H H H O H ^CH20CH3 CH3 CH

; H H H O H SCH3 Cl CH
H H H O H CF3 Cl CH
, CH3 H H H O H -OCH ~ OCH3 CH

i x 34 Table III

~C/ OH Y' S R ~ R~ N ~

R Rl R2 W 8 Y' Q m.p.(C) 5-F H H ~ O H OCH3 O
5-Cl H H O H OCH3 5-NO2 H H O H OCa3 O

5-Cl H H o H CH3 O
H H H H H ca2 H H H H Cl CH2 H H H o H CH3 2 H H H H H O

` ` 120353 x 35 Table III_(continued) R _ 2 W R8 y' Q p.tC) 4-CH3 H H O H Cl O

H H H ~ S H CH3 O

~S H H H ! o CH3 CH3 o H H CH3 OCH3 o H H H O H OC2H5 o H H OC2~5 CH2 lZ03534 Table IIIa Rl R2 R ~ R8 N ~
R 12 W _8 Y m.p.(C) H CH3 CH3 o H CH3 H CH3 CH3 o H OCH3 5-Cl H H O H OCH3 5-~2 H H O H OCH3 5-Cl H H o H CH3 H H H H
H H H H Cl H H H H H

lZ03534 Table IIIa (continued) R _ 2 W 8 y' m. p. (C) S-CH3 H H ~ OCH3 4-CH ~ H H O H OCH3 4-CH3 H H O H Cl 4-OCH2cH2cH3 H H O H OCH3 . H H H CH3 CH3 H H H O H C2~5 lZ~3534 Table IV
Rl R2 o / "
C--O-C-Rll X

R ~ SO2NHCN ~ ~ N
R8 N ~
X

R Rl R2 R11 W 8 X Y m.p.(C) H H H -CH3 o HCH3 OCH3 15 H H H -CH3 o H3 OCH3 H H H -CH2CH3 o HCH3 OCH3 H H H -CH2CH3 o H3 OCH3 H H H ~ o HCH3 OCH3 H H H ~ o HOCH3 OCH3 H H H ~ O H CH3 OCH3 Cl H H H ~ 2 H 3 OCH3 H H CH3 CH3 o H OCH3 OCH3 H CH3 CH3 CH3 o H 3 OCH3 5-F H H CH3 o H 3 OCH3 6-Cl H H CH3 H -H3 OCH3 x 39 Table IV (continued) R Rl R2 Rll W R8 X Y m.p.(C) 4-OCH3 H H CH3 O H OCH3 . OCH3 5-CF3 H H CH3 O H OCH3 OC~3 3-Cl H H CH3 H CH3 OCH3 6-Cl H H CH3 H CH3 OCH3 10 H H H CH3 O H Cl C1 H H H CH3 O H Cl OCH3 H H H CH3 O H Br OCH3 H H H CH3 O H CH2CH3 aCH3 lS H H H CH3 O H CH(cH3)2 CH3 H H H ~ ~ H Cl Cl H H H ~ Q H OCH3 OCH3 H H H -CH-CH2 O H CH3 ~ OCH3 H H H -C~CH O H CH3 OCH3 H H H -C~CCH3 O H OCH3 CH3 ~ H H ~n-C5~1) O H OCH3 CH3 H H H CH20CH3 o H OCH3 CH3 H H H ~ O H OCH3 OCH3 3; H H H ~ O H OCH3 CH3 Tab ~ ontinued) R _ R~ Rll W 8 X y m.p.(C.) H H H CH3 ~ CF3 OCH3 ,CH3 H H H CH3 O H Br OCH3 H H H CH20CH3 o H SCH3 CH3 H H H ~ O H SCH3 OCH3 l; 'H H ~ O H SCH3 CH3 H . H H CH3 O H CF3 OCH3 H H H ~ Cl OCH3 CH3 H H H Cl OCH3 CH3 H H H ~ O H OCH3 OCH3 H a H CH3 S H CH3 OCH3 H ~ a CH3 S H OCH3 OCH3 H H H ca3 CH3 CH3 CH3 ~ :.H H CH3 O CH3 CH3 OCH3 H a H CH3 CH3 OCH3 OCH3 a H H CH3 O OCH3 CH3 OCH3 lZ03534 x 41 Table V
Rl ~R2 o C- O-C-Rll X

R ~ S02NHC~ ~ ~ Z

R Rl R2 Rll W 8 X Y Z ~ P.( C) H H H H O HOCH3 OCH3 ~H
a H H -CH3 O HCH3 CH3 CH

H H H CH2CH3 o HOCH3 OCH3 CH

H H H CH2Cl O HCa3 OCH3 CH
H H H Ca2CH.CH2 O HCH OCH CH

H, H H ~ ~ 3 OCH3 CH

H H H ~ O HOCH3 OCH3 CH

H H H ~ Cl o HCH3 OCH3 CH

H H H ~ No2 O HOCH3 OCH3 CH

H H CH3 CH3 o HOCH3 OCH3 CH

5-F H H Ca3 O HOCH3 OCH3 CH
3.5 6-ClH H CH3 HOCH3 OCH3 CH
H H H ~ O HOCH 3 OCH3 CH
Cl ;

~Z03534 x 42 Table V (continuet) R _ 211 W 8 X Y Z (C) 55-No2 H H CH3 0 H OCH3 OCH3 CH

4-Cl H H CH3 0 H CH3 OCH3 CH
6-Cl H H CH3 0 H CH3 OCH3 CH
10 H H H CH3 0 ~ Cl Cl CH
H H H CH3 0 H Cl OCH3 CH
H H H CH3 0 H Br OCH3 CH
H H H CH3 0 H Q 2CH3 ~CH3 15~ H H CH3 0 H OCH(cH3)2 cH3 CH

H H H C~3 0 H SCH3 OCH3 CH

H H H CH3 0 H CH2OCH3 0c 3 CH

. H H H ~ O H C1 Cl CH

25H H H ~ O H OCH3 OCH3 CH
H H H CH3 0 H CH3 CCl H H C~3 0 H H CH -CCH

H H H CH3 0 H Cl Cl C-CH2CH2Cl H H H CH3 0 H H CH3 c-cH2cH

H H CH3 0 H CH3 CH3 c-cH2cH~cl H H H CH3 0 H H CH3 c-cH2cH-c~2 lZ~353 x 43 Table V (continued) R 1 R2 Rll W R8 X Y Z m.~.(C) H H H -CH~CH2 S H CH3 OCH3 CH
H H H -C~CCH3 S H CH3 OCH3 CH
H H H -C~CCH3 S H OCH3 CH3 CH
H H H -(n-C5Hll) S ~ OCH3 CH3 CH
H H H -C~2CH3 S H OCH3 CH3 CH
H H H ~ S H OCH3 OCH3 CH

H H H ~ S H OCH3 CH3 CH

~ H H CH3 S H CF3 OCH3 CH

a H H ~ S H CH3 OCH3 CH

H H H ~ NO2 S H OCH3 OCH3 CH

Cl H H H ~ S H CH3 OCH3 CH
Cl H H H ~ S H CH3 OCH3 CH

H H H H3C ~ S H CH3 OCH3 CH

iZ03534 , Table V (continuet) Rl R2 Rll W R8 X Y Z m.p.(C) _ H a H CH3 O OCH CH3 CH3 CH

~30 ~203534 x 4s Table VI
Rl ~R2 0 C O-C-R11 y~
R ~ SO2NH ~ O ~

R Rl R2 Rll W R8 Y' Q . m-P-(C) H H H CH3 O H CH3 o H H H CH2Cl O H OCH3 O

H H H ~ O H CH3 O

H H H ~ O H OCH3 O

Cl H H H ~ O H OCH3 O

5-Cl H H CH3 H OCH3 O

Table VI (continued) R Rl R2 11 W R8 Y' Q m.p.~ C) 5-CH3 H H CH3 O H OCH3 o 5-NO2 H H CH3 O H OCH3 o 3-CF3 H H CH3 o H OCH3 O
5-Cl H H CH3 H CH3 o 6-Cl H H CH O H CH3 o H H H CH3 O H Cl CH2 H H H CH3 ~ CH3 CH3 O

H H H CH, o OCH3 OCH3 CH2 H H H Cl O H OC2H5 CH2 ~ .

x 47 Table VI (continued~
R Rl R2 R 11 W R8Y' Q m.p. (C) S H H H ~ O HCH3 o H H H -CH-CH2 O HCH3 o H H H -C~CH O H CH3 O
H H H -(n-C5Hll) O HCH3 O

5-CH3 H H ~ O HCH3 o 4-OC2H5 H H -CH~CH2 O HCH3 o ~--~N02 H H H ~ O HCH3 O

H H H 02N ~ O HCH3 o Cl H H H ~ O HCH3 o Cl H H H ~ O HCH3 o 2 5 H H 3 ~ O HCH,~
Br Br H H ~ ~ HOCH3 O

Cl Cl 3 0 H H -CH2CH-CH2 O HCH3 o H H H CHBr2 O HOCH3 O
H H H CH2Cl O HOCH3 O

--CH Cl Cl H H H -CH2-CH-CH2 H 3 o 120353~

~able VIa _ Rl R2 0 / ............ .
C o-C-Rll y ' ~SO2~

R Rl R2 Rll W R8 Y' m.p.(C) H H H H o H CH3 H 'H H CH3 o H OCH3 H H H CH2Cl O H OCH3 H H H CH2cH~cH2 O H OCH3 H H H ~ O H CH3 H H H ~ O H OCH3 Cl H H H ~ O H OCH3 H H CH3 CH3 o H OCH3 5-F H H . CH3 o H OCH3 5-Cl H H CH3 o H OCH3 lZ03534 Table VIa (continued) R Rl R2 R 1l W 8 Y' m.p.(C) H H H ~ O H CH3 H H H -CH'CH O H CH3 H H H -(n-C5Hll) O H CH3 5-CH3 H H ~ O H CH3 4-CH,3 H H CH3 O H CH3 ~--~N2 H H ~ NO2 CH3 H H H 2 ~ O H C~3 H H H ~ O H CH3 Cl H H . H ~ O H CH3 25 H H 3 ~ O H CH4 Br Br H H H -CH2CH-CH2 O H OC~3 Cl Cl H H -CH2CH-CH2 o H CH3 H H H CHBr2 O H OCH3 H H H CH2Cl O H OCH3 -CH Cl Cl H H H -CH2-CH-CH 0 H OCH3 , ~z~3~i3 o 50 Table VIatcontinued) R Rl R2 Rll W R8 Y~

S S-CH3 H H CH3 o H OCH3 5-Cl H H CH3 H CH3 6-Cl H H CH3 O a CH3 H H H CH3 o H , H

H H H CH3 o H Cl H H H CH3 ~ OCH3 H R H CH3 , OC~3 OCH3 ~ H H CH3 o H OC2H5 , lZ03534 x 51 Table VII
-/ ..
, C OcNHRl2 S R ~ S02NHCN

R Rl R2 R12 ~ 8 X Y m.p. (C) H H H H o HCH3 OCH3 H H H H o HCH3 OCH3 H H H -CH3 o HCH3 CH3 H ~ H -CH3 o HCH3 OCH3 H H H -CH3 o HCH3 OCH3 H H H CH2CH3 o HCH3 OCH3 H H H H2CH3 o H 3 CH3 H H H CH(CH3)2o H 3 CH3 H H H CH(CH3)2o HCH3 OCH3 H H H ~ o HCH3 OCH3 . H H H ~ ' O HCH3 OCH3 H H H ~ o HOCH3 OCH3 H H H CH2 ~ o HCH3 OCH3 H H H ~ No2 o HH3 OCH3 H H C~3 CH3 o HC 3 OCH3 H C~3 CH3 CH3 o HC 3 OCH3 5-F H H CH3 HCa3 OC~3 4-Cl H H CH3 o HOCH3 OCH3 \

x 52 Table VII (continued) R ~ R2 R12 W 8 X Y (C) S 5-CH3 H H CH3 ~ OCH3 OCH3 3-N02 H H CH3 o H CH3 CH3 5-Cl H H CH3 H CH3 OCH3 6-Cl H H CH3 H CH3 OCH3 H H a CH3 O H Cl Cl H H H CH3 O H Cl OCH3 H H H CH3 H Br OCH3 H H H CH3 O H CH2CH.3 OCH3 H H H CH3 O H CH(CH3)2 CH3 2 a H H H CH3 O H CH20CH3 OCH3 H H H ~ O H Cl Cl H H H ~ O H OCH3 OCH3 lZ03534 x ~3 Table VII (continued) H H H CH2-(CH2)4CH3O H CH3 OCH3 H H H -CH2-CH~CH-CH3O H CH3 OCH3 H H H ~ CH3 OCH3 H H Cl F O H OCH3 CH3 H H H ~ C2H5 H OCH3 f OCH3 H H CH3 ~ No2O H OCH3 CH3 H H H ~ CN O H OCH3 CH3 Br _ ~CH3 H H H ~ CH3 OCH3 H H H ~ SO2CH3O H CH3 OCH3 OCH3_ 2~ H H H ~ Cl O H CH3 OCH3 H H H ~ SCH3 OCH3 OCH3 H' H H ~ CF3 H CH3 OCH3 Cl H H H ~ O H OCH3 OCH3 H H H H2C ~ H OCH3 OCH3 H H H H2C ~ H3 H OCH3 CH3 H H H H2C ~ / ~3 OCH3 Table VII tcontinued) R R1 2 12 W R8 X Y m.p.(C) 5-oC2H5 H H CH3 H OCH3 OCH3 ~ CH3 6-CH ~ H H CH3 O H OCH3 OCH3 3-CF3 H H CH3 H ~CH3 OCH3 H : H H CH3 O CH3 CH3 OCH3 ; H H H CH3 O CH3 OCH oc~3 H . H H CH3 O OCH3 CH3 OCH3 lZ03534 ` x 5s Table VIII

Rl ~ / 2 O X
`R ~ SO2NHCN ~ ~ Z
~8 N ~
R Rl R2 12 W R8 X Y Z (oCj _ H H H H ~ CH3 OCH3 CH

H H H -CH(C~3)2 O H OCH3 OCH3 CH -H H H -CH(cH3)2 H CH3 OCH3 C~
H H H ~ O H CH3 OCH3 CH

H H H ~ O H CH3 OCH3 CH

H H H ~ O H OCH3 OCH3 CH

H H H -CH2 ~ 3 OCH3 ~ H H ~ N2 H OCH3 OCH3 CH

H CH3 CH3 CH3 ~ CH3 OCH3 CH

5-Cl H H CH3 H OCH3 OCH3 CH
H H H CH2 ~ O OCH3 OC 3 CH

` 1203539 x 56 Table VIlI (continued) R Rl R2R 12W R8 ~ m.p 5-CH3 H HH3 O H oOcCHH3 H3 CH

5-OCH3 H HCH3 O H oCH333 4-CF3 H HHH3 o H coHc33 OCH3 CH
6-Cl H HH3 H CH3 3 H H H 3 O H Cl OCH CH
H H H 3 O H Br 3 HH 'H HH3 o H 2CH3 3CH
15 H HH HH3 o H 3)2 CH3 CH

HH HH HH 3 O H CH2ocH3 OCH CHH

2 O H H H 3 o H H CH3 CH

H H H ~3 o H C1 Cl CH

2 5 H H H ~) O HOCH3 3 CH

3 O ~ ~ C 13 o H E3 CH3 C~3 3 a 3 CH~ O Cl 3 ~CY3 35 H H H 3 O H CH3 CH3 C-cH2cH2cl H H 3 o H CH3 3 H2CH CH2 3 O H H 3 CH2cH CH2 Table VIII (conelnued) R _ R2 R 12 U R8 H H H CH2-(CH2)4CH3 O H CH3 OCH3 CH

H H H ~ O H OCH3 OCH3 CH

H H Cl F o H OCH3 OCH3 CH

0 H H H ~ C2H5 H OCH3 CH3 CH

H H CH3 ~ No2 O H OCH3 CH3 CH

H H H ~ CN O H OCH3 CH3 CH
H H B ~ C!33 oc~3 CH

H H H ~ S2CH3 O H CH3 OCH3 CH

H H ~SCH3 OCH3 OCH3 CH

H H H ~ CF3 H .CH3 OCH3 CH

H H H ~ Cl O H OCH3 OCH3 CH
H H 2C ~ CH ~ OCH3 CH3 CH

~Z~353 Table VIII (continued) 5-C2 5 H H CH3 ~ H OCH3 CH3 ~ CH H CH3 o H OCH3 CH3 CH

s-CH3 CH3 H CH3 o H OCH3 OCH3 CH

H H HCH3 S H CH3 oCH3 CH

l; H H HCH3 O CH3 CH3 3 H H HCH3 o 3 CH3 3 H H - H CH3 o 3 CH3 OCH3 CH

!

'I' --.. ~..

~2~353 ` x 59 Table IX

~ / ..
C--OCNHR12 Y' R ~ ~ N--<

~ R8 N ~

R 1 2 12 W 8 Y~ ~ m.p. (C) H ~1 H -CH2CH3 0 H CH3 O
H H H -CH(CH3)2 0 H CH3 O
H H H -CH(CH3)2 0 H OCH3 0 H H H _0 0 H OCH3 0 20 H H H CH2CH.cH2 o H OCH3 0 H H H ~> O H Ca3 o 25 H H H ~> O H OCH3 0 H H H CH2 ~ O H OCH3 0 30 H 3 3 CH3 o ~ OCH3 0 3-F H a CH3 H OCH3 0 5-Cl H a CH3 H OCH30 x ~;n Table IX (continued) R Rl R2 R12 W ~8 Y Q m.p.(C) 5-CH3 H H CH3 O H OCH3 o 5-NO2 H H CH3 O H OCH3 o 4-OCH3 H H CH3 O H OCH3 o 5-CF3 H H CH3 O H OCH3 o 5-Cl H H CH3 H CH3 o 6-Cl H H CH3 H Q 3 o H H H CH3 H Cl CH2 H H a CH3 S H OCH3 H H H CH3 ¦ O H OC2H5 O
H a H CH3 ~ H OC2H5 CH2 lZ~353~

Table IX (continuet) R 1 2 R12 W R8 Y' Q
H H H -CH2-(CH2)4CH3 O a OCH3 O
a ~ H Ca2-CH-CH-CH3 H CH3 o H H H ~ O H OCH3 o H H H ~ F O H OCH3 o H H H ~ CN O H OCH3 o H H H ~ 3 H H H ~ SO2CH3 o H OCH3 O
H H H ~ SCH3 H CH3 O

. H a H ~ O H Cl O

H H a -CH2 ~ CH3 C H Cl O

H H H -CH2 ~ CH O a OCH3 O

2 5 5-OC2H5 a H CH3 H OCH3 ~ CH3 4-CH ~ H ~ CH3 H OCH3 5-CF3 H H ~ ~2 H OCH3 .

o Table IXa Rl ~R2 o R ~ SO2N~CN, ~ ~

R Rl R2 R12 W R8 y~ m p.(C) lS ~ H H -CH3 H .CH3 H ~ H -CH3 O H OCH3 H H H -CH(CH3)2 H CH3 H H H -CH(CH3)2 O H OCH3 20 H H H ~ ' ~ OCH3 H H H CH2CH~CH2 O H OCH3 H H H ~ O a CH3 25 H H H ~ O H OCH3 H H H C~2 ~ O H OCH3 H C~3 CH3 CH3 . O H oocHa3 5-Cl H H c~3 H OCH3 0 ~3 Table IXa(contin ~d) R Rl R2 R 12 W ~8 Y' m p.(C) S-C~ H ~ C~3 0 H 3 5-Cl H H CH3 H 3 - 10 6-Cl H H CH3 H C 3 lS HH H CH3 o H OCH3 H H H CH3 S HH OcHH3 HH HK H CH3 oc33 H a H CH C 3 OC 3 ~ H H CH33 OCH3 CH3 H H H CH OCH3 C~3 H HH HH ccH33 oo HH OC2 5 1,Z0353~
. ~

Tabl _IX ~

R Rl R2 R12 W R8 y- m p.(C) H H H -cH2-tcH2)4cH3 O H OCH3 H H H CH2-CH'CH-CH3 H CH3 H H H ~ .............. O H OCH3 H ~ H ~ F O H OCH3 H H H ~ CN O H OCH3 8r ,CH3 H H N ~

H H H ~ S2CH3 0 H OCH3 H H H ~ SCc~3 H CH3 H H H ~ O H Cl H H B -CH2 ~ 3 O H Cl H H H -CH2 ~ CH o H OCH3 2' 4 CH ~ H H CH3 H OGH3 C~
30 5-CF3 3 - H H ~ ~2 H OCH3 ~353~

Table X

Rl R2 0 C--o-C-Rl3 g R ~ S02NHC~
R~ X ~

R Rl R2 R13 W R8 X Y m.p.t~C) H H H -CH3 o H 3 3 H ~ H -CH3 o HCH3 OCH3 H H H ~ o HC~3 OCH3 H H H ~ O H C 3 OCH3 H H H ~ Cl O H C~3 OCH3 H H ~ Cl o H 3 0CH3 3 33 ~ CH3 OCH3 5-Cl H H CH3 H CH3 OCH3 x 66 Table X ~continued) R _ 2 ~ 13 W R8 X Y m-p 5 3-N2 H HCH3 o H OCH3 OCH3 5-CF3 R HCH3 o H OCH3 OCH3 5-Cl H H3 O H CH3 OCH3 6-Cl H H3 o H CH3 OCH3 10 H H - H3 O H Cl Cl H H HCH3 O R Cl OCH3 H H HCH3 O ~ Br OCH3 H H H3 o ~ CH2CH3 OCH3 H ~ 3 ~ H2CH3 CH3 l; H H H3 0 R ( 3)2 CH3 R H HCH3 o H CH2OCH3 CH3 H H H3 o H CH2C~3 OCH3 H H H~ O ~ Cl Cl 2; H H H ~ ~ OCH3 OCX3 s l;~V3534 x 67 Table X ~continued) R Rl R2 R13 W R8 X Y ~.p.(C) 4-CH3 H H CH3 o H 3 3 \ CH3 H H H CH2(CH2)4CH3 O H OCH3 3 4-CF3 a H CH3 H OCH3 3 H H H CH3 H Cl OCH3 6-C2H5 H H CH3 H Cl Cl l; H a H ~ CH3 O H OCH3 3 H a H CH3 S CH3 CH3 CH3 H H H C~3 S OCH3 CH3 M 3 H H ~ CH3 S OCH3 CH3 OCH3 3i ..

1203~34 x 68 Table XI
Rl R2 o R ~ S02NHCN ~ O
R8 ~--~

R Rl R2 ~ 3W R8 X y Z m.p.(C) H ~ H -CH3 CH3 C 3 CH
H a H -CH3 H OCH3 OCH3 CH
H H H -CH2CH3 H CH3 gCH3 CH

H H H ~ C1 H CH3 CH3 CH

H H ~ CH3 C 3 CH

H H H ~ O H OCH3 OCH3 CH

H H ~ Cl o H CH3 OCH3 CH

H H H ~ C1 0 H OCH3 OCH3 CH

H H CH3 Ca3 o H OCH3 3 CH
H C~3 CH3 ~3 H 3 3 CH
S-F H a CH3 H OCH3 3 CH
4-Cl H H C~3 H OCH3 OCH3 CH

lZQ35~'~
x 69 Table XI (continued) l R2 13 W R8 ~ y Z (C) 5 5-~2 H H CH3 O H OCH3 OCH3 CH

5-Cl H H CH3 H CH3 OCH3 CH
6-Cl H H CH3 H Ca3 OCH3 CH
10 ~ H H CH3 a Cl Cl CH
H H H CH3 O H Cl OCH3 CH
H H H CH3 O H Br OCH3 CH
H H H CH3 O H CH2CH3 ~ca3 H H H CH3 O H CH2cH3 Q 3 CH
15 H H H CH3 a OCH(CH3)2 CH3 CH

H H H C~3 O H H OCH3 CH

H H a ~ O H Cl Cl . CH

25 ~ H H ~ O H OCa3 OCH3 CH
H H H CH3 O H H Ca3 CCl H H H Ca3 O H CH3 CH3 C-CN

H H H Ca3 O H H CH3 3 H H H CH3 O H H CH3 CCa2CH3 H H H CH3 O B Cl Cl C`CH2CH2 H a H Ca3 0 H H CH3 C-Ca2CH2Cl H H H CH3 H ca3 ca3 C-CH2CH2Cl H H a CH3 ~ CH3 CH3 C C 2C 2 H H H CH3 O H a CH3 C-CH2CH-CH2 120353~

Table XI (continued) R Rl R2 R13 W R8 X Y Z m.p.(C) H H H CH2(CH2)4C~3 O HOCH3 OCH3 CH

H H H CH3 H Cl Cl CH
6-C2H5 H H CH3 H Cl Cl CH

1~ H H H ~ CH3 HOCH3 OCH3 CH

~203534 x 71 Table XII
Rl R2 0 ~C OCORL3 y R ~ .. ~ ~O ~

R Rl 2 ~3 W _ Y' Q m.p.(C) H a H -CH3 O H CH3 lS H H H ~ O H CH3 O

H H H ~ O H OCH3 O

H H H ~ Cl O H OCH3 O

H H C 3 3 H OCH3 o 5-Cl H H ca3 H OCH3 O
3-CH3 H H CH3 O H OCH3 o 5-NO2 H H CH3 O H OCH3 o 5-OCH3 H ~ CH3 H OCa3 o 4-CF3 H H CH3 H OCH3 o 5-Cl H H CH3 H Ca3 o 6-Cl H H CH3 H CH3 o H H H Ca3 ~ H O

H H H CH3 o H Cl CH2 H H H C~3 O H OCH3 CH2 Table XII (continue~?

R 1 2 13 W 8 Y Q ~.P.( C) S / C~3 ~ CH3 H H H CH2(CH2)4CH3 O H OCH3 H H H ~ CH3 H OCH3 ; Cl C1 O H CH3 H H H ~ O H OCH3 H H H CH3 o CH3 3 H H H CH3 o CH3 3 CH2 H H H CX3 o OCa3 3 lZ0353.~.

Table XIIa Rl ~R2 0 R ~--So2~lc~ ~

R Rl R2 R~ 3 W R8 y ~ m p . ~ C) H H HH -CCHH33 H HH Ccc333 H H H ~3 0 H CH3 H H H ~> O H OCH3 2 0 H H H ~} Cl O H OCH3 S-F Q3 C~3 C113 O ~ OC~3 5-Cl a ~ ca3 0 a OCH3 3-CH3 H aH ccaH33 O 8 OC 3 S-OCI13 ~ 3 CH3 OCI!3 6-Cl H H CH3 a c~3 H ~ H CH3 H H
H H H CH3 o H H
H H H Ca3 o H Cl H ' a a ca3 o a ca3 H B a ca3 o H OCH3 T~ble XIIa(continuedj R 1 2 13 W R8 Y' m p.(C) c~3 H H H CH2(CH2)4CH3 O H OCH3 H H H ~ CH3 OCH3 H H ~ Cl O H CH3 Cl H H H ~ o H OCH3 - H H H CH3 S H oc~3 H a H CH3 S H CX3 H H H ca3 S H OCH3 H H H CH3 o CH3 3 a H H CH3 O C 3 3 H H H C~3 O C 3 3 H H a CH3 OCH3 CH3 H H H C~3 O OCH3 CH3 Formulations Useful formulations of the compounds of Formula I
can be prepared in conventional ways. They include dusts, granules, pellets, so,lutions, suspensions, emulsions, wettable powders, emulsifiable concen-trates 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.
lG High strength compositions are primarily used as intermediates for further formulation. The formula-tions, broadly, contain about 0.1% to 99% by weight of active ingredient(s) and at least one of a) about 0.1% to ~ surfactant(s) and b) zbout 1~ to 99.9%
solid or liquid diluent~s). More specifically, they ~ill contain these ingredients in the following approximate proportions:
Table XIII
-Active*
2G Ingredient Diluent(s) Surfactant(s) Wettable Powders20-90 0-74 1-10 Oil Suspensions, Emulsions, Solu-tions (including ~mulsifiable Concentrates 3_50 40-95 0-lS
Aqueous Suspensions 10-50 40-84 1-20 Dusts 1-25 70-99 0-S
Granules and Pellets 0.1-95 5-99.9 0-li High Strength Compositions gO-99 0-lG 0-2 Active ingredient plus at least one of a surfactant or a diluent eguals 10~ weight percent.

~20353~
x 76 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 s~rfactant to active ingredient are S 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 n ~ 2nd Ed., Dorland Books, Caldwell, New Jersey.
lG The more absorptive diluents are preferred for wettable powders and the denser ones for dusts. Typical liquid diluents and solvents are described in ~arsden, "Sol-vents ~uide", 2nd Ed., Interscience, New York, l9S0.
Solubili~y under 0.1% is preferred for suspension l; concentrates: solution concentrates are preferably stable against phase separation at 0C. "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood, New Jersey, as well as Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical 2G Publishing Co., ~nc., New York 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth, et~.
The methods of making such compositions are 2; well known. Solutions are prepared by simply mixing the ingredients. Fine solid composi-tions 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. Patent 3,060,084). Granules and pellets may be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See J. E. ~rowning, HAgglomeration~, Chemical Engineering, December 4, 1967, pp. 147ff and_"Perry's Chemical Engineer's Handbook", 5th Ed., McGraw-~ill, New York, 1973, pp. 8-57ff.

. lza3s3~
x 77 For further information regarding the art of formulAtion, see for example:
H. M. Loux, U.S. Patent 3,235,361, February lS, 1966, Co~. 6, line 16 through Col. 7, line 19 and 5 Examples 10 through 41.
R. W. Luckenbaugh, U.S. Patent 3,309,192, ~iarch 14, 1967, Col. 5, line 43 through Col. 1, line 62 ana Examples 8, 12, 15, 39, 41, 52, 53, ~8, 132, 138-140, 162-164, 166, 167 and 163-182.
H. Gysin and E. Knusli, U.S. Patent 2,891,855, June 23, lgS9, Col. 5, line 66 through Col. 5, line 17 and Examples 1-4.
G. C. Klingman, "Weed Control as a Science", -John Wil~y & sons, Inc., New York, 1961, pp. 81-96.
1~ J. D. Fryer and S. A. Evans, "Weed Control Handbook", 5th Ed., Blackwell Scientific Publica-tions, Oxford, 1968, pp. 101-103.
In the following examples, all parts are by weight unless otherwise indicated.
2G ~xample Wettable Powder ~-r(4,6-~imethQxypyrimidin-2-yl2~mino-carbonyl]-2-(hydroxymethyl2-benzenesulfonamide 80%
2~ sodium alkylnaphthalenesulfonate 2%
sodium ligninsulfonate 2%
synthetic amorphous silica 3%
kaolinite 13%
The ingredients are blended, ham~er-milled until all the solids are essentially under 50 microns and then reblended and packaged.

3~

lZ0353 ,~ 78 Example 9 Wettable Powder N-1(4-6-Dimethoxy-1,3,5-triazin-2-yl)amino-~ carbonyl]-2-~hydroxymethyl)- .
S benzenesulfonamide 50%
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 of essentially all below 10 microns in diameter. The product is reblended before packaging.
Example I0 Granule ~
wettable powder of Example 9 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.
_xamole il Extruded Pellet N-[~4,6-Dimethoxypyrimidin-2-yl)amino-carbonyll-2-~hydroxymethyl)-benzenesulfonamide 25%
anhydrous sodium sulfate 10%
crude calcium ligninsulfonate 5%
sodium alkylnaphthalenesulfonate1%
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 lZ03534 x 7q 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 recycled.
Example 12 Oil Sus~ension N-[(4,6-Dimethoxy-1,3,5-triazin-2-yl)amino-carbonyl~-2-(hydroxymethyl)-benzenesulfonamide 25%
polyoxyethylene sorbitol hexaoleate 5%
highly aliphatic hydrocarbon oil 70~
The ingredients are ground together in a sand mill until the solid particles hav.e been reduced to under about 5 microns. The resulting thick suspension l; may be applied directly, but preferably a ter being extended with oils or emulsified in water.
Example 13 h'ettable Powder -N-[(4,5-Dimethoxypyrimidin-2-yl)amino-2C carbonyl]-2-(hydroxymethyl)-benzenesulfonamide 20%
sodium alkylnaphthalenesulfonate 4%
sodium ligninsulfonate 4%
low viscosity methyl cellulose3%
2~ attapulgite 69%
The ingredients are thoroughly blended. After grinding in a hammer-mill to produce particles essen-tially all below 100 microns, the material is re-blended and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) and packaged.

3s :1203534 Example 14 Low Strength Granule N-t(4,6-Dimethoxy-1,3,5-~riazin-2-yl)-àminocarbonyl]-2-(hydroxymethyl)-benzenesulfonamide 1%
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 ~lender. 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 15 Aqueous Suspension N-[(4,6-Dimethoxypyrimidin-2-yl)-aminocarbonyl~-2-(hydroxymethyl)-benzenesulfonamide 40 polyacrylic acid thickener0.3%
dodecylphenol polyethylene qlycol ether 0.5%
disodium phosphate lS
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 16 Solution N-[(4,6-Dimethoxypyrimidin-2-yl)-aminoca_bonyl~-2-(hydroxymethyl)-benzenesulfonamide, sodium salt 5%
water 95%

x 81 The salt is added directly to the water with stirring to produce the solution, which may then be packaged for use.
Example 17 S Low Strength Granule N-~(4,6-Dimethoxypyrimidin-2-yl)-aminocarbonyl]-2-~hydroxy~ethyl)-benzenesulfonamide 0.1%
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 b~ender. After spraying of the solution has been'~ompleted, the material is warmed to evaporate the solvent. The material is allowed to cool and then packaged.
Example 18 Granule N-[(4,6-Dimethoxy-1,3,5-triazin-2-yl)-2G aminocarbonyl]-2-(hydroxymethyl)-benzenesulfonamide 80%
~etting agent lS
crude ligninsulfonate salt (containing 5-20~ of the natural sugars) 10~
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 fluidiza-tion 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 constant is reduced to the desired leYel, generally less than 1~. The material is then ,~ 82 discharged, screened to the desired size range, gener-ally 14-100 mesh (1410-149 microns), and packaged for use.
Example 19 High Strength Concentrate N-[~4,6-Dimethoxypyrimidin-2-yll-aminocarbonyl]-2-(hydroxymethyl)-benzenesulfonamide 99%
silica aerogel o 5%
synthetic amorphous silica0.5%
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 concéntrate may be formulated further if necessary.
Example 20 Wettable Powder N-[(4,6-Dimethoxy-1,3,5-triazin-2-yl)-aminocarbonyl~-2-~hydroxymethyl)-benzenesulfonamide 90%
dioctyl sodium sulfosuccinate 0.1%
synthetic fine silica 9.9%
The ingredients ase blended and ground in a hammer-mill to produce particles essentially all be-low 100 microns. The material is sifted through a U.S.S. No. 50 screen and then packaged.
Example 21 Wettable Powder N-[(4,6-Dimethoxy-1,3,5-triazin-2-yl)-aminocarbonyl~-2-(hydroxymethyl)-benzenesulfonamide 40%
sodium ligninsulfonate 20%
montmorillonite clay 40%
The ~ngredients 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.

x 83 Example 22 Oil Suspension N-t(4,6-Dimethoxy-1,3,5-triazin-2-yl)-aminocarbonyl~-2-(hydroxymethyl)-S benzenesulfonamideblend of polyalcohol carboxylic esters and oil soluble petroleum sulfonates 6%
xylene 59~
The ingredients are combined and ground together in a sand mill to produce particles essentially all belo~ 5 microns. The product can be used dire~tly, extended with oils, or emulsified in water.

lZ03534 x 84 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 com-5 plete control of all vegetation is desired, such as around fuel storage tanks, ammunition depots, industrial storage areas, oil well sites, drive-in theaters, around billboards, highway and railroad structures.
By properly selecting rate and time of application, compounds of this invention may be used to modify plant growth beneficially, and also selectively control weeds in crops such as wheat.
The precise amount of the compound of Formula I
to be used in any given situation will vary according to the particular end result desired, the amount o~
foliage present, the weeds to he controlled, the soil type, the formulation and mode of application, weather conditions, etc. Since so many variables play a role, it is not possible to state a rate of application suitable for all situations. Broadly speaking, the compounds of this invention are used at levels of about 0.05 to 20 kg/ha with a preferred range of 0.1 to 10 kg/ha. In general, the higher rates of application from within this range will be selected for adverse conditions or where extended persistence in soil is desired.
The compounds of Formula I may be combined with other herbicides and are particularly use ul in combi-nation with 3-(3,4-dichlorophenyl)-1,1-dimethylurea (diuron); the triazines such as 2-chloro-4-(ethyl-2mino)-6-(isopropylamino)-s-triazine (atrazine); the uracils such as 5-bromo-3-sec-butyl-6-methyluracil (bromacil); N-(phosponomethyl)glycine ~glyphosate);
3-cyclohexyl-1-methyl-6-dimethylamino-s-triazine-2,4(1~,3~)-dione (hexazinone); N,N-dimethyl-2,2-1203~3~

x 85 diphenylacetamide (diphenamide); 2,4-dichlorophenoxy-acetic acid (2,4-d) (and closely related compounds);
4-chloro-2-butynyl-3-chlorophenylcarbamate (barban);
S-(2,3-dichloroallyl)diisopropylthiocarbamate S (diallate); S-(2,3,3-trichloroallyl)diisopropyl-thiocarbamate (triallate); 1,2-dimethyl-3,5-di-phenyl-lH-pyrazolium methyl sulfate (difenzoquat methyl sulfate); methyl 2-t4-(2,4-dichlorophenoxy)-phenoxy~propanoate (diclofop methyl) 4-amino-6-tert-10 butyl-3-(methylthio)-l~2~4-triazin-5(4H)one (metri-buzin); 3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea (linuron); 3-isopropyl-lH-2,1,3-benzothiodiazin-4(3H)-one-2,2-dioxide (bentazon); ~,,~-trifluoro-2,6-dini~'ro-N,N-dipropyl-~-toluidine (trifluralin);
15 1,1'-dimethyl-4,4'-bipyridinium ion (paraquat);
2-chloro-2',6'-diethyl(methoxymethyl)acetanilide talachlor); l,l-dimethyl-3-(a,~,~-trifluoro-_-tolyl)urea ~fluometuron); S-(4-chlorobenzyl)N,N-diethylthiolcarbamate (benthiocarb); N-(butoxy-20 methyl)-2-chloro-2l~6l-diethylacetanilide (butachlor); and 5-[2-chloro-5-(trifluoromethyl)-phenoxy]-2-nitrobenzoic acid, methyl ester . (acifluorfen-methyl).

lZ0353~

x 86 Test Procedure A
Seeds of crabgrass (Digitaria spp.), barnyard-grass ~Echinochloa crusgalli), wild oats (Avena fatua), cassia ~Cassia tora), morninsglory (Ipomoea spp.), 5 cocklebur ~Xanthium spp.), sorghum, corn, soy~ean, rice, wheat and nutsedge tubers (Cyperus rotundus) were planted in a growth medium and treated pre-emergence with the chemicals dissolved in a non-phytotoxic solvent. At the same time, cotton having five leaves ~including cotyledonary ones), bush beans with the third trifoliolate leaf expanding, crabgrass with two leaves, barnyardgrass with two leaves, wild oats with one leaf, cassia with three leaves (including cotyledonary ones), morningglory with four leaves ~including the cotyledonary ones), - cocklebur with four leaves (including the coty-ledonary ones), sorghum with three leaves, corn with three leaves, soybean with two cotyledonary leaves, rice with two leaves, wheat with one leaf, and nut-sedge with three to five leaves were sprayed.
Treated plants and controls were maintained in a - greenhouse for 16 days, then all species were com~ared to controls and visually rated for response to treat-ment.
Ratings for compounds tested by this pro-cedure are recorded in Table XIV.
O = no effect 10 = maximum effect C 5 chlorosis or necrosis D = defoliation E S emergence inhibition G = growth retardation H = formative effects 6Y = abscised buds or flowers.
3;

120353~l Table XIV

~ CH20 lo I I ~ s02N~C~H ~ o$

kglha O. 05 POSI-EMERGE~CE
BUSH BEA~ 5C, 10D, 6Y
COTIO~ 3C, 4H, 8G
MORNI~GGLORY 2G
COCKLEB~.~R 5C, 9 CASSIA 5C, 9G
N~'TSEDGE lC, 9G
CBRAB~G.ARDGRA5s 3C, 9H
WILD OATS lC, 3G
W~EAT 0 COR~ 2C, 9H _ SOYBE~ 9C
RICE ZC, 9G~ -~~
SORGHUM ZC, YH ~-PRE-EMERGEXCE
MORNI'~GGLORY 8G
COCXLEB~~R 9H
CASSIA lC, 8G
NUTSEDGE _ lOE
CRABGRASS ~
BARNYARDGRASS 2C, 9H
WILD OATS 8G, O
WH~AI 6G, O
COR~ lC, 9H
SOY~EAN ZC, 8H

SORGHE.-~ C, G

lZ03534 Table ~rv s ~ CH2 S02NHCNH--< 0 0~
.

kg/ha 1 0 05 POST-EMERGE~CE
BUSHBF~ 2 7 6Y
COTIO~
MORNINGGLORY lC

CASSIA lC
NUTSEDGE O

BA~ARDGRASS
WILD OAIS O
_~HEAI O
CO~N 2C, 9H
SOYBE~ lC, 6H
RICE lC, 4G
SORGHU~ 2C, 9H
PRE-EMERGENCE
MOR~ GGLORY 2 ~OCKLEBUR
CASSIA lC
NUTSEDGE O
CRABGRASS O
BARNYARDGRASS 2C, 7H
WILD OATS O
WHEAT O

SOYBEA~ 2C, 3H
RICE lC
SORGH~.I 2C, 9H

Claims (19)

WHAT IS CLAIMED IS:

1. A compound selected from wherein L is OH, OC(O)R11, OC(O)NHR12 or OC(O)OR13;
R is H, F, Cl, Br, NO2, CF3, C1-C3 alkyl or C1-C
alkoxy;
R1 is H or C1-C4 alkyl;
R2 is H or CH3;
R8 is H, CH3 or OCH3;
R11 is H, C1-C5 alkyl, C2-C3 alkenyl, C2-C3 alkynyl, C3-C4 cycloalkyl, , C1-C4 alkyl substituted with 1-4 substituents selected from 0-3 F, 0-3 Cl or 0-3 Br or C2-C3 alkenyl substituted with 1-3 Cl;
R12 is H, C1-C6 alkyl, C3-C4 alkenyl, C5-C6 cycloalkyl, or or C5-C6 cycloalkyl substituted with CH3;
R13 is C1-C6 alkyl or ;

R14 and R15 are independently H, NO2, CH3, Cl or OCH3;
R16 is H, F, Cl, Br, C1-C3 alkyl, NO2, CN, SO2CH3, OCH3, SCH3 or CF3;
R17 is H, Cl or C1-C3 alkyl;
R18 is H, CH3 or Cl;
A is , or W is O or S;
X is H, Cl, Br, CH3, CH2CH3, C1-C3 alkoxy, CF3, SCH3 or CH2OCH3;
Y is CH3 or OCH3;
Z is N CH, CCl, CBr, CCN, CCH3, CCH2CH3, CCH2CH2Cl or CCH2CH=CH2;
y1 is H, CH3, OCH3 or OCH2CH3; and Q is O or CH2;
and their agriculturally suitable salts;
provided that when W is S, then R8 is H.

2. A compound of Claim 1 where Z is N, CH, CCl, CBr, or CCH3, W is O and R8 is H or CH3.

3. A compound of Claim 1 where L is OH;
R is H; R1 and R2 are CH3; and R8 is H or CH3;

A is ; Z i s CH or N; X and Y are independently CH3 or OCH3; and W is O.

4. A compound of Claim 2 where Z is CH or N; X is CH3 or OCH3; and R1 is H or CH3.

5. A compound of Claim 4 where R and R8 are H, and A is

6. A compound of Claim 5 where R11, R12 and R13 are C1-C3 alkyl.

7. A compound of Claim 5 where L is OH.

8. The compound of Claim 1, N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-(hydroxy-methyl)benzenesulfonamide.

9. The compound of Claim 1, N-[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]-2-(hydroxymethyl)benzenesulfonamide.

10. The compound of Claim 1, N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-2-(hydroxy-methyl)benzenesulfonamide.

11. The compound of Claim 1, N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-2-(hydroxymethyl)benzenesulfonamide.

12. The compound of Claim 1, N-[(4,6-dimethyl-1,3,5-triazin-2-yl)aminocarbonyl]-2-(hydroxymethyl)benzenesulfonamide.

13. The compound of Claim 1, N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-2-(hydroxymethyl)benzenesulfonamide.

14. A method for the control of undesirable vegetation consisting of applying to the locus of such undesirable vegetation a herbicidally effective amount of a compound of Claim 1.

15. A method for the control of undesirable vegetation comprising applying to the locus of such undesirable vegetation a herbicidally effective amount of a compound of Claim 2.

16. A method for the control of undesirable vegetation comprising applying to the locus of such undesirable vegetation a herbicidally effective amount of a compound of Claim 3.

17. A method for the control of undesirable vegetation comprising applying to the locus of such undesirable vegetation a herbicidally effective amount of a compound of Claim 4.

18. A method for the control of undesirable vegetation comprising applying to the locus of such undesirable vegetation a herbicidally effective amount of the compound of Claim 5.

19. A method for the control of undesirable vegetation comprising applying to the locus of such undesirable vegetation a herbicidally effective amount of the compound of Claim 6.