Benezenesulfonylisocyanates

BACKGROUND OF THE INVENTION
This invention relates to novel compounds of Formula I, to compositions containing them and to their method of use as general and selective pre- and post-emergence herbicides. The invention also includes novel intermediates useful in preparing the compounds of Formula I.
Netherlands Pat. No. 121,788, published Sept. 15, 1966, teaches the preparation of compounds of Formula (i), and their use as general or selective herbicides: ##STR1## wherein R.sub.1 and R.sub.2 may independently be alkyl of 1-4 carbon atoms; and
R.sub.3 and R.sub.4 may independently be hydrogen, chlorine or alkyl of 1-4 carbon atoms.
Compounds of Formula (ii), and their use as antidiabetic agents, are reported in J. Drug. Res. 6, 123 (1974): ##STR2## wherein R is pyridyl.
In U.S. Pat. No. 4,127,405, compounds are disclosed of the general formula: ##STR3## R.sub.3 and R.sub.6 are independently hydrogen, fluorine, chlorine, bromine, iodine, alkyl of 1-4 carbon atoms, alkoxy of 1-4 carbon atoms, nitro, trifluoromethyl, cyano, CH.sub.3 S(O).sub.n -- or CH.sub.3 CH.sub.2 S(O).sub.n --;
R.sub.4 is hydrogen, fluorine, chlorine, bromine or methyl;
R.sub.5 is hydrogen, fluorine, chlorine, bromine, methyl or methoxy;
R.sub.7 is hydrogen, fluorine, chlorine, bromine, alkyl of 1-2 carbon atoms or alkoxy of 1-2 carbon atoms;
R.sub.8 is hydrogen, methyl, chlorine or bromine;
R.sub.9 and R.sub.10 are independently hydrogen, methyl, chlorine or bromine;
W and Q are independently oxygen or sulfur;
n is 0, 1 or 2;
X is hydrogen, chlorine, bromine, methyl, ethyl, alkoxy of 1-3 carbon atoms, trifluoromethyl CH.sub.3 S-- or CH.sub.3 OCH.sub.2 --; and
Z is methyl or methoxy; or their agriculturally suitable salts; provided that:
(a) when R.sub.5 is other than hydrogen, at least one of R.sub.3, R.sub.4, R.sub.6 and R.sub.7 is other than hydrogen and at least two of R.sub.3, R.sub.4, R.sub.6 and R.sub.7 must be hydrogen;
(b) when R.sub.5 is hydrogen and all of R.sub.3, R.sub.4, R.sub.6 and R.sub.7 are other than hydrogen, then all of R.sub.3, R.sub.4, R.sub.6 and R.sub.7 must be either chlorine or methyl; and
(c) when R.sub.3 and R.sub.7 are both hydrogen, at least one of R.sub.4, R.sub.5 or R.sub.6 must be hydrogen.
In particular, the patent discloses orthosubstituted compounds wherein the substitution is C.sub.1 -C.sub.4 alkyl.
The presence of undesired vegetation causes substantial damage to useful crops, especially agricultural products that satisfy man's basic food needs, such as soybeans, corn, wheat and the like. The current population explosion and concomitant world food shortage demand improvements in the efficiency of producing these crops. Preventing or minimizing the loss of a portion of such valuable crops by killing, or inhibiting the growth of undesired vegetation is one way of improving this efficiency.
A wide variety of materials useful for killing, or inhibiting (controlling) the growth of undesired vegetation is available; such materials are commonly referred to as herbicides. However, the need exists for still more effective herbicides that destroy or retard weeds without causing significant damage to useful crops.
SUMMARY OF THE INVENTION
This invention relates to novel compounds of Formula I and their agriculturally suitable salts, suitable agricultural compositions containing them, and their method of use as general and selective pre-emergence and post-emergence herbicides and as plant growth regulants. ##STR4## wherein L is S(O).sub.n R.sub.7 or OR.sub.9 ;
R is H, F, Cl, Br, NO.sub.2, CF.sub.3, C.sub.1 -C.sub.3 alkyl or C.sub.1 -C.sub.3 alkoxy;
R.sub.1 is H or C.sub.1 -C.sub.4 alkyl;
R.sub.2 is H or CH.sub.3 ;
R.sub.7 is C.sub.1 -C.sub.4 alkyl;
R.sub.8 is H, CH.sub.3 or OCH.sub.3 ;
R.sub.9 is C.sub.1 -C.sub.6 alkyl, C.sub.3 -C.sub.4 alkenyl, CH.sub.2 CF.sub.3, CF.sub.2 CF.sub.2 H or C.sub.5 -C.sub.6 cycloalkyl;
n is 0, 1 or 2;
A is ##STR5## W is O or S; X is H, Cl, Br, CH.sub.3, CH.sub.2 CH.sub.3, C.sub.1 -C.sub.3 alkoxy, CF.sub.3, SCH.sub.3 or CH.sub.2 OCH.sub.3 ;
Y is CH.sub.3 or OCH.sub.3 ;
Z is N, CH, CCl, CBr, CCN, CCH.sub.3, CCH.sub.2 CH.sub.3, CCH.sub.2 CH.sub.2 Cl or CCH.sub.2 CH.dbd.CH.sub.2 ;
Y.sup.1 is H, CH.sub.3, OCH.sub.3 or OCH.sub.2 CH.sub.3 ; and
Q is O or CH.sub.2 ;
and their agriculturally suitable salts; provided that when n is 1, then W is O; and when W is S, then R.sub.8 is H.
PREFERRED COMPOUNDS
Preferred in increasing order for their higher activity and/or more favorable ease of synthesis are:
(1) Compounds of the generic scope wherein Z is N, CH, CCl, CBr or CCH.sub.3 ; W is O; and R.sub.8 is H or CH.sub.3 ;
(2) Compounds of Preferred (1) wherein Z is N or CH, X is CH.sub.3 or OCH.sub.3, provided that when n is 1 or 2, then Z is CH;
(3) Compounds of Preferred (2) wherein A is ##STR6## and R, R.sub.1, R.sub.2 and R.sub.8 are H; (4) Compounds of Preferred (3) wherein R.sub.9 is C.sub.1 -C.sub.4 alkyl; and
(5) Compounds of Preferred (4) wherein R.sub.7 and R.sub.9 are CH.sub.3.
Specifically Preferred for highest activity and/or most favorable ease of synthesis are:
N-�(4,6-Dimethylpyrimidin-2-yl)aminocarbonyl!-2-methoxymethyl)benzenesulfonamide;
N-�(4-Methoxy-6-methylpyrimidin-2-yl)aminocarbonyl!-2-(methoxymethyl)benzenesulfonamide;
N-�(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl!-2-(methoxymethyl)benzenesulfonamide;
N-�(4,6-Dimethyl-1,3,5-triazin-2-yl)aminocarbonyl!-2-(methoxymethyl)benzenesulfonamide;
N-�(4-Methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl!-2-(methoxymethyl)benzenesulfonamide;
N-�(4,6-Dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl!-2-(methoxymethyl)benzenesulfonamide;
N-�(4,6-dimethylpyrimidin-2-yl)aminocarbonyl!-2-(methylthiomethyl)benzenesulfonamide;
N-�(4-Methoxy-6-methylpyrimidin-2-yl)aminocarbonyl!-2-(methylthiomethyl)benzenesulfonamide;
N-�(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl!-2-(methylthiomethyl)benzenesulfonamide;
N-�(4,6-Dimethyl-1,3,5-triazin-2-yl)aminocarbonyl!-2-(methylthiomethyl)benzenesulfonamide;
N-�(4-Methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl!-2-(methylthiomethyl)benzenesulfonamide;
N-�(4,6-Dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl!-2-(methylthiomethyl)benzenesulfonamide;
N-�(4,6-Dimethylpyrimidin-2-yl)aminocarbonyl!-2-(methylsulfinylmethyl)benzenesulfonamide;
N-�(4-Methoxy-6-methylpyrimidin-2-yl)aminocarbonyl!-2-(methylsulfonylmethyl)benzenesulfonamide;
N-�(4-Methoxy-6-methylpyrimidin-2-yl)aminocarbonyl!-2-(methylsulfinylmethyl)benzenesulfonamide;
N-�(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl!-2-(methylsulfonylmethyl)benzenesulfonamide;
N-�(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl!-2-(methylsulfinylmethyl)benzenesulfonamide; and
N-�(4,6-Dimethylpyrimidin-2-yl)aminocarbonyl!-2-(methylsulfonylmethyl)benzenesulfonamide.
N-�(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl!-2-(butoxymethyl)benzenesulfonamide;
N-�(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl!-2-(ethoxymethyl)benezenesulfonamide;
N-�(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl!-2-(1-methylpropyloxymethyl)benezenesulfonamide.
This invention also relates to novel compounds of Formula II which are useful intermediates for the preparation of herbicidal compounds of Formula I. ##STR7## wherein L, R, R.sub.1, R.sub.2, R.sub.7 and R.sub.9 are as previously defined;
n is 0 or 2; and
Z is CH or N.
This invention also relates to novel compounds of Formula III which are useful intermediates for the preparation of the compounds of Formula I. ##STR8## wherein L, R, R.sub.1, R.sub.2, R.sub.7 and R.sub.9 are as previously defined,
and;
n is 0 or 2.
Preferred are compounds of Formula III wherein
R is H, Cl, Br or OCH.sub.3 ;
R.sub.1 is H or CH.sub.3 ;
R.sub.2 is H;
R.sub.7 is C.sub.1 -C.sub.2 alkyl; and
R.sub.9 is C.sub.1 -C.sub.2 alkyl.
Specifically preferred are 2-(methoxymethyl)benzenesulfonylisocyanate and 2-(methylthiomethyl)benzenesulfonylisocyanate.
DETAILED DESCRIPTION OF THE INVENTION
As shown in Equation 1, the compounds of Formula I can be prepared by reacting an appropriate 2-aminoheterocycle of Formula IV with an appropriately substituted sulfonyl isocyanate of Formula III; R, R.sub.1, L, R.sub.2, R.sub.8 and A being as previously defined; and wherein n is 0 or 2. ##STR9##
The reaction is best carried out in inert aprotic organic solvents such as methylene chloride, tetrahydrofuran or acetonitrile, at ambient pressure and temperature. The mode of addition is not critical; however, it is often convenient to add the sulfonyl isocyanate to a stirred suspension of the aminoheterocycle. Since isocyanates usually are liquids, their addition is more easily controlled.
The reaction is generally exothermic. In some cases, the desired product is insoluble in the warm reaction medium and crystallizes from it in pure form. Products soluble in the reaction medium are isolated by evaporation of the solvent, trituration of the solid residue with solvents such as 1-chlorobutane, ethyl ether or pentane and filtration.
The intermediate sulfonyl isocyanate of Formula III can be prepared by reacting corresponding sulfonamides with phosgene in the presence of an alkyl isocyanate such as butyl or cyclohexyl isocyanate at reflux in a solvent such as chlorobenzene, according to the procedure of H. Ulrich and A. A. Y. Sayigh, Newer Methods of Preparative Organic Chemistry, Vol. VI, p. 223-241, Academic Press, New York and London, W. Foerst, Ed. In cases where formation of the desired sulfonyl isocyanate is difficult by the above procedure, the preformed sulfonylurea from the reaction of butyl isocyanate with the appropriate sulfonamide is treated with phosgene according to the above reference.
Alternatively, the process of Ulrich and Sayigh can be improved by the addition of a tertiary base to the reaction mixture as shown by Equation 2. ##STR10##
A mixture of the appropriate benzenesulfonamide V, an alkyl isocyanate and a catalytic amount of 1,4-diaza�2,2,2!bicyclooctane (DABCO) in xylene or other inert solvent of sufficiently high boiling point (e.g. >135.degree.) is heated to approximately 135.degree.. Phosgene is added to the mixture until an excess is present as indicated by a drop in the boiling point. (The mixture is heated further to drive off the excess phosgene). After the mixture is cooled and filtered to remove a small amount of insoluble by-products, the solvent and alkyl isocyanate are distilled in-vacuo leaving a residue which is the crude sulfonyl isocyanate III.
The preparation of these sulfonamides from sulfonyl chlorides with either ammonium hydroxide or anhydrous ammonia is widely reported in the literature, e.g. Crossley et al., J. Am. Chem. Soc., 60, 2223 (1938), and P. A. Rossy et al., J. Org. Chem. 45, 617 (1980).
Benzenesulfonyl chlorides are best prepared by diazotization of the appropriate aniline with sodium nitrite in concentrated hydrochloric acid, followed by reaction of the diazonium salt with sulfur dioxide and cupric chloride in acetic acid according to the teaching of R. A. Abramovitch, J. Org. Chem. 43, 1218 (1978).
Anilines are obtained by reduction of the appropriate nitrobenzenes with iron powder in acetic acid as reported by D. C. Owsley and J. J. Bloomfield, Synthesis, 118 (1977).
The o-alkoxymethyl- or o-alkylthioymethylnitrobenzenes VII are in turn prepared via "Williamson Synthesis", according to Equations 3a or 3b. ##STR11##
"Williamson Synthesis" has been widely used for the preparation of ethers as reviewed by W. Theilheimer, Syn. Methods of Org. Chem., Vol. VII, p. 112.
Procedure 3a is most useful when R.sub.5 X' is a alkylthio or a primary alkoxy group, and R.sub.1 and R.sub.2 are both H. The reaction is carried out by mixing o-nitrobenzyl chloride and sodium methoxide or sodium alkylmercaptide (for preparation see Org. Syn., Coll. Vol. II, 345) in methanol under reflux or at room temperature, respectively.
Procedure 3a is, however, not applicable in cases where R.sub.5 X' is a branched alkoxy whose corresponding alkoxide anion is a stronger base than it is a nucleophile, and/or either R.sub.1 or R.sub.2 or both are alkyl groups. In the presence of a strong base and/or an .alpha.-alkyl substituent on o-nitrobenzyl chloride the base-catalyzed elimination rather than the desired SN.sub.2 displacement occurs, giving rise to 2,2'-dinitrostilbene or other o-nitroalkenylbenzenes. In order to avoid these undesired reactions, a more general procedure, 3b, can be employed. The appropriate benzyl alcohol is first treated with base, such as sodium hydride, in an inert organic solvent, typically tetrahydrofuran or glyme, followed by displacement on an alkyl halide, as described by C. A. Brown and D. Barton, Synthesis, 434 (1974), and B. A. Stoochnoff and N. L. Benoiton, Tet. Lett., 21 (1973).
Alternatively, o-alkoxymethyl or o-alkylthio methylbenzenesulfonyl chlorides, XI, can be obtained from an appropriately substituted .alpha.-hydroxy-o-toluenesulfonic acid-.alpha.-sultone, IX, via ring-opening reaction with an alkoxide or alkylmercaptide anion as depicted in Equation 4. ##STR12##
Reaction 4a is closely related to the alkylation of acyloxides and acetamide with sultones as disclosed by J. H. Helberger et al., Ann., 565, 22 (1949). Conversion of the sulfonic acid salt to the sulfonyl chloride is then carried out according to the teaching of Org. Synthesis, Coll. Vol. IV, 846, 693.
Benzenesulfonamides of Formula XIII can also be derived from compound XII as illustrated in Equation 5. ##STR13##
Preparation of o-sulfamylbenzoic acid esters, XII, from saccharin or sulfobenzoic acid anhydride is well known in the art, e.g., B. Loev and M. Kormendy, J. Org. Chem. 27, 1703 (1962). The esters XII, can be readily reduced to the ethers XIII with diborane in a suitable organic solvent, e.g., tetrahydrofuran, in the presence of fifteen folds of boron trifluorideetherate under reflux for 18 hours, as described by R. P. Graber and M. B. Meyers, J. Org. Chem. 26, 4773 (1961).
The o-alkylsulfinyl- and o-alkylsulfonylmethylbenzenesulfonylureas are made from their corresponding o-alkylthiomethylbenzenesulfonylureas by means of peroxide oxidation. Reaction of the sulfide-sulfonylurea with aqueous hydrogen peroxide in acetic acid at room temperature for half an hour affords exclusively the sulfoxidesulfonylurea. If the sulfide or sulfoxide is allowed to react for 72 hours under the same conditions, the sulfone is obtained. Oxidation for 20 hours often results in a mixture of both sulfoxide and sulfone, which can be readily separated by column chromatography and eluted with ethyl acetate. Sulfonylureas described above are generally stable under these reaction conditions. They will however, split into heterocyclicamine and o-alkylsulfonylbenzenesulfonamide if heated. A general procedure for peroxide oxidation of sulfides to sulfones can be found in the paper by A. M. Van Arendonk and E. C. Kliderer, J. Am. Chem. Soc., 62, 3521 (1940).
The synthesis of heterocyclic amine derivatives 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 the above series.
2-Amino-1,3,5-triazines can be synthesized according to the methods described by E. M. Smolin and L. Rapaport in "s-Triazines and Derivatives", Vol. XIII of the same series.
The preparation of fused ring pyrimidine amines are disclosed in various publications, such as: Braken et al., J. Am. Chem. Soc., 69, 3072 (1947); Mitten and Bharlacharya, Quart. J. Ind. Chem. Soc., 4, 152 (1927), Schrage and Hitchings, J. Org. Chem., 16, 1153 (1951); Svab et al., Coll. Czech Commun. 32, 1582 (1967); and unexamined European Patent 15683.
Many of the compounds of this invention can also be made by the method shown below.
The intermediates of Formula II, where R, R.sub.1, R.sub.2 and L are defined as above, Z is CH or N and n is 0, are novel and can conveniently be prepared by reacting a sulfonamide of Formula V with a 4,6-dichloroheterocyclic isocyanate of Formula XIV. ##STR14##
One or both of the halogen atoms on the heterocyclic ring of the compound of Formula II can be displaced by an alkoxide of 1-3 carbons to give compounds of Formula XV, where R.sub.6 is C.sub.1 -C.sub.3 alkyl and Y" is Cl or OCH.sub.3. ##STR15##
The process for the preparation of compounds of Formula XIV and XV is described in copending patent applications U.S. Ser. No. 193,190 and U.S. Ser. No. 192,681.
As shown in Equation 6, compounds of Formula I, in which W is sulfur and R, R.sub.1, R.sub.2 and A are as previously defined and R.sub.8 is H are prepared by reaction of an appropriately substituted sulfonamide V with a heterocyclic isothiocyanate of Formula XVI. ##STR16## The reaction of Equation 6 is best carried out by dissolving or suspending the sulfonamide and isothiocyanate in a polar solvent such as acetone, acetonitrile, ethyl acetate or methylethylketone, adding an equivalent of a base such as potassium carbonate and stirring the mixture at ambient temperature up to the reflux temperature for one to twenty-four hours. In some cases, the product precipitates from the reaction mixture and can be removed by filtration. The product is stirred in dilute 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 Equation 6 are prepared, for example, according to the method of Japan Patent Application Pub: Kokai No. 51-143686, June 5, 1976, or that of W. Abraham and G. Barnikow, Tetrahedron 29, 691-7 (1973).
Compounds of Formula I wherein W is oxygen are also conveniently prepared by reacting the appropriately substituted sulfonamide V with the appropriate methyl pyrimidinyl carbamate or methyltriazinyl carbamate in the presence of an equimolar amount of trimethylaluminum according to the procedure of Equation 7. ##STR17##
The reaction of Equation 7 is best carried out in methylene chloride at 25.degree. to 40.degree. for 24 to 96 hours under a nitrogen atmosphere. The product is isolated by the addition of an aqueous acetic acid solution followed by extraction of the product into methylene chloride or direct filtration of a product of low solubility. The product is purified by trituration with solvents such as n-butyl chloride or ether or subjected to column chromatography.

In the following examples, all temperatures are .degree.C. unless otherwise specified, all melting points are not corrected and all parts are by weight.
EXAMPLE 1
o-Methylthiomethylnitrobenzene
To a stirred solution of 10.8 g (0.2 mol) of sodium methoxide in 70 ml of methanol at room temperature was added dropwise 12 ml (10.8 g, 0.22 mol) of methyl mercaptan through a gas addition funnel connected to a dry-ice condenser. The resulting mixture was stirred at room temperature for 1 hour and then added dropwise to a stirred solution of 30.0 g (0.175 mole) of o-nitrobenzyl chloride in 120 ml of methanol over 1 hour, while the temperature rose to 40.degree. C. The reaction mixture was then diluted with 300 ml of water, and extracted 3 times with methylene chloride. The methylene chloride extracts were washed with dilute hydrochloric acid, dried, and concentrated to afford 38.6 g (96%) of yellow oil.
NMR (CDCl.sub.3).delta.: 1.97 (3H, s, CH.sub.3); 3.97 (2H, s, CH.sub.2); 7.3-8.1 (4H, m, 4 aromatic H's).
EXAMPLE 2
o-Methylthiomethylaniline
Iron powder (60 g, 1.0 g-atom) was added slowly through a solid addition funnel to a solution of 53.5 g (0.29 mol) of o-methylthiomethylnitrobenzene in 210 ml of glacial acetic acid and 600 ml of absolute ethanol under reflux over a period of 45 minutes. The mixture was then refluxed for 3 hours. The iron powder was filtered off and the filtrate was diluted with 800 ml of water. The aqueous mixture was extracted twice with 200 ml ethyl acetate and twice with 200 ml ether. The combined organic extracts were washed with water, dried and concentrated to yield 48 g (75% pure) of orange oil.
NMR (CDCl.sub.3).delta.: 1.90 (3H, s, CH.sub.3); 3.60 (2H, s, CH.sub.2); 5.72 (2H, bs, NH.sub.2); and 6.5-7.3 (4H, m, 4 aromatic H's).
EXAMPLE 3
o-Methylthiomethylbenzenesulfonyl chloride
To a mixture containing 48 g (75% pure, 0.23 mol) of o-methylthiomethylaniline in 280 ml of acetic acid and 90 ml of concentrated hydrochloric acid at 0.degree. was added a solution of 20 g (0.3 mol) of sodium nitrite in 50 ml of water. The resulting diazonium salt solution was then added through a dropping funnel to a mixture of 50 ml of sulfur dioxide and 12 g of cupric chloride in 140 ml of acetic acid and 140 ml of ether at 0.degree. C. The mixture was allowed to stand at 0.degree. C. overnight and then poured into 1 l of ice-water. Extraction with ether, washing, drying and evaporation of the solvent gave 26 g (50%) of red oil.
NMR (CDCl.sub.3).delta.: 2.46 (3H, s, CH.sub.3); 4.67 (2H, s, CH.sub.2); 7.2-8.0 (4H, m, 4 aromatic H's); plus one equivalent of o-methylthiomethylchlorobenzene; 2.07 (3H, s, CH.sub.3); 4.18 (2H, s, CH.sub.2); and 7.0-7.5 (aromatic H's).
The product was used for the next step without further purification.
EXAMPLE 4
o-Methylthiomethylbenzenesulfonamide
To a solution of 26 g (50% pure, 55 mmol) of o-methylthiomethylbenzenesulfonyl chloride in 250 ml of methylene chloride was added 4.5 ml of anhydrous ammonia at 0.degree.-5.degree. over 1 hour. Stirring was continued at 0.degree.-5.degree. C. for 2 hours. The solid precipitate was filtered off and the filtrate was evaporated to dryness to afford 24.8 g of orange residue. The crude product was triturated in ether, resulting in light pink crystals: m.p. 119.degree.-124.degree. C.
NMR (CDCl.sub.3).delta.: 2.05 (3H, s, CH.sub.3); 4.18 (2H, s, CH.sub.2); 6.72 (2H, bs, NH.sub.2); 7.2-7.8 (3H, m, aromatic H's, m- & p-); and 8.0 (1H, dd, aromatic H, o--).
EXAMPLE 5
o-Methylthiomethylbenzenesulfonyl isocyanate
Phosgene (2.5 ml, 35 mmol) was added portionwise into a nitrogen-purged mixture containing 6.8 g (31 mmol) of o-methylthiomethylbenzenesulfonamide, 0.1 g of DABCO, and 3.8 g (38 mmol) of n-butyl isocyanate in 60 ml of dry xylene, while the temperature was maintained at 130.degree.-135.degree. C. between additions. Stirring was continued for 1 hour at 130.degree.-135.degree. C. The mixture was cooled to room temperature and the solid was filtered off under nitrogen. The filtrate was concentrated to yield 9.0 g (theo 7.6 g) of oil: IR cm.sup.-1 2240 (N.dbd.C.dbd.O), no NH at ca 3300. The oil was taken up in 90 ml of dry methylene chloride.
EXAMPLE 6
�N-(4,6-Dimethylpyrimidin-2-yl)aminocarbonyl!-2-methylthiomethylbenzenesulfonamide
A solution of o-methylthiomethylbenzenesulfonyl isocyanate in dry methylene chloride (15 ml of the above solution from Example 5, 5 mmol) was added with a syringe into a nitrogen-purged flask containing 0.6 g (5 mmol) of 2-amino-4,6-dimethylpyrimidine and a trace of DABCO. The mixture was refluxed for 21/2 hours. The solvent was removed in-vacuo to yield 1.8 g of white solid: m.p. 173.degree.-183.degree. C. The unreacted pyrimidine can be removed by washing with dilute hydrochloric acid.
NMR (DMSO-d.sub.6): 1.90 (3H, s, SCH.sub.3); 2.37 (6H, pyrimidine 4 & 6-CH.sub.3 's); 4.08 (2H, s, CH.sub.2); 7.03 (1H, s, pyrimidine 5-H); 7.64 (3H, m, benzene H's, m- & p-); 8.16 (1H, m, benzene H, o-); 10.6 (1H, bs, SO.sub.2 NHCONH); and SO.sub.2 NHCONH not detectable. ##STR18##
EXAMPLE 7
�N-((4,6-Dimethylpyrimidin-2-yl)aminocarbonyl!-2-methylsulfinylmethylbenzenesulfonamide
One ml of 30% aqueous hydrogen peroxide was added to a suspension of 0.5 g (1.4 mmol) of �N-(4,6-dimethylpyrimidinyl)aminocarbonyl!-o-methylthiomethylbenzenesulfonamide in 15 ml of glacial acetic acid at room temperature. The mixture turned clear in 10 minutes and was stirred for a further 30 minutes. It was then diluted with water and extracted with methylene chloride. The organic extracts were washed, dried and concentrated to give 0.5 g (100%) of white solid: m.p. 176.degree.-184.degree. C.
NMR (DMSO-d.sub.6).delta.: 2.40 (1H, s, pyrimidine 4- & 6-CH.sub.3 's); 2.57 (3H, s, SCH.sub.3); 4.55 (2H, ABq, J=12 Hz, ##STR19## 7.02 (1H, s, pyrimidine 5-H); 7.6 (3H, m, benzene m- & p- H's); 8.18 (1H, m, benzene O-H); 10.5 (1H, bs, SO.sub.2 NHCONH); and SO.sub.2 NH not detectable.
EXAMPLE 8
�N-(4,6-Dimethylpyrimidin-2-yl)aminocarbonyl!-2-methylsulfonylmethylbenzenesulfonamide
A mixture of 0.1 g (0.2 mmol) of �N-(4,6-dimethylpyrimidinyl)aminocarbonyl!-o-methylsulfinylmethylbenzenesulfonamide and 0.3 ml of 30% hydrogen peroxide in 5 ml of acetic acid was stirred at room temperature for 3 days. The resulting white solid precipitate was filtered to afford 30 mg of the desired product: m.p. 222.degree.-225.degree. C.
NMR (DMSO-d.sub.6).delta.: 2.42 (6H, s, pyrimidine 4- & 6-CH.sub.3 's); 2.94 (3H, s, SCH.sub.3); 5.10 (2H, s, CH.sub.2); 7.00 (1H, s, pyrimidine 5-H); 7.7 (3H, m, benzene m- & p-H's); 8.1 (1H, m, benzene O-H); 10.5 (1H, bs, SO.sub.2 NHCONH); and SO.sub.2 NH not detectable.
Using the proper reactants and the methods described above, the compounds in Tables I-VI can be prepared.
EXAMPLE 8a
2-(1-Methylethoxymethyl)benzenesulfonamide
To 4.9 g 2-(aminosulfonyl)benzoic acid, 1-methylethyl ester in 37 ml BF.sub.3.Et.sub.2 O at a temperature 0.degree.-10.degree. was added over 45 min, 40 ml at 1 molar solution at BH.sub.3 in THF. The mixture was refluxed overnight. The resulting cloudy yellow solution was concentrated on a rotary evaporator, acidified with 10% HCl, diluted with 300 ml H.sub.2 O and then extracted with three 100 ml portions of ether. The ether extracts were dried with magnesium sulfate and then concentrated to 4.1 g of wet solid. The product was further purufied to an oil by column chromatrography on silica with methylene chloride.
NMR (CDCl.sub.3).delta.: 1.20 (6H, (CH.sub.3).sub.2); 3.72 (1H, --CH); 4.88 (2H, CH.sub.2); 7.2 (2H, MH.sub.2); and 7.3-79 (4H, aromatic)
The product was converted to the corresponding sulfonylisocyanate by the procedure of Example 5. The resulting sulfonylisocyanate was used to prepare the corresponding sulfonylureas by the procedure of Example 6.
Using the proper reactants and the methods described above, the compounds of Tables I-VI can be prepared.
TABLE I__________________________________________________________________________ ##STR20##L R R.sub.1 R.sub.2 X Y Z m.p.__________________________________________________________________________ (.degree.C.)OCH.sub.3 H H H CH.sub.3 CH.sub.3 CH 164-167.degree.OCH.sub.3 H H H OCH.sub.3 CH.sub.3 CH 163-166.degree.OCH.sub.3 ##STR21## H H OCH.sub.3 OCH.sub.3 CH 171-176.degree.SCH.sub.3 H H H CH.sub.3 CH.sub.3 CH 173-183.degree.SCH.sub.3 H H H OCH.sub.3 CH.sub.3 CH 173-184.degree.SCH.sub.3 H H H OCH.sub.3 OCH.sub.3 CH 165-181.degree. ##STR22## H H H CH.sub.3 CH.sub.3 CH 176- 184.degree. ##STR23## H H H OCH.sub.3 CH.sub.3 CH 142-150.degree. ##STR24## H H H OCH.sub.3 OCH.sub.3 CH 178-184.degree. ##STR25## H H H CH.sub.3 CH.sub.3 CH 222-225.degree. ##STR26## H H H OCH.sub.3 CH.sub.3 CH 195-198.degree. ##STR27## H H H OCH.sub.3 OCH.sub.3 CH 193-199.degree.OCH.sub.3 H CH.sub.3 H CH.sub.3 CH.sub.3 CHOCH.sub.3 H CH.sub.3 H OCH.sub.3 CH.sub.3 CHOCH.sub.3 H CH.sub.3 H OCH.sub.3 OCH.sub.3 CHSCH.sub.3 H CH.sub.3 H CH.sub.3 CH.sub.3 CHSCH.sub.3 H CH.sub.3 H OCH.sub.3 CH.sub.3 CHSCH.sub.3 H CH.sub.3 H OCH.sub.3 OCH.sub.3 CH ##STR28## H CH.sub.3 H CH.sub.3 CH.sub.3 CH ##STR29## H CH.sub.3 H OCH.sub. 3 CH.sub.3 CH ##STR30## H CH.sub.3 H OCH.sub.3 OCH.sub.3 CH ##STR31## H CH.sub.3 H CH.sub.3 CH.sub.3 CH ##STR32## H CH.sub.3 H OCH.sub.3 CH.sub.3 CH ##STR33## H CH.sub.3 H OCH.sub.3 OCH.sub.3 CHOCH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CHOCH.sub.3 H CH.sub.3 CH.sub.3 OCH.sub.3 CH.sub.3 CHOCH.sub.3 ##STR34## CH.sub.3 CH.sub.3 OCH.sub.3 OCH.sub.3 CHSCH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CHSCH.sub.3 H CH.sub.3 CH.sub.3 OCH.sub.3 CH.sub.3 CHSCH.sub.3 H CH.sub.3 CH.sub.3 OCH.sub.3 OCH.sub.3 CH ##STR35## H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH ##STR36## H CH.sub.3 CH.sub.3 OCH.sub.3 CH.sub.3 CH ##STR37## H CH.sub.3 CH.sub.3 OCH.sub.3 OCH.sub.3 CH ##STR38## H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH ##STR39## H CH.sub.3 CH.sub.3 OCH.sub.3 CH.sub.3 CH ##STR40## H CH.sub.3 CH.sub.3 OCH.sub.3 OCH.sub.3 CHOCH.sub.2 CH.sub.3 H H H CH.sub.3 CH.sub.3 CH 133-140.degree.OCH.sub.2 CH.sub.3 H H H OCH.sub.3 CH.sub.3 CH 124-130.degree.OCH.sub.2 CH.sub.3 H H H OCH.sub.3 OCH.sub.3 CH 122-127.degree.SCH.sub.2 CH.sub.3 H H H CH.sub.3 CH.sub.3 CHSCH.sub.2 CH.sub.3 H H H OCH.sub.3 CH.sub.3 CHSCH.sub.2 CH.sub.3 H H H OCH.sub.3 OCH.sub.3 CH ##STR41## H H H CH.sub.3 CH.sub.3 CH ##STR42## H H H OCH.sub.3 CH.sub.3 CH ##STR43## H H H OCH.sub.3 OCH.sub.3 CH ##STR44## H H H CH.sub.3 CH.sub.3 CH ##STR45## H H H OCH.sub.3 CH.sub.3 CH ##STR46## H H H OCH.sub.3 OCH.sub.3 CHOCH(CH.sub.3).sub.2 H H H CH.sub.3 CH.sub.3 CH 165-171.degree.OCH(CH.sub.3).sub.2 H H H OCH.sub.3 CH.sub.3 CH 147-150.degree.OCH(CH.sub.3).sub.2 H H H OCH.sub.3 OCH.sub.3 CH 120-130.degree.SCH(CH.sub.3).sub.2 H H H CH.sub.3 CH.sub.3 CHSCH(CH.sub.3).sub.2 H H H OCH.sub.3 CH.sub.3 CHSCH(CH.sub.3).sub.2 H H H OCH.sub.3 OCH.sub.3 CH ##STR47## H H H CH.sub.3 CH.sub.3 CH ##STR48## H H H OCH.sub.3 CH.sub.3 CH ##STR49## H H H OCH.sub.3 OCH.sub.3 CH ##STR50## H H H CH.sub.3 CH.sub.3 CH ##STR51## H H H OCH.sub.3 CH.sub.3 CH ##STR52## H H H OCH.sub.3 OCH.sub.3 CHO(CH.sub.2).sub.3 CH.sub.3 H H H CH.sub.3 CH.sub.3 CH 136-142.degree.O(CH.sub.2).sub.3 CH.sub.3 H H H OCH.sub.3 CH.sub.3 CH 134-139.degree.O(CH.sub.2).sub.3 CH.sub.3 H H H OCH.sub.3 OCH.sub.3 CH 116-121.degree.OCH(CH.sub.3)CH.sub.2 CH.sub.3 H H H CH.sub.3 CH.sub.3 CH 112-121.degree.OCH(CH.sub.3)CH.sub.2 CH.sub.3 H H H OCH.sub.3 CH.sub.3 CH 125-128.degree.OCH(CH.sub.3)CH.sub.2 CH.sub.3 H H H OCH.sub.3 OCH.sub.3 CH 114-116.degree.OCH.sub.3 H H H CH.sub.3 CH.sub.3 N 123-135.degree.OCH.sub.3 H H H OCH.sub.3 CH.sub.3 N 137-140.degree.OCH.sub.3 H H H OCH.sub. 3 OCH.sub.3 N 138-143.degree.SCH.sub.3 H H H CH.sub.3 CH.sub.3 N 162-180.degree.SCH.sub.3 H H H OCH.sub.3 CH.sub.3 N 141-150.degree.SCH.sub.3 H H H OCH.sub.3 OCH.sub.3 N 113-133.degree. ##STR53## H H H CH.sub.3 CH.sub.3 N 169-172.degree. ##STR54## H H H OCH.sub.3 CH.sub.3 N 166-171.degree. ##STR55## H H H OCH.sub.3 OCH.sub.3 N 161-167.degree. ##STR56## H H H CH.sub.3 CH.sub.3 N 212-216.degree. ##STR57## H H H OCH.sub.3 CH.sub.3 N 185-189.degree. ##STR58## H H H OCH.sub.3 OCH.sub.3 N 189-195.degree.OCH.sub.3 H CH.sub.3 H CH.sub.3 CH.sub.3 NOCH.sub.3 H CH.sub.3 H OCH.sub.3 CH.sub.3 NOCH.sub.3 ##STR59## CH.sub.3 H OCH.sub.3 OCH.sub.3 NSCH.sub.3 H CH.sub.3 H CH.sub.3 CH.sub.3 NSCH.sub.3 H CH.sub.3 H OCH.sub.3 CH.sub.3 NSCH.sub.3 H CH.sub.3 H OCH.sub.3 OCH.sub.3 N ##STR60## H CH.sub.3 H CH.sub.3 CH.sub.3 N ##STR61## H CH.sub.3 H OCH.sub.3 CH.sub.3 N ##STR62## H CH.sub.3 H OCH.sub.3 OCH.sub.3 N ##STR63## H CH.sub.3 H CH.sub.3 CH.sub.3 N ##STR64## H CH.sub.3 H OCH.sub.3 CH.sub.3 N ##STR65## H CH.sub.3 H OCH.sub.3 OCH.sub.3 NOCH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 NOCH.sub.3 H CH.sub.3 CH.sub.3 OCH.sub.3 CH.sub.3 NOCH.sub.3 ##STR66## CH.sub.3 CH.sub.3 OCH.sub.3 OCH.sub.3 NSCH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub. 3 NSCH.sub.3 H CH.sub.3 CH.sub.3 OCH.sub.3 CH.sub.3 NSCH.sub.3 H CH.sub.3 CH.sub.3 OCH.sub.3 OCH.sub.3 N ##STR67## H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 N ##STR68## H CH.sub.3 CH.sub.3 OCH.sub.3 CH.sub.3 N ##STR69## H CH.sub.3 CH.sub.3 OCH.sub.3 OCH.sub.3 N ##STR70## H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 N ##STR71## H CH.sub.3 CH.sub.3 OCH.sub.3 CH.sub.3 N ##STR72## H CH.sub.3 CH.sub.3 OCH.sub.3 OCH.sub.3 NOCH.sub.2 CH.sub.3 H H H CH.sub.3 CH.sub.3 NOCH.sub.2 CH.sub.3 H H H OCH.sub.3 CH.sub.3 N 118-124.degree.OCH.sub.2 CH.sub.3 H H H OCH.sub.3 OCH.sub.3 N 131-140.degree.SCH.sub.2 CH.sub.3 H H H CH.sub.3 CH.sub.3 NSCH.sub.2 CH.sub.3 H H H OCH.sub.3 CH.sub.3 NSCH.sub.2 CH.sub.3 H H H OCH.sub.3 OCH.sub.3 N ##STR73## H H H CH.sub.3 CH.sub.3 N ##STR74## H H H OCH.sub.3 CH.sub.3 N ##STR75## H H H OCH.sub.3 OCH.sub.3 N ##STR76## H H H CH.sub.3 CH.sub.3 N ##STR77## H H H OCH.sub.3 CH.sub.3 N ##STR78## H H H OCH.sub.3 OCH.sub.3 NOCH(CH.sub.3).sub.2 H H H CH.sub.3 CH.sub.3 N 134-137.degree.OCH(CH.sub.3).sub.2 H H H OCH.sub.3 CH.sub.3 NOCH(CH.sub.3).sub.2 H H H OCH.sub.3 OCH.sub.3 NSCH(CH.sub.3).sub.2 H H H CH.sub.3 CH.sub.3 NSCH(CH.sub.3).sub.2 H H H OCH.sub.3 CH.sub.3 NSCH(CH.sub.3).sub.2 H H H OCH.sub.3 OCH.sub.3 N ##STR79## H H H CH.sub.3 CH.sub.3 N ##STR80## H H H OCH.sub.3 CH.sub.3 N ##STR81## H H H OCH.sub.3 OCH.sub.3 N ##STR82## H H H CH.sub.3 CH.sub.3 N ##STR83## H H H OCH.sub.3 CH.sub.3 N ##STR84## H H H OCH.sub.3 OCH.sub.3 NO(CH.sub.2).sub.3 CH.sub.3 H H H CH.sub.3 CH.sub.3 N 98-105.degree.O(CH.sub.2).sub.3 CH.sub.3 H H H OCH.sub.3 CH.sub.3 N 84-98.degree.O(CH.sub.2).sub.3 CH.sub.3 H H H OCH.sub.3 OCH.sub.3 N 125-128.degree. ##STR85## H H H CH.sub.3 CH.sub.3 N 105-110.degree. ##STR86## H H H OCH.sub.3 OCH.sub.3 N 112-121.degree.OCH.sub.3 H H Cl CH.sub.3 NOC.sub.2 H.sub.5 H CH.sub.3 H CH.sub.3 CH.sub.3 N ##STR87## H CH.sub.3 CH.sub.2 H CH.sub.3 CH.sub.2 OCH.sub.3 CHOCH.sub.2 CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.2 CH.sub.2 H OCH.sub.2 CH.sub.3 CH.sub.3 N ##STR88## H (CH.sub.3).sub.2 CH H OCH.sub.2 CH.sub.2 CH.sub.3 CH.sub.3 CHOCH(CH.sub.3).sub.2 H CH(CH.sub.2).sub.3 H CF.sub.3 CH.sub.3 NOCH(CH.sub.3)CH.sub.2 CH.sub.3 H ##STR89## H Cl OCH.sub.3 CHSCH.sub.2 CH.sub.2 CH.sub.3 H ##STR90## H OCH.sub.3 OCH.sub.3 NSCH(CH.sub.3)CH.sub.2 CH.sub.3 H ##STR91## H OCH.sub.2 CH.sub.3 OCH.sub.3 CHOC(CH.sub.3).sub.3 F H H SCH.sub.3 CH.sub.3 NOCH.sub.2 CF.sub.3 3-Cl H H CH.sub.3 OCH.sub.3 CHOCF.sub.2 CF.sub.2 H 5-Br H H CF.sub.3 OCH.sub.3 NOCH.sub.2 CHCH.sub.2 3-NO.sub.2 H H OCH.sub.2 CH.sub.3 CH.sub.3 CHOCH.sub.2 C(CH.sub.3)CH.sub.2 4-CF.sub.3 H H OCH.sub.2 CH.sub.2 CH.sub.3 OCH.sub.3 N ##STR92## 5-CH.sub.3 H H CH.sub.2 CH.sub.3 CH.sub.3 CH ##STR93## H H H CH.sub.3 CH.sub.3 CH ##STR94## H H H CH.sub.3 OCH.sub.3 NOCH.sub.3 H H H Br CH.sub.3 CHOCH.sub.3 H H H CH.sub.2 OCH.sub.3 CH.sub.3 N ##STR95## 5-CH.sub.3 CH.sub.2 H H Br CH.sub.3 N ##STR96## 6-CH.sub.3 CH.sub.2 CH.sub.2 H H CH.sub. 3 CH.sub.3 CH ##STR97## 3-(CH.sub.3).sub.2 CH H H OCH.sub.3 CH.sub.3 NOCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 4-CH.sub.3 O H H OCH.sub.3 OCH.sub.3 CHOCH.sub.2 CH.sub.2 CHCH.sub.2 5-CH.sub.3 CH.sub.2 O H H OCH.sub.2 OCH.sub.3 OCH.sub.3 NOCH.sub.2 CHCHCH.sub.2 5-CH.sub.3 CH.sub.2 CH.sub.2 O H H CH.sub.3 CH.sub.3 CHOCH.sub.2 CH(CH.sub.3).sub.2 5-(CH.sub.3).sub.2 CHO H H OCH.sub.3 CH.sub.3 NOCH.sub.3 H H H OCH.sub.3 CH.sub.3 CClSCH.sub.3 H H H CH.sub.3 CH.sub.3 CBrOC.sub.2 H.sub.5 H H H OCH.sub.3 OCH.sub.3 CCNOCH.sub.2 CH.sub.2 CH.sub.3 H H H Cl CH.sub.3 CCH.sub.3 ##STR98## H H H Br CH.sub.3 CCH.sub.2 CH.sub.3 ##STR99## H H H OCH.sub.3 OCH.sub.3 CCH.sub.2 CH.sub.2 ClOCH(CH.sub. 3).sub.2 H H H OCH.sub.3 CH.sub.3 CCH.sub.2 CHCH.sub.2OC(CH.sub.3).sub.3 H H H OCH.sub.3 OCH.sub.3 CHOCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 H H H OCH.sub.3 OCH.sub.3 NOCH.sub.2 CH(CH.sub.3).sub.2 H H H OCH.sub.3 CH.sub.3 CH__________________________________________________________________________
TABLE Ia______________________________________ ##STR100##L R R.sub.1 R.sub.2 X Y Z m.p. (.degree.C.)______________________________________OCH.sub.3 H H H CH.sub.3 CH.sub.3 CHOCH.sub.3 H H H OCH.sub.3 CH.sub.3 CHOCH.sub.3 H H H OCH.sub.3 OCH.sub.3 CHSCH.sub.3 H H H CH.sub.3 CH.sub.3 CHSCH.sub.3 H H H OCH.sub.3 CH.sub.3 CHSCH.sub.3 H H H OCH.sub.3 OCH.sub.3 CH ##STR101## H H H CH.sub.3 CH.sub.3 CH ##STR102## H H H OCH.sub.3 CH.sub.3 CH ##STR103## H H H OCH.sub.3 OCH.sub.3 CH ##STR104## H H H CH.sub.3 CH.sub.3 CH ##STR105## H H H OCH.sub.3 CH.sub.3 CH ##STR106## H H H OCH.sub.3 OCH.sub.3 CHOCH.sub.3 H CH.sub.3 H CH.sub.3 CH.sub.3 CHOCH.sub.3 H CH.sub.3 H OCH.sub.3 CH.sub.3 CHOCH.sub.3 ##STR107## CH.sub.3 H OCH.sub.3 OCH.sub.3 CHSCH.sub.3 H CH.sub.3 H CH.sub.3 CH.sub.3 CHSCH.sub.3 H CH.sub.3 H OCH.sub.3 CH.sub.3 CHSCH.sub.3 H CH.sub.3 H OCH.sub.3 OCH.sub.3 CH ##STR108## H CH.sub.3 H CH.sub.3 CH.sub.3 CH ##STR109## H CH.sub.3 H OCH.sub.3 CH.sub.3 CH ##STR110## H CH.sub.3 H OCH.sub.3 OCH.sub.3 CH ##STR111## H CH.sub.3 H CH.sub.3 CH.sub.3 CH ##STR112## H CH.sub.3 H OCH.sub.3 CH.sub.3 CH ##STR113## H CH.sub.3 H OCH.sub.3 OCH.sub.3 CHOCH.sub.3 H H H CH.sub.3 CH.sub.3 NOCH.sub.3 H H H OCH.sub.3 CH.sub.3 NOCH.sub.3 ##STR114## H H OCH.sub.3 OCH.sub.3 NSCH.sub.3 H H H CH.sub.3 CH.sub.3 NSCH.sub.3 H H H OCH.sub.3 CH.sub.3 NSCH.sub.3 H H H OCH.sub.3 OCH.sub.3 N ##STR115## H H H CH.sub.3 CH.sub.3 N ##STR116## H H H OCH.sub.3 CH.sub.3 N ##STR117## H H H OCH.sub.3 OCH.sub.3 N ##STR118## H H H CH.sub.3 CH.sub.3 N ##STR119## H H H OCH.sub.3 CH.sub.3 N ##STR120## H H H OCH.sub.3 OCH.sub.3 NOCH.sub.3 H CH.sub.3 H CH.sub.3 CH.sub.3 NOCH.sub.3 H CH.sub.3 H OCH.sub.3 CH.sub.3 NOCH.sub.3 ##STR121## CH.sub.3 H OCH.sub.3 OCH.sub.3 NSCH.sub.3 H CH.sub.3 H CH.sub.3 CH.sub.3 NSCH.sub.3 H CH.sub.3 H OCH.sub.3 CH.sub.3 NSCH.sub.3 H CH.sub.3 H OCH.sub.3 OCH.sub.3 N ##STR122## H CH.sub.3 H CH.sub.3 CH.sub.3 N ##STR123## H CH.sub.3 H OCH.sub.3 CH.sub.3 N ##STR124## H CH.sub.3 H OCH.sub.3 OCH.sub.3 N ##STR125## H CH.sub.3 H CH.sub.3 CH.sub.3 N ##STR126## H CH.sub.3 H OCH.sub.3 CH.sub.3 N ##STR127## H CH.sub.3 H OCH.sub.3 OCH.sub.3 N______________________________________
TABLE 1b______________________________________ ##STR128##L R R.sub.1 R.sub.2 X Y Z m.p. (.degree.C.)______________________________________OCH.sub.3 H H H CH.sub.3 CH.sub.3 CHOCH.sub.3 H H H OCH.sub.3 CH.sub.3 CHOCH.sub.3 ##STR129## H H OCH.sub.3 OCH.sub.3 CHSCH.sub.3 H H H CH.sub.3 CH.sub.3 CHSCH.sub.3 H H H OCH.sub.3 CH.sub.3 CHSCH.sub.3 H H H OCH.sub.3 OCH.sub.3 CH ##STR130## H H H CH.sub.3 CH.sub.3 CH ##STR131## H H H OCH.sub.3 CH.sub.3 CH ##STR132## H H H OCH.sub.3 OCH.sub.3 CH ##STR133## H H H CH.sub.3 CH.sub.3 CH ##STR134## H H H OCH.sub.3 CH.sub.3 CH ##STR135## H H H OCH.sub.3 OCH.sub.3 CHOCH.sub.3 H CH.sub.3 H CH.sub.3 CH.sub.3 CHOCH.sub.3 H CH.sub.3 H OCH.sub.3 CH.sub.3 CHOCH.sub.3 ##STR136## CH.sub.3 H OCH.sub.3 OCH.sub.3 CHSCH.sub.3 H CH.sub.3 H CH.sub.3 CH.sub.3 CHSCH.sub.3 H CH.sub.3 H OCH.sub.3 CH.sub.3 CHSCH.sub.3 H CH.sub.3 H OCH.sub.3 OCH.sub.3 CH ##STR137## H CH.sub.3 H CH.sub.3 CH.sub.3 CH ##STR138## H CH.sub.3 H OCH.sub.3 CH.sub.3 CH ##STR139## H CH.sub.3 H OCH.sub.3 OCH.sub.3 CH ##STR140## H CH.sub.3 H CH.sub.3 CH.sub.3 CH ##STR141## H CH.sub.3 H OCH.sub.3 CH.sub.3 CH ##STR142## H CH.sub.3 H OCH.sub.3 OCH.sub.3 CH______________________________________
TABLE II__________________________________________________________________________ ##STR143##L R R.sub.1 R.sub.2 Z m.p. (.degree.C.)__________________________________________________________________________OCH.sub.3 H H H CHOCH.sub.3 H H H CHOCH.sub.3 ##STR144## H H CHSCH.sub.3 H H H CHSCH.sub.3 H H H CHSCH.sub.3 H H H CH ##STR145## H H H CH ##STR146## H H H CH ##STR147## H H H CHOCH.sub.3 H H H NOCH.sub.3 H H H NOCH.sub.3 ##STR148## H H NSCH.sub.3 H H H NSCH.sub.3 H H H NSCH.sub.3 H H H N ##STR149## H H H N ##STR150## H H H N ##STR151## H H H N ##STR152## 3-CH.sub.3 CH.sub.2 H H NSCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 4-CH.sub.3 CH.sub.2 CH.sub.2 H H CH ##STR153## 5-(CH.sub.3).sub.2 CH H H NOCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 5-CH.sub.3 O H H CHOCH.sub.2 CH.sub.2 CHCH.sub.2 5-CH.sub.3 CH.sub.2 O H H NOCH.sub.2 CHCHCH.sub.2 4-CH.sub.3 CH.sub.2 CH.sub.2 O H H CHOCH.sub.2 CH(CH.sub.3).sub.2 6-(CH.sub.3).sub.2 CHO H H N ##STR154## H H H CH ##STR155## H H H NOCH.sub.3 H H H NSCH.sub.3 H H CH.sub.3 CHOC.sub.2 H.sub.5 H CH.sub.3 H NSCH.sub.3 H CH.sub.3 CH.sub.2 H CHOCH.sub.2 CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.2 CH.sub.2 H N ##STR156## H (CH.sub.3).sub.2 CH H CHOCH(CH.sub.3).sub.2 H (CH(CH.sub.2).sub.3 H NOCH(CH.sub.3)CH.sub.2 CH.sub.3 H ##STR157## H CHSCH.sub.2 CH.sub.2 CH.sub.3 H ##STR158## H NSCH(CH.sub.3)CH.sub.2 CH.sub.3 H ##STR159## H CHOC(CH.sub.3).sub.3 4-F H H NOCH.sub.2 CF.sub.3 5-Cl H H CHOCF.sub.2 CF.sub.2 H 5-Br H H NOCH.sub.2 CHCH.sub.2 3-NO.sub.2 H H CHOCH.sub.2 C(CH.sub.3)CH.sub.2 4-CF.sub.3 H H NSCH.sub.2 CH.sub.2 CH.sub.3 6-CH.sub. 3 H H CH__________________________________________________________________________
TABLE III__________________________________________________________________________ ##STR160##L R R.sub.1 R.sub.2 Y.sup.1 Q__________________________________________________________________________OCH.sub.3 H H H CH.sub.3 OOCH.sub.3 H H H CH.sub.3 O OSCH.sub.3 H H H CH.sub.3 OSCH.sub.3 H H H CH.sub.3 O O ##STR161## H H H CH.sub.3 O ##STR162## H H H CH.sub.3 O O ##STR163## H H H CH.sub.3 O ##STR164## H H H CH.sub.3 O OOCH.sub.3 H H H H OOCH.sub.3 H H H CH.sub.3 CH.sub. 2OCH.sub.3 H H H CH.sub.3 O CH.sub.2SCH.sub.3 H H H H OSCH.sub.3 H H H CH.sub.3 CH.sub.2SCH.sub.3 H H H CH.sub.3 O CH.sub.2OCH.sub.3 H H H CH.sub.3 CH.sub.2 O OSCH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3 OOC.sub.2 H.sub.5 H CH.sub.3 H CH.sub.3 O O ##STR165## H CH.sub.3 CH.sub.2 CH.sub.2 H H O ##STR166## H (CH.sub.3).sub.2 CH H CH.sub.3 CH.sub.2OCH(CH.sub.3).sub.2 H CH(CH.sub.2).sub.3 H CH.sub.3 O CH.sub.2OCH(CH.sub.3)CH.sub.2 CH.sub.3 H ##STR167## H CH.sub.3 OSCH.sub.2 CH.sub.2 CH.sub.3 H ##STR168## H CH.sub.3 O OOC(CH.sub.3).sub.3 3-F H H H OOCH.sub.2 CF.sub.3 4-Cl H H CH.sub.3 CH.sub.2OCF.sub.2 CF.sub.2 H 5-Br H H CH.sub.3 O CH.sub.2OCH.sub.2 CHCH.sub.2 5-NO.sub.2 H H CH.sub.3 OOCH.sub.2 C(CH.sub.3)CH.sub.2 6-CF.sub.3 H H CH.sub.3 O O ##STR169## H H H CH.sub.3 O ##STR170## H H H CH.sub.3 CH.sub.2 ##STR171## 3-CH.sub.3 CH.sub.2 H H H O ##STR172## 4-CH.sub.3 CH.sub.2 CH.sub.2 H H CH.sub.3 CH.sub.2 ##STR173## 5-(CH.sub.3).sub.2 CH H H CH.sub.3 O CH.sub.2OCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 5-CH.sub.3 O H H CH.sub.3 OOCH.sub.2 CH.sub.2 CHCH.sub.2 5-CH.sub.3 CH.sub.2 O H H CH.sub.3 O OOCH.sub.2 CH(CH.sub.3).sub.2 5-(CH.sub.3).sub.2 CHO H H H O__________________________________________________________________________
TABLE IV______________________________________ ##STR174##L R R.sub.1 R.sub.2 Y.sup.1 Q______________________________________OCH.sub.3 H H H CH.sub.3 OOCH.sub.3 H H H CH.sub.3 O OSCH.sub.3 H H H CH.sub.3 OSCH.sub.3 H H H CH.sub.3 O O ##STR175## H H H CH.sub.3 O ##STR176## H H H CH.sub.3 O O ##STR177## H H H CH.sub.3 O ##STR178## H H H CH.sub.3 O OOCH.sub.3 H H H H OOCH.sub.3 H H H CH.sub.3 CH.sub.2OCH.sub.3 H H H CH.sub.3 O CH.sub.2SCH.sub.3 H H H H OSCH.sub.3 H H H CH.sub.3 CH.sub.2SCH.sub.3 H H H CH.sub.3 O CH.sub.2OCH.sub.3 H H H CH.sub.3 CH.sub.2 O CH.sub.2SCH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3 OOC.sub.2 H.sub.5 H CH.sub.3 H CH.sub.3 O OOCH.sub.2 CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.2 CH.sub.2 H H O ##STR179## H (CH.sub.3).sub.2 CH H CH.sub.3 CH.sub.2OCH(CH.sub.3).sub.2 H CH(CH.sub.2).sub.3 H CH.sub.3 O CH.sub.2OCH(CH.sub.3)CH.sub.2 CH.sub.3 H ##STR180## H CH.sub.3 OSCH.sub.2 CH.sub.2 CH.sub.3 H ##STR181## H CH.sub.3 O OOC(CH.sub.3).sub.3 3-F H H H OOCH.sub.2 CF.sub.3 4-Cl H H CH.sub.3 CH.sub.2OCF.sub.2 CF.sub.2 H 5-Br H H CH.sub.3 O CH.sub.2OCH.sub.2 CHCH.sub.2 5-NO.sub.2 H H CH.sub.3 OOCH.sub.2 C(CH.sub.3)CH.sub.2 6-CF.sub.3 H H CH.sub.3 O O ##STR182## H H H CH.sub.3 O ##STR183## H H H CH.sub.3 CH.sub.2______________________________________
TABLE V______________________________________ ##STR184##L R R.sub.1 R.sub.2______________________________________OCH.sub.3 H H HOCH.sub.3 H H CH.sub.3OCH.sub.3 ##STR185## CH.sub.3 CH.sub.3SCH.sub.3 H H HSCH.sub.3 H H CH.sub.3SCH.sub.3 H CH.sub.3 CH.sub.3 ##STR186## H H H ##STR187## H H CH.sub.3 ##STR188## H CH.sub.3 CH.sub.3OCH.sub.3 H C.sub.2 H.sub.5 HOC.sub.2 H.sub.5 H CH.sub.3 HSCH.sub.3 H CH.sub.3 CH.sub.2 HOCH.sub.2 CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.2 CH.sub.2 H ##STR189## H (CH.sub.3).sub.2 CH HOCH(CH.sub.3).sub. 2 H CH(CH.sub.2).sub.3 HOCH(CH.sub.3)CH.sub.2 CH.sub.3 H ##STR190## HSCH.sub.2 CH.sub.2 CH.sub.3 H ##STR191## HSCH(CH.sub.3)CH.sub.2 CH.sub.3 H CH.sub.3CHCH.sub.2 CH.sub.3 HOC(CH.sub.3).sub.3 4-F H HOCH.sub.2 CF.sub.3 5-Cl H HOCF.sub.2 CF.sub.2 H 5-Br H HOCH.sub.2 CHCH.sub.2 3-NO.sub.2 H HOCH.sub.2 C(CH.sub.3)CH.sub.2 4-CF.sub.3 H HSCH.sub.2 CH.sub.2 CH.sub.3 6-CH.sub.3 H H ##STR192## 3-CH.sub.3 CH.sub.2 H H ##STR193## 5-(CH.sub.3).sub.2 CH H HOCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 5-CH.sub.3 O H HOCH.sub.2 CH.sub.2 CHCH.sub.2 5-CH.sub.3 CH.sub.2 O H HOCH.sub.2 CH(CH.sub.3).sub.2 5-(CH.sub.3).sub.2 CHO H H ##STR194## H H H ##STR195## H H H______________________________________
TABLE VI______________________________________ ##STR196##L R R.sub.1 R.sub.2 A______________________________________OCH.sub.3 H H H ##STR197##OCH.sub.3 H H H ##STR198##OCH.sub.3 H H H ##STR199##OCH.sub.3 H H H ##STR200##OCH.sub.3 H H H ##STR201##OCH.sub.3 H H H ##STR202##OCH.sub.3 H H H ##STR203##OCH.sub.3 H H H ##STR204##OCH.sub.3 H H ##STR205##OCH.sub.3 H H H ##STR206##OCH.sub.3 H H H ##STR207##OCH.sub.3 H H H ##STR208##OCH.sub.3 H H H ##STR209##OCH.sub.3 H H H ##STR210##OCH.sub.3 H H H ##STR211##OCH.sub.3 H CH.sub. 3 H ##STR212##OCH.sub.3 H CH.sub.3 H ##STR213##OCH.sub.3 H CH.sub.3 H ##STR214##OCH.sub.3 H CH.sub.3 H ##STR215##OCH.sub.3 H CH.sub.3 H ##STR216##OCH.sub.3 H CH.sub.3 H ##STR217##OCH.sub.3 H CH.sub.3 CH.sub.3 ##STR218##OCH.sub.3 H CH.sub.3 CH.sub.3 ##STR219##SCH.sub.3 H H H ##STR220##SCH.sub.3 H H H ##STR221##SCH.sub.3 H H H ##STR222##SCH.sub.3 H H H ##STR223##SCH.sub.3 H H H ##STR224##SCH.sub.3 H H H ##STR225##SCH.sub.3 H H H ##STR226##SCH.sub.3 H H H ##STR227##SCH.sub.3 H H H ##STR228##SCH.sub.3 H H H ##STR229##SCH.sub.3 H H H ##STR230##SCH.sub.3 H H H ##STR231##SCH.sub.3 H H H ##STR232##SCH.sub.3 H H H ##STR233##SCH.sub.3 H H H ##STR234##SCH.sub.3 H CH.sub.3 H ##STR235##SCH.sub.3 H CH.sub.3 H ##STR236##SCH.sub.3 H CH.sub.3 H ##STR237##SCH.sub.3 H CH.sub.3 H ##STR238##SCH.sub.3 H CH.sub.3 H ##STR239##SCH.sub.3 H CH.sub.3 H ##STR240##SCH.sub.3 H CH.sub.3 CH.sub.3 ##STR241##SCH.sub.3 H CH.sub.3 CH.sub.3 ##STR242## ##STR243## H H H ##STR244## ##STR245## H H H ##STR246## ##STR247## H H H ##STR248## ##STR249## H H H ##STR250## ##STR251## H H H ##STR252## ##STR253## H H H ##STR254## ##STR255## H H H ##STR256## ##STR257## H H H ##STR258## ##STR259## H H H ##STR260## ##STR261## H H H ##STR262## ##STR263## H H H ##STR264## ##STR265## H H H ##STR266## ##STR267## H H H ##STR268## ##STR269## H H H ##STR270## ##STR271## H H H ##STR272## ##STR273## H CH.sub.3 H ##STR274## ##STR275## H CH.sub.3 H ##STR276## ##STR277## H CH.sub.3 H ##STR278## ##STR279## H CH.sub.3 H ##STR280## ##STR281## H CH.sub.3 H ##STR282## ##STR283## H CH.sub.3 H ##STR284## ##STR285## H CH.sub.3 CH.sub.3 ##STR286## ##STR287## H CH.sub.3 CH.sub.3 ##STR288##______________________________________
FORMULATIONS
Useful formulations of the compounds of Formula I can be prepared in conventional ways. They include dusts, granules, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates and the like. Many of these may be applied directly. Sprayable formulations can be extended in suitable media and used at spray volumes of from a few liters to several hundred liters per hectare. High strength compositions are primarily used as intermediates for further formulation. The formulations, broadly, contain about 0.1% to 99% by weight of active ingredient(s) and at least one of (a) about 0.1% to 20% surfactant(s) and (b) about 1% to 99.9% solid or liquid diluent(s). More specifically, they will contain these ingredients in the following approximate proportions:
TABLE VII______________________________________ Active* Ingredient Diluent(s) Surfactant(s)______________________________________Wettable Powders 20-90 0-74 1-10Oil Suspensions, 3-50 40-95 0-15Emulsions, Solu-tions (includingEmulsifiableConcentratesAqueous Suspensions 10-50 40-84 1-20Dusts 1-25 70-99 0-5Granules and 0.1-95 5-99.9 0-15PelletsHigh Strength 90-99 0-10 0-2Compositions______________________________________ *Active ingredient plus at least one of a surfactant or a diluent equals 100 weight percent.
Lower or higher levels of active ingredient can, of course, be present depending on the intended use and the physical properties of the compound. Higher ratios of surfactant to active ingredient are sometimes desirable, and are achieved by incorporation into the formulation or by tank mixing.
Typical solid diluents are described in Watkins, et al., "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books, Caldwell, New Jersey. The more absorptive diluents are preferred for wettable powders and the denser ones for dusts. Typical liquid diluents and solvents are described in Marsden, "Solvents Guide", 2nd Ed., Interscience, New York, 1950. Solubility under 0.1% is preferred for suspension concentrates; solution concentrates are preferably stable against phase separation at 0.degree. C. "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood, N.J., as well as Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co., Inc., New York 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth, etc.
The methods of making such compositions are well known. Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer or fluid energy mill. Suspensions are prepared by wet milling (see, for example, Littler, U.S. Pat. No. 3,060,084). Granules and pellets may be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See J. E. Browning, "Agglomeration", Chemical Engineering, Dec. 4, 1967, pp. 147ff and "Perry's Chemical Engineer's Handbook", 5th Ed., McGraw-Hill, New York, 1973, pp. 8-57ff.
For further information regarding the art of formulation, see for example:
H. M. Loux, U.S. Pat. No. 3,235,361, Feb. 15, 1966, Col. 6, line 16 through Col. 7, line 19 and Examples 10 through 41.
R. W. Luckenbaugh, U.S. Pat. No. 3,309,192, Mar. 14, 1967, Col. 5, line 43 through Col. 1, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182.
H. Gysin and E. Knusli, U.S. Pat. No. 2,891,855, June 23, 1959, Col. 5, line 66 through Col. 5, line 17 and Examples 1-4.
G. C. Klingman, "Weed Control as a Science", John Wiley & Sons, Inc., New York, 1961, pp. 81-96.
J. D. Fryer and S. A. Evans, "Weed Control Handbook", 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pp. 101-103.
In the following examples, all parts are by weight unless otherwise indicated.
EXAMPLE 9
______________________________________Wettable Powder______________________________________N--�(4,6-dimethylpyrimidin-2-yl)amino- 80%carbonyl!-2-(methoxymethyl)benzene-sulfonamidesodium alkylnaphthalenesulfonate 2%sodium ligninsulfonate 2%synthetic amorphous silica 3%kaolinite 13%______________________________________
The ingredients are blended, hammer-milled until all the solids are essentially under 50 microns and then reblended.
EXAMPLE 10
______________________________________Wettable Powder______________________________________N--�(4-methoxy-6-methylpyrimidin-2-yl- 50%aminocarbonyl!-2-(methoxymethyl)-benzenesulfonamidesodium 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 active essentially all below 10 microns in diameter. The product is reblended before packaging.
EXAMPLE 11
______________________________________Granule______________________________________wettable powder of Example 10 5%attapulgite granules 95%(U.S.S. 20-40 mesh; 0.84-0.42 mm)______________________________________
A slurry of wettable powder containing .apprxeq.25% solids is sprayed on the surface of attapulgite granules in a double-cone blender. The granules are dried and packaged.
EXAMPLE 12
______________________________________Extruded Pellet______________________________________N--�(4,6-dimethoxypyrimidin-2-yl)amino- 25%carbonyl!-2-(methoxymethyl)benzene-sulfonamideanhydrous sodium sulfate 10%crude calcium ligninsulfonate 5%sodium alkylnaphthalenesulfonate 1%calcium/magnesium bentonite 59%______________________________________
The ingredients are blended, hammer-milled and then moistened with about 12% water. The mixture is extruded as cylinders about 3 mm diameter which are cut to produce pellets about 3 mm long. These may be used directly after drying, or the dried pellets may be crushed to pass a U.S.S. No. 20 sieve (0.84 mm openings). The granules held on a U.S.S. No. 40 sieve (0.42 mm openings) may be packaged for use and the fines recycled.
EXAMPLE 13
______________________________________Oil Suspension______________________________________N--�(4,6-dimethyl-1,3,5-triazin-2-yl)- 25%aminocarbonyl!-2-(methoxymethyl)ben-zenesulfonamidepolyoxyethylene sorbitol hexaoleate 5%highly aliphatic hydrocarbon oil 70%______________________________________
The ingredients are ground together in a sand mill until the solid particles have been reduced to under about 5 microns. The resulting thick suspension may be applied directly, but preferably after being extended with oils or emulsified in water.
EXAMPLE 14
______________________________________Wettable Powder______________________________________N--�(4-methoxy-6-methyl-1,3,5-triazin- 20%2-yl)aminocarbonyl!-2-(methoxymethyl)-benzenesulfonamidesodium alkylnaphthalenesulfonate 4%sodium ligninsulfonate 4%low viscosity methyl cellulose 3%attapulgite 69%______________________________________
The ingredients are thoroughly blended. After grinding in a hammer-mill to produce particles essentially all below 100 microns, the material is reblended and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) and packaged.
EXAMPLE 15
______________________________________Low Strength Granule______________________________________N--�4,6-dimethoxy-1,3,5-triazin-2-yl)- 1%aminocarbonyl!-2-(methoxymethyl)-benzenesulfonamideN,N--dimethylformamide 9%attapulgite granules 90%(U.S.S. 20-40 sieve)______________________________________
The active ingredient is dissolved in the solvent and the solution is sprayed upon dedusted granules in a double cone blender. After spraying of the solution has been completed, the blender is allowed to run for a short period and then the granules are packaged.
EXAMPLE 16
______________________________________Aqueous Suspension______________________________________N--�4,6-dimethylpyrimidin-2-yl)aminocar- 40%bonyl!-2-(methylthiomethyl)benzene-sulfonamidepolyacrylic acid thickener 0.3%dodecylphenol polyethylene glycol 0.5%etherdisodium phosphate 1%monosodium phosphate 0.5%polyvinyl alcohol 1.0%Water 56.7%______________________________________
The ingredients are blended and ground together in a sand mill to produce particles essentially all under 5 microns in size.
EXAMPLE 17
______________________________________Solution______________________________________N--�(4-methoxy-6-methylpyrimidin-2-yl)- 5%aminocarbonyl!-2-(methylthiomethyl)-benzenesulfonamide, sodium saltwater 95%______________________________________
The salt is added directly to the water with stirring to produce the solution, which may then be packaged for use.
EXAMPLE 18
______________________________________Low Strength Granule______________________________________N--�(4,6-dimethoxypryimidin-2-yl)- 0.1%aminocarbonyl!-2-(methylthio-methyl)benzenesulfonamideattapulgite granules 99.9%(U.S.S. 20-40 mesh)______________________________________
The active ingredient is dissolved in a solvent and the solution is sprayed upon dedusted granules in a double cone blender. After spraying of the solution has been completed, the material is warmed to evaporate the solvent. The material is allowed to cool and then packaged.
EXAMPLE 19
______________________________________Granule______________________________________N--�(4,6-dimethyl-1,3,5-triazin-2-yl- 80%aminocarbonyl!-2-(methylthiomethyl)--benzenesulfonamidewetting agent 1%crude ligninsulfonate salt (containing 10%5-20% of the natural sugars)attapulgite clay 9%______________________________________
The ingredients are blended and milled to pass through a 100 mesh screen. This material is then added to a fluid bed granulator, the air flow is adjusted to gently fluidize the material, and a fine spray of water is sprayed onto the fluidized material. The fluidization and spraying are continued until granules of the desired size range are made. The spraying is stopped, but fluidization is continued, optionally with heat, until the water constant is reduced to the desired level, generally less than 1%. The material is then discharged, screened to the desired size range, generally 14-100 mesh (1410-149 microns), and packaged for use.
EXAMPLE 20
______________________________________High Strength Concentrate______________________________________N--�(4-methoxy-6-methyl-1,3,5-triazin- 99%2-yl)aminocarbonyl!-2-(methylthio-methyl)benzenesulfonamidesilica aerogel 0.5%synthetic amorphous silica 0.5%______________________________________
The ingredients are blended and ground in a hammer-mill to produce a material essentially all passing a U.S.S. No. 50 screen (0.3 mm opening). The concentrate may be formulated further if necessary.
EXAMPLE 21
______________________________________Wettable Powder______________________________________N--�(4,6-dimethylpyrimidin-2-yl)amino- 90%carbonyl!-2-(methylsulfonylmethyl)-benzenesulfonamidedioctyl sodium sulfosuccinate 0.1%synthetic fine silica 9.9%______________________________________
The ingredients are blended and ground in a hammer-mill to produce particles essentially all below 100 microns. The material is sifted through a U.S.S. No. 50 screen and then packaged.
EXAMPLE 22
______________________________________Wettable Powder______________________________________N--�4,6-dimethoxy-1,3,5-triazin-2-yl)- 40%aminocarbonyl!-2-(methylthiomethyl)-benzenesulfonamidesodium ligninsulfonate 20%montmorillonite clay 40%______________________________________
The ingredients are thoroughly blended, coarsely hammer-milled and then air-milled to produce particles essentially all below 10 microns in size. The material is reblended and then packaged.
EXAMPLE 23
______________________________________Oil Suspension______________________________________N--�(4-methoxy-6-methylpyridin-2-yl)- 35%aminocarbonyl!-2-(methylsulfonyl-methyl)benzenesulfonamideblend of polyalcohol carboxylic 6%esters and oil soluble petroleumsulfonatesxylene 59%______________________________________
The ingredients are combined and ground together in a sand mill to produce particles essentially all below 5 microns. The product can be used directly, extended with oils, or emulsified in water.
EXAMPLE 24
______________________________________Dust______________________________________N--�(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl!- 10%2-(methylthiomethyl)benzene-sulfonamideattapulgite 10%Pyrophyllite 80%______________________________________
The active ingredient is blended with attapulgite and then passed through a hammer mill to produce particles substantially all below 200 microns. The ground concentrate is then blended with powdered pyrophyllite until homogeneous.
UTILITY
The compounds of the present invention are active herbicides. They have utility for broad-spectrum pre- and/or post-emergence weed control in areas where complete control of all vegetation is desired, such as around fuel storage tanks, ammunition depots, industrial storage areas, oil-well sites, drive-in theaters, around billboards, highway and railroad structures. By properly selecting compound rate, time and method of application, compounds of this invention may also be used to modify plant growth beneficially, or to selectively control weeds in cereal crops.
The precise amount of the compounds of Formula I to be used in any given situation will vary according to the particular end result desired, the amount of foliage present, the crop species involved, the types of weeds to be 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 0.01 to 20 kg/ha with a preferred range of 0.01 to 10 kg/ha. In general, the lower rates of application from within this range are suggested for use on lighter soils and/or those having a low organic matter content, for selective weed control or for plant growth regulation, whereas the higher rates will be selected for adverse conditions or where extended persistence in soil is desired.
The compounds of the invention may be used in combination with any other commercial herbicide examples of which are those of the triazine, triazole, uracil, urea, amide, diphenylether, carbamate bipyridylium types.
The activity of these compounds was discovered in greenhouse tests. The tests are described and the data resulting from them are shown below.
0=no effect
10=maximum effect
C=chlorosis or necrosis
D=defoliation
E=emergence inhibition
G=growth retardation
H=formative effects
U=unusual pigmentation
X=axillary stimulation
6Y=abscised buds or flowers
6F=delayed flowering.
S=albinism
TEST A
Seeds of crabgrass (Digitaria spp.), barnyardgrass (Echinochloa crusgalli), wild oats (Avena fatua), cassia (Cassia tora), morningglory (Ipomoea sp.), cocklebur (Xanthium spp.), sorghum, corn, soybean, 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 solution of the compounds of Table A. At the same time, cotton having five leaves (including cotyledonary ones), bush beans with the third trifoliate leaf expanding, crabgrass, barnyardgrass and wild oats with two leaves, cassia with three leaves (including cotyledonary ones), morningglory and cocklebur with four leaves (including the cotyledonary ones), sorghum and corn with four leaves, soybean with two cotyledonary leaves, rice with three leaves, wheat with one leaf, and nutsedge with three to five leaves were sprayed with a non-phytotoxic solvent solution of the compounds of Table A. Other containers of the above untreated weeds and crops were treated pre- or post-emergence with the same non-phytotoxic solvent so as to provide a solvent control. A set of untreated control plants was also included for comparison. Pre-emergence and post-emergence treated plants and controls were maintained in a greenhouse for sixteen days, then all treated plants were compared with their respective controls and rated visually for response to treatment. The data in Table A shows that some compounds of this invention are very effective as herbicides and often cause little or no injury to cereal crops.
TABLE A POST-EMERGENCE MORN- BARN- BUSH- COT- ING COCKLE- NUT- CRAB- YARD- WILD SOY- SOR- kg/ha BEAN TON GLORY BUR CASSIA SEDGE GRASS GRASS OATS WHEAT CORN BEAN RICE GHUM ##STR289## 0.4 9C 9C 10C 9C 9C 9C 9C 10C 9C 9C 9C 9C 9C 9C ##STR290## 0.4 9C 9C 10C 10C 9C 9C 9C 10C 9C 9C 9C 9C 9C 10C ##STR291## 0.4 9C 9C 10C 10C 9C 9C 6C,9G 9C 6C,9G 9C 9C 9C 9C 9C ##STR292## 0.4 9C 7C 9G 10C 10C 9C 10C 9C 10C 6C,9G 9C 10C 9C 10C 10C ##STR293## 0.4 9C 10C 10C 9C 9C 8C 9C 10C 5C,9G 10C 9C 9C 10C 10C ##STR294## .04 9C 9C 10C 10C 9C 9C 2C,6G 9C 2C 1C 7C,9C 9C 9C 1C,9H ##STR295## .04 3C,6Y,7G 3C,3H,8G 3C,6H 3C,8G 3C 5G 1C,5G 10C 9C 2C,6G 1C,5H 1C,2G 2C,8G 2C,8G ##STR296## .04 9C 9C 5C,9G 5C,9G 2C,6G 2C,8G 9C 9C 9C 9C 7C,9C 6C,9G 6C,9G 3D,9G ##STR297## .04 9C 9C 10C 10C 9C 6C,8G 10C 9C 9C 5C,9G 5C,9C 9C 5C,9G 9C ##STR298## .04 3H,7G 1H 1H 5C,9G 0 0 0 0 0 0 0 1H 0 0 ##STR299## .04 6C,6Y, 9G 3H,4C,9G 1C,2G 4C,9G 2C 0 0 5H 0 0 8H 2C,7X,8G 2C,7G 2C,8G ##STR300## .04 2C,6Y,9G 3C,5H 2C,7G 2C,6G 2C 0 5G 3H 0 0 4C,9G 2C,5X,8G 9C 1C,6H ##STR301## .04 4S,5G,6P 3C,5H 3C,8H 3C,5G 1C 2C,6G 1C 4C,8H 4C,9H 2C,7G 2C,5G 3H 4C,9G 1C,9G ##STR302## .04 6C,6Y,9G 7C,9G 10C 6C,9G 4C,7G 2C,9G 3C,7G 6C,9H 2C 0 3D,9G 2C,9G 3C,9G 2C,8G ##STR303## .04 6C,6Y,9G 6C,9G 9C 5C,9G 6C,8G 8G 5C,9G 9C 4C,8G 3C,6G 5C,9G 3C,9G 5C,9G 4D,9G ##STR304## .04 5C,6Y,8G 9C 10C 10C 6C,9G 6C,9G 2C,7G 9C 0 0 3U,9H 4C,9G 3C,9G 2U,9G ##STR305## .04 9C 9C 10C 9C 5C,9G 2C,9G 3C,9H 9C 3C,9H 2C,4G 10C 6C,9G 6C,9G 9C ##STR306## .04 1C,2H 3C,3H,9G 4C,9G 4C,9G 2C,4H 2C 1C 4C,9H 5C,9H 1C 0 2H 6C,9G 4C,9H ##STR307## .05 1C,4G,6Y 2C,3H,7G 2H 2C,7G 2C 2C,9G 0 0 0 0 2C,7H 5H 5G 2C,9H ##STR308## .05 9D,9G,6Y 2C,3H,8G 2C,9G 4C,9G 3C,8G 5C,9G 5G 3C,9H 2C,5G 1C,3G 2U,9G 5C,9G 1C,8G 2U,9G ##STR309## .05 9C 3C,9G 3C,9G 6C,9G 2C,8H 6C,9G 3C,5H 3C,9H 2C,7G 0 2C,8H 6C,9G 3C,8G 2C,9H ##STR310## .05 9C 5C,9G 6C,9G 6C,9G 2C,5H 1C 2G 1C,4H 0 0 2C,9G 2C,9G 9 1C,9G ##STR311## .05 0 0 0 0 0 0 0 0 0 0 0 0 0 0 ##STR312## .04 3C,9G,6Y 2C,2H,7G 2C 1C 1C 0 0 1C 0 0 2C,9H 1C,6H 2C,8G 2C,8H ##STR313## .04 4S,9G,6Y 1C,2G 1C 0 0 0 0 1C,2H 0 0 2C,9H 1C,5H 2C,8G 2C,6H ##STR314## 0.05 3C,7G,6Y 0 4G 4G 0 0 3G 1H 0 0 2C,7H 1H 2G 2C,9H ##STR315## 0.05 2C,6G,6Y 2G 1H,3G 0 0 0 0 0 0 0 1C,5H 4H 2G 1C,6H ##STR316## .05 9C 6C,9G 3C,7G 9C 3C,9G 9C 2C,5G 6C,9H 9H 2C,9G 3C,9G 2C,9G,5X 3C,9G 4U,9G ##STR317## .05 9C 9C 5C,9G 9C 6C,9G 9C 2C,7G 9C 2C,9G 2C,9G 5U,9G 4C,9G 3C,9G 3C,9G ##STR318## .05 9C 6C,9G 9C 9C 2C,9G 9C 1C,3G 4C,9H 0 0 2U,9G 4C,9G 2C,9G 1U,9G ##STR319## .05 9C 9C 10C 9C 5C,9G 2C,8G 1C,2G 3C,9H 4G 0 5U,9G 4C,9G 6G 2U,9G ##STR320## .05 9C 9C 9C 9C 5C,9G 2C,8G,5X 1C 1C,3G 0 0 2C,9H 3H,9G,7X 6G 1C,7G ##STR321## .05 0 1C,3H 1C,6C 1C 1C,8G 1C,7G 1C,6H 6G 0 2C,7H 2H,8G 5G 2C,9G ##STR322## .05 6S,9G,6Y 3C,7G 2C,6G 3C,9H 2C,5G 4G 2C,8G 2C,8H 1C,6G 1G 1U,9G 3C,9G 8G 3C,9H ##STR323## .05 2C,9G,6Y 1C,5G 1C,5G 1C,9G 1C,3G 1C,7G 1C,5G 2C,9H 2G 0 2C,7G 2C,8G 2C,8G 3C,9G ##STR324## .05 2C,5G,6Y 1C,1H 2C,9G 2C,9G 1C 0 0 0 0 0 2C,8H 2C,9H 0 2C,9G ##STR325## 0.05 5S,9G,6Y 2C,5G 1C,7G 3G,6F 3C 0 0 0 0 0 2G 1C,9G 0 2C,8G ##STR326## 0.05 2C 4G 2C,7G 1C,3G 2C 2C,8G 2G 2H 0 0 2C,7H 1C,8G 1C,3G 2C,9G ##STR327## 0.05 4S,9G,6Y 3C,3H 4C,9G 2C,9G 2C,7G 2C,8G 7G 9H 1C,4G 2G 8G 9C 1C,8G 1C,9G ##STR328## 0.05 9D,9G,6Y 2C,3H 6B,8G 3C,9G 2C 1C,9G 2C,5G 8H 1H 1G 2C,8H 9C 7G 9G ##STR329## 0.05 3C,9G,6Y 0 10C 1C,2G 0 0 0 0 0 0 1C,6G 2C,8G 0 2G PRE-EMERGENCE MORNING COCKLE- NUT- CRAB- BARNYARD WILD kg/ha GLORY BUR CASSIA SEDGE GRASS GRASS OATS WHEAT CORN SOYBEAN RICE SORGHUM ##STR330## 0.4 9G 9G 9G 10E 2C,9G 5C,9H 4C,9H 9H 10E 9H 10E 6C,9H ##STR331## 0.4 9C 9G 3C,9G 10E 3C,9G 6C,9H 5C,9H 10H 10E 9H 10E 10H ##STR332## 0.4 9G 9H 2C,9G 10E 2C,9G 7C,9H 1C,9G 9G 9H 9H 10E 6C,9H ##STR333## .04 9C 9H 5C,9G 10E 2C,8G 6C,9H 6C,9H 9G 9H 9H 10E 10H ##STR334## .04 9C 9G 2C,9G 1C,9G 3C,8G 5C,9H 5C,9H 1C,9G 9H 9H 10E 3C,9H ##STR335## .04 9C 9H 2C,9G 9G 3C,5G 3C,9H 1C,8G 5G 9H 9H 10E 9H ##STR336## .04 9G 9H 3C,7H 9G 2C,6G 2C,9H 3C,9G 9G 2C,9H 2C,2H 10E 2C,9G ##STR337## .04 9C 9H 4C,9G 10E 5C,9G 6C,9H 4C,9G 3C,9G 10H 8H 10E 7C,9H ##STR338## .04 9C 9H 9C 10E 6C,9H 6C,9H 4C,9G 9G 10H 9H 10E 6C,9H ##STR339## .04 5G 5H 6G 0 0 0 0 0 0 0 0 0 ##STR340## .04 9G 9H 8G 0 0 2C,7H 7G 2G 9H 6H 5H 2C,9G ##STR341## .04 7G 9H 5G 0 0 6H 3G 0 1C,8H 1C,3H 1C,9H 3C ##STR342## .04 8H 10H 2C,5G 2C,8H 0 2C 6G 4G 3C,8H 2C 9H 5C,8G ##STR343## .04 9G 9H 6C,9G 10E 5C,9G 6C,9H 4C,7G 2C,7G 6C,9G 9H 9H 6C,9H ##STR344## .04 9C 9H 5C,8G 10E 5C,9G 5C,9H 5C,8G 1C,9G 3C,9G 8H 10E 6C,9H ##STR345## .04 10C 9H 6C,9G 10E 2C,7G 5C,9H 2C,8G 0 5C,9H 9H 10E 10H ##STR346## .04 4C,9G 9H 5C,9G 10E 5C,9G 6C,9H 5C,8G 9G 10H 9H 10E 10H ##STR347## .04 8H 9H 2C 0 0 1C,6H 9G 0 2C,6H 2C 2C,9H 4C,9H ##STR348## .05 6G 9H 2C,5H 2G 0 1H 2C,5G 1C,4G 2C,8H 2C 2C,6G 1C,7H ##STR349## .05 9G 9H 1C,9G 9G 3G 4C,9H 4C,9G 1C,9G 10H 9H 2C,8G 2C,9H ##STR350## .05 9G 9H 9G 10E 2C,5G 3C,9H 1C,7G 3G 2C,9H 9H 4C,8H 2C,8H ##STR351## .05 2C,9G 2C,9H 5C,9G 5G 0 7H 0 0 3C,9G 2C,8H 2C,5G 2C,9H ##STR352## .05 10E 0 0 0 0 0 0 0 0 0 0 0 ##STR353## 0.4 2C,6H 9H 5C 0 0 1C 0 0 2C,8H 1C,3G 2C,5G 2C,9H ##STR354## 0.4 1C 0 0 0 0 1C,2H 0 0 2C,8H 2C 1C,5G 1C,7G ##STR355## 0.05 0 0 0 0 0 1C 0 0 9H 1C 0 2C,4G ##STR356## 0.05 0 0 0 0 0 0 0 0 3G 1C 3G 2C ##STR357## .05 9G 9H 1C,9G 10E 1C,4G 2C,9H 1C,9G 9G 1C,9G 2C,3G 10E 5C,9G ##STR358## .05 9G 9H 2C,9G 10E 2C,6G 6C,9H 3C,9G 2C,9G 9H 9H 9H 3C,9H ##STR359## .05 9G 9H 2C,9G 10E 2C,6G 3C,9H 2C,9H 2C,7G 2U,9G 9H 4C,9H 2C,9G ##STR360## .05 9G 9H 3C,9G 6G 1C 2C,8H 5G 2G 9G 8H 8H 2C,9G ##STR361## .05 9G 9H 2C,9G 8G 1C,2G 2C,8H 1C,3G 0 2C,9H 7H 6G 2C,8G ##STR362## .05 0 0 1C 0 1C 1C,5G 2C,7G 3G 2C,7G 1C 2C 2C,6G ##STR363## .05 1H,7G 9H 2C,6G 1C,7G 1C,5G 2C,9H 2C,8G 1C,8G 2C,9G 9H 4C,9H 2C,9H ##STR364## .05 1C 5H 2C,3G 9G 2C 3C,9H 2C,7G 5G 2C,8G 5G 2C,9H 2C,9G ##STR365## .05 9G 9H 0 0 0 1C,5G 0 0 2C,7G 1C 2C 3C,9H ##STR366## 0.05 8G 9H 1C 0 0 1C 0 0 1C,3G 3G 2C 2C,8G ##STR367## 0.05 2G 9H 0 5G 4G 3C,6G 1C,6G 3G 2C,6G 1C,1H 3C,7G 1C,8G ##STR368## 0.05 9G 9H 1C,7G 9G 2C,6G 1C,9H 8G 8G 9G 9H 4C,9H 2C,9H ##STR369## 0.05 8G 8H 2C,8G 8G 2C,5G 2C,8H 2C,6G 1C,3G 2C,9H 9H 5C,9H 9G ##STR370## 0.05 9G 9G 1C 0 0 1C 0 0 1C,5G 2H 1C,4G 3C,8H
The following compounds ##STR371## demonstrated virtually no activity when tested at low levels. It is thought they would be herbicidally active when tested at higher levels.
TEST B
Two plastic bulb pans were filled with fertilized and limed Fallsington silt loam soil. One pan was planted with corn, sorghum, Kentucky bluegrass and several grassy weeds. The other pan was planted with cotton, soybeans, purple nutsedge (Cyperus rotundus), and several broadleaf weeds. The following grassy and broadleaf weeds were planted: crabgrass (Digitaria sanguinalis), barnyardgrass (Echinochloa crusgalli), wild oats (Avena fatua), johnsongrass (Sorghum halepense), dallisgrass (Paspalum dilatatum), giant foxtail (Setaria faberii), cheatgrass (Bromus secalinus), mustard (Brassica arvensis), cocklebur (Xanthium pennsylvanicum), pigweed (Amaranthus retroflexus), morningglory (Ipomoea hederacea), cassia (Cassia tora), teaweed (Sida spinosa), velvetleaf (Abutilon theophrasti), and jimsonweed (Datura stramonium). A 12.5 cm diameter plastic pot was also filled with prepared soil and planted with rice and wheat. Another 12.5 cm pot was planted with sugarbeets. The above four containers were treated pre-emergence with several test compounds within the scope of the invention.
Twenty-eight days after treatment, the plants were evaluated and visually rated for response to the chemical treatments utilizing the rating system described previously for Test A. The data are summarized in Table B.
TABLE B__________________________________________________________________________PRE-EMERGENCE ON FALLSINGTON SILT LOAM SOIL__________________________________________________________________________ ##STR372## ##STR373##Rate kg/ha 0.03 0.12 0.01 0.015 0.03 0.12__________________________________________________________________________Crabgrass 4G 7G,3C 0 3G 5G 7G,3CBarnyardgrass 8G,5H 10C 5G 7G,3H 9G,8C 9G,9CSorghum 9G,9C 10E 2G 7G,3H 10C 10CWild Oats 7G,5H 9G,9C 0 5G 5G,3C 9G,9CJohnsongrass 8G,4C 9G,9C 3G 6G,3H 8G,5H 9G,5CDallisgrass 3G 7G,5C 2G 2G 3G 8G,8CGiant foxtail 4G 5G 3G 9E 6G 9G,9CKy. bluegrass 7G,3C 10C 4G 7G,5E 7G,5C 10CCheatgrass 8G 10E -- 5G 7G 10ESugarbeets 9G,9C 10C 5G 10C 10C 10CCorn 5G,2H 9G,9C 0 5G 7G,5H 10CMustard 10C 10C 8G,7C 9G,8C 10C 10CCocklebur 5G 7G 0 0 3G 8GPigweed 9G,9C 10E 0 3G 10E 10ENutsedge 5G 5E,9G 0 0 5G 8GCotton 4G,3H 8G 0 0 7G,3H 8G,4CMorningglory 3G 7G 3G 3G 6G 9GCassia 7G 9G,8C 0 6G 9G,6C 9G,8CTeaweed 5G 7G,3C 0 3G 5G 7G,5CVelvetleaf 8G,5H 9G,8C 0 2G 9G 9G,8CJimsonweed 6G 7G 0 4G 8G,8C 9G,9CSoybean 3G 6G,5H 0 3G 7G,5H 9G,8CRice 10E 10E 5G 7G,3H 8G,7C 10EWheat 5G,3C 7G,7C 0 0 5G,3C 6G,3C__________________________________________________________________________ ##STR374## ##STR375##Rate kg/ha 0.03 0.12 0.03 0.12__________________________________________________________________________Crabgrass 2G 5G 0 5GBarnyardgrass 7G,5H 10C 3G 5G,3HSorghum 8G,5H 10C 8G,3H 9G,8CWild Oats 5G,3H 6G,4C 3G 7G,4CJohnsongrass 6G 7G,5H 6G 8G,5HDallisgrass 0 5G 0 0Giant foxtail 0 7G,7C 0 2GKy. bluegrass 8G,8C 10C 4G,3C 8G,8CCheatgrass 5G 7G,3C 0 5GSugarbeets 9G,9C 10C 9G,9C 10CCorn 3H 9G,9C 3H 7G,3HMustard 10C 10C 10C 10CCocklebur 4G 7G 4G 6G,3HPigweed 10E 10E 9G,8C 9G,9CNutsedge 7G 8G,4C 0 5GCotton 6G 7G,5H 3G 7G,5HMorningglory 3G 9G,3C 3G 6GCassia 8G 9G,8C 3G 8GTeaweed 4G 7G,3C 3G 7G,5HVelvetleaf 8G,3H 9G,9C 7G 9G,5CJimsonweed 8G,8C 9G,8C 6G 9G,9CSoybean 4G,3H 7G,5H 4G 7G,5HRice 8G,5C 10C 7G,3C 10EWheat 3G 3G 0 3G__________________________________________________________________________ ##STR376## ##STR377##Rate kg/ha 0.03 0.12 0.03 0.12__________________________________________________________________________Crabgrass 5G 6G 0 0Barnyardgrass 4G 7G,5H 2G 5GSorghum 9G,9C 10C 6G,3H 8G,5HWild Oats 6G,2C 6G,4C 0 4GJohnsongrass 6G 7G,3H 0 6G,3HDallisgrass 0 5G 0 3GGiant foxtail 0 6G 0 0Ky. bluegrass 7G,6C 8G,9C 3G 6GCheatgrass 0 6G,3C 0 0Sugarbeets 10C 10C 8G,9C 10CCorn 7G,5H 8G,9C 5G 6G,3HMustard 10C 10C 9G,9C 10CCocklebur 6G 7G,5H 7G 6G,3HPigweed 10E 10E 8G 10CNutsedge 5G 7G 0 3GCotton 8G,5H 9G,3C 7G,3H 8GMorningglory 8G 9G,8C 8G,5H 9G,3CCassia 9G,3C 9G,8C 9G,4C 9G,6CTeaweed 7G,3C 8G,5C 6G,3C 7G,3CVelvetleaf 9G,5C 9G,5C 8G,5H 9G,7CJimsonweed 9G,9C 10C 7G,4C 9G,7CSoybean 8G,5H 9G,8C 7G,5H 8G,5HRice 6G,3C 7G,6C 6G 0Wheat 0 3G 0 0__________________________________________________________________________ ##STR378## ##STR379##Rate kg/ha 0.03 0.12 0.03 0.12__________________________________________________________________________Crabgrass 0 3G 2G 6G,3HBarnyardgrass 4G 7G 8G,5H 9G,9CSorghum 6G,3H 10C 10C 10EWild Oats 2G 5G,5C 5G 5G,5CJohnsongrass 5G 8G,5H 9G,9C 10CDallisgrass 0 4G 3G 8G,8CGiant foxtail 5G 7G 8G,5H 10CKy. bluegrass 5G 7G,5C 6G,3C 10CCheatgrass 10E 8G,9C 7C 10ESugarbeets 6G,5C 9G,9C 8G,8C 10CCorn 0 4G 6G,3H 8G,8CMustard 9G,8C 9G,8C 10C 10CCocklebur 3G 5G 4G 7G,7CPigweed 6G 8G 8G,5C 10CNutsedge 5G 7G 7G 10CCotton 3G 4G 6G,3H 8G,5HMorningglory 2C 8G,5H 6G,3H 8G,5HCassia 3G 5G,3H 7G,5H 8G,7CTeaweed 3G 7G 4G 8G,5HVelvetleaf -- 5G,3H 8G,5H 8G,5HJimsonweed 3G 8G,5H 8G,5H 9G,6CSoybean 4G,3H 5G,5H 5G,5H 7G,5HRice 6G 7G,3H 10E 10EWheat 2G 4G 3G 5G__________________________________________________________________________ ##STR380## ##STR381##Rate kg/ha 0.03 0.12 0.03 0.12__________________________________________________________________________Crabgrass 0 0 0 3GBarnyardgrass 4G 7G,8C 4G 7G,8CSorghum 10C 9G,9C 9G,9C 10CWild Oats 3G 5G 3G 7G,3HJohnsongrass 6G,3H 7G,3H 4G,2H 9G,8CDallisgrass -- -- -- --Giant foxtail 5G 7G,3H 3G 6G,3HKy. bluegrass 6G 7G,5C 5G 7G,5CCheatgrass -- -- -- --Sugarbeets 8G,9C 10C 7G,8C 10CCorn 3G 9G,8C 0 4G,3HMustard 9G,9C 10C 9G,9C 10CCocklebur 6G,2C 6G,5H 4G 7G,3HPigweed 0 6G 3G 8G,8CNutsedge 4G 6G 4G 9G,8ECotton 4G,5H 6G,5H 3G 5G,3HMorningglory 4G,3H 8G,5H 4G,3H 7G,5HCassia 2C 5G,3C 2G 6G,3CTeaweed 3G,2C 5G,3H 2G 3G,2CVelvetleaf 2C 8G,5H 4G 6G,5HJimsonweed 5G,5H 7G,5C 3G 8G,5HSoybean 4G,5H 6G,5H 3G 5G,3HRice 6G 8G,5C 6G 8G,5CWheat 2G 3G 2G 4G__________________________________________________________________________ ##STR382## ##STR383##Rate kg/ha 0.03 0.12 0.03 0.12__________________________________________________________________________Crabgrass 3G 3G 3G 9G,8CBarnyardgrass 8G,8C 10C 7G,8C 10CSorghum 10C 10C 10C 10CWild Oats 2G 4G 5G 8G,8CJohnsongrass 7G,3H 9G,9C 9G,8C 10CDallisgrass -- -- -- --Giant foxtail 5G 8G,3H 7G,3H 10CKy. bluegrass 6G 7G,3C 7G,5C 10CCheatgrass -- -- -- --Sugarbeets 10C 10C 10C 10CCorn 7G,5H 9G,9C 6G,5H 10CMustard 10C 10C 9G,9C 10CCocklebur 3G 7G,5H 4G 8G,5HPigweed 8G,8C 9G,8C 8G,7C 10CNutsedge 10E 10E 6G 10ECotton 6G,5H 6G,5H 4G 8G,5HMorningglory 4G,3H 8G,5H 6G,3H 8G,5HCassia 7G,5C 8G,6C 7G,5C 9G,8CTeaweed 3G,2C 5G,3H 0 6G,5HVelvetleaf 7G,5H 8G,5H 6G,5H 8G,3HJimsonweed 8G,7C 8G,5C 5G 8G,7CSoybean 6G,5H 7G,5H 7G,5H 8G,5HRice 7G 8G,5C 8G,7C 10CWheat 0 2G 3G 5G__________________________________________________________________________ ##STR384## Rate kg/ha 0.25__________________________________________________________________________ Crabgrass 0 Barnyardgrass 0 Sorghum 7G,5H Wild Oats 4G Johnsongrass 3G Dallisgrass 0 Giant foxtail 0 Ky. bluegrass 0 Cheatgrass 4G Sugarbeets 10C Corn 0 Mustard 9G,9C Cocklebur 0 Pigweed 0 Nutsedge 0 Cotton 4G,3H Morningglory 4G,2H Cassia 3G Teaweed 0 Velvetleaf 6G Jimsonweed 0 Soybean 0 Rice 6G Wheat 0__________________________________________________________________________
TEST C
Twenty-five cm diameter plastic pots filled with Fallsington silt loam were planted with soybeans, cotton, alfalfa, corn, rice, wheat, sorghum, velvetleaf (Abutilon theophrasti), sesbania (Sesbania exaltata), Cassia (Cassia tora), morningglory (Ipomoea hederacea), jimsonweed (Datura stramonium), cocklebur (Xanthium pennsylvanicum), crabgrass (Digitaria spp.), nutsedge (Cyperus rotundus), barnyardgrass (Echinochloa crusgalli), giant foxtail (Setaria faberii) and wild oats (Avena fatua). Approximately two weeks after planting, the young plants and the soil around them were sprayed overall with the test chemicals dissolved in a non-phytotoxic solvent. Two weeks after treatment, all species were compared to untreated controls and visually rated for response to treatment. The rating system was as described previously for Test A. The data are presented in Table C. Several of the compounds tested by this procedure are useful for the post-emergence control of weeds in wheat.
TEST C__________________________________________________________________________ ##STR385## ##STR386##Rate kg/ha 0.06 0.015 0.06 0.015__________________________________________________________________________Soybeans 10G,7C 10G,5C 10G,9C 10G,8CVelvetleaf 9C 9C 10C 9CSesbania 10C 10G,9C 10C 10CCassia 10G,7C 10G,4C 10G,8C 10G,7CCotton 9G,4C 7G,3C 9C 9CMorningglory 10G,5C 3G 10C 10CAlfalfa 6G,2C 2G 9G,6C 9G,6CJimsonweed -- 3G,2C -- --Cocklebur 7C,10G 4G 8G,3C 5G,3CCorn 8G,4U 5G,3H 9G,7C 8G,4UCrabgrass 3G,1C 1C 6G,1C 3GRice 8G,3C 8G,2C 10G,5C 10G,5CNutsedge 8G,3C 3G,2C 9G,6C 7GBarnyardgrass 8G,4C 8G 8G,4C 8G,2CWheat 6G 1G 8G,2C 6G,2CGiant Foxtail 3G,1C 0 8G 6G,1CWild Oats 7G,2C 5G 9G,3C 8G,2CSorghum 8G,4C 8G,2C 9G,3C 9G,2C__________________________________________________________________________ ##STR387## ##STR388##Rate kg/ha 0.06 0.015 0.06 0.015__________________________________________________________________________Soybeans 10G,8C 10G,8C 10G,7C 10G,4CVelvetleaf 10C 10C 10G,8C 5G,1CSesbania 10C 10C 10G,9C 10G,6CCassia 10G,8C 10G,7C 10G,7C 10G,5CCotton 10G,6C 9G,6C 6G,3C 5G,3CMorningglory 10C 10C 10C 6G,2CAlfalfa 8C 10G,7C 8C 6G,3CJimsonweed -- -- -- --Cocklebur 10C 1G 10G,6C 5G,3CCorn 7G,5H 6G,5H 8G,5C 8G,4UCrabgrass 3G 0 0 0Rice 9G,5C 8G,1C 10G,7C 9GNutsedge 9G,5C 8G 3G,1C 2GBarnyardgrass 3C,8G 8G 3C,8G 3C,5GWheat 2G,1C 1C 0 0Giant Foxtail 7G,2C 7G 5G 5GWild Oats 0 0 1C 0Sorghum 8G,2C 4G 8G,3U 7G,3C__________________________________________________________________________ ##STR389## ##STR390##Rate kg/ha 0.06 0.015 0.25 0.06__________________________________________________________________________Soybeans 10G,8C 10G,7C 9G,6C 7G,4CVelvetleaf 10C 10C 9G,5C 7G,3CSesbania 10C 10C 4C,7G --Cassia 10G,8C 10G,8C 8G,4C 5G,3CCotton 10G,7C 10G,7C 8G,5C 7G,3CMorningglory 10C 10C 9G,5C 7G,4CAlfalfa 10C 9C 4C,9G 4C,9GJimsonweed -- 5G,2C -- --Cocklebur 10G,7C 10G,7C 10G,5C 10G,5CCorn 8G,5U 8G,4U 8G,8U 7G,7UCrabgrass 1G 1G 6G,3C 5GRice 8G,3C 6G 9G,6C 8G,5CNutsedge 1G 2G 7G,1C 3GBarnyardgrass 7G,3C 3G 10C 8G,5CWheat 0 0 5G,2C 4GGiant Foxtail 4G 4G,1C -- --Wild Oats 0 0 7G,4C 7G,4CSorghum 8G,3C 7G,3C 8G,5C 8G,4C__________________________________________________________________________ ##STR391## ##STR392##Rate kg/ha 0.25 0.06 0.12 0.03__________________________________________________________________________Soybeans 10G,7C 10G,7C 1H 1HVelvetleaf 10G,5C 7G,3C 3G,1C 5G,1CSesbania -- -- 1C 0Cassia 5C,8G 4C,7G 3C 0Cotton 9G,5C 4G,2C 2C 0Morningglory 9G,6C 9G,6C 7G,3C 6G,3CAlfalfa 9C 8C 3C,5G 3C,5GJimsonweed -- -- 3G --Cocklebur 10G,7C 10G,5C -- 0Corn 9G,9U 7G,9U 5G,3C 1G,2CCrabgrass 8G,6C 6G,3C 5G,1C 0Rice 8G,7C 9C 9G,3C 9G,2CNutsedge 7G,2C 5G,2C 4G,1C 0Barnyardgrass 10C 10C 9G,3C 3GWheat 7G,2C 5G 5G 0Giant Foxtail -- 10C 8G,3C 5G,2CWild Oats 8G,6C 8G,4C 8C --Sorghum 9G,6C 9G,4C 9G,4C 9G,3C__________________________________________________________________________ ##STR393## ##STR394##Rate kg/ha 0.12 0.03 0.12 0.03__________________________________________________________________________Soybeans 10G,7C 10G,6C 10G,6C 9G,5CVelvetleaf 7G,3C 4G,2C 8G,3C 5G,3CSesbania 10G,8C 9G,3C 8G,3C 5G,3CCassia 9G,5C 6G,4C 8G,6C 8G,6CCotton 8G,4C 7G,4C 8G,4C 6G,3CMorningglory 10G,7C 9G,3C 9G,4C 9G,3CAlfalfa 9C 8C 8C 7G,3CJimsonweed -- 10G,6C 8G,4C --Cocklebur 10G,7C 10G,6C 10G,6C 9G,3CCorn 8G,3C 5G,3C 10C 8G,5UCrabgrass 6G,1C 5G,2C 3C,7G 0Rice 8G,3C 5G 8C 8G,3CNutsedge 8G,3C 0 9G 3CBarnyardgrass 9G,2C 8G 10C 10CWheat 2G 0 7C 2GGiant Foxtail 8G,4C 8G,4C 10C 10CWild Oats -- 5G,3C 10C 8G,4CSorghum 9G,4C 9G,4C 10C 9G,4C__________________________________________________________________________ ##STR395## ##STR396##Rate kg/ha 0.03 0.12 0.03__________________________________________________________________________Soybeans 10G,7C 10G,7C 10G,7CVelvetleaf 7G,5C 10G,1C 9G,5CSesbania 9G,6C 10G,8C 10G,8CCassia 10G,7C 10G,7C 9G,5CCotton 8G,3C 9G,5C 9G,5CMorningglory 9G,4C 10G,8C 10G,5CAlfalfa 9C 9C 7CJimsonweed 7G,3C 9G,7C 5GCocklebur 10G,6C 10G,8C 10G,7CCorn 9G,2C 10C 9CCrabgrass 0 7G,3C 5GRice 7G 9G,3C 9G,3CNutsedge 9G,4C 10C 9G,3CBarnyardgrass 8C 10C 9CWheat 0 3G 1GGiant Foxtail 7G,3C 10C 8CWild Oats 1G 10C --Sorghum 9G,4C 10C 10C__________________________________________________________________________
TEST D
Two ten-inch in diameter plastic pans lined with polyethylene liners were filled with prepared Fallsington silt loam soil. One pan was planted with seeds of wheat (Triticum aestivum), barley (Hordeum vulgare), wild oats (Avena fatua), downy brome (Bromus tectorum), cheatgrass (Bromus secalinus), blackgrass (Alopecurus myosuroides), annual bluegrass (Poa annua), green foxtail (Setaria viridis), quackgrass (Agropyron repens), Italian ryegrass (Lolium multiflorum) and ripgut brome (Bromus rigidus). The other pan was planted with seeds of Russian thistle (Salsola kali), tansy mustard (Descuraina pinnata), smartweed (Polygonum pennsylvanicum), tumble mustard (Sisymbrium altissium) kochia (Kochia scoparia), shepherd's purse (Capsella bursa-pastoris), Matricaria inodora, black nightshade (Solanum nigrum), yellow rocket (Barbarea vulgaris), wild mustard (Brassica kaber) and wild buckwheat (Polygonum convolvulus). The above two pans were treated pre-emergence. At the same time two pans in which the above plant species were growing were treated post-emergence. Plant height at the time of treatment ranged from 1-15 cm depending on plant species.
The compounds applied were diluted with a non-phytotoxic solvent and sprayed over-the-top of the pans. An untreated control and a solvent alone control were included for comparison. All treatments were maintained in the greenhouse for 20 days at which time the treatments were compared to the controls and the effects visually rated in accordance with the rating system described for Test A. The recorded data are presented in Table D. The data indicate that certain compounds from within the scope of this invention have utility for weed control in cereal crops, such as wheat and barley.
TABLE D__________________________________________________________________________ ##STR397## ##STR398## Post-emergence Pre-emergence Post-emergence Pre-emergence Post-emergence Pre-emergence__________________________________________________________________________Rate kg/ha 0.06 0.06 0.25 0.25 0.25 0.25wheat 0 0 0 0 0 0barley 0 1C,2G 0 2C,2G 0 0wild oats 0 0 0 2G 0 0downy brome 1G 2C,2G 5C,4G 7C,6G 0 2Gcheatgrass 2G 2G 3C,7G 7C,8G 0 1Gblackgrass 2G 2C,3G 6G 3C,7G 2C,4G 2Gannual bluegrass 5G 5G 3C,6G 1C,7G 2G 3Ggreen foxtail 0 0 1C,1G 3C,4G 1C,2G 0quackgrass 0 1C,3G 0 4C,6G 1C,1G 0Italian ryegrass 2G 3G 1C,3G 4C,7G 3G 0ripgut brome 0 2G 0 3C,4G 0 0Russian thistle 10C 2C,3G 10C 3C,5G 2G 2Gtansy mustard 10C 10C 10C 10C 7C,6G 1C,2Gsmartweed -- -- -- -- -- --jimhill mustard 10C 8C,8G 10C 9C,9G 8C,7G 2C,2GKochia 0 7G 2C,3G 8G 5C,7G 3Gshepherd's purse 10C 9C,9G 10C 9C,9G 3C,4G 1C,2Gfalse chamomile 9C,9G 7C,8G 10C 8C,9G 0 0black nightshade 7C,8G 3C,7G 10C 7C,8G 2C,4G 1Gyellow rocket 9C,9G 7C,8G 10C 9C,9G 3C,5G 0wild mustard 10C 9C,8G 10C 9C,9G 10C 3C,5Gwild buckwheat 7C,7G 4C,6G 10C 8C,7G 1C,2G 1C,2G__________________________________________________________________________ ##STR399## ##STR400## Post-emergence Pre-emergence Post-emergence Pre-emergence Post-emergence Pre-emergence__________________________________________________________________________Rate kg/ha 0.06 0.06 0.015 0.015 0.06 0.06wheat 2C,2G 0 0 1C 0 1C,1Gbarley 7C,6G 0 0 0 3G 3Gwild oats 7C,7G 0 0 2C 0 1C,2Gdowny brome 6C,7G 2C,3G 0 2C,3G 2C,2G 5C,4Gcheatgrass 5C,6G 1C,3G 0 7C,7G 5C,6G 8C,8Gblackgrass 2C,3G 2C,3G 0 7C,8G 7C,8C 7C,8Gannual bluegrass 1C,2G 1C,5G 0 2C,3G 2C,3G 4C,7Ggreen foxtail 1C,1G 0 0 3G 3C,5G 6C,7Gquackgrass 5C,5G 0 0 1G 1C,2G 3C,4GItalian ryegrass 10C 0 0 0 1C 1C,6Gripgut brome 7C,7G 0 0 0 2G 1C,3GRussian thistle 0 2G 3C,4G 0 10C 10Ctansy mustard 2C,2G 5C,7G 10C 3C,5G 10C 10Csmartweed -- -- -- -- -- --jimhill mustard 7C,6G 3C,7G 10C 4C,8G 10C 9C,9GKochia 2G 3G 2C,2G 2G 7C,6G 3C,7Gshepherd's purse 3C,2G 3C,8G 5C,4G 7C,9G 10C 9C,9Gfalse chamomile 1C,2G 3G 3C,4G 2C,3G 7C,6G 7C,8Gblack nightshade 0 1C,2G 0 2C,2G 2C,4G 4C,7Gyellow rocket 1C,2G 7C,8G 2C,3G 8C,9G 10C 9C,9Gwild mustard 3C,4G 1C,4G 10C 7C,7G 10C 9C,9Gwild buckwheat 0 2C,2G 2C,3G 3G 8C,7G 7C,7G__________________________________________________________________________ ##STR401## Post-emergence Pre-emergence Post-emergence Pre-emergence__________________________________________________________________________ Rate kg/ha 0.015 0.015 0.06 0.06 wheat 1C,1G 0 6C,5G 0 barley 3C,2G 3G 8C,7G 3C,7G wild oats 6C,4G 2C,2G 10C 6C,6G downy brome 10C 3C,7G 10C 10C cheatgrass 8C,6G 7C,8G 10C 10C blackgrass 10C 7C,7G 10C 10C annual bluegrass 3C,5G 7C,8G 10C 10C green foxtail 8C,7G 3C,7G 10C 10C quackgrass 8C,7G 5G 10C 7C,7G Italian ryegrass 2C,3C 3G 10C 6C,7G ripgut brome 3C,4G 2G 10C 3C,7G Russian thistle 7C,6G 5C,4G 8C,7G 6C,7G tansy mustard 10C 9C,9G 10C 10C smartweed -- -- -- -- jimhill mustard 10C 8C,8G 10C 10C Kochia 0 3G 4C,5G 3C,7G shepherd's purse 8C,7G 9C,9G 10C 9C,9G false chamomile 7C,6G 3C,5G 10C 7C,8G black nightshade 0 2C,5G 3C,5G 3C,8G yellow rocket 10C 4C,8G 10C 9C,8G wild mustard 10C 7C,7G 10C 9C,9G wild buckwheat 7C,6G 3C,4G 9C,8G 4C,5G__________________________________________________________________________

Number	Name	Date
2990326	Aumuller et al.	Jun 1961
3409644	Muller et al.	Nov 1968
4293701	Pallos et al.	Oct 1981
4305884	Levitt	Dec 1981

Benezenesulfonylisocyanates

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