Herbicidal compounds

This invention relates to novel herbicides for weed control in agriculture, horticulture and other fields where it is desired to control unwanted plant growth, such as grassy or broadleaf plant species. The invention also relates to intermediates for the production of such herbicides.
One aspect of this invention relates to herbicidal compounds of the formula
Q-Ar-NHet Formula I
where Q-Ar is a substituted phenyl radical (e.g. of the formula ##STR2## in which the substituent Q is at the 5-position (meta to the nitrogen of said formula I); and where
Q is a group of the formula:
--CR.sup.1 (R.sup.2)C(R.sup.3)(R.sup.4)Q' or --CR.sup.1 .dbd.C(R.sup.4)Q' in which Q' is a carboxylic acid group (i.e. COOH) or a salt, ester, amide, or nitrile of such carboxylic acid group. Thus Q' may be:
CO.sub.2 H,
CO.sub.2 Z,
CO.sub.2 R.sup.5,
CON(R.sup.6)(R.sup.7), or
CN.
In another aspect of this invention Q' may be an aldehydic or ketonic group, e.g. --CHO or --COR.sup.5.
Z may be a salt-forming cation, such as one which forms a base addition salt with a carboxylic acid (e.g., a sodium, potassium, calcium, ammonium, magnesium, or mono-, di- or tri(C.sub.1-4 alkyl)ammonium or sulfonium or sulfoxonium ion). R.sup.5 may be alkyl, cycloalkyl of 3 to 6 carbon atoms (e.g. cyclopropyl or cyclopentyl), or aralkyl such as benzyl or substituted benzyl (e.g., halobenzyl, alkylbenzyl, or haloalkylbenzyl, such as 4-chlorobenzyl or 4-trifluoromethylbenzyl). R.sup.6 and R.sup.7 may each, independently, be hydrogen, hydroxy, alkyl, cycloalkyl, alkenyl, alkynyl (e.g., propynyl), alkoxy, phenyl, benzyl, or SO.sub.2 R.sup.8 in which R.sup.8 is the same as R.sup.6 other than hydrogen or SO.sub.2 R.sup.8, or any of the foregoing carrying additional substituents; such additional substituents may be halogen, haloalkyl (e.g. chloroethyl), halophenyl (e.g. chlorophenyl), or halobenzyl (e.g. chlorobenzyl); alkyl; or cyano.
In the foregoing formula for Q, R.sup.1, R.sup.2 and R.sup.3 may each, independently, be hydrogen, alkyl such as lower alkyl (e.g. methyl) or halogen such as chlorine, bromine, or fluorine, while R.sup.4 may be hydrogen or lower alkyl.
In Formula I above Ar and NHet are so chosen that when Q is methoxy or propargyloxy (instead of Q having the formula given above) the compound is a herbicide. Compounds in which Q in Formula I is methoxy or propargyloxy are, for convenience, here designated as Methoxy Analogs and the Propargyloxy Analogs of the claimed novel compounds. Such Methoxy Analogs and Propargyloxy Analogs are well known in the art.
Preferably, "Ar" carries a substituent (i.e. other than hydrogen) at the 2-position or the 4-position of the phenyl radical, most preferably at both the 2-and 4-positions.
X may be hydrogen; halogen such as chlorine, bromine, or fluorine (preferably fluorine or chlorine); alkyl such as lower alkyl (e.g. methyl); haloalkyl such as halo lower alkyl (e.g. CF.sub.3, CH.sub.2 F or CHF.sub.2); alkoxy such as lower alkoxy (e.g. methoxy); or NO.sub.2 ; and
Y may be hydrogen; halogen such as chlorine, bromine, or fluorine (preferably bromine or chlorine); alkyl such as lower alkyl (e.g. methyl); alkoxy such as lower alkoxy (e.g. methoxy); alkylthio such as lower alkylthio (e.g. methylthio); haloalkyl such as halo lower alkyl (e.g. fluoroalkyl); halo lower alkylsulfinyl (e.g. --SOCF.sub.3); or haloalkoxy such as halo lower alkoxy (e.g. as --OCHF.sub.2).
Presently preferred X and Y substituents are: 2-F, 4-Cl; 2-F, 4-Br; 2,4-Cl.sub.2 ; 2-Br, 4-Cl; and 2-F,4-CF.sub.3.
In the preferred compounds of this invention, NHet and Ar (or X and Y) are so chosen that the Methoxy Analog or the Propargyloxy Analog of such preferred compound has marked herbicidal properties, such Analog showing at least 50% kill of at least one of the following plant species when applied under at least one of the following modes at the rate of 0.5 kg/ha, and more preferably showing such 50% kill when applied at the rate of 0.1 kg/ha:
Species: velvetleaf (Abutilon theophrasti), green foxtail (Setaria viridis); Modes: pre-emergent, postemergent. Testing for such herbicidal activity may be carried out in the manner described below under the heading "Herbicidal Activity".
NHet is a monovalent nitrogen-containing organic group. NHet may be one of the following groups, for example: ##STR3## where R.sup.a and R.sup.b are, for example, independently, alkyl or haloalkyl or other radicals such as those disclosed in U.S. Pat. Nos. 4,318,731; 4,398,943; 4,404,019; 4,743,291; 4,702,945; 4,705,557; 4,702,763; 4,761,174 and lnternational patent publications WO 85/01637, WO 85/04307, WO 87/00730, WO 87/03782, WO 86/04481 and WO 88/01133; ##STR4## where R is, for example, alkyl or haloalkyl or other radical, such as those disclosed in U.S. Pat. No. 4,734,124 and International patent publications WO 85/01939 and WO 87/03873; ##STR5## where R.sup.c and R.sup.d are each H or together constitute a double bond and R.sup.e is, for example, an alkyl, haloalkyl or other radical, such as those disclosed in U.S. Pat. Nos. 4,755,217 and 4,766,233 and International patent publication WO 86/00072; ##STR6## where Z.sup.a is halo, alkyl, alkoxy, alkylsulfonyl, etc., and R.sup.f and R.sup.g may be alkyl, or taken together may be alkylene for instance, such as disclosed in Derwent Abstracts accession nos. 84-090669 (British patent 2,127,410); 85-100678 (European patent 138,527); 86-04852 and 88-101642; ##STR7## where, for instance, X.sup.a and Y.sup.a may be O or S and A may be (CH.sub.2).sub.n such as disclosed in Derwent Abstracts aCCession nos. 86-133831, 87-215141 (European patent 230,874) and 86-140810; ##STR8## where Y.sup.b may be O or S, such as disclosed in Derwent Abstracts accession nos. 85-240363 and 87-21541; ##STR9## where, for instance, R.sup.h and R.sup.i may together constitute an alkylene group, such as disclosed in Derwent Abstracts accession no. 86-133830; ##STR10## where, for instance, R.sup.j and R.sup.k together constitute an alkylene group, such as disclosed in Derwent Abstracts accession nos. 88-191726, 88-163183 and 88-243443; ##STR11## where, for instance, n is 0, 1, or 2; W is O or S; and R.sup.mm and R.sup.m may be H; or R.sup.mm may be Cl and R.sup.m may be H; or R.sup.mm and R.sup.m together form a double bond such as disclosed in U.S. Pat. No. 4,179,276 and Derwent Abstracts accession nos. 88-163183 and 88-243443; ##STR12## such as disclosed in Derwent Abstracts accession nos. 84-214701, 88-163183 and 88-243443; ##STR13## where, for instance, R.sup.n is lower alkyl, alkenyl, alkynyl or cycloalkyl such as disclosed in European patent 69855 and Derwent Abstracts accession no. 84-027480; ##STR14## where R.sup.o is lower alkyl or cycloalkyl such as disclosed in Derwent Abstracts accession nos. 84-246947, 87-238787 or 88-190606 (International patent publication WO 8804653) and U.S. Patent Nos. 3,385,862; 3,836,539; and 3,876,413; ##STR15## where R.sup.p is, for instance, lower alkyl, e.g., isopropyl; ##STR16## where, for example, R.sup.q is H, alkyl, alkenyl or alkynyl and R.sup.r and R.sup.s are H or lower alkyl, such as disclosed in Derwent Abstracts accession no. 88-092987 (European patent 262428); ##STR17## where, for example R.sup.t is hydrocarbyl group such as propyl, and R.sup.u may be H or hydroxycarbonyl, such as disclosed in Derwent Abstracts accession nos. 88-168716 (German patent 3636552) and 88-243443; ##STR18## where R.sup.v is alkylene which may be substituted, such as disclosed in Derwent Abstracts accession nos. 84-034261 and 84-090045; ##STR19## where X.sup.b is O or S, such as disclosed in Derwent Abstracts accession no. 87-040749; ##STR20## where R.sup.w is, for example, alkylene such as tetramethylene; ##STR21## where R.sup.x and R.sup.y may together constitute an alkylene group which may be interrupted by O, S or vinylene, such as disclosed in U.S. Pat. No. 4,521,242 and Derwent Abstracts accession no. 86-180564.
U.S. Pat. No. 4,439,229 and lnternational patent publication WO 87/07602 also disclose other NHet rings which may be used, such rings being illustrated, for example, at column 4 line 25 to column 5 line 20 of U.S. Pat. No. 4,439,229 and at pages 12 to 14 of WO 87/07602. It will be seen that many of the suitable NHet groups comprise a 5- or 6-membered heterocyclic ring having one to four ring-nitrogen atoms and having the formula ##STR22## where M represents the balance of the heterocyclic ring and R.sup.z represents hydrogen or a substituent group.
Particularly suitable compounds are those whose Methoxy Analog or Propargyloxy Analog, e.g., an Analog of the formula ##STR23## is a plant-membrane disrupting herbicide which acts as an inhibitor of the enzyme protoporphyrinogen oxidase, its I.sub.50 for that enzyme being less than 1 .mu.M preferably less than about 0.3 .mu.M, e.g. an I.sub.50 of about 0.1 or 0.03 or 0.01 .mu.M or less. A test for such inhibition is set forth in Appendix C below.
One test for the membrane (plasmalemma) disruption capacity is the Efflux Experiment described in the article by Halling and Peters in Plant Physiology, 84, 1114-5 (1987). In such a test (described in more detail in Appendix A below), the Methoxy or Propargyloxy analog preferably shows a total efflux of at least 50% at a treatment rate of 100 .mu.M, preferably at a treatment rate of 1 .mu.M or less, such as 100 nM; highly active materials, such as 1-(4-chloro-2-fluoro-5-propargyloxyphenyl)-3-methyl-4-difluoromethyl-.DELTA..sup.2 -1,2,4-triazolin-5-one, give total efflux percentages of over 90% at 100 nM concentration.
Another test of the capacity of a material for disrupting the plasmalemma of plant material is the Light-Induced Greening Inhibition Test described more particularly in Appendix B below. This test measures the capacity to inhibit the light-greening of dark-bleached Chlamydomonas reinhardi mutant y-1 (a type of algae which when grown in the dark does not make chlorophyll, so that the mass of algae becomes bleached owing to the presence of new non-green cells, and which produces chlorophyll again when it is exposed to light). The compounds of this invention preferably are those whose Methoxy or Propargyloxy analog has the ability to inhibit the light-greening by at least 50% when used at a concentration of 10.sup.-5 M, more preferably at a concentration of 10.sup.-6 M or less, e.g., 10.sup.-7 M. In addition, the compound should be one whose Methoxy or Propargyloxy Analog, when used at said concentration in the Light-Greening Inhibition Test, gives a supernatant which shows a light absorption peak at about 405 nm which is higher than the chlorophyll peak (the peak at about 668 nm in this system), e.g. the supernatant shows a 405 nm peak whose height is 2, 3 or 4 times the height of the 668 nm peak.
Representative compounds of this invention are listed in Table 1 below.
One may describe many of the compounds of this invention by the formulas ##STR24## in which Q', R.sup.1, R.sup.2, R.sup.3 and R.sup.4 have the meanings set forth above and the substituent R.sup.1 on the tetrazolinone ring may be any of those known in the prior art discussed above.
X may be hydrogen; halogen such as chlorine, bromine, or fluorine (preferably fluorine or chlorine); alkyl such as lower alkyl (e.g. methyl); haloalkyl such as halo lower alkyl (e.g., CF.sub.3, CH.sub.2 F or CHF.sub.2); alkoxy such as lower alkoxy (e.g., methoxy); or nitro; and Y may be hydrogen; halogen such as chlorine, bromine, or fluorine (preferably bromine or chlorine); alkyl such as lower alkyl (e.g. methyl); alkoxy such as lower alkoxy (e.g. methoxy); haloalkyl such as halo lower alkyl (e.g. fluoroalkyl); alkylthio such lower alkylthio (e.g. methylthio); halo lower alkylsulfinyl (e.g., --SOCF.sub.3); or halo lower alkoxy (e.g., --OCHF.sub.2).
Presently preferred X and Y substituents are 2-F, 4-Cl; 2-F, 4-Br; 2,4-Cl.sub.2 ; 2-Br, 4-Cl; and 2-F, 4-CF.sub.3.
In each aspect of the invention it is often preferable that any alkyl, alkenyl, alkynyl or alkylene moiety (such as the hydrocarbon moiety of an alkoxy or haloalkoxy group) has up to about 6 carbon atoms, e.g., 1 to 4 or 5 carbon atoms, and that any cycloalkyl moiety have 3 to 7 ring carbon atoms, more preferably 3 to 6 carbon atoms.
Any acidic compound of this invention, including sulfonamides in which NR.sup.6 R.sup.7 is NHSO.sub.2 R.sup.8, may be converted to the corresponding base addition salt, such as a salt in which the salt-forming cation is Z (Z being as described above).
The present compounds may be prepared by methods described in the literature or in the following Examples or by methods analogous and similar thereto and within the skill of the art. In the Example below a compound of the formula ##STR25## (such as the compound shown in Example 1E of International patent publication WO/03873, published July 2, 1987, in which X=F, Y=Cl and R=--(CH.sub.2).sub.3 F) is reacted (according to a procedure described by Doyle et al., J. Org. Chem. 42, 2431 (1977)) with an alkyl nitrite, a copper (II) halide, and an olefinic compound having the formula C(R.sup.1)(R.sup.2).dbd.C(R.sup.4)Q' to form a compound of formula I above in which Q is --C(R.sup.1)(R.sup.2)C(R.sup.3)(R.sup.4)Q' and in which R.sup.3 is halogen and R.sup.2 is hydrogen. That compound may be dehydrohalogenated (e.g., with sodium hydride or other suitable base) to yield a compound of formula II above in which Q is --C(R.sup.1).dbd.C(R.sup.4)Q'. To produce the latter, one may also use the method of Example 1 below starting with a compound of the formula ##STR26## such as the 3-amino-6-chloro-4-fluorocinnamic acid ethyl ester described in Japanese published application 59-15538 of Sep. 4, 1984. The amino group is converted to an NHet group, as by a method described in the above-mentioned International patent publication WO 85/01939 forming a compound of the formula ##STR27## The reactant C(R.sup.1)R.sup.2 .dbd.C(R.sup.4)Q' may be, for example, methyl acrylate, ethyl acrylate, methyl methacrylate, methyl 3-chloroacrylate, methacrolein, vinyl methyl ketone, ethyl crotonate, acrylonitrile, methacrylonitrile or the like.
The --C(R.sup.1).dbd.C(R.sup.4)CO.sub.2 R.sup.5 group may be hydrogenated or halogenated to form a compound in which Q is --C(R.sup.1)(R.sup.2)C(R.sup.3)(R.sup.4)Q' and R.sup.2 and R.sup.3 are hydrogen (from hydrogenation as in Example 1D below) or R.sup.2 and R.sup.3 are halogen (from halogenation as in Example 2). When Q' is CO.sub.2 H, the acidic compound of formula I may be converted to the corresponding amide, such as by first treating with a reagent such as thionyl chloride to form the acid halide (wherein Q' is, for example, --COCl) and then reacting with ammonia or an amine. Alternative methods of amide formation may involve known carbodiimidemediated coupling.
The invention is illustrated further in the following Examples. In this application all temperatures are in .degree.C. unless otherwise indicated.

EXAMPLE 1
Ethyl 3-[2-Chloro-4-fluoro-5-[4-(3-fluoropropyl)-1,4-dihydro-5-oxo-5H-tetrazol-1-yl]phenyl]propionate
Step A Ethyl 3-[2-chloro-4-fluoro-5-(1,4-dihydro-5-oxo-5H-tetrazol-1-yl)phenyl]-propenoate
A stirred mixture of 8.06 g (0.0449 mole) of ethyl 3-(5-amino-2-chloro-4-fluorophenyl)propenoate and 5.32 g (0.0269 mole) of trichloromethyl chloroformate in 200 mL of 1,4-dioxane was heated at reflux for approximately three hours. The solvent was removed by distillation under reduced pressure, leaving a residue. To this residue was added 50 mL of trimethylsilyl azide, and the resultant mixture was stirred and heated at reflux for approximately 18 hours. The mixture was cooled and was diluted with toluene. The organic mixture was washed with water. The organic phase was evaporated under reduced pressure, leaving a residue. This residue was dissolved in ethyl acetate and was washed in succession with 1N hydrochloric acid, an aqueous, saturated sodium bicarbonate solution, and water. The washed organic phase was dried over anhydrous magnesium sulfate and was filtered. The filtrate was evaporated under reduced pressure leaving a residue. This residue was purified by column chromatography on silica gel to yield ethyl 3-[2=chloro-4-fluoro-5-(1,4-dihydro-5-oxo-5H-tetrazol-1-yl)phenyl]propenoate as a solid, mp 106.degree.-109.degree. C.
The ir and nmr spectra were consistent with the proposed structure.
Step B 3-Fluoropropyl methanesulfonate
To an ice cold, stirred solution of 19.0 g (0.244 mole) of 3-fluoropropanol and 39.5 g (0.300 mole) of triethylamine in 300 mL of methylene chloride was added dropwise 34.4 g (0.300 mole) of methanesulfonyl chloride. The resultant mixture was allowed to warm to room temperature and was stirred for approximately 18 hours. The mixture was poured into water and was washed with an aqueous, saturated sodium bicarbonate solution. The organic phase was dried over anhydrous magnesium sulfate and was filtered. The filtrate was distilled under reduced pressure to yield 41.3 g of 3-fluoropropyl methanesulfonate as a liquid, bp 116.degree. C./15 mm Hg.
The nmr spectrum was consistent with the proposed structure.
Step C Ethyl 3-[2-chloro-4-fluoro-5-[4-(3-fluoropropyl)-1,4-dihydro-5-oxo-5H-tetrazol-1-yl]phenyl]propenoate
To a stirred mixture of 2.62 g (0.00830 mole) of ethyl 3-[2-chloro-4-fluoro-5-(1,4-dihydro-5-oxo-5H-tetrazol-1-yl)phenyl]propenoate in 20 mL of N,N-dimethylformamide was added 1.46 g (0.00939 mole) of 3-fluoropropyl methanesulfonate and 1.30 g (0.00939 mole) of potassium carbonate. The reaction mixture was heated at 50.degree.-60.degree. C. and was stirred at that temperature for approximately 18 hours. The mixture was cooled and was poured into ice water. This mixture was extracted with ethyl acetate. The extract was dried over anhydrous magnesium sulfate and was filtered. The filtrate was evaporated under reduced pressure to yield 0.76 g of ethyl 3-[2-chloro-4-fluoro-5-[4-(3-fluoropropyl)-1,4-dihydro-5-oxo-5H-tetrazol-1-yl]phenyl]propenoate as an oil, compound 4 of Table 1.
The nmr spectrum was consistent with the proposed structure.
Step D Ethyl 3-[2-chloro-4-fluoro-5-[4-(3-fluoropropyl)-1,4-dihydro-5-oxo-5H-tetrazol-1-yl]phenyl]propionate
The hydrogenation of 0.45 g (0.0012 mole) of ethyl 3-[2-chloro-4-fluoro-5-[4-(3-fluoropropyl)-1,4-dihydro-5-oxo-5H-tetrazol-1-yl]phenyl]propenoate with approximately 0.1 g of platinum (IV) oxide in ethyl acetate yielded 0.43 g of ethyl 3-[2-chloro-4-fluoro-5[4-(3-fluoropropyl)-1,4-dihydro-5-oxo-5-H-tetrazol-1-yl]phenyl]propionate as an oil, compound 1 of Table 1.
The nmr and ir spectra were consistent with the proposed structure.
EXAMPLE 2
Ethyl 2,3-Dibromo-3-[2-chloro-4-fluoro-5-[4-(3-fluoropropyl)-1,4-dihydro-5-oxo-5H-tetrazol-1-yl]phenyl]propionate
The bromination of 0.34 g (0.00091 mole) of ethyl 3-[2-chloro-4-fluoro-5-[4-(3-fluoropropyl)-1,4-dihydro-5-oxo-5H-tetrazol-1-yl]phenyl]propenoate with five drops of bromine in 10 mL of methylene chloride yielded 0.38 g of ethyl 2,3-dibromo-3-[2-chloro-4-fluoro-5-[4-(3-fluoropropyl)-1,4-dihydro-5-oxo-5H-tetrazol-1yl]phenyl]propionate as an oil, compound 2 of Table 1.
The nmr and ir spectra were consistent with the proposed structure.
EXAMPLE 3
Ethyl 2-chloro-3-[2-chloro-4-fluoro-5-[4-(3-fluoropropyl)-1,4-dihydro-5-oxo-5H-tetrazol-1-yl]phenyl]propionate
To an ice cold, stirred mixture of 5.54 g (0.0553 mole) of ethyl acrylate, 10 mL of acetonitrile, 0.43 g (0.0042 mole) of tert-butyl nitrite, and 0.45 g (0.0033 mole) of copper (II) chloride was added a solution of 0.80 g (0.0028 mole) of 1-(5-amino-4-chloro-2-fluorophenyl)-1,4-dihydro-4-(3-fluoropropyl)-5H-tetrazol-5-one (which may be prepared as described in International patent publication WO 87/03873, Example 1 A-E) in 10 mL of acetonitrile. The reaction mixture was stirred at room temperature for five hours and then was diluted with 2N hydrochloric acid. The acidic mixture was extracted with three portions of diethyl ether. The extracts were combined and dried over anhydrous magnesium sulfate. The dried organic phase was filtered and the filtrate was evaporated leaving a residue. This residue was purified by column chromatography on silica gel, eluting with n-heptane: ethyl acetate (2:1) to yield 1.1 g of ethyl 2-chloro-3-[2-chloro-4-fluoro-5-[4-(3-fluoropropyl)-1,4-dihydro-5-oxo-5H-tetrazol-1-yl]phenyl]propionate as an oil, compound 3 of Table 1.
The nmr spectrum was consistent with the proposed structure.
EXAMPLE 4
Methyl 3-[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenyl]propionate
Step A Methyl 2-Chloro-3-[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenyl]propionate
To a cold (0.degree. C.), stirred mixture of 28.7 g (0.333 mole) of methyl acrylate, 2.51 g (0.0244 mole) of tert-butyl nitrite, and 2.6 g (0.019 mole) of copper (II) chloride in 50 mL of acetonitrile was added dropwise a solution of 5.0 g (0.016 mole) of 1-(5-amino-2,4-dichlorophenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one in 15 mL of acetonitrile. After complete addition the reaction mixture was allowed to war to room temperature and was stirred for approximately 18 hours. The reaction mixture was diluted with 15 mL of 2N hydrochloric acid solution. The mixture was extracted with four portions of diethyl ether. The combined extracts were dried over anhydrous magnesium sulfate, filtered, and the filtrate evaporated under reduced pressure to give an oil. The oil was purified by column chromatography on silica gel, eluting with n-heptane:ethyl acetate (4:1) to give 5.0 g of methyl 2-chloro-3-[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenyl]propionate as an oil, Compound A3 of Table 1A.
Step B Methyl 3-[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenyl]propenoate
To a stirred, cold (0.degree. C.) solution of 4.16 g (0.0100 mole) of methyl 2-chloro-3-[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenyl]propionate in 15 mL of N,N-dimethylformamide was added portionwise 0.29 g (0.012 mole) of sodium hydride. After complete addition the reaction mixture was allowed to warm to room temperature and was stirred for 30 minutes. The reaction mixture was heated at 60.degree. C. for six hours and then was stirred at room temperature for approximately 18 hours. The reaction mixture was poured into ice water, and the resultant aqueous mixture was extracted with four portions of diethyl ether. The extracts were combined and washed successively with water and an aqueous, saturated sodium chloride solution. The washed organic phase was dried over anhydrous magnesium sulfate and was filtered. The filtrate was evaporated under reduced pressure to give a white foam. The foam was purified by column chromatography on silica gel, eluting with n-heptane:ethyl acetate (4:1), to give 1.63 g of methyl 3-[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenyl]propenoate as a solid, m.p. 148.degree.-151.degree. C., Compound A39 of Table 1A.
Step C Methyl 3-[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenyl]propionate
Hydrogenation of 0.59 g (0.0016 mole) of methyl 3-[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenyl]propenoate (Compound A39) over approximately 0.2 g (0.0009 mole) of platinum (IV) oxide in approximately 15 mL of ethyl acetate gave after filtration and concentration 0.59 g of methyl 3-[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenyl]propionate as a clear oil, which crystallized upon standing. The crystals were triturated with petroleum ether and recovered by filtration, m.p. 70.degree.-73.degree. C., Compound Al of Table 1A.
EXAMPLE 5
Methyl 2,3-dibromo-3-[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)-phenyl]propionate
In a manner similar to that of Abbott and Althoresen, Org. Syn., Coll. Vol. 2, pg 270, 0.24 g (0.00063 mole) of methyl 3-[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenyl]propenoate (Compound A39) was treated with six drops of bromine in 15 mL of carbon tetrachloride to give 0.40 g of methyl 2,3-dibromo-3-[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenyl]propionate as a solid, Compound A10 of Table 1A.
The nmr spectrum was consistent with the proposed structure.
EXAMPLE 6
N-Cyclopropyl-2-chloro-3-[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenyl]propionamide
Step A 2-Chloro-3-[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenyl]propionic acid
To a stirred mixture of 26.3 g (0.366 mole) of acrylic acid, 2.83 g (0.275 mole) of tert-butyl nitrite, and 2.94 g (0.0220 mole) of copper (II) chloride in 75 mL of acetonitrile was added slowly 5.65 g (0.0183 mole) of 1-(5-amino-2,4-dichlorophenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one. The reaction mixture was stirred at room temperature for three hours. The reaction mixture was poured into 2N hydrochloric acid solution, and the whole was extracted with diethyl ether. The organic phase was dried over anhydrous magnesium sulfate, filtered, and the filtrate evaporated under reduced pressure to give a yellow solid. The solid was triturated with water and was filtered. The filter cake was dried to give 5.9 g of 2-chloro-3-[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-2-yl)phenyl]propionic acid, Compound A2 of Table 1A.
The nmr spectrum was consistent with the proposed structure. A similarly prepared sample of Compound A2 had a melting point of 138.degree.-141.degree. C.
Step B N-Cyclopropyl-2-chloro-3-[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenyl]propionamide
A stirred solution of 0.50 g (0.0013 mole) of 2-chloro-3-[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-,1,2,4-triazol-1-yl)phenyl]propionic acid (Compound A2), 0.071 g (0.0013 mole) of cyclopropylamine, 0.17 g (0.0013 mole) of 1-hydroxybenzotriazole hydrate, and 0.18 g (0.0014 mole) of N,N-diisopropylethylamine in approximately 15 mL of tetrahydrofuran was cooled to 0.degree. C. To this cold mixture was added 0.26 g (0.0013 mole) of 1,3-dicyclohexylcarbodiimide. After complete addition, the reaction mixture was allowed to warm to room temperature and was stirred for approximately 18 hours. The reaction mixture was filtered. The filtrate was diluted with carbon tetrachloride and was washed in succession with a 1N hydrochloric acid solution, an aqueous 10% sodium hydroxide solution, water, and an aqueous saturated sodium chloride solution. The organic phase was dried over anhydrous magnesium sulfate, filtered, and the filtrate was evaporated under reduced pressure to give 0.43 g of N-cyclopropyl-2-chloro-3-[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenyl]propionamide as a solid, m.p. 139.degree.-143.degree. C., Compound A17 of Table 1A.
The nmr and ir spectra were consistent with the proposed structure.
EXAMPLE 7
N-Methyl-N-methoxy-2-chloro-3-[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenyl]propionamide
A mixture of 0.50 g (0.0013 mole) of 2-chloro-3-[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenyl]propionic acid (Compound A2) and 5 mL of thionyl chloride was stirred at reflux for three hours. The mixture was cooled, and excess thionyl chloride was removed by distillation under reduced pressure leaving a residue. The residue was added to a cold solution of 0.13 g (0.0014 mole) of N,O-dimethylhydroxylamine hydrochloride and 0.11 g (0.0014 mole) of pyridine in 20 mL of tetrahydrofuran. The resultant mixture was stirred at room temperature for approximately 18 hours. The reaction mixture was diluted with diethyl ether and was washed in succession with a 1N hydrochloric acid solution, an aqueous 10% sodium hydroxide solution, water, and an aqueous saturated sodium chloride solution. The washed organic phase was dried over anhydrous magnesium sulfate and was filtered. The filtrate was evaporated under reduced pressure to give 0.37 g of N-methyl-N-methoxy-2-chloro-3-[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenyl]propionamide as an oil, Compound A22 of Table 1A.
The nmr and ir spectra were consistent with the proposed structure.
EXAMPLE 8
N-methylsulfonyl-2-chloro-3-[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenyl]propionamide
In a manner similar to Example 7, the reaction of 0.50 g (0.0013 mole) of 2-chloro-3-[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenyl]propionic acid (Compound A2) with 5 mL of thionyl chloride produced a residue. To this residue was added 0.50 g (0.0052 mole) of methanesulfonamide. The mixture was stirred and heated at 120.degree. C. for two hours. The mixture was cooled, diluted with methylene chloride, and a resultant precipitate was removed by filtration. The filtrate was washed with water. The organic phase was dried over anhydrous magnesium sulfate, filtered, and the filtrate evaporated under reduced pressure to give 0.21 g of N-methylsulfonyl-2-chloro-3-[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenyl]propionamide as a foam, Compound A25 of Table 1A.
The nmr and ir spectra were consistent with the proposed structure.
EXAMPLE 9
2-Chloro-3-[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenyl]-N-(4-chlorophenyl)propionamide
A stirred solution of 0.50 g (0.0013 mole) of 2-chloro-3-[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenyl]propionic acid (Compound 2), 0.16 g (0.0013 mole) of 4-chloroaniline, 0.17 g (0.0013 mole) of 1-hydroxybenzotriazole hydrate, and 0.18 g (0.0014 mole) of N,N-diisopropylethylamine in approximately 15 mL of tetrahydrofuran was cooled to 0.degree. C. To this cold reaction mixture was added 0.26 g (0.0013 mole) of 1,3-dicyclohexylcarbodiimide. After complete addition, the reaction mixture was allowed to warm to room temperature and was stirred for approximately 18 hours. The reaction mixture was filtered. The filtrate was diluted with carbon tetrachloride and was washed in succession with a 1N hydrochloric acid solution, an aqueous 10% sodium hydroxide solution, water, and an aqueous saturated sodium chloride solution. The organic phase was dried over anhydrous magnesium sulfate, filtered, and the filtrate evaporated under reduced pressure to give 0.28 g of 2-chloro-3-[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenyl]-N-(4-chlorophenyl)propionamide as an oil, Compound A23 of Table 1A.
The nmr and ir spectra were consistent with the proposed structure.
EXAMPLE 10
2-Chloro-3-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-trizol-1-yl)phenyl]-N-(4-methylphenylsulfonyl)propionamide
To a stirred solution of 0.19 g (0.0012 mole) of 1,1'-carbonyldiimidazole in 3 mL of tetrahydrofuran was added a solution of 0.45 g (0.0012 mole) of 2-chloro-3-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenyl]propionic acid (prepared by the method of Example 6, Step A, from 1-(5-amino-4-chloro-2-fluorophenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one) in 5 mL of tetrahydrofuran.
The reaction mixture was diluted With 5 mL of tetrahydrofuran. The mixture was stirred at room temperature for 30 minutes and then was heated at reflux for 30 minutes. The reaction mixture was cooled to room temperature, and 0.20 g (0.0012 mole) of para-toluene-sulfonamide was added. The mixture was stirred for approximately 10 minutes, and 0.17 g (0.0012 mole) of 1,8-diazabicyclo [5.4.0]undec-7-ene was added. The resultant mixture was stirred at room temperature for approximately 18 hours. The reaction mixture was partitioned between diethyl ether and 1N hydrochloric acid solution. The organic phase was washed in succession with water and an aqueous saturated sodium chloride solution. The washed organic phase was dried over anhydrous magnesium sulfate, filtered, and the filtrate evaporated under reduced pressure leaving a residue. This residue was purified by column chromatography on silica gel, eluting with n-heptane:ethanol:chloroform (1:1:1), to yield 0.23 g of 2-chloro-3-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenyl]-N-(4-methylphenylsulfonyl)propionamide as a solid, m.p. 267.degree.-269.degree. C., Compound A38 of Table 1A.
The nmr spectrum was consistent with the proposed structure.
HERBICIDAL ACTIVITY
The plant test species used in demonstrating the herbicidal activity of compounds of this invention include cotton (Gossypium hirsutum var. DPL61), soybean (Glycine max var. Williams), field corn (Zea mays var. Pioneer 3732), wheat (Triticum aestivium var. Wheaton), rice (Oryza sativa var. Labelle), morningglory (Ipomea lacumosa or Ipomea hederacea), wild mustard (Brassica kaber), velvetleaf (Abutilon theophrasti), barnyardgrass (Echinochloa crus-galli), green foxtail (Setaria viridis), and johnsongrass (Sorghum halepense).
Preparation of Flats
Preemergence
Two disposable fiber flats (8 cm.times.15 cm.times.25 cm) for each rate of application for each candidate herbicide for preemergence testing are filled to an approximate depth of 6.5 cm with steam sterilized sandy loam soil. The soil is leveled and impressed with a template to provide six evenly spaced furrows 13 cm long and 0.5 cm deep in each flat. Seeds of cotton, soybean, corn, rice and wheat are planted in five of the furrows of the first flat (the sixth furrow is left unplanted), and seeds of wild mustard, morningglory, velvetleaf, barnyardgrass, green foxtail, and johnsongrass are planted in the six furrows of the second flat. The template is again employed to firmly press the seeds into place. A topping soil of equal portions of sand and sandy loam soil is placed uniformly on top of each flat to a depth of approximately 0.5 cm. The flats are first watered, then sprayed with a solution of test compound as described below. Postemergence:
Two flats for each rate of application for each herbicide candidate are also prepared for postemergence application. The postemergence flats are prepared in the same manner as discussed above for the preemergence flats. The prepared flats are watered for 8-11 days, then the foliage of the emerged tests plants is sprayed with a solution of test compound as described below.
Application of Herbicides
In both the preemergence and postemergence tests, the candidate herbicides are applied as aqueous acetone solutions, usually at rates equivalent to 8.0 kilograms/hectare (kg/ha) and/or submultiples thereof, i.e., 4.0 kg/ha, 2.0 kg/ha, and so on.
The four flats (2 preemergence, 2 postemergence) are placed together and sprayed with 30 mL of test solution containing an appropriate amount of the test compound, i.e., approximately 7.5 mL of the test solution is sprayed on each of the four flats. Preemergence applications are made as sprays to the soil surface. Postemergence applications are made as sprays to the foliage. After treatment, the two preemergence flats are watered regularly at the soil surface for approximately 2 weeks, at which time phytotoxicity data are recorded. In the postemergence test the foliage is kept dry for 24 hours after treatment, then watered regularly for approximately 2 weeks, and phytotoxicity data recorded.
Preparation of Test Solutions
For flats of the size described above, an application rate of 8.0 kg/ha of active ingredient is equivalent to 0.06 g of active ingredient/flat (0.24 g/4 flats). A stock solution of 0.48 g of the candidate herbicide in 60 mL of a 50:50 mixture of water and acetone containing 0.5% (v/v) of sorbitan monolaurate emulsifier/solubilizer is divided into two 30 mL portions, each containing 0.24 g of the candidate herbicide. For the 8.0 kg/ha application, one of the 30 mL portions is sprayed undiluted onto the four flats (7.5 mL/flat). The remaining 30 mL portion of the stock solution is diluted with an additional 30 mL of the aqueous acetone/emulsifier mixture to provide 60 mL of a solution containing 0.24 g of candidate herbicide. As above, this solution is divided into two 30 mL portions, each containing 0.12 g of candidate herbicide. One of the 30 mL portions is applied, without further dilution, to the four flats for the 4.0 kg/ha rate. The remaining 30 mL portion is further diluted with an equal amount of aqueous acetone/emulsifier mixture, and the resulting 60 mL solution of 0.12 g candidate herbicide is divided into two 30 mL portions each containing 0.06 g of candidate herbicide. One of the 30 mL (0.06 g active) portions is used for the 2.0 kg/ha application rate and the other is used in the preparation of lower rate test solutions by the same serial dilution technique.
Phytotoxicity data are taken as percent control. Percent control is determined by a method similar to the 0 to 100 rating system disclosed in "Research Methods in Weed Science," 2nd ed., B. Truelove, Ed.; Southern Weed Science Society; Auburn University, Auburn, Ala., 1977. The rating system is as follows:
______________________________________Herbicide Rating SystemRating DescriptionPercent of Main Crop WeedControl Categories Description Description______________________________________ 0 No effect No crop No weed reduction control or injury10 Slight dis- Very poor weed coloration control or stunting20 Slight Some dis- Poor weed effect coloration, control stunting or stand loss30 Crop injury Poor to more pronounced cient weed but not lasting control40 Moderate injury, Deficient weed crop usually control recovers50 Moderate Crop injury Deficient to effect more lasting, moderate weed recovery doubt- control ful60 Lasting crop Moderate weed injury, no control recovery70 Heavy injury and Control some- stand loss what less than satisfactory80 Severe Crop nearly des- Satisfactory troyed, a few to good weed survivors control90 Only occasional Very good to live plants left excellent control100 Complete Complete crop Complete weed effect destruction destruction______________________________________
Herbicidal data at selected application rates are given for various compounds of the invention in Tables 2, 2A, 3, and 3A below. The test compounds are identified in the tables by numbers which correspond to those in Table 1. The abbreviation "kg/ha" in Tables 2 and 3 means kilograms per hectare.
For herbicidal application, the active compounds are formulated into herbicidal compositions by admixture in herbicidally effective amounts with adjuvants and carriers normally employed in the art for facilitating the dispersion of active ingredients for the particular utility desired, recognizing the fact that the formulation and mode of application of a toxicant may affect the activity of the material in a given application. Thus, for agricultural use the present herbicidal compounds may be formulated as granules of relatively large particle size, as water-soluble or water-dispersible granules, as powdery dusts, as wettable powders, as emulsifiable concentrates, as solutions, or as any of several other known types of formulations, depending on the desired mode of application.
These herbicidal compositions may be applied either as water-diluted sprays, or dusts, or granules to the areas in which suppression of vegetation is desired. These formulations may contain as little as 0.1%, 0.2% or 0.5% to as much as 95% or more by weight of active ingredient.
Dusts are free flowing admixtures of the active ingredient with finely divided solids such as talc, natural clays, kieselguhr, flours such as walnut shell and cottonseed flours, and other organic and inorganic solids which act as dispersants and carriers for the toxicant; these finely divided solids have an average particle size of less than about 50 microns. A typical dust formulation useful herein is one containing 1.0 part or less of the herbicidal compound and 99.0 parts of talc.
Wettable powders, also useful formulations for both pre- and postemergence herbicides, are in the form of finely divided particles which disperse readily in water or other dispersant. The wettable powder is ultimately applied to the soil either as a dry dust or as an emulsion in water or other liquid. Typical carriers for wettable powders include Fuller's earth, kaolin clays, silicas, and other highly absorbent, readily wet inorganic diluents. Wettable powders normally are prepared to contain about 5-80% of active ingredient, depending on the absorbency of the carrier, and usually also contain a small amount of a wetting, dispersing or emulsifying agent to facilitate dispersion. For example, a useful wettable powder formulation contains 80.8 parts of the herbicidal compound, 17.9 parts of Palmetto clay, and 1.0 part of sodium lignosulfonate and 0.3 part of sulfonated aliphatic polyester as wetting agents. Other wettable powder formulations are:
______________________________________Component % by Wt.______________________________________Active ingredient 40.00Sodium lignosulfonate 20.00Attapulgite clay 40.00Total 100.00Active ingredient 90.00Dioctyl sodium sulfosuccinate 0.10Synthetic fine silica 9.90Total 100.00Active ingredient 20.00Sodium alkylnaphthalenesulfonate 4.00Sodium lignosulfonate 4.00Low viscosity methyl cellulose 3.00Attapulgite clay 69.00Total 100.00Active ingredient 25.00Base: 75.0096% hydrated aluminum magnesium silicate 2% powdered sodium lignosulfonate 2% powdered anionic sodium alkyl-naphthalenesulfonateTotal 100.00______________________________________
Frequently, additional wetting agent and/or oil will be added to the tank-mix for postemergence application to facilitate dispersion on the foliage and absorption by the plant.
Other useful formulations for herbicidal applications are emulsifiable concentrates (ECs) which are homogeneous liquid or paste compositions dispersible in water or other dispersant, and may consist entirely of the herbicidal compound and a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthas, isophorone, or other non-volatile organic solvent. For herbicidal application these concentrates are dispersed in water or other liquid carrier, and normally applied as a spray to the area to be treated. The percentage by weight of the essential active ingredient may vary according to the manner in which the composition is to be applied, but in general comprises 0.5 to 95% of active ingredient by weight of the herbicidal composition.
The following are specific examples of emulsifiable concentrate formulations:
______________________________________Component % by Wt.______________________________________Active ingredient 53.01Blend of alkylnaphthalenesulfonate 6.00and polyoxyethylene ethersEpoxidized soybean oil 1.00Xylene 39.99Total 100.00Active ingredient 10.00Blend of alkylnaphthalenesulfonate 4.00and polyoxyethylene ethersXylene 86.00Total 100.00______________________________________
Flowable formulations are similar to ECs except that the active ingredient is suspended in a liquid carrier, generally water. Flowables, like ECs, may include a small amount of a surfactant, and contain active ingredient in the range of 0.5 to 95%, frequently from 10 to 50%, by weight of the composition. For application, flowables may be diluted in water or other liquid vehicle, and are normally applied as a spray to the area to be treated.
The following are specific examples of flowable formulations:
______________________________________Component: % by Wt.______________________________________Active ingredient 46.00Colloidal magnesium aluminum silicate 0.40Sodium alkylnaphthalenesulfonate 2.00Paraformaldehyde 0.10Water 40.70Propylene glycol 7.50Acetylenic alcohols 2.50Xanthan gum 0.80Total 100.00Active ingredient 45.00Water 48.50Purified smectite clay 2.00Xanthan gum 0.50Sodium alkylnaphthalenesulfonate 1.00Acetylenic alcohols 3.00Total 100.00______________________________________
Typical wetting, dispersing or emulsifying agents used in agricultural formulations include, but are not limited to, the alkyl and alkylaryl sulfonates and sulfates and their sodium salts; alkylaryl polyether alcohols; sulfated higher alcohols; polyethylene oxides; sulfonated animal and vegetable oils; sulfonated petroleum oils; fatty acid esters of polyhydric alcohols and the ethylene oxide addition products of such esters; and the addition product of long-chain mercaptans and ethylene oxide. Many other types of useful surface-active agents are available in commerce. The surface-active agent, when used, normally comprises from 1 to 15% by weight of the composition.
Other useful formulations include simple solutions or suspensions of the active ingredient in a relatively non-volatile solvent such as Water, corn oil, kerosene, propylene glycol, or other suitable solvents. The following illustrate specific suspensions:
______________________________________ % by Wt.______________________________________Oil Suspension:Active ingredient 25.00Polyoxyethylene sorbitol hexaoleate 5.00Highly aliphatic hydrocarbon oil 70.00Total 100.00Aqueous Suspension:Active ingredient 40.00Polyacrylic acid thickener 0.30Dodecylphenol polyethylene glycol ether 0.50Disodium phosphate 1.00Monosodium phosphate 0.50Polyvinyl alcohol 1.00Water 56.70Total 100.00______________________________________
Other useful formulations for herbicidal applications include simple solutions of the active ingredient in a solvent in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene, or other organic solvents. Granular formulations, wherein the toxicant is carried on relatively coarse particles, are of particular utility for aerial distribution or for penetration of cover crop canopy. Pressurized sprays, typically aerosols wherein the active ingredient is dispersed in finely divided form as a result of vaporization of a low boiling dispersant solvent carrier, such as the Freon fluorinated hydrocarbons, may also be used. Water-soluble or water-dispersible granules are also useful formulations for herbicidal application of the present compounds. Such granular formulations are free-flowing, non-dusty, and readily water-soluble or water-miscible. The soluble or dispersible granular formulations described in U.S. Pat. No. 3,920,442 are useful herein with the present herbicidal compounds. In use by the farmer on the field, the granular formulations, emulsifiable concentrates, flowable concentrates, solutions, etc., may be diluted with water to give a concentration of active ingredient in the range of say 0.1% or 0.2% to 1.5% or 2%.
The active herbicidal compounds of this invention may be formulated and/or applied with insecticides, fungicides, nematicides, plant growth regulators, fertilizers, or other agricultural chemicals and may be used as effective soil sterilants as well as selective herbicides in agriculture. In applying an active compound of this invention, whether formulated alone or with other agricultural chemicals, an effective amount and concentration of the active compound is of course employed; for example, with Compound 3 (Table 1) applied postemergently, an amount in the range of about 15 to 125 g/ha, such as about 30 to 60 g/ha, may be employed for control of broad leaf weeds with tolerance for crops such as wheat and maize. For field use, where there are losses of herbicide, higher application rates (e.g. four times the rates mentioned above) may be employed.
The active herbicidal compounds of this invention may be used in combination with other herbicides, e.g. they may be mixed with, say, an equal or larger amount of a known herbicide such as chloroacetanilide herbicides such as 2-chloro-N-(2,6-diethylphenyl)-N-(methoxymethyl)acetamide (alachlor), 2-chloro-N-(2-ethyl-6-methylphenyl-N-(2-methoxy-1-methylethyl)acetamide (metolachlor), and N-chloroacetyl-N-(2,6-diethylphenyl)-glycine (diethatyl-ethyl); benzothiadiazinone herbicides such as 3-(1-methylethyl)-(1H)-2,1,3-benzothiadiazin-4-(3H)-one-2,2-dioxide (bentazon); triazine herbicides such as 6-chloro-N-ethyl-N-(1-methylethyl)-1,3,5-triazine-2,4-diamine (atrazine), and 2-[4-chloro-6-(ethylamino)-1,3,5-triazin-2-yl]amino-2-methylpropanenitrile (cyanazine); dinitroaniline herbicides such as 2,6-dinitro-N,N-dipropyl-4-(trifluoromethyl)benzeneamine (trifluralin); aryl urea herbicides such as N'-(3,4-dichlorophenyl)-N,N-dimethylurea (diuron) and N,N-dimethyl-N'-[3-(trifluoromethyl)phenyl]urea (fluometuron); and 2-[(2-chlorophenyl)methyl]-4,4-dimethyl-3-isoxazolidinone.
It is apparent that various modifications may be made in the formulation and application of the compounds of this invention without departing from the inventive concepts herein as defined in the claims.
TABLE 1______________________________________ ##STR28##Cmpd. No. X Y Q______________________________________ 1 F Cl CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2 H.sub.5 2 F Cl CH(Br)CH(Br)CO.sub.2 C.sub.2 H.sub.5 3 F Cl CH.sub.2 CH(Cl)CO.sub.2 C.sub.2 H.sub.5 4 F Cl CHCHCO.sub.2 C.sub.2 H.sub.5 5 Cl Cl CH.sub.2 CH.sub.2 CO.sub.2 CH.sub.3 6 Cl Cl CH.sub.2 CH(Cl)CO.sub.2 H 7 Cl Cl CH.sub.2 CH(Cl)CO.sub.2 CH.sub.3 8 Cl Cl CH.sub.2 CH(Cl)CO.sub.2 C.sub.2 H.sub.5 9 Cl Cl CH.sub.2 CH(Br)CO.sub.2 C.sub.2 H.sub.510 Cl Cl CH.sub.2 CH(Cl)CO.sub.2 CH(CH.sub.3).sub.211 Cl Cl CH.sub.2 CH(Cl)CO.sub.2 CH(CH.sub.3)CH.sub.2 CH.sub.312 Cl Cl CH.sub.2 CH(Cl)CO.sub.2 CH.sub.2 C.sub.6 H.sub.513 Cl Cl CH(Br)CH(Br)CO.sub.2 CH.sub.314 Cl Cl CH(Br)CH(Br)CO.sub.2 C.sub.2 H.sub.515 Cl Cl CH(CH.sub.3)CH(Cl)CO.sub.2 C.sub.2 H.sub.516 F Cl CH.sub.2 C(Cl)(CH.sub.3)CO.sub.2 CH.sub.317 Cl Cl CH.sub.2 CH(Cl)C(O)NH.sub.218 Cl Cl CH.sub.2 CH(Cl)C(O)NHCH.sub.319 Cl Cl CH.sub.2 CH(Cl)C(O)N(CH.sub.3).sub.220 Cl Cl CH.sub.2 CH(Cl)C(O)NH-cyclopropyl21 Cl Cl CH.sub.2 CH(Cl)C(O)NHCH.sub.2 CHCH.sub.222 Cl Cl CH.sub.2 CH(Cl)C(O)NHCH.sub.2 CN23 Cl Cl CH.sub.2 CH(Cl)C(O)NHOH24 Cl Cl CH.sub.2 CH(Cl)C(O)NHOCH.sub.325 Cl Cl CH.sub.2 CH(Cl)C(O)N(CH.sub.3)OCH.sub.326 Cl Cl CH.sub.2 CH(Cl)C(O)NHC.sub.6 H.sub.4 -4-Cl27 Cl Cl CH.sub.2 CH(Cl)C(O)NHCH.sub.2 C.sub.6 H.sub.4 -4-Cl28 Cl Cl CH.sub.2 CH(Cl)C(O)NHSO.sub.2 CH.sub.329 Cl Cl CH.sub.2 CH(Cl)C(O)NHSO.sub.2 C.sub.6 H.sub.4 -4-Cl30 Cl Cl CH.sub.2 CH(Cl)C(O)NHSO.sub.2 C.sub.6 H.sub.4 -4-CH.sub.331 F Cl CH.sub.2 CH(CH.sub.3)CO.sub.2 CH.sub.332 F Cl CH.sub.2 CH(Cl)C(O)NH-cyclopropyl33 F Cl CH.sub.2 CH(Cl)C(O)NHCH.sub.2 CN34 F Cl CH.sub.2 CH(Cl)C(O)N(CH.sub.3)OCH.sub.335 F Cl CH.sub.2 CH(Cl)C(O)NHSO.sub.2 CH.sub.336 F Cl CH.sub.2 CH(Cl)C(O)NHSO.sub.2 CF.sub.337 F Cl CH.sub.2 CH(Cl)C(O)NHSO.sub.2 C.sub.6 H.sub.4 -2-Cl38 F Cl CH.sub.2 CH(Cl)C(O)NHSO.sub.2 C.sub.6 H.sub.4 -3-Cl39 F Cl CH.sub.2 CH(Cl)C(O)NHSO.sub.2 C.sub.6 H.sub.4 -4-Cl40 F Cl CH.sub.2 CH(Cl)C(O)NHSO.sub.2 CH(CH.sub.3).sub.241 F Cl CH.sub.2 CH(Cl)C(O)NHSO.sub.2 C.sub.6 H.sub.4 -4-CH.sub.342 Cl Cl CHCHCO.sub.2 CH.sub.343 Cl Cl CHCHCO.sub.2 C.sub.2 H.sub.544 Cl Cl CHCHCO.sub.2 CH.sub.2 C.sub.6 H.sub.545 F Cl CHC(CH.sub.3)CO.sub.2 CH.sub.346 Cl Cl CH.sub.2 CH(Cl)CN47 F Cl CH.sub.2 CH(Cl)CO.sub.2 CH.sub.348 F Cl CH.sub.2 CH(Cl)COOH49 Cl Cl CH.sub.2 CH(Cl)COCH.sub.350 Cl Cl CH.sub.2 CH(Cl)CONHCH.sub.2 CH.sub.2 CH.sub.351 Cl Cl CH.sub.2 CH(Cl)CONHCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.352 Cl Cl CH.sub.2 CH(Cl)CONHCH(CH.sub.3)CH.sub.2 CH.sub.353 Cl Cl CH.sub.2 CH(Cl)CONH-cyclopentyl54 Cl Cl CHCHCONH-cyclopentyl55 Cl Cl CHCHCONHCH.sub.2 CH.sub.2 CH.sub.356 Cl Cl CHCHCONHCH(CH.sub.3)CH.sub.2 CH.sub.357 F Cl CHCHCO.sub.2 CH.sub.358 F Cl CH.sub.2 CH(Cl)CO.sub.2 CH(CH.sub.3).sub.259 Cl Cl CH.sub.2 CH(Cl)CONHCH(CH.sub.3).sub.260 Cl Cl CHCHCONHCH(CH.sub.3).sub.261 Cl Cl CH.sub.2 CH(Cl)CONHC.sub.2 H.sub.562 Cl Cl CHCHCONHC.sub.2 H.sub.563 F Cl CH.sub.2 CH(Cl)CHO64 F Cl CH.sub.2 CH(Cl)CO.sub.2 K65 F Cl CH.sub.2 CH(Cl)CO.sub.2 NH(C.sub.2 H.sub.5).sub.366 Cl Cl CH.sub.2 CH(Cl)CO.sub.2 Na67 Cl Cl CH.sub.2 CH(Cl)CO.sub.2 NH(C.sub.2 H.sub.5).sub.3______________________________________
TABLE 1A______________________________________ ##STR29##Cmpd No. X Y Q______________________________________ A1 Cl Cl CH.sub.2 CH.sub.2 CO.sub.2 CH.sub.3 A2 Cl Cl CH.sub.2 CH(Cl)CO.sub.2 H A3 Cl Cl CH.sub.2 CH(Cl)CO.sub.2 CH.sub.3 A4 Cl Cl CH.sub.2 CH(Cl)CO.sub.2 C.sub.2 H.sub.5 A5 F Cl CH.sub.2 CH(Cl)CO.sub.2 C.sub.2 H.sub.5 A6 Cl Cl CH.sub.2 CH(Br)CO.sub.2 C.sub.2 H.sub.5 A7 Cl Cl CH.sub.2 CH(Cl)CO.sub.2 CH(CH.sub.3).sub.2 A8 Cl Cl CH.sub.2 CH(Cl)CO.sub.2 CH(CH.sub.3)CH.sub.2 CH.sub.3 A9 Cl Cl CH.sub.2 CH(Cl)CO.sub.2 CH.sub.2 C.sub.6 H.sub.5A10 Cl Cl CH(Br)CH(Br)CO.sub.2 CH.sub.3A11 Cl Cl CH(Br)CH(Br)CO.sub.2 C.sub.2 H.sub.5A12 Cl Cl CH(CH.sub.3)CH(Cl)CO.sub. 2 C.sub.2 H.sub.5A13 F Cl CH.sub.2 C(Cl)(CH.sub.3)CO.sub.2 CH.sub.3A14 Cl Cl CH.sub.2 CH(Cl)C(O)NH.sub.2A15 Cl Cl CH.sub.2 CH(Cl)C(O)NHCH.sub.3A16 Cl Cl CH.sub.2 CH(Cl)C(O)N(CH.sub.3).sub.2A17 Cl Cl CH.sub.2 CH(Cl)C(O)NH-cyclopropylA18 Cl Cl CH.sub.2 CH(Cl)C(O)NHCH.sub.2 CHCH.sub.2A19 Cl Cl CH.sub.2 CH(Cl)C(O)NHCH.sub.2 CNA20 Cl Cl CH.sub.2 CH(Cl)C(O)NHOHA21 Cl Cl CH.sub.2 CH(Cl)C(O)NHOCH.sub.3A22 Cl Cl CH.sub.2 CH(Cl)C(O)N(CH.sub.3)OCH.sub.3A23 Cl Cl CH.sub.2 CH(Cl)C(O)NHC.sub.6 H.sub.4 -4-ClA24 Cl Cl CH.sub.2 CH(Cl)C(O)NHCH.sub.2 C.sub.6 H.sub.4 -4-ClA25 Cl Cl CH.sub.2 CH(Cl)C(O)NHSO.sub.2 CH.sub.3A26 Cl Cl CH.sub.2 CH(Cl)C(O)NHSO.sub.2 C.sub.6 H.sub.4 -4-ClA27 Cl Cl CH.sub.2 CH(Cl)C(O)NHSO.sub.2 C.sub.6 H.sub.4 -4-CH.sub.3A28 F Cl CH.sub.2 CH(CH.sub.3)CO.sub.2 CH.sub.3A29 F Cl CH.sub.2 CH(Cl)C(O)NH-cyclopropylA30 F Cl CH.sub.2 CH(Cl)C(O)NHCH.sub.2 CNA31 F Cl CH.sub.2 CH(Cl)C(O)N(CH.sub.3)OCH.sub.3A32 F Cl CH.sub.2 CH(Cl)C(O)NHSO.sub.2 CH.sub.3A33 F Cl CH.sub.2 CH(Cl)C(O)NHSO.sub.2 CF.sub.3A34 F Cl CH.sub.2 CH(Cl)C(O)NHSO.sub.2 C.sub.6 H.sub.4 -2-ClA35 F Cl CH.sub.2 CH(Cl)C(O)NHSO.sub.2 C.sub.6 H.sub.4 -3-ClA36 F Cl CH.sub.2 CH(Cl)C(O)NHSO.sub.2 C.sub.6 H.sub.4 -4-ClA37 F Cl CH.sub.2 CH(Cl)C(O)NHSO.sub.2 CH(CH.sub.3).sub.2A38 F Cl CH.sub.2 CH(Cl)C(O)NHSO.sub.2 C.sub.6 H.sub.4 -4-CH.sub.3A39 Cl Cl CHCHCO.sub.2 CH.sub.3A40 Cl Cl CHCHCO.sub.2 C.sub.2 H.sub.5A41 F Cl CHCHCO.sub.2 C.sub.2 H.sub.5A42 Cl Cl CHCHCO.sub.2 CH.sub.2 C.sub.6 H.sub.5A43 F Cl CHC(CH.sub.3)CO.sub.2 CH.sub.3A44 Cl Cl CH.sub.2 CH(Cl)CNA45 F Cl CH.sub.2 CH(Cl)CO.sub.2 CH.sub.3A46 F Cl CH.sub.2 CH(Cl)COOHA47 Cl Cl CH.sub.2 CH(Cl)COCH.sub.3A48 Cl Cl CH.sub.2 CH(Cl)CONHCH.sub.2 CH.sub.2 CH.sub.3A49 Cl Cl CH.sub.2 CH(Cl)CONHCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3A50 Cl Cl CH.sub.2 CH(Cl)CONHCH(CH.sub.3)CH.sub.2 CH.sub.3A51 Cl Cl CH.sub.2 CH(Cl)CONH-cyclopentylA52 Cl Cl CHCHCONH-cyclopentylA53 Cl Cl CHCHCONHCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3A54 Cl Cl CHCHCONHCH(CH.sub.3)CH.sub.2 CH.sub.3A55 F Cl CHCHCO.sub.2 CH.sub.3A56 F Cl CH.sub.2 CH(Cl)CO.sub.2 CH(CH.sub.3).sub.2A57 Cl Cl CH.sub.2 CH(Cl)CONHCH(CH.sub.3).sub.2A58 Cl Cl CHCHCONHCH(CH.sub.3).sub.2A59 Cl Cl CH.sub.2 CH(Cl)CONHC.sub.2 H.sub.5A60 Cl Cl CHCHCONHC.sub.2 H.sub.5A61 F Cl CH.sub.2 CH(Cl)CHO______________________________________
TABLE 1B______________________________________ ##STR30## ##STR31##Cmpd No. X Y Q______________________________________ B1 F Cl CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2 H.sub.5 B2 F Cl CH(Br)CH(Br)CO.sub.2 C.sub.2 H.sub.5 B3 F Cl CH.sub.2 CH(Cl)CO.sub.2 C.sub.2 H.sub.5 B4 F Cl CHCHCO.sub.2 C.sub.2 H.sub.5 B5 Cl Cl CH.sub.2 CH.sub.2 CO.sub.2 CH.sub.3 B6 Cl Cl CH.sub.2 CH(Cl)CO.sub.2 H B7 Cl Cl CH.sub.2 CH(Cl)CO.sub.2 CH.sub.3 B8 Cl Cl CH.sub.2 CH(Cl)CO.sub.2 C.sub.2 H.sub.5 B9 Cl Cl CH.sub.2 CH(Br)CO.sub.2 C.sub.2 H.sub.5B10 Cl Cl CH.sub.2 CH(Cl)CO.sub.2 CH(CH.sub.3).sub.2B11 Cl Cl CH.sub.2 CH(Cl)CO.sub.2 CH(CH.sub.3)CH.sub.2 CH.sub.3B12 Cl Cl CH.sub.2 CH(Cl)CO.sub.2 CH.sub.2 C.sub.6 H.sub.5B13 Cl Cl CH(Br)CH(Br)CO.sub.2 CH.sub.3B14 Cl Cl CH(Br)CH(Br)CO.sub.2 C.sub.2 H.sub.5B15 Cl Cl CH(CH.sub.3)CH(Cl)CO.sub.2 C.sub.2 H.sub.5B16 F Cl CH.sub.2 C(Cl)(CH.sub.3)CO.sub.2 CH.sub.3B17 Cl Cl CH.sub.2 CH(Cl)C(O)NH.sub.2B18 Cl Cl CH.sub.2 CH(Cl)C(O)NHCH.sub.3B19 Cl Cl CH.sub.2 CH(Cl)C(O)N(CH.sub.3).sub.2B20 Cl Cl CH.sub.2 CH(Cl)C(O)NH-cyclopropylB21 Cl Cl CH.sub.2 CH(Cl)C(O)NHCH.sub.2 CHCH.sub.2B22 Cl Cl CH.sub.2 CH(Cl)C(O)NHCH.sub.2 CNB23 Cl Cl CH.sub.2 CH(Cl)C(O)NHOHB24 Cl Cl CH.sub.2 CH(Cl)C(O)NHOCH.sub.3B25 Cl Cl CH.sub.2 CH(Cl)C(O)N(CH.sub.3)OCH.sub.3B26 Cl Cl CH.sub.2 CH(Cl)C(O)NHC.sub.6 H.sub.4 -4-ClB27 Cl Cl CH.sub.2 CH(Cl)C(O)NHCH.sub.2 C.sub.6 H.sub.4 -4-ClB28 Cl Cl CH.sub.2 CH(Cl)C(O)NHSO.sub.2 CH.sub.3B29 Cl Cl CH.sub.2 CH(Cl)C(O)NHSO.sub.2 C.sub.6 H.sub.4 -4-ClB30 Cl Cl CH.sub.2 CH(Cl)C(O)NHSO.sub.2 C.sub.6 H.sub.4 -4-CH.sub.3B31 F Cl CH.sub.2 CH(CH.sub.3)CO.sub.2 CH.sub.3B32 F Cl CH.sub.2 CH(Cl)C(O)NH-cyclopropylB33 F Cl CH.sub.2 CH(Cl)C(O)NHCH.sub.2 CNB34 F Cl CH.sub.2 CH(Cl)C(O)N(CH.sub.3)OCH.sub.3B35 F Cl CH.sub.2 CH(Cl)C(O)NHSO.sub.2 CH.sub.3B36 F Cl CH.sub.2 CH(Cl)C(O)NHSO.sub.2 CF.sub.3B37 F Cl CH.sub.2 CH(Cl)C(O)NHSO.sub.2 C.sub.6 H.sub.4 -2-ClB38 F Cl CH.sub.2 CH(Cl)C(O)NHSO.sub.2 C.sub.6 H.sub.4 -3-ClB39 F Cl CH.sub.2 CH(Cl)C(O)NHSO.sub.2 C.sub.6 H.sub.4 -4-ClB40 F Cl CH.sub.2 CH(Cl)C(O)NHSO.sub.2 CH(CH.sub.3).sub.2B41 F Cl CH.sub.2 CH(Cl)C(O)NHSO.sub.2 C.sub.6 H.sub.4 -4-CH.sub.3B42 Cl Cl CHCHCO.sub.2 CH.sub.3B43 Cl Cl CHCHCO.sub.2 C.sub.2 H.sub.5B44 Cl Cl CHCHCO.sub.2 CH.sub.2 C.sub.6 H.sub.5B45 F Cl CHC(CH.sub.3)CO.sub.2 CH.sub.3B46 Cl Cl CH.sub.2 CH(Cl)CNB47 F Cl CH.sub.2 CH(Cl)CO.sub.2 CH.sub.3B48 F Cl CH.sub.2 CH(Cl)COOHB49 Cl Cl CH.sub.2 CH(Cl)COCH.sub.3B50 Cl Cl CH.sub.2 CH(Cl)CONHCH.sub.2 CH.sub.2 CH.sub.3B51 Cl Cl CH.sub.2 CH(Cl)CONHCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3B52 Cl Cl CH.sub.2 CH(Cl)CONHCH(CH.sub.3)CH.sub.2 CH.sub.3B53 Cl Cl CH.sub.2 CH(Cl)CONH-cyclopentylB54 Cl Cl CHCHCONH-cyclopentylB55 Cl Cl CHCHCONHCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3B56 Cl Cl CHCHCONHCH(CH.sub.3)CH.sub.2 CH.sub.3B57 F Cl CHCHCO.sub.2 CH.sub.3B58 F Cl CH.sub.2 CH(Cl)CO.sub.2 CH(CH(CH.sub.3).sub.2B59 Cl Cl CH.sub.2 CH(Cl)CONHCH(CH.sub.3).sub.2B60 Cl Cl CHCHCONHCH(CH.sub.3).sub.2B61 Cl Cl CH.sub.2 CH(Cl)CONHC.sub.2 H.sub.5B62 Cl Cl CHCHCONHC.sub.2 H.sub.5B63 F Cl CH.sub.2 CH(Cl)CHOB64 F Cl CH.sub.2 CH(Cl)CO.sub.2 KB65 F Cl CH.sub.2 CH(Cl)CO.sub.2 NH(C.sub.2 H.sub.5).sub.3B66 Cl Cl CH.sub.2 CH(Cl)CO.sub.2 NaB67 Cl Cl CH.sub.2 CH(Cl)CO.sub.2 NH(C.sub.2 H.sub.5).sub.2______________________________________
Other representative compounds are compounds C1 to C67 which are identical with each of compounds B1 to B67 above except that in each case NHet is ##STR32##
Other representative compounds are compounds D1 to D67 which are identical with each of compounds B1 to B67 above except that in each case NHet is ##STR33##
Other representative compounds are compounds E1 to E67 which are identical with each of compounds B1 to B67 above except that in each case NHet is ##STR34##
Other representative compounds are compounds F1 to F67 which are identical with each of compounds B1 to B67 above except that in each case NHet is ##STR35##
Other representative compounds are compounds G1 to G67 which are identical with each of compounds B1 to B67 above except that in each case NHet is ##STR36##
Other representative compounds are compounds H1 to H67 which are identical with each of compounds B1 to B67 above except that in each case NHet is ##STR37##
Other representative compounds are compounds I1 to I67 which are identical with each of compounds B1 to B67 above except that in each case NHet is ##STR38##
Other representative compounds are compounds J1 to J67 which are identical with each of compounds B1 to B67 above except that in each case NHet is ##STR39##
Other representative compounds are compounds K1 to K67 which are identical with each of compounds B1 to B67 above except that in each case NHet is ##STR40##
Other representative compounds are compounds M1 to M67 which are identical with each of compounds B1 to B67 above except that in each case NHet is ##STR41##
Other representative compounds are compounds N1 to N67 which are identical with each of compounds B1 to B67 above except that in each case NHet is ##STR42## where R.sup.n is isopropyl.
Other representative compounds are identical to compounds N1 to N67 except that R.sup.n is CH.sub.3. Other representative compounds are those which are identical to N1 to N67 except that R.sup.n is C.sub.2 H.sub.5. Still other representative compounds are identical to N1 to N67 except that R.sup.n is CH.sub.2 CH.sub.2 CH.sub.3. Other representative compounds are identical to N1 to N67 except that R.sup.n is CH.sub.2 CH.sub.2 CH.sub.2 F.
Other representative compounds are compounds P1 to P67 which are identical with each of compounds B1 to B67 above except that in each case NHet is ##STR43##
Other representative compounds are compounds Q1 to Q67 which are identical with each of compounds B1 to B67 above except that in each case NHet is ##STR44##
Other representative compounds are compounds R.sup.1 to R67 which are identical with each of compounds B1 to B67 above except that in each case NHet is ##STR45##
Other representative compounds are compounds S1 to S67 which are identical with each of compounds B1 to B67 above except that in each case NHet is ##STR46##
Other representative compounds are compounds T1 to T67 which are identical with each of compounds B1 to B67 above except that in each case NHet is ##STR47##
Other representative compounds are compounds U1 to U67 which are identical with each of compounds B1 to B67 above except that in each case NHet is ##STR48##
Other representative compounds are compounds V1 to V67 which are identical with each of compounds B1 to B67 above except that in each case NHet is ##STR49##
Other representative compounds are compounds W1 to W67 which are identical with each of compounds B1 to B67 above except that in each case NHet is ##STR50##
Other representative compounds are compounds X1 to X67 which are identical with each of compounds B1 to B67 above except that in each case NHet is ##STR51##
Other representative compounds are compounds XA1-XA67 which are identical to each of compounds B1 to B67 above except that in each case NHet is ##STR52##
TABLE 2______________________________________Preemergence Herbicidal Activity% Control @ 0.5 kg/haCmpd. No.Species 1 2 3 4______________________________________Cotton 30 20 95 40Soybean 5 5 0 10Corn 5 10 5 5Rice 30 5 20 20Wheat 5 5 15 30Morningglory 10 80 100 80Wild Mustard 100 100 100 100Velvetleaf 100 100 100 100Barnyardgrass 80 40 20 80Green Foxtail 70 0 60 70Johnsongrass 90 5 70 70______________________________________
TABLE 2A______________________________________PREEMERGENCE HERBICIDAL ACTIVITY(% CONTROL)______________________________________ Compound No. 1A 2A 3A Rate (kg/ha)Species 0.5 0.5 0.5______________________________________Cotton 0 90 50Soybean 0 0 5Field Corn 30 10 10Rice 60 10 5Wheat 5 0 5Morningglory 50 100 95Wild Mustard 70 90 100Velvetleaf 95 100 100Barnyardgrass 30 5 70Green Foxtail 50 10 85Johnsongrass 50 30 50______________________________________ Compound No. 4A 5A 6A Rate (kg/ha)Species 0.5 0.5 0.5______________________________________Cotton 70 90 30Soybean 5 0 5Field Corn 10 5 10Rice 15 10 5Wheat 10 20 0Morningglory 100 100 50Wild Mustard 100 100 60Velvetleaf 100 100 100Barnyardgrass 40 20 0Green Foxtail 5 5 0Johnsongrass 70 40 5______________________________________ Compound No. 7A 8A 9A Rate (kg/ha)Species 0.5 0.5 0.5______________________________________Cotton 90 80 80Soybean 0 0 0Field Corn 15 10 10Rice 15 5 30Wheat 0 0 5Morningglory 90 40 100Wild Mustard 100 90 95Velvetleaf 95 100 100Barnyardgrass 50 5 70Green Foxtail 50 10 30Johnsongrass 20 60 85______________________________________ Compound No. 10A 11A 12A Rate (kg/ha)Species 0.5 0.5 0.5______________________________________Cotton 5 10 50Soybean 10 0 0Field Corn 0 20 40Rice 15 40 30Wheat 0 5 60Morningglory 30 50 100Wild Mustard 100 100 95Velvetleaf 100 100 100Barnyardgrass 85 100 95Green Foxtail 100 95 100Johnsongrass 50 90 85______________________________________ Compound No. 13A 14A 15A Rate (kg/ha)Species 0.5 0.5 0.5______________________________________Cotton 30 90 80Soybean 0 95 95Field Corn 10 95 95Rice 5 95 95Wheat 20 95 95Morningglory 100 100 95Wild Mustard 100 100 100Velvetleaf 100 100 100Barnyardgrass 60 100 95Green Foxtail 5 100 100Johnsongrass 30 100 100______________________________________ Compound No. 16A 17A 18A Rate (kg/ha)Species 0.5 0.5 0.5______________________________________Cotton 80 60 70Soybean 90 100 90Field Corn 95 95 90Rice 95 90 90Wheat 95 100 95Morningglory 70 100 95Wild Mustard 100 100 100Velvetleaf 100 100 100Barnyardgrass 95 100 90Green Foxtail 100 100 100Johnsongrass 95 100 95______________________________________ Compound No. 19A 22A 23A Rate (kg/ha)Species 0.5 0.5 0.5______________________________________Cotton 20 40 15Soybean 50 5 5Field Corn 80 85 0Rice 60 30 5Wheat 95 90 0Morningglory 100 95 15Wild Mustard 100 100 95Velvetleaf 100 100 100Barnyardgrass 95 100 5Green Foxtail 95 100 95Johnsongrass 100 95 20______________________________________ Compound No. 24A 25A 26A Rate (kg/ha)Species 0.5 0.5 0.5______________________________________Cotton 30 80 85Soybean 10 5 5Field Corn 5 80 50Rice 5 40 40Wheat 5 85 50Morningglory 50 100 80Wild Mustard 100 100 100Velvetleaf 100 100 100Barnyardgrass 70 70 15Green Foxtail 100 95 60Johnsongrass 50 80 50______________________________________ Compound No. 27A 28A 29A Rate (kg/ha)Species 0.5 0.25 0.5______________________________________Cotton 10 0 100Soybean 5 0 100Field Corn 70 5 100Rice 40 5 100Wheat 70 15 100Morningglory 85 20 100Wild Mustard 100 50 100Velvetleaf 100 100 100Barnyardgrass 80 40 100Green Foxtail 95 0 100Johnsongrass 70 20 100______________________________________ Compound No. 30A 31A 33A Rate (kg/ha)Species 0.25 0.5 0.25______________________________________Cotton 80 70 10Soybean 80 100 0Field Corn 85 95 15Rice 95 85 0Wheat 95 95 5Morningglory 100 100 85Wild Mustard 100 100 90Velvetleaf 100 100 95Barnyardgrass 80 100 5Green Foxtail 100 100 5Johnsongrass 85 95 15______________________________________ Compound No. 34A 36A 37A Rate (kg/ha)Species 0.25 0.25 0.25______________________________________Cotton 95 30 70Soybean 0 0 5Field Corn 5 15 30Rice 5 5 40Wheat 5 10 15Morningglory 100 100 100Wild Mustard 95 100 100Velvetleaf 100 100 100Barnyardgrass 5 90 30Green Foxtail 0 85 0Johnsongrass 10 10 30______________________________________ Compound No. 39A 40A 41A Rate (kg/ha)Species 0.5 0.5 0.5______________________________________Cotton 30 10 20Soybean 10 15 0Field Corn 30 30 10Rice 60 40 10Wheat 10 5 30Morningglory 5 20 95Wild Mustard 95 100 100Velvetleaf 95 100 100Barnyardgrass 80 90 10Green Foxtail 100 100 70Johnsongrass 95 30 20______________________________________ Compound No. 42A 43A Rate (kg/ha)Species 0.5 0.5______________________________________Cotton 90 5Soybean 5 5Field Corn 5 10Rice 15 10Wheat 5 10Morningglory 20 80Wild Mustard 80 100Velvetleaf 10 100Barnyardgrass 20 50Green Foxtail 50 100Johnsongrass 20 40______________________________________
TABLE 3______________________________________Postemergence Herbicidal Activity% Control @ 0.5 kg/haCmpd. No.Species 1 2 3 4______________________________________Species Cotton 100 90 100 100Soybean 70 60 90 75Corn 60 50 30 70Rice 40 15 50 30Wheat 30 40 95 70Morningglory 85 95 100 90Wild Mustard 100 100 100 100Velvetleaf 100 100 100 100Barnyardgrass 50 10 15 50Green Foxtail 60 30 15 90Johnsongrass 90 -- 95 80______________________________________
TABLE A______________________________________POSTEMERGENCE HERBICIDAL ACTIVITY(% CONTROL)______________________________________ Compound No. 1A 2A 3A Rate (kg/ha)Species 0.5 0.5 0.5______________________________________Cotton 95 100 100Soybean 50 40 60Field Corn 50 30 60Rice 20 30 40Wheat 30 40 20Morningglory 90 9500Wild Mustard 80 95 100Velvetleaf 100 100 100Barnyardgrass 50 30 70Green Foxtail 50 15 95Johnsongrass 30 ND 80______________________________________ Compound No. 4A 5A 6A Rate (kg/ha)Species 0.5 0.5 0.5______________________________________Cotton 90 100 100Soybean 80 80 40Field Corn 50 50 40Rice 50 60Wheat 50 80 30Morningglory 100 100 90Wild Mustard 100 100 95Velvetleaf 100 100 100Barnyardgrass 85 90 20Green Foxtail 50 100 15Johnsongrass ND 70 10______________________________________ Compound No. 7A 8A 9A Rate (kg/ha)Species 0.5 0.5 0.5______________________________________Cotton 100 100 100Soybean 80 50 95Field Corn 40 40 50Rice 40 20 20Wheat 40 40 20Morningglory 100 100 100Wild Mustard 100 100 100Velvetleaf 100 100 100Barnyardgrass 60 40 20Green Foxtail 30 40 15Johnsongrass 40 30 40______________________________________ Compound No. 10A 11A 12A Rate (kg/ha)Species 0.5 0.5 0.5______________________________________Cotton 100 95 100Soybean 60 40 60Field Corn 50 50 70Rice 20 15 50Wheat 40 30 95Morningglory 90 90 100Wild Mustard 95 70 95Velvetleaf 100 100 100Barnyardgrass 70 90 95Green Foxtail 40 50 85Johnsongrass ND ND 95______________________________________ Compound No. 13A 14A 15A Rate (kg/ha)Species 0.5 0.5 0.5______________________________________Cotton 100 100 100Soybean 70 85 95Field Corn 50 70 90Rice 50 30 90Wheat 90 90 90Morningglory 100 100 100Wild Mustard 100 100 95Velvetleaf 100 100 100Barnyardgrass 95 95 100Green Foxtail 100 95 100Johnsongrass 70 ND 90______________________________________ Compound No. 16A 17A 18A Rate (kg/ha)Species 0.5 0.5 0.5______________________________________Cotton 95 100 100Soybean 80 100 80Field Corn 80 100 70Rice 70 95 80Wheat 80 100 90Morningglory 100 100 95Wild Mustard 85 100 85Velvetleaf 100 100 100Barnyardgrass 100 95 70Green Foxtail 95 100 100Johnsongrass 85 95 80______________________________________ Compound No. 19A 22A 23A Rate (kg/ha)Species 0.5 0.5 0.5______________________________________Cotton 100 100 70Soybean 90 50 40Field Corn 95 85 60Rice 80 40 25Wheat 100 80 30Morningglory 100 100 90Wild Mustard 80 80 80Velvetleaf 100 100 90Barnyardgrass 60 85 20Green Foxtail 90 90 40Johnsongrass 95 95 40______________________________________ Compound No. 24A 25A 26A Rate (kg/ha)Species 0.5 0.5 0.5______________________________________Cotton 100 100 100Soybean 80 70 90Field Corn 60 85 60Rice 10 60 40Wheat 20 60 40Morningglory 100 100 100Wild Mustard 80 100 95Velvetleaf 100 100 100Barnyardgrass 40 30 70Green Foxtail 80 70 95Johnsongrass 60 100 60______________________________________ Compound No. 27A 28A 29A Rate (kg/ha)Species 0.5 0.25 0.5______________________________________Cotton 100 80 100Soybean 80 60 95Field Corn 85 80 100Rice 60 50 95Wheat 80 60 100Morningglory 100 85 100Wild Mustard 100 90 100Velvetleaf 100 100 100Barnyardgrass 30 30 100Green Foxtail 60 95 100Johnsongrass 80 60 100______________________________________ Compound No. 30A 31A 33A Rate (kg/ha)Species 0.25 0.5 0.25______________________________________Cotton 100 100 100Soybean 85 85 80Field Corn 80 70 50Rice 70 60 15Wheat 100 100 20Morningglory 100 100 100Wild Mustard 100 100 100Velvetleaf 100 100 100Barnyardgrass 50 95 30Green Foxtail 100 95 15Johnsongrass 95 95 20______________________________________ Compound No. 34A 36A 37A Rate (kg/ha)Species 0.25 0.25 0.25______________________________________Cotton 100 100 100Soybean 60 40 70Field Corn 30 60 70Rice 20 10 40Wheat 50 20 20Morningglory 100 100 100Wild Mustard 100 100 100Velvetleaf 100 100 100Barnyardgrass 60 90 50Green Foxtail 70 100 5Johnsongrass 50 30 30______________________________________ Compound No. 39A 30A 41A Rate (kg/ha)Species 0.5 0.5 0.5______________________________________Cotton 70 90 100Soybean 40 40 95Field Corn 70 50 70Rice 40 15 70Wheat 30 40 70Morningglory 70 90 100Wild Mustard 100 80 100Velvetleaf 100 95 100Barnyardgrass 70 80 95Green Foxtail 80 40 100Johnsongrass 85 ND 80______________________________________ Compound No. 42A 43A Rate (kg/ha)Species 0.5 0.5______________________________________Cotton 100 100Soybean 40 100Field Corn 70 100Rice 15 60Wheat 15 95Morningglory 100 100Wild Mustard 90 100Velvetleaf 100 100Barnyardgrass 5 95Green Foxtail 10 100Johnsongrass 60 70______________________________________

Number	Name	Date	Kind
4318731	Kajioka et al.	Mar 1982
4439229	Swithenbank	Mar 1984

Number	Date	Country
0011693	Jun 1980	EPX
0275131	Jul 1988	EPX
0300387	Jan 1989	EPX
0300398	Jan 1989	EPX
3603789	Aug 1987	DEX
56-53662	May 1981	JPX
58-225070	Dec 1983	JPX

Herbicidal compounds

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Entry
PCT International Application No. WO 87/07602, Published Dec. 17, 1987.
PCT International Application No. 86/04481, published Aug. 14, 1986.
PCT International Application No. WO 85/01939, published May 19, 1985.