Benzylsulfonyl isocyanates

BACKGROUND OF THE INVENTION
This invention relates to novel benzylsulfonylureas. The compounds of this invention and their agriculturally suitable salts, are useful as agricultural chemicals, e.g., herbicides.
Netherlands Pat. No. 121,788, published Sept. 15, 1966, discloses the preparation of compounds of the following Formula 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.
U.S. Pat. No. 3,637,366 discloses compounds having the formula: ##STR2## wherein R.sub.1 is hydrogen or lower saturated aliphatic acyl; and
R.sub.2 is hydrogen, 2-pyrimidinyl, pyridyl, amidino, acetyl or carbamoyl.
The disclosed compounds are said to provide control of crabgrass, cress, endive, clover and Poa annua.
French Pat. No. 1,468,747 discloses the following para-substituted phenylsulfonamides as being useful as antidiabetic agents: ##STR3## wherein R=H, halogen, CF.sub.3 or alkyl.
Logemann et al., Chem. Ab., 53, 18052g (1959), disclose a number of sulfonamides, including uracil derivatives and those having the formula: ##STR4## wherein R is butyl, phenyl or ##STR5## and R.sub.1 is hydrogen or methyl.
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.
Wojciechowski, J. Acta. Polon. Pharm. 19, p. 121-5 (1962) [Chem. Ab., 59 1633 e] describes the synthesis of N-[(2,6-dimethoxypyrimidin-4-yl)aminocarbonyl]-4-methylbenzenesulfonamide: ##STR6## Based upon similarity to a known compound, the author speculated that the foregoing compound might have a hypoglycemic activity.
Substituted-pyrimidinyl sulfonylureas of the following formula, which are also para-substituted on the phenyl ring, are disclosed in Farmco Ed. Sco., 12, 586 (1957) [Chem. Ab., 53, 18052 g (1959)]: ##STR7## wherein R=H or CH.sub.3.
U.S. Pat. No. 4,127,405 teaches compounds which are useful for controlling weeds in wheat having the formula: ##STR8## wherein R.sub.1 is ##STR9## 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 atom;
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
Y 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.
The presence of undesired vegetation causes substantial damage to useful crops, especially agricultural products that satisfy man's basic food and fiber needs, such as cotton, rice, corn, wheat, and the like. The current population explosion and concomitant world food and fiber shortage demand improvements in the efficiency of producing these crops. Preventing or minimizing loss of a portion of such valuable crops by killing, or inhibiting the growth of undesired vegetation is one way of improving this efficiency. A wide variety of materials useful for killing or inhibiting (controlling) the growth of undesired vegetation is available; such materials are commonly referred to as herbicides. The need still exists however, for more effective herbicides.
SUMMARY OF THE INVENTION
This invention relates to compounds of Formula I and their agriculturally suitable salts, suitable agricultural compositions containing them, and their method-of-use as general and selective pre- and/or post-emergence herbicides and as plant growth regulants. ##STR10## wherein R.sub.1 is F, Cl, Br, CF.sub.3, C.sub.1 -C.sub.3 alkoxy, C.sub.1 -C.sub.3 alkyl, NO.sub.2, CO.sub.2 R.sub.4, SO.sub.2 R.sub.5, SO.sub.2 NR.sub.6 R.sub.7, SO.sub.2 N(OCH.sub.3)CH.sub.3, SO.sub.2 OCH.sub.2 CF.sub.3, OSO.sub.2 R.sub.5 or CH.sub.2 L;
L is SO.sub.2 NR.sub.6 R.sub.7, OCH.sub.3, OC.sub.2 H.sub.5, CO.sub.2 CH.sub.3 or CO.sub.2 C.sub.2 H.sub.5 ;
R.sub.2 is H, Cl, Br, F, CF.sub.3 or OCH.sub.3 ;
R.sub.4 is C.sub.1 -C.sub.3 alkyl, CH.sub.2 CH.dbd.CH.sub.2, CH.sub.2 CH.sub.2 Cl, or CH.sub.2 CH.sub.2 OCH.sub.3 ;
R.sub.5 is C.sub.1 -C.sub.3 alkyl or CF.sub.3 ;
R.sub.6 and R.sub.7 are independently C.sub.1 -C.sub.3 alkyl;
R.sub.8 is H or CH.sub.3 ;
R.sub.9 is H or C.sub.1 -C.sub.3 alkyl;
R.sub.3 is ##STR11## W is O or S; X is CH.sub.3, OCH.sub.3 or Cl;
Y is CH.sub.3, C.sub.2 H.sub.5, OCH.sub.3, OC.sub.2 H.sub.5, CH.sub.2 OCH.sub.3, NH.sub.2, NHCH.sub.3 or N(CH.sub.3).sub.2 ;
Z is CH or N;
X.sub.1 is H, Cl, CH.sub.3, OCH.sub.3 or OC.sub.2 H.sub.5 ;
X.sub.2 is CH.sub.3, C.sub.2 H.sub.5, OCH.sub.3 or OC.sub.2 H.sub.5 ;
X.sub.3 is CH.sub.3 or OCH.sub.3 ; and
Y.sub.1 is CH.sub.3 or OCH.sub.3 ;
and their agriculturally suitable salts; provided that:
(1) when W is S, then R.sub.8 is H;
(2) the total number of carbon atoms of R.sub.6 and R.sub.7 is less than or equal to 4; and
(3) when X is Cl, then Z is CH and Y is NH.sub.2, NHCH.sub.3, N(CH.sub.3).sub.2 or OCH.sub.3.
Preferred for their higher herbicidal activity and/or more favorable ease of synthesis are:
(1) Compounds of Formula I wherein
R.sub.2 is H;
R.sub.8 is H; and
W is O;
(2) Compounds of Preferred (1) wherein
R.sub.1 is CF.sub.3, NO.sub.2, C.sub.1 -C.sub.3 alkoxy, CO.sub.2 R.sub.4, SO.sub.2 R.sub.5, SO.sub.2 NR.sub.6 R.sub.7, SO.sub.2 N(OCH.sub.3)CH.sub.3 or OSO.sub.2 R.sub.5 ;
R.sub.9 is H;
X.sub.3 is OCH.sub.3 ; and
Y.sub.1 is OCH.sub.3 ;
(3) Compounds of Preferred (2) wherein
R.sub.4 is CH.sub.3 or C.sub.2 H.sub.5 ;
R.sub.5 is CH.sub.3 or CF.sub.3 ; and
R.sub.6 and R.sub.7 are independently CH.sub.3 or C.sub.2 H.sub.5 ;
(4) Compounds of Preferred (3) wherein R.sub.3 is ##STR12## (5) Compounds of Preferred (4) wherein R.sub.1 CF.sub.3, NO.sub.2, CO.sub.2 CH.sub.3, SO.sub.2 CH.sub.3, SO.sub.2 N(CH.sub.3).sub.2, SO.sub.2 N(OCH.sub.3)CH.sub.3 or OSO.sub.2 CH.sub.3 ; and
(6) Compounds of Preferred (5) wherein X and Y are independently CH.sub.3 or OCH.sub.3.
Specifically preferred are:
N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-1-(2-nitrophenyl)methanesulfonamide, m.p. 207.degree.-208.degree.;
N-[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]-1-(2-nitrophenyl)methanesulfonamide, m.p. 185.degree.-188.degree.;
N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-1-(2-nitrophenyl)methanesulfonamide, m.p. 194.degree.-195.degree.;
N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-1-(2-nitrophenyl)methanesulfonamide, m.p. 165.degree.-168.degree.;
N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-1-(2-nitrophenyl)methanesulfonamide, m.p. 192.degree.-194.degree.;
2-[[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]aminosulfonylmethyl]benzoic acid, methyl ester, m.p. 179.degree.-183.degree.;
2-[[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]aminosulfonylmethyl]benzoic acid, methyl ester, m.p. 154.degree.-156.degree.;
2-[[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]aminosulfonylmethyl]benzoic acid, methyl ester, m.p. 162.degree.-165.degree.;
2-[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]aminosulfonylmethyl]benzoic acid, methyl ester, m.p. 135.degree.-140.degree.;
2-[[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]aminosulfonylmethyl]benzoic acid, methyl ester, m.p. 165.degree.-167.degree.;
2-[[(4,6-dimethyl-1,3,5-triazin-2-yl)aminocarbonyl]aminosulfonylmethyl]benzoic acid, methyl ester, m.p. 125.degree.-130.degree.; and
N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-1-(2-methylsulfonyloxyphenyl)methanesulfonamide, m.p. 202.degree.-204.degree.(d).
This invention also relates to compounds of Formula II which are useful intermediates for the preparation of the herbicidal compounds of Formula I: ##STR13## wherein R.sub.1 is F, Cl, Br, CF.sub.3, C.sub.1 -C.sub.3 alkoxy, C.sub.1 -C.sub.3 alkyl, NO.sub.2, CO.sub.2 R.sub.4, SO.sub.2 R.sub.5, SO.sub.2 NR.sub.6 R.sub.7, SO.sub.2 N(OCH.sub.3)CH.sub.3, SO.sub.2 OCH.sub.2 CF.sub.3, OSO.sub.2 R.sub.5 or CH.sub.2 L;
L is SO.sub.2 NR.sub.6 R.sub.7, OCH.sub.3, OC.sub.2 H.sub.5, CO.sub.2 CH.sub.3 or CO.sub.2 C.sub.2 H.sub.5 ;
R.sub.2 is H, Cl, Br, F, CF.sub.3 or OCH.sub.3 ;
R.sub.4 is C.sub.1 -C.sub.3 alkyl, CH.sub.2 CH.dbd.CH.sub.2, CH.sub.2 CH.sub.2 Cl, or CH.sub.2 CH.sub.2 OCH.sub.3 ;
R.sub.5 is C.sub.1 -C.sub.3 alkyl or CF.sub.3 ;
R.sub.6 and R.sub.7 are independently C.sub.1 -C.sub.3 alkyl; and
R.sub.9 is H or C.sub.1 -C.sub.3 alkyl;
provided that the total number of carbon atoms of R.sub.6 and R.sub.7 is less than or equal to 4.
Preferred intermediates for their more favorable ease of synthesis and/or the higher herbicidal activity of the derived products are:
(1) Compounds of Formula II wherein R.sub.2 is H;
(2) Compounds of Preferred (1) wherein R.sub.1 is CF.sub.3, NO.sub.2, C.sub.1 -C.sub.3 alkoxy, CO.sub.2 R.sub.4, SO.sub.2 R.sub.5, SO.sub.2 NR.sub.6 R.sub.7, SO.sub.2 N(OCH.sub.3)CH.sub.3 or OSO.sub.2 R.sub.5 ; and
(3) Compounds of Preferred (2) wherein
R.sub.4 is CH.sub.3 or C.sub.2 H.sub.5 ;
R.sub.5 is CH.sub.3 or CF.sub.3 ; and
R.sub.6 and R.sub.7 are independently CH.sub.3 or C.sub.2 H.sub.5.
Especially preferred as a selective herbicide for rice are compounds of the following formula: ##STR14## wherein R.sub.1 is Cl, NO.sub.2, CO.sub.2 CH.sub.3, SO.sub.2 CH.sub.3 OSO.sub.2 CH.sub.3 or SO.sub.2 N(CH.sub.3).sub.2
SYNTHESIS
The compounds of Formula I, where W=O, may be prepared as shown below in Equation 1 by the reaction of an appropriate benzenemethanesulfonyl isocyanate, II with an appropriate aminoheterocycle, III. ##STR15## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.8 and R.sub.9 are as previously defined.
The reaction of Equation 1 is best carried out in an inert aprotic solvent such as methylene chloride, tetrahydrofuran or acetonitrile at a temperature between 20.degree. and 80.degree.. A catalytic amount of 1,4-diazabicyclo[2,2,2]octane (DABCO) may be used to accelerate the reaction. In cases in which the products are insoluble in the reaction solvent, they may be isolated by simple filtration. When the products are soluble, they may be isolated by evaporation of the solvent and trituration of the residue with solvents such as 1-chlorobutane, diethyl ether or methanol and filtration.
Compounds of Formula I in which W=S and R.sub.8 =H may be prepared by the reaction shown in Equation 2. ##STR16## wherein R.sub.1, R.sub.2, R.sub.3, and R.sub.9 are as previously defined.
The reaction of Equation 2 is best carried out by suspending the sulfonamide, the isothiocyanate and an equivalent of a base such as anhydrous potassium carbonate in a solvent such as acetone, methyl ethyl ketone, acetonitrile or ethyl acetate. The reaction is stirred at 25.degree.-80.degree. for 1 to 24 hours. In some cases, the product precipitates from the reaction mixture and can be filtered off, suspended in dilute mineral acid, filtered again and washed with cold water. If the product does not precipitate, it can be isolated by evaporation of the solvent, trituration of the residue with dilute mineral acid and filtration of the insoluble product.
The heterocyclic isothiocyanates, V, which are used in the procedure of Equation 2 are prepared 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, G91-7 (1973) both of which are herein incorporated by reference.
The benzenemethanesulfonyl isocyanates of Formula II may be prepared as shown in Equation 3, by phosgenation of the sulfonamides of Formula IV in the presence of butyl isocyanate. The sulfonyl isocyanates of Formula II may also be prepared, as shown in Equation 4, by phosgenation of the butyl ureas of Formula VI. ##STR17## wherein R.sub.1, R.sub.2 and R.sub.9 are as previously defined.
The above reaction is carried out by heating a mixture of the appropriate sulfonamide (IV), an alkyl isocyanate such as butyl isocyanate and a catalytic amount of a tertiary amine such as 1,4-diazabicyclo[2,2,2]octane (DABCO) in xylene, or other inert solvent of boiling point .gtoreq.135.degree., to approximately 135.degree.. Phosgene is then added to the mixture over a 1-6 hour period at 125.degree.-135.degree. until an excess of phosgene is present as indicated by a permanent drop in the boiling point to less than 130.degree.. The mixture is cooled and filtered to remove a small amount of insoluble by-products. The solvent and the alkyl isocyanate are distilled off in vacuo leaving a residue of the crude, sulfonyl isocyanate, II, which can be used without further purification. ##STR18## wherein R.sub.1, R.sub.2 and R.sub.9 are as previously defined.
The compounds of Formula VI are conveniently prepared by stirring a mixture of the sulfonamides, IV, anhydrous potassium carbonate, and n-butyl isocyanate in acetone or methyl ethyl ketone at 25.degree.-80.degree. until all of the isocyanate has reacted. The products are isolated by quenching in dilute mineral acid and recrystallizing the solid product. The compounds VI are treated with phosgene and a catalytic amount of DABCO in refluxing xylene or chlorobenzene in a manner analogous to that described in Equation 3. The sulfonamides of Formula IV can be prepared from the appropriately substituted benzyl chlorides or benzyl bromides VII by the sequence of reactions described in Equation 5 below. ##STR19## wherein: A is chlorine or bromine; and
R.sub.1, R.sub.2 and R.sub.9 are as previously defined.
Equation (5a)
In Equation (5a) a benzyl halide of Formula VII is reacted with thiourea in protic solvents such as methanol or ethanol, or aprotic solvents such as methylene chloride or benzene. Temperatures of 40.degree.-80.degree. over one-half to 4 hours are typically required to complete the reaction. The product salts, VIII, are isolated by cooling and filtration or by concentration to remove the solvent. The salts, VIII, are generally sufficiently pure to be carried on directly to step (5b) without further purification.
Equation (5b)
In Equation (5b), the hydrochloride salts VIII (A=chlorine) are suspended in water and contacted with at least three equivalents of chlorine at between 5.degree. and 20.degree.. When the corresponding hydrobromide salts VIII (A=bromine) are used, it is generally advantageous to exchange the bromide ion for the nitrate ion before chlorination by treatment with an aqueous solution of one equivalent of silver nitrate; the precipitated silver bromide is removed by filtration and the filtrate treated as described above. The product sulfonyl chlorides of Formula IX are isolated by filtration and washing with water. No further purification of the sulfonyl chlorides IX is necessary.
Equation (5c)
In Equation (5c), the sulfonyl chlorides of Formula IX are suspended in an aprotic solvent such as diethyl ether, 1-chlorobutane, methylene chloride, or tetrahydrofuran and contacted with an excess of anhydrous ammonia at a temperature of 0.degree. to 25.degree.. The product sulfonamides of Formula IV are isolated by filtration and washing with water to remove the by-product ammonium chloride and concentrating the organic solution. Frequently, the crude sulfonamides may be used directly to prepare the sulfonyl isocyanates of Formula II. However, they may also be purified first by recrystallization from a suitable organic solvent such as ethanol, acetonitrile or chloroform.
The synthesis of heterocyclic amine derivatives such as those depicted by Formula III has been reviewed in "The Chemistry of Heterocyclic Compounds", a series published by Interscience Publ., New York and London. Aminopyrimidines are described by D. J. Brown in "The Pyrimidines", Vol. XVI of the above series.
The synthesis of the bicyclic pyrimidines of Formula III is described in the following references:
Braker, Sheehan, Spitzmiller and Lott, J. Am. Chem. Soc., 69, 3072 (1947);
Mitter and Bhattacharya, Quart. J. Indian. Chem. Soc., 4, 152 (1927);
Shrage and Hitchings, J. Org. Chem., 16, 1153 (1951);
E. Bisayni et al., Bull. Soc. Chem. Fr., 803 (1969);
Caldwell, Kornfeld and Donnell, J. Am. Chem. Soc., 63, 2188 (1941); and
Fissekis, Myles and Brown, J. Org. Chem., 29, 2670 (1964).
All of the above are herein incorporated by reference.
Agriculturally suitable salts of compounds of Formula I are also useful herbicides and can be prepared in a number of ways known to the art. For example, metal salts can be made by treating compounds of Formula I with a solution of an alkali or alkaline earth metal salts having a sufficiently basic anion (e.g. hydroxide, alkoxide, carbonate or hydride) quaternary amine salts can be made by similar techniques. Detailed examples of such techniques are given in U.S. Pat. No. 4,127,405, the disclosure of which is herein incorporated by reference.
The compounds of this invention and their preparation are further illustrated by the following examples wherein temperatures are given in degrees centigrade and all parts are by weight unless otherwise indicated.

EXAMPLE 1
2-Nitrophenylmethyl carbamidothioate hydrochloride
A solution of 153.9 g of o-nitrobenzylchloride and 68.5 g of thiourea in 900 ml of #2B ethanol was stirred at reflux temperature (80.degree.) for 11/4 hours. The solution was cooled to 60.degree. and 1.1 liters of 1-chlorobutane was added. Further cooling to 15.degree. produced a heavy precipitate. The precipitate was filtered, washed with 1-chlorobutane and dried to yield 185.9 g of 2-nitrophenylmethyl carbamimidothioate hydrochloride, m.p. 190.degree.-192.degree..
NMR (DMSO-d.sub.6).delta.: 4.85 (s, 1.84, --CH.sub.2 --); 7.4-8.4 (m, 4.2H, 4 aromatics); 9.7 (broad singlet, 4.0H, 4 NH's).
EXAMPLE 2
2-Nitrophenylmethanesulfonyl chloride
To a suspension of 34.7 g of the product of Example 1 in 300 ml of water was added 24.0 ml of liquid chlorine at 10.degree.-15.degree. over a 45 minute period. After stirring an additional 30 minutes at 10.degree.-12.degree. the product was filtered off, washed with water and air dried in a fume hood overnight to give 31.6 g of 2-nitrophenylmethanesulfonyl chloride, m.p. 62.5.degree.-64.0.degree..
EXAMPLE 3
2-Nitrophenylmethanesulfonamide
To a suspension of 29.4 g of the product of Example 2 in 250 ml of diethyl ether was added 6.5 ml of anhydrous ammonia at 5.degree.-15.degree.. After stirring at 15.degree.-25.degree. for 1 hour, the product was filtered off, washed with ether, and water and oven dried at 60.degree. to give 20.5 g of 2-nitrophenylmethanesulfonamide, m.p.=134.degree.-136.degree..
NMR (DMSO-d.sub.6).delta.: 4.7 (s, 1.8H, --CH.sub.2 --); 6.8-7.3 (broad singlet, 1.8H, --SO.sub.2 NH.sub.2); 7.5-8.3 (m, 4.4H, 4 aromatics).
EXAMPLE 4
2-Nitrophenylmethanesulfonyl isocyanate
A solution of 9.0 g of the product of Example 3, 4.2 g of butyl isocyanate and 0.1 g of DABCO in 80 ml of dry xylenes was heated to 136.degree.. To this solution was added 3.0 ml of liquid phosgene at such a rate as to maintain the temperature between 125.degree. and 136.degree.. This addition required about 21/2 hours. The solution was cooled to 25.degree., filtered under nitrogen and stripped in vacuo to give crude 2-nitrophenylmethanesulfonyl isocyanate as a viscous, moisture-sensitive oil showing a sulfonyl isocyanate peak in the infrared at 2230 cm.sup.-1.
EXAMPLE 5
N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-1-(2-nitrophenyl)methanesulfonamide
Under a nitrogen atmosphere, a mixture of 2.2 g of the product of Example 4, 0.9 g of 4,6-dimethoxy-2-aminopyrimidine and a few crystals of DABCO in 15 ml of dry acetonitrile was heated at 50.degree.-55.degree. for 1 hour, followed by stirring at room temperature overnight. The product was filtered, washed first with acetonitrile then 1-chlorobutane and oven dried in vacuo at 60.degree. to give 1.8 g of N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-1-(2-nitrophenyl)methanesulfonamide, m.p.=207.degree.-208.degree.(d).
NMR (DMSO-d.sub.6).delta.: 3.8 (s, 6.1H, Het-OCH.sub.3 's); 5.3 (s, 1.8H, --CH.sub.2 --); 6.0 (s, 1.0H, Het-H); 7.7-8.3 (m, 4.1H, 4 aromatics); 10.9 (s, 1.0 H, NH); .about.12.5 (broad singlet, 0.9H, NH).
Anal. Calcd. for C.sub.14 H.sub.15 N.sub.5 O.sub.7 S: C, 42.31; H, 3.80; N, 17.63. Found: C, 42.6, 42.6; H, 3.9, 3.9; and N, 17.7, 17.8.
EXAMPLE 6
2-(Methylsulfonyl)phenylmethyl carbamimidothioate hydrobromide
A solution of 36.5 g of 2-(methylsulfonyl)benzyl bromide and 11.4 g of thiourea in 500 ml absolute ethanol was stirred at reflux temperature for 11/2 hours and then allowed to cool to room temperature. Upon standing, the solution yielded white feather-like crystals which were collected by filtration, washed with cold 1-chlorobutane, and dried in vacuo. The yield of 2-(methylsulfonyl)phenylmethyl carbamimidothioate hydrobromide, m.p. 203.degree.-206.degree. C., was 36.3 g.
NMR (DMSO-d.sub.6).delta.: 3.3 (s, 3H, --CH.sub.3); 4.9 (s, 2H, --CH.sub.2 --); 7.6-8.1 (m, 4H, aromatics); 9.4 (broad singlet, 4H, NH's).
EXAMPLE 7
2-(Methylsulfonyl)phenylmethanesulfonyl chloride
A solution of 29.5 g of the product from Example 6 in 450 ml water was reacted with 15.5 g of silver nitrate in 45 ml water. The resulting precipitate of silver bromide was removed by filtration and washed with 50 ml water. The aqueous filtrate was then diluted with 180 ml of glacial acetic acid and reacted with 15 ml of liquid chlorine at 0.degree.-5.degree. C., added over a period of 30 minutes. The reaction mixture was stirred for an additional 13/4 hours while the temperature was allowed to rise to 25.degree. C. The light yellow solid was collected by filtration, washed with water and air-dried in a fume hood overnight to yield 22 g of 2-(methylsulfonyl)phenylmethanesulfonyl chloride which was used without further purification.
NMR (DMSO-d.sub.6).delta.: 3.4 (s, 3H, --CH.sub.3); 4.4 (s, 2H, --CH.sub.2 --); 7.5-7.9 (m, 4H, aromatics).
EXAMPLE 8
2-(Methylsulfonyl)phenylmethanesulfonamide
To a suspension of 22 g of the product from Example 7 in 500 ml dry diethyl ether was added 25 ml anhydrous ammonia at 0.degree.-5.degree. C. The reaction mixture was stirred at 5.degree.-15.degree. C. for 45 minutes and then allowed to warm to room temperature over a one hour period. The solvent was removed in vacuo and the resulting solids were washed with water and ether. Further evaporation of the solvent in vacuo afforded 4.6 g of (2-methylsulfonyl)phenylmethanesulfonamide, m.p. 124.degree.-127.degree. C., as a tan solid.
NMR (DMSO-d.sub.6).delta.: 3.3 (s, 3H, --CH.sub.3); 5.0 (s, 2H, --CH.sub.2 --); 7.6-7.8 (m, 3H, aromatics); 8.0 (m, 1H, aromatic).
IR(KBr): 3320, 3260, 1340, 1300, 1150 cm.sup.-1.
EXAMPLE 9
N-[(n-butyl)aminocarbonyl]-2-(methylsulfonyl)phenylmethanesulfonamide
A mixture of 5.0 g of the product from Example 8, 4.2 g of anhydrous potassium carbonate, and 3.4 ml of n-butyl isocyanate in 60 ml methyl ethyl ketone was heated to reflux tiemperature for 5 hours. After cooling to room temperature, the solution was poured into 200 ml ice-water. This aqueous solution was acidified to ca. pH 1 by the slow addition of concentrated hydrochloric acid resulting in a white precipitate. The solids were filtered, washed with water, 1-chlorobutane, and then dried in a vacuum desiccator to give 6.2 g of N-[(n-butyl)aminocarbonyl]-2-(methylsulfonyl)phenylmethanesulfonamide as a tan solid, m.p. 149.degree.-151.degree. C. (dec.).
NMR (DMSO-d.sub.6).delta.: 0.9-1.6 (m, 7H, --CH.sub.2 CH.sub.2 CH.sub.3); 3.0-3.2 (m, 2H, --CH.sub.2 --); 3.4 (s, 3H, --CH.sub.3); 5.4 (s, 2H, --CH.sub.2 --); 6.6 (br s, 1H, N-H); 7.6-7.9 (m, 3H, aromatics); 8.0-8.2 (m, 1H, aromatic).
IR(KBr): 3350, 3250, 1700, 1320, 1150 cm.sup.-1.
EXAMPLE 10
2-(Methylsulfonyl)phenylmethanesulfonyl isocyanate
A suspension of 5.5 g of the product from Example 9 and 0.1 g of 1,4-diazabicyclo[2.2.2]octane (DABCO) in 100 ml dry xylenes was heated to 125.degree.-130.degree. C. under an atmosphere of nitrogen. At this temperature, 2.5 ml of phosgene was added dropwise at a rate that maintained the temperature above 120.degree. C. After completion of the addition (ca. one hour), the solution was heated at 125.degree. C. for another two hours. After cooling to room temperature, the mixture was filtered under nitrogen and concentrated in vacuo to afford crude 2-(methylsulfonyl)phenylmethanesulfonyl isocyanate as a yellow semisolid which was carried on to the next step without purification. The IR spectrum of this intermediate displayed a characteristic isocyanate absorption at 2240 cm.sup.-1.
EXAMPLE 11
N-[(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl]-2-(methylsulfonyl)phenylmethanesulfonamide
To a solution of 3.0 g of the product from Example 10 in 30 ml dry dichloromethane was added 1.2 g of 4,6-dimethoxy-2-aminopyrimidine and the yellow homogeneous solution was stirred at room temperature overnight. The desired product, which had precipitated, was collected by filtration, washed with 1-chlorobutane, and dried in vacuo. The yield of N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-(methylsulfonyl)phenylmethanesulfonamide, m.p. 180.degree.-182.degree. C., was 2.4 g of white solid.
NMR (DMSO-d.sub.6).delta.: 3.8 (s, 6H, heterocyclic OCH.sub.3 's); 5.4 (s, 2H, --CH.sub.2 --); 6.0 (s, 1H, heterocyclic H); 7.6-8.0 (m, 4H, aromatics); 10.6 (br s, 1H, N-H).
IR(KBr): 1730, 1610, 1580, 1370, 1350, 1150 cm.sup.-1.
EXAMPLE 12
1-(2-Nitrophenyl)ethyl carbamimidothioate hydrobromide
A solution of 33.5 g of 1-(2-nitrophenyl)ethyl bromide and 11.4 g of thiourea in 375 ml absolute ethanol was stirred at reflux temperature for 31/2 hours. The reaction mixture was allowed to cool to room temperature and was concentrated to one-half volume in vacuo. The solution was then cooled to ca. -60.degree. C. and 1-chlorobutane was added until a gummy solid formed. The supernatant was decanted and the residue dried in vacuo to give 38 g of 1-(2-nitrophenyl)ethyl carbamimidothioate hydrobromide as a light orange solid which was not further purified.
NMR (DMSO-d.sub.6).delta.: 3.7 (br d, J=7 Hz, 3H, --CH.sub.3); 5.5 ##STR20## 7.5-8.0 (m, 4H, aromatics); 9.4 (br s, 4H, N-H's).
EXAMPLE 13
1-(2-Nitrophenyl)ethanesulfonyl chloride
A solution of 37.6 g of the product from Example 12 in 700 ml water was reacted with 21.9 g of silver nitrate in 60 ml water. The resulting precipitate of silver bromide was removed by filtration and washed with water. Glacial acetic acid (250 ml) was added to the aqueous filtrate and this solution was cooled to 0.degree. C. and treated with 23 ml of liquid chlorine, added over a period of about 45 minutes. After being stirred for one hour at 0.degree.-5.degree. C., the reaction mixture was allowed to warm to room temperature over an additional one hour period. The solids which had formed were filtered and washed with water. Air-drying overnight in a fume hood gave 27.5 g of 1-(2-nitrophenyl)ethanesulfonyl chloride as a light yellow solid.
NMR (DMSO-d.sub.6).delta.: 2.1 (d, J=7 Hz, 3H, --CH.sub.3); 6.2 ##STR21## 7.6-8.1 (m, 4H, aromatics);
IR(KBr): 1530, 1350, 1160 cm.sup.-1.
EXAMPLE 14
1-(2-Nitrophenyl)ethanesulfonamide
Liquid anhydrous ammonia (10 ml) was added to a stirred suspension of the product from Example 13 in 350 ml dry diethyl ether at 0.degree.-5.degree. C. over a period of 20 minutes. The reaction mixture was stirred at 0.degree.-5.degree. C. for 30 minutes and was allowed to warm to room temperature over a two hour period. The solids were filtered and washed with diethy ether. Concentration of the filtrate in vacuo gave a yellow solid which was washed with water, 1-chlorobutane, and then dried under vacuum to yield 17 g of 1-(2-nitrophenyl)ethanesulfonamide as a pale yellow solid, m.p. 107.degree.-109.degree. C.
NMR (DMSO-d.sub.6).delta.: 1.7 (d, J=7 Hz, 3H, --CH.sub.3); 5.0 ##STR22## 7.0 (br s, 2H, NH.sub.2); 7.4-8.0 (m, 4H, aromatics).
IR(KBr): 3340, 3260, 1350, 1310, 1160 cm.sup.-1.
EXAMPLE 15
1-(2-Nitrophenyl)ethanesulfonyl isocyanate
A mixture of 16 g of the product from Example 14, 8.0 ml of n-butyl isocyanate, and 0.2 g of 1,4-diazabicyclo[2.2.2]octane (DABCO) in 125 ml dry xylenes was heated to 130.degree.-135.degree. C. for 11/2 hours. To this solution was added 6 ml of phosgene at a rate which maintained the temperature above 130.degree. C. After completion of the addition (ca. one hour), the solution was cooled and filtered under nitrogen. The filtrate was concentrated in vacuo to give the crude 1-(2-nitrophenyl)ethanesulfonyl isocyanate as a viscous orange oil. The IR spectrum of this compound displayed a characteristic isocyanate absorption at 2240 cm.sup.-1.
EXAMPLE 16
N-[(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl]-1-(2-nitrophenyl)ethanesulfonamide
A solution of 4.0 g of the product from Example 15 and 2.2 g of 4,6-dimethoxy-2-aminopyrimidine in 29 ml dry acetonitrile was heated to ca. 60.degree. C. for 11/2 hours and then stirred at room temperature overnight. The product, which had precipitated, was collected and washed with 1-chlorobutane and then dried in vacuo. The yield of N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-1-(2-nitrophenyl)ethanesulfonamide was 3.1 g white solid, m.p. 168.degree.-170.degree. C.
NMR (DMSO-d.sub.6).delta.: 1.8 (d, J=7 Hz, 3H, --CH.sub.3); 3.8 (s, 6H, heterocyclic OCH.sub.3 's); 5.6 (q, J=7 Hz, 1H, ##STR23## 5.8 (s, 1H, heterocyclic H); 7.6-8.0 (m, 4H, aromatics); 10.6 (br s, 1H, N-H).
IR(KBr): 1720, 1610, 1580, 1360, 1200, 1150 cm.sup.-1.
Using the procedures and examples described above and choosing the appropriate aminoheterocyclic and sulfonyl isocyanate, the compounds described in Tables 1-8 may be prepared.
The sulfonylisocyanate intermediates described in Table 9 may also be prepared using the procedures and examples described above.
TABLE 1__________________________________________________________________________ ##STR24##R.sub.1 R.sub.2 W R.sub.8 R.sub.9 X Y m.p. (.degree.C.)__________________________________________________________________________NO.sub.2 H O H H CH.sub.3 O CH.sub.3 O 207-208.degree. (d)NO.sub.2 H O H H CH.sub.3 O CH.sub.3 194-195.degree. (d)NO.sub.2 H O H H CH.sub.3 CH.sub.3 192-194.degree. (d)Cl H O H H CH.sub.3 O CH.sub.3 O 209-211.degree. (d)Cl H O H H CH.sub.3 O CH.sub.3 184-185.degree. (d)Cl H O H H CH.sub.3 CH.sub.3 202- 204.degree. (d)CO.sub.2 CH.sub.3 H O H H CH.sub.3 O CH.sub.3 O 179-183.degree.CO.sub.2 CH.sub.3 H O H H CH.sub.3 CH.sub.3 O 162-165.degree.CO.sub.2 CH.sub.3 H O H H CH.sub.3 CH.sub.3 165-167.degree.CH.sub.3 H O H H CH.sub.3 O CH.sub.3 O 214-216.degree. (d)CH.sub.3 H O H H CH.sub.3 CH.sub.3 O 173-175.degree. (d)CH.sub.3 H O H H CH.sub.3 CH.sub.3 192-193.5.degree. (d)F H O H H CH.sub.3 O CH.sub.3Br H O H H CH.sub.3 O CH.sub.3CH.sub.3 O H O H H CH.sub.3 O CH.sub.3 ##STR25## H O H H CH.sub.3 O CH.sub.3CO.sub.2 CH.sub.2 CH.sub.2 Cl H O H H CH.sub.3 O CH.sub.3CO.sub.2 CH.sub.2 CHCH.sub.2 H O H H CH.sub.3 O CH.sub.3CO.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 H O H H CH.sub.3 O CH.sub.3CH.sub.3 SO.sub.2 H O H H CH.sub.3 O CH.sub.3n-C.sub.3 H.sub.7 SO.sub.2 H O H H CH.sub.3 O OCH.sub.3 179-181.degree.CF.sub.3 SO.sub.2 H O H H CH.sub.3 O CH.sub.3CF.sub.3 H O H H CH.sub.3 O CH.sub.3 ##STR26## H O H H CH.sub.3 O CH.sub.3CO.sub.2 C.sub.2 H.sub.5 H O H H CH.sub.3 CH.sub.3CO.sub.2 C.sub.2 H.sub.5 H O H H CH.sub.3 CH.sub.3 OCO.sub.2 C.sub.2 H.sub.5 H O H H CH.sub.3 O CH.sub.3 OSO.sub.2 N(CH.sub.3).sub.2 H O H H CH.sub.3 O CH.sub.3 142-145.degree.SO.sub.2 N(CH.sub.3).sub.2 H O H H CH.sub.3 O CH.sub.3 O 167-170.degree. ##STR27## H O H H CH.sub.3 O CH.sub.3 ##STR28## H O H H CH.sub.3 O CH.sub. 3CH.sub.3 SO.sub.2 O H O H H CH.sub.3 O CH.sub.3 169-171.degree. (d)n-C.sub.3 H.sub.7 SO.sub.2 O H O H H CH.sub.3 O CH.sub.3CF.sub.3 SO.sub.2 O H O H H CH.sub.3 O CH.sub.3NO.sub.2 3-Cl O H H CH.sub.3 O CH.sub.3NO.sub.2 5-Cl O H H CH.sub.3 O CH.sub.3NO.sub.2 6-Cl O H H CH.sub.3 O CH.sub.3NO.sub.2 5-Br O H H CH.sub.3 O CH.sub.3NO.sub.2 5-F O H H CH.sub.3 O CH.sub.3NO.sub.2 5-CF.sub.3 O H H CH.sub.3 O CH.sub.3NO.sub.2 5-OCH.sub.3 O H H CH.sub.3 O CH.sub.3CO.sub.2 CH.sub.3 5-Cl O H H CH.sub.3 O CH.sub.3CO.sub.2 CH.sub.3 5-CF.sub.3 O H H CH.sub.3 O CH.sub.3CO.sub.2 CH.sub.3 6-Cl O H H CH.sub.3 O CH.sub.3CO.sub.2 CH.sub.3 5-Br O H H CH.sub.3 O CH.sub.3CO.sub.2 CH.sub.3 5-F O H H CH.sub.3 O CH.sub.3CO.sub.2 CH.sub.3 5-OCH.sub.3 O H H CH.sub.3 O CH.sub.3CO.sub.2 CH.sub.3 H O H H CH.sub.3 CH.sub.3 CH.sub.2 OCO.sub.2 CH.sub.3 H O H H CH.sub.3 O CH.sub.3 CH.sub.2 OCO.sub.2 CH.sub.3 H O H H CH.sub.3 CH.sub.3 OCH.sub.2CO.sub.2 CH.sub.3 H O H H CH.sub.3 O CH.sub.3 OCH.sub.2CH.sub.3 SO.sub.2 O H O H H CH.sub.3 O CH.sub.3 O 202-204.degree. (d)CH.sub.3 SO.sub.2 O H O H H CH.sub.3 CH.sub.3 172-178.degree. (d)CH.sub.3 SO.sub.2 H O H H CH.sub.3 O CH.sub.3 O 180-182.degree.NO.sub.2 H O H CH.sub.3 CH.sub.3 O CH.sub.3 O 168-170.degree.NO.sub.2 H O H CH.sub.3 CH.sub.3 O CH.sub.3 119-121.degree.NO.sub.2 H O H CH.sub.3 CH.sub.3 CH.sub.3 140-144.degree.NO.sub.2 H S H H CH.sub.3 O CH.sub.3CO.sub.2 CH.sub.3 H O H CH.sub.2 CH.sub.3 CH.sub.3 O CH.sub.3CO.sub. 2 CH.sub.3 H O H i-C.sub.3 H.sub.7 CH.sub.3 O CH.sub.3CO.sub.2 CH.sub.3 H O CH.sub.3 H CH.sub.3 O CH.sub.3CO.sub.2 CH.sub.3 H O H H Cl CH.sub.3 OCl H O CH.sub.3 H CH.sub.3 O CH.sub.3 OCl H S H H CH.sub.3 O CH.sub.3Cl H O H H Cl NH.sub.2Cl H O H H Cl NHCH.sub.3CH.sub.3 H O H H Cl N(CH.sub.3).sub.2CH.sub.3 H S H H CH.sub.3 O CH.sub.3CH.sub.2 CH.sub.3 H O CH.sub.3 H CH.sub.3 O CH.sub.3 Oi-C.sub.3 H.sub.7 H O H H CH.sub.3 O CH.sub.3SO.sub.2 OCH.sub.2 CF.sub.3 H O H H CH.sub.3 O CH.sub.3CO.sub.2 CH.sub.3 H O H H CH.sub.3 O CH.sub.2 CH.sub.3OCH.sub.2 CH.sub.3 H O H H CH.sub.3 O CH.sub.3 ##STR29## H O H H CH.sub.3 O CH.sub.3CH.sub.2 SO.sub.2 N(CH.sub.3).sub.2 H O H H CH.sub.3 O CH.sub.3 ##STR30## H O H H CH.sub.3 O CH.sub.3CH.sub.2 SO.sub.2 N(CH.sub.3)Et H O H H CH.sub.3 O CH.sub.3CH.sub.2 OCH.sub.3 H O H H CH.sub.3 O CH.sub.3CH.sub.2 OEt H O H H CH.sub.3 O CH.sub.3CH.sub.2 CO.sub.2 CH.sub.3 H O H H CH.sub.3 O CH.sub.3CH.sub.2 CO.sub.2 Et H O H H CH.sub.3 O CH.sub.3OCH.sub.3 H O H H CH.sub.3 O CH.sub.3CO.sub.2 CH.sub.3 H O H H CH.sub.3 O NH.sub.2CO.sub.2 CH.sub.3 H O H H CH.sub.3 O NHCH.sub.3CO.sub.2 CH.sub.3 H O H H CH.sub.3 O N(CH.sub.3).sub.2CO.sub.2 CH.sub.3 H O H H CH.sub.3 NH.sub.2CO.sub.2 CH.sub.3 H O H H CH.sub.3 NHCH.sub.3CO.sub.2 CH.sub.3 H O H H CH.sub.3 N(CH.sub.3).sub.2CO.sub.2 CH.sub.3 H O H H CH.sub. 3 CH.sub.2 CH.sub.3__________________________________________________________________________
TABLE 2__________________________________________________________________________ ##STR31##R.sub.1 R.sub.2 W R.sub.8 R.sub.9 X Y m.p. (.degree.C.)__________________________________________________________________________NO.sub.2 H O H H CH.sub.3 O CH.sub.3 O 185-188.degree. (d)NO.sub.2 H O H H CH.sub.3 O CH.sub.3 165-168.degree. (d)NO.sub.2 H O H H CH.sub.3 CH.sub.3Cl H O H H CH.sub.3 O CH.sub.3 O 198-199.degree. (d)Cl H O H H CH.sub.3 O CH.sub.3 193-195.degree. (d)Cl H O H H CH.sub.3 CH.sub.3 212-214.degree. (d)CO.sub.2 CH.sub.3 H O H H CH.sub.3 O CH.sub.3 O 154-156.degree.CO.sub.2 CH.sub.3 H O H H CH.sub.3 CH.sub.3 O 135-140.degree.CO.sub.2 CH.sub.3 H O H H CH.sub.3 CH.sub.3 125-130.degree.CH.sub.3 H O H H CH.sub.3 O CH.sub.3 O 185-189.degree. (d)CH.sub.3 H O H H CH.sub.3 CH.sub.3 O 177-179.degree. (d)CH.sub.3 H O H H CH.sub.3 CH.sub.3 197.5-199.degree. (d)F H O H H CH.sub.3 O CH.sub.3Br H O H H CH.sub.3 O CH.sub.3CH.sub.3 O H O H H CH.sub.3 O CH.sub.3 ##STR32## H O H H CH.sub.3 O CH.sub.3CO.sub.2 CH.sub.2 CH.sub.2 Cl H O H H CH.sub.3 O CH.sub.3CO.sub.2 CH.sub.2 CHCH.sub.2 H O H H CH.sub.3 O CH.sub.3CO.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 H O H H CH.sub.3 O CH.sub.3CH.sub. 3 SO.sub.2 H O H H CH.sub.3 O CH.sub.3 181-184.degree.n-C.sub.3 H.sub.7 SO.sub.2 H O H H CH.sub.3 O CH.sub.3 170-172.degree.CF.sub.3 SO.sub.2 H O H H CH.sub.3 O CH.sub.3CF.sub.3 H O H H CH.sub.3 O CH.sub.3 ##STR33## H O H H CH.sub.3 O CH.sub.3CO.sub.2 C.sub.2 H.sub.5 H O H H CH.sub.3 CH.sub.3CO.sub.2 C.sub.2 H.sub.5 H O H H CH.sub.3 CH.sub.3 OCO.sub.2 C.sub.2 H.sub.5 H O H H CH.sub.3 O CH.sub.3 OSO.sub.2 N(CH.sub.3).sub.2 H O H H CH.sub.3 O CH.sub.3 ##STR34## H O H H CH.sub.3 O CH.sub.3 ##STR35## H O H H CH.sub.3 O CH.sub.3CH.sub.3 SO.sub.2 O H O H H CH.sub.3 O CH.sub.3 176-179.degree. (d)n-C.sub.3 H.sub.7 SO.sub.2 O H O H H CH.sub.3 O CH.sub.3CF.sub.3 SO.sub.2 O H O H H CH.sub.3 O CH.sub.3NO.sub.2 3-Cl O H H CH.sub.3 O CH.sub.3NO.sub.2 5-Cl O H H CH.sub.3 O CH.sub.3NO.sub.2 6-Cl O H H CH.sub.3 O CH.sub.3NO.sub.2 5-Br O H H CH.sub.3 O CH.sub.3NO.sub.2 5-F O H H CH.sub.3 O CH.sub.3NO.sub.2 5-CF.sub.3 O H H CH.sub.3 O CH.sub.3NO.sub.2 5-OCH.sub.3 O H H CH.sub.3 O CH.sub.3CO.sub.2 CH.sub.3 5-Cl O H H CH.sub.3 O CH.sub.3CO.sub.2 CH.sub.3 5-CF.sub.3 O H H CH.sub.3 O CH.sub.3CO.sub.2 CH.sub.3 6-Cl O H H CH.sub.3 O CH.sub.3CO.sub.2 CH.sub.3 5-Br O H H CH.sub.3 O CH.sub.3CO.sub.2 CH.sub.3 5-F O H H CH.sub.3 O CH.sub.3CO.sub.2 CH.sub.3 5-OCH.sub.3 O H H CH.sub.3 O CH.sub.3CO.sub.2 CH.sub.3 H O H H CH.sub. 3 CH.sub.3 CH.sub.2 OCO.sub.2 CH.sub.3 H O H H CH.sub.3 O CH.sub.3 CH.sub.2 OCO.sub.2 CH.sub.3 H O H H CH.sub.3 CH.sub.3 OCH.sub.2CO.sub.2 CH.sub.3 H O H H CH.sub.3 O CH.sub.3 OCH.sub.2CH.sub.3 SO.sub.2 O H O H H CH.sub.3 O CH.sub.3 O 187-192.degree. (d)CH.sub.3 SO.sub.2 O H O H H CH.sub.3 CH.sub.3 155-161.degree. (d)NO.sub.2 H O H CH.sub.3 CH.sub.3 O CH.sub.3 O 166-169.degree.NO.sub.2 H O H CH.sub.3 CH.sub.3 O CH.sub.3 147-149.degree.NO.sub.2 H S H H CH.sub.3 O CH.sub.3NO.sub.2 H O CH.sub.3 H CH.sub.3 O CH.sub.3CO.sub.2 CH.sub.3 H S H H CH.sub.3 O CH.sub.3CO.sub.2 CH.sub.3 H O H CH.sub.2 CH.sub.3 CH.sub.3 O CH.sub.3CO.sub.2 CH.sub.3 H O H i-C.sub.3 H.sub.7 CH.sub.3 O CH.sub.3CO.sub.2 CH.sub.3 H O CH.sub.3 H CH.sub.3 O CH.sub.3CO.sub.2 CH.sub.3 H O H H CH.sub.3 NH.sub.2CO.sub.2 CH.sub.3 H O H H CH.sub.3 O NHCH.sub.3CO.sub.2 CH.sub.3 H O H H CH.sub.3 N(CH.sub.3).sub.2CO.sub.2 CH.sub.3 H O H H CH.sub.3 O CH.sub.2 CH.sub.3CO.sub.2 CH.sub.3 H O H H CH.sub.3 CH.sub.2 CH.sub.3Cl H S H H CH.sub.3 O CH.sub.3Cl H O H H CH.sub.3 O NH.sub.2Cl H O H H CH.sub.3 NHCH.sub.3Cl H O H H CH.sub.3 O N(CH.sub.3).sub.2Cl H O H H CH.sub.3 O CH.sub.2 CH.sub.3CH.sub.3 H S H H CH.sub.3 O CH.sub.3CH.sub.3 H O H CH.sub.3 CH.sub.3 O CH.sub.3CH.sub.2 CH.sub.3 H O H H CH.sub.3 O CH.sub.3i-C.sub.3 H.sub.7 H O H H CH.sub.3 O CH.sub.3SO.sub.2 OCH.sub.2 CF.sub.3 H O H H CH.sub.3 O CH.sub.3OEt H O H H CH.sub.3 O CH.sub.3 ##STR36## H O H H CH.sub.3 O CH.sub.3CH.sub.2 SO.sub.2 N(CH.sub.3).sub.2 H O H H CH.sub.3 O CH.sub.3 ##STR37## H O H H CH.sub.3 O CH.sub.3CH.sub.2 SO.sub.2 N(CH.sub.3)Et H O H H CH.sub.3 O CH.sub.3CH.sub.2 OCH.sub.3 H O H H CH.sub.3 O CH.sub.3CH.sub.2 OCH.sub.2 CH.sub.3 H O H H CH.sub.3 O CH.sub.3CH.sub.2 CO.sub.2 CH.sub.3 H O H H CH.sub.3 O CH.sub.3CH.sub.2 CO.sub.2 Et H O H H CH.sub.3 O CH.sub.3OCH.sub.3 H O H H CH.sub.3 O CH.sub.3__________________________________________________________________________
TABLE 3__________________________________________________________________________ ##STR38##R.sub.1 R.sub.2 W R.sub.8 R.sub.9 X.sub.1 m.p. (.degree.C.)__________________________________________________________________________NO.sub.2 H O H H CH.sub.3NO.sub.2 H O H H CH.sub.3 OCl H O H H CH.sub.3Cl H O H H CH.sub.3 OCO.sub.2 CH.sub.3 H O H H CH.sub.3CO.sub.2 CH.sub.3 H O H H CH.sub.3 OCH.sub.3 H O H H CH.sub.3F H O H H CH.sub.3Br H O H H CH.sub.3 ##STR39## H O H H CH.sub.3CH.sub.3 H O H H CH.sub.3 OCO.sub.2 CH.sub.2 CH.sub.2 Cl H O H H CH.sub.3CO.sub.2 CH.sub.2 CHCH.sub.2 H O H H CH.sub.3CO.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 H O H H CH.sub.3CH.sub.3 SO.sub.2 H O H H CH.sub.3n-C.sub.3 H.sub.7 SO.sub.2 H O H H CH.sub.3CF.sub.3 SO.sub.2 H O H H CH.sub.3CF.sub.3 H O H H CH.sub.3 ##STR40## H O H H CH.sub.3SO.sub.2 N(CH.sub.3).sub.2 H O H H CH.sub.3 ##STR41## H O H H CH.sub.3 ##STR42## H O H H CH.sub.3CH.sub.3 SO.sub.2 O H O H H CH.sub.3n-C.sub.3 H.sub.7 SO.sub.2 O H O H H CH.sub.3CF.sub.3 SO.sub.2 O H O H H CH.sub.3NO.sub.2 3-Cl O H H CH.sub.3NO.sub.2 5-Cl O H H CH.sub.3NO.sub.2 6-Cl O H H CH.sub.3NO.sub.2 5-Br O H H CH.sub.3NO.sub.2 5-CF.sub.3 O H H CH.sub.3NO.sub.2 5-OCH.sub.3 O H H CH.sub.3CO.sub.2 CH.sub.3 5-Cl O H H CH.sub.3CO.sub.2 CH.sub.3 5-CF.sub.3 O H H CH.sub.3CO.sub.2 CH.sub.3 6-Cl O H H CH.sub.3CO.sub.2 CH.sub.3 5-Br O H H CH.sub.3CO.sub.2 CH.sub.3 5-F O H H CH.sub.3CO.sub.2 CH.sub.3 5-OCH.sub.3 O H H CH.sub.3NO.sub.2 H O H H HCO.sub.2 CH.sub.3 H O H H HCl H O H H HSO.sub.2 N(CH.sub.3).sub.2 H O H H HNO.sub.2 H O H H OCH.sub.2 CH.sub.3NO.sub.2 H O H CH.sub.3 CH.sub.3NO.sub.2 H S H H HCO.sub.2 CH.sub.3 H O H CH.sub. 3 CH.sub.3CO.sub.2 CH.sub.3 H O H CH.sub.2 CH.sub.3 CH.sub.3 OCO.sub.2 CH.sub.3 H O H i-C.sub.3 H.sub.7 HCO.sub.2 CH.sub.3 H O CH.sub.3 H CH.sub.3CO.sub.2 CH.sub.3 H O H H OCH.sub.2 CH.sub.3CO.sub.2 CH.sub.3 H O H H ClCl H S H H HCl H O CH.sub.3 H CH.sub.3 OCl H O H H ClCl H O H H OCH.sub.2 CH.sub.3CH.sub.3 H S H H HCH.sub.2 CH.sub.3 H O H H CH.sub.3i-C.sub.3 H.sub.7 H O H H CH.sub.3SO.sub.2 OCH.sub.2 CF.sub.3 H O H H CH.sub.3OEt H O H H CH.sub.3 ##STR43## H O H H CH.sub.3CH.sub.2 SO.sub.2 N(CH.sub.3).sub.2 H O H H CH.sub.3 ##STR44## H O H H CH.sub.3CH.sub.2 SO.sub.2 N(CH.sub.3)Et H O H H CH.sub.3CH.sub.2 OCH.sub.3 H O H H CH.sub.3CH.sub.2 OCH.sub.2 CH.sub.3 H O H H CH.sub.3CH.sub.2 CO.sub.2 CH.sub.3 H O H H CH.sub.3CH.sub.2 CO.sub.2 Et H O H H CH.sub.3OCH.sub.3 H O H H CH.sub.3__________________________________________________________________________
TABLE 4__________________________________________________________________________ ##STR45##R.sub.1 R.sub.2 W R.sub.8 R.sub.9 X.sub.1 m.p. (.degree.C.)__________________________________________________________________________NO.sub.2 H O H H CH.sub.3NO.sub.2 H O H H CH.sub.3 OCl H O H H CH.sub.3Cl H O H H CH.sub.3 OCO.sub.2 CH.sub.3 H O H H CH.sub.3CO.sub.2 CH.sub.3 H O H H CH.sub.3 OCH.sub.3 H O H H CH.sub.3F H O H H CH.sub.3Br H O H H CH.sub.3 ##STR46## H O H H CH.sub.3CH.sub.3 H O H H CH.sub.3 OCO.sub.2 CH.sub.2 CH.sub.2 Cl H O H H CH.sub.3CO.sub.2 CH.sub.2 CHCH.sub.2 H O H H CH.sub.3CO.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 H O H H CH.sub.3CH.sub.3 SO.sub.2 H O H H CH.sub.3n-C.sub.3 H.sub.7 SO.sub.2 H O H H CH.sub.3CF.sub.3 SO.sub.2 H O H H CH.sub.3CF.sub.3 H O H H CH.sub.3 ##STR47## H O H H CH.sub.3SO.sub.2 N(CH.sub.3).sub.2 H O H H CH.sub.3 ##STR48## H O H H CH.sub.3 ##STR49## H O H H CH.sub.3CH.sub.3 SO.sub.2 O H O H H CH.sub.3n-C.sub.3 H.sub.7 SO.sub.2 O H O H H CH.sub.3CF.sub.3 SO.sub.2 O H O H H CH.sub.3NO.sub.2 3-Cl O H H CH.sub.3NO.sub.2 5-Cl O H H CH.sub.3NO.sub.2 6-Cl O H H CH.sub.3NO.sub.2 5-Br O H H CH.sub.3NO.sub.2 5-CF.sub.3 O H H CH.sub.3NO.sub.2 5-OCH.sub.3 O H H CH.sub.3CO.sub.2 CH.sub.3 5-Cl O H H CH.sub.3CO.sub.2 CH.sub.3 5-CF.sub.3 O H H CH.sub.3CO.sub.2 CH.sub.3 6-Cl O H H CH.sub.3CO.sub.2 CH.sub.3 5-Br O H H Ch.sub.3CO.sub.2 CH.sub.3 5-F O H H CH.sub.3CO.sub.2 CH.sub.3 5-OCH.sub.3 O H H CH.sub.3NO.sub.2 H O H H HCO.sub.2 CH.sub.3 H O H H HCl H O H H HSO.sub.2 N(CH.sub.3).sub.2 H O H H HNO.sub.2 H O H H OCH.sub.2 CH.sub.3NO.sub.2 H O H CH.sub.3 CH.sub.3NO.sub.2 H S H H HCO.sub.2 CH.sub.3 H O H CH.sub.3 CH.sub.3CO.sub.2 CH.sub.3 H O H CH.sub.2 CH.sub.3 CH.sub.3 OCO.sub.2 CH.sub.3 H O H i-C.sub.3 H.sub.7 HCO.sub.2 CH.sub.3 H O CH.sub.3 H CH.sub.3CO.sub.2 CH.sub.3 H O H H OCH.sub.2 CH.sub.3CO.sub.2 CH.sub.3 H O H H ClCl H S H H HCl H O CH.sub.3 H CH.sub.3 OCl H O H H ClCl H O H H OCH.sub.2 CH.sub.3CH.sub.3 H S H H HCH.sub.2 CH.sub.3 H O H H CH.sub.3i-C.sub.3 H.sub.7 H O H H CH.sub.3SO.sub.2 OCH.sub.2 CF.sub.3 H O H H CH.sub.3OEt H O H H CH.sub.3 ##STR50## H O H H CH.sub.3CH.sub.2 SO.sub.2 N(CH.sub.3).sub.2 H O H H CH.sub.3 ##STR51## H O H H CH.sub.3CH.sub.2 SO.sub.2 N(CH.sub.3)Et H O H H CH.sub.3CH.sub. 2 OCH.sub.3 H O H H CH.sub.3CH.sub.2 OCH.sub.2 CH.sub.3 H O H H CH.sub.3CH.sub.2 CO.sub.2 CH.sub.3 H O H H CH.sub.3CH.sub.2 CO.sub.2 Et H O H H CH.sub.3OCH.sub.3 H O H H CH.sub.3__________________________________________________________________________
TABLE 5__________________________________________________________________________ ##STR52##R.sub.1 R.sub.2 W R.sub.8 R.sub.9 X.sub.1 m.p. (.degree.C.)__________________________________________________________________________NO.sub.2 H O H H CH.sub.3NO.sub.2 H O H H CH.sub.3 ONO.sub.2 H O H H OCH.sub.2 CH.sub.3NO.sub.2 H O H H ClNO.sub.2 H O CH.sub.3 H HNO.sub.2 H S H H CH.sub.3NO.sub.2 H O H CH.sub.3 CH.sub.3CO.sub.2 CH.sub.3 H O H H CH.sub.3CO.sub.2 CH.sub.3 H O H H CH.sub.3 OCO.sub.2 CH.sub.3 H O H H OCH.sub. 2 CH.sub.3CO.sub.2 CH.sub.3 H O H H ClCO.sub.2 CH.sub.3 H O H H HCO.sub.2 CH.sub.3 H S H H HCO.sub.2 CH.sub.3 H O H CH.sub.2 CH.sub.3 CH.sub.3CO.sub.2 CH.sub.3 H O H i-C.sub.3 H.sub.7 CH.sub.3CO.sub.2 CH.sub.3 H O CH.sub.3 H HCl H O H H CH.sub.3Cl H O H H CH.sub.3 OCl H O H H OCH.sub.2 CH.sub.3Cl H O H H ClCl H O H H HCl H S H H HCl H O CH.sub.3 H CH.sub.3CH.sub.3 H O H H CH.sub.3CH.sub.3 H O H H CH.sub.3 OCH.sub.3 H O H H OCH.sub.2 CH.sub.3CH.sub.2 CH.sub.3 H O H H ClCH.sub.2 CH.sub.3 H S H H Hi-C.sub.3 H.sub.7 H O H H CH.sub.3SO.sub.2 OCH.sub.2 CF.sub.3 H O H H CH.sub.3OEt H O H H CH.sub.3 ##STR53## H O H H CH.sub.3CH.sub.2 SO.sub.2 N(CH.sub.3).sub.2 H O H H CH.sub.3 ##STR54## H O H H CH.sub.3CH.sub.2 SO.sub.2 N(CH.sub.3)Et H O H H CH.sub.3CH.sub.2 OCH.sub.3 H O H H CH.sub.3CH.sub.2 OCH.sub.2 CH.sub.3 H O H H CH.sub.3CH.sub.2 CO.sub.2 CH.sub.3 H O H H CH.sub.3CH.sub.2 CO.sub.2 Et H O H H CH.sub.3OCH.sub.3 H O H H CH.sub.3F H O H H CH.sub.3Br H O H H CH.sub.3 ##STR55## H O H H CH.sub.3CO.sub.2 CH.sub.2 CH.sub.2 Cl H O H H CH.sub.3CO.sub.2 CH.sub.2 CHCH.sub.2 H O H H CH.sub.3CO.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 H O H H CH.sub.3CH.sub.3 SO.sub.2 H O H H CH.sub.3CF.sub.3 H O H H CH.sub.3 ##STR56## H O H H CH.sub.3SO.sub.2 N(CH.sub.3).sub.2 H O H H CH.sub.3 ##STR57## H O H H CH.sub.3 ##STR58## H O H H CH.sub.3CH.sub.3 SO.sub.2 O H O H H CH.sub.3n-C.sub.3 H.sub.7 SO.sub.2 O H O H H CH.sub.3CF.sub.3 SO.sub.2 O H O H H CH.sub.3NO.sub.2 3-Cl O H H CH.sub.3NO.sub.2 5-Cl O H H CH.sub.3NO.sub.2 6-Cl O H H CH.sub.3NO.sub.2 5-Br O H H CH.sub.3NO.sub.2 5-CF.sub.3 O H H CH.sub.3NO.sub.2 5-OCH.sub.3 O H H CH.sub.3CO.sub.2 CH.sub.3 5-Cl O H H CH.sub.3CO.sub.2 CH.sub.3 5-CF.sub.3 O H H CH.sub.3CO.sub.2 CH.sub.3 6-Cl O H H CH.sub.3CO.sub.2 CH.sub.3 5-Br O H H CH.sub.3CO.sub.2 CH.sub.3 5-F O H H CH.sub.3CO.sub. 2 CH.sub.3 5-OCH.sub.3 O H H CH.sub.3__________________________________________________________________________
TABLE 6__________________________________________________________________________ ##STR59##R.sub.1 R.sub.2 W R.sub.8 R.sub.9 X.sub.2 m.p. (.degree.C.)__________________________________________________________________________NO.sub.2 H O H H CH.sub.3NO.sub.2 H O H H CH.sub.3 CH.sub.2Cl H O H H CH.sub.3Cl H O H H CH.sub.3 CH.sub.2CO.sub.2 CH.sub.3 H O H H CH.sub.3CO.sub.2 CH.sub.3 H O H H CH.sub.3 CH.sub.2CH.sub.3 H O H H CH.sub.3F H O H H CH.sub.3Br H O H H CH.sub. 3 ##STR60## H O H H CH.sub.3CH.sub.3 H O H H CH.sub.3 CH.sub.2CO.sub.2 CH.sub.2 CH.sub.2 Cl H O H H CH.sub.3CO.sub.2 CH.sub.2 CHCH.sub.2 H O H H CH.sub.3CO.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 H O H H CH.sub.3CH.sub.3 SO.sub.2 H O H H CH.sub.3n-C.sub.3 H.sub.7 SO.sub.2 H O H H CH.sub.3CF.sub.3 SO.sub.2 H O H H CH.sub.3CF.sub.3 H O H H CH.sub.3 ##STR61## H O H H CH.sub.3SO.sub.2 N(CH.sub.3).sub.2 H O H H CH.sub.3 ##STR62## H O H H CH.sub.3 ##STR63## H O H H CH.sub.3CH.sub.3 SO.sub.2 O H O H H CH.sub.3n-C.sub.3 H.sub.7 SO.sub.2 O H O H H CH.sub.3CF.sub.3 SO.sub.2 O H O H H CH.sub.3NO.sub.2 3-Cl O H H CH.sub.3NO.sub.2 5-Cl O H H CH.sub.3NO.sub.2 6-Cl O H H CH.sub.3NO.sub.2 5-Br O H H CH.sub.3NO.sub.2 5-CF.sub.3 O H H CH.sub.3NO.sub.2 5-OCH.sub.3 O H H CH.sub.3CO.sub.2 CH.sub.3 5-Cl O H H CH.sub.3CO.sub.2 CH.sub.3 5-CF.sub.3 O H H CH.sub.3CO.sub.2 CH.sub.3 6-Cl O H H CH.sub.3CO.sub.2 CH.sub.3 5-Br O H H CH.sub.3CO.sub.2 CH.sub.3 5-F O H H CH.sub.3CO.sub.2 CH.sub.3 5-OCH.sub.3 O H H CH.sub.3NO.sub.2 H O H H CH.sub.3 ONO.sub.2 H O H H OCH.sub.2 CH.sub.3NO.sub.2 H S H H CH.sub.3NO.sub.2 H O H CH.sub.3 CH.sub.2 CH.sub.3CO.sub.2 CH.sub.3 H O CH.sub.3 H CH.sub.3CO.sub.2 CH.sub.3 H O H CH.sub.2 CH.sub.3 CH.sub.3CO.sub.2 CH.sub.3 H O H i-C.sub.3 H.sub.7 CH.sub.3CO.sub.2 CH.sub.3 H S H H CH.sub.3CO.sub.2 CH.sub.3 H O H H CH.sub.3 OCO.sub.2 CH.sub.3 H O H H OCH.sub.2 CH.sub.3Cl H O H H CH.sub.3 OCl H O H H OCH.sub.2 CH.sub.3Cl H O CH.sub.3 H CH.sub.3Cl H O H CH.sub.3 CH.sub.3CH.sub.3 H S H H CH.sub.3CH.sub.3 H O H H CH.sub.3 OCH.sub.2 CH.sub.3 H O H H OCH.sub.2 CH.sub.3i-C.sub.3 H.sub.7 H O H H CH.sub.3SO.sub.2 OCH.sub.2 CF.sub.3 H O H H CH.sub.3OCH.sub.2 CH.sub.3 H O H H CH.sub.3 ##STR64## H O H H CH.sub.3CH.sub.2 SO.sub.2 N(CH.sub.3).sub.2 H O H H CH.sub.3 ##STR65## H O H H CH.sub.3CH.sub.2 SO.sub.2 N(CH.sub.3)Et H O H H CH.sub.3CH.sub.2 OCH.sub.3 H O H H CH.sub.3CH.sub.2 OCH.sub.2 CH.sub.3 H O H H CH.sub.3CH.sub.2 CO.sub.2 CH.sub.3 H O H H CH.sub.3CH.sub.2 CO.sub.2 Et H O H H CH.sub.3OCH.sub.3 H O H H CH.sub.3__________________________________________________________________________
TABLE 7__________________________________________________________________________ ##STR66##R.sub.1 R.sub.2 W R.sub.8 R.sub.9 X.sub.3 Y.sub.1 m.p. (.degree.C.)__________________________________________________________________________NO.sub.2 H O H H CH.sub.3 O CH.sub.3 ONO.sub.2 H O H H CH.sub.3 O CH.sub.3NO.sub.2 H O H H CH.sub.3 CH.sub.3NO.sub.2 H S H H CH.sub.3 O CH.sub.3NO.sub.2 H O CH.sub.3 H CH.sub.3 O CH.sub.3NO.sub.2 H O H CH.sub.3 CH.sub.3 O CH.sub.3Cl H O H H CH.sub.3 O CH.sub.3 OCl H O H H CH.sub.3 O CH.sub.3Cl H O H H CH.sub.3 CH.sub.3Cl H S H H CH.sub.3 O CH.sub.3Cl H O CH.sub.3 H CH.sub.3 O CH.sub.3CO.sub.2 CH.sub.3 H O H H CH.sub.3 O CH.sub.3 OCO.sub.2 CH.sub.3 H O H H CH.sub.3 O CH.sub.3CO.sub.2 CH.sub.3 H O H H CH.sub.3 CH.sub.3CO.sub.2 CH.sub.3 H S H H CH.sub.3 O CH.sub.3CO.sub.2 CH.sub.3 H O CH.sub.3 H CH.sub.3 O CH.sub.3CO.sub.2 CH.sub.3 H O H CH.sub.2 CH.sub.3 CH.sub.3 O CH.sub.3CO.sub.2 CH.sub.3 H O H i-C.sub.3 H.sub.7 CH.sub.3 O CH.sub.3CH.sub.3 H O H H CH.sub.3 O CH.sub.3 OCH.sub.3 H O H H CH.sub.3 O CH.sub.3CH.sub.3 H O H H CH.sub.3 CH.sub.3CH.sub.3 H S H H CH.sub.3 O CH.sub.3CH.sub.3 H O CH.sub.3 H CH.sub.3 O CH.sub.3CH.sub.3 H O H CH.sub.3 CH.sub.3 O CH.sub.3F H O H H CH.sub.3 O CH.sub.3Br H O H H CH.sub.3 O CH.sub.3CH.sub.3 O H O H H CH.sub.3 O CH.sub.3 O ##STR67## H O H H CH.sub.3 O CH.sub.3 OCO.sub.2 CH.sub.2 CH.sub.2 Cl H O H H CH.sub.3 O CH.sub.3 OCO.sub.2 CH.sub.2 CHCH.sub.2 H O H H CH.sub.3 O CH.sub.3 OCO.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 H O H H CH.sub.3 O CH.sub.3 OCH.sub.3 SO.sub.2 H O H H CH.sub.3 O CH.sub.3 On-C.sub.3 H.sub.7 SO.sub.2 H O H H CH.sub.3 O CH.sub.3 OCF.sub.3 SO.sub.2 H O H H CH.sub.3 O CH.sub.3 OCF.sub.3 H O H H CH.sub.3 O CH.sub.3 O ##STR68## H O H H CH.sub.3 O CH.sub.3 OSO.sub.2 N(CH.sub.3).sub.2 H O H H CH.sub.3 O CH.sub.3 O ##STR69## H O H H CH.sub.3 O CH.sub.3 O ##STR70## H O H H CH.sub.3 O CH.sub.3 OCH.sub.3 SO.sub.2 O H O H H CH.sub.3 O CH.sub.3 On-C.sub.3 H.sub.7 SO.sub.2 O H O H H CH.sub.3 O CH.sub.3 OCF.sub.3 SO.sub.2 O H O H H CH.sub.3 O CH.sub.3 ONO.sub.2 3-Cl O H H CH.sub.3 O CH.sub.3 ONO.sub.2 5-Cl O H H CH.sub.3 O CH.sub.3 ONO.sub.2 6-Cl O H H CH.sub.3 O CH.sub.3 ONO.sub.2 5-Br O H H CH.sub.3 O CH.sub.3 ONO.sub.2 5-F O H H CH.sub.3 O CH.sub.3 ONO.sub.2 5-CF.sub.3 O H H CH.sub.3 O CH.sub.3 ONO.sub.2 5-OCH.sub.3 O H H CH.sub.3 O CH.sub.3 OCO.sub.2 CH.sub.3 5-Cl O H H CH.sub.3 O CH.sub.3CO.sub.2 CH.sub.3 5-CF.sub.3 O H H CH.sub.3 O CH.sub.3 OCO.sub.2 CH.sub.3 6-Cl O H H CH.sub.3 O CH.sub.3 OCO.sub.2 CH.sub.3 5-Br O H H CH.sub.3 O CH.sub.3 OCO.sub.2 CH.sub.3 5-F O H H CH.sub.3 O CH.sub.3 OCO.sub.2 CH.sub.3 5-OCH.sub.3 O H H CH.sub.3 O CH.sub.3 OCH.sub.2 CH.sub.3 H O H H CH.sub.3 O CH.sub.3 Oi-C.sub.3 H.sub.7 H O H H CH.sub.3 O CH.sub.3 OSO.sub.2 OCH.sub.2 CF.sub.3 H O H H CH.sub.3 O CH.sub.3 OOCH.sub.2 CH.sub.3 H O H H CH.sub.3 O CH.sub.3 O ##STR71## H O H H CH.sub.3 O CH.sub.3 OCH.sub.2 SO.sub.2 N(CH.sub.3).sub.2 H O H H CH.sub.3 O CH.sub.3 O ##STR72## H O H H CH.sub.3 O CH.sub.3 OCH.sub.2 SO.sub.2 N(CH.sub.3)Et H O H H CH.sub.3 O CH.sub.3 OCH.sub.2 OCH.sub.3 H O H H CH.sub.3 O CH.sub.3 OCH.sub.2 OCH.sub.2 CH.sub.3 H O H H CH.sub.3 O CH.sub.3 OCH.sub.2 CO.sub.2 CH.sub.3 H O H H CH.sub.3 O CH.sub.3 OCH.sub.2 CO.sub.2 Et H O H H CH.sub.3 O CH.sub.3 O__________________________________________________________________________
TABLE 8__________________________________________________________________________ ##STR73##R.sub.1 R.sub.2 W R.sub.8 R.sub.9 X.sub.3 Y.sub.1 m.p. (.degree.C.)__________________________________________________________________________NO.sub.2 H O H H CH.sub.3 O CH.sub.3 ONO.sub.2 H O H H CH.sub.3 O CH.sub.3NO.sub.2 H O H H CH.sub.3 CH.sub.3NO.sub.2 H S H H CH.sub.3 O CH.sub.3NO.sub.2 H O CH.sub.3 H CH.sub.3 O CH.sub.3NO.sub.2 H O H CH.sub.3 CH.sub.3 O CH.sub.3Cl H O H H CH.sub.3 O CH.sub.3 OCl H O H H CH.sub.3 O CH.sub.3Cl H O H H CH.sub.3 CH.sub.3Cl H S H H CH.sub.3 O CH.sub.3Cl H O CH.sub.3 H CH.sub.3 O CH.sub.3CO.sub.2 CH.sub.3 H O H H CH.sub.3 O CH.sub.3 OCO.sub.2 CH.sub.3 H O H H CH.sub.3 O CH.sub.3CO.sub.2 CH.sub.3 H O H H CH.sub.3 CH.sub.3CO.sub.2 CH.sub.3 H S H H CH.sub.3 O CH.sub.3CO.sub.2 CH.sub.3 H O CH.sub.3 H CH.sub.3 O CH.sub.3CO.sub.2 CH.sub.3 H O H CH.sub.2 CH.sub.3 CH.sub.3 O CH.sub.3CO.sub.2 CH.sub.3 H O H i-C.sub.3 H.sub.7 CH.sub.3 O CH.sub.3CH.sub.3 H O H H CH.sub.3 O CH.sub.3 OCH.sub.3 H O H H CH.sub.3 O CH.sub.3CH.sub.3 H O H H CH.sub.3 CH.sub.3CH.sub.3 H S H H CH.sub.3 O CH.sub.3CH.sub.3 H O CH.sub.3 H CH.sub.3 O CH.sub.3CH.sub.3 H O H CH.sub.3 CH.sub. 3 O CH.sub.3F H O H H CH.sub.3 O CH.sub.3Br H O H H CH.sub.3 O CH.sub.3CH.sub.3 O H O H H CH.sub.3 O CH.sub.3 O ##STR74## H O H H CH.sub.3 O CH.sub.3 OCO.sub.2 CH.sub.2 CH.sub.2 Cl H O H H CH.sub.3 O CH.sub.3 OCO.sub.2 CH.sub.2 CHCH.sub.2 H O H H CH.sub.3 O CH.sub.3 OCO.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 H O H H CH.sub.3 O CH.sub.3 OCH.sub.3 SO.sub.2 H O H H CH.sub.3 O CH.sub.3 On-C.sub.3 H.sub.7 SO.sub.2 H O H H CH.sub.3 O CH.sub.3 OCF.sub.3 SO.sub.2 H O H H CH.sub.3 O CH.sub.3 OCF.sub.3 H O H H CH.sub.3 O CH.sub.3 O ##STR75## H O H H CH.sub.3 O CH.sub.3 OSO.sub.2 N(CH.sub.3) H O H H CH.sub.3 O CH.sub. 3 O ##STR76## H O H H CH.sub.3 O CH.sub.3 O ##STR77## H O H H CH.sub.3 O CH.sub.3 OCH.sub.3 SO.sub.2 O H O H H CH.sub.3 O CH.sub.3 On-C.sub.3 H.sub.7 SO.sub.2 O H O H H CH.sub.3 O CH.sub.3 OCF.sub.3 SO.sub.2 O H O H H CH.sub.3 O CH.sub.3 ONO.sub.2 3-Cl O H H CH.sub.3 O CH.sub.3 ONO.sub.2 5-Cl O H H CH.sub.3 O CH.sub.3 ONO.sub.2 6-Cl O H H CH.sub.3 O CH.sub.3 ONO.sub.2 5-Br O H H CH.sub.3 O CH.sub.3 ONO.sub.2 5-F O H H CH.sub.3 O CH.sub.3 ONO.sub.2 5-CF.sub.3 O H H CH.sub.3 O CH.sub.3 ONO.sub.2 5-OCH.sub.3 O H H CH.sub.3 O CH.sub.3 OCO.sub.2 CH.sub.3 5-Cl O H H CH.sub.3 O CH.sub.3CO.sub.2 CH.sub.3 5-CF.sub.3 O H H CH.sub.3 O CH.sub.3 OCO.sub.2 CH.sub.3 6-Cl O H H CH.sub.3 O CH.sub.3 OCO.sub.2 CH.sub.3 5-Br O H H CH.sub.3 O CH.sub.3 OCO.sub.2 CH.sub.3 5-F O H H CH.sub.3 O CH.sub.3 OCO.sub.2 CH.sub.3 5-OCH.sub.3 O H H CH.sub.3 O CH.sub.3 OCH.sub.2 CH.sub.3 H O H H CH.sub.3 O CH.sub.3 Oi-C.sub.3 H.sub.7 H O H H CH.sub.3 O CH.sub.3 OSO.sub.2 OCH.sub.2 CF.sub.3 H O H H CH.sub.3 O CH.sub.3 OOCH.sub.2 CH.sub.3 H O H H CH.sub.3 O CH.sub.3 O ##STR78## H O H H CH.sub.3 O CH.sub.3 OCH.sub.2 SO.sub.2 N(CH.sub.3).sub.2 H O H H CH.sub.3 O CH.sub.3 O ##STR79## H O H H CH.sub.3 O CH.sub.3 OCH.sub.2 SO.sub.2 N(CH.sub.3)Et H O H H CH.sub.3 O CH.sub. 3 OCH.sub.2 OCH.sub.3 H O H H CH.sub.3 O CH.sub.3 OCH.sub.2 OCH.sub.2 CH.sub.3 H O H H CH.sub.3 O CH.sub.3 OCH.sub.2 CO.sub.2 CH.sub.3 H O H H CH.sub.3 O CH.sub.3 OCH.sub.2 CO.sub.2 Et H O H H CH.sub.3 O CH.sub.3 O__________________________________________________________________________
TABLE 9______________________________________ ##STR80##R.sub.1 R.sub.2 R.sub.9 IR SO.sub.2 NCO______________________________________NO.sub.2 H H 2230 cm.sup.-1Cl H H 2240 cm.sup.-1CO.sub.2 CH.sub.3 H H 2230 cm.sup.-1CH.sub.3 H H 2250 cm.sup.-1F H HBr H H ##STR81## H HCH.sub.3 SO.sub.2 H H 2240 cm.sup.-1CF.sub.3 SO.sub.2 H HCF.sub.3 H HSO.sub.2 N(CH.sub.3).sub.2 H H 2240 cm.sup.-1 ##STR82## H HCH.sub.3 SO.sub.2 O H H 2240 cm.sup.-1CF.sub.3 SO.sub.2 O H HNO.sub.2 3-Cl HNO.sub.2 5-Cl HNO.sub. 2 6-Cl HNO.sub.2 5-Br HNO.sub.2 5-CF.sub.3 HNO.sub.2 5-OCH.sub.3 HNO.sub.2 H CH.sub.3 2240 cm.sup.-1CO.sub.2 CH.sub.3 H CH.sub.3CO.sub.2 CH.sub.3 H CH.sub.2 CH.sub.3CO.sub.2 CH.sub.3 H i-C.sub.3 H.sub.7Cl H CH.sub.3CH.sub.3 H CH.sub.3CH.sub.2 CH.sub.3 H Hi-C.sub.3 H.sub.7 H HSO.sub.2 OCH.sub.2 CF.sub.3 H HOCH.sub.2 CH.sub.3 H H ##STR83## H HCH.sub.2 SO.sub.2 N(CH.sub.3).sub.2 H H ##STR84## H HCH.sub.2 SO.sub.2 N(CH.sub.3)Et H HCH.sub.2 OCH.sub.3 H HCH.sub.2 OCH.sub.2 CH.sub.3 H HCH.sub.2 CO.sub.2 CH.sub.3 H HCH.sub.2 CO.sub.2 Et H HOCH.sub.3 H H______________________________________
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 10______________________________________ Active Weight Percent Ingredient Diluent(s) Surfactant(s)______________________________________Wettable Powders 20-90 0-74 1-10Oil Suspensions, 3-50 40-95 0-15Emulsions, Solutions(including EmulsifiableConcentrates)Aqueous Suspension 10-50 40-84 1-20Dusts 1-25 70-99 0-5Granules and Pellets 0.1-95 5-99.9 0-15High 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, N.J., but other solids, either mined or manufactured, may be used. The more absorptive diluents are preferred for wettable powders and the denser ones for dusts. Typical liquid diluents and solvents are described in Marsden, "Solvents Guide," 2nd Ed., Interscience, New York, 1950. Solubility under 0.1% is preferred for suspension concentrates; solution concentrates are preferably stable against phase separation at 0.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 foaming, caking, corrosion, microbiological growth, etc.
The methods of making such compositions are well known. Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer or fluid energy mill. Suspensions are prepared by wet milling (see, for example, Littler, U.S. Pat. No. 3,060,084). Granules and pellets may be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See J. E. Browning, "Agglomeration", Chemical Engineering, December 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. 3,233,361, Feb. 15, 1966, Col. 6, line 16 through Col. 7, line 19 and Examples 10 through 41;
R. W. Luckenbaugh, U.S. Pat. No. 3,309,192, Mar. 14, 1967, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 58, 132, 138-140, 162-164, 166, 167 and 169-182;
H. Gysin and E. Knusli, U.S. Pat. No. 2,891,855, June 23, 1959, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4;
G. C. Klingman, "Weed Control as a Science", John Wiley & Sons, Inc., New York, 1961, pp. 81-96; and
J. D. Fryer and S. A. Evans, "Weed Control Handbook", 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pp. 101-103.
In the following examples, all parts are by weight unless otherwise indicated.
EXAMPLE 17
______________________________________Wettable Powder______________________________________N--[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-1- 80%(2-nitrophenyl)methanesulfonamidesodium alkylnaphthalenesulfonate 2%sodium ligninsulfonate 2%synthetic amorphous silica 3%kaolinite 13%______________________________________
The ingredients are blended, hammer-milled until all the solids are essentially under 50 microns, reblended, and packaged.
EXAMPLE 18
______________________________________Wettable Powder______________________________________N--[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]-1- 50%(2-nitrophenyl)methanesulfonamidesodium alkylnaphthalenesulfonate 2%low viscosity methyl cellulose 2%diatomaceous earth 46%______________________________________
The ingredients are blended, coarsely hammer-milled and then air-milled to produce particles essentially all below 10 microns in diameter. The product is reblended before packaging.
EXAMPLE 19
______________________________________Granule______________________________________Wettable Powder of Example 18 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 20
______________________________________Extruded Pellet______________________________________N--[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-1- 25%(2-nitrophenyl)methanesulfonamideanhydrous 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 21
______________________________________Oil Suspension______________________________________N--[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocar- 25%bonyl]-1-(2- nitrophenyl)methanesulfonamidepolyoxyethylene 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 22
______________________________________Wettable Powder______________________________________N--[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-1- 20%(2-nitrophenyl)methanesulfonamidesodium 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 23
______________________________________Low Strength Granule______________________________________2-[[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]amino- 1%sulfonylmethyl] benzoic acid, methyl esterN,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 24
______________________________________Aqueous Suspension______________________________________N--[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-1- 40%(2-methylsulfonyloxyphenyl)methanesulfonamidepolyacrylic acid thickener 0.3%dodecylphenol polyethylene glycol ether 0.5%disodium phosphate 1%monosodium phosphate 0.5%polyvinyl alcohol 1.0%water 56.7%______________________________________
The ingredients are blended and ground together in a sand mill to produce particles essentially all under 5 microns in size.
EXAMPLE 25
______________________________________Solution______________________________________2-[[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocar- 5%bonyl]aminosulfonylmethyl]benzoic acid,methyl esterwater 95%______________________________________
The salt is added directly to the water with stirring to produce the solution, which may then be packaged for use.
EXAMPLE 26
______________________________________Low Strength Granule______________________________________2-[[(4,6-dimethyl-1,3,5-triazin-2-yl)aminocarbonyl]- 0.1%aminosulfonylmethyl]benzoic acid, methylesterattapulgite 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 27
______________________________________Granule______________________________________N--[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-1- 80%(2-nitrophenyl)methanesulfonamidewetting agent 1% -crude ligninsulfonate salt (containing 10% 25-20% of the natural sugars)attapulgite clay 9%______________________________________
The ingredients are blended and milled to pass through a 100 mesh screen. This material is then added to a fluid bed granulator, the air flow is adjusted to gently fluidize the material, and a fine spray of water is sprayed onto the fluidized material. The fluidization and spraying are continued until granules of the desired size range are made. The spraying is stopped, but fluidization is continued, optionally with heat, until the water content is reduced to the desired level, generally less than 1%. The material is then discharged, screened to the desired size range, generally 14-100 mesh (1410-149 microns), and packaged for use.
EXAMPLE 28
______________________________________High Strength Concentrate______________________________________N--[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-1- 99%(2-nitrophenyl)methanesulfonamidesilica 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 29
______________________________________Wettable Powder______________________________________N--[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]-1- 90%(2-nitrophenyl)methanesulfonamidedioctyl 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 30
______________________________________Wettable Powder______________________________________2-[[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]- 40%aminosulfonylmethyl]benzoic acid, methylestersodium 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 31
______________________________________Oil Suspension______________________________________2-[[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]amino- 35%sulfonylmethyl]benzoic acid, methyl esterblend 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 32
______________________________________Dust______________________________________2-[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocar- 10%bonyl]aminosulfonylmethyl]benzoic acid,methyl esterattapulgite 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, parking lots, drive-in theaters, around billboards, highway and railroad structures or under perimeter fences. Alternatively, the subject compounds are useful for the selective pre- or post-emergence weed control in crops, such as wheat, barley, corn, rice and soybeans.
The rates of application for the compounds of the invention are determined by a number of factors, including their use as selective or general herbicides, the crop species involved, the types of weeds to be controlled, weather and climate, formulations selected, mode of application, amount of foliage present, etc. In general terms, the subject compounds should be applied at levels of around 0.01 to 10 kg/ha, the lower rates being suggested for use on lighter soils and/or those having a low organic matter content, for selective weed control or for situations where only short-term persistence is required.
The compounds of the invention may be used in combination with any other herbicides, examples of which are those of the triazine, triazole, uracil, urea, amide, diphenylether, carbamate and bipyridylium types. Especially useful are combinations of the compounds of this invention with S-(4-chlorobenzyl)-N,N-diethylthiolcarbamate; 2-chloro-2',6'-diethyl-N-(butoxymethyl)acetanilide; S-ethyl-N,N-hexamethylenethiolcarbamate; 1-.alpha.,.alpha.-dimethylbenzyl-3-p-tolylurea; 1-(.alpha.,.alpha.-dimethylbenzyl)-3-methyl-3-phenylurea; 2,4-dichlorophenyl-3-methoxy-4-nitrophenyl ether; 2,4,6-trichlorophenyl-4'-nitrophenyl ether; 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-5-pyrazolyl-p-toluenesulfonate; O-ethyl-O-(3-methyl-6-nitrophenol)-N-sec-butyl phosphoramid-thioate; S-(1-methyl-1-phenethyl)piperidine-1-carbathioate; 2-chloro-2',6'-diethyl-N-(N-propoxyethyl)acetanilide; 4-ethoxymethoxybenz-2',3'-dichloranilide; 2-benzthiazol-2-iloxy-N-methylacetoanilide; 5-t-butyl-3-(2,4-dichloro-5-isopropoxyphenyl)-1,3,4-oxadiazol-2-one; 3',4'-dichloropropionanilide; and N-(1-ethylpropyl)-2,6-dinitro-3,4-xylidine.
The herbicidal properties of the subject compounds were discovered in a number of greenhouse tests. The test procedures and results follow.
TEST A
Seeds of crabgrass (Digitaria sp.), barnyardgrass (Echinochloa crusgalli), wild oats (Avena fatua), cassia (Cassia tora), morningglory (Ipomoea sp.), cocklebur (Xanthium sp.), sorghum, corn, soybean, rice, wheat and nutsedge tubers (Cyperus rotundus) were planted in a growth medium and treated preemergence 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 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. Treated plants and controls were maintained in a greenhouse for sixteen days, whereupon all species were compared to controls and visually rated for response to treatment. The ratings are based on a numerical scale extending from 0=no injury, to 10=complete kill. The accompanying descriptive symbols have the following meanings:
C=chlorosis/necrosis;
D=defoliation;
E=emergence inhibition;
G=growth retardation;
H=formative effects;
S=albinism;
U=unusual pigmentation; and
6Y=abscised buds or flowers.
The ratings for the compounds tested by this procedure are presented in Table A. It will be seen that certain of the compounds tested have utility for selective weed control in corn, rice and wheat. ##STR85##
TABLE A__________________________________________________________________________ Cmpd. 1 Cmpd. 2 Cmpd. 3 Cmpd. 4 Cmpd. 5 Cmpd. 6 Cmpd. 7 Cmpd. Cmpd. 9Rate kg/ha 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4__________________________________________________________________________POST-EMERGENCEBush bean 7C,9G,6Y 5C,9G,6Y 5C,9G,6Y 9D,9G,6Y 3C,9G,6Y 9C 9C 6C,9G 9CCotton 6C,9G 6C,9G 3C,3H,8G 6C,9G 2C,2H,7G 6C,9G 6C,9G 7C,9G 9CMorningglory 10C 5C,9G 9C 10C 2C,9H 10C 10C 5C,9G 10CCocklebur 3C,9G 4G 9C 9C 3C,9G 2C,8G 9C 9C 10CCassia 1C,9G 1C,2H 3C,7G 2C,4G 1C 6C,9G 6C,9G 5C,9G 9CNutsedge 4C,9G 1C,7G 9G 2C,8G 0 9C 6C,9G 1C,8G 2C,9HCrabgrass 2G 2C,7G 1H 2C,8G 0 4C,8G 5C,9G 4G 9CBarnyardgrass 3G 2C,5H 2C,8H 3C,9H 0 2C,6G 5C,9H 2C,9H 9CWild Oats 0 3G 0 2C,3G 0 2G 1C,9G 1C,6G 2C,7GWheat 0 2G 0 2C,3G 0 4G 1C,9G 4G 2C,9GCorn 0 9G 2C,9H 3C,9G 2C,5H 1C,8H 5C,9G 2C,9H 5U,9GSoybean 2C,9G 2C,9G 3C,9G 3C,9G 1C,4H 5C,9G 9C 3C,9H 5C,9GRice 1C 3C,9G 8G 2C,9G 2G 5G 5C,9G 1C,8G 5C,9GSorghum 1C,5G 1C,9G 9G 10C 2C,8H 2C,8G 9C 9G 9C__________________________________________________________________________ Cmpd. 10 Cmpd. 11 Cmpd. 12 Cmpd. 13 Cmpd. 14 Cmpd. 15 Cmpd. 16 Cmpd. Cmpd. 18Rate kg/ha 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4__________________________________________________________________________POST-EMERGENCEBush bean 9D,9G,6Y 4C,9G,6Y 3C,5G,6Y 5C,8G,6Y 4S,8G,6Y 5S,9G,6Y 0 0 9CCotton 5C,9G 6C,9G 3C,2H,5G 5C,9G 3C,3H,5G 5C,9G 0 1C,3H 9CMorningglory 10C 5C,9G 3C,7G 4C,9G 3C,8G 3C,9G 0 0 10CCocklebur 3C,9H 4C,9G 1C,4G 3G 3C,8H 3C,9G 0 0 3C,9GCassia 3C,4H 5C 1C 3C 2C 3C 0 0 3C,7GNutsedge 7G 1C,6G 4G 1C 3C,9G 0 0 0 9CCrabgrass 1C,3H 1C,5G 1C 2G 0 1C,3G 0 0 9CBarnyardgrass 3C,8H 9H 0 3G 0 3C,9H 0 0 6C,9HWild Oats 2G 0 0 0 0 0 0 0 7GWheat 2G 0 0 0 0 3G 0 0 2C,8GCorn 5C,9H 3C,9H 0 1C,4G 1C,3H 2C,7H 0 0 3U,9GSoybean 3C,9G 2C,7G 1C,2H 2C,4H 1C,3H 1C,3H 0 1C,6G 6C,9GRice 2C,8G 2C,8G 0 1C,6G 3G 1C,6G 0 0 2C,6GSorghum 3C,9H 2C,9G 0 2C,8H 1C,3G 2C,9H 0 0 2C,9G__________________________________________________________________________ Cmpd. 19 Cmpd. 20 Cmpd. 21 Cmpd. 22 Cmpd. 23 Cmpd. 24 Cmpd. 25 Cmpd. 26 Cmpd. 27 Cmpd. Cmpd. 29Rate kg/ha 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4__________________________________________________________________________POST-EMERGENCEBush bean 5C,9G 6C,9G 9C 3C,9G,6Y 4S,8G,6Y 1C 1C 0 2C,6F 1C 2C,5GCotton 6C,9G 6C,9G 6C,9G 6C,9G 2C,2H 0 2C,2H 2C,4G 2C,2H 1C 1C,2GMorningglory 5C,9G 4C,9G 4C,9G 2C,7G 2C,5H 0 2C,7H 2C,2H 4C,9G 1C 2CCocklebur 4G 6C,9G 9C 3C,9G 3C 0 0 0 3C,7G 1C 1C,5GCassia 2C,3G 3C,3H 4C,3H 3C 2C 0 2C 0 3C 0 5GNutsedge 9G 2C,8G 2C,8G 1C,9G 3C,8G 0 0 0 2G 0 1CCrabgrass 5C,8G 3C,8G 6C,9G 1C,4G 3C,8G 0 1C,7G 0 2C,5G 0 0Barnyardgrass 3C,9H 2C,9H 5C,9H 3C,8H 4C,9H 0 1C,5H 0 3C,8H 0 0Wild Oats 3C,8G 2C,8G 9G 4G 1C,9G 0 0 0 0 0 0Wheat 4C,8G 4C,7G 3C,9G 4G 2C,9G 0 0 0 8G 0 0Corn 8U,9C 2U,9G 8U,9G 2C,8G 2C,8G 0 1C,6H 0 2C,7H 0 0Soybean 4C,8G 9C 5C,9G 2C,9G 2C,2H 0 2C 0 1C,1H 1C 1CRice 5C,9G 4C,8G 4C,9G 2C,7C 4C,7G 0 1C,5G 0 2C,7G 0 0Sorghum 9C 3C,9G 9C 2C,9G 3C,9G 0 2C,9G 0 9G 0 0__________________________________________________________________________ Cmpd. 30 Cmpd. 31 Cmpd. 32 Cmpd. 33 Cmpd. 34 Cmpd. Cmpd.36 Rate kg/ha 0.4 0.4 0.4 0.4 0.4 0.4 0.4__________________________________________________________________________ POST-EMERGENCE Bush bean 9C 5C,9G,6Y 1C 0 0 0 0 Cotton 9C 5C,8G 0 1C 0 0 0 Morningglory 10C 4C,8H 1C 0 0 0 0 Cocklebur 9C 4C,9G 0 1C,6H 0 0 0 Cassia 9C 4C,6H 0 0 0 0 0 Nutsedge 9C 9C 0 0 0 0 0 Crabgrass 9C 9C 2G 0 0 0 0 Barnyardgrass 9C 9C 0 0 0 0 0 Wild Oats 2C,9G 0 2G 0 0 0 0 Wheat 3C,9G 5U,9G 0 0 0 0 0 Corn 5U,9C 7U,9C 1C 0 0 0 0 Soybean 5C,9G 5C,9G 3H 0 0 0 0 Rice 3C,9G 5C,9G 2G 0 0 0 0 Sorghum 5U,9C 10C 2C,5G 0 0 0 0__________________________________________________________________________ Cmpd. 1 Cmpd. 2 Cmpd. 3 Cmpd. 4 Cmpd. 5 Cmpd. 6 Cmpd. 7 Cmpd. 8 Cmpd. Cmpd. 10Rate kg/ha 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4__________________________________________________________________________PRE-EMERGENCEMorningglory 9G 9G 9C 9G 8H 9G 10C 9C 9C 1C,8GCocklebur 9H 9H 9H 9H 9H 9H 9H 9H 9H 1HCassia 6C,9G 3C,5H 8G 3C,8G 3H 8G 2C,9G 5C,8G 2C,9G 3CNutsedge 10E 7G 10E 1C,9G 0 10E 10E 10E 9G 1CCrabgrass 2C 2C 1H 2C,5G 2G 2C,6G 5C,9G 2C,8G 5C,9G 1C,5GBarnyardgrass 3C 2C,6H 3C,9G 3C,9H 0 2C,9H 9H 4C,9G 9C,9H 2C,6HWild Oats 0 2C,5G 2C,6G 1C,5G 0 5G 1C,8G 2C,8G 4C,9G 5GWheat 0 9G 7G 2C,9H 0 5G 9G 7G 2C,9G 6GCorn 2C,9H 9G 2C,9H 10H 1C,3G 9G 5C,9G 9G 10H 2C,8GSoybean 9G,2H,7X 2C,6H 2C,7H 9H 1C 9H 9H 8H 9H 1CRice 3C,8G 10E 3C,9H 10E 2C,6G 2C,8G 10E 5C,9H 10E 4C,8HSorghum 7H 5C,9H 9H 8C,9H 1C,3G 9G 6C,9G 2C,9G 5C,9H 3C,9G__________________________________________________________________________ Cmpd. 11 Cmpd. 12 Cmpd. 13 Cmpd. 14 Cmpd. 15 Cmpd. 16 Cmpd. 17 Cmpd. 18 Cmpd. 19 Cmpd. Cmpd. 21Rate kg/ha 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4__________________________________________________________________________PRE-EMERGENCEMorningglory 8G 9G 9G 8G 9G 0 1C,5H 9G 5C,9G 9C 9GCocklebur 4C,9G 2C,5H 9G 8H 8H 0 3G 9H 9H 9H 9HCassia 3C 2C 2C 5G 2C 0 2C 9G 4C,7G 2C,8G 4C,9GNutsedge 3G 2C,8G 3G 4G 5G 0 0 10E 10E 10E 10ECrabgrass 2C 2C 1C 0 1C,3G 0 0 2C,9G 9G,4C 4C,9G 5C,9GBarnyardgrass 3C,9H 2C 1C,3G 4G 8H,2C 0 1C 9H 9H 9H 9HWild Oats 4G 0 2G 2G 5G 0 0 1C,8G 4C,9H 3C,9H 4C,9HWheat 6G 0 7G 2G 8G 0 0 9G 9H 9H 3C,9HCorn 2C,8G 2C 2C,8G 1C,6G 9G 0 0 9G 9H 9H 10ESoybean 2C,6G 1H 1C 1C 2C 0 0 9H 9H 9H 9HRice 3C,8G 4G 5C,8H 1C,6G 5C,9H 0 0 10E 10E 10E 10ESorghum 2C,9G 5G 3C,8H 2C,7H 3C,9H 0 0 5C,9H 5C,9G 6C,9G 6C,9H__________________________________________________________________________ Cmpd. 22 Cmpd. 23 Cmpd. 24 Cmpd. 25 Cmpd. 26 Cmpd. 27 Cmpd. 28 Cmpd. 29 Cmpd. 30 Cmpd. Cmpd. 32Rate kg/ha 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4__________________________________________________________________________PRE-EMERGENCEMorningglory 3C,6G 2C 6G 9G 2C,9G 9G 1C,3H 2C 9C 2C,4H 0Cocklebur 9H 3H 2H 5H 2C 7H 0 2G 9H 2C,6H 0Cassia 3C 2C 1C 2C 2C 2C 2C 2C 5C,9G 3C 0Nutsedge 10E 1C 0 1C 0 0 1C,8G 4G 10E 2C,5G 0Crabgrass 4G 3G 0 3G 2G 1C,5G 2G 2G 2C,9G 3C,6G 0Barnyardgrass 3C,8G 4C,8G 2C 2C,5G 4G 2C,8H 1C 1C,2H 2C,9H 9H 0Wild Oats 2C,8G 8G 0 2C 1C 1C 0 3G 2C,9G 2C,4G 0Wheat 2C,8G 1C,8G 0 1C,7G 2G 1C,9G 0 2G 2C,9G 5C,9H 0Corn 3C,8H 4C,8H 2C,4G 2C,8G 2C,7G 2C,9G 1C 1C,3G 3C,9G 10H 1C,3HSoybean 1C,2H 3G 0 0 0 1C,2G 1C,1H 2G 9H 2C,6H 0Rice 9H 2C,8H 1C 2G 0 3G 0 1C 10E 9H 1CSorghum 2C,9G 2C,9G 1C,5G 1C,9G 2C,4G 5C,9H 1C 1C,7G 2C,9H 6C,9H 2C,4H__________________________________________________________________________ Cmpd. 33 Cmpd. 34 Cmpd. Cmpd. 36 Rate kg/ha 0.4 0.4 0.4 0.4__________________________________________________________________________ PRE-EMERGENCE Morningglory 0 0 0 0 Cocklebur 0 0 0 0 Cassia 0 0 0 0 Nutsedge 0 0 0 0 Crabgrass 0 0 0 0 Barnyardgrass 0 0 0 0 Wild Oats 0 0 0 0 Wheat 0 0 0 0 Corn 0 0 0 0 Soybean 0 0 0 0 Rice 0 0 0 0 Sorghum 0 0 0 0__________________________________________________________________________
It is noted that certain compounds tested showed no activity at the levels tested but it is thought they would have activity 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 pensylvanicum), 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.
It should be noted that some of the compounds tested are useful as pre- or post-emergence treatment for weed control in crops such as wheat.
TABLE 8__________________________________________________________________________PRE-EMERGENCE ONFALLSINGTON SILT LOAM__________________________________________________________________________ Compound 1 Compound 2 Compound 3 Compound 4 Compound 6 Compound Compound 8Rate kg/ha .060 .250 .060 .250 .060 .250 .060 .250 .060 .250 .060 .250 .060__________________________________________________________________________Crabgrass 0 0 0 0 0 3G 0 0 0 0 0 6G 0Barnyardgrass 0 0 0 0 0 3G 2G 4G 0 4G 4G 8G,5H 0Sorghum 2G 4G 6G,3H 8G,5H 0 4G,2H 7G,5H 9G,9C 3G 6G,3H 9G,9C 10C 4G,3HWild Oats 0 0 0 0 0 0 0 3G 0 0 3G 2G 0Johnsongrass 0 5E 5G,3H 5G,5H 0 4G 7G,5H 8G,5H 0 3H 7G,5H 8G,5H 0Dallisgrass 0 0 0 0 0 0 0 0 0 0 2G 3G 0Giant foxtail 0 0 0 0 0 3G 0 5G,3H 0 0 5G,2C 8G,5H 0Ky. bluegrass 0 3G 0 3G 0 4G 0 0 0 3G 5G 6G 0Cheatgrass 0 0 0 3G 0 0 0 5G 0 0 5G 5G,2C 0Sugarbeets 3G 7G,5H 0 5G,3H 3G 8G,8C 6G 8G,8C 4G 6G 7G,5H 8G,8C 6GCorn 0 0 0 0 0 0 0 5G,3H 0 0 3G 2C 0Mustard 8G,5C 9G,8C 4G 5G,5H 7G,5H 9G,8C 5G,3H 7G,5H 9G,9C 10C 7G,3H 8G,8C 8G,8CCocklebur 0 0 0 0 0 0 0 0 0 0 0 0 0Pigweed 6G 9G,9C 3G 10C 3G 9G,9C 0 9G,8C 10E 10E 0 5G 5G,5CNutsedge 0 0 0 0 0 0 0 0 0 9G 0 5G 5GCotton 0 0 0 2G 0 0 0 4G,3H 0 4G 0 5G,5H 2HMorningglory 0 0 0 3G 0 3H 0 5G,5H 0 3G 4G,5H 8G,5C 0Cassia 0 0 0 0 0 3G 0 3G 0 3G 0 8G,3C 0Teaweed 0 0 0 0 0 6G,3C 0 0 0 5G 3G 5G,2C 5G,2CVelvetleaf 0 3G,3H 0 0 0 3G,3H 0 2C 5G,3H 7G,5H 2G 5G,3H 3G,3HJimsonweed 0 0 0 0 0 0 0 2G 0 5G,5C 0 5G,3C 5G,3CSoybean 0 0 0 2G 0 2G 0 4G,2H 3G 5G,2H 3G 7G,3C 0Rice 0 0 4G 6G,3H 3G 5G 3G 7G,3H 3G 5G 5G 7G,3C 4GWheat 0 0 0 0 0 0 0 3G 0 3G 3G 3G 0__________________________________________________________________________ Compound 8 Compound 9 Compound 18 Compound 19 Compound Compound 21 Rate kg/ha .250 .060 .250 .030 .120 .030 .120 .030 .120 .030 .120__________________________________________________________________________ Crabgrass 0 3G 6G 5G 6G 4G 6G,3C 4G 5G 5G 7G,3C Barnyardgrass 6G,2H 7G,3H 8G,7C 3G 4G 2G 4G 3G 3G 2G 5G Sorghum 8G,5H 10C 10C 7G,3H 9G,3H 9G,5H 10C 4G,3H 6G,5H 9G,9C 10C Wild Oats 3G 2G 4G 0 0 3G 6G 0 3G 4G 6G Johnsongrass 3H 7G,5H 8G,5H 4G 6G,3H 7G,3H 8G,5H 2G 5G,3H 5G 7G,3H Dallisgrass 3G 3G 6G 0 0 0 2G 0 0 2G 3G Giant foxtail 3G 8G,5H 9G,9C 0 4G 3G 7G,5H 0 4G,3C 6G,3C 8G,5H Ky. bluegrass 3G 6G 7G,3C 3G 5G 6G,3H 6G,5C 3G 5G 7G,7C 8G,8C Cheatgrass 3G 8G,8C 8G,9C 0 5G 8G 10E 0 5G 8G 10E Sugarbeets 7G,5C 8G,8C 9G,9C 4G,3H 6G,3H 4G,3H 6G,5H 3G 7G,5H 6G,5H 7G,7C Corn 4G,3H 6G,5H 8G,5H 0 3G,3H 0 6G,5H 0 3G 3G 9G,9C Mustard 9G,9C 10C 10C 7G,7C 9G,9C 4G 7G,8C 8G,3C 8G,8C 6G,3H 8G,8C Cocklebur 3H 5G,4H 6G,5H 0 4G,3H 0 0 -- 3G 3G 3G Pigweed 10E 8G 10E 0 -- -- -- -- -- -- -- Nutsedge 8G 4G 7G 7G 9G,5C 0 0 0 6G 0 5G Cotton 6G,5H 4G 8G,5H 3G 4G,3H 0 3G 0 0 0 3G Morningglory 3G,5H 7G,5H 9G,5C 0 0 0 4G,3H 0 0 4G,3H 7G,5H Cassia 4G 8G,3C 9G,5C 3G 4G 0 0 0 0 0 2C Teaweed 6G,2C 5G,2C 6G,2C 6G 6G 4G 3G 0 3G -- 3G Velvetleaf 8G,5H 3G,3H 6G,5H 4G 5G,3H 0 3G 0 3G 0 2G Jimsonweed 5G,3C 7G,5C 8G,8C 0 5G,5C 0 3G 0 5G,3C 4G 7G,3C Soybean 4G,2C 3G,2C 8G,5H 3G 5G 3G 2G,2C 0 2G 0 3G Rice 5G 9G,9C 10E 0 5G,3H 7G,3H 10E 3G 4G 7G,3H 9G,9C Wheat 4G 4G 5G 0 2G 3G 5G 0 0 4G 6G__________________________________________________________________________
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 pensylvanicum), crabgrass (Digitaria sp.), nutsedge (Cyperus rotundus), barnyardgrass (Echinochloa crusgalli), giant foxtail (Setaria faberii) and wild oats (Avena fatua). Approximately 21/2 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. Selected compounds tested by this procedure are useful for the post-emergence control of weeds in wheat, corn, rice and soybeans.
TABLE C Over-the-Top Soil/Foliage Treatment Compound 1 Compound 2 Compound 3 Compound 4 Compound 6 Compound 7 Compound 8 Rate kg/ha 0.063 0.250 0.250 1.0 0.250 0.063 0.063 0.063 0.031 0.063 0.125 0.250 0.500 0.125 0.500 0.125 0.016 0.063 0.125 Soybeans 8G,5C 9G,9C 10G,7C 10G,3C 8G,5C 4G,3C 8G,4C 9G,1C 7G,5C 8G,7C 8G,7C 8G,6C 10G,9C 10G,2C 10G,4C 10C 10G,5C 10G,3C 10G,6C Velvetleaf 9G,5C 10G,6C 10C 9G,9C 2C 1C 8G,3C 7G,5C 4C 5G,1C 4G,5C 3C 9G,9C 9G,5C 9G,8C 9G,8C 9G,3C 9G,5C 10C Sesbania 9G,4C 9G,6C 8G,4C 9G,7C 0 0 7G,5C 8G,4C 1C 0 3G,2C 5G,2C 10C 10C 10C 10C 9G,5C 10C 10C Cassia 8G,4C 6G,6C 7G,3C 10G,1C 4G 0 7G,1C 7G 0 2G 3C 1G 10G,5C 10G,5C 10G,5C 10G,5C 4G 9G,4C 7G,4C Cotton 6G 8G,3C 9G,4C 9G,6C 1C 0 3G 6G,2C 1C 1G,1C 6G,2C 1G,1C 10G,8C 9G,4C 9G,9C 9G,8C 4G,2C 6G 8G,4C Morningglory 9G,2C 9G,3C 9G,7C 8G,8C 6G,5C 6G,3C 8G,5C 7G,5C 7G,2C 7G,5C 8G,2C 8G,6C 10C 10C 9G,8C 9G,8C 8G,3C 9G,9C 10G,2C Alfalfa 7G,2C 6G,2C 7G 9G,9C 1C 1C 1C 5G 2C 1G,2C 6G,3C 4G,5C 7G,6C 7G 10G 8G 2G 0 7G Jimsonweed 8G 5G 5G 4G,6C 0 0 1C 0 7G 0 7G -- 0 2G,2C -- -- 8G 9G 5G Cocklebur 2G 8G 3G 8G,1C 0 0 8G,2C 7G,4C 3G,3C 1G,5C 8G 8G,8C 10G,9C 9G,1C 8G,4C 1G 8G,3C 9G,4C -- Sunflower 10G,2C 10G,5C 5G,2C 9G,5C 0 0 9G,7C 9G,3C 2C,1H 8G,7C 9G,5C 9G,7C 9G,8C 7G 10G,5C 8G 6G 8G 9G,2C Mustard 10C 10C 9G,9C 10C 9G,9C 9G,6C 10C 9G 8G,8C 8G,8C 9G,5C 9G,9C 10C 10C 10G 9G,5C 10C 10C 9G,8C Sugarbeets 7G 8G 9G,5C 9G,5C 8G,5C 5G 8G 8G,4C 8G 8G,3C 8G 9G,7C 10C 8G,7C 9G,8C 9G,2C 3G 5G 8G Corn 0 3G 0 2U 8G,1C 5G,2C 5G,2H 8G,2H 8G,5H 5G,1U 9G,7U 7G,3U 6G,2H 5G 10C 9G,2U 3G,3H 8G,3H 9G,2C Crabgrass 0 0 0 0 1C 2C 0 3G 0 1C 0 1G,2C 0 6G 9G,5C 9G 0 3G 3G Rice 0 0 0 0 6G,1C 5G,1C 0 0 4G 3G 6G,3C 5G,1C 4G 4G 5G,5C 8G,2C 1G 0 0 Nutsedge 6G 8G 3G 7G 0 0 5G 6G 0 0 0 0 8G 8G 9G 3G 6G 6G,2C 6G Barnyardgrass 0 0 0 8G,2C 0 0 0 2G 2G 5G,3C 6G,3H 8G,3C 3G,2C 3G,2C 8G,6C 8G,4C 0 4G,4H 7G,5C Wheat 0 0 0 0 0 0 0 4G 0 1G 4G 3G 0 0 5G,5C 5G 0 0 3G Giant foxtail 0 2G 0 0 0 0 0 6G,2C 0 2G 4G 5G,3C 0 0 9G 9G 0 2G 5G Wild Oats 0 0 2G 0 0 0 0 0 0 0 0 0 0 0 7G,5C 8G 0 0 2G Sorghum 0 2G 0 0 7G 6G 8G,2H 2C 7G 7G,2U 10C 7G,6U 5G 3G 10G,5U 9G,5C 2H 7G 5G Johnsongrass 0 0 -- -- -- -- -- -- 4G -- 8G -- -- -- -- -- -- -- -- Field Bindweed 3G 3G -- -- -- -- -- -- -- -- 0 -- -- -- -- -- -- -- -- Com- pound 8 Compound 9 Compound 10 Compound 11 Compound 18 Compound 19 Compound 20 Compound 21 Compound 22 Compound 23 Rate kg/ha 0.500 0.500 0.125 0.500 0.125 0.031 0.500 0.125 0.125 0.031 0.125 0.031 0.125 0.031 0.125 0.031 0.125 0.031 0.125 0.031 Soybeans 10G,7C 10G,5C 9G,8C 9G,6C 2G,1C 2G,1C 8G,5C 5G,5C 10C 10C 9G,7C 7G,6C 9G,8C 9G,7C 10G,3C 9G,8C 7G,4C 6G,3C 5G 3G Velvetleaf 8G,9C 8G,7C 7G,5C 7G,5C 9G,7C 4G,4C 4G,3C 0 10C 10C 6G 6G,2C 9G,4C 6G 9G,5C 5G,4C 7G,4C 5G,2C 0 0 Sesbania 10C 9G,9C 9G,8C 8G,4C 7G 5G 2C 0 10C 10C 0 0 9G,9C 7G,7C 8G 4G 7G,6C 4G 0 0 Cassia 10G 9G,5C 9G,7C 3G,2C 0 0 5G,4C 2C 10C 9G,9C 3G,3C 1G,1C 9G,8C 5G,6C 9G,4C 8G 8G,6C 2G,2C 2C 0 Cotton 9G,4C 10G,9C 9G,9C 8G,5C 9G,7C 5G,3C 2G,3C 1C 10C 10C 9G 3G 9G,7C 9G,3C 9G,5C 8G,3C 7G,3C 2G 2G 0 Morningglory 10G,2C 9G,9C 10G,7C 9G,5C 8G,3C 8G,3C 7G 4G 10C 10C 2C 0 9G,7C 8G,2C 9G,3C 7G 8G,2C 2G 0 2G Alfalfa 7G,3C 7G,4C 6G,4C 2G,4C 3G 3G 5G 1G 10C 10C 2G,2C 2C 9G,7C 6G,3C 10C 8G,3C 4G,3C 0 2C 2C Jimsonweed -- 6C 4C -- -- 0 0 0 9G,7C 9G,4C 9G -- -- 6G,2C 9G,7C 8G,2C 4G 2G 2C 0 Cocklebur 10G 10C 10G,7C 7G,2C 10G,3C 2G 10G,4C -- 9G,9C 9G,7C 8G 0 9G,9C 6G 9G,5C 9G,2C 2G 2G 2G 0 Sunflower 9G,7C 10C 10C 8G,3C 8G,2C 5G,2C 6G,5C 0 10C 10C 5G 0 10C 8G,5C 8G,7C 6G 2G,3C 1G 0 0 Mustard 9G,7C 10C 10C 9G,9C 9G,9C 8G,5C 9G,5C 0 10C 10C 9G 7G 10C 9G,9C 10C 10C 10C 7G,5C 4G,4C 0 Sugarbeets 9G,2C 8G,7C 8G,7C 8G,4C 9G,7C 8G,5C 8G,7C 3G 10C 10C 6G,6C 2G,3C 9G 8G 9G,7C 6G 2G 4G 4G 0 Corn 9G,1C 10C 10C 7G,1H 7G,1C 7G,1C 9G 9G 9G,9C 9G,9C 9G,3C 8G 9G,7C 7G,3H 9G,9C 10C 3G,2H 0 3G 0 Crabgrass 5G 8G,3C 8G,3C 1G 8G,3C 7G,2C 3G 4G 8G,5C 7G -- 5G 7G 0 8G,4C 4G,3C 0 0 0 0 Rice 5G 9G,6C 9G,4C 5G 8G,1C 8G,1C 2G 4G,2C 8G,4C 5G,2C 8G,7C 8G,7C 6G,4C 5G 10C 10C 3G 0 0 0 Nutsedge 8G 7G,4C 3G 4G 9G,2C 8G,4C 0 0 10C 10C 0 0 9C 8G 10C 9G 0 0 0 0 Barnyardgrass 7G,5C 8G,7C 7G,5C 7G,4C 7G,4C 8G,5C 7G 8G,4C 9G,5C 8G 0 0 9G,4C 6G 9G,8C 2G 0 0 0 0 Wheat 6G 7G,3C 7G 5G 6G,2C 6G,2C 0 0 9G,3C 9G,2C 8G 8G 8G,2C 5G 9G,8C 8G,4C 0 2G 0 0 Giant foxtail 3G 9G,5C 8G,3C 7G 8G,1C 8G,3C 5G 5G 9G,5C 8G 9G,9C 9G,9C 8G,2C 5G 9G,5U 9G,2C 1G 0 3G 0 Wild Oats 3G 6G 5G 2G 1G 3G 0 0 9G,3C 8G 8G,2C 7G 8G,4C 5G,1C 7G 0 0 0 0 0 Sorghum 7G,1C 9G,7U 9G,4U 8G,1C 8G,1C 9G,1U 8G,1U 6G,2U 9C,7C 9G,7C 6G,6C 6G,4C 9G,6C 8G 10C 8G,5C 6G 5G,5C 6G 4G Johnsongrass -- -- -- -- -- -- -- -- 9G,8U 9G,8U 9G,7C 9G,6C 8G,7U 7G,3U -- -- 2G 0 3G 0 Field Bindweed -- -- -- -- -- -- -- -- -- 5G 4G,5C 4G,5C 5G 8G -- -- 3G 0 -- --
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 pensylvanicum), 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 nonphytotoxic 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. The recorded data are presented in Table D. One of the compounds has utility for pre- and or post-emergence weed control in wheat and barley.
TABLE D__________________________________________________________________________ 5 Compound 2 Compound 1 Pre- Post- Pre-Emergence Post Emergence Emergence EmergenceRate kg/ha 1/2 1 1/2 1 1/8 1/8__________________________________________________________________________wheat 1C,1G 1C,2G 1C,1G 0 7G 4C,7Gbarley 0 1G 2C 1C 8G 5C,6Gwild oats 1C,2G 1C,3G 1C 0 2C,6G 5C,6Gdowny brome 5G 5G 0 0 10C 7C,9Gcheatgrass 1C,6G 2C,8G 0 0 10C 10Cblackgrass 4G 1C,5G 2G 0 6C,8G 5C,8Gannual bluegrass 1C,5G 4G 0 5G 7C,9G 6C,8Ggreen foxtail 4G 6G 2G 2C,5G 8C,9G 9C,9Gquackgrass 5G 6G 2G 4G 4C,8G 5C,9GItalian ryegrass 1C,4G 1C,5G 1G 6G 5C,8G 4C,7Gripgut brome 5G 2C,7G 3G 3G 6C,9G 10CRussian thistle 0 0 1C,2G 7C,8G 5C,4G 10Ctansy mustard 10E 10E 10C 10C 10C 10Csmartweed -- -- -- -- -- --tumble mustard 10C 10C 10C 10C 10C 10Ckochia 3C,8G 2C,8G 3C,7G 2C,8G 9C,9G 10Cshepherd's purse 10C 10C 10C 10C 10C 10CMatricaria inodora 9G 9G 10C 10C 9G 10Cblack nightshade 6G 8G 0 3G 3C,8G 10Cyellow rocket 9G 9G 10C 10C 8C,9G 10Cwild mustard 10C 10C 10C 10C 10C 10Cwild buckwheat 2C,8G 2C,9G 10C 10C 6C,7G 10C__________________________________________________________________________
TEST E
A series of simulated rice paddy tests were conducted in a greenhouse. Compounds selected from within the scope of the present invention were formulated and applied directly to the paddy water three days after transplanting of rice. "Early" plant response ratings (less than one week after application) were taken in some of the tests; "late" plant response ratings (5 to 6 weeks after application) were taken in all tests.
TABLE E______________________________________ Barnyard- Water Arrow-Rate Rice Rice grass Chestnut headai/ha Early Late late late late______________________________________Compound 1 50 -- 0 0 9G 1G,2H200 -- 0 0 3G 0Compound 6 50 0 0 10C 10C 4G200 0 0 9C 10C 5G,3HCompound 8 25 0 0 6G,8E 5G 9G100 0 0 9G,9E 10C 10G,5CCompound 18 50 0 4G 8C 10C 6G200 0 9G 10C 10C 10ECompound 22 50 0 0 0 0 0200 0 0 0 0 0______________________________________
Several of the compounds tested provided excellent control of weeds in rice without damage to the rice.

Number	Name	Date
4238621	Levitt	Dec 1980
4371391	Levitt	Feb 1983
4394153	Levitt	Jul 1983

	Number	Date	Country
Parent	306212	Sep 1981
Parent	203638	Nov 1980

Benzylsulfonyl isocyanates

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