Herbicidal phenoxy esters of N-(heterocyclic)aminocarbonyl)sulfamic acid

BACKGROUND OF THE INVENTION
This invention relates to novel phenoxy esters, such as N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]sulfamic acid, 2-(trifluoromethylthio)phenyl ester, and their use in controlling undesired vegetation.
U.S. Pat. No. 4,191,553 discloses and claims N-(heterocyclicaminocarbonyl)arylsulfamates of the following general formula ##STR1## where R.sub.1 is H, OCH.sub.3 or alkyl of 1-3 carbons;
R.sub.2 is H, Cl, F, Br, NO.sub.2, alkyl of 1-4 carbons, alkoxy of 1-4 carbons, CF.sub.3 or ##STR2## R.sub.3 is H, Cl, F, Br, CH.sub.3 or alkoxy of 1-4 carbons; R.sub.4 is H, Cl, F, Br, NO.sub.2, alkyl of 1-4 carbons, alkoxy of 1-4 carbons, CN or ##STR3## R.sub.5 is H, Cl, F, Br, CH.sub.3, NO.sub.2 or CF.sub.3 ; R.sub.6 is H, Cl, F, Br, alkyl of 1-4 carbons or alkoxy of 1-4 carbons;
R.sub.7 is Na--O--, OH or alkoxy of 1-4 carbons; X is CH.sub.3, CH.sub.3 CH.sub.2, alkoxy of 1-3 carbons, CH.sub.3 OCH.sub.2, CH.sub.3 OCH.sub.2 CH.sub.2 O, CH.sub.3 S, CH.sub.3 CH.sub.2 S, CF.sub.3 or Cl;
Y is CH.sub.3, CH.sub.3 CH.sub.2, alkoxy of 1-3 carbons, CH.sub.3 OCH.sub.2, CH.sub.3 OCH.sub.2 CH.sub.2 O, CH.sub.3 S or CH.sub.3 CH.sub.2 S; and
Z is CH or N.
These compounds are described as general and selective pre- and post-emergence herbicides and as plant growth regulants.
U.S. patent application Ser. No. 152021 now U.S. Pat. No. 4,452,628, issued June 5, 1984, discloses and claims herbicidally effective compounds of the general formula ##STR4## wherein W can be O or S; R can be CF.sub.3 ;
A can be S(O).sub.n, where n is 0, 1 or 2;
R.sup.1 can be H, F, Cl, Br or CH.sub.3 ;
E can be CH or N; and
X and Y can be CH.sub.3 or OCH.sub.3.
It is taught that these compounds can be applied either pre- or post-emergence for the control of undesired vegetation in non-crop areas or for selective weed control in certain crops, such as wheat.
South African Pat. No. 814874 discloses N-phenylsulfonyl-N'-pyrimidinyl- and triazinylureas of the formula ##STR5## wherein X can be a sulfinyl or sulfonyl bridge; A can be an alkyl radical which is substituted by halogen;
E can be CH or N;
Z can be O or S;
R.sub.1 and R.sub.2 can be H; and
R.sub.3 and R.sub.4 can be H or alkyl,
among other values.
U.S. Pat. No. 4,394,153, issued July 19, 1983 to Reap discloses herbicidal sulfamoylureas incorporating an ortho sulfonate ester or amide.
SUMMARY OF THE INVENTION
This invention relates to novel compounds of Formula I, to suitable agricultural compositions containing them as an active ingredient, and to their method-of-use as pre-emergent or post-emergent herbicides or plant growth regulants. ##STR6## wherein R is QR.sub.1, SO.sub.2 NR.sub.2 R.sub.3 or OSO.sub.2 NR.sub.2 R.sub.3 ;
R.sub.1 is C.sub.1 --C.sub.3 alkyl, CH.sub.2 CH.dbd.CH.sub.2, CF.sub.3, CF.sub.2 H or CF.sub.2 CF.sub.2 H;
R.sub.2 and R.sub.3 are independently C.sub.1 -C.sub.3 alkyl;
R.sub.4 is H, CH.sub.3, OCH.sub.3, Cl, NO.sub.2, F or CF.sub.3 ;
Q is O, S, S(O) or SO.sub.2 ;
X is CH.sub.3 or OCH.sub.3 ;
Y is CH.sub.3, OCH.sub.3, C.sub.2 H.sub.5, OC.sub.2 H.sub.5, CH.sub.2 OCH.sub.3, CH(OCH.sub.3).sub.2, Cl, Br or ##STR7## and Z is CH or N;
and their agriculturally suitable salts provided that:
(1) the total number of carbon atoms of R.sub.2 and R.sub.3 is less than or equal to 4;
(2) when Y is Cl or Br, then Z is CH and X is OCH.sub.3 ; and
(3) when Q is O, then R.sub.1 is CF.sub.3, CF.sub.2 H or CF.sub.2 CF.sub.2 H.
Preferred for reasons of their higher herbicidal activity, greater plant-growth-regulant activity and/or more favorable ease of synthesis are:
(1) Compounds of Formula I where R is QR.sub.1 or SO.sub.2 NR.sub.2 R.sub.3 ; Q is O, S or SO.sub.2 ; R.sub.1 is C.sub.1 -C.sub.3 alkyl, CH.sub.2 CH.dbd.CH.sub.2, CF.sub.3 or CF.sub.2 H; and R.sub.4 is H.
(2) Compounds of Preferred (1) where R.sub.1 is CH.sub.3, CF.sub.3 or CF.sub.2 H; R.sub.2 and R.sub.3 are CH.sub.3 ; and Q is O or S.
Specifically preferred for reasons of their highest herbicidal activity, greatest plant-growth-regulant activity and/or most favorable ease of synthesis are:
N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]sulfamic acid, 2-(trifluoromethylthio)phenyl ester; and
N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]sulfamic acid, 2-(difluoromethylthio)phenyl ester.
DETAILED DESCRIPTION OF THE INVENTION
Synthesis
The compounds of Formula I, where R is other than S(O)R.sub.1, can be prepared, as shown in Scheme I, by reacting an appropriate 2-aminopyrimidine or 2-aminotriazine of Formula II with an appropriately substituted aryloxysulfonyl isocyanate of Formula III.
Scheme I ##STR8##
The reaction is best carried out in an inert organic solvent such as methylene chloride or acetonitrile. The mode of addition is not critical, however, it is often convenient to add a solution of the isocyanate III to a stirred suspension of the aminoheterocycle II.
The reaction is generally exothermic. In some cases, the compounds of Formula I are insoluble in the reaction solvent and crystallize from it in pure form. Products which are soluble in the reaction solvent can be isolated by evaporation of the solvent and trituration of the residue with solvents such as ethyl ether, 1-chlorobutane, hexane or ethanol.
The sulfoxides of Formula IV, of this invention, can be prepared by oxidation of sulfides of Formula V as shown in Scheme II.
Scheme II ##STR9##
The sulfoxides of Formula IV can be prepared by oxidation of sulfides V by treatment with one molar equivalent of m-chloroperoxybenzoic acid in a halogenated hydrocarbon solvent such as methylene chloride or chloroform.
Alternatively, sulfoxides of Formula IV can be prepared by oxidation of sulfides V by treatment with one molar equivalent of hydrogen peroxide in acetic acid.
The intermediate aryloxysulfonyl isocyanates of Formula III, where R is other than S(O)R.sub.1, can be prepared according to the procedure of Lohaus, Chem. Ber., 105, 2791 (1972), by reacting a substituted phenol of Formula VI, where R is other than S(O)R.sub.1, with chlorosulfonyl isocyanate and heating to reflux in solvents such as chlorobenzene or xylene (Scheme III).
Scheme III ##STR10##
Phenols of Formula VI, where R is other than SOR.sub.1, OCF.sub.3, OCF.sub.2 H or OCF.sub.2 CF.sub.2 H can be prepared from the corresponding aniline by hydrolysis of benzenediazonium salts as described in "Survey of Organic Syntheses", C. A. Buehler and D. E. Pearson, Wiley Interscience Publishers, pp 255-257, and references cited therein.
In addition, phenols of Formula VI where R is SR.sub.1 and R.sub.1 is other than CF.sub.3, CF.sub.2 H or CF.sub.2 CF.sub.2 H can be prepared by alkylation of commercially available o-mercaptophenol as described in Tetrahedron 26, 4449 (1970).
Phenols of Formula VI where R is OCF.sub.3, OCF.sub.2 H or OCF.sub.2 CF.sub.2 H can be prepared by the method shown in Scheme IV. Alkylation of the commercially available o-benzyloxyphenol VII with tetrafluoroethylene, chlorodifluoromethane or chlorotrifluoromethane gives the respective bis-ether of Formula VIII, where R.sub.5 is CF.sub.3, CF.sub.2 H or CF.sub.2 CF.sub.2 H. Hydrogenolysis of compounds of Formula VIII gives phenols of Formula IX where R.sub.5 is CF.sub.3, CF.sub.2 H or CF.sub.2 CF.sub.2 H.
Scheme IV ##STR11##
The synthesis of the heterocyclic amines of Formula II has been reviewed in "The Chemistry of Heterocyclic Compounds", a series published by Interscience Publishers. 2-Aminopyrimidines are described by D. J. Brown in "The Pyrimidines" in Vol. XVI of the series; 2-aminotriazines are described by E. M. Smolin and L. Rapoport in "s-Triazines and Derivatives", in Vol. XIII of the series, both of the teachings of which are herein incorporated by reference.

The compounds of this invention 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-(Trifluoromethylthio)phenol
A. Concentrated sulfuric acid (22.1 g) was added at .about.15.degree. to a solution of 18.4 g of 2-(trifluoromethylthio)benzenamine in 80 ml of acetic acid. To the resulting white suspension, 7.8 g of sodium nitrite was added portionwise over 10-15 minutes at 10.degree.-15.degree.. When addition of sodium nitrite was complete, 25 ml of acetic acid was added and the resulting yellow suspension stirred 15 minutes.
B. A mixture of 90 ml of concentrated sulfuric acid and 150 ml water was heated to 125.degree.-135.degree.. To the sulfuric acid solution, the diazonium sulfate prepared in Part A was added dropwise over 15-30 minutes during simultaneous steam distillation. The aqueous distillate was extracted with methylene chloride. The organic solution was washed with water, dried over anhydrous magnesium sulfate and decolorized with charcoal. The organic solution was filtered and the solvent evaporated under reduced pressure to give 16.0 g of the crude phenol.
EXAMPLE 2
2-(Trifluoromethylthio)phenoxysulfonyl isocyanate
A solution of 15.0 g of 2-(trifluoromethylthio)phenol in 100 ml of chlorobenzene was cooled to 0.degree. and 11.2 g of chlorosulfonyl isocyanate was added dropwise. The resulting solution was allowed to warm to room temperature, then heated at reflux for 2.25 hours. The reaction solution was cooled and the solvent evaporated under reduced pressure. Distillation of the residual oil gave 12.6 g of the title sulfonyl isocyanate as a yellowish liquid bp 85.degree.-92.degree. (0.5-3.0 mm).
EXAMPLE 3
N-[4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl]sulfamic acid, 2-(trifluoromethylthio)phenyl ester
To a solution of 0.7 g of 2-amino-4,6-dimethoxypyrimidine in 10 ml of methylene chloride was added 1.5 g of 2-(trifluoromethylthio)phenoxysulfonyl isocyanate. The reaction solution exotherms mildly and is then stirred at ambient temperature for 3 hours. The solvent was evaporated at reduced pressure. Trituration of the residual solid with 1-chlorobutane gave 1.4 g of light yellow solid, m.p. 128.degree.-130.degree..
EXAMPLE 4
1-(Phenylmethoxy)-2-(1,1,2,2-tetrafluoroethoxy)benzene
A Hastelloy pressure vessel was charged with 50 g of o-(benzyloxy)phenol, 2.3 g of potassium hydroxide, and 79 ml of N,N-dimethylformamide. The vessel was evacuated, and then charged with 26 g of tetrafluoroethylene. The vessel was sealed and heated at 85.degree. internal temperature for 4 hours, and then cooled, vented and the contents poured into ice water. The resulting aqueous mixture was extracted with 1-chlorobutane. The organic solution was washed successively with 1N sodium hydroxide solution, twice with water, and saturated brine. The organic solution was then dried over anhydrous magnesium sulfate, filtered and the solvent evaporated under reduced pressure to yield a residual orange oil, which was distilled, giving 60.65 g of the title compound as a colorless oil, bp 120.degree.-130.degree. (0.2 mm).
EXAMPLE 5
2-(1,1,2,2-Tetrafluoroethoxy)phenol
A solution of 58.6 g of 1-(phenylmethoxy)-2-(1,1,2,2-tetrafluoroethoxy)benzene in 200 ml methanol was blanketed with nitrogen and 1.0 g of 10% palladium on charcoal added. The mixture was hydrogenated at 50 psi hydrogen for 3 hours. The reaction mixture was filtered to remove catalyst and the filtrate concentrated under reduced pressure to give an oil, which darkened on standing. The oil was distilled, bp 25.degree.-32.degree. (0.2 mm), to give the phenol as a colorless oil, which solidified on standing. The infrared spectrum showed OH absorption at 3570 cm.sup.-1.
EXAMPLE 6
2-(1,1,2,2-Tetrafluoroethoxy)phenoxysulfonyl isocyanate
Chlorosulfonyl isocyanate (4.4 ml) was added to a cooled solution of 10.5 g of 2-(1,1,2,2-tetrafluoroethoxy)phenol in 50 ml chlorobenzene. The reaction solution was heated at reflux for 2.3 hours, then cooled and the solvent evaporated under reduced pressure, giving the sulfonyl isocyanate as an oil. The infrared spectrum showed NCO absorption at 2255 cm.sup.-1. The crude sulfonyl isocyanate was dissolved in and then diluted with acetonitrile to a volume of 50 ml, giving an approximately 1 molar solution of the isocyanate.
EXAMPLE 7
N-[(4,6-Dimethoxy-1,3,5-triazin-2-yl)aminosulfonyl]-sulfamic acid, 2-(1,1,2,2-tetrafluoroethoxy)phenylester
To 0.78 g of 2-amino-4,6-dimethoxy-1,3,5-triazine was added 5 ml of the 1M acetonitile solution of the sulfonyl isocyanate prepared in Example 6. Dissolution of the aminotriazine occurred and the mixture was stirred overnight. The resulting suspension was filtered and the solid rinsed with acetonitrile to give 0.53 g of white solid, m.p. 157.degree.-162.degree. (dec).
Mass-spectral analysis showed a characteristic fragment pattern for the title compound ##STR12##
EXAMPLE 8
2-(Dimethylaminosulfamoyl)phenoxysulfonyl isocyanate
To 5.2 ml (0.06 mole) chlorosulfonyl isocyanate in 75 ml dry xylenes was added 10.1 g (0.05 mole) of 2-(dimethylaminosulfamoyl)phenol in 15 ml xylenes, keeping the reaction temperature <5.degree. C. This mixture was then heated to reflux temperature for 1 hour. The reaction solution was then cooled and the solvent evaporated to give an oil. The infrared spectrum showed NCO absorption at 2270 cm.sup.-1.
EXAMPLE 9
N-[(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl]sulfamic acid, 2-(dimethylaminosulfamoyl)phenyl ester
To a solution of 0.54 g 2-amino-4,6-dimethoxypyrimidine in 10 ml methylene chloride was added 1.6 g of 2-(dimethylaminosulfamoyl)phenoxysulfonyl isocyanate. The reaction exothermed (23.degree.-32.degree. C.) and was stirred at room temperature for 2 hours. The solvent was evaporated at reduced pressure. The resultant orange oil was triturated with ethanol and white solids filtered to give 0.6 g, m.p. 115.degree.-117.degree. C.
Mass-spectral analysis showed a characteristic fragment pattern for the title compound. ##STR13##
By the procedures of Examples 1-9, the following compounds can be prepared. Tables I and II are meant to be illustrative of the breadth of this invention and are not meant to be all-inclusive.
TABLE I______________________________________ ##STR14##R X Y R.sub.4 m.p. (.degree.C.)______________________________________SCF.sub.3 CH.sub.3 OCH.sub.3 H 136-139.degree.SCF.sub.3 OCH.sub.3 OCH.sub.3 H 128-130.degree.SCF.sub.3 CH.sub.3 CH.sub.3 H 126-129.degree.SCF.sub.3 OCH.sub.3 OC.sub.2 H.sub.5 HSCF.sub.3 OCH.sub.3 Cl H 145- 146.5.degree.SCF.sub.3 CH.sub.3 CH(OCH.sub.3).sub.2 HSCF.sub.3 OCH.sub.3 ##STR15## HSCF.sub.3 OCH.sub.3 CH.sub.2 OCH.sub.3 HSCF.sub.3 OCH.sub.3 C.sub.2 H.sub.5 HSOCF.sub.3 CH.sub.3 OCH.sub.3 HSOCF.sub. 3 OCH.sub.3 OCH.sub.3 HSOCF.sub.3 OCH.sub.3 Cl HSOCF.sub.3 CH.sub.3 OC.sub.2 H.sub.5 HSO.sub.2 CF.sub.3 OCH.sub.3 OCH.sub.3 H 82-86.degree.(d)SO.sub.2 CF.sub.3 CH.sub.3 CH.sub.3 H 122-124.degree.SO.sub.2 CF.sub.3 CH.sub.3 OCH.sub.3 H 89-95.degree.SO.sub.2 CF.sub.3 OCH.sub.3 Cl HSCF.sub.2 H OCH.sub.3 OCH.sub.3 HSCF.sub.2 H CH.sub.3 OCH.sub.3 HSCF.sub.2 H CH.sub.3 CH.sub.3 HSOCF.sub.2 H CH.sub.3 CH.sub.3 HSOCF.sub.2 H OCH.sub.3 OCH.sub.3 HSOCF.sub.2 H CH.sub.3 OCH.sub.3 HSO.sub.2 CF.sub.2 H CH.sub.3 CH.sub.3 HSO.sub.2 CF.sub.2 H OCH.sub.3 OCH.sub.3 HSO.sub.2 CF.sub.2 H CH.sub.3 OCH.sub.3 HSCF.sub.2 CF.sub.2 H CH.sub.3 OCH.sub.3 HSCF.sub.2 CF.sub.2 H OCH.sub.3 OCH.sub.3 HSCF.sub.2 CF.sub.2 H CH.sub.3 OCH.sub.3 HSOCF.sub.2 CF.sub.2 H CH.sub.3 OCH.sub.3 HSO.sub.2 CF.sub.2 CF.sub.2 H OCH.sub.3 OCH.sub.3 HSCH.sub.3 CH.sub.3 CH.sub.3 H 83-119SCH.sub.3 OCH.sub.3 OCH.sub.3 H 151-158SCH.sub.3 CH.sub.3 OCH.sub.3 H 90-125SOCH.sub.3 CH.sub.3 CH.sub.3 HSOCH.sub.3 OCH.sub.3 OCH.sub.3 HSOCH.sub.3 CH.sub.3 OCH.sub.3 HSO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 HSO.sub.2 CH.sub.3 OCH.sub.3 OCH.sub.3 HSO.sub.2 CH.sub.3 CH.sub.3 OCH.sub.3 HSOC.sub.2 H.sub.5 CH.sub.3 OCH.sub.3 HSO.sub.2 C.sub.2 H.sub.5 OCH.sub.3 OCH.sub.3 HSO.sub.2 C.sub.3 H.sub.7 CH.sub.3 OCH.sub.3 HSO.sub.2 C.sub.3 H.sub.7 OCH.sub.3 OCH.sub.3 HSO.sub.2 N(CH.sub.3).sub.2 CH.sub.3 CH.sub.3 H 107-123SO.sub.2 N(CH.sub.3).sub.2 OCH.sub.3 OCH.sub.3 H 117-131SO.sub.2 N(CH.sub.3).sub.2 CH.sub.3 OCH.sub.3 H 104-131SO.sub.2 N(CH.sub.3)C.sub.2 H.sub.5 CH.sub.3 CH.sub.3 HSO.sub.2 N(CH.sub.3)C.sub.2 H.sub.5 OCH.sub.3 CH.sub.3 HSO.sub.2 N(CH.sub.3)C.sub.2 H.sub.5 OCH.sub.3 OCH.sub.3 HSO.sub.2 N(CH.sub.3 )C.sub.3 H.sub.7 CH.sub.3 OCH.sub.3 HSO.sub.2 N(CH.sub.3)C.sub.3 H.sub.7 CH.sub.3 CH.sub.3 HSO.sub.2 N(CH.sub.3)C.sub.3 H.sub.7 OCH.sub.3 OCH.sub.3 HOCF.sub.2 CF.sub.2 H CH.sub.3 CH.sub.3 H gumOCF.sub.2 CF.sub.2 H OCH.sub.3 CH.sub.3 H gumOCF.sub.2 CF.sub.2 H OCH.sub.3 OCH.sub.3 H 136-139.degree.OCF.sub.2 CF.sub.2 H OCH.sub.3 Cl H 115-118.degree.OCF.sub.3 OCH.sub.3 OCH.sub.3 HOCF.sub.3 CH.sub.3 OCH.sub.3 HOCF.sub.3 CH.sub.3 CH.sub.3 HOCF.sub.2 H CH.sub.3 CH.sub.3 HOCF.sub.2 H CH.sub.3 OCH.sub.3 HOCF.sub.2 H OCH.sub.3 OCH.sub.3 HOCF.sub.2 H OCH.sub.3 CH(OCH.sub.3).sub.2 HOSO.sub.2 N(CH.sub.3).sub.2 OCH.sub.3 OCH.sub.3 H 115-117OSO.sub.2 N(CH.sub.3).sub.2 OCH.sub.3 CH.sub.3 H oilOSO.sub.2 N(CH.sub.3).sub.2 CH.sub.3 CH.sub.3 H oilSCH.sub.2 CHCH.sub.2 OCH.sub.3 OCH.sub.3 HSCH.sub.2 CHCH.sub.2 OCH.sub.3 CH.sub.3 HSCH.sub.2 CH CH.sub.2 CH.sub.3 CH.sub.3 HOSO.sub.2 N(CH.sub.3)C.sub.2 H.sub.5 OCH.sub.3 OCH.sub.3 HOSO.sub.2 N(CH.sub.3)C.sub.2 H.sub.5 OCH.sub.3 CH.sub.3 HOSO.sub.2 N(CH.sub.3)C.sub.2 H.sub.5 CH.sub.3 CH.sub.3 HOSO.sub.2 N(CH.sub.3)C.sub.3 H.sub.7 OCH.sub.3 OCH.sub.3 HOSO.sub.2 N(CH.sub.3).sub.2 CH.sub.3 OCH.sub.2 CH.sub.3 HSCH.sub.3 OCH.sub.3 C.sub.2 H.sub.5 HOSO.sub.2 N(CH.sub.3).sub.2 OCH.sub.3 C.sub.2 H.sub.5 HSCH.sub.3 OCH.sub.3 CH.sub.2 OCH.sub.3 HSCH.sub.3 CH.sub.3 CH(OCH.sub.3).sub.2 HSCH.sub.3 OCH.sub.3 CH(OCH.sub.3).sub.2 HSO.sub.2 N(CH.sub.3).sub.2 OCH.sub.3 CH(OCH.sub.3).sub.2 HSO.sub.2 N(CH.sub.3).sub.2 CH.sub.3 CH(OCH.sub.3).sub.2 HSO.sub.2 N(CH.sub.3).sub.2 OCH.sub.3 Cl HSO.sub.2 N(CH.sub.3).sub.2 OCH.sub.3 Br HSCH.sub.3 OCH.sub.3 Br HSO.sub.2 N(CH.sub.3).sub.2 OCH.sub.3 ##STR16## HSO.sub.2 N(CH.sub. 3).sub.2 CH.sub.3 ##STR17## HSCH.sub.3 OCH.sub.3 OCH.sub.3 3-CH.sub.3SCH.sub.3 OCH.sub.3 CH.sub.3 3-CH.sub.3SCH.sub.3 CH.sub.3 CH.sub.3 3-CH.sub.3SCH.sub.3 OCH.sub.3 OCH.sub.3 5-ClSCH.sub.3 OCH.sub.3 CH.sub.3 5-ClSCH.sub.3 CH.sub.3 CH.sub.3 5-ClSCH.sub.3 OCH.sub.3 OCH.sub.3 5-OCH.sub.3SCH.sub.3 OCH.sub.3 CH.sub.3 5-OCH.sub.3SCH.sub.3 CH.sub.3 CH.sub.3 5-OCH.sub.3SCH.sub.3 OCH.sub.3 OCH.sub.3 5-CF.sub.3SCH.sub.3 OCH.sub.3 CH.sub.3 5-CF.sub.3SCH.sub.3 CH.sub.3 CH.sub.3 5-CF.sub.3SCH.sub.3 OCH.sub.3 OCH.sub.3 5-NO.sub.2SCH.sub.3 OCH.sub.3 CH.sub.3 5-NO.sub.2SCH.sub.3 CH.sub.3 CH.sub.3 5-NO.sub.2SCH.sub.3 OCH.sub.3 OCH.sub.3 5-FSCH.sub.3 OCH.sub.3 OCH.sub.3 6-CH.sub.3SCH.sub.3 OCH.sub.3 CH.sub.3 6-CH.sub.3SCH.sub.3 CH.sub.3 CH.sub.3 6-CH.sub.3______________________________________
TABLE II______________________________________ ##STR18##R X Y R.sub.4 m.p. (.degree.C.)______________________________________SCF.sub.3 CH.sub.3 OCH.sub.3 H 87-89.degree.SCF.sub.3 OCH.sub.3 OCH.sub.3 HSCF.sub.3 CH.sub.3 CH.sub.3 HSCF.sub.3 OCH.sub.3 OC.sub.2 H.sub.5 HSCF.sub.3 CH.sub.3 CH(OCH.sub.3).sub.2 HSCF.sub.3 OCH.sub.3 ##STR19## HSCF.sub.3 OCH.sub.3 CH.sub.2 OCH.sub.3 HSCF.sub.3 OCH.sub.3 C.sub.2 H.sub.5 HSOCF.sub.3 CH.sub.3 OCH.sub.3 HSOCF.sub.3 OCH.sub.3 OCH.sub.3 HSOCF.sub.3 CH.sub.3 OC.sub.2 H.sub.5 HSO.sub.2 CF.sub.3 OCH.sub.3 OCH.sub.3 H gumSO.sub.2 CF.sub.3 CH.sub.3 CH.sub.3 H 122-124.degree.SO.sub.2 CF.sub.3 CH.sub.3 OCH.sub.3 H 111-114.degree.SCF.sub.2 H OCH.sub.3 OCH.sub.3 HSCF.sub.2 H CH.sub.3 OCH.sub.3 HSCF.sub.2 H CH.sub.3 CH.sub.3 HSOCF.sub.2 H CH.sub.3 CH.sub.3 HSOCF.sub.2 H OCH.sub.3 OCH.sub.3 HSOCF.sub.2 H CH.sub.3 OCH.sub.3 HSO.sub.2 CF.sub.2 H CH.sub.3 CH.sub.3 HSO.sub.2 CF.sub.2 H OCH.sub.3 OCH.sub.3 HSO.sub.2 CF.sub.2 H CH.sub.3 OCH.sub.3 HSCF.sub.2 CF.sub.2 H CH.sub.3 OCH.sub.3 HSCF.sub.2 CF.sub.2 H OCH.sub.3 OCH.sub.3 HSCF.sub.2 CF.sub.2 H CH.sub.3 OCH.sub.3 HSOCF.sub.2 CF.sub.2 H CH.sub.3 OCH.sub.3 HSO.sub.2 CF.sub.2 CF.sub.2 H OCH.sub.3 OCH.sub.3 HSCH.sub.3 CH.sub.3 CH.sub.3 HSCH.sub.3 OCH.sub.3 OCH.sub.3 H 204SCH.sub.3 CH.sub.3 OCH.sub.3 H 87-163SOCH.sub.3 CH.sub.3 CH.sub.3 HSOCH.sub. 3 OCH.sub.3 OCH.sub.3 HSOCH.sub.3 CH.sub.3 OCH.sub.3 HSO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 HSO.sub.2 CH.sub.3 OCH.sub.3 OCH.sub.3 HSO.sub.2 CH.sub.3 CH.sub.3 OCH.sub.3 HSOC.sub.2 H.sub.5 CH.sub.3 OCH.sub.3 HSO.sub.2 C.sub.2 H.sub.5 OCH.sub.3 OCH.sub.3 HSO.sub.2 C.sub.3 H.sub.7 CH.sub.3 OCH.sub.3 HSO.sub.2 C.sub.3 H.sub.7 OCH.sub.3 OCH.sub.3 HSO.sub.2 N(CH.sub.3).sub.2 CH.sub.3 CH.sub.3 HSO.sub.2 N(CH.sub.3).sub.2 OCH.sub.3 OCH.sub.3 H oilSO.sub.2 N(CH.sub.3).sub.2 CH.sub.3 OCH.sub.3 H 88-119SO.sub.2 N(CH.sub.3)C.sub.2 H.sub.5 CH.sub.3 CH.sub.3 HSO.sub.2 N(CH.sub.3)C.sub.2 H.sub.5 OCH.sub.3 CH.sub.3 HSO.sub.2 N(CH.sub.3)C.sub.2 H.sub.5 OCH.sub.3 OCH.sub.3 HSO.sub.2 N(CH.sub.3)C.sub.3 H.sub.7 CH.sub.3 OCH.sub.3 HSO.sub.2 N(CH.sub.3)C.sub.3 H.sub.7 CH.sub.3 CH.sub.3 HSO.sub.2 N(CH.sub.3)C.sub.3 H.sub.7 OCH.sub.3 OCH.sub.3 HOCF.sub.2 CF.sub. 2 H CH.sub.3 CH.sub.3 H 97-115.degree.OCF.sub.2 CF.sub.2 H OCH.sub.3 CH.sub.3 H 139-140.degree.OCF.sub.2 CF.sub.2 H OCH.sub.3 OCH.sub.3 H 157-162.degree.(d)OCF.sub.3 OCH.sub.3 OCH.sub.3 HOCF.sub.3 CH.sub.3 OCH.sub.3 HOCF.sub.3 CH.sub.3 CH.sub.3 HOCF.sub.2 H CH.sub.3 CH.sub.3 HOCF.sub.2 H CH.sub.3 OCH.sub.3 HOCF.sub.2 H OCH.sub.3 OCH.sub.3 HOCF.sub.2 H OCH.sub.3 CH(OCH.sub.3).sub.2 HOSO.sub.2 N(CH.sub.3).sub.2 OCH.sub.3 CH.sub.3 H 126-128.5OSO.sub.2 N(CH.sub.3).sub.2 OCH.sub.3 OCH.sub.3 H 142-147OCH.sub.2 CHCH.sub.2 OCH.sub.3 OCH.sub.3 HSCH.sub.2 CHCH.sub.2 OCH.sub.3 OCH.sub.3 HOSO.sub.2 N(CH.sub.3)C.sub.2 H.sub.5 OCH.sub.3 OCH.sub.3 HOSO.sub.2 N(CH.sub.3)C.sub.2 H.sub.5 OCH.sub.3 CH.sub.3 HOSO.sub.2 N(CH.sub.3)C.sub.3 H.sub.7 OCH.sub.3 OCH.sub.3 HSCH.sub.3 OCH.sub.3 OCH.sub.3 3-CH.sub.3SCH.sub.3 OCH.sub.3 OCH.sub.3 6-CH.sub.3SCH.sub.3 OCH.sub.3 OCH.sub.3 5-ClSCH.sub.3 OCH.sub.3 OCH.sub.3 5-FSCH.sub.3 OCH.sub.3 OCH.sub.3 5-CF.sub.3SCH.sub.3 OCH.sub.3 OCH.sub.3 5-NO.sub.2______________________________________
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 inert diluent(s). More specifically, they will contain these ingredients in the following approximate proportions:
TABLE III______________________________________ 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 as may be seen in 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, "Weel 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 10
Wettable Powder
______________________________________N--[(4,6-dimethoxypyrimidin-2-yl)amino- 80%carbonyl]sulfamic acid,2-(trifluoromethylthio)phenyl estersodium alkylnaphthalenesulfonate 2%sodium ligninsulfonate 2%synthetic amorphous silica 3%kaolinite 13%______________________________________
The ingredients are blended, hammer-milled until all the solids are substantially under 50 microns, reblended, and packaged.
EXAMPLE 11
Wettable Powder
______________________________________N--[(4,6-dimethoxypyrimidin-2-yl)amino- 50%carbonyl]sulfamic acid,2-(difluoromethylthio)phenyl estersodium alkylnaphthalenesulfonate 2%low-viscosity methyl cellulose 2%diatomaceous earth 46%______________________________________
The ingredients are blended, coarsely hammer-milled and then air-milled to produce particles substantially all below 10 microns in diameter. The product is reblended before packaging.
EXAMPLE 12
Granule
______________________________________Wettable Powder of Example 11 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 while tumbling in a double-cone blender. The granules are dried and packaged.
EXAMPLE 13
Extruded Pellet
______________________________________N--[(4,6-dimethoxypyrimidin-2-yl)amino- 25%carbonyl]sulfamic acid,2-(trifluoromethylthio)phenyl esteranhydrous 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 can be used directly after drying, or the dried pellets can be crushed to pass a U.S. Ser. No. 20 sieve (0.84 mm openings). The granules held on a U.S. Ser. No. 40 sieve (0.42 mm openings) can be packaged for use and the fines recycled.
EXAMPLE 14
Oil Suspension
______________________________________N--[(4,6-dimethoxypyrimidin-2-yl)amino- 25%carbonyl]sulfamic acid,2-(trifluoromethylthio)phenyl esterpolyoxyethylene 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 can be applied directly, but preferably after being extended with oils or emulsified in water.
EXAMPLE 15
Wettable Powder
______________________________________N--[(4,6-dimethoxypyrimidin-2-yl)amino- 20%carbonyl]sulfamic acid,2-(trifluoromethylthio)phenyl estersodium 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 substantially all below 100 microns, the material is reblended and sifted through a U.S. Ser. No. 50 sieve (0.3 mm opening) and packaged.
EXAMPLE 16
Low Strength Granule
______________________________________N--[(4,6-dimethoxypyrimidin-2-yl)amino- 1%carbonyl]sulfamic acid,2-(trifluoromethylthio)phenyl 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 17
Aqueous Suspension
______________________________________N--[(4,6-dimethoxyprimidin-2-yl)amino- 40%carbonyl]sulfamic acid,2-(trifluoromethylthio)phenyl esterpolyacrylic 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 substantially all under 5 microns in size.
EXAMPLE 18
Solution
______________________________________N--[(4,6-dimethoxypyrimidin-2-yl)amino- 5%carbonyl]sulfamic acid,2-(difluoromethylthio)phenyl ester,sodium saltwater 95%______________________________________
The salt is added directly to the water with stirring to produce the solution, which can then be packaged for use.
EXAMPLE 19
Low Strength Granule
______________________________________N--[(4,6-dimethoxypyrimidin-2-yl)amino- 0.1%carbonyl]sulfamic acid,2-(difluoromethylthio)phenyl esterattapulgite 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 20
Granule
______________________________________N--[(4,6-dimethoxypyrimidin-2-yl)amino- 80%carbonyl]sulfamic acid,2-(trifluoromethylthio)phenyl esterwetting agent 1%crude ligninsulfonate salt (containing 10%5-20% of the natural sugars)attapulgite clay 9%______________________________________
The ingredients are blended and milled to pass through a 100 mesh screen. This material is then added to a fluid-bed granulator, the air flow is adjusted to gently fluidize the material, and a fine spray of water is sprayed onto the fluidized material. The fluidization and spraying are continued until granules of the desired size range are made. The spraying is stopped, but fluidization is continued, optionally with heat, until the water 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 21
High Strength Concentrate
______________________________________N--[(4,6-dimethoxypyrimidin-2-yl)amino- 99%carbonyl]sulfamic acid,2-(trifluoromethylthio)phenyl estersilica aerogel 0.5%synthetic amorphous silica 0.5%______________________________________
The ingredients are blended and ground in a hammer-mill to produce a material substantially all passing a U.S. Ser. No. 50 screen (0.3 mm opening). The concentrate may be formulated further if necessary.
EXAMPLE 22
Wettable Powder
______________________________________N--[(4,6-dimethoxypyrimidin-2-yl)amino- 90%carbonyl]sulfamic acid,2-(trifluoromethylthio)phenyl esterdioctyl sodium sulfosuccinate 0.1%synthetic fine silica 9.9%______________________________________
The ingredients are blended and ground in a hammer-mill to produce particles substantially all below 100 microns. The material is sifted through a U.S. Ser. No. 50 screen and then packaged.
EXAMPLE 23
Wettable Powder
______________________________________N--[(4,6-dimethoxypyrimidin-2-yl)amino- 40%carbonyl]sulfamic acid,2-(difluoromethylthio)phenyl estersodium ligninsulfonate 20%montmorillonite clay 40%______________________________________
The ingredients are thoroughly blended, coarsely hammer-milled and then air-milled to produce particles substantially all below 10 microns in size. The material is reblended and then packaged.
EXAMPLE 24
Oil Suspension
______________________________________N--[(4,6-dimethoxypyrimidin-2-yl)amino- 35%carbonyl]sulfamic acid,2-(trifluoromethylthio)phenyl 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 substantially all below 5 microns. The product can be used directly, extended with oils, or emulsified in water.
EXAMPLE 25
Dust
______________________________________N--[(4,6-dimethoxypyrimidin-2-yl)amino- 10%carbonyl]sulfamic acid,2-(trifluoromethylthio)phenyl 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
Test results indicate that the compounds of the present invention are active herbicides. They should 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. Alternatively, some of the subject compounds should be useful for the selective weed control in rice.
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 0.125 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 can be used in combination with any other commercial herbicide, examples of which are those of the triazine, triazole, uracil, urea, amide, diphenyl ether, carbamate and bipyridylium types. They may also be used in combination with mefluidide.
The herbicidal properties of the subject compounds were discovered in a number of greenhouse tests. The test procedures and results follow. ##STR20##
TEST A
Seeds of crabgrass (Digitaria spp.), barnyardgrass (Echinochloa crusgalli), wild oats (Avena fatua), sicklepod (Cassia obtusifolia), morningglory (Ipomoea spp.), cocklebur (Xanthium pensylvanicum), sorghum, corn, soybean, sugar beet, rice, wheat, and purple nutsedge )Cyperus rotundus) tubers were planted and treated pre-emergence with the test chemicals dissolved in a non-phytotoxic solvent. At the same time, these crop and weed species, along with cotton and bush bean, were treated with a soil/foliage application. At the time of treatment, the plants ranged in height from 2 to 18 cm. Treated plants and controls were maintained in a greenhouse for sixteen days, after which all species were compared to controls and visually rated for response to treatment. The ratings, summarized in Table A, 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;
E=emergence inhibition;
G=growth retardation;
H=formative effect; and
6Y=abscised buds or flowers.
The herbicidal and plant-growth-regulatory activity may be seen in the following Table A.
TABLE A POST-EMERGENCE Cmpd. 1 Cmpd. 2 Cmpd. 3 Cmpd. 4 Cmpd. 5 Cmpd. 6 Cmpd. 7 Cmpd. 8 Cmpd. 9 Cmpd. 10 Compound 11 Compound 12 Rate kg/ha 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 2.0 0.05 2.0 0.05 Bush bean 0 0 7C,9G,6Y 3C,2H,6Y 2C,4H 0 2C,3G 2C,5G,6Y 2C,4G 2C 0 1C,4G 4C,9G,6Y 4C Cotton 1C 0 3C,5H 2C 2C 1C 3C 3C,5H 2C 3C 0 0 3C,6H 3C Morningglory 0 1C 6C,9G 1C 2C,2H 2C 6C,9G 5C,9G 4C,8H 9C 2C 0 5C,9G 1C Cocklebur 2H 1C,6G 9C 2C,6H 2C,5H 2C,9G 6C,9G 6C,9G 5C,9G 4H 3C,9H 0 9C 4H Sicklepod 0 0 2C,4H 1C 2C,2H 0 1C,3G 3C,4G 2C,3G 1C,2H 1C 0 3C,4H 0 Nutsedge 0 0 2C,9G 0 0 0 2G 5G 0 0 0 0 3C,9G 0 Crabgrass 0 0 0 0 0 0 2G 2G 2G 0 0 0 3G 0 Barnyardgrass 0 0 0 0 0 0 2G 1H 0 0 0 0 4H 0 Wild Oats 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Wheat 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Corn 0 0 0 1H 0 1H 3C,7G 1H 0 2G 0 0 0 0 Soybean 0 2G 5C,9G 0 2H 1H,2G 9C 5C,9G 3C,9G 2C,7G 1C 0 2C,6G 1C Rice 0 0 0 0 0 1C 0 0 0 2C,4G 0 0 0 4G Sorghum 0 0 0 2C 3C 0 2C,3G 1C 2C,3H 2C,3G 0 0 2C,3G 0 Sugar beet 3G 3G 3C,8G 2C,7G 3C,7G 3G 5C,8G 2C,8G 3C,8H 5C,8G 0 0 9C 0 Compound 13 Compound 14 Compound 15 Compound 16 Cmpd. 17 Compound 20 Cmpd. 21 Cmpd. 22 Compound 23 Rate kg/ha Rate g/ha 2.0 0.05 2.0 0.05 0.05 2.0 2.0 0.05 0.05 400 2000 400 400 400 2000 Bush bean 3C,8G,6Y 2C,8G,6Y 0 3G 0 3C,6G,6Y 2C,2H 2C 2C -- -- -- -- -- -- Cotton 3C,9G 4C 0 0 0 3C,3H 4C 1C 2C 4C,8G 5C,9G 2C,5G 1C 1C,5G 3C,8G Morningglory 5C,9G 4C,5G 0 2C 2C 5C,9G 4C,9H 2C,2H 2C 4C,8G 5C,9G 1C 2C,5G 2G 2C,5G Cocklebur 9C 2C,9G 4C,9H 0 4C,9G 5C,9G 5C,9H 0 1C,5G 10C 9C 5C,9G 9C 2C,8G 5C,9G Sicklepod 3C,8H 2C 1C 0 2C 4C,5H 4C 0 1C 5C,9G 9C 3C,7G 1C 1C 2C,5H Nutsedge 9C 2C,5G 0 0 0 2C,8G 2C,8G 0 0 2C,7G 6C,9G 8G 7G 0 0 Crabgrass 2C,5G 0 0 0 0 1C 1C 0 0 4G 3C,6G 1C 3G 0 3G Barnyardg rass 2C,4G 0 0 0 0 2C,4H 3C,5H 0 0 3C,7H 3C,9H 4H 2H 2H 4G Wild Oats 0 0 0 0 0 0 0 0 0 0 1C 0 0 0 0 Wheat 0 0 0 0 0 0 0 0 0 0 2G 0 0 0 0 Corn 1C,3G 0 0 0 0 1C,4H 1C,5G 0 0 2C,5H 2C,8H 3C,8H 2H 1H 2C,6H Soybean 9C 1C,3H 1C 0 0 3C,9H 3C,6H 1C,1H 1H 4C,8G 5C,9G 3C,7G 0 2C,2H 3C,8G Rice 1C 0 0 0 0 2C,5H 5G 0 0 2G 1C,4G 1C 0 0 1C Sorghum 3G 1C 0 0 0 2C,8H 2C,7G 0 0 3C,9H 4C,9H 3C,7H 5G 1C,3H 3C,9H Sugar beet 9C 2G 3C,5H 0 2C,6H 9C 3C,7H 1C 2C,5G 5C,9G 5C,9G 3C,5H 1C,3G 1C,2H 2C,4G Cmpd. 24 Cmpd. 25 Cmpd. 26 Cmpd. 27 Cmpd. 28 Compound 29 Compound 30 Cmpd. 31 Cmpd. 32 Cmpd. 33 Cmpd. 34 Rate g/ha Rate kg/ha 400 400 400 400 400 50 400 400 50 0.40 0.40 0.40 0.40 Bush bean -- -- -- -- -- 6Y,4C,9G 5C,9G,6Y Cotton -- 1C 10C 0 2C,2H 4C,8G 4C,9G 9C 3C,5G 5C,9G 2C 4C,6G 4C,8G Morningglory 0 2C 8C 1C 3C,5H 9C 9C 10C 9C 10C 3C,8G 5C,9G 4C,8G Cocklebur 5C,9G 3C,8H 4C,9G 2C 3C,5H 9C 10C 9C 9C 9C 3C,8H 4C,9H 4C,9H Sicklepod 0 2C 2C,2H 0 3C,8G 4C,6G 6C,9G Cassia 5C,9G 1C,4G 3C,6G 3G 1C 1C Nutsedge 0 0 0 0 0 2C,9G 8G 9C 3C,7G 2C 0 0 0 Crabgrass 0 2C 2C 0 2C 7G 2C,8G 2G 0 0 0 0 0 Barnyardgrass 1C 2C 2C,5G 0 2C 2C,8H 3C,9H 7G 0 2G 0 0 0 Wild Oats 0 0 0 0 0 1H 2C,4G 0 0 0 0 0 0 Wheat 0 0 1C 0 0 1H 2C,7G 0 0 0 0 0 0 Corn 1H 1C 2G 0 0 2C,9H 9G 2C,6G 0 3C,7H 0 0 0 Soybean 2H 0 2C,9G 0 2C,2H 4C,9G 5C,9G 3C,9G 3C,5H 4C,8H 2H 5H 3C,9G Rice 0 0 2C,2G 0 3C,4G 3C,5G 4C,9G 0 0 2C 0 0 0 Sorghum 2G 1C 2C,8H 0 3C,8H 2C,9H 4C,9G 2C,7H 2C,9H 2C,6G 0 2C,8H 2C,8H Sugar beet 2C,2H 2C,3H 4C,9G 2C,3G 3C,9G 5C,9G 9C 9C 5C,9G 5C,8G 2C 4C,8H 4C,7G PRE-EMERGENCE Cmpd. 1 Cmpd. 2 Cmpd. 3 Cmpd. 4 Cmpd. 5 Cmpd. 6 Cmpd. 7 Cmpd. 8 Cmpd. 9 Cmpd. 10 Compound 11 Compound 12 Rate kg/ha 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 2.0 0.05 2.0 0.05 Morningglory 0 2C,8G 10C 1H 2C,2H 5G 9G 8G 2C,8G 9G 2G 0 9G 2C Cocklebur 0 8H 9H 1H 8H 4G 9H 8H 2C,8H 3H -- 0 -- 0 Sicklepod 0 2C 5H 0 2C 0 7G 7G 1C 0 0 0 2C,4G 0 Nutsedge 0 0 8G 0 0 0 5G 5G 0 0 0 0 8G 0 Crabgrass 0 0 2G 0 0 0 0 0 0 1C 0 0 2G 0 Barnyardgrass 0 0 2H 1C 0 0 1C 2C 2H 0 0 0 2C,5G 0 Wild Oats 0 2G 0 0 0 0 1C 0 0 0 0 0 0 0 Wheat 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Corn 0 2G 5G 2C,5H 2C,9H 0 2C,7G 2C,2G 7G 2C 0 0 2C,7G 0 Soybean 0 1H 2C,4H 1H 2H 0 7G 2C,4H 2C,3G 2C 0 0 2C,3H 0 Rice 0 1C 2G 0 2C,4G 0 2C,5G 2C,3G 2C 2C 1C 0 2C,5G 0 Sorghum 0 0 3G 2C,8G 2C,8H 1C 2C,7G 2C 2C,7G 2C,5G 0 0 2C,8H 0 Sugar beet 0 2C,7G 10E 2C,6G 2C,8G 2C,6G 5C,9G 2C,9G 5C,9G 5C,9G 1C 0 5C,9G 4G Compound 13 Compound 14 Compound 15 Compound 16 Cmpd. 17 Compound 20 Cmpd. 21 Cmpd. 22 Compound 23 Rate kg/ha Rate g/ha 2.0 0.05 2.0 0.05 0.05 2.0 2.0 0.05 0.05 400 2000 400 400 400 2000 Morningglory 9G 7G 2C,4H 0 2C 9G 9G 2C 2C 9H 9G 9C 0 9G 8G Cocklebur 9H 2H 0 0 0 9H 9H 0 -- 8H 9H 9G 8H 8G 9G Sicklepod 8G 0 0 0 0 3C 4C,4H 0 0 9G 9G 9G 9G 9G 9G Nutsedge 9G 0 0 0 0 5G 5G 0 0 10E 10E 10E 10E 4G 10E Crabgrass 0 0 0 0 0 2G 2G 0 0 4G 2C,5G 2G 2G 3G 4G Barnyardgrass 2C,5H 0 0 0 0 2C,6H 8H 0 1C 2C,7G 3C,9H 3C,5G 2G 2C 2G Wild Oats 0 0 0 0 0 0 2C,3G 0 0 5G 3C,8G 3G 2G 2G 4G Wheat 0 0 0 0 0 4G 6G 0 0 4G 7G 2G 0 4G 2C,8G Corn 2C,6G 1C 1C 0 1C,3G 1C,9H 2C,7G 0 0 2C,9H 9G 2C,5G 4G 2C,8G 8G Soybean 6H 1C 0 0 0 2C,3H 1C,1H 0 0 2C,5H 3C,5H 5H 0 1C 2C,5H Rice 2C,4G 1C 0 0 2C 2C,6G 2C,6H 0 0 8G 4C,9H 5G 5G 2G 2C,7G Sorghum 2C,5G 0 2G 0 2C,5G 3C,9H 2C,8H 5G 0 5C,9H 5C,9H 6G 2C,6G 2C,9H 4C,9H Sugar beet 10E 10E 1C 0 4H 5C,9G 4C,9G 4H 2C,5G 5C,9G 10E 9G 8G 5G 8G Cotton 2C,9G 2C,9G 9G 5G 8G 8G Cmpd. 24 Cmpd. 25 Cmpd. 26 Cmpd. 27 Cmpd. 28 Compound 29 Compound 30 Cmpd. 31 Cmpd. 32 Cmpd. 33 Cmpd. 34 Rate g/ha Rate kg/ha 400 400 400 400 400 50 400 400 50 0.40 0.40 0.40 0.40 Morningglory 0 0 9C 0 2G 9G 9C 9C 9G 9H 7H 9H 9G Cocklebur -- 0 9H 0 3H 9H 9H 9H 9H 9H 8H 9H 9H Sicklepod 9G 0 3H,3C 0 0 9G 9G Cassia 4C,9G 0 3C,7G 0 3C 3C Nutsedge 0 0 0 0 10E 9G 10E 10E 0 6G 0 0 0 Crabgrass 2G 0 0 0 2G 2G 2G 1C 1C 1C 0 0 0 Barnyardgrass 0 0 3C,8G 0 1C 2C,3G 9H,4C 4C,8H 1C 4C,6G 0 3C,3H 2C Wild Oats 2G 0 2C 0 0 1C 2C,6G 2C 0 1C 0 0 0 Wheat 0 0 2C 0 0 3G 2C,7G 0 0 1C 0 0 0 Corn 5G 0 3C,8H 0 2G 3C,9H 2C,9H 9H 7G 3C,7G 0 4C,9H 2C,8H Soybean 0 0 2C,5H 0 1C 3C,6H 3C,7H 8H 1C,1H 3C,8H 0 4G 1C Rice 2G 0 3C,8H 0 1C 3C,9H 5C,9H 5G 0 6G 0 3C,5G 2G Sorghum 2C,9G 0 4C,9G 0 3C,7G 4C,9H 6C,9H 2C,9H 8G 8H 0 9C 2C,9H Sugar beet 2C,8G 0 5C,9G 0 2C,5G 4C,9G 10E 5C,9G 5C,9G 4C,9G 4C,8H 9C 6C,9G Cotton 2G 0 3C,6G 0 0 9G 5G 2C,9G 3G 7G 7G
TEST B
Two plastic bulb pans were filled with fertilized and limed Woodstown sandy loam. 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), 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 plated with rice and wheat. Another 12.5-cm pot was planted with sugar beets. 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 with the rating system described previously for Test A. A summary of the data may be seen in Table B.
TABLE B______________________________________PRE-EMERGENCE ONWOODSTOWN SANDY LOAMRate kg/ha 0.03 0.12 0.03 0.12______________________________________ Compound 2 Compound 6Crabgrass 0 0 0 2GBarnyardgrass 0 0 0 0Sorghum 0 2G 0 0Wild Oats 0 0 0 0Johnsongrass 0 0 0 0Dallisgrass 0 0 0 0Giant foxtail 0 0 0 0Ky. bluegrass 0 0 0 0Cheatgrass 0 0 0 0Sugar beets 0 0 0 0Corn 0 0 0 0Mustard 5G 8G 6G 9GCocklebur 0 2G 0 2GNutsedge 0 0 0 3GCotton 0 0 0 2GMorningglory 0 3G 0 2GSicklepod 0 0 0 0Teaweed 0 0 0 6GVelvetleaf 0 2G 0 0Jimsonweed 0 2G 0 0Soybean 0 0 0 0Rice 2G 2G 0 0Wheat 0 0 0 0 Compound 7 Compound 8Crabgrass 0 0 0 0Barnyardgrass 0 3G 0 2GSorghum 0 5G 0 2GWild Oats 0 2G 0 2GJohnsongrass 0 4G 0 4GDallisgrass 0 0 0 0Giant foxtail 0 2G 0 0Ky. bluegrass 0 0 0 0Cheatgrass 0 0 2G 3GSugar beets 7G 8G 6G 8GCorn 0 0 0 0Mustard 9G 10C 10C 10CCocklebur 2G 6G 2G 6GNutsedge 2G 8G 6G 8GCotton 4G 6G 6G 7GMorningglory 4G 5G 3G 4GSicklepod 0 3G 3G 4GTeaweed 2G 6G 5G 7GVelvetleaf 2G 8G 4G 7GJimsonweed 6G 9G 6G 9GSoybean 0 3G,2C 2G 4GRice 0 0 2G 3GWheat 0 0 0 2G Compound 9 Compound 10Crabgrass 0 0 0 0Barnyardgrass 0 2G 0 2GSorghum 0 7G 0 0Wild Oats 0 0 0 0Johnsongrass 0 0 0 0Dallisgrass 0 0 0 0Giant foxtail 0 0 0 0Ky. bluegrass 0 0 0 0Cheatgrass 0 3G 0 2GSugar beets 3G 9G 0 7GCorn 0 0 0 0Mustard 9G 9G 7G 9GCocklebur 3G 7G 0 0Nutsedge 0 2G 0 0Cotton 0 2G 0 0Morningglory 2G 3G 0 3GSicklepod 3G 4G 0 0Teaweed 3G 3G 0 2GVelvetleaf 0 7G 0 2GJimsonweed 0 5G 0 4GSoybean 0 2G,3C 0 2G,2CRice 0 0 0 4GWheat 0 0 0 2G______________________________________
TEST C
Two ten-inch in diameter plastic pans lined with polyethylene liners were filled with prepared Woodstown sandy loam soil. One pan was planted with seeds of wheat (Triticum aestivum), barley (Hordeum vulgare), wild oats (Avena fatua), cheatgrass (Bromus secalinus), blackgrass (Alopecurus myosuroides), annual bluegrass (Poa annua), green foxtail (Setaria viridis), 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), cleavers (Galium aparine), tumble mustard (Sisymbrium altissium), kochia (Kochia scoparia), shepherd's purse (Capsella bursa-pastoris), Matricaria inodora, black nightshade (Solanum nigrum), yellow rocket (Barbarea vulgaris), rapeseed (Brassica napus), 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 test compound was diluted with a non-phytotoxic solvent and sprayed over the top of the pans. An untreated control and a solvent-alone control were included for comparison. The treatments were maintained in the greenhouse for 19-21 days at which time the treatments were compared to the controls and the effects visually rated. The recorded data may be seen in Table C.
TABLE C______________________________________ Compound 1 Pre-Emergence Post-EmergenceRate kg/ha 0.015 0.06 0.015 0.06______________________________________wheat 0 0 0 2Gbarley 0 0 0 3Gwild oats 0 0 0 2Gdowny brome -- -- -- --cheatgrass 0 0 0 4Gblackgrass 3G 0 0 3Gannual bluegrass 2G 0 0 3Ggreen foxtail 3G 0 0 0quackgrass -- -- -- --Italian ryegrass 3G 2G 0 2Gripgut brome -- -- -- --Russian thistle 0 0 0 0tansy mustard -- -- 5G 7Gsmartweed -- -- 0 3Gtumble mustard 8G 9G 0 10Ckochia 0 0 0 0shepherd's purse 8G 10C 6G 10CMatricaria inodora 9G 9C 8G 7C,9Gblack nightshade 3G 5G 3G 4Gyellow rocket 7G 8G 3G 7Gwild mustard 6G 9G 6G 7Gwild buckwheat 0 3G 2G 5GVeronica persica 2G 4G______________________________________
TEST D
12-cm Diameter waxed paper cups were partially filled with Woodstown sandy loam. About 750 ml of water was added to each cup to bring the water level to a point 3 cm above the soil surface. Japonica rice seed was added to one set of pots, the seeds coming to rest on the soil surface (direct seeded rice). Japonica rice seedlings in the 2.5 leaf stage were transplanted into a second set of pots. Five days after seeding and transplanting Compound No. 8, dissolved in a small volume of acetone, was injected into the water of the simulated rice paddy. The rates of application and the crop response ratings made 10 days after treatment are shown in Table D.
TABLE D______________________________________Compound RateNo. (g/ha) Transpl. Rice Direct-seeded Rice______________________________________8 0.25 0 0 1 0 30 4 0 60 16 0 50 62 0 50 250 0 50 1000 0 80______________________________________
It will be seen that transplanted rice, in particular, is highly tolerant of Compound No. 8.
TEST E
16-cm Diameter glazed clay Waguer pots, equipped with a stoppered drain opening near the bottom of the side wall, were partially filled with Woodstown sandy loam. About 1500 ml of water was added to each pot to bring the water level to a point 3 cm above the soil surface. Direct-seeded Japonica rice was "planted" and Japonica rice seedlings were transplanted as described in Test D. Also, a number of barnyardgrass (Echinochloa orusgalli) seeds were added to each pot. At the same time, seedlings or tubers of the following species were transplanted into the muddy soil, water plantain (Alisma trivale), Scirpus (Scirpus mucranatus), and Cyperus (Cyperus difformis). The weed species selected for this test are of economic importance in major rice-growing areas. The chemical treatments were applied as described in Test D, within hours after transplanting of 2 additional species: water chestnut (Eleocharis spp.) and arrowhead (Sagittaria latifolia). Shortly after treatment, the drain hole was opened to drop the water level by 2 cm. Water was then added to restore the water level to its original height. The following day, the draining and refilling process was repeated. The pots were then maintained in the greenhouse. Rates of application and plant response ratings made 21 days after treatment are summarized in Table E.
TABLE E______________________________________Compound No. 8______________________________________Rate (g/ha) 30 125Transpl. Rice 10 20Direct-seeded Rice 50 70Echinochloa 50 70Eleocharis 100 100Sagittaria 100 100Scirpus 50 80Cyperus 100 100Alisum 90 100______________________________________
The data indicate that Compound 8 has potential utility for selective weed control in rice.
TEST F
The test procedure of Test E was repeated utilizing a different range of treatment rates. In addition to the above-mentioned species, Monocharia (Monocharia vaginalis) seeds were added to each pot in the same manner as barnyardgrass seed. The plant response ratings, taken 21 days after treatment, are given in Table F. They confirm the selective properties observed in previous tests.
TABLE F______________________________________Compound No. 8______________________________________Rate (g/ha) 2 8 16 30 125Transpl. Rice 0 0 0 0 20Direct-seeded Rice 0 0 0 0 20Echinochloa 0 0 25 50 70Eleocharis 0 60 100 100 100Sagittaria 0 0 50 85 100Scirpus 0 0 0 50 80Cyperus 0 50 75 75 100Alisum 0 50 30 90 100Monocharia 0 25 80 -- --______________________________________

Number	Date	Country
3105453	Oct 1982	DEX
3151450	Jul 1983	DEX
3225471	Jan 1984	DEX

Herbicidal phenoxy esters of N-(heterocyclic)aminocarbonyl)sulfamic acid

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