Herbicidal o-alkylsulfonyloxy- and o-alkylsulfonylaminobenzenesulfonamides

BACKGROUND OF THE INVENTION
This invention relates to ortho(sulfonyl)oxybenzene sulfonamides and their use as herbicides.
Netherlands Pat. No. 121,788, published Sept. 15, 1966, teaches the preparation of compounds of Formula (I), and their use as general or selective herbicides: ##STR1## wherein R.sub.1 and R.sub.2 may independently by alkyl of 1-4 carbon atoms; and
R.sub.3 and R.sub.4 may independently be hydrogen, chlorine or alkyl of 1-4 carbon atoms.
Compounds of Formula (II), and their use as antidiabetic agents, are reported in J. Drug. Res. 6, 123 (1974): ##STR2## wherein R is pyridyl.
In U.S. Pat. No. 4,127,405, compounds are disclosed of the general formula: ##STR3## R.sub.3 and R.sub.6 are independently hydrogen, fluorine, chlorine, bromine, iodine, alkyl of 1-4 carbon atoms, alkoxy of 1-4 carbon atoms, nitro, trifluoromethyl, cyano, CH.sub.3 S(O).sub.n -- or CH.sub.3 CH.sub.2 S(O).sub.n --;
R.sub.4 is hydrogen, fluorine, chlorine, bromine or methyl;
R.sub.5 is hydrogen, fluorine, chlorine, bromine, methyl or methoxy;
R.sub.7 is hydrogen, fluorine, chlorine, bromine, alkyl of 1-2 carbon atoms or alkoxy of 1-2 carbon 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 suitble salts; provided that:
(a) when R.sub.5 is other than hydrogen, at least one of R.sub.3, R.sub.4, R.sub.6 and R.sub.7 is other than hydrogen and at least two of R.sub.3, R.sub.4, R.sub.6 and R.sub.7 must be hydrogen;
(b) when R.sub.5 is hydrogen and all of R.sub.3, R.sub.4, R.sub.6 and R.sub.7 are other than hydrogen, then all of R.sub.3, R.sub.4, R.sub.6 and R.sub.7 must be either chlorine or methyl; and
(c) when R.sub.3 and R.sub.7 are both hydrogen, at least one of R.sub.4,
R.sub.5 or R.sub.6 must be hydrogen.
In particular, the patent discloses orthosubtituted compounds wherein the substitution is C.sub.1 -C.sub.4 alkyl.
The presence of undesired vegetation causes substantial damage to useful crops, especially agricultural products that satisfy man's basic food needs, such as soybeans, corn, wheat and the like. The current population explosion and concomitant world food shortage demand improvements in the efficiency of producing these crops. Preventing or minimizing the loss of a portion of valuable crops by killing, or inhibiting the growth of undesired vegetation is one way of improving this efficiency.
A wide variety of materials useful for killing, or inhibiting (controlling) the growth of undesired vegetation is available; such materials are commonly referred to as herbicides. However, the need exists for still more effective herbicides that destroy or retard weeds without causing significant damage to useful crops.
SUMMARY OF THE INVENTION
This invention relates to novel compounds of Formula I, agriculturally suitable compositions containing them, and their method of use as general as well as selective pre-emergence herbicides. ##STR4## where W is O or S;
Q is O or NR.sub.5 ;
R.sub.1 is C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkyl substituted with 1-3 atoms of F, Cl or Br, CH.sub.2 CH.sub.2 OCH.sub.3, CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 or ##STR5## R.sub.2 is H, F, Cl, Br, OCH.sub.3, NO.sub.2, CF.sub.3 or C.sub.1 -C.sub.2 alkyl;
R.sub.3 is H, F, Cl, Br or CH.sub.3 ;
R.sub.4 is H, CH.sub.3 or OCH.sub.3 ;
R.sub.5 is C.sub.1 -C.sub.4 alkyl;
R.sub.6 and R.sub.7 are independently H, F, Cl, Br, CH.sub.3, CF.sub.3, NO.sub.2 or OCH.sub.3 ;
A is ##STR6## X is NH.sub.2, N(CH.sub.3).sub.2, NHCH.sub.3, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkyl substituted with 1-3 atoms of F, Cl or Br, CH.sub.2 OCH.sub.3, CH.sub.2 OCH.sub.2 CH.sub.3, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.2 alkylthio, C.sub.3 -C.sub.4 alkenyloxy, C.sub.3 -C.sub.4 alkynyloxy, OCH.sub.2 CH.sub.2 OCH.sub.3 or C.sub.2 -C.sub.4 alkoxy substituted with 1-3 atoms of F, Cl or Br;
n is 1 or 2;
Y is H, CH.sub.3, OCH.sub.3 or Cl;
X.sub.1 is O or CH.sub.2 ;
Y.sub.1 is H, CH.sub.3, OCH.sub.3 or Cl;
X.sub.2 and Y.sub.2 are independently CH.sub.3 or OCH.sub.3 ; and
Z is CH, N, CCH.sub.3, CBr, CCl, CF, CI,
CC.sub.2 H.sub.5, CCH.sub.2 CH.sub.2 Cl or CCH.sub.2 CH.dbd.CH.sub.2 ; provided that:
(1) when Y is Cl, then Z is other than N and X is NH.sub.2, NHCH.sub.3, N(CH.sub.3).sub.2, CH.sub.3 or OCH.sub.3 ;
(2) when Y is H, then X is OCH.sub.3, CH.sub.3 or CH.sub.2 OCH.sub.3, and Z is other than N;
(3) when W is S, then R.sub.4 is H; and
(4) when R.sub.4 is OCH.sub.3, then Q is O.
Preferred for reasons of higher herbicidal activity and/or more favorable ease of synthesis are:
(1) Compounds of the generic scope where R.sub.5 is CH.sub.3, W is O, and R.sub.4 is H or CH.sub.3 ;
(2) Compounds of Preferred (1) where R.sub.1 is C.sub.1 -C.sub.4 alkyl, CF.sub.3, CH.sub.2 CH.sub.2 OCH.sub.3 or CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 ;
(3) Compounds of Preferred (2) where R.sub.2 is H or Cl;
(4) Compounds of Preferred (3) where R.sub.3 is H;
(5) Compounds of Preferred (4) where R.sub.1 is C.sub.1 -C.sub.3 alkyl or CF.sub.3 ; Q is O; A is ##STR7## and Z is CH or N; (6) Compounds of Preferred (5) where R.sub.4 is H;
(7) Compounds of Preferred (6) where X and Y are independently CH.sub.3 or OCH.sub.3, and R.sub.1 is CH.sub.3 ; and
(8) Compounds of the generic scope where
Q is ##STR8## R.sub.5 is CH.sub.3 or CH.sub.3 CH.sub.2 ; R.sub.2 is C.sub.1 -C.sub.3 alkyl or CF.sub.3 ;
R.sub.2 and R.sub.3 are H;
X is CH.sub.3, OCH.sub.3, N(CH.sub.3), CH.sub.2 OCH.sub.3, OCH.sub.2 CH.sub.3 or OCH.sub.2 CF.sub.3 ;
Y is CH.sub.3, OCH.sub.3 or Cl; and
Z is CH or N.
Specifically preferred for highest herbicidal activity and/or most favorable ease of synthesis are:
N-[(4,6dimethoxypyrimidin-2-yl)aminocarbonyl]-2-hydroxy-5-chlorobenzenesulfonamide methanesulfonate;
N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-hydroxybenzenesulfonamide, methanesulfonate;
2-hydroxy-N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]benzenesulfonamide, methanesulfonate; and
N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-2-hydroxybenzenesulfonamide, methanesulfonate.
All of the above compounds show selectivity on wheat.
N-[(4,6dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]-2-hydroxybenzenesulfonamide, methanesulfonate;
2-hydroxy-N-[(4methoxy-6-methyl-1,3,5-triazin-2-yl)-aminocarbonyl]benzenesulfonamide, methanesulfonate;
N-[(4,6-dimethyl-1,3,5-triazin-2-yl)aminocarbonyl]-2-hydroxybenzenesulfonamide, methanesulfonate;
N-[(4,6-dimethoxy-1,3,5-triazin-2-yl)(methyl)aminocarbonyl]-2-hydroxybenzenesulfonamide, methanesulfonate;
N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-hydroxybenzenesulfonamide, 1propanesulfonate, which shows selectivity on rice and corn; and
2-hydroxy-N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-aminocarbonyl]benzenesulfonamide, 1- propanesulfonate, which shows selectivity on soybeans.
This invention also relates to compounds of Formula II which are useful intermediates for the preparation of the herbicidal compounds of Formula I: ##STR9## where W is O or S;
Q is O or NR.sub.5 ;
R.sub.1 is C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkyl substituted with 1-3 atoms of F, Cl or Br, CH.sub.2 CH.sub.2 OCH.sub.3, CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3, or ##STR10## R.sub.2 is H, F, Cl, Br, OCH.sub.3, NO.sub.2 or C.sub.1 -C.sub.2 alkyl; R.sub.3 is H, F, Cl, Br or CH.sub.3 ;
R.sub.5 is C.sub.1 -C.sub.4 alkyl; and
R.sub.6 and R.sub.7 are independently H, F, Cl, Br, CH.sub.3, CF.sub.3, NO.sub.2 or OCH.sub.3.
Preferred intermediates, for reasons of more favorable ease of synthesis and/or higher herbicidal activity of the compounds of Formula I, are:
(1) Compounds of Formula II where Q is O, R.sub.2 and R.sub.3 are H, R.sub.1 is CH.sub.3 or CF.sub.3, and W is O.
This invention also relates to compounds of Formula VII which are useful intermediates for the preparation of the herbicidal compounds of Formula I: ##STR11## where Q is O or NR.sub.5 ;
R.sub.1 is C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkyl substituted with 1-3 atoms of F, Cl or Br, CH.sub.2 CH.sub.2 OCH.sub.3, CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3, or ##STR12## R.sub.2 is H, F, Cl, Br, OCH.sub.3, NO.sub.2 or C.sub.1 -C.sub.2 alkyl; R.sub.3 is H, F, Cl, Br or OCH.sub.3 ; R.sub.5 is C.sub.1 -C.sub.4 alkyl;
R.sub.6 and R.sub.7 are independently H, F, Cl, Br, CH.sub.3, CF.sub.3, NO.sub.2 or OCH.sub.3 ; and
Z is CH or N.
Synthesis
The compounds of this invention can be made as outlined below. The compounds of Formula (IV), (VI), (XII) or (XIV) in which Q is oxygen can be prepared by reacting an appropriate 2-aminopyrimidine, 2-aminotriazine or 2-aminobicyclopyrimidine of Formula (III), (V), (XI) or (XIII) with an appropriately substituted sulfonylisocyanate or isothiocyanate, of Formula (II), where Q is oxygen and R.sub.1, R.sub.2, R.sub.3, R.sub.4, X, Y, Z, X.sub.1, X.sub.2, Y.sub.1, Y.sub.2, W and n are as previously defined.
The reaction is best carried out in inert solvents such as methylene chloride and acetonitrile. The mode of addition is not critical, however, it is often convenient to add a solution of the isocyanate or isothiocyanate of Formula (II) to a stirred suspension of the aminoheterocycle (III), (V), (XI) or (XIII).
The reaction is generally exothermic. In some cases, the desired product is insoluble in the reaction medium and crystallizes from it in pure form. Products soluble in the reaction medium are isolated by evaporation of the solvent and trituration of the residue with solvents such as diethyl ether, 1-chlorobutane, or hexanes and filtration. ##STR13##
Some of the compounds of this invention, where Z is CH or N, may also be prepared by reacting a sulfonamide of Formula VIII with a 4,6-dichloroheterocyclic isocyanate of Formula IX. ##STR14##
One or both of the halogen atoms on the heterocyclic ring of the compound of Formula VII can be displaced by an alkoxide of OR.sub.8, to give compounds of Formula X, where R.sub.8 is C.sub.1 -C.sub.4 alkyl, C.sub.3 -C.sub.4 alkenyl, C.sub.3 -C.sub.4 alkynyl, CH.sub.2 CH.sub.2 OCH.sub.3 or C.sub.2 -C.sub.4 alkyl substituted with 1-3 atoms of F, Cl or Br, and Y" is Cl or OCH.sub.3. ##STR15##
The process for the preparation of compounds of Formula X is described in our patent application Ser. No. 193,190, filed Oct. 14, 1980.
Compounds of Formula IV, VI, XII and XIV in which Q is ##STR16## are best prepared by the procedure of Equation 5 wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5 and A are as previously defined. ##STR17##
The reaction of Equation 5 is best carried out in methylene chloride at 25.degree. to 40.degree. C. for 24 to 96 hours under a nitrogen atmosphere. The product can be isolated by the addition of an aqueous acetic acid solution followed by extraction of the product into methylene chloride or direct filtration of a product of low solubility. The product can ordinarily be purified by trituration with solvents such as n-butyl chloride or ether or by column chromatography.
Further details of this reaction and the preparation of the carbamates of Formula III can be found in unexamined European Patent Application 174-73.
Sulfonamides of Formula VIII in which Q is ##STR18## are readily prepared as shown by Equations 6 and 7. ##STR19## M is an alkali metal.
The reaction of Equation 6 is carried out in an aprotic solvent such as dimethylformamide at temperatures ranging from about ambient to reflux for periods ranging from 1/4 to 24 hours.
The product is isolated by removing the solvent at reduced pressure and pouring the reaction mixture into H.sub.2 O. The crude product is extracted with an organic solvent such as methylene chloride. The solution of the product is dried with a standard drying agent such as MgSO.sub.4, filtered, and concentrated. The crude product is further purified by usual techniques such as recrystallization or chromatography.
The reduction of the nitro compounds such as XIX to anilines XX is achieved by procedures well known to those skilled in the art.
Anilines of Formula XX are converted to sulfonyl chlorides by well known procedures. For further details, see H. L. Yale and F. Sowinski, J. Org. Chem., 25, 1824 (1960).
Sulfonamides of Formula VIII in which Q is ##STR20## are obtained by treatment of sulfonyl chlorides of Formula XXI with NH.sub.3 by procedures known to those skilled in the art.
Sulfonamides of Formula VIII in which Q is oxygen, prepared as described in Research Disclosure, pg. 52, (1978), may conveniently be converted to the corresponding isocyanates or isothiocyanates of Formula II by methods described in U.S. Pat. No. 4,127,405.
The synthesis of the heterocyclicamine derivatives has been reviewed in "The Chemistry of Heterocyclic Compounds", a series published in Interscience Publ., New York and London.
2-Aminopyrimidines are described by D. J. Brown in "The Pyrimidines", Vol. XVI of the above series which are herein incorporated by reference.
The preparation of amino bicyclopyrimidines are described in unexamined European Pat. No. 15683.
The aminoheterocyclic intermediates of Formula III, V, XI or XIII in which R.sub.4 is CH.sub.3, may be prepared by the following procedure, or by obvious modifications thereof. ##STR21##
A solution of the amine XV in concentrated hydrochloric acid is contacted with an aqueous sodium nitrite solution and the chloro compound XVI is isolated by filtration of the acidic solution (see for example, Bee and Rose, J. Chem. Soc. C., 2051 (1966) for the case in which Z is CH and X and Y are OCH.sub.3). Displacement of the chlorine may be accomplished by heating with an excess of methylamine in water to obtain the methylaminoheterocycle XXIV.
N-Methoxyamino heterocycles can be prepared by procedures reported in the literature [see, for example, Belgian Pat. No. 618,563 and J. T. Shaw, et al., J. Org. Chem., 27 4054 (1962)] and the procedure illustrated below. ##STR22##
Chloro compound XXIII is reacted with hydroxylamine to form derivative XXV which may be alkylated with methyl bromide to afford the N-methoxy heterocyclic amine XXVI. This compound may alternately be prepared in one step by treatment of XXIII and O-methyl hydroxylamine hydrochloride with an alkali metal hydroxide such as sodium hydroxide.

The compounds of this invention and their preparation are further illustrated by the following examples, wherein temperatures are given in degrees centigrade and parts are by weight unless otherwise indicated.
EXAMPLE 1
2-Hydroxybenzenesulfonyl isocyanate, methanesulfonate
To 10.0 g (0.04 mole) 2-hydroxybenzenesulfonamide, methanesulfonate, suspended in 75 ml dry xylenes was added 4.0 g (0.04 mole) N-butylisocyanate and a catalytic amount of 1,4-diazobicyclo[2.2.2]-octane (.about.0.05 g). This mixture was rapidly heated to reflux temperature (.about.135.degree. C.) and 4.0 ml of phosgene was slowly added (at such a rate as to keep the reaction temperature greater than 128.degree. C.). The phosgene addition required .about.11/2 hours. The reaction was cooled to room temperature, filtered under N.sub.2, and the solvent evaporated under reduced pressure. The infrared spectrum of the resultant oil was consistent for 2-hydroxybenzenesulfonyl isocyanate, methanesulfonate (2210 cm.sup.-1).
EXAMPLE 2
N-[(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl]-2-hydroxybenzenesulfonamide, methanesulfonate
To a suspension of 0.6 g 2-amino-4,6-dimethoxypyrimidine in 10 ml dry methylene chloride is added 1.1 g 2-hydroxybenzenesulfonylisocyanate, methanesulfonate. The reaction exotherms (21.degree. C.-29.degree. C.) and is then stirred 1/2 hour. The solvent is evaporated under reduced pressure. The resultant mixture is triturated with diethylether and filtered to give 1.2 g tan solid m.p. 165.degree.-166.degree. C. The infrared spectrum shows absorption bands at 1740, 1615, 1590, 1360 cm.sup.-1.
Calc. for C--38.9, H--3.73, N--12.9. Found C--38.3, H--3.63, N--13.0.
EXAMPLE 3
2-Hydroxy-N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]benzenesulfonamide, methanesulfonate
To a suspension of 0.6 g 2-amino-4-methoxy-6-methylpyrimidine in 10 ml dry methylene chloride is added 1.1 g 2-hydroxybenzenesulfonylisocyanate, methanesulfonate. The reaction exotherms mildly and is then stirred for 1/2 hour. The solvent is evaporated under reduced pressure. The resultant mixture is triturated with diethylether and filtered to give 0.95 g white solid m.p. 189.degree.-190.degree. C. The infrared spectrum shows absorption bands at 1700, 1615, 1560, 1370 cm.sup.-1.
Calc. for C--40.4, H--3.87, N--13.4. Found C--40.2, H--3.77, N--13.6.
EXAMPLE 4
N-[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]-2-hydroxybenzenesulfonamide, methanesulfonate
To a suspension of 0.6 g 2-amino-4,6-dimethoxy-1,3,5-triazine in 10 ml dry methylene chloride is added 1.1 g 2-hydroxybenzenesulfonylisocyanate, methanesulfonate. The reaction exotherms mildly and is then stirred for about 1 hour. The solvent is evaporated under reduced pressure. The resultant mixture is triturated with diethylether and filtered to give 1.4 g tan solid m.p. 163.degree.-166.degree. C. The infrared spectrum shows absorption bands at 1715, 1600, 1550, 1350 cm.sup.-1.
EXAMPLE 5
Preparation of N-methyl-N-(2-nitrophenyl)methanesulfonamide
To 3.2 g of N-methyl methanesulfonamide in 50 ml of dry dimethylformamide is added 1.47 g of potassium methoxide. The mixture is stirred for 15 minutes. 2.8 g of 2-Fluoronitrobenzene is added and the mixture is heated to reflux for two hours. The dimethylformamide is removed on a rotary evaporator. The concentrated reaction mixture is poured into water. The crude product is extracted with CH.sub.2 Cl.sub.2. The crude extracts are dried with MgSO.sub.4, filtered and concentrated on a rotary evaporator. The crude product is purified by recrystallization from butyl chlorideethyl acetate. 3.4 g of product with m.p. 144.degree.-145.degree. C. is obtained.
EXAMPLE 6
N-(2-Aminophenyl)-N-methyl methanesulfonamide
50.2 g of N-methyl-N-(2-nitrophenyl)methanesulfonamide, prepared by the procedure of Example 5, is added to 220 ml of concentrated HCl and contacted with 183.3 g of SnCl.sub.2.2H.sub.2 O. The mixture is heated on a steam bath for one hour. The reaction mixture is treated with enough 5-10% NaOH to raise the pH to 9 while maintaining the temperature of the mixture less than 25.degree. C. The crude reaction mixture is then extracted with CH.sub.2 Cl.sub.2. The CH.sub.2 Cl.sub.2 extracts are dried with MgSO.sub.4 and then filtered and concentrated on a rotary evaporator. The solid product obtained (38.1 g), m.p. 138.degree.-139.degree. was used without further purification in the next step.
EXAMPLE 7
2-[N-methyl-N-(methylsulfonyl)amino]benzenesulfonamide
Diazotization
20.0 g of amine from Example 6 is combined with 50 ml of acetic acid, 30 ml of H.sub.2 O and 39.4 g of concentrated aqueous hydrochloric acid; the mixture is cooled to 0.degree.-5.degree. C. A solution of 7.2 g of NaNO.sub.2 in 20 ml of H.sub.2 O is added dropwise over a period of 15-30 minutes, while maintaining the temperature. The reaction mixture is stirred for 30 minutes at 0.degree.-10.degree. C. and then used in the subsequent coupling step.
Coupling
The diazonium salt from the preceding step is added dropwise over 15-30 minutes to a solution of 22.3 ml SO.sub.2, 350 ml of acetic acid and 1.35 g of CuCl cooled to 12.degree.-15.degree. C. After the addition is completed the reaction is stirred at 10.degree.-15.degree. C. for one hour. The cooling bath was removed and the reaction mixture was stirred at ambient temperature for 12 hours. The crude reaction mixture was then poured into water and extracted with ether. The ether extract was backextracted with H.sub.2 O and then dried with MgSO.sub.4, filtered and concentrated to the wet solid sulfonyl chloride which was used in the next step without further purification.
Amination
The crude product from the preceding step was taken up in 175 ml of tetrahydrofuran and cooled to 0.degree.-5.degree. C. 75 ml of concentrated aqueous ammonia was added dropwise while maintaining the temperature. The reaction mixture was allowed to warm to ambient temperature over a period of one hour. The crude reaction mixture was poured into water. The crude product was extracted with CH.sub.2 Cl.sub.2, dried with MgSO.sub.4, filtered and concentrated on a rotary evaporator. 10.8 g of product with m.p. 137.degree.-139.degree. was obtained and used in the next step without further purification.
EXAMPLE 8
N-[(4,6-dimethoxypyrimidin-2-yl)]-2-[(methyl)(methylsulfonyl)amino]benzenesulfonamide
1.5 g of sulfonamide from Example 8 is added to 60 ml of dry methylene chloride under N.sub.2. 3.6 ml of 2M solution of (CH.sub.3).sub.3 Al in hexane was added. The mixture was stirred for 15 minutes and 1.2 g of ##STR23## was added. The mixture was refluxed for 16 hours. 50 ml of H.sub.2 O was added dropwise cautiously followed by enough acetic acid to lower the pH of the reaction mixture to 2-3. The crude product is then extracted with CH.sub.2 Cl.sub.2, dried with MgSO.sub.4, filtered and concentrated on a rotary evaporator. The crude solid product was triturated with butyl chloride-ethyl acetate. 1.2 g of product with m.p. 228.degree.-230.degree. was obtained.
Using the procedures similar to those of Examples 1-8, the following compounds can be prepared.
TABLE I__________________________________________________________________________ ##STR24##R.sub.1 R.sub.2 R.sub.3 R.sub.4 Q W Y X Z m.p.__________________________________________________________________________ (.degree.C.)CH.sub.3 H H H O O OCH.sub.3 OCH.sub.3 CH 165-166CH.sub.3 H H H O O OCH.sub.3 CH.sub.3 CH 189-190CH.sub.3 H H H O O CH.sub.3 CH.sub.3 CH 204-205CH.sub.3 H H H O O OCH.sub.3 OCH.sub.3 N 163-166CH.sub.3 H H H O O OCH.sub.3 CH.sub.3 N 170-173CH.sub.3 H H H O O CH.sub.3 CH.sub.3 N 181-184(CH.sub.2).sub.3 CH.sub.3 H H H O O OCH.sub.3 OCH.sub.3 CH 158-162(CH.sub.2).sub.2 CH.sub.2 Cl H H H O O OCH.sub.3 OCH.sub.3 CHCCl.sub.3 H H H O O OCH.sub.3 OCH.sub.3 CH ##STR25## H H H O O OCH.sub.3 CH.sub.3 CH 216-219 ##STR26## H H H O O OCH.sub.3 CH.sub.3 CH ##STR27## H H H O O OCH.sub.3 CH.sub.3 CH ##STR28## H H H O O OCH.sub.3 CH.sub.3 CH ##STR29## H H H O O OCH.sub.3 CH.sub.3 CH ##STR30## H H H O O OCH.sub.3 CH.sub.3 CH ##STR31## H H H O O OCH.sub.3 CH.sub.3 CH ##STR32## H H H O O OCH.sub.3 CH.sub.3 CH ##STR33## H H H O O OCH.sub.3 CH.sub.3 CHCH.sub.3 5-Cl H H O O OCH.sub.3 OCH.sub.3 CH 174-176CH.sub.3 6-CH.sub.3 H H O O OCH.sub.3 CH.sub.3 CHCH.sub.3 5-F H H O O OCH.sub.3 CH.sub.3 CHCH.sub.3 5-NO.sub.2 H H O O OCH.sub.3 CH.sub.3 CHCH.sub.3 5-Br H H O O OCH.sub.3 CH.sub.3 CHCH.sub.3 5-OCH.sub.3 H H O O OCH.sub.3 CH.sub.3 CHCH.sub.3 5-CF.sub.3 H H O O OCH.sub.3 CH.sub.3 CHCH.sub.3 5-Cl 4-Cl H O O OCH.sub.3 CH.sub.3 CHCH.sub.3 5-CH.sub.3 4-CH.sub.3 H O O OCH.sub.3 CH.sub.3 CHCH.sub. 3 H H CH.sub.3 O O OCH.sub.3 OCH.sub.3 N 91-96CH.sub.3 H H H NCH.sub.3 O OCH.sub.3 OCH.sub.3 CH 228-230CH.sub.3 H H H ##STR34## O OCH.sub.3 OCH.sub.3 CHCH.sub.3 H H H O O Cl OCH.sub.3 CHCH.sub.3 H H H O O OCH.sub.3 (CH.sub.2).sub.3 CH.sub.3 CHCH.sub.3 H H H O O CH.sub.3 OCH.sub.2 CF.sub.3 NCH.sub.3 H H H O O CH.sub.3 OCH.sub.2 CCl.sub.3 NCH.sub.3 H H H O O CH.sub.3 OCH.sub.2 CBr.sub.3 NCH.sub.3 H H H O O CH.sub.3 OCH.sub.2 CH.sub.2 Cl NCH.sub.3 H H H O O CH.sub.3 H CHCH.sub.3 H H H O O CH.sub.3 (CH.sub.2).sub.3 CH.sub.3 CHCH.sub.3 H H H O O CH.sub.3 CH.sub.2 CH.sub.2 Cl CHCH.sub.3 H H H O O CH.sub.3 CH.sub.2 CF.sub.3 CHCH.sub.3 H H H O O CH.sub.3 O(CH.sub.2).sub.3 CH.sub.3 NCH.sub.3 H H H O O CH.sub.3 OCH.sub.2 CHCH.sub.2 NCH.sub.3 H H H O O CH.sub.3 ##STR35## NCH.sub.3 H H H O O CH.sub.3 OCH.sub.2 CCH NCH.sub.3 H H H O O CH.sub.3 OCH.sub.2 CCCH.sub.3 NCH.sub.3 H H H O O CH.sub.3 CH.sub.2 OCH.sub.3 CHCH.sub.3 H H H O O CH.sub.3 SCH.sub.3 CHCH.sub.3 H H H O O CH.sub.3 S(CH.sub.2)CH.sub.3 CHCH.sub.3 H H H O O CH.sub.3 CH.sub.3 CBrCH.sub.3 H H H O O CH.sub.3 CH.sub.3 CICH.sub.3 H H H O O CH.sub.3 CH.sub.3 CFCH.sub.3 H H H O O CH.sub.3 CH.sub.3 CClCH.sub.3 H H H O S OCH.sub.3 OCH.sub.3 NCH.sub.3 H H H O S OCH.sub.3 CH.sub.3 NCH.sub.3 H H H O S CH.sub.3 CH.sub.3 NCH.sub.3 H H H O S OCH.sub.3 CH.sub.3 CHCH.sub.3 H H H O S OCH.sub.3 OCH.sub.3 CHCH.sub.3 H H H O S CH.sub.3 CH.sub.3 CHCH.sub.3 3-Cl H H O O OCH.sub.3 OCH.sub.3 CH 134-142CH.sub.3 3-Cl H H O O OCH.sub.3 OCH.sub.3 N 165-170CH.sub.3 3-Cl 5-Cl H O O OCH.sub.3 CH.sub.3 N 210(dec)CH.sub.3 3-Cl 5-Cl H O O OCH.sub.3 OCH.sub.3 N 200(dec)CH.sub.3 H H H NCH.sub.2 CH.sub.3 O OCH.sub.3 OCH.sub.3 CHCH.sub.3 H H H N(CH.sub.2).sub.2 CH.sub.3 O OCH.sub.3 OCH.sub.3 CHCH.sub.3 H H H NCH.sub.3 O OCH.sub.3 CH.sub.3 CH 220-222CH.sub.3 H H H NCH.sub.3 O CH.sub.3 CH.sub.3 CH 216-218CH.sub.3 H H H NCH.sub.3 O OCH.sub.3 CH.sub.3 N 218-221(d)CH.sub.2 CH.sub.3 H H H O O OCH.sub.3 OCH.sub.3 CH 189-191CH.sub.2 CH.sub.3 H H H O O OCH.sub.3 CH.sub.3 CH 160-162CH.sub.2 CH.sub.3 H H H O O CH.sub.3 CH.sub.3 CH 196-198CH.sub.2 CH.sub.3 H H H O O OCH.sub.3 OCH.sub.3 NCH.sub.2 CH.sub.3 H H H O O OCH.sub.3 CH.sub.3 NCH.sub.2 CH.sub.3 H H H O O CH.sub.3 CH.sub.3 NCH.sub.2 CH.sub.3 H H CH.sub.3 O O OCH.sub.3 OCH.sub.3 N(CH.sub.2).sub.3 CH.sub.3 H H H O O OCH.sub.3 CH.sub.3 CH(CH.sub.2).sub.3 CH.sub.3 H H H O O CH.sub.3 CH.sub.3 CH 201-202(CH.sub.2).sub.3 CH.sub.3 H H H O O OCH.sub.3 OCH.sub.3 N 150-153(CH.sub.2).sub.3 CH.sub.3 H H H O O OCH.sub.3 CH.sub.3 N 161-163(CH.sub.2).sub.3 CH.sub.3 H H H O O CH.sub.3 CH.sub.3 N(CH.sub.2).sub.3 CH.sub.3 H H H O O H CH.sub.3 CCl 135-140(CH.sub.2).sub.2 CH.sub.3 H H H O O OCH.sub.3 OCH.sub.3 CH 172-174(CH.sub.2).sub.2 CH.sub.3 H H H O O OCH.sub.3 CH.sub.3 CH 183-186(CH.sub.2).sub.2 CH.sub.3 H H H O O CH.sub.3 CH.sub.3 CH 182-184(CH.sub.2).sub.2 CH.sub.3 H H H O O OCH.sub.3 OCH.sub.3 N 151-154(CH.sub.2).sub.2 CH.sub.3 H H H O O OCH.sub.3 CH.sub.3 N 144-147(CH.sub.2).sub.2 CH.sub.3 H H H O O CH.sub.3 CH.sub.3 N(CH.sub.2).sub.2 CH.sub.3 H H CH.sub.3 O O OCH.sub.3 OCH.sub.3 CH(CH.sub.2).sub.2 CH.sub.3 H H H O O H CH.sub.3 CCl 185-190CF.sub.3 H H H O O OCH.sub.3 OCH.sub.3 CH 129-131CH.sub.2 CH.sub.2 Br H H H O O OCH.sub.3 OCH.sub.3 CHCH.sub.2 CH.sub.2 OCH.sub.3 H H H O O OCH.sub.3 OCH.sub.3 CHCH.sub. 2 CH.sub.2 OCH.sub.3 H H H O O OCH.sub.3 CH.sub.3 CHCH.sub.2 CH.sub.2 OCH.sub.3 H H H O O CH.sub.3 CH.sub.3 CHCH.sub.2 CH.sub.2 OCH.sub.3 H H H O O OCH.sub.3 CH.sub.3 N(CH.sub.2).sub.2 CH.sub.2 OCH.sub.3 H H H O O OCH.sub.3 OCH.sub.3 CHCH.sub.3 H H H O O Cl NH.sub.2 CHCH.sub.3 H H H O O Cl NHCH.sub.3 CHCH.sub.3 H H H O O Cl N(CH.sub.3).sub.2 CHCH.sub.3 H H H O O CH.sub.3 CH.sub.2 OCH.sub.3 CHCH.sub.2 CH.sub.3 H H H O O CH.sub.3 CH.sub.2 OCH.sub.3 CH(CH.sub.2).sub.2 CH.sub.3 H H H O O CH.sub.3 CH.sub.2 OCH.sub.3 CHCH.sub.3 H H H O O CH.sub.3 CH.sub.2 OCH.sub.2 CH.sub.3 CHCH.sub.3 H H H O O CH.sub.3 CH.sub.2 CH.sub.3 CHCH.sub.3 H H H O O CH.sub.3 CH.sub.2 CH.sub.2 CH.sub.3 CHCH.sub.3 H H H O O CH.sub.3 CH.sub.2 CH.sub.2 Br CHCH.sub.3 H H H O O CH.sub.3 OCH.sub.2 CH.sub.3 CHCH.sub.3 H H H O O CH.sub.3 O(CH.sub.2).sub.2 CH.sub.3 CHCH.sub.3 H H H O O CH.sub.3 OCH.sub.2 CHCH.sub.2 CHCH.sub.3 H H H O O CH.sub.3 ##STR36## CHCH.sub.3 H H H O O CH.sub.3 OCH.sub.2 CCH CHCH.sub.3 H H H O O CH.sub.3 OCH.sub.2 CCCH.sub.3 CHCH.sub.3 H H H O O CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.3 CHCH.sub.3 H H H O O CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.3 NCH.sub.3 H H H O O CH.sub.3 OCH.sub.2 (CH.sub.2).sub.2 CHCH.sub.3 H H H O O CH.sub.3 OCH.sub.2 (CH.sub.2).sub.3 CHCH.sub.3 H H H O O H CH.sub. 3 CClCH.sub.3 H H H O O Cl CH.sub.3 CCH.sub.2 CH.sub.2 ClCH.sub.3 H H H O O OCH.sub.3 OCH.sub.3 CH.sub.3CH.sub.3 H H H O O OCH.sub.3 OCH.sub.3 CH.sub.2 CH.sub.3CH.sub.3 H H H O O OCH.sub.3 OCH.sub.3 CCH.sub.2 CHCH.sub.2CH.sub.3 5-Cl H H O O OCH.sub.3 CH.sub.3 CH 179-181CH.sub.3 5-Cl H H O O CH.sub.3 CH.sub.3 CH 204-205CH.sub.3 5-Cl H H O O OCH.sub.3 OCH.sub.3 N 180-186CH.sub.3 5-Cl H H O O OCH.sub.3 CH.sub.3 N 184-187CH.sub.3 5-Cl H H O O H CH.sub.3 CCl 210-211CH.sub.3 5-CH.sub.3 H H O O OCH.sub.3 OCH.sub.3 CH 171-174CH.sub.3 5-CH.sub.3 H H O O OCH.sub.3 CH.sub.3 CH 181-188CH.sub.3 5-CH.sub.3 H H O O CH.sub.3 CH.sub.3 CH 180-183CH.sub.3 5-CH.sub.3 H H O O OCH.sub.3 CH.sub.3 N 159-161CH.sub.3 5-CH.sub.3 H H O O OCH.sub.3 OCH.sub.3 N 178-181CH.sub.3 5-CH.sub.3 H H O O CH.sub.3 CH.sub.3 NCH.sub.3 5-CH.sub.3 H CH.sub.3 O O OCH.sub.3 OCH.sub.3 N 133-136CH.sub.3 5-CH.sub.2 CH.sub.3 H H O O OCH.sub.3 CH.sub.3 CH ##STR37## H H H O O OCH.sub.3 OCH.sub.3 CH 221-223 ##STR38## H H H O O CH.sub.3 CH.sub.3 CH 182-186 ##STR39## H H H O O OCH.sub.3 CH.sub.3 N 184-186 ##STR40## H H H O O OCH.sub.3 OCH.sub.3 N 169-172 ##STR41## H H H O O CH.sub.3 CH.sub.3 N ##STR42## H H H O O H CH.sub.3 CCl 193-195 ##STR43## H H CH.sub.3 O O OCH.sub.3 OCH.sub.3 N 143-145CH.sub.3 H H OCH.sub.3 O O OCH.sub.3 OCH.sub.3 CH ##STR44## H H H O O OCH.sub.3 OCH.sub.3 CHCF.sub.3 H H H O O OCH.sub.3 CH.sub.3 CH 135-140(d)CF.sub.3 H H H O O CH.sub.3 CH.sub.3 CH 190-193(d)CF.sub.3 H H H O O OCH.sub.3 OCH.sub.3 NCF.sub.3 H H H O O OCH.sub.3 CH.sub.3 NCF.sub.3 H H H O O CH.sub.3 CH.sub.3 N 200 (d)CF.sub.3 H H CH.sub.3 O O OCH.sub.3 OCH.sub.3 N 144-148(d)CF.sub.3 H H H ##STR45## O OCH.sub.3 OCH.sub.3 CH 195-197CF.sub.3 H H H ##STR46## O OCH.sub.3 CH.sub.3 CH 199-200CF.sub.3 H H H ##STR47## O CH.sub.3 CH.sub.3 CH 221-224CF.sub.3 H H H ##STR48## O OCH.sub.3 OCH.sub.3 N 151-154CF.sub.3 H H H ##STR49## O OCH.sub.3 CH.sub.3 N 180-182CF.sub.3 H H H ##STR50## O CH.sub.3 CH.sub.3 N 200-201CF.sub.3 H H CH.sub.3 ##STR51## O OCH.sub.3 OCH.sub.3 NCH.sub.2 CH.sub.3 H H H O O Cl OCH.sub.3 CHCH.sub.2 CH.sub.2 CH.sub.3 H H H O O Cl OCH.sub.3 CHCH.sub.3 H H H O O OCH.sub.3 N(CH.sub.3).sub.2 CHCH.sub.2 CH.sub.3 H H H O O OCH.sub.3 N(CH.sub.3).sub.2 NCH.sub.2 CH.sub.2 CH.sub.3 H H H O O OCH.sub.3 N(CH.sub.3).sub.2 CHCH.sub.2 CH.sub.3 H H H O O Cl N(CH.sub.3).sub.2 CHCH.sub.2 CH.sub.2 CH.sub.3 H H H O O Cl N(CH.sub.3).sub.2 CHCH.sub.3 H H H ##STR52## O Cl OCH.sub.3 CHCF.sub.3 H H H ##STR53## O Cl OCH.sub.3 CHCH.sub.3 H H H ##STR54## O OCH.sub.3 N(CH.sub.3).sub.2 CHCF.sub.3 H H H ##STR55## O OCH.sub.3 N(CH.sub.3).sub.2 NCH.sub.3 H H H ##STR56## O Cl N(CH.sub.3).sub.2 CHCF.sub.3 H H H ##STR57## O Cl N(CH.sub.3).sub.2 CHCH.sub.3 H H H ##STR58## O CH.sub.3 CH.sub.3 N 212-213CH.sub.3 H H H ##STR59## O OCH.sub.3 OCH.sub.3 N 224-227CH.sub.3 5-CF.sub.3 H H O O Cl OCH.sub.3 CHCH.sub.3 5-CF.sub.3 H H O O CH.sub.3 OCH.sub.3 CHCH.sub.3 5-CF.sub.3 H H O O CH.sub.3 CH.sub.3 CHCH.sub.3 5-CF.sub.3 H H O O CH.sub.3 O CH.sub.3 O NCH.sub.3 5-CF.sub.3 H H O O CH.sub.3 CH.sub.3 NCH.sub.3 5-CF.sub.3 H H O O CH.sub.3 OCH.sub.3 NCH.sub.3 5-CF.sub.3 H H O O OCH.sub.3 N(CH.sub.3).sub.2 NCH.sub.3 CH.sub.2 5-CF.sub.3 H H O O Cl OCH.sub.3 CHCH.sub.3 CH.sub.2 5-CF.sub.3 H H O O CH.sub.3 O CH.sub.3 O CHCH.sub.3 CH.sub.2 5-CF.sub.3 H H O O CH.sub.3 CH.sub.3 CHCH.sub.3 CH.sub.2 5-CF.sub.3 H H O O CH.sub.3 OCH.sub.3 CHCH.sub.3 CH.sub.2 5-CF.sub.3 H H O O CH.sub.3 O CH.sub.3 O NCH.sub.3 CH.sub.2 5-CF.sub.3 H H O O CH.sub.3 CH.sub.3 O NCH.sub.3 CH.sub.2 5-CF.sub.3 H H O O CH.sub.3 CH.sub.3 NCH.sub.3 CH.sub.2 5-CF.sub.3 H H O O CH.sub.3 O N(CH.sub.3).sub.2 NCH.sub.3 5-CF.sub.3 H H ##STR60## O Cl OCH.sub.3 CHCH.sub.3 5-CF.sub.3 H H ##STR61## O CH.sub.3 O CH.sub.3 O CHCH.sub.3 5-CF.sub.3 H H ##STR62## O CH.sub.3 CH.sub.3 CHCH.sub.3 5-CF.sub.3 H H ##STR63## O CH.sub.3 CH.sub.3 O CHCH.sub.3 5-CF.sub.3 H H ##STR64## O CH.sub.3 CH.sub.3 NCH.sub.3 5-CF.sub.3 H H ##STR65## O CH.sub.3 O CH.sub.3 O NCH.sub.3 5-CF.sub.3 H H ##STR66## O CH.sub.3 CH.sub.3 O NCH.sub.3 5-CF.sub.3 H H ##STR67## O CH.sub.3 O N(CH.sub.3).sub.2 NCH.sub.3 5-Cl H H ##STR68## O CH.sub.3 CH.sub.3 CHCH.sub.3 5-Cl H H ##STR69## O CH.sub.3 O CH.sub.3 O CHCH.sub. 3 5-Cl H H ##STR70## O CH.sub.3 O CH.sub.3 CHCH.sub.3 5-Cl.sub.3 H H ##STR71## O Cl CH.sub.3 O CHCH.sub.3 5-Cl H H ##STR72## O CH.sub.3 CH.sub.3 NCH.sub.3 5-Cl H H ##STR73## O CH.sub.3 O CH.sub.3 O NCH.sub.3 5-Cl H H ##STR74## O CH.sub.3 O CH.sub.3 NCH.sub.3 5-Cl H H ##STR75## O CH.sub.3 O N(CH.sub.3).sub.2 N__________________________________________________________________________
TABLE II__________________________________________________________________________ ##STR76##R.sub.1 R.sub.2 R.sub.3 R.sub.4 Q W X.sub.1 Y.sub.1 n m.p. (.degree.C.)__________________________________________________________________________CH.sub.3 H H H O O O H 1CH.sub.3 H H H O O O CH.sub.3 1CH.sub.3 H H H O O O OCH.sub.3 1CH.sub.3 H H H O O O H 2CH.sub.3 H H H O O O CH.sub.3 2CH.sub.3 H H H O O O OCH.sub.3 2CH.sub.3 H H H ##STR77## O O OCH.sub.3 2CH.sub.3 5-Cl H H O O O CH.sub.3 1CH.sub.3 5-Cl H H O O O OCH.sub.3 1CH.sub.3 5-Cl H H O O CH.sub.2 CH.sub.3 1CH.sub.3 5-Cl H H O O CH.sub.2 OCH.sub.3 1CH.sub.3 5-Cl H H O O O CH.sub.3 2CH.sub.3 5-Cl H H O O O OCH.sub.3 2(CH.sub.2).sub.3 CH.sub.3 H H H O O O OCH.sub.3 1(CH.sub.2).sub.2 CH.sub.2 Cl H H H O O O OCH.sub.3 1 ##STR78## H H H O O O OCH.sub.3 1 ##STR79## H H H O O O OCH.sub.3 1 ##STR80## H H H O O O OCH.sub.3 1(CH.sub.2).sub.2 CH.sub.3 H H H O O O OCH.sub.3 1CH.sub.2 CH.sub.2 Cl H H H O O O OCH.sub. 3 1CH.sub.2 CH.sub.2 Cl H H H O O O CH.sub.3 1CH.sub.2 CH.sub.2 Cl H H H O O O OCH.sub.3 2CH.sub.3 5-F H H O O O OCH.sub.3 1CH.sub.3 5-Cl 4-Cl H O O O OCH.sub.3 1CH.sub.3 6-CH.sub.3 H H O O O OCH.sub.3 1CH.sub.3 H H H ##STR81## O O OCH.sub.3 2CH.sub.3 H H H ##STR82## O O CH.sub.3 1CH.sub.3 H H H O S O OCH.sub.3 1CH.sub.3 H H H O S O CH.sub.3 1CH.sub.3 H H CH.sub.3 O O O CH.sub.3 1CH.sub.3 H H CH.sub.3 O O CH.sub.2 CH.sub.3 1CF.sub.3 H H H O O O CH.sub.3 1CH.sub.2 CH.sub.2 OCH.sub.3 H H H O O O CH.sub.3 1CH.sub.3 H H OCH.sub.3 O O O CH.sub.3 1CH.sub.3 H H H O O CH.sub.2 OCH.sub.3 2CH.sub.3 H H H O O O Cl 1CH.sub.3 H H H O O O Cl 2__________________________________________________________________________
TABLE III______________________________________ ##STR83## m.p.R.sub.1 R.sub.2 R.sub.3 R.sub.4 Q W X.sub.2 Y.sub.2 (.degree.C.)______________________________________CH.sub.3 H H H O O OCH.sub.3 OCH.sub.3CH.sub.3 H H H O O OCH.sub.3 CH.sub.3CH.sub.3 H H H O S OCH.sub.3 OCH.sub.3CH.sub.3 H H CH.sub.3 O O OCH.sub.3 OCH.sub.3CH.sub.3 H H H O O CH.sub.3 CH.sub.3CH.sub.3 H H CH.sub.3 O O CH.sub.3 CH.sub.3CH.sub.3 H H H ##STR84## O OCH.sub.3 OCH.sub.3CF.sub.3 H H H O O OCH.sub.3 OCH.sub.3CH.sub.2 CH.sub.2 OCH.sub.3 H H H O O OCH.sub.3 OCH.sub.3 ##STR85## H H H O O OCH.sub.3 OCH.sub.3CH.sub.3 5-Cl H H O O OCH.sub.3 OCH.sub.3CH.sub.3 5-CH.sub.3 H H O O OCH.sub.3 OCH.sub.3CH.sub.3 H H OCH.sub.3 O O OCH.sub.3 OCH.sub.3______________________________________
TABLE IV______________________________________ ##STR86## m.p.R.sub.1 R.sub.2 R.sub.3 R.sub.4 Q W X.sub.2 Y.sub.2 (.degree.C.)______________________________________CH.sub.3 H H H O O OCH.sub.3 OCH.sub.3CH.sub.3 H H H O O OCH.sub.3 CH.sub.3CH.sub.3 H H H O S OCH.sub.3 OCH.sub.3CH.sub.3 H H CH.sub.3 O O OCH.sub.3 OCH.sub.3CH.sub.3 H H H O O CH.sub.3 CH.sub.3CH.sub.3 H H CH.sub.3 O O CH.sub.3 CH.sub.3CH.sub.3 H H H ##STR87## O OCH.sub.3 OCH.sub.3CF.sub.3 H H H O O OCH.sub.3 OCH.sub.3CH.sub.2 CH.sub.2 OCH.sub.3 H H H O O OCH.sub.3 OCH.sub.3 ##STR88## H H H O O OCH.sub.3 OCH.sub.3CH.sub.3 5-Cl H H O O OCH.sub.3 OCH.sub.3CH.sub.3 5-CH.sub.3 H H O O OCH.sub.3 OCH.sub.3CH.sub.3 H H OCH.sub.3 O O OCH.sub.3 OCH.sub.3______________________________________
TABLE V______________________________________ ##STR89##R.sub.1 R.sub.2 R.sub.3 W IR (cm.sup.-1)______________________________________CH.sub.3 H H O 2210 -n-Bu H H O 2220CH.sub.3 5-Cl H O 2210C.sub.2 H.sub.5 H H O 2210 -n-Pr H H O 2210CH.sub.3 5-CH.sub.3 H O 2230CH.sub.3 3-Cl H O 2220CF.sub.3 H H O 2220______________________________________
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 VI______________________________________ Active Weight Percent* Ingredient Diluent(s) Surfactants(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, Dec. 4, 1967, pp. 147ff. and "Perry's Chemical Engineer's Handbook", 5th Ed., McGraw-Hill, New York, 1973, pp. 8-57ff.
For further information regarding the art of formulation, see for example:
H. M. Loux, U.S. Pat. No. 3,235,361, Feb. 15, 1966, Col. 6, line 16 through Col. 7, line 19 and Examples 10 through 41;
R. W. Luckenbaugh, U.S. Pat. No. 3,309,192, Mar. 14, 1967, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182;
H. Gysin and E. Knusli, U.S. Pat. No. 2,891,855, June 23, 1959, Col. 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 Hand-book", 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pp. 101-103.
In the following examples, all parts are by weight unless otherwise indicated.
EXAMPLE 9
Wettable powder
N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-hydroxybenzenesulfonamide, methanesulfonate--80%
sodium alkylnaphthalenesulfonate--2%
sodium ligninsulfonate--2%
synthetic amorphous silica--3%
kaolinite--13%
The ingredients are blended, hammer-milled until all the solids are essentially under 50 microns and then reblended.
EXAMPLE 10
Wettable Powder
2-hydroxy-N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]benzenesulfonamide, methanesulfonate--50%
sodium alkylnaphthalenesulfonate--2%
low viscosity methyl cellulose--2%
diatomaceous earth--46%
The ingredients are blended, coarsely hammer-milled and then air-milled to produce particles essentially all below 10 microns in diameter. The product is reblended before packaging.
EXAMPLE 11
Granule
Wettable Powder of Example 10--5%
attapulgite granules (U.S.S. 20-40 mesh; 0.84-0.42 mm)--95%
A slurry of wettable powder containing .apprxeq.25% solids is sprayed on the surface of attapulgite granules in a double-cone blender. The granules are dried and packaged.
EXAMPLE 12
Extruded Pellet
2-hydroxy-N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-aminocarbonyl]benzenesulfonamide, methanesulfonate--25%
anhydrous sodium sulfate--10%
crude calcium ligninsulfonate--5%
sodium alkylnaphthalenesulfonate--1%
calcium/magnesium bentonite--59%
The ingredients are blended, hammer-milled and then moistened with about 12% water. The mixture is extruded as cylinders about 3 mm diameter which are cut to produce pellets about 3 mm long. These may be used directly after drying, or the dried pellets may be crushed to pass a U.S.S. No. 20 sieve (0.84 mm openings). The granules held on a U.S.S. No. 40 sieve (0.42 mm openings) may be packaged for use and the fines recycled.
EXAMPLE 13
Oil Suspension
N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-2-hydroxybenzenesulfonamide, methanesulfonate--25%
polyoxyethylene sorbitol hexaoleate--5%
highly aliphatic hydrocarbon oil--70%
The ingredients are ground together in a sand mill until the solid particles have been reduced to under about 5 microns. The resulting thick suspension may be applied directly, but preferably after being extended with oils or emulsified in water.
EXAMPLE 14
Wettable Powder
N-[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]-2-hydroxybenzenesulfonamide, methanesulfonate--20%
sodium alkylnaphthalenesulfonate--4%
sodium ligninsulfonate--4%
low viscosity methyl cellulose--3%
attapulgite--69%
The ingredients are thoroughly blended. After grinding in a hammer-mill to produce particles essentially all below 100 microns, the material is reblended and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) and packaged.
EXAMPLE 15
Low Strength Granule
N-[(4,6-dimethoxy-1,3,5-triazin-2-yl)(methyl)aminocarbonyl]-2-hydroxybenzenesulfonamide, methanesulfonate--1%
N,N-dimethylformamide--9%
attapulgite granules (U.S.S. 20-40 sieve)--90%
The active ingredient is dissolved in the solvent and the solution is sprayed upon dedusted granules in a double cone blender. After spraying of the solution has been completed, the blender is allowed to run for a short period and then the granules are packaged.
EXAMPLE 16
Aqueous Suspension
N-[(4,6-dimethyl-1,3,5-triazin-2-yl)aminocarbonyl]-2-hydroxybenzenesulfonamide, methanesulfonate--40%
polyacrylic 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 17
Solution
N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-2-hydroxybenzenesulfonamide, methanesulfonate, sodium salt--5%
water--95%
The salt is added directly to the water with stirring to produce the solution, which may then be packaged for use.
EXAMPLE 18
Low Strength Granule
2-hydroxy-N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]benzenesulfonamide, methanesulfonate--0.1%
attapulgite granules (U.S.S. 20-40 mesh)--99.9%
The active ingredient is dissolved in a solvent and the solution is sprayed upon dedusted granules in a double-cone blender. After spraying of the solution has been completed, the material is warmed to evaporate the solvent. The material is allowed to cool and then packaged.
EXAMPLE 19
Granule
N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-hydroxybenzenesulfonamide, methanesulfonate--80%
wetting agent--1%
crude ligninsulfonate salt (containing 5-20% of the natural sugars)--10%
attapulgite clay--9%
The ingredients are blended and milled to pass through a 100 mesh screen. This material is then added to a fluid bed granulator, the air flow is adjusted to gently fluidize the material, and a fine spray of water is sprayed onto the fluidized material. The 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 20
High Strength Concentrate
N-[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]-2-hydroxybenzenesulfonamide, methanesulfonate--99%
silica aerogel--0.5%
synthetic amorphous silica--0.5%
The ingredients are blended and ground in a hammer-mill to produce a material essentially all passing a U.S.S. No. 50 screen (0.3 mm opening). The concentrate may be formulated further if necessary.
EXAMPLE 21
Wettable Powder
2-hydroxy-N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-aminocarbonyl]benzenesulfonamide, methanesulfonate--90%
dioctyl sodium sulfosuccinate--0.1%
synthetic fine silica--9.9%
The ingredients are blended and ground in a hammer-mill to produce particles essentially all below 100 microns. The material is sifted through a U.S.S. No. 50 screen and then packaged.
EXAMPLE 22
Wettable Powder
N-[(4,6-dimethyl-1,3,5-triazin-2-yl)aminocarbonyl]-2-hydroxybenzenesulfonamide, methanesulfonate--40%
sodium ligninsulfonate--20%
montmorillonite clay--40%
The ingredients are thoroughly blended, coarsely hammer-milled and then air-milled to produce particles essentially all below 10 microns in size. The material is reblended and then packaged.
EXAMPLE 23
Oil Suspension
2-hydroxy-N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-aminocarbonyl]benzenesulfonamide, 1-propanesulfonate--35%
blend of polyalcohol carboxylic esters and oil soluble petroleum sulfonates--6%
xylene--59%
The ingredients are combined and ground together in a sand mill to produce particles essentially all below 5 microns. The product can be used directly, extended with oils, or emulsified in water.
EXAMPLE 24
Dust
N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-hydroxybenzenesulfonamide, 1-propanesulfonate--10%
attapulgite--10%
Pyrophyllite--80%
The active ingredient is blended with attapulgite and then passed through a hammer-mill to produce particles substantially all below 200 microns. The ground concentrate is then blended with powdered pyrophyllite until homogeneous.
Utility
The compounds of the present invention are active herbicides. They have utility for broad-spectrum pre- and/or post-emergence weed control in areas where complete control of all vegetation is desired, such as around fuel storage tanks, ammunition depots, industrial storage areas, oil-well sites, drive-in theaters, around billboards, highway and railroad structures. By properly selecting rate, time and method of application, compounds of this invention may also be used to modify plant growth beneficially, and also to selectively control weeds in crops such as wheat, barley, rice, corn and soybeans.
The precise amount of the compounds of Formula I to be used in any given situation will vary according to the particular end result desired, the amount of foliage present, the weeds to be controlled, the crop species involved, the soil type, the formulation and mode of application, weather conditions, etc. Since so many variables play a role, it is not possible to state a rate of application suitable for all situations. Broadly speaking, the compounds of this invention are used at levels of about 0.001 to 20 kg/ha with a preferred range of 0.01 to 10 kg/ha. In general, the higher rates of application from within this range will be selected for adverse conditions or where extended persistence in soil is desired.
The compounds of Formula I may be combined with other herbicides and are particularly useful in combination with the ureas: such as 3-(3,4-dichlorophenyl)-1,1-dimethylurea (diuron); the triazines: such as 2-chloro-4-(ethylamino)-6-(isopropylamino)-s-triazine (atrazine); the uracils: such as 5-bromo-3-sec-butyl-6-methyluracil (bromacil); N-(phosponomethyl)glycine(glyphosate); 3-cyclohexyl-1-methyl-6-dimethylamino-s-triazine-2,4(1H,3H)-dione(hexazinone); N,N-dimethyl-2,2-diphenylacetamide(diphenamid); 2,4-dichlorophenoxyacetic acid (2,4-D) (and closely related compounds); 4-chloro-2-butynyl-3-chlorophenylcarbamate(barban); S-(2,3-dichloroallyl)-diisopropylthiocarbamate(diallate); S-(2,3,3-trichloroallyl)-diisopropylthiocarbamate(triallate); 1,2-dimethyl-3,5-diphenyl-1H-pyrazolium methyl sulfate (difenzoquat methyl sulfate); methyl 2-[4-(2,4-dichlorophenoxy)-phenoxy]propanoate(diclofop methyl); 4-amino-6-tert-butyl-3-(methylthio)-1,2,4-triazin-5(4H)-one (metribuzin); 3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea (linuron); 3-isopropyl-1H-2,1,3-benzothiodiazin-4(3H)-one-2,2-dioxide(bentazon); .alpha.,.alpha.,.alpha.-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine(trifluralin); 1,1'-dimethyl-4,4'-bipyridinium ion (paraquat); monosodium methanearsonate (MSMA); 2-chloro-2',6'-diethyl(methoxymethyl)acetanilide(alachlor); 1,1-dimethyl-3-(.alpha.,.alpha.,.alpha.-trifluoro-m-tolyl)-urea(fluometuron); 5-[2-chloro-4-(trifluoromethyl)-phenoxy]-2 -nitrobenzoic acid, methyl ester(acifluorofen-methyl); 3-amino-2,5-dichlorobenzoic acid (chloramben); N-(2-chloroethyl)-2,6-dinitro-N-propyl-4-trifluoromethyl)aniline(fluchloralin); 3,4-dinitro-N,N-dipropylsulfanilamide(oryzalin); N-(1-ethylpropyl)-3,4-dimethyl-2,6-dinitrobenzeneamine(pendimethalin); N-(cyclopropylmethyl)-.alpha.,.alpha.,.alpha.-trifluoro-2,6-dinitro-N-propyl-p-toluidine(profluralin); 2-chloro-N-(2ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide(metolachlor); 4-(6-chloroquinoxalinyl-2-oxy)phenoxypropionate C.sub.1 -C.sub.5 alkyl esters, such as methyl ester, butyl ester, ethyl ester, pentyl ester; ethoxyethoxyethyl 4-(6-chloroquinoxalinyl-2-oxy)phenoxypropionate; butyl 2-[4-[5-(trifluoromethyl)-2-pyridinyloxy]phenoxy]propanoate(fluazifop-butyl); N-[2,4-dimethyl-5-]](trifluoromethyl)sulfonyl]amino]phenyl]acetamide(mefluidide); 2-[1-(ethoxyimino)butyl]-5-[2-(ethylthio)propyl]-3-hydroxy-2-cyclohexene-1-one (sethoxydim); 2-s-butyl-4,6-dinitrophenol(dinoseb); 4-(2,4-dichlorophenoxy)butyric acid (2,4-DB); propargyl 2-[4-(3,5-dichloropyridin-2-yloxy)phenoxy]propanoate (CGA 82725); methyl 2-[4-(3-chloro-5-trifluoromethylpyridin-2-yloxy)phenoxy]propanoate (DOWCO 453); 5-(2-chloro-4-trifluoromethylphenoxy)-N-methylsulfonyl-2-nitrobenzamide(fomesafen); 2-[1-(2,5-dimethylphenyl)ethylsulfonyl]pyridine-N-oxide (UBI-S-734); and 2-chloro-1-(3-ethoxy-4-nitrophenoxy)-4-(trifluoromethyl)benzene(oxyfluorfen).
The activity of these compounds was discovered in greenhouse tests. The tests are described and data resulting from them are shown below.
Test A
Seeds of crabgrass (Digitaria spp.), barnyard-grass (Echinochloa crusgalli), wild oats (Avena fatua), cassia (Cassia tora), morningglory (Ipomoea sp.), cocklebur (Xanthium spp.), sorghum, corn, soybean, rice, wheat and nutsedge tubers (Cyperus rotundus) were planted in a growth medium and treated pre-emergence with the chemicals dissolved in a non-phytotoxic solvent solution of the compounds of Table A. At the same time, cotton having five leaves (including cotyledonary ones), bush beans with the third trifoliate leaf expanding, crabgrass and barnyardgrass with two leaves, 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-five leaves were sprayed with a non-phytotoxic solvent solution of the compounds of Table A. Other containers of the above mentioned weeds and crops were treated pre- or post-emergence with the same non-phytotoxic solvent so as to provide a solvent control. A set of untreated control plants was also included for comparison. Pre-emergence and post-emergence treated plants and controls were maintained in a greenhouse for sixteen days, then all treated plants were compared with their respective controls and rated visually for response to treatment.
The following rating system was used:
0=no effect
10=maximum effect
C=chlorosis or necrosis
D=defoliation
E=emergence inhibition
G=growth retardation
H=formative effects
U=unusual pigmentation
6Y=abscised buds or flowers
P=terminal bud kill
B=burn
X=axillary stimulation ##STR90##
TABLE A__________________________________________________________________________ Cmpd. Cmpd. 1 2 Cmpd. 3 Cmpd. 4 Cmpd. 5 Cmpd. 6 Cmpd. 7 Cmpd. 8 Cmpd. Cmpd. 10Rate kg/ha 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.05 0.05 0.05__________________________________________________________________________POST-EMERGENCEBush bean 9C 9C 9C 9C 9C 9C 1C,2G 10G,9C 9G,3H,6C 7G,3H,7CCotton 10C 9C 10C 9C 9C 9C 9C 10G,9C 10G,8C 10G,8CSorghum 9C 10C 9C 2C,9H 2C,9H 6C,9G 1C,3G 10G,4C 10C 10G,9CCorn 5C,9G 9C 9C 4U,9G 6C,9G 6C,9H 3C,9H 7G,5H 10G,8C 10G,3HSoybean 9C 9C 9C 9C 9C 9C 9C 10G,7C 10G,8C 7G,7CWheat 1C,2G 5C,9G 5C,9G 0 0 1C 0 0 3C,2C 3G,2CWild Oats 2C,9G 4C,9G 5C,9G 0 1C,4G 3C,9G 0 0 9G,3C 10G,6CRice 9C 9C 9C 9C 9C 9C 6G 8G,3C 10C 10CBarnyardgrass 10C 10C 10C 4C,9H 5C,9H 9C 0 10G,6C 10C 10G,9CCrabgrass 9C 9C 9C 4C,9G 2C,9G 9C 3G 0 8G,3C 0Morningglory 10C 10C 10C 10C 10C 10C 9C 10G,9C 7G,9C 10G,5CCocklebur 10C 10C 9C 10C 9C 9C 9C 10G,9C 10C 10G,7CCassia 9C 9C 9C 9C 9C 6C,9G 5C,9G 10C 10G,8C 10G,8CNutsedge 9C 9C 9C 1C,5G 5G 1C,5G 2C,5G 10G,7C 10G,6C 10G,7C__________________________________________________________________________ Cmpd. Cmpd. 11 12 Cmpd. 13 Cmpd. 14 Cmpd. 15 Cmpd. 16 Cmpd. 17 Cmpd. 18 Cmpd. Cmpd. 20Rate kg/ha 0.05 0.05 0.05 0.05 0.1 0.1 0.05 0.05 0.05 0.05__________________________________________________________________________POST-EMERGENCEBush bean 2C,2H 1C,2H 6C,9G,6Y 6C,9G,6Y 0 0 3C,5G,6Y 9C,7G 6C,7G,6Y 2GCotton 3C,2H,6G 1C 3C,3H,9G 3C,3H,9G 0 0 7C,6G 8C,7G 9C,6G 5C,4GSorghum 0 6H 0 0 0 0 3C,4G 2C,4G 2C,4G 4C,5GCorn 0 0 0 0 0 0 4C,3U,4G 5C,6G 0 10CSoybean 2H,6G 1H 2H,6G 2H,5G 0 0 6C,7G 10C 7C,6G 4C,5GWheat 0 0 0 0 0 0 0 0 2C,2G 0Wild Oats 0 0 0 0 0 0 2C 3C,4G 3G 4C,5GRice 1C 0 0 0 0 0 2C,3G 3C,4G 3C,5G 3C,4GBarnyardgrass 2H 0 0 0 0 0 10C 7C,6G 2C,3G 7C,6GCrabgrass 0 0 0 0 0 0 2C,3G 0 0 2C,2GMorningglory 9C 1C,5G 4C,9H 3C,9H 0 0 10C 5C,4G 10C 10CCocklebur 3C,9G 1C 4C,9H 2C,8G 0 0 10C 8C,7G 10C 10CCassia 0 0 3C 1C 0 0 8C,7G 3C,4G 3C,4G 2CNutsedge 0 0 0 0 0 0 10C 6C,4G 5C,4G 0__________________________________________________________________________ Cmpd. 21 Cmpd. 22 Cmpd. 30 Cmpd. 31 Cmpd. 32 Cmpd. 33 Cmpd. 34 Cmpd. Cmpd. 36Rate kg/ha 0.05 0.1 0.05 0.05 0.05 0.05 0.05 0.1 0.05__________________________________________________________________________POST-EMERGENCEBush bean 9C,6G,6Y 3C,4G,6Y 3C,9G,6Y 9C 9D,9G,6Y 9D,9G,6Y 4C,6G,6Y 2G 5C,9G,6YCotton 9C,5G 0 5G,9G 6C,9G 3H,6C,9G 6C,9G 3H,6C,9G 3C,3H,7G 9CSorghum 6C,5G 0 10C 2C,9G 9C 3C,9G 1C,6H 1C,3G 9CCorn 7C,6G 0 10C 7U,9G 1C,9G 3U,9G 1C,5G 0 1C,2GSoybean 5C,6G 0 2C,9G 4C,9G 5C,9G 3C,9G 2C,9G 2C,9G 2C,8GWheat 2C,3G 0 9C 2C,7G 9C 1C,3G 0 0 0Wild Oats 8C,7G 0 2C,8G 1C,8G 9C 1C,2G 0 0 2GRice 2C,3G 0 10C 3C,9G 9C 2C,9G 8G 0 4C,9GBarnyardgrass 10C 0 10C 9C 10C 10C 3C,7H 0 3C,9HCrabgrass 7C,6G 0 6C,9G 6G 2C,5G 1C,3G 1C,3G 0 2C,4GMorningglory 10C 0 9C 10C 10C 3C,9G 9C 6C,9G 9CCocklebur 10C 0 9C 10C 9C 6C,9G 6C,9G 4C,9G 10CCassia 5C,3G 0 9C 9C 9C 3C,7G 3C,5G 2C 5C,9GNutsedge 3C,4G 0 9C 1C,9G 4C,9G 2C,7G 1C,3G 1C,2G 9G__________________________________________________________________________ Cmpd. 37 Cmpd. 38 Cmpd. 39 Cmpd. 40 Cmpd. 23 Cmpd. 24 Cmpd. 25 Cmpd. 26 Cmpd. Cmpd. 28Rate kg/ha 0.05 0.05 0.05 0.4 0.05 0.05 0.05 0.05 0.05 0.4__________________________________________________________________________POST-EMERGENCEBush bean 9C 4C,9G,6Y 9C 0 3G 1H 0 3C,9G,6Y 1C,2G,6Y 0Cotton 9C 5C,9G 9C 1C 0 0 0 2C 1C 0Sorghum 3U 10C 1C 4G 0 2G 0 0 3G 0Corn 2C 2C,4G 1C 0 0 3G 0 2C,3G 1C 0Soybean 2C 1H,6G 1H 0 7G 1H 0 2H 2H 0Wheat 0 0 0 0 0 0 0 0 0 0Wild Oats 1C 5G 2G 0 0 0 0 0 0 0Rice 2C 7G 0 2G 0 4G 0 0 4G 0Barnyardgrass 10C 3C,7H 2G 0 0 0 0 0 0 0Crabgrass 3C 2C,5G 1C 5G 0 3G 0 0 1C 0Morningglory 9C 2C,9G 9C 3G 0 2G 0 2C,6H 1C 3BCocklebur 10C 9C 10C 3G 2G 1C 0 2C,6G 3C,6H 0Cassia 5G 0 0Nutsedge 1C 8G 2G 3G 0 0 0 0 1C 0__________________________________________________________________________ Cmpd. 29 Cmpd. 41 Cmpd. 42 Compound 43 Compound 44 Cmpd. 45 Cmpd. 46 Cmpd. Cmpd. 48Rate kg/ha 0.05 0.4 0.4 2 6 2 6 0.05 0.05 0.05 0.05__________________________________________________________________________POST-EMERGENCEBush bean 0 9C 9C 0 3C 0 0 4C,9G,6Y 9C 9C 4C,8G,6YCotton 0 10C 4C,3H,9G 0 3C 0 2C 6C,9G 6C,9G 8C,9G 3CSorghum 0 6U,9G 2C,9G 0 0 0 2C 2C,9G 5C,9G 8U,9G 2C,9HCorn 0 2U,9H 5U,9G 0 0 0 0 3G 3C,9H 5U,9G 3C,9HSoybean 0 9C 9C 0 1C 0 3G 1C,8H 5C,9G 9C 2C,6G,5XWheat 0 2G 0 0 0 0 0 1C 1C 1C 0Wild Oats 0 1C,8G 0 0 0 0 0 2C,8G 3C,9G 2C,9G 2C,7GRice 0 6C,9G 6C,9G 0 0 0 0 3C,9G 5C,9G 5C,9G 2C,8G,5XBarnyardgrass 0 5C,9H 1C,6G 0 1C 0 0 5C,9H 9C 6C,9H 2C,8HCrabgrass 0 2C,6G 4G 0 0 0 0 3C,7H 4C,9H 9C 0Morningglory 1C,2G 6C,9G 6C,9G 0 0 0 1C,3G 6C,9G 9C 7C,9G 3C,8HCocklebur 0 10C 9C 0 0 0 0 5C,9G 9C 9C 1C,4GCassia 9C 4C,7H 0 1C 0 0 3C,6H 5C,9H 5C,9G 1C,3GNutsedge 0 2C,8G 2C,5G 0 0 0 0 5C,9G 10C 9C 3G__________________________________________________________________________ Cmpd. 49 Cmpd. 50 Cmpd. 51 Cmpd. 52 Cmpd. 53 Cmpd. 54 Cmpd. Cmpd. 56 Rate kg/ha 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05__________________________________________________________________________ POST-EMERGENCE Bush bean 9C 9C 0 3C,3H,6Y 4C,9G,6Y 1C 3C,9G,6Y 9C Cotton 6C,9G 6C,9G 0 2C,2H 4C,7H 1C,2G 2C,6G 6C,9G Sorghum 9C 9C 0 2C,4G 1C,3G 0 2C,9H 2G Corn 9C 7U,9C 0 1C,5H 1C 0 3U,9G 0 Soybean 9C 4C,9G 0 2C,6H 2C,8H 1H 3C,9G 2C,8H Wheat 2U,9G 2C 0 0 0 0 0 0 Wild Oats 3C,9G 2C,4G 0 0 0 0 0 0 Rice 6C,9G 5C,9G 0 4G 4G 0 1C,6G 0 Barnyardgrass 9C 5C,8H 0 2C,4H 2H 0 4H 0 Crabgrass 9C 3C,9G 0 0 0 0 0 0 Morningglory 4C,9H 4C,9H 0 3C,7H 3C,8G 2C,7H 3C,9G 6C,9G Cocklebur 4C,9H 4C,9G 0 3C,9G 4C,9G 4G 3C,9H 9C Cassia 5C,7H 4C,6H 0 3C 1C,3G 1C 0 5C,8G Nutsedge 2C,4G 3G,5X 0 8G 1C,8G 0 0 0__________________________________________________________________________ Cmpd. Cmpd. 1 2 Cmpd. 3 Cmpd. 4 Cmpd. 5 Cmpd. 6 Cmpd. 7 Cmpd. 8 Cmpd. Cmpd. 10Rate kg/ha 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.05 0.05 0.05__________________________________________________________________________PRE-EMERGENCESorghum 7C,9H 6C,9H 10H 1C,9G 5C,9H 7C,9H 0 8G,5G 9G,9C 9G,9CCorn 2U,9G 10E 10E 3C,9H 9H 9H 3G 6G 9G 9G,9CSoybean 9H 9H 9H 9H 9H 9H 1C,2H 8G,5H 9G,5H 8G,5CWheat 5G 5C,9H 1C,9H 3G 0 8G 0 0 7G 7GWild Oats 1U,9G 5C,9H 4C,9H 8G 1C,7G 3C,9G 0 5G,3H 8G,3C 7G,5HRice 10E 10E 10E 10E 10E 10E 1C 8G,6C 8G,8C 10EBarnyardgrass 5C,9H 9C 3C,9H 7C,9H 2C,9H 7C,9H 0 8G,5H 9G,6C 8G,5HCrabgrass 9C 6C,9G 2C,8G 2C,5G 2C,6G 1C,6G 0 3G 5G,3H 3GMorningglory 9G 9G 9C 9C 9C 9C 1C,3G 8G,5C 8G,9C 8G,9CCocklebur 9H 9H 9H 9H 9H 9H 8H 8G,3H 9G,9P 9G,9PCassia 9C 5C,9G 6C,9G 6C,9G 6C,9G 6C,9G 2C,2H 9G,5C 9G,9C 8C,9GNutsedge 10E 10E 10E 1C,7G 1C,6G 6G 0 10E 10E 10E__________________________________________________________________________ Cmpd. Cmpd. 11 12 Cmpd. 13 Cmpd. 14 Cmpd. 15 Cmpd. 16 Cmpd. 17 Cmpd. 18 Cmpd. Cmpd. 20Rate kg/ha 0.05 0.05 0.05 0.05 0.1 0.1 0.05 0.05 0.05 0.05__________________________________________________________________________PRE-EMERGENCESorghum 0 0 0 0 0 0 3C,6G 5C,8G 7C,7G 7C,8GCorn 0 0 0 0 0 0 3C,6G 7C,6G 0 7C,8GSoybean 0 0 0 0 0 0 7C,8G 7C,8G 7C,6G 6C,7GWheat 0 0 0 0 0 0 0 3C,5G 0 0Wild Oats 0 0 0 0 0 0 2C 7C,6G 2C,6G 2C,5GRice 3G 0 0 0 0 0 10E 8C,8G 8C,7G 10EBarnyardgrass 0 0 0 0 0 0 7C,8G 7C,7G 7C,5G 7C,7GCrabgrass 0 0 0 0 0 0 2C,2G 3G,2C 0 4C,5GMorningglory 7G 0 3C,9G 4C,9G 0 0 7C,7G 10C 7C,6G 10CCocklebur 5H 0 8H,3C 7H,3C 0 0 8C,7G 3C,5G 5C,6G 10CCassia 0 0 2C 0 0 0 8C,8G 7C,6G 5C,4G 5G,6CNutsedge 0 0 0 0 0 0 10E 10E 10E 0__________________________________________________________________________ Cmpd. 21 Cmpd. 22 Cmpd. 30 Cmpd. 31 Cmpd. 32 Cmpd. 33 Cmpd. 34 Cmpd. Cmpd. 36Rate kg/ha 0.05 0.1 0.05 0.05 0.05 0.05 0.05 0.1 0.05__________________________________________________________________________PRE-EMERGENCESorghum 7C,8G 0 1C,9H 4C,9G 3C,9H 2C,9G 2C,7G 0 2C,9HCorn 8C,8G 0 1C,9G 2C,9G 2C,9H 1C,9G 1C,8G 0 2C,5GSoybean 7C,6G 0 1C,9G 8H 3C,7H 9H 1C,9H 0 1C,4HWheat 0 0 9G 9G 3C 0 0 0 0Wild Oats 5C,6G 0 8G 2C,9H 1C,9G 1C,5G 0 0 1C,6GRice 10E 0 10E 2C,9H 10E 9H 2C,5G 0 3C,9HBarnyardgrass 8C,8G 0 5C,9H 2C,9H 2C,9H 3C,8H 1C,5H 0 2C,8HCrabgrass 5C,7G 0 2C,8G 2C,9G 1C,3G 1C,3G 0 0 1CMorningglory 10C 0 9G 9C 9G 1C,9H 2C,9G 0 9GCocklebur 10C 0 9H 9H 9H 9H 9H 0 9HCassia 7C,6G 0 2C,9G 2C,9G 2C,9G 9G,3C 6C,9G 0 2C,8GNutsedge 7C,5G 0 10E 10E 10E 1C,9G 3G 0 9G__________________________________________________________________________ Cmpd. 37 Cmpd. 38 Cmpd. 39 Cmpd. 40 Cmpd. 23 Cmpd. 24 Cmpd. 25 Cmpd. 26 Cmpd. Cmpd. 28Rate kg/ha 0.05 0.05 0.05 0.4 0.05 0.05 0.05 0.05 0.05 0.4__________________________________________________________________________PRE-EMERGENCESorghum 2C,9H 2C,9H 1C,7G 0 0 4H 0 0 0 0Corn 2C,8H 2C,7H 1C,3G 0 0 0 0 0 0 0Soybean 2C,5G 2G 1C 1H 1H 1C,1H 0 0 0 0Wheat 3G 0 0 0 0 0 0 0 0 0Wild Oats 1C,8G 1C,6G 0 0 0 0 0 0 0 0Rice 2C,8H 2C,6G 2C 0 0 2C 0 0 0 0Barnyardgrass 2C,9H 3C,5G 1C,4H 0 0 0 0 0 0 0Crabgrass 1C,3G 1C 1C 2G 0 1C 0 0 0 0Morningglory 9G 1C,6G 9G 3G 0 0 0 0 0 0Cocklebur 9H 9H 9H 5H 0 2C 0 0 9H 0Cassia 2C,8H 1C 2C,9H 0 0 0 0 0 0 0Nutsedge 9G 5G 2G 0 0 3G 0 0 0 0__________________________________________________________________________ Cmpd. 29 Cmpd. 41 Cmpd. 42 Compound 43 Compound 44 Cmpd. 45 Cmpd. 46 Cmpd. Cmpd. 48Rate kg/ha 0.05 0.4 0.4 2 6 2 6 0.05 0.05 0.05 0.05__________________________________________________________________________PRE-EMERGENCESorghum 0 5C,9H 5C,9G 0 1C,5G 0 2C 3C,9H 10H 3C,9H 1CCorn 0 2U,9G 2C,9G 0 2C,5G 0 1C,2G 2C,8G 9G 9G 1C,3GSoybean 0 9H 4C,8H 0 0 0 0 2C,2H 9H 9H 1HWheat 0 8G 2C,8G 0 0 0 0 0 5G 0 0Wild Oats 0 4C,8G 2C,8G 0 1C,4G 0 0 3C,8H 3C,9H 9H 3GRice 0 10E 10E 0 1C 0 1C 4C,8H 5C,9H 10E 1CBarnyardgrass 0 4C,9H 4C,9G 0 5C,8H 0 5C 3C,7H 6C,9H 4C,9H 2CCrabgrass 0 5G 1C,4G 0 2G 0 0 1C,5G 3C,8H 2C,8G 0Morningglory 0 9C 9C 0 3C 0 2C 3C,9H 2C,9H 2H,9G 1CCocklebur 0 9H 9H 0 2C,8H 0 5H 2C,8H 9H 9H 0Cassia 0 4C,9G 3C,7G 0 3G 0 5G 5C 3C,9G 5C,9G 1CNutsedge 0 1C,9G 8G 0 0 0 0 10E 10E 10E 0__________________________________________________________________________ Cmpd. 49 Cmpd. 50 Cmpd. 51 Cmpd. 52 Cmpd. 53 Cmpd. 54 Cmpd. Cmpd. 56 Rate kg/ha 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05__________________________________________________________________________ PRE-EMERGENCE Sorghum 10H 5C,9H 0 2C,6G 1C,4G 0 1C,4G 4G Corn 3C,9G 2C,9G 0 3C,7G 1C,4G 1C,5G 3C,7G 0 Soybean 3C,5H 2C,5H 0 1C 1C 1H 1C 0 Wheat 1C 2C 0 0 0 0 0 0 Wild Oats 3C,9G 2C,5G 0 0 0 0 0 0 Rice 9H 9H 0 1C,3G 1C,4G 2G 1C,3G 2G Barnyardgrass 3C,9H 3C,9H 0 2C,8H 3C 2C 1C 2C Crabgrass 1C 1C 0 1C 1C 0 0 0 Morningglory 4C,9H 2C,9G 0 6H,2C 8G,2C 0 8H,2C 9C Cocklebur -- 9H 0 3C,8H -- 0 -- 9H Cassia 3C,3H 2C,3H 0 1C 0 0 0 5C,9G Nutsedge 1C 3G 0 1C,8G 9G 0 0 5G__________________________________________________________________________
It is noted that certain compounds such as 15, 16, 22-25, 28 and 29 show little if any activity at the levels tested. It is thought that they would demonstrate herbicidal activity at higher rates.
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 routundus), 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), sicklepod (Cassia obtusifolia), teaweed (Sida spinosa), velvetleaf (Abutilon theophrasti), and jimsonweed (Datura stramonium). A 12.5 cm diameter plastic pot was also filled with prepared soil and planted with rice and wheat. Another 12.5 cm pot was planted with sugarbeets. The above four containers were treated pre-emergence with several test compounds within the scope of the invention.
Twenty-eight days after treatment, the plants were evaluated and visually rated for response to the chemical treatments utilizing the rating system described previously for Test A. The data are summarized in Table B.
TABLE B__________________________________________________________________________PRE-EMERGENCE ONFALLSINGTON SILT LOAM Compound 1 Compound 2 Compound 3 Compound 36 Compound 39Rate kg/ha 0.03 0.12 0.03 0.12 0.007 0.015 0.03 0.12 0.06 0.25 0.06 0.25__________________________________________________________________________Crabgrass 7G,2H 8G,3H 7G,3H 8G,3H 0 0 5G 6G 2G 4G 2G 2GBarnyardgrass 8G,3H 9G,9C 9G,8C 10C 2G 2G 8G,3H 9G,9C 4G 6G,5H 4G 5GSorghum 9G,9C 10C 10C 10E 2G 4G 10C 10E 6G,3H 8G,5H 4G 4G,2HWild Oats 6G 10C 8G,5C 9G,9C 0 0 10C 10C 4G 4G 3G 3GJohnsongrass 8G,7C 10C 9G,9C 10C 0 3G 10C 10C 4G,3H 6G,3H 4G 3GDallisgrass 7G 9G,9C 8G,3H 8G,3H 0 3G 6G 8G,3H 4G 5G 3G 0Giant foxtail 6G,3C 8G,5C 5G,3C 10C 0 3G 3C 7G,3C 4G 6G,3H 0 2GKy. bluegrass 8G,9C 10C 8G,9C 10C 0 2G 10C 8G,8C 6G 7G 2G 4GCheatgrass 8G,9C 9G,9C 10E 10E 0 -- 10E 10E 6G 7G 0 3GSugarbeets 10C 10C 10C 10C -- 4G 10C 10C 6G,6C 8G,9C 9G,8C 10CCorn 5G,3U 8G,5H 7G,5H 10C 0 0 10C 10C 3G 4G 2G 4GMustard 10C 10C 10C 10C 5G 7G,3C 10C 10C 10E 10E 8G,8C 8G,9CCocklebur 6G -- 5G 10C 0 0 7G 8G,5H -- 8G,7C 8G,5H 10CPigweed 10C 10E 7G 10E 0 10E 9G,9C 10C 5G,5C 9G,9C 4G 6G,4CNutsedge 10E 10E 6G 10E 0 0 10E 10E 7G 10E 4G 6GCotton 8G 9G,5C 6G,3H 9G,8C 0 0 8G,3C 9G,7C 4G 8G,3H 8G,3H 9G,5CMorningglory 5G 9G,9C 7G 9G,5C 3G 3G 8G 9G,7C 4G 8G,9C 9G 9G,3CCassia 8G,8C 10C 7G,4C 9G,9C 0 0 9G,8C 9G,8C 6G 8G,8C 5G,3C 7G,8CTeaweed 6G 9G,8C 6G,3H 8G,6C -- 0 4G 10C 5G,3C 6G,3C 6G,2C 6G,3CVelvetleaf 9G,8C 10C 8G,8C 9G,9C 0 0 8G,5E 9G,8C 5G,3H 8G,8C 7G,3H 8C,9CJimsonweed 7G,3C 9G,8C 9G,9C 9G,9C 0 0 8G,8C 9G,9C 3G 5G,5C 7G,3C 8G,5CSoybean 8G,5H 9G,8C 7G,5H 9G,8C 0 0 8G,5H 9G,8C 2G 5G,3H 3G 4GRice 8G,3H 10E 8G,7C 10E 3G 6G,3H 10E 10E 3G 5G 0 0Wheat 0 3G 5G 8G,9C 0 0 5G 7G,3C 0 0 0 0__________________________________________________________________________
Test C
The high herbicidal activity of two of the compounds from within the scope of the invention is evident from the results obtained in this test. The experiment concerned pre-emergence applications on soil. The containers used were 25 cm diameter plastic pots filled with Fallsington silt loam. One set of pots was planted to weeds, the seeds of which were uniformly mixed with the top 1.2 cm layer of soil. The species selected were: johnsongrass (Sorghum halepense), barnyardgrass (Echinochloa crusgalli), crabgrass (Digitaria sanguinalis), giant foxtail (Setaria faberii), velvetleaf (Abutilon theophrasti), jimsonweed (Datura stramonium), mustard (Brassica arvensis), and pigweed (Amaranthus retroflexus). Another set of pots was planted to the following crops with from one to four species per pot: corn (planting depth 3.7 cm), cotton, soybeans, sunflower, Clinton oats, wheat, Black Valentine beans, rice, sorghum, peas, flax, and peanuts (all at 2.5 cm depth), cucumbers, cabbage, alfalfa, safflower, sugarbeets, tomato, spinach, barley, and Kentucky bluegrass (all at 1.2 cm depth). Immediately after planting, the test chemical was applied to the soil surfaces dissolved in a nonphytotoxic solvent. One pot from the weed phase and one of each of the crop species were left untreated for the purpose of comparison. The treated and untreated pots were promptly watered with approximately 4 mm of simulated rainfall and then held in a greenhouse for several weeks. Visual weed and crop response ratings were made 28 days after treatment utilizing the rating system as described above for Test A. The data are given in Table C.
TABLE C__________________________________________________________________________PRE-EMERGENCE ONFALLSINGTON SILT LOAM SOIL Compound 1 Compound 2Rate kg/ha 0.0035 0.0075 0.0150 0.03 0.0075 0.015 0.030 0.06__________________________________________________________________________Corn 5G,3C 9G,9CCotton 7G,3H 10ESoybean 4G,2H 9G,5HPeanut 6G 8G,3HSunflower 5G 9G,5HOats 4G 6G,2CWheat 2G 5GSorghum 7G,5H 10ESugarbeet 9G,9C 10EPea 10E 10EFlax 6G 10EAlfalfa 8G,6C 8G,6CBean 0 8G,5HSpinach 8G,5H 9G,9CCabbage 8G,6C 8G,7CTomato 4G 5C,8GRice 6G 10ESafflower 7G,4C 8G,7CCucumber 5G 9G,5HKy. bluegrass 7G 6G,5HBarley 3G 8G,7CBroadleaves 3G 4G 6G,2H -- 5G,3C 7G,5C 9G,8C --Grasses 0 0 2G -- 6G,3C 8G,4C 9G,6C --__________________________________________________________________________
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, presented in Table D, indicate that certain compounds from within the scope of the invention have utility for pre- and/or post-emergence weed control in cereal crops such as wheat and barley.
TABLE D__________________________________________________________________________Pre-Emergence Compound 1 Compound 2Rate kg/ha 0.002 0.008 0.008 0.015 0.03 0.06 0.002 0.008 0.008 0.015 0.03 0.06__________________________________________________________________________wheat 0 0 0 0 0 2C,3G 0 0 0 2C,2G 2C,4G 4C,6Gbarley 0 0 0 1C,6G 1C,1G 6C,8G 0 3G 3C,4G 5C,7G 6C,7G 8C,8Gwild oats 0 0 0 3C,7G 0 8C,8G 0 2C,5G 2G 8C,8G 7C,6G 9C,8Gdowny brome 3G 2C,5G 1G 5C,7G 2C,7G 10C 6G 7C,7G 3C,7G 10C 7C,8G 10Ccheatgrass 5G 4C,7G 3G 10C 5C,8G 10C 5C,7G 10C 5C,8G 10C 10C 10Cblackgrass 3G 5C,6G 2G 10C 3C,7G 10C 3C,6G 7C,7G 3C,7G 10C 8C,7G 10Cannual bluegrass 5G 2C,6G 1C,2G 7C,8G 5C,7G 10C 1C,6G 7C,7G 2C,5G 10C 5C,6G 10Cgreen foxtail 0 2G 3C,4G 3C,5G 7C,7G 9C,8G 0 4C,5G 2C,4G 6C,7G 4C,6G 9C,9Gquackgrass 3G 3C,5G 0 8G 2C,3G 10C 4G 3C,6G 4G 8C,9G 7C,7G 9C,9GItalian ryegrass 0 3C,5G 0 4G 1C,3G 4C,7G 3G 5C,7G 5C,7G 9C,9G 7C,8G 10Cripgut brome 2G 2C,4G 0 2C,5G 0 5C,7G 5G 6G 3C,4G 9C,9G 6C,7G 9C,9GRussian thistle 0 0 1G 8C,7G 2C,3G 8C,8G 0 1C,1G 3C,4G 9C,9G 5C,6G 10Ctansy mustard 6G 8C,8G 8C,8G 10C 10C 10C 3C,8G 8C,9G 7C,8G 10C 9C,9G 10Csmartweed -- -- -- -- -- -- -- -- -- -- -- --tumble mustard 3C,8G 10C 7C,7G 10C 10C 10C 7C,8G 10C 10C 10C 10C 10Ckochia 1G 5G 3G 9C,8G 7C,8G 10C 2G 5G 7C,8G 8C,9G 9C,8G 9C,9Gshepherd's purse 3C,5G 8C,8G 9C,8G 10C 10C 10C 8C,8G 8C,8G 10C 10C 10C 10CMatricaria inodora 4G 7C,8G 7C,7G 10C 7C,8G 10C 5C,8G 7C,8G 7C,7G 10C 7C,8G 10Cblack nightshade 2C,4G 4C,6G 6C,7G 8G 7C,7G 3C,8G 3C,4G 3C,4G 5C,6G 2C,7G 7C,6G 5C,8Gyellow rocket 2C,7G 4C,8G 7C,7G 10C 8C,9G 10C 8G 2C,9G 7C,7G 10C 10C 10Cwild mustard 5C,6G 8C,8G 7C,7G 10C 8C,8G 10C 7C,8G 8C,8G 7C,8G 10C 9C,8G 10Cwild buckwheat 3G 2C,4G 1C,2G 3C,6G 3C,4G 4C,8G 2C,1G 3C,4G 3C,2G 3C,4G 4C,5G 5C,6G__________________________________________________________________________ Pre-Emergence Post-Emergence Compound 3 Compound 36 Compound 1 Compound 2Rate kg/ha 0.008 0.03 0.015 0.06 0.002 0.008 0.008 0.015 0.03 0.06 0.002 0.008__________________________________________________________________________wheat 0 1C,2G 0 0 0 0 0 0 0 1C,2G 0 1Gbarley 2G 7C,6G 0 0 0 0 0 3C,5G 2C,2G 7C,6G 0 3Gwild oats 1G 7C,7G 0 0 0 1C 0 3C,2G 2G 3C,3G 0 2C,5Gdowny brome 4G 10C 3G 6G 3G 5C,7G 4C,5G 3G 7C,7G 3C,4G 3C,5G 7C,7Gcheatgrass 2C,5G 10C 7G 10C 4C,7G 8C,7G 8C,7G 10C 10C 10C 6C,7G 10Cblackgrass 7C,7G 10C 6G 3C,7G 6G 4C,5G 7C,7G 10C 10C 10C 2C,6G 7C,7Gannual bluegrass 3C,4G 5C,6G 6G 7C,7G 3G 3C,6G 3C,5G 5C,4G 6C,7G 10C 5C,6G 10Cgreen foxtail 2C,3G 5C,4G 2G 3C,5G 4G 7C,7G 7C,7G 3C,4G 7C,8G 7C,6G 3C,5G 4C,5Gquackgrass 0 3C,4G 0 2G 3G 6G 2C,3G 6C,5G 3C,6G 7C,6G 1C,6G 4C,6GItalian ryegrass 3G 7C,7G 1G 3G 2G 2G 0 3G 2C,4G 4C,5G 1C,5G 3C,6Gripgut brome 0 10C 2G 2C,7G 2G 5G 0 2G 2C,3G 3C,5G 4G 1C,7GRussian thistle 0 7C,7G 0 1G 2C,3G 10C 9C,7G 10C 10C 10C 5C,4G 8C,7Gtansy mustard 4C,5G 9C,9G 2G 2C,5G 10C 10C 10C 10C 10C 10C 10C 10Csmartweed -- -- -- -- -- -- -- -- -- -- -- --tumble mustard 7G 10C 5G 3C,7G 4C,6G 10C 10C 10C 10C 10C 7C,8G 8C,8Gkochia 6G 10C 0 5C,6G 3G 4G 10C 8C,7G 10C 10C 5G 10Cshepherd's purse 7C,7G 10C 7G 3C,8G 10C 10C 10C 10C 10C 10C 10C 10CMatricaria inodora 6C,7G 7C,7G 3C,8G 7C,8G 7C,7G 10C 9C,7G 10C 9C,8G 10C 10C 10Cblack nightshade 3C,4G 5C,6G 4G 1C,5G 4G 4C,6G 1C,1G 0 3C,7G 4C,5G 2G 3C,5Gyellow rocket 7G 7C,7G 3C,8G 10C 3G 10C 10C 10C 10C 10C 10C 10Cwild mustard 5C,7G 7C,8G 7C,8G 10C 10C 10C 10C 10C 10C 10C 10C 10Cwild buckwheat 0 2C,3G 3G 1C,4G 2C,4G 5C,5G 6C,5G 10C 7C,6G 10C 2C,2G 3C,5G__________________________________________________________________________ Post-Emergence Compound 2 Compound 3 Compound 36 0.008 0.015 0.03 0.06 0.008 0.03 0.015 0.06__________________________________________________________________________ wheat 1G 5C,5G 1C,2G 7C,7G 0 1C,2G 0 0 barley 2C,3G 7C,6G 4C,6G 10C 0 4C,6G 0 0 wild oats 5G 7C,7G 5C,6G 8C,7G 0 7C,5G 0 0 downy brome 7C,7G 7C,7G 8C,7G 10C 6C,7G 7C,7G 0 3G cheatgrass 10C 10C 10C 10C 7C,7G 10C 1G 3C,5G blackgrass 7C,7G 10C 10C 10C 4C,5G 10C 2G 5C,4G annual bluegrass 6C,5G 10C 10C 10C 4C,6G 5C,7G 2G 3G green foxtail 7C,8G 6C,6G 8C,8G 7C,7G 2C,4G 6C,7G 1G 2G quackgrass 6G 7C,6G 4C,6G 10C 2C,3G 4C,6G 0 0 Italian ryegrass 3C,6G 10C 5C,7G 10C 3C,6G 5C,6G 0 0 ripgut brome 3G 4C,6G 4C,4G 9C,8G 1C,2G 3C,4G 0 2G Russian thistle 10C 10C 10C 10C 3C,2G 10C 0 2G tansy mustard 10C 10C 10C 10C 8C,7G 10C 5C,4G 7C,8G smartweed -- -- -- -- -- -- -- -- tumble mustard 10C 10C 10C 10C 10C 10C 10C 10C kochia 10C 7C,6G 10C 10C 4G 10C 0 0 shepherd's purse 10C 10C 10C 10C 9C,8G 10C 7C,8G 10C Matricaria inodora 7C,7G 10C 8C,7G 10C 6C,5G 9C,8G 7C,7G 9C,8G black nightshade 1C,1G 0 3C,4G 2G 4G 8C,8G 2G 4C,5G yellow rocket 8C,8G 10C 10C 10C 2C,5G 10C 7C,7G 10C wild mustard 10C 10C 10C 10C 10C 10C 10C 10C wild buckwheat 6C,6G 10C 7C,8G 10C 2C,2G 5C,6G 1C,2G 5C,4G__________________________________________________________________________
Test E
Test samples were formulated and applied directly to the paddy water three days after transplanting of rice. The test was maintained in a greenhouse, and plant response ratings were taken at the stated intervals after application. The data indicate:
______________________________________Compound 1 Barnyard- WaterRate Rice Rice grass* Chestnut**g/ha 4 Days 4 Weeks 4 Weeks 4 Weeks______________________________________1 0 0 0 7G4 0 0 0 8G8 0 0 0 9G______________________________________Compound 36 Barnyard- Water Arrow-Rate, Rice Rice grass* Chestnut** head***g/ha 1 Week 8 Weeks 8 Weeks 8 Weeks 8 Weeks______________________________________ 25 0 0 0 10C 0100 0 0 0 10C 0______________________________________ *Echinochloa spp. **Eleocharis spp. ***Sagittaria spp.
It may be seen that compounds from within the scope of the invention can be used for selective weed control in rice.
Test F
The test chemicals, dissolved in a non-phytotoxic solvent, were applied in an overall spray to the foliage and surrounding soil of selected plant species. One day after treatment, plants were observed for rapid burn injury. Approximately fourteen days after treatment, all species were visually compared to untreated controls and rated for response to treatment. The rating system was as described previously for Test A. The data are presented in Table F.
All plant species were seeded in Woodstown sandy loam soil and grown in a greenhouse. The following species were grown in soil contained in plastic pots (25 cm diameter by 13 cm deep): 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 spp.), nutsedge (Cyperus rotundus), barnyardgrass (Echinochloa crusgalli), giant foxtail (Setaria faberii) and wild oats (Avena fatua). The following species were grown in soil in a paper cup (12 cm diameter by 13 cm deep): sunflower, sugarbeets, and mustard. All plants were sprayed approximately 14 days after planting.
Some of the compounds tested by this procedure are useful for the post-emergence control of weeds in wheat. Compound 39 has utility for the post-emergence control of weeds in soybeans and corn.
TABLE F__________________________________________________________________________Over-the-Top Soil/Foliage Treatment__________________________________________________________________________ Com- pound Compound 1 Compound 2 Compound 3 36Rate kg/ha 0.06 0.015 0.007 0.003 0.06 0.015 0.06 0.015 0.007 0.003 0.12__________________________________________________________________________Soybeans 10G,7C 10G,7C 9G,5C 9G,5C 9C 10G,8C 10G,6C 10G,4C 9G,7C 10G,5C 10CVelvetleaf 10G,7C 8G,3C 9G,9C 10G,9C 10G,4C 5G 7G,2C 5G 8G,8C 7G 10CSesbania 9C 9C 10C 10C 10C 9C 9C 9C 8G,5C 9G,8C 10CCassia 10G,7C 8G,2C 9G,5C 10G,5C 10G,7C 7G,3C 10G,7C 5G,3C 10G,5C 8G,4C 10CCotton 10G,7C 7G,3C 10G,9C 10C 10G,6C 7G,3C 10G,6C 10G,6C 10C 8G,2C 9G,9CMorningglory 10G,5C 9G,4C 10G,8C 10G,8C 10C 8G,2C 9G,4C 9G,3C 10G,8C 7G,1H 10CAlfalfa 9C 5C 6G,2C 6G,2C 10C 7C 9C 8C 7G 6G,2C 9GJimsonweed 9C 7G,3C 0 0 10C -- 9G,3C -- -- 0 0Cocklebur 10G,7C 9G,3C 7G 5G 10G,8C 10G,7C 10G,7C 10G,7C 4G,5C 3G 10CCorn 10C 9G,7C 8G,2H 9G,1H 10C 10G,7U 10C 9G,6C 9G 9G,1H 2G,1CCrabgrass 8G,4C 2C 5G 0 10C 6G,1C 7G,4C 0 5G,1C 0 5GRice 8G,3C 3G,1C 8G,5C 7G,2C 10C 6G,3C 8G,5C 7G,3C 9G,7C 9G,7C 5GNutsedge 10C 10C 5G 3G 10C 2C 9G,4C 9G,3C 7G 5G 7G,5CBarnyardgrass 10C 10C 9G,4C 9G,2C 10C 6G,3C 10C 9C 9G,4C 9G,2C 9G,5CWheat 0 0 0 1G 9C 1C 8C 1C 6G 3G 2GGiant foxtail 10G,3C 7G,3C 5G 5G 10C -- -- -- 0 0 3G,2CWild Oats 6G 3G 3G 3G 10C 5C,3C 10C 7G,3C 5G 4G 3GSorghum 10C 9C 8G,3C 7G,4U 10C 8G,5C 10C 9C 7G,3U 9G,6U 7G,3CMustard -- -- 10C 10C -- -- -- -- 10C 9G,9C 10CSunflower -- -- 10C 10C -- -- -- -- 10C 10G,9C 10CSugarbeets -- -- 10C 9G,9C -- -- -- -- 10C 9G,9C 9G,3C__________________________________________________________________________ Compound 36 Compound 39 Rate kg/ha 0.06 0.015 0.12 0.06 0.03 0.015 0.015 0.015 0.007__________________________________________________________________________ Soybeans 9G,9C 9G,7C 10G,7C 9G,9C 4G 0 0 3G 0 Velvetleaf 10C 8G,7C 9G,7C 8G,5C 10G,5C 8G,4C 8G,3C 8G,3C 7G,3C Sesbania 10C 10C 10C 9G,4C 10G,7C 8G,6C 9G,4C 5G,4C 7G,4C Cassia 9G,3C 8G,3C 9G,7C 5G,5C 8G,5C 5G,5C 8G,4C 4G,6C 5G,3C Cotton 8G,8C 4G,4C 9G,7C 9G,6C 9G,5C 8G,4C 8G,4C 8G,4C 6G,3C Morningglory 10C 8G,4C 9G,8C 9G,5C 9G,4C 9G,5C 9G,4C 10G,3C 9G,6C Alfalfa 5G,3C 7G 9G,8C 10C 9G,5C 5G,2C 9G,5C 7G 7G,3C Jimsonweed 0 0 0 -- -- -- 8G 2C -- Cocklebur 10C 10C 10G,7C 10G,5C 10G,5C 9G,5C 10G,5C 10G,4C 9G,4C Corn 1G,2C 1G,1C 0 0 3G,2C 0 1G,2C 0 2G Crabgrass 0 0 0 0 0 0 0 0 0 Rice 4G 2G 0 0 4G 1G 3G 0 2G Nutsedge 7G,5C 0 1G 0 3G 0 0 0 5G Barnyardgrass 8G,5C 6G,2C 0 0 3G 0 0 0 2G Wheat 0 0 0 0 0 0 0 0 0 Giant foxtail 2C 0 0 0 2G 0 2G 0 1G Wild Oats 0 0 0 0 2G 0 1G 2G 0 Sorghum 5G,2C 2G,2C 0 0 5G 0 4G 5G 3G Mustard 10C 10C 10C 10C 10G,5C 10G,5C 10G,5C 9G 10G,5C Sunflower 10C 10C 10C 10C 10G,8C 10G,8C 10G,8C 10C 10G,8C Sugarbeets 9G,5C 8G 10G,5C 10C 9G,3C 10G,5C 9G,3C 9G 10G,4C__________________________________________________________________________
Test G
This test demonstrates the broadleaf herbicidal properties of compound 39. Approximately 12 soybean plants were grown in a 25 cm. diameter plastic pot. In another pot of equal size the following broadleaf plant species were grown: sugarbeets, velvetleaf, Sesbania, Cassia, mustard, morningglory, alfalfa, jimsonweed, and cocklebur. The plant foliage and surrounding soil were treated with the test chemical dissolved in a non-phytotoxic solvent as an overall spray at the rate of 0.015 kg/ha, when the plants were 17 days old. Visual ratings of herbicidal effects were made 22 days after treatment utilizing the rating system described for Test A.
TABLE G______________________________________Rate 0.015______________________________________Soybeans 0Sugarbeets 9GVelvetleaf 9G,9CSesbania 8G,8CCassia 7G,4CMustard 10CMorningglory 9G,9CAlfalfa 8G,4CJimsonweed 0Cocklebur 10P,2C______________________________________
The data indicate that the compound tested provides excellent post-emergence control of broadleaved weeds in soybeans.
Test H
Test samples of compound 17 were formulated in a non-phytotoxic solvent and applied to the water surface of tub-paddies, three days after transplanting of rice plants into the paddies. The paddy soil contained various weed propagules which were sprouting (except for Scirpus, as explained below). The paddies were maintained in a greenhouse, and plant response ratings (TABLE) were taken about six weeks after application.
TABLE H______________________________________Rate, Barnyard- Water Arrow-g ai/ha Rice grass* Chestnut* head* Scirpus*______________________________________2.5 0 9E 7G,2C 6G,3H --10 0 10E 10C 9G,7C --20 0 10E 9G,9C 10G,2C --______________________________________ *Echinochloa sp., Eleocharis sp., Saqittaria sp., and Scirpus sp. Scirpus failed to become established and could not be rated.
The data above demonstrate excellent control of weeds that are often found in rice cultures and excellent rice tolerance to the application.

Number	Name	Date
4127405	Levitt	Nov 1978
4190432	Levitt	Feb 1980
4479821	Meyer et al.	Oct 1984

	Number	Date	Country
Parent	262813	May 1981
Parent	168344	Jul 1980

Herbicidal o-alkylsulfonyloxy- and o-alkylsulfonylaminobenzenesulfonamides

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