Herbicidal substituted pyrazole compounds

Description

CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of U.S. provisional application No. 60/019,403, filed Nov. 15, 1995.
FIELD OF THE INVENTION
In one aspect, this invention relates to novel substituted pyrazole compounds and derivatives thereof which exhibit unexpectedly desirable herbicidal activity. In other aspects, this invention relates to herbicidal compositions containing a substituted pyrazole compound or derivative thereof and an agriculturally acceptable carder and to a method of controlling undesirable vegetation by applying to an area where control is desired an herbicidally effective mount of a substituted pyrazole compound or derivative thereof.
BACKGROUND OF THE INVENTION
The need for effective herbicides needs no special emphasis. The control of weeds and undesirable vegetation is of great economic importance since weed competition inhibits the production of foliage, fruit or seed of agricultural crops. The presence of weeds can reduce harvesting efficiency and the quality of the harvested crop. Weeds on non-cropped areas may cause a fire hazard, undesirable drifting of sand or snow, and/or irritation to persons with allergies. Thus, suppression of undesirable weed growth is very advantageous.
Accordingly, it is an object of this invention to provide effective novel herbicidal compounds, as well as to provide novel herbicidal compositions and novel methods of controlling weeds.
SUMMARY OF THE INVENTION
In one aspect, this invention is directed to compounds of formula (I): ##STR2## wherein: R.sup.1 is optionally substituted C.sub.1 -C.sub.6 alkyl or C.sub.1 -C.sub.6 haloalkyl;
R.sup.2 is optionally substituted C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 haloalkyl or C.sub.3 -C.sub.6 cycloalkyl;
R.sup.3 is hydrogen, halogen, C.sub.1 -C.sub.6 alkyl or C.sub.1 -C.sub.6 haloalkyl;
R.sup.4 is optionally substituted C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 haloalkyl, optionally substituted C.sub.1 -C.sub.6 alkoxy, optionally substituted C.sub.3 -C.sub.6 cycloalkyl, optionally substituted (C.sub.1 -C.sub.6)alkoxy (C.sub.1 -C.sub.6)alkyl, optionally substituted C.sub.2 -C.sub.6 alkenyl, optionally substituted C.sub.2 -C.sub.6 alkynyl, optionally substituted aryl, optionally substituted heteroaryl, or an optionally substituted five or six membered heterocyclic ring containing one or more heteroatoms selected from O, N or S;
R.sup.5 is hydrogen, optionally substituted C.sub.1 -C.sub.6 alkyl or (C.sub.1 -C.sub.6)alkoxy or (C.sub.1 -C.sub.6) alkyl;
R.sup.6, R.sup.7, R.sup.8 and R.sup.9 are independently selected from hydrogen, halogen, optionally substituted C.sub.1 -C.sub.6 alkyl, optionally substituted C.sub.2 -C.sub.6 alkenyl, optionally substituted C.sub.2 -C.sub.6 alkynyl, optionally substituted C.sub.1 -C.sub.6 alkoxy, (C.sub.1 -C.sub.6)alkoxy-(C.sub.1 -C.sub.6)alkyl, C.sub.1 -C.sub.6 haloalkyl, C.sub.1 -C.sub.6 haloalkoxy, cyano, nitro, --S(O).sub.P --R.sup.10 wherein p is 0, 1 or 2 and R.sup.10 is C.sub.1 -C.sub.3 alkyl or C.sub.1 -C.sub.3 haloalkyl, --OSO.sub.2 R.sup.11 wherein R.sup.11 is C.sub.1 -C.sub.3 alkyl, --CO.sub.2 H, --COR.sup.12, --COOR.sup.12, or --NHCOR.sup.12 wherein R.sup.12 is C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 haloalkyl, optionally substituted C.sub.3 -C.sub.6 cycloalkyl, optionally substituted aryl, optionally substituted heteroaryl, (C.sub.1 -C.sub.6)alkoxy-(C.sub.1 -C.sub.6)alkyl or C.sub.1 -C.sub.6 alkylthio, --CONR.sup.13 R.sup.14 or --NR.sup.13 R.sup.14 wherein R.sup.13 and R.sup.14 may be the same or different and are each hydrogen, C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 haloalkyl, optionally substituted C.sub.3 -C.sub.6 cycloalkyl, optionally substituted C.sub.2 -C.sub.6 alkenyl, optionally substituted C.sub.2 -C.sub.6 alkynyl optionally substituted aryl, optionally substituted heteroaryl, (C.sub.1 -C.sub.6)alkoxy-(C.sub.1 -C.sub.6)alkyl or C.sub.1 -C.sub.6 alkylthio, or R.sup.13 and R.sup.14 together with the N to which they are bound may form a ring having 3-8 members, one or more of which may be O, S or N; and
A is O, S, SO or SO.sub.2 ;
Y is O or S;
X is a carbon-carbon single bond, S, C.dbd.O or C.dbd.N;
and agriculturally acceptable salts thereof.
In another aspect, this invention is directed to an herbicidal composition containing (A) a compound of formula (Ia) ##STR3## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, A and Y have the same meanings as above and Z is a carbon-carbon single bond, O, S, C.dbd.O or C.dbd.N; or an agriculturally acceptable salt thereof; and
(B) a carrier therefor.
In still another aspect, this invention is directed to a method for controlling undesirable vegetation by applying to an area where such vegetation control is desired an herbicidally effective amount of a compound of formula (Ia): ##STR4## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, A, Y and Z have the same meanings as above, or an agriculturally acceptable salt thereof.
DETAILED DESCRIPTION OF THE INVENTION
The novel herbicidal compounds of this invention are of the formula (I): ##STR5## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, A, Y and X have the same meanings as above; and agriculturally acceptable salts thereof.
Preferably, R.sup.1 is C.sub.1 -C.sub.3 alkyl or C.sub.1 -C.sub.3 haloalkyl; R.sup.2 is C.sub.1 -C.sub.3 alkyl or C.sub.1 -C.sub.3 haloalkyl; R.sup.3 is hydrogen; and R.sup.5 is hydrogen.
Particularly preferred compounds include: N-�4-Methyl-2-�1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl!oxyphenyl!cyclopropane carboxamide; N-�4-Methyl-2-�1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl!oxyphenyl!isopropane carboxamide and N-�4-Methyl-2-�1-methyl-3-(trifluoromethyl)-1 H-pyrazol-5-yl!oxyphenyl!ethane carboxamide.
In another aspect, this invention is directed to a herbicidal composition containing (A) a compound of formula (Ia) ##STR6## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, A, Y and Z have the same meanings as above or an agriculturally acceptable salt thereof; and
(B) a carrier therefor.
In still another aspect, this invention is directed to a method for controlling undesirable vegetation by applying to an area where such vegetation control is desired an herbicidally effective amount of a compound formula (Ia): ##STR7## Wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, A, Y and Z have the same meanings as above, or an agriculturally acceptable salt thereof.
The formulae given above are intended to include tautomeric forms of the structures drawn therein, as well as physically distinguishable modifications of the compounds which may arise, for example, from different ways in which the molecules are arranged in a crystal lattice, or from the inability of parts of the molecule to rotate freely in relation to other parts, or from geometrical isomerism, or from intra molecular or intermolecular hydrogen bonding, or otherwise.
As employed herein "substituted" is intended to mean that the "substituted" group has one or more of the following substituents: halogen (i.e., fluorine, chlorine, bromine and iodine); C.sub.1 -C.sub.4 alkyl; C.sub.1 -C.sub.4 alkylthio; (C.sub.1 -C.sub.4)alkoxy; (C.sub.1 -C.sub.4)alkoxy-(C.sub.1 -C.sub.4)alkyl; (C.sub.1 -C.sub.6)alkoxyCO--; C.sub.1 -C.sub.4 alkyl-S(O).sub.P --; nitro; nitrile; cyano; carboxy and salts, amides and esters thereof, alkanoyl of 2 to 4 carbon atom; amino optionally substituted with one or two C.sub.1 -C.sub.4 alkyl; phenyl optionally substituted with one or more C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 alkyl-S(O).sub.P --, nitro, halogen, fluorine, chlorine, bromine, cyano, or CF.sub.3 groups; a five or six membered heterocyclic ring containing one or more heteroatoms selected from O, N or S; a five or six membered heterocyclic tins containing one or more heteroatoms selected from O, N or S optionally substituted with one or more C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 alkyl-S(O).sub.P --, nitro, halogen, fluorine, chloride, bromine, cyano, or CF.sub.3 groups.
The term "optionally substituted aryl" is intended to include aryl groups, such as phenyl, which are unsubstituted or are substituted with one or more of the foregoing substituents. Similarly, the term "optionally substituted heteroaryl" is intended to include heteroaryl groups, such as pyridyl, pyrimidyl, triazinyl, thienyl, furyl and thiazolyl, which are unsubstituted or are substituted with one or more of the substituents listed above.
The expression "salts, amides and esters thereof" used above in relation to carboxy substitution includes, for example, salts formed from alkali metals (e.g., sodium, potassium and lithium), alkaline earth metals (e.g., calcium and magnesium), the ammonium ion and substituted ammonium ions wherein one, two, three or four of the hydrogen atoms have been replaced by optionally substituted C.sub.1 -C.sub.6 hydrocarbyl moieties as defined above. Likewise, the carboxy substitution includes esters and amides which may be formed from the carboxy group and an optionally substituted C.sub.1 -C.sub.6 hydrocarbyl moiety in the case of the ester, or an optionally substituted C.sub.1 -C.sub.6 hydrocarbyl amine in the case of the amide.
In the above definitions, the term "halogen" includes fluoro, chloro, bromo and iodo groups. In polyhalogenated groups, the halogens may be the same or different.
The compounds of the present invention have been found to be active herbicides, possessing utility as pre-emergence and post-emergence herbicides. These compounds are useful against a wide range of plant species including broadleaf, grassy and perennial species. The compounds of this invention have also been found to be particularly effective in controlling undesirable vegetation typically found in rice crops.
The terms "herbicide" and "herbicidal" are used herein to denote the inhibitive control or modification of undesired plant growth. Inhibitive control and modification include all deviations from natural development, such as, total killing, growth retardation, defoliation, desiccation, regulation, stunting, tillering, stimulation, leaf burn and dwarfing. The term "herbicidally effective mount" is used to denote any amount which achieves such control or modification when applied to the undesired plants themselves or to the area in which these plants are growing. The term "plants" is intended to include germinated seeds, emerging seedlings and established vegetation, including both roots and above-ground portions.
The term "agriculturally acceptable salt" is easily determined by one of ordinary skill in the art and includes hydrohalide, acetic, sulfonic, phosphonic, inorganic and organic acid salts.
In general, the compounds of this invention may be prepared by treatment of an amine (II) with an acid chloride, acid anhydride, chlorothio formate, chloroformate or similar reagent in the presence of a suitable base and in a suitable solvent, according to the procedures described, for example, in J. March, Advanced Organic Chemistry, third edition, pp. 370-377, J. Wiley and Sons, New York (1985) and references therein. Many of these amines (II) are believed to be novel and are to be considered as yet another aspect of the present invention. Alternatively amine (II) may be treated sequentially with phosgene, or a phosgene equivalent, and an appropriate alcohol or thiol to generate (Ia) wherein R.sup.5 is hydrogen. Such procedures are well known in the literature (for example see Babad, H. and Zeiler, A. G., Chem Rev., 1973, 73, 75) �SCHEME 1! ##STR8##
Compounds of formula (Ia) wherein R.sup.5 is hydrogen may be convened readily into compounds of formula (Ia) wherein R.sup.5 is alkyl, alkoxyalkyl etc. by treatment with a suitable base, such as an alkali metal hydride and an appropriate alkylating agent (such as an alkyl halide) in a suitable solvent. Such reactions are well known to those skilled in the art, and need no further description here.
The amine (II) my be prepared by reduction of the corresponding nitro compound (III); such reductions are widely described in the literature. Those skilled in the art will know that the reduction my be carried out using a variety of reducing agents such as hydrogen in the presence of a catalyst, sodium borohydride in the; presence of a palladium catalyst, a sulfide or a metal such as iron in the presence of an acid; the particular method of choice will depend on, amongst other things, the compatibility of the reductants with other substituents present in the molecule. References to a variety of methods suitable for the reduction of aromatic nitro groups may be found in H. O. House, Modern Synthetic Reactions, ed. R. Breslow, W. A. Benjamin Inc., New York, 1965. �SCHEME 2! ##STR9##
When A is oxygen, the nitrobenzene of formula (III) may be prepared by reacting a compound of type (IV), where Hal is halogen such as fluorine or chlorine, with a hydroxypyrazole (V). The reaction is preferably carried out in an organic solvent such as N,N-dimethylformamide, dimethylsulfoxide, acetonitrile, a lower alcohol or a lower alkyl ketone and in the presence of a suitable base such as an alkali metal carbonate, hydroxide or alkoxide. Moderate temperatures, for example from 0.degree. to 100 .degree. C. are suitably employed. �SCHEME 3!. ##STR10## Compounds of the type (IV) are commercially available, or can be made by methods known in the literature.
Hydroxypyrazoles of the type (V) can be made by methods known in the art. Hydroxypyrazoles of the type (V), wherein R.sup.3 is halogen, may be made, for example by reaction of an unsubstituted pyrazole (R.sup.3 is H) with a halogenating agent such as sulfuryl chloride or N-bromosuccinimide in a suitable solvent. Compounds of the type (V), (R.sup.3 is hydrogen or alkyl) may be prepared by treatment of an appropriate .beta.-ketoester (VI) with an alkylhydrazine in a suitable solvent, as described, for example by DeStevens et al., JACS, 81, 6292, (1959) �SCHEME 4!. ##STR11## Such a procedure may produce a mixture of 5-hydroxy-(V) and 3-hydroxy-pyrazoles (VII), though normally these can be separated if desired by conventional purification techniques (see, for example, L. F. Lee et al., J. Heterocyclic Chem., 27, 243, �1990!).
Compounds wherein A is sulfur may be synthesized starting with compounds of formula (V). The hydroxy group at the 5-position of formula (V) is convened to its corresponding mercaptan. In a typical reaction, compounds of formula (V) are dissolved in a suitable solvent such as toluene and a stoichiometric excess of Lawesson's reagent �2,4-bis (4-methoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,4-disulfide! is added. The reaction mixture is heated to reflux and this temperature is maintained for about 10 hours. Subsequently, the reaction mixture is cooled and stirred at room temperature for about 18 hours. Next, the reaction mixture is poured into aqueous sodium carbonate, or the like, to quench the reaction. The resulting aqueous phase is acidified with a strong protic acid such as concentrated hydrochloric acid. The resulting acidic solution is worked up with conventional techniques to yield the desired mercaptan of formula (VIII). ##STR12##
The compounds of formula VIII are treated in the same manner as compounds of formula V to produce the corresponding intermediate compound in Scheme 3, wherein the pyrazole ring is linked to the phenyl ring via a sulfur atom. This sulfur intermediate is then treated as in Schemes 2 and 1 to generate the compounds of formula I and Ia wherein A is sulfur.
The compounds of the present invention are useful as herbicides and can be applied in a variety of ways known to those skilled in the art, at various concentrations. The compounds are useful in controlling the growth of undesirable vegetation by pre-emergent or post-emergent application to the locus where control is desired. The compositions of this invention comprise a compound of formula (Ia) above and a suitable carrier, which carriers are well known to one of ordinary skill in the art.
In practice, the compounds are applied as formulations containing the various adjuvants and carriers known to or used in the industry for facilitating dispersion. The choice of formulation and mode of application for any given compound may affect its activity, and selection will be made accordingly. The compounds of the invention may thus be formulated as wettable powders, as emulsifiable concentrates, as powders or dusts, as flowables, as solutions, suspensions or emulsions, or in controlled-release forms such as microcapsules. These formulations may contain as little as about 0.5% to as much as about 95% or more by weight of active ingredient. The optimum mount for any given compound will depend upon the nature of plants to be controlled. The rate of application will generally vary from about 0.01 to about 11.5 kilograms per hectare, preferably from about 0.02 to about 4.5 kilograms per hectare.
Wettable powders are in the form of finely divided particles which disperse readily in water or other liquid carriers. The particles contain the active ingredient retained in a solid matrix. Typical solid matrices include fuller's earth kaolin clays, silicas and other readily wettable organic or inorganic solids. Wettable powder normally contain about 5% to about 95% of the active ingredient plus a small amount of wetting, dispersing, or emulsifying agent.
Emulsifiable concentrates are homogeneous liquid compositions dispersible in water or other liquid, and may consist entirely of the active compound with a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthas, isophorone and other nonvolatile organic solvents. In use, these concentrates are dispersed in water or other liquid and normally applied as a spray to the area to be treated. The amount of active ingredient may range from about 0.5% to about 95% of the concentrate.
Dusts are free-flowing admixtures of the active ingredient with finely divided solids such as talc, clays, flours and other organic and inorganic solids which act as dispersants and carriers.
Microcapsules are typically droplets or solutions of the active material enclosed in an inert porous shell which allows escape of the enclosed material to the surrounds at controlled rates. Encapsulated droplets are typically about 1 to 50 microns in diameter. The enclosed material typically constitutes about 50 to 95% of the weight of the capsule, and may include solvent in addition to the active compound. Shell of membrane materials include natural and synthetic rubbers, cellulosic materials, styrene-butadiene copolymers, polyacrylonitriles, polyacrylates, polyesters, polyamides, polyureas, polyurethanes and starch xanthates.
Other useful formulations for herbicidal applications include simple solutions of the active ingredient in a solvent in which it is completely soluble al the desired concentration, such as water, acetone, alkylated naphthalenes, xylene and other organic solvents. Pressurized sprayers, wherein the active ingredient is dispersed in finely-divided form as a result of vaporization of a low boiling dispersant solvent carrier may also be used.
Many of these formulations include wetting, dispersing or emulsifying agents. Examples are alkyl and alkylaryl sulfonates and sulfates and their salts; polyhydric alcohols; polyethoxylated alcohols; esters and fatty amines. These agents when used normally comprise from 0.1% to 15% by weight of the formulation.
Each of the above formulations can be prepared as a package containing the herbicide together with other ingredients of the formulation (diluents, emulsifiers, surfactants, etc.). The formulations can also be prepared by a tank mix method, in which the ingredients are obtained separately and combined at the grower site.
The compounds of the present invention are also useful when combined with other herbicides and/or defoliants, desiccants, growth inhibitors, and the like. These other materials can comprise from about 5% to about 95% of the active ingredients in the formulations. These combinations frequently provide a higher level of effectiveness in controlling weeds and often provide results unattainable with separate formulations of the individual herbicides.
Examples of other herbicides, defoliants, desiccants and plant growth inhibitors with which the compounds of this invention can be combined are:
A. Benzo-2,1,3-thiadiazin-4-one-2,2-dioxides such as bentazone;
B. hormone herbicides, particularly the phenoxyalkanoic acids such as MCPA, MCPA-thioethyl, dichlorprop, 2,4,5-T, MCPB, 2,4-D2,4-DB, mecoprop, trichlopyr, fluroxypyr, clopyralid, and their derivatives (e.g. salts, esters and amides);
C. pyrazole derivatives such as pyrazoxyfen, pyrazolate and benzofenap;
D. dinitrophenols and their derivatives (e.g. acetates such as DNOC, dinoterb, dinoseb and its ester, dinoseb acetate;
E. dinitroaniline herbicides such as dinitramine, trifluralin ethalfluralin, pendimethalin; and oryzalin;
F. arylurea herbicides such as diuron, flumeturon, metoxuron, neburon, isoproturon, chlorotoluron, chloroxuron, linuron, monolinuron, chlorobromuron, daimuron, and methabenzthiazuron;
G. phenylcarbamoyloxyphenylcarbamates such as phenmedipham and desmedipham;
H. 2-phenylpyridazin-3-ones such as chloridazon, and norflurazon;
I. uracil herbicides such as lenacil, bromacil and termacil;
J. triazine herbicides such as atrazine, simazine, aziprotryne, cyanazine, prometryn, dimethametryn, simetryne, and terbutryn;
K. phosphorothioate herbicides such as piperophos, bensulide, and butamifos;
L. thiolcarbamate herbicides such as cycloate, vernolate, molinate, thiobencarb, butylate*, EPTC*, triallate, diallate, ethyl esprocarb, tiocarbazil, pyridate, and dimepiperate;
M. 1,2,4-triazin-5-one herbicides such as metamitron and metribuzin;
N. benzoic acid herbicides such as 2,3,6-TBA, dicamba and chloramben;
O. anilide herbicides such as pretilachlor, butachlor, the corresponding alachlor, the corresponding compound propachlor, propanil, metazachlor, metolachlor, acetochlor, and dimethachlor;
P. dihaiobenzonitrile herbicides such as dichlobenil, bromoxynil and ioxynil;
Q. haloalkanoic herbicides such as dalapon, TCA and salts thereof,
R. diphenylether herbicides such as lactofen, fluroglycofen or salts or esters thereof; nitrofen, bifenox, acifluorfen and salts and esters thereof, oxyfluorfen and fomesafen; chlornitrofen and chlomethoxyfen;
S. phenoxyphenoxypropionate herbicides such as diclofop and esters thereof such the methyl ester, fluazifop and esters thereof; haloxyfop and esters thereof; quizalofop and esters thereof and fenoxaprop and esters thereof such as the ethyl ester;
T. triketone and cyclohexanedione herbicides such as alloxydim and salts thereof; sethoxydim, cycloxydim, sulcotrione, tralkoxydim, and clethodim;
U. sulfonyl urea herbicides such as chlorosulfuron, sulfometuron, metsulfuron and esters thereof; benzsulfuron and esters thereof such as the ester thereof methyl, DPX-M6313, chlorimuron and esters such as the ethyl ester thereof; pirimisulfuron and esters such as the methyl ester thereof, DPX-LS300 and pyrazosulfuron;
V. imidazolidinone herbicides such as imazaquin, imazamethabenz, imazapyr and isopropylammonium salts thereof, imazathapyr;
W. arylanilide herbicides such as flamprop and esters thereof, benzoylpropethyl diflufenican;
X. amino acid herbicides such as glyphosate and gluyfosinate and their salts and esters, sulphosate, and bilanafos;
Y. organoarsenical herbicides such as MSMA;
Z. herbicidal amide derivative such as napropamide, propyzamide, carbetamide, tebutam, bromobutide, isoxaben, naproanilide, diphenamid, and naptalam;
AA. 4-benzoylisoxazole and 2-cyano-1,3-dione herbicides.
BB. miscellaneous herbicides including ethofumesate, cinmethylin, difenzoquat and salts thereof such as the methyl sulfate salt, clomazone, oxadiazon, bromofenoxim, barban, tridiphane, flurochloridone, quinchlorac and mefanacet; and
CC. contact herbicides, examples of which include bipyridylium herbicides such as those in which the active entity is paraquat and those in which the active entity is diquat.
* These compounds are preferably employed in combination with a safener such as 2,2-dichloro-N,N-di-2-propenylacetamide (dichlormid).
These formulations can be applied to the areas where control is desired by conventional methods. Dust and liquid compositions, for example, can be applied by the use of powerdusters, boom and hand sprayers and spray dusters. The formulations can also be applied from airplanes as a dust or a spray or by rope wick applications. The following are examples of typical formulations:
______________________________________5% dust: 5 parts active compound 95 parts talc2% dust: 2 parts active compound 1 part highly dispersed silicic acid 97 parts talc______________________________________
These dusts are formed by mixing the components then grinding the mixture to the desired particle size.
Wettable powders:
______________________________________70%: 70 parts active compound 5 parts sodium dibutylnaphthylsulfonate 3 parts naphthalenesulfonic acid/phenolsulfonic acid/phenol-sulfonic acid/formaldehyde condensate (3:2:1) 10 parts kaolin 12 parts Champagne chalk40%: 40 parts active compound 5 parts sodium lignin sulfonate 1 part sodium dibutylnaphthalene sulfonic acid 54 parts silicic acid25% 25 parts active compound 4.5 parts calcium lignin sulfate 1.9 parts Champagne Chalk/-hydroxyethyl cellulose (1:1) 8.3 parts sodium aluminum silicate 16.5 parts kieselguhr 46 parts kaolin10% 10 parts active compound 3 parts of a mixture of sodium salts of saturated fatty alcohol sulfates 5 parts naphthalenesulfonic acid/formaldehyde condensate 82 parts kaolin______________________________________
These wettable powders are prepared by intimately mixing the active compounds with the additives in suitable mixers, and grinding the resulting mixture in mills or rollers.
Emulsifiable concentrate:
______________________________________25% 25 parts active substance 2.5 parts epoxidized vegetable oil 10 parts of an alkylarylsulfonate/fatty alcohol polyglycol ether mixture 57.5 parts xylene______________________________________
The amount of the present compositions which constitute a herbicidally effective amount depends upon the nature of the seeds or plants to be controlled. The rate of application of active ingredients varies from about 0.01 to about 28 kilograms per hectare, preferably about 0.02 to about 11 kilograms per hectare with the actual amount depending on the overall costs and the desired results. It will be readily apparent to one skilled in the art that compositions exhibiting lower herbicidal activity will require a higher dosage than more active compounds for the same degree of control.

EXAMPLES
The following examples are intended to further illustrate the present invention and are not intended to limit the scope of this invention in any manner whatsoever.
Example 1
N-�4-Methyl-2-�1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl!oxyphenyl!-cyclopropane carboxamide Compound 1
A. Preparation of 5-hydroxy-1-methyl-3-trifluoromethylpyrazole
A. Methyl hydrazine (13.3 ml, 11.5 g, 0.25 mol) was added dropwise to a chilled (ice-bath) solution of ethyl 4,4,4-trifluoroacetoacetate (46.0 g, 0.25 mmol) in toluene (250 ml) at such a rate that the temperature of the reaction could be maintained below 10.degree. C. (ice-bath cooling). Once the addition was complete the ice-bath was removed and stirring continued at room temperature for 1 hour and then at reflux (Dean-Stark) for 3 h. The mixture was allowed to cool to room temperature and allowed to stand over 3 days. The precipitate was collected by filtration and washed with hexane to give 5-hydroxy-1-methyl-3-trifluoromethylpyrazole (30.7 g) as a colorless solid, m.p. 170.degree.-173.degree. C.
B. Preparation of 5-Methyl1-�1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl!oxy-2-nitrobenzene
5-Hydroxy-1-methyl-3-trifluoromethylpyrazole (8.30 g, 50 mmol) and powdered potassium carbonate (8.29 g, 60 mmol) were stirred together in dimethylsulfoxide (40 ml) for 30 minutes. 3-Fluoro-4-nitrotoluene (7.76 g, 50 mmol) was added and the mixture heated at 70.degree. C. for 17 h, then cooled to room temperature. The mixture was partitioned between diethyl ether and water, the ethereal extract washed with water and brine, dried over magnesium sulfate, filtered and the filtrate evaporated. The residue was further purified by flash column chromatography over silica gel, and the desired fraction collected and triturated with hexane to give the desired product as a pale yellow solid (6.20 g), m.p. 88.degree.-90.degree. C.
C. Preparation of2-Amino-5-methyl-1-�1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl!oxyphenyl!oxybenzene
5% Palladium on charcoal (0.2 g) was added to a solution of the compound prepared in B above (2.00 g, 6.6 mmol) in ethanol (50 ml) and the mixture shaken in a Parr hydrogenator at 50 p.s.i. for 2 h. The catalyst was removed by filtration and the filtrate evaporated in vacuo. The residue was further purified by flash column chromatography over silica gel, and the desired amine obtained as a pale pink oil (1.73 g).
D. Preparation of N-�4-Methyl-2-�l-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl!oxyphenyl!cyclopropane carboxamide
Cyclopropylcarbamyl chloride (0.22 ml, 0.25 g, 2.4 mmol) was added to a mixture of triethylamine (0.50 ml. 0.36 g, 3.6 mmol) and the amine prepared in C above (0.66 g, 2.4 mmol) in dichloromethane (10 ml) and the mixture stirred at room temperature for 23 h. The mixture was partitioned between diethyl ether and water, the ethereal extract washed with water and brine, dried over magnesium sulfate, filtered and the filtrate evaporated. Trituration with hexane gave Compound 1 (0.56 g) as a colorless solid, m.p. 126.degree.-128.degree. C.
Example 2
Starting from the amine prepared in Example 1 C, Compounds 2-5 were prepared by similar processes using appropriate starting materials.
Example 3
Preparation of Isopropyl N-�4,5-dichloro-2-�1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl!oxybenzenecarbamate Compound 18
A. Preparation of4,5-Dichloro-1-�1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl!oxy-2-nitrobenzene
5-Hydroxy-1-methyl-3-trifluoromethylpyrazole (7.0 g, 40 mmol) and powdered potassium carbonate (11.4 g, 80 mmol) were stirred together in dimethylsulfoxide (40 ml) for 30 minutes. 4,5-Dichloro-2-fluoronitrobenzene (7.9 g, 50 mmol) was added and the mixture stirred at room temperature for 18 h. The mixture was partitioned between diethyl ether and water, the ethereal extract washed with water and brine, dried over magnesium sulfate, filtered and the filtrate evaporated. The residue was further purified by flash column chromatography over silica gel, to give the desired product (5.9 g) as a light yellow solid, m.p. 99.degree.-100.degree. C.
B. Preparation of 2-Amino-4,5-dichloro-2-�1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl!oxybenzene
Raney Nickel (ca. 0.5 g) was added to a solution of the compound prepared in A above (5.5 g, 16 mmol) in ethanol (100 ml) and the mixture shaken in a Parr hydrogenator at 50 p.s.i. for 2 h. The catalyst was removed by filtration and the filtrate evaporated in vacuo to give the desired product as a pale solid (4.7 g), m.p. 126.degree.-128.degree..degree. C.
C. Preparation of Isopropyl N-�4,5-dichloro-2-�1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl!oxybenzenecarbamate
The amine prepared in B above (1.0 g, 3 mmol) was added to a chilled (ice-bath) mixture of isopropylchloroformate (1M solution in toluene, 7 ml, 7 mmol) and triethylamine (0.6 g, mmol) and the mixture stirred for 18 h. The mixture was partitioned between diethyl ether and water, the ethereal extract washed with water and brine, dried over magnesium sulfate, filtered and the filtrate evaporated. The residue was further purified by flash column chromatography over silica gel, to give the desired product (0.2 g) as a colorless solid, m.p. 125.degree.-126.degree. C.
Example 4
N-�4-Methoxy-2-�1-methyl-3(trifluoromethyl)-1H-pyrazol-5-yl!oxyphenyl!cyclopropanecarboxamide Compound 20
A. Preparation of 5-Fluoro-1-�2-methyl-3(trifluoromethyl)-1H-pyrazol-5-yl!oxy-2-nitrobenzene
5-Hydroxy-1-methyl-3trifluoromethylpyrazole (8.3 g, 50 mmol) and powdered potassium carbonate (8.3 g 60 mmol) were stirred together in dimethylsulfoxide (40 ml) for 30 minutes. 2,4-Difluoronitrobenzene (7.9 g, 50 mmol) was added and the mixture stirred at room temperature for 18 h. The mixture was partitioned between diethyl ether and water, the ethereal extract washed with water and brine, dried over magnesium sulfate, filtered and the filtrate evaporated. The residue was further purified by flash column chromatography over silica gel, to give the desired product (2.3 g) as a solid. m.p. 68.degree.-70.degree. C.
B. Preparation of 5-Methoxy-1-�1-methyl-3(trifluoromethyl)-1H-pyrazol-5-yl!oxy-2-nitrobenzen
The compound prepared in A above (1.5 g, 5 mmol) was dissolved in methanol (20 ml) and sodium methoxide (25% solution in methanol, 1.1 ml, 5 mmol) added. The mixture was stirred at room temperature for 3 h, then partitioned between diethyl ether and water. The ethereal extract was washed with water and brine, dried over magnesium sulfate, filtered and the filtrate evaporated. The residue was triturated with hexane to give the desired product (0.8 g) as a yellow solid.
C. Preparation of2-Amino-5-methoxy-1-�1-methyl-3(trifluoromethyl)-1H-pyrazol-5-yl!oxybenzene
Raney Nickel (ca. 0.08 g) was added to a solution of the compound prepared in B above (0.8 g, 2.5 mmol) in methanol (50 ml) and the mixture shaken in a Parr hydrogenator at 50 p.s.i. for 1 h. The catalyst was removed by filtration and the filtrate evaporated in vacuo. The product was used without further purification in D below.
D. Preparation of N-�4-Methoxy-2-�1-methyl-3(trifluoromethyl)-1H-pyrazol-5-yl!oxyphenyl!cyclopropanecarboxamide
Cyclopropylcarbamyl chloride (0.2 g, 1.4 mmol) was added to a mixture of triethylamine (0.3 g, 2.8 mmol) and the amine prepared in C above (0.4 g, 1.4 mmol) in dichloromethane (10 ml) and the mixture stirred at room temperature for 30 minutes. The mixture was partitioned between diethyl ether and water, the ethereal extract washed with water and brine, dried over magnesium sulfate, filtered and the filtrate evaporated. Trituration with hexane gave Compound 20 (0.4 g) as a colorless solid, m.p. 140.degree.-142.degree. C.
Example 5
N-�4-Methyl-2-�1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl!thiophenyl!-cyclopropane carboxamide Compound 142
A. Preparation of 5-thio-1-methyl-3-trifluoromethylpyrazole
A. 5-hydroxy-1-methyl-3-trifluoromethylpyrazole (30 g, 180 mmol) (Example 1, Part A) was dissolved in toluene (250 mL). Lawesson's reagent (36.5 g, 90 mmol) was added and the mixture was heated to reflux for 8 hours. An additional 10.0 g (20 mmol) of Lawesson's reagent was added and the mixture continued at reflux for 2 hours. The mixture was allowed to cool, stirring at room temperature for 18 hours. The solution was poured into saturated aqueous sodium carbonate solution and partitioned. The resulting aqueous phase was acidified to pH 2 with concentrated hydrochloric acid. The mixture was extracted with diethyl ether, dried over magnesium sulfate, filtered and the filtrate evaporated to give the desired product as a yellow oil (26 g).
B. Preparation of 5-Methyl-1-�1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl!thio-2-nitrobenzene
B. The thiol prepared in step A above, (5 g, 17 mmol) was dissolved in 4-methyl-2-pentanone (50 mL). To this was added 3-fluoro-4-nitrotoluene (2.6 g, 17 mmol) and the mixture was stirred for 5 min. Potassium carbonate (3.2 g, 22 mmol) was added and the mixture was heated to reflux for 2 hours. The heat was removed and the mixture was cooled to room temperature. The mixture was poured into water and this was neutralized with acetic acid. The resulting mixture was partitioned between diethyl ether and water, the ethereal extract was washed with water, dried over magnesium sulfate, filtered and the filtrate evaporated. Trituration with hexane gave the desired compound (2.0 g) as a yellow solid, m.p. 98.degree.-100 .degree. C.
C. Preparation of 2-Amino-5-methyl-1-�1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl!thiobenzene
C. The nitrotoluene prepared above (1.8 g, 5.7 mmol) was added to methanol (50 mL). Palladium on carbon (0.1 g, 5%) was added and the mixture was hydrogenated at 50 p.s.i. for 3 hours. The catalyst was removed by filtration and the filtrate evaporated. The resulting residue was triturated with hexane to give the desired product as a yellow solid (0.8 g) m.p. 64.degree.-68.degree. C.
D. Preparation of N-�4-Methyl-2-�1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl!thiophenyl!cyclopropane carboxamide
D. Cyclopropanecarbonyl chloride (0.3 g, 3 mmol) and triethylamine (0.5 g, 4.5 mmol) were added dropwise to a chilled (ice-bath) solution of the aniline prepared in Step C above (0.7 g, 2.4 mmol) in dichloromethane (20 mL). The reaction was stirred at room temperature for 24 hours, then partitioned between diethyl ether and water. The ethereal extract was dried over magnesium sulfate, filtered and the filtrate evaporated. Trituration with hexane gave Compound 142 (0.55 g) as a yellow solid, m.p. 162.degree.-164.degree. C.
Example 6
Preparation of lsopropyl N-�4,5-dichloro-2-�1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl!thiobenzenecarbamate Compound 143
Triphosgene (0.6 g, 2 mmol) was added to a solution of the aniline prepared in Step C in Example 5 above (1.25 g, 4 mmol) in ethyl acetate (20 mL) and the mixture was heated at reflux for 1 hour. The mixture was cooled to room temperature and the solvent removed by rotary evaporation. The residue was dissolved in isopropanol (20 mL) and stirred at room temperature for 1 hour, then the solvent was evaporated. Trituration with hexane gave Compound 2 (1.0 g) as a colorless solid, m.p. 118.degree.-120.degree. C.
TABLE I__________________________________________________________________________ ##STR13##Comp.No. R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 R.sup.6 R.sup.7 R.sup.8 R.sup.9 A m.sup.a Z m.p.__________________________________________________________________________ (.degree.C.)1 CH.sub.3 CF.sub.3 H cyclopropyl H H CH.sub.3 H H O 0 -- 126-1282 CH.sub.3 CF.sub.3 H tert-butyl H H CH.sub.3 H H O 0 -- 73-753 CH.sub.3 CF.sub.3 H CF.sub.3 H H CH.sub.3 H H O 0 -- 95-974 CH.sub.3 CF.sub.3 H CH(CH.sub.3).sub.2 H H CH.sub.3 H H O 0 -- 130-1325 CH.sub.3 CF.sub.3 H CH.sub.2 CH.sub.3 H H CH.sub.3 H H O 0 -- 96-986 CH.sub.3 CF.sub.3 H CH(CH.sub.3).sub.2 H H CH.sub.3 H H O 1 O 68-707 CH.sub.3 CF.sub.3 H C.sub.2 H.sub.5 H H CH.sub.3 H H O 1 O8 CH.sub.3 CF.sub.3 H cyclopropyl H H F H H O 0 -- 125-1279 CH.sub.3 CF.sub.3 H CH(CH.sub.3).sub.2 H H F H H O 1 O 125-12710 CH.sub.3 CF.sub.3 H cyclopropyl H H CI H H O 0 -- 130-13211 CH.sub.3 CF.sub.3 H C.sub.2 H.sub.5 H H CI H H O 1 O 93-9712 CH.sub.3 CF.sub.3 H C.sub.2 H.sub.5 H H CH.sub.3 H H O 1 S 90-9213 CH.sub.3 CF.sub.3 H cyclopropyl H H H CH.sub.3 H O 0 -- 138-14014 CH.sub.3 CF.sub.3 H cyclopropyl H H CI Cl H O 0 -- 158-16015 CH.sub.3 CF.sub.3 H CH(CH.sub.3).sub.2 H H H CH.sub.3 H O 1 O --18 CH.sub.3 CF.sub.3 H CH(CH.sub.3).sub.2 H H H CH.sub.3 H O 0 -- 125-12817 CH.sub.3 CF.sub.3 H CH(CH.sub.3).sub.2 H H Cl CI H O 1 O 92-9418 CH.sub.3 CF.sub.3 H CH(CH.sub.3).sub.2 H H Cl CI H O 0 -- 144-14519 CH.sub.3 CF.sub.3 H cyclopropyl H H OCH.sub.3 H H O 0 -- 140-14220 CH.sub.3 CF.sub.3 H CH.sub.3 H H CH.sub.3 H H O 0 -- 142-14421 CH.sub.3 CF.sub.3 H 1-methylcyclopropyl H H CH.sub.3 H H O 0 -- 100-10322 CH.sub.3 CF.sub.3 H CH(Cl).sub.2 H H CH.sub.3 H H O 0 -- 130-13223 CH.sub.3 CF.sub.3 H CHCH.sub.2 H H CH.sub.3 H H O 0 -- 147-14924 CH.sub.3 CF.sub.3 H CHC(CH.sub.3).sub.2 H H CH.sub.3 H H O 0 -- 116-11825 CH.sub.3 CF.sub.3 H CH.sub.2 C(CH.sub.3)CH.sub.2 H H CH.sub.3 H H O 0 -- 83-8526 CH.sub.3 isopropyl H cyclopropyl H H CH.sub.3 H H O 0 -- 135-13727 CH.sub.3 CF.sub.3 H CH(CH.sub.3)CH.sub.2 CH.sub.3 H H CH.sub.3 H H O 1 S 93-9528 CH.sub.3 CF.sub.3 H CH(CH.sub.3).sub.2 H H CH.sub.3 H H O 1 S 104-10529 CH.sub.3 CF.sub.3 H CH.sub.2 C(CH.sub.3).sub.3 H H CH.sub.3 H H O 0 -- 142-14330 CH.sub.3 CF.sub.3 H CH.sub.2 CH(CH.sub.3).sub.2 H H CH.sub.3 H H O 0 -- 128-13031 CH.sub.3 C.sub.2 F.sub.5 H C.sub.2 H.sub.5 H H CH.sub.3 H H O 1 O32 CH.sub.3 C.sub.2 F.sub.5 H cyclopropyl H H CH.sub.3 H H O 0 -- 161-16333 CH.sub.3 CF.sub.3 H CH(CH.sub.3).sub.2 H H OCH.sub.3 H H O 0 -- 128-13034 CH.sub.3 CF.sub.3 H CH(CH.sub.3).sub.2 H H OCH.sub.3 H H O 1 O 77-7935 CH.sub.3 cyclopropyl H cyclopropyl H H CH.sub.3 H H O 0 -- 133-13536 CH.sub.3 isopropyl H C.sub.2 H.sub.5 H H CH.sub.3 H H O 1 O 71-7437 CH.sub.3 cyclopropyl H CH(CH.sub.3).sub.2 H H CH.sub.3 H H O 0 -- 129-13138 CH.sub.3 cyclopropyl H CH(CH.sub.3).sub.2 H H CH.sub.3 H H O 1 O --39 CH.sub.3 CF.sub.3 H cyclopropyl CH.sub.3 H CH.sub.3 H H O 0 -- 75-7740 CH.sub.3 CF.sub.3 H cyclopropyl CH.sub.3 OCH.sub.2 H CH.sub.3 H H O 0 -- 103-10541 CH.sub.3 CF.sub.3 Br cyclopropyl H H CH.sub.3 H H O 0 -- 163-16542 CH.sub.3 CF.sub.3 H C.sub.2 H.sub.5 H H OCH.sub.3 H H O 1 S 80-8343 CH.sub.3 CF.sub.3 H C.sub.2 H.sub.5 H H OCH.sub.3 H H O 1 O44 CH.sub.3 CF.sub.3 H CH.sub.2 Cl H H CH.sub.3 H H O 0 -- 105-10745 CH.sub.3 CF.sub.3 H CH.sub.3 H H CH.sub.3 H H O 1 O46 CH.sub.3 CF.sub.3 H CH.sub.2 -cyclopentane H H CH.sub.3 H H O 0 -- 135-13747 CH.sub.3 CF.sub.3 H CH.sub.2 CH(CH.sub.3).sub.2 H H CH.sub.3 H H O 1 O 108-11048 CH.sub.3 CF.sub.3 H CH.sub.2 C(CH.sub.3).sub.3 H H CH.sub.3 H H O 1 O 103-10549 CH.sub.3 CF.sub.3 H cyclopentyl H H CH.sub.3 H H O 1 O 83-8550 CH.sub.3 CF.sub.3 H CHNOH H H CH.sub.3 H H O 0 -- 161-16651 CH.sub.3 CF.sub.3 H CH.sub.2 -c-propyl H H CH.sub.3 H H O 1 O 82-8452 CH.sub.3 CF.sub.3 H CH(CH.sub.3)CH.sub.2 CH.sub.3 H H CH.sub.3 H H O 1 O 38-4053 CH.sub.3 CF.sub.3 H CH.sub.2 CF.sub.3 H H CH.sub.3 H H O 1 O 84-8554 CH.sub.3 CF.sub.3 H CH.sub.2 CHCH.sub.2 H H CH.sub.3 H H O 1 O 70-7455 CH.sub.3 CF.sub.3 H CH.sub.2 C(CH.sub.3)CH.sub.2 H H CH.sub.3 H H O 1 O 87-9056 CH.sub.3 CF.sub.3 H CH.sub.2 C.CH H H CH.sub.3 H H O 1 O 98-10057 CH.sub.3 CF.sub.3 H (CH.sub.2).sub.5 Br H H CH.sub.3 H H 0 0 -- 117-11858 CH.sub.3 CF.sub.3 H CH.sub.2 CH.sub.2 CH.sub.3 H H CH.sub.3 H H. O 1 O 94-9559 CH.sub.3 CF.sub.3 H CH.sub.2 CH(CH.sub.3).sub.2 H H CH.sub.3 H H O 1 S 100-10260 CH.sub.3 CF.sub.3 H cyclopropyl H H H H H O 0 -- 123-12661 CH.sub.3 CF.sub.3 H CH(CH.sub.3).sub.2 H H H H H O 1 O 74-7762 CH.sub.3 CF.sub.3 Br cyclopropyl H H H H H O 0 -- 139-14163 CH.sub.3 CF.sub.3 Br CH(CH.sub.3).sub.2 H H H H H O 1 O --64 CH.sub.3 CF.sub.3 H cyclopropyl H H SCH.sub.3 H H O 0 -- 117-12065 CH.sub.3 CF.sub.3 H CH.sub.2 CH(CH.sub.3).sub.2 H H CH.sub.3 H H O 1 S --66 CH.sub.3 CF.sub.3 H C.sub.2 H.sub.5 H H CH.sub.3 H H O 1 S --67 CH.sub.3 CF.sub.3 H cyclopropyl H H O.sub.2 H.sub.5 H H O 0 -- 173-17568 CH.sub.3 CF.sub.3 H CH(CH.sub.3).sub.2 H H OCH.sub.2 CH.sub.3 H H O 1 O 83-8569 CH.sub.3 CF.sub.3 Br CH(CH.sub.3).sub.2 H H Br H H O 1 O 131-13370 CH.sub.3 CF.sub.3 H CH(CH.sub.3).sub.2 H H CH.sub.3 H H O 1 S 95-9871 CH.sub.3 CF.sub.3 H CH.sub.2 -cyclopropane H H CH.sub.3 H H O 0 -- 95-9772 CH.sub.3 CF.sub.3 H CH(CH.sub.3)CO.sub.2 -n-C.sub.4 H.sub.9 H H CH.sub.3 H H O 1 O --73 CH.sub.3 CF.sub.3 H CH(CH.sub.3)CH.sub.2 CO.sub.2 C.sub.2 H.sub.5 H H CH.sub.3 H H O 1 O --74 CH.sub.3 CF.sub.3 Br CH(CH.sub.3).sub.2 H H I H H O 1 O 148-15075 CH.sub.3 CF.sub.3 H ##STR14## H H CH.sub.3 H H O 1 O 80-8376 CH.sub.3 CF.sub.3 H ##STR15## H H CH.sub.3 H H O 1 O --77 CH.sub.3 CF.sub.3 H CH.sub.2 CH.sub.2 OCH.sub.3 H H CH.sub.3 H H O 1 O --78 CH.sub.3 CF.sub.3 H CH.sub.2 C(CH.sub.3).sub.2 COOCH.sub.3 H H CH.sub.3 H H O 1 O 84-8579 CH.sub.3 CF.sub.3 H CH.sub.2 CH.sub.2 N(CH.sub.3).sub.2 H H CH.sub.3 H H O 1 O --80 CH.sub.3 CF.sub.3 H CH.sub.2 CH.sub.2 Br H H CH.sub.3 H H O 1 O 78-8081 CH.sub.3 CF.sub.3 H CH(CH.sub.3)CH.sub.2 Cl H H CH.sub.3 H H O 1 O --82 CH.sub.3 CF.sub.3 H CH.sub.2 CCl.sub.3 H H CH.sub.3 H H O 1 O 108-11083 CH.sub.3 CF.sub.3 H phenyl H H CH.sub.3 H H O 0 -- 140-14284 CH.sub.3 CF.sub.3 H 4-F-phenyl H H CH.sub.3 H H O 0 -- 152-15485 CH.sub.3 CF.sub.3 H 2-methylcyclopropyl H H CH.sub.3 H H O 0 -- 132-13486 CH.sub.3 CF.sub.3 H 4-CN-phenyl H H CH.sub.3 H H O 0 -- 158-16087 CH.sub.3 CF.sub.3 H OCH(C.sub.2 H.sub.5)C.CH H H CH.sub.3 H H O 1 O 70-7288 CH.sub.3 CF.sub.3 H CH.sub.2 CH.sub.2 F H H CH.sub.3 H H O 1 O 60-6289 CH.sub.3 CF.sub.3 H CH(CH.sub.3)C.CH H H CH.sub.3 H H O 1 O 112-11390 CH.sub.3 CF.sub.3 H CH(CH.sub.3)CHCHCH.sub.3 H H CH.sub.3 H H O 1 O 64-6691 CH.sub.3 CF.sub.3 H CH(CH.sub.3)CHCH.sub.2 H H CH.sub.3 H H O 1 O 64-6692 CH.sub.3 CF.sub.3 H ##STR16## H H CH.sub.3 H H O 1 O 80-8393 CH.sub.3 CF.sub.3 H CH(CH.sub.3)CF.sub.3 H H CH.sub.3 H H O 1 O 92-9494 CH.sub.3 CF.sub.3 H CHNOCH.sub.3 H H CH.sub.3 H H O 0 --95 CH.sub.3 CF.sub.3 H COCH.sub.3 H H CH.sub.3 H H O 0 --96 CH.sub.3 CF.sub.3 H C(CH.sub.3).sub.3 H H CH.sub.3 H H O 1 O 95-9797 CH.sub.3 CF.sub.3 H CH.sub.2 OCH.sub.3 H H CH.sub.3 H H O 0 -- 92-9498 CH.sub.3 CF.sub.3 H C(Cl).sub.3 H H CH.sub.3 H H O 0 -- 105-10999 CH.sub.3 CF.sub.3 H 3-pyridyl H H CH.sub.3 H H O 0 -- 99-100100 CH.sub.3 C.sub.2 F.sub.5 H CH.sub.2 CH(CH.sub.3).sub.2 H H CH.sub.3 H H O 0 -- 148-150101 CH.sub.3 C.sub.2 F.sub.5 H CHC(CH.sub.3).sub.2 H H CH.sub.3 H H O 0 -- 113-115102 CH.sub.3 C.sub.2 F.sub.5 H CH.sub.2 C(CH.sub.3).sub.3 H H CH.sub.3 H H O 0 -- 128-130103 CH.sub.3 C.sub.2 F.sub.5 H CH(CH.sub.3).sub.2 H H CH.sub.3 H H O 1 O 85-87104 CH.sub.3 CF.sub.3 H CH.sub.3 H H H H H O 0 -- 105-110105 CH.sub.3 CF.sub.3 H CH(CH.sub.3).sub.2 H H CI H H O 0 -- 82-84106 CH.sub.3 CF.sub.3 H 3-tetrahydrofuryl H H CH.sub.3 H H O 1 O 86-88107 CH.sub.3 CF.sub.3 H 3-methylcyclopentyl H H CH.sub.3 H H O 1 O 88-90108 CH.sub.3 CF.sub.3 H C(CH.sub.3)CH.sub.2 H H CH.sub.3 H H O 1 O 67-69109 CH.sub.3 CF.sub.3 H CH(CH.sub.2 F).sub.2 H H CH.sub.3 H H O 1 O 108-110110 CH.sub.3 CF.sub.3 H CH.sub.2 CH.sub.2 Cl H H CH.sub.3 H H O 0 -- 98-100111 CH.sub.3 CF.sub.3 H 2-furyl H H CH.sub.3 H H O 0 -- 99-100112 CH.sub.3 CF.sub.3 H ##STR17## H H CH.sub.3 H H O 0 -- gum113 CH.sub.3 CF.sub.3 H C(CH.sub.3).sub.2 CH.sub.2 Cl H H CH.sub.3 H H O 0 -- 93-95114 CH.sub.3 CF.sub.3 H CHCHCHCH.sub.3 H H CH.sub.3 H H O 0 -- 155-157115 CH.sub.3 CF.sub.3 H CH.sub.2 CO.sub.2 CH.sub.2 CH.sub.3 H H CH.sub.3 H H O 0 -- 110-112116 CH.sub.3 CF.sub.3 H CH.sub.2 CH.sub.2 CO2CH.sub.3 H H CH.sub.3 H H O 0 -- 102-103117 CH.sub.3 CF.sub.3 H CO.sub.2 CH.sub.3 H H CH.sub.3 H H O 0 -- 142-144118 CH.sub.3 CF.sub.3 H cyclopropyl H H Br H H O 0 -- 130-132119 CH.sub.3 CF.sub.3 Cl CH(CH.sub.3).sub.2 H H CH.sub.3 H H O 1 O 91-93120 CH.sub.3 CF.sub.3 H C(CH.sub.3)CH.sub.2 H H CH.sub.3 H H O 0 -- 88-90121 CH.sub.3 CF.sub.3 H 5-nitro-2-furyl H H CH.sub.3 H H O 0 -- 155-158122 CH.sub.3 CF.sub.3 H cyclobutyl H H CH.sub.3 H H O 0 -- 122-123123 CH.sub.3 CF.sub.3 H (CH.sub.2).sub.3 CO.sub.2 CH.sub.2 CH.sub.3 H H CH.sub.3 H H O 0 -- 93-95124 CH.sub.3 CF.sub.3 H CH.sub.2 -2-thiophenyl H H CH.sub.3 H H O 0 -- 104-105125 CH.sub.3 CF.sub.3 H CHClCH.sub.3 H H CH.sub.3 H H O 0 -- 127-129126 CH.sub.3 CF.sub.3 H CF.sub.2 CF.sub.3 H H CH.sub.3 H H O 0 -- 58-60127 CH.sub.3 CF.sub.3 H C(Br)CH.sub.2 H H CH.sub.3 H H O 0 -- 83-84128 CH.sub.3 CF.sub.3 H CH(Br)CH.sub.3 H H CH.sub.3 H H O 0 -- 134-135129 CH.sub.3 CF.sub.3 H ##STR18## H H CH.sub.3 H H O 0 -- 135-137130 CH.sub.3 CF.sub.3 H CHC(CH.sub.3)CF.sub.3 H H CH.sub.3 H H O 0 -- 163-165131 CH.sub.3 CF.sub.3 H CHCHCl H H CH.sub.3 H H O 0 -- 154-155132 CH.sub.3 CF.sub.3 H 2,2-dichlorocyclopropyl H H CH.sub.3 H H O 0 -- 144-145133 CH.sub.3 CF.sub.3 H C(Cl)CCl.sub.2 H H CH.sub.3 H H O 0 -- 97-100134 CH.sub.3 CF.sub.3 H 3-methyl-2-thiophenyl H H CH.sub.3 H H O 0 -- 123-125135 CH.sub.3 CF.sub.3 H CHC(CF.sub.3).sub.2 H H CH.sub.3 H H O 0 -- 158-160136 CH.sub.3 CF.sub.3 H CH.sub.2 SCH.sub.3 H H CH.sub.3 H H O 0 -- 119-121137 CH.sub.3 CF.sub.3 H 2-cyanocyclopropyl H H CH.sub.3 H H O 0 -- 110-112138 CH.sub.3 CF.sub.3 H cyclopentyl H H CH.sub.3 H H O 0 -- 143-144139 CH.sub.3 CF.sub.3 H cyclopropyl H H CN H H O 0 -- 154-158140 CH.sub.3 CF.sub.3 H CH(CH.sub.3).sub.2 H H CN H H O 1 O 101-103141 CH.sub.3 CF.sub.3 H CH.sub.2 C(CH.sub.3).sub.3 H H CN H H O 0 -- 101-l04142 CH.sub.3 CF.sub.3 H cyclopropyl H H CH.sub.3 H H S 0 -- 162-164143 CH.sub.3 CF.sub.3 H CH(CH.sub.3).sub.2 H H CH.sub.3 H H S 1 O 118-120144 CH.sub.3 CF.sub.3 H CHC(CH.sub.3).sub.2 H H CH.sub.3 H H S 0 -- 124-125145 CH.sub.3 CF.sub.3 H CH(CH.sub.3).sub.2 H H CH.sub.3 H H S 1 N 195146 CH.sub.3 CF.sub.3 H 2-methylcyclopropyl H H CH.sub.3 H H S 0 -- 161-162147 CH.sub.3 CF.sub.3 H C(Cl)CH.sub.2 H H CH.sub.3 H H O 0 -- 68-70148 CH.sub.3 CF.sub.3 H CH(CH.sub.3).sub.2 H H CH.sub.3 H H SO 1 O 110-112149 CH.sub.3 CF.sub.3 H CH(CH.sub.3).sub.2 H H CH.sub.3 H H SO.sub.2 1 O 148-149150 C.sub.2 H.sub.5 CF.sub.3 H cyclopropyl H H CH.sub.3 H H O 0 -- 138-140151 C.sub.2 H.sub.5 CF.sub.3 H CH(CH.sub.3).sub.2 H H CH.sub.3 H H O 1 O 100-102152 C.sub.2 H.sub.5 CF.sub.3 H CH(CH.sub.3).sub.2 H H CH.sub.3 H H O 0 -- 140-142153 CH.sub.3 CF.sub.3 H CHC(CH.sub.3).sub.2 H H CH.sub.3 H H S 0 -- 103-104154 C.sub.2 H.sub.5 CF.sub.3 H 2-methylcyclopropyl H H CH.sub.3 H H O 0 -- 148-150__________________________________________________________________________ .sup.a When m is 0, Z is a carboncarbon single bond linking the carbonyl carbon to R.sup.4.
HERBICIDAL SCREENING TESTS
The compounds listed in the foregoing table were tested for herbicidal activity by various methods and at various rates of application. The results of some of these tests are given below. Results obtained in herbicidal screening are affected by a number of factors including: the amount of sunlight, soft type, soil pH, temperature, humidity, depth of planting, plant growth stage, application rate as well as many other factors. All testing procedures are administered with the least amount of variability possible. State of the art equipment and techniques are employed to enable the screening process to remain consistent and reliable.
PRE-EMERGENCE HERBICIDAL SCREENING TEST
On the day preceding treatment, seeds of several different weed species were planted in sandy loam soil containing only trace organic matter. Propagules were sown in individual rows using one species per row across the width of an aluminum flat. Seeding depths ranged from 1.0 to 1.5 cm and plant densities ranged from 3 to 25 plants per row depending on individual plant species.
The grass weeds planted (Table II) were broadleaf signalgrass (Brachiaria platyphylla) "BRAPP"; large crabgrass (Digitaria sanguinalis) "DIGSA"; barnyardgrass (Echinochloa crusgalli) "ECHCG"; rigid ryegrass (Lolium rigidum) "LOLRI"; fall panicum (Panicum dichotomiflorum) "PANDI"; giant foxtail (Setari faberi) "SETFA"; green foxtail (Setaria viridis) "SETVI"; blackgrass (Alopecurus myosuroides) "ALOMY"; wild oat (Avena fatua)"AVEFA" and Johnsongrass (Sorghum halepense) "SORHA".
The broadleaf weeds planted (Table III) were velvetleaf (Abutilon theophrasti) "ABUTH"; redroot pigweed (Amaranthus retroflexus) "AMARE"; common lambsquarters (Chenopodium album) "CHEAL"; ivyleaf morningglory (Ipomoea hederacea) "IPOHE"; common purslane (Portulaca oleracea) "POROL"; common cockleburr (Xanthium strumarium) "XANST"; and catchweed bedstraw (Galium aparine) "GALAP". Additionally, yellow nutsedge (Cyperus esculentus) "CYPES" nutlets were also sown.
Solutions of the test compounds were prepared by weighing out an appropriate amount of the test compound to provide an application rate of 0.25 kilograms per hectare (kg/ha), then dissolving the compound in a 50:50 mixture of deionized water and acetone containing 0.5% v/v Tween 20.RTM.(polyoxyethylene sorbitan monolaurate emulsifier) as a surfactant. Additional solvents, not exceeding 15% of spray volume, were used if needed to dissolve the compound.
The soil surface was sprayed inside an enclosed linear spray table with the nozzle set above the soil line. The spray table was calibrated to deliver 400 L/ha with the application rate being 0.25 kg/ha. After treatment, the flats were; placed into a greenhouse and watered as needed. The greenhouse environmental systems provided the plants with natural and artificial lighting to attain 14 hours of light per day. Day and night temperatures were maintained at 29.degree. and 21.degree. C., respectively.
The degree of weed control was evaluated and recorded 17-21 days after treatment as a percentage of weed control as compared to the growth of the same species of the same age in an untreated control flat. Percent control is the total injury to the plants due to all factors including: inhibited emergence, stunting, malformation, chlorosis and other types of plant injury. The results of the pre-emergence screening tests are shown in Tables II and III below. The control ratings range from 0 to 100 percent, where 0 represents no effect with growth equal to the untreated control and where 100 represents complete kill. The symbol "-" indicates that no test was performed at the 0.25 kg/ha level of application.
TABLE II__________________________________________________________________________PRE-EMERGENCE SCREENINGCOMP.NO. BRAPP DIGSA ECHCG LOLRI PANDI SETFA SETVI ALOMY AVEFA SORHA__________________________________________________________________________1 100 100 100 100 100 100 100 100 100 1002 35 50 15 20 40 40 50 20 5 253 0 0 0 0 0 0 15 0 0 04 100 100 100 85 100 100 100 100 100 1005 100 100 100 75 100 100 100 95 90 906 100 100 100 100 100 100 100 100 100 1007 100 100 98 60 100 100 100 90 75 958 50 100 40 20 60 100 90 60 15 409 35 65 15 15 50 40 98 30 5 1510 100 100 100 98 100 100 100 95 90 10011 60 100 25 35 50 70 100 65 10 3512 90 100 100 65 100 100 100 98 75 10013 0 0 0 0 0 5 5 0 0 014 60 90 30 35 60 65 70 50 50 4015 0 0 5 5 0 0 5 0 0 016 0 0 0 0 0 0 5 0 0 017 10 20 25 0 15 15 20 25 0 1018 15 25 15 0 25 25 35 35 10 2519 100 100 100 90 100 100 100 98 85 10020 65 100 50 20 100 90 90 50 50 5021 100 100 70 25 98 100 100 90 70 7022 0 0 0 0 0 5 35 0 0 023 50 80 60 40 70 60 80 40 25 6024 100 100 100 50 100 100 100 98 65 10025 100 100 100 85 100 100 100 98 90 10026 80 100 90 20 100 100 100 80 50 10027 90 100 5 10 70 80 90 40 10 5028 100 100 100 40 100 100 100 100 40 10029 100 100 100 80 100 100 100 100 95 10030 100 100 100 100 100 100 100 100 100 10031 90 100 60 30 95 100 -- 70 5 10032 100 100 100 100 100 100 100 100 80 10033 100 100 90 20 100 100 80 80 80 9034 100 100 90 70 100 100 100 100 50 9035 60 90 10 0 70 0 100 20 0 2036 0 0 0 0 0 0 0 0 0 037 0 40 0 0 0 0 90 0 0 --39 0 -- 0 0 0 0 0 0 0 --40 0 -- 0 0 0 0 0 0 0 --41 0 -- 0 0 5 10 5 0 0 042 85 -- 70 30 95 100 100 85 25 9043 40 -- 20 0 35 100 100 50 5 1544 0 0 0 0 0 0 0 0 0 045 90 100 50 20 90 100 100 90 60 7046 80 100 70 50 100 100 100 85 65 7047 35 85 5 0 15 60 90 20 10 1548 60 50 5 0 30 30 35 0 0 1049 60 100 25 15 50 90 100 35 10 5050 0 0 0 0 0 0 0 0 0 051 10 50 0 0 50 60 100 30 0 052 70 100 40 30 90 100 100 60 10 1053 80 100 30 30 100 100 100 40 5 8054 40 100 10 0 90 90 100 30 0 055 30 100 20 20 50 80 100 40 0 2056 80 100 30 20 100 100 100 70 5 4057 0 0 0 0 0 0 30 0 0 058 90 100 10 0 90 90 100 40 20 059 90 100 35 60 95 100 100 55 25 2560 0 20 0 0 0 0 50 0 0 064 25 90 0 0 40 10 10 0 0 2065 5 10 0 0 -- 20 90 30 0 066 70 100 10 0 90 90 100 70 10 6067 20 30 0 0 0 0 70 0 0 068 0 0 0 0 0 0 0 0 0 070 95 100 100 70 -- 100 100 90 40 2071 0 20 0 5 30 10 20 10 20 072 0 0 0 0 0 0 0 0 0 073 0 0 0 0 0 0 0 0 0 075 0 0 0 0 0 0 0 0 0 076 5 0 0 0 0 0 0 0 0 078 30 0 0 0 0 0 0 0 0 079 -- 0 0 0 0 0 0 0 0 080 0 30 0 0 0 0 0 0 0 081 100 100 60 30 70 100 100 70 40 7082 100 100 30 50 100 100 100 95 20 6083 30 20 0 0 40 0 100 0 0 084 100 98 60 40 100 98 100 60 60 8085 100 100 100 100 100 100 100 100 100 10086 30 100 5 0 40 40 80 0 0 087 20 100 20 40 30 30 100 80 40 4088 50 100 30 0 50 70 100 70 30 2089 100 100 80 80 100 100 100 90 80 9090 0 0 0 0 0 0 30 30 0 091 80 100 80 80 90 90 100 90 40 4092 45 0 0 0 0 0 0 0 0 093 100 100 80 65 100 100 100 75 70 7094 10 98 5 10 15 70 100 20 0 1595 0 0 0 0 0 0 0 0 0 096 100 100 65 50 100 100 100 90 60 5097 0 0 0 0 0 0 0 0 0 098 25 100 15 10 40 50 100 60 25 599 5 100 0 0 15 15 40 20 5 5100 100 100 100 70 100 100 100 100 80 100101 100 100 100 80 100 100 100 90 50 70102 100 100 85 60 100 100 100 75 25 80103 100 100 100 100 100 100 100 100 70 100105 85 100 80 80 98 100 100 90 70 80106 30 100 30 10 -- 90 100 50 10 20107 40 100 10 30 -- 100 100 70 10 10108 100 100 100 100 -- 100 100 90 100 90110 40 100 40 30 -- 100 100 70 70 30111 0 20 0 0 -- 0 70 5 0 0112 0 0 0 0 -- 0 0 0 0 0113 0 0 0 0 -- 0 0 0 0 0114 5 70 0 0 -- 10 70 0 0 0115 0 0 0 0 -- 0 0 0 0 0116 0 -- 0 0 -- 0 0 0 0 0117 0 0 0 0 -- 0 0 0 0 0118 80 100 100 100 -- 100 100 100 80 100119 0 0 0 0 -- 0 0 0 0 0120 20 100 70 30 -- 60 100 20 20 50121 0 0 0 0 -- 0 0 0 0 0122 60 100 80 50 -- 100 100 70 70 80123 0 0 0 0 -- 0 0 0 0 0124 0 100 0 20 -- 90 100 10 0 30125 0 90 0 0 -- 0 80 0 0 0126 10 100 100 0 -- 70 100 20 20 0142 100 100 80 80 -- 100 100 100 80 100__________________________________________________________________________
TABLE III__________________________________________________________________________PRE-EMERGENCE SCREENINGCOMP.NO. ABUTH AMARE CHEAL IPOHE POROL XANST GALAP CYPES__________________________________________________________________________1 100 100 100 100 100 50 100 752 5 65 40 0 85 0 -- 53 0 25 0 0 0 0 -- 04 100 100 100 65 100 20 90 655 40 100 0 10 10 0 -- 406 100 100 100 40 100 0 90 307 20 100 100 30 100 0 95 --8 20 100 60 60 100 0 40 259 10 100 35 20 100 0 -- 1010 100 100 100 100 100 15 -- 7511 10 90 30 20 100 0 -- 512 100 100 80 25 100 0 -- 4013 0 0 0 0 0 0 0 014 50 100 70 15 100 0 -- 515 0 0 0 0 0 0 0 016 0 0 0 0 0 0 10 017 0 25 5 0 25 0 -- 018 0 98 20 0 50 0 -- 019 100 100 100 75 100 15 90 3520 50 90 5 15 35 0 -- 2521 25 100 100 20 100 0 -- 2522 0 35 0 0 50 0 -- 023 15 40 30 20 70 0 -- 524 5 100 100 65 100 0 -- 3525 100 100 100 80 100 -- -- 6026 10 100 100 30 90 0 -- --27 0 100 30 5 90 0 -- 028 100 100 100 20 100 10 -- --29 100 100 100 70 100 10 -- 8030 100 100 100 70 100 30 -- 10031 0 100 100 0 100 0 -- --32 100 100 100 98 100 5 -- 7033 70 100 100 60 100 0 -- 3034 0 100 100 20 100 0 -- 035 0 100 90 20 20 0 -- 036 0 40 0 0 0 0 -- --37 0 80 10 0 0 0 -- --39 0 0 0 0 0 0 -- --40 0 0 0 0 0 0 -- --41 0 50 20 0 0 0 -- 042 35 93 85 8 100 0 -- 3043 0 90 100 5 95 0 -- 044 0 0 0 0 0 0 -- 045 0 100 100 5 100 0 -- 2046 20 98 80 30 100 0 -- --47 0 60 65 10 98 0 -- 048 0 15 40 0 90 0 -- 049 0 70 100 20 100 0 -- 050 0 0 0 0 0 0 -- 051 0 70 50 0 80 0 20 052 30 100 100 10 100 0 20 2053 0 100 90 0 100 0 50 054 0 100 60 0 100 0 20 055 10 90 90 2 80 0 30 056 20 100 100 20 100 0 30 2057 0 20 0 0 0 0 0 3058 0 100 70 0 30 0 50 059 85 98 100 20 100 0 50 060 0 100 30 0 20 0 0 064 0 90 95 0 100 0 0 065 0 70 0 0 20 0 0 066 0 100 100 10 100 0 20 067 0 40 90 0 0 0 0 068 0 0 0 0 0 0 0 070 30 100 100 50 100 0 70 071 0 0 0 0 40 0 30 072 0 0 0 0 0 0 0 073 0 0 0 0 0 0 0 078 0 0 0 0 0 0 0 079 0 0 20 0 0 0 0 080 0 20 40 0 20 0 0 081 20 80 100 40 100 0 60 082 70 98 100 20 100 0 70 083 0 70 70 0 20 0 0 084 50 60 100 0 100 0 40 085 100 100 100 100 100 40 90 5086 0 90 100 0 90 -- 40 087 0 100 70 0 100 0 30 088 0 80 50 0 100 0 90 1089 30 100 95 30 100 0 40 3090 0 0 0 0 60 0 -- 091 20 100 80 50 100 0 80 1092 -- 0 0 0 0 0 0 093 20 98 98 40 98 50 80 2094 -- 60 0 0 0 0 40 095 30 0 0 0 0 0 0 096 15 100 100 15 100 0 70 2097 0 0 0 0 0 0 -- 098 5 90 100 10 100 0 40 099 0 35 100 0 50 0 0 0100 100 100 100 100 100 20 98 5101 100 100 100 60 100 0 75 20102 100 100 100 60 100 0 70 0103 95 100 100 70 100 5 60 5105 20 100 98 30 100 0 85 10106 0 95 100 20 90 0 5 0107 70 70 100 5 100 0 10 0108 100 100 100 100 100 0 90 70110 0 95 0 0 40 0 80 10111 0 90 0 0 0 0 0 0112 0 0 20 0 0 0 0 0113 0 20 0 0 0 0 0 0114 0 30 20 0 50 0 0 0115 0 0 0 0 0 0 0 0116 0 -- 20 0 0 0 0 --117 0 0 0 0 0 0 -- 0118 100 100 100 100 100 10 70 70119 0 40 0 0 0 0 0 0120 0 30 90 0 100 0 0 --121 0 0 0 0 0 0 0 0122 0 90 20 5 100 0 100 50123 0 40 0 0 0 0 -- 0124 0 90 40 0 100 0 20 0125 0 70 0 0 0 0 0 0126 0 100 100 0 100 0 -- 0142 100 100 100 60 100 10 95 30__________________________________________________________________________
POST-EMERGENCE HERBICIDAL SCREENING TEST
The soil was prepared with the same methodology described for the pre-emergence test. The following species were used.
The grass weeds planted were "BRAPP"; "ECHCG"; "LOLRI"; "PANDI"; "SETFA"; "SETVI"; "ALOMY"; "AVEFA" and "SORHA".
The broadleaf weeds planted were "ABUTH"; "AMARE"; "CHEAL"; "IPOHE"; "POROL"; "XANST"; "GALAP" and scentless chamomile (Matricaria perforata) "MATIN". Additionally, "CYPES" nutlets were also sown.
Post-emergence flats were placed in the greenhouse under the same environmental conditions as described for the pre-emergence flats and watered as needed. Plants were grown for 10 to 12 days (or to the appropriate growth stage) prior to compound application. Grasses were sprayed at a 3 to 4 leaf stage and broadleaves at a 1 to 2 leaf stage. Yellow nutsedge was 5 to 7 cm tall at application.
Plants were sprayed 30.5 cm (12 inches) above the foliage with the same spray solution as prepared for the pre-emergence test. The application rate was 0.25 kg/ha. Treated plants were then returned to a greenhouse and watered daily without wetting the foliage. The degree of weed control was evaluated 17-21 days after application and recorded as percentage of control as compared to the growth of the same species in an untreated control flat of the same age. The percent control scale (0-100%) used to evaluate the pre-emergence treatment was also applied to the post-emergence treatment. The post-emergence screening test results are shown in Table IV (grass weeds) and Table V (broadleaf weeds) below.
TABLE IV__________________________________________________________________________POST EMERGENCE SCREENINGCOMP.NO. BRAPP ECHCG LOLRI PANDI SETFA SETVI ALOMY AVEFA SORHA__________________________________________________________________________1 40 75 70 50 85 90 95 90 752 10 0 5 0 5 5 10 0 03 5 0 0 5 10 15 5 0 04 30 15 15 30 65 50 85 75 05 25 5 10 15 25 15 55 50 56 15 20 5 10 20 15 90 50 157 5 0 8 5 10 20 85 10 108 0 5 5 0 15 30 35 10 59 5 5 0 0 0 10 10 5 010 5 10 10 10 10 20 88 60 1511 5 0 0 5 0 10 10 8 012 10 35 10 25 10 50 93 50 5013 0 0 0 0 0 0 0 0 514 0 0 0 0 0 5 5 0 015 0 0 0 0 0 0 0 0 016 0 0 0 0 0 0 0 5 017 0 0 0 0 0 0 5 0 018 0 0 0 0 0 0 0 0 019 5 20 8 10 0 85 70 65 2020 0 0 0 0 0 0 30 15 021 5 0 0 5 5 5 50 25 022 3 15 0 10 5 10 0 0 023 0 5 5 10 15 10 10 0 024 15 70 20 25 75 80 75 55 5025 40 65 75 30 90 90 70 65 7527 -- 0 0 8 10 10 15 20 028 10 15 10 15 20 25 75 60 4529 5 60 20 15 75 65 90 90 6530 60 75 45 60 70 85 90 90 8031 5 0 5 15 10 10 20 15 2032 75 60 20 30 75 70 90 85 7033 0 0 0 5 10 55 40 20 034 5 10 5 5 8 45 60 45 2035 0 0 0 5 0 0 0 5 036 0 0 0 0 0 0 0 0 1537 0 0 0 0 0 5 0 0 039 0 0 20 0 0 20 0 0 040 0 0 0 0 0 0 20 10 041 0 0 0 0 0 0 0 0 042 30 0 0 20 10 20 70 40 3043 0 0 0 20 10 0 40 0 3044 0 0 0 0 0 0 0 0 045 5 0 5 5 8 8 40 10 846 5 0 8 10 8 5 20 15 047 5 0 5 8 10 5 5 10 548 3 0 0 5 5 0 5 8 049 5 0 5 10 10 15 10 15 550 0 0 0 0 0 0 0 0 051 10 0 5 5 8 5 5 10 552 8 0 10 10 5 20 20 15 2053 10 0 5 10 5 40 10 10 554 5 0 10 5 5 5 5 8 555 5 0 5 10 10 15 10 15 056 5 0 5 10 0 10 25 5 557 10 0 0 5 0 10 0 3 058 0 0 10 10 0 10 10 10 1059 10 0 0 0 0 10 60 30 060 5 0 0 0 0 0 0 0 064 0 0 0 40 0 0 0 0 065 15 0 10 10 5 15 15 10 1066 10 0 10 25 10 15 10 15 067 0 0 0 0 0 5 0 0 1568 5 0 0 0 0 0 0 0 070 20 5 10 30 5 15 60 50 1071 15 0 8 10 0 5 30 65 572 5 0 0 0 0 0 0 0 073 0 0 0 0 0 0 0 0 075 5 5 0 0 0 5 10 0 076 0 5 0 0 0 0 15 0 077 10 0 0 5 5 5 5 0 078 5 0 0 0 0 0 0 0 079 0 0 0 0 0 0 0 0 080 5 0 0 0 5 5 0 0 581 10 0 10 10 10 20 50 35 582 15 0 10 15 15 15 40 15 083 10 0 5 5 5 5 60 30 584 5 0 5 5 5 10 70 75 085 65 85 60 80 60 80 99 100 8586 5 10 5 10 20 5 5 10 587 5 10 5 10 15 15 15 20 1088 10 10 5 10 10 10 20 5 1089 5 10 15 5 20 40 60 35 590 5 10 5 8 10 10 5 0 091 8 10 10 10 15 15 50 40 592 0 0 0 0 0 0 0 0 093 15 20 10 15 20 25 70 50 1594 15 0 0 5 15 5 5 0 095 0 0 0 0 0 0 0 0 096 10 0 15 10 10 10 25 20 097 0 0 0 0 0 0 0 0 098 15 5 10 10 10 25 45 65 099 5 0 5 5 0 0 5 0 0100 15 60 35 15 70 70 75 85 5101 10 60 15 15 25 75 65 75 0102 15 10 10 10 5 20 20 35 10103 10 30 15 5 5 30 30 25 5105 10 0 5 8 0 15 35 15 5106 30 0 0 -- 0 0 10 5 0107 10 0 0 0 0 0 10 10 0108 30 30 30 70 20 10 90 90 10110 10 0 5 -- 10 5 25 45 0111 5 0 0 -- 10 10 5 0 0112 0 0 0 -- 0 0 0 0 0113 0 0 0 -- 0 0 0 0 0114 5 0 0 -- 10 10 5 10 0115 0 0 0 -- 0 0 0 0 0116 0 0 0 -- 0 0 0 0 0117 0 0 0 -- 0 0 5 0 0118 10 15 15 -- 10 20 90 90 0__________________________________________________________________________
TABLE V__________________________________________________________________________POST-EMERGENCE SCREENINGCOMP.NO. ABUTH AMARE CHEAL IPOHE POROL XANST GALAP MATIN CYPES__________________________________________________________________________1 60 90 90 60 98 60 90 80 352 15 15 15 20 60 5 30 5 03 0 20 15 0 10 0 30 0 54 15 75 65 65 80 0 95 75 55 10 30 0 30 40 0 100 15 56 20 65 100 80 80 50 100 40 107 10 65 90 55 50 10 98 30 08 10 50 40 50 65 10 50 30 59 10 35 30 60 60 15 35 15 010 10 90 65 65 75 15 95 90 1011 5 50 45 25 60 5 99 0 812 30 60 40 35 100 8 98 0 1513 0 10 0 5 3 0 3 0 014 10 65 35 40 85 0 85 0 515 0 5 0 0 0 0 0 0 016 0 0 0 5 0 -- 5 0 017 0 40 50 20 5 10 30 0 018 0 35 5 10 10 0 10 5 019 15 60 70 40 65 10 95 98 020 0 5 0 20 10 0 50 20 021 60 55 50 80 60 5 35 0 522 5 25 40 30 30 0 35 0 023 5 5 20 55 10 3 10 90 024 5 15 95 100 95 60 80 65 525 65 100 85 88 88 15 90 65 1527 20 60 70 30 85 15 15 10 1028 30 65 100 60 98 35 100 40 529 60 25 100 70 98 35 100 80 530 30 80 95 75 100 35 100 100 531 15 50 100 55 85 40 60 0 1032 40 35 100 60 95 40 100 95 1533 10 40 50 70 90 0 65 50 034 25 60 85 65 95 40 60 5 535 0 8 15 60 70 3 25 5 036 0 5 10 15 50 0 5 0 037 0 5 10 35 15 0 10 5 039 0 0 0 0 20 0 -- 0 040 0 0 0 0 0 10 -- 0 041 0 10 0 10 30 0 -- 0 042 30 80 40 60 85 30 -- 0 043 30 70 90 50 90 30 -- 20 1044 0 0 5 15 15 0 -- 3 045 10 60 50 55 35 30 -- 5 046 5 50 15 30 55 5 -- 10 047 20 70 60 50 85 10 -- 20 048 5 60 45 40 45 35 -- 5 049 60 70 85 55 95 60 -- 10 550 0 0 3 8 10 3 -- 0 051 40 60 50 15 70 10 -- 5 1052 45 50 100 60 90 35 -- 5 1053 35 50 85 55 85 5 -- 5 1054 10 70 55 15 95 5 -- 5 855 30 40 25 50 75 5 -- 5 1056 30 75 50 50 90 15 -- 5 1057 3 10 0 5 8 0 -- 5 058 15 50 35 60 85 10 -- 0 1059 0 30 90 60 50 30 30 40 1060 8 50 15 60 40 0 15 8 064 20 20 40 70 30 5 40 30 065 25 80 100 85 80 40 50 25 566 10 85 100 90 95 25 60 5 1567 0 20 20 30 60 10 10 5 068 0 30 10 15 25 10 15 0 070 55 65 100 85 85 30 80 75 1071 5 10 5 30 25 0 50 10 072 5 15 20 10 15 0 10 0 573 0 5 5 5 0 0 10 0 075 15 10 20 15 15 0 25 10 076 0 15 10 10 5 0 35 20 077 10 25 5 15 35 5 25 5 078 20 15 15 15 15 0 5 0 079 0 0 0 5 0 0 5 0 080 10 8 30 20 50 0 25 5 581 55 65 65 75 90 40 35 15 1582 70 80 95 25 65 25 75 40 2083 25 5 75 60 30 10 40 30 584 45 40 75 50 85 20 70 60 585 80 75 100 70 90 40 95 100 1586 35 65 95 65 40 20 55 70 1087 25 75 90 40 70 20 55 80 1588 15 40 35 15 60 0 50 0 589 10 70 95 30 90 25 85 25 1590 10 65 50 10 25 15 25 70 591 15 80 100 60 90 30 70 50 1092 0 5 5 15 10 0 5 -- 093 70 100 95 70 90 50 40 -- 2094 0 40 10 20 15 0 5 -- 095 15 0 0 0 0 0 0 -- 096 50 55 60 60 90 20 55 40 1597 0 0 10 0 0 0 10 0 098 60 100 75 15 85 15 60 -- 1599 0 45 35 20 40 10 40 0 0100 85 88 90 50 95 35 80 98 5101 100 100 70 65 90 25 75 40 10102 35 88 80 100 80 25 65 95 10103 75 80 100 80 95 30 65 50 10105 40 80 60 60 65 40 100 30 10106 5 40 70 80 50 50 30 -- 0107 5 50 70 70 40 10 50 -- 0108 50 70 40 80 70 10 90 -- 0110 10 40 5 5 50 0 20 -- 5111 5 20 10 20 26 0 5 -- 5112 0 0 0 0 0 0 0 -- 0113 0 65 15 5 20 0 10 -- 0114 15 50 10 25 30 0 10 -- 0115 0 0 0 0 5 0 0 -- 0116 0 5 0 5 40 0 10 -- 0117 0 0 0 0 0 0 0 -- 0118 60 100 100 80 100 15 100 -- 10142 5 80 100 45 60 15 80 --__________________________________________________________________________
POST FLOODING POST EMERGENCE HERBICIDAL SCREENING TEST
Seeds of three weeds species were seeded into 8.9.times.8.9 cm pots. The pots were previously filled with clay soil which contained 2.2% organic matter and had a pH of 5.7. The weed species were Echinochloa crus-galli ("ECHCG"); Cyperus serotinus ("CYPDI"); and Sagittaria pygmaea ("SAGPY"). In addition, the rice hybrid "Kosihikara" (Oryza sativa) was also seeded.
The pots were placed into a 10 liter plastic tubs, lined with a plastic bag. At an early growth stage, the rice plants were transplanted into an 8.9.times.8.9 cm pot, 3 plants per pot at a depth of 2 cm. The pots were placed into the tubs with the weed species. The tubs were flooded with water to a depth of 2-3 cm.
At a middle growth stage the tubs were injected with the test material in acetone at a rate of 0.25 kg per hectare. The degree of weed control was evaluated and recorded 22 days after treatment as a percentage of weed control as compared to the growth of the same species of the same age in an untreated control flat. Percent control is the total injury to the plants due to all factors including: inhibited emergence, stunting, malformation, albinism, chlorosis and other types of plant injury. The control ratings range from 0 to 100 percent, where 0 represents no effect with growth equal to the untreated control and where 100 represents complete kill. The s2.symbol "-" indicates that no test was performed at the 0.25 kg/ha level of application. Representative results of the inventive compounds are shown in Table VI.
TABLE VI______________________________________POST FLOODING POST EMERGENCECOMP.NO. ECHCG CYPDI SAGPY______________________________________1 100 100 906 90 100 7012 10 35 024 98 95 6032 100 -- 8046 70 40 5085 100 100 90100 100 100 50101 90 100 60142 85 100 85118 75 100 90______________________________________
Although the invention has been described with reference to preferred embodiments and examples thereof, the scope of the present invention is not limited only to those described embodiments. As will be apparent to persons skilled in the art, modifications and adaptations to the above-described invention can be made without departing from the spirit and scope of the invention, which is defined and circumscribed by the appended claims.

Claims

1. A compound of formula (I), ##STR19## wherein: R.sup.1 is optionally substituted C.sub.1 -C.sub.6 alkyl or C.sub.1 -C.sub.6 haloalkyl;
R.sup.2 is optionally substituted C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 haloalkyl or C.sub.3 -C.sub.6 cycloalkyl;
R.sup.3 is hydrogen, halogen, C.sub.1 -C.sub.6 alkyl or C.sub.1 -C.sub.6 haloalkyl;
R.sup.4 is optionally substituted C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 haloalkyl, optionally substituted C.sub.1 -C.sub.6 alkoxy, optionally substituted C.sub.3 -C.sub.6 cycloalkyl, optionally substituted (C.sub.1 -C.sub.6) alkoxy(C.sub.1 -C.sub.6)alkyl, optionally substituted C.sub.2 -C.sub.6 alkenyl, optionally substituted C.sub.2 -C.sub.6 alkynyl, optionally substituted aryl, optionally substituted heteroaryl, or an optionally substituted five or six membered heterocyclic ring containing one or more heteroatoms selected from O, N or S;
R.sup.5 is hydrogen, optionally substituted C.sub.1 -C.sub.6 alkyl or (C.sub.1 -C.sub.6)alkoxy-(C.sub.1 -C.sub.6)alkyl;
R.sup.6, R.sup.7, R.sup.8 and R.sup.9 are independently selected from hydrogen, halogen, optionally substituted C.sub.1 -C.sub.6 alkyl, optionally substituted C.sub.2 -C.sub.6 alkenyl, optionally substituted C.sub.2 -C.sub.6 alkynyl, optionally substituted C.sub.1 -C.sub.6 alkoxy, (C.sub.1 -C.sub.6)alkoxy-(C.sub.1 -C.sub.6)alkyl, C.sub.1 -C.sub.6 haloalkyl, C.sub.1 -C.sub.6 haloalkoxy, cyano, nitro, --S(O).sub.p --R.sup.10 wherein p is 0, 1 or 2 and R.sup.10 is C.sub.1 -C.sub.3 alkyl or C.sub.1 -C.sub.3 haloalkyl, --OSO.sub.2 R.sup.11 wherein R.sup.11 is C.sub.1 -C.sub.3 alkyl, --CO.sub.2 H, --COR.sup.12, --COOR.sup.12 or --NHCOR.sup.12 wherein R.sup.12 is C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 haloalkyl, optionally substituted C.sub.3 -C.sub.6 cycloalkyl, optionally substituted aryl, optionally substituted heteroaryl, (C.sub.1 -C.sub.6)alkoxy-(C.sub.1 -C.sub.6)alkyl or C.sub.1 -C.sub.6 alkylthio, --CONR.sup.13 R.sup.14 or --NR.sup.13 R.sup.14 wherein R.sup.13 and R.sup.14 may be the same or different and are each hydrogen, C.sub.1 optionally substituted C.sub.3 -C.sub.6 cycloalkyl, optionally substituted C.sub.2 -C.sub.6 alkenyl, optionally substituted C.sub.2 -C.sub.6 alkynyl, optionally substituted aryl, optionally substituted heteroaryl, (C.sub.1 -C.sub.6)alkoxy-(C.sub.1 -C.sub.6)alkyl or C.sub.1 -C.sub.6 alkylthio, or R.sup.13 and R.sup.14 together with the N to which they are bound may form a ring having 3-8 members, one or more of which may be O, S or N; and
A is O, S, SO or SO.sub.2 ;
Y is O or S;
X is a carbon-carbon single bond or S;
or an agriculturally acceptable salt thereof.
2. A compound according to claim 1, wherein R.sup.1 is C.sub.1 -C.sub.3 alkyl or C.sub.1 -C.sub.3 haloalkyl; R.sup.2 is C.sub.1 -C.sub.3 alkyl or C.sub.1 -C.sub.3 haloalkyl; R.sup.3 is hydrogen; and R.sup.5 is hydrogen.
3. A compound according to claim 1, wherein R.sup.1 is methyl; R.sup.2 is trifluoromethyl; R.sup.3 is hydrogen; R.sup.4 is cyclopropyl; R.sup.5 is hydrogen; R.sup.6 is hydrogen; R.sup.7 is methyl; R.sup.8 is hydrogen; R.sup.9 is hydrogen and X is a carbon-carbon single bond.
4. A compound according to claim 1, wherein R.sup.1 is methyl; R.sup.2 is trifluoromethyl; R.sup.3 is hydrogen; R.sup.4 is isopropyl; R.sup.5 is hydrogen; R.sup.6 is hydrogen; R.sup.7 is methyl; R.sup.8 is hydrogen; R.sup.9 is hydrogen and X is a carbon-carbon single bond.
5. A compound according to claim 1, wherein R.sup.1 is methyl; R.sup.2 is trifluoromethyl; R.sup.3 is hydrogen; R.sup.4 is ethyl; R.sup.5 is hydrogen; R.sup.6 is hydrogen; R.sup.7 is methyl; R.sup.8 is hydrogen; R.sup.9 is hydrogen and X is a carbon-carbon single bond.
6. A compound according to claim 1, wherein R.sup.1 is methyl; R.sup.2 is trifluoromethyl; R.sup.3 is hydrogen; R.sup.4 is cyclopropyl; R.sup.5 is hydrogen; R.sup.6 is hydrogen; R.sup.7 is chloro; R.sup.8 is hydrogen; R.sup.9 is hydrogen and X is a carbon-carbon single bond.
7. A compound according to claim 1, wherein R.sup.1 is methyl; R.sup.2 is trifluoromethyl; R.sup.3 is hydrogen; R.sup.4 is isopropenyl; R.sup.5 is hydrogen; R.sup.6 is hydrogen; R.sup.8 is hydrogen; R.sup.9 is hydrogen and X is a carbon-carbon single bond.
8. An herbicidal composition comprising an herbicidally effective amount of a compound according to formula (Ia), ##STR20## wherein: R.sup.1 is optionally substituted C.sub.1 -C.sub.6 alkyl or C.sub.1 -C.sub.6 haloalkyl;
R.sup.2 is optionally substituted C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 haloalkyl or C.sub.3 -C.sub.6 cycloalkyl;
R.sup.3 is hydrogen, halogen; C.sub.1 -C.sub.6 alkyl or C.sub.1 -C.sub.6 haloalkyl;
R.sup.4 is optionally substituted C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 haloalkyl, optionally substituted C.sub.1 -C.sub.6 alkoxy, optionally substituted C.sub.3 -C.sub.6 cycloalkyl, optionally substituted (C.sub.1 -C.sub.6) alkoxy(C.sub.1 -C.sub.6)alkyl, optionally substituted C.sub.2 -C.sub.6 alkenyl, optionally substituted C.sub.2 -C.sub.6 alkynyl, optionally substituted aryl, optionally substituted heteroaryl, or an optionally substituted five or six membered heterocyclic ring containing one or more heteroatoms selected from O, N or S;
R.sup.5 is hydrogen, optionally substituted C.sub.1 -C.sub.6 alkyl or (C.sub.1 -C.sub.6)alkoxy-(C.sub.1 -C.sub.6)alkyl;
R.sup.6, R.sup.7, R.sup.8 and R.sup.9 are independently selected from hydrogen; halogen, optionally substituted C.sub.1 -C.sub.6 alkyl, optionally substituted C.sub.2 -C.sub.6 alkenyl, optionally substituted C.sub.2 -C.sub.6 alkynyl, optionally substituted C.sub.1 -C.sub.6 alkoxy, (C.sub.1 -C.sub.6)alkoxy-(C.sub.1 -C.sub.6)alkyl, C.sub.1 -C.sub.6 haloalkyl, C.sub.1 -C.sub.6 haloalkoxy, cyano, nitro, --S(O).sub.P --R.sup.10 wherein p is 0, 1 or 2 and R.sup.10 is C.sub.1 -C.sub.3 alkyl or C.sub.1 -C.sub.3 haloalkyl, --OSO.sub.2 R.sup.11 wherein R.sup.11 is C.sub.1 -C.sub.3 alkyl, --CO.sub.2 H, --COR.sup.12, --COOR.sup.12 or --NHCOR.sup.12 wherein R.sup.12 is C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 haloalkyl, optionally substituted C.sub.3 -C.sub.6 cycloalkyl, optionally substituted aryl, optionally substituted heteroaryl, (C.sub.1 -C.sub.6)alkoxy-(C.sub.1 -C.sub.6 )alkyl or C.sub.1 -C.sub.6 alkylthio, --CONR.sup.13 R.sup.14 or --NR.sup.13 R.sup.14 wherein R.sup.13 and R.sup.14 may be the same or different and are each hydrogen, C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 haloalkyl, optionally substituted C.sub.3 -C.sub.4 cycloalkyl, optionally substituted C.sub.2 -C.sub.6 alkenyl, optionally substituted C.sub.2 -C.sub.6 alkynyl, optionally substituted aryl, optionally substituted heteroaryl, (C.sub.1 -C.sub.6)alkoxy-(C.sub.1 -C.sub.6)alkyl or alkylthio, or R.sup.13 and R.sup.14 together with the N to which they are bound may form a ring having 3-8 members, one or more of which may be O, S or N; and
A O, S, SO or SO.sub.2 ;
Y is O or S;
X is a carbon-carbon single bond or S;
or an agriculturally acceptable salt thereof; and
a carrier therefor.
9. An herbicidal composition according to claim 8, wherein R.sup.1 is C.sub.1 -C.sub.3 alkyl or C.sub.1 -C.sub.3 haloalkyl; R.sup.2 is C.sub.1 -C.sub.3 alkyl or C.sub.1 -C.sub.3 haloalkyl; R.sup.3 is hydrogen; and R.sup.5 is hydrogen.
10. An herbicidal composition according to claim 8, wherein R.sup.1 is methyl; R.sup.2 is trifluoromethyl; R.sup.3 is hydrogen; R.sup.4 is cyclopropyl; R.sup.5 is hydrogen; R.sup.6 is hydrogen; R.sup.7 is methyl; R.sup.8 is hydrogen; R.sup.9 is hydrogen and Z is a carbon-carbon single bond.
11. An herbicidal composition according to claim 8, wherein R.sup.1 is methyl; R.sup.2 is trifluoromethyl; R.sup.3 is hydrogen; R.sup.4 is isopropyl; R.sup.5 is hydrogen; R.sup.6 is hydrogen; R.sup.7 is methyl; R.sup.8 is hydrogen; R.sup.9 is hydrogen and Z is a carbon-carbon single bond.
12. An herbicidal composition according to claim 8, wherein R.sup.1 is methyl; R.sup.2 is trifluoromethyl; R.sup.3 is hydrogen; R.sup.4 is ethyl; R.sup.5 is hydrogen; R.sup.6 is hydrogen; R.sup.7 is methyl; R.sup.8 is hydrogen; R.sup.9 is hydrogen and Z is a carbon-carbon single bond.
13. An herbicidal composition according to claim 8, wherein R.sup.1 is methyl; R.sup.2 is trifluoromethyl; R.sup.3 is hydrogen; R.sup.4 is cyclopropyl; R.sup.5 is hydrogen; R.sup.6 is hydrogen; R.sup.7 is chloro; R.sup.8 is hydrogen; R.sup.9 is hydrogen and Z is a carbon-carbon single bond.
14. A method for controlling undesirable vegetation comprising applying to an area where control is desired an herbicidally effective amount of a compound of formula (Ia), ##STR21## wherein: R .sup.1 is optionally substituted C.sub.1 -C.sub.6 alkyl or C.sub.1 -C.sub.6 haloalkyl;
R .sup.2 is optionally substituted C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 haloalkyl or C.sub.3 -C.sub.6 cycloalkyl;
R .sup.3 is hydrogen, halogen, C.sub.1 -C.sub.6 alkyl or C.sub.1 -C.sub.6 haloalkyl;
R.sup.4 is optionally substituted C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 haloalkyl, optionally substituted C.sub.1 -C.sub.6 alkoxy, optionally substituted C.sub.3 -C.sub.6 cycloalkyl, optionally substituted (C.sub.1 -C.sub.6) alkoxy(C.sub.1 -C.sub.6)alkyl, optionally substituted C.sub.2 -C.sub.6 alkenyl, optionally substituted C.sub.2 -C.sub.6 alkynyl, optionally substituted aryl, optionally substituted heteroaryl, or an optionally substituted five or six member heterocyclic ring containing one or more heteroatoms selected from O, N or S;
R.sup.5 is hydrogen, optionally substituted C.sub.1 -C.sub.6 alkyl or (C.sub.1 -C.sub.6)alkoxy-(C.sub.1 -C.sub.6)alkyl;
R.sup.6, R.sup.7, R.sup.8 and R.sup.9 are independently selected from hydrogen, halogen, optionally substituted C.sub.1 -C.sub.6 alkyl, optionally substituted C.sub.2 -C.sub.6 alkenyl, optionally substituted C.sub.2 -C.sub.6 alkynyl, optionally substituted C.sub.1 -C.sub.6 alkoxy, (C.sub.1 -C.sub.6)alkoxy-(C.sub.1 -C.sub.6)alkyl, C.sub.1 -C.sub.6 haloalkyl, C.sub.1 -C.sub.6 haloalkoxy, cyano, nitro, --S(O).sub.P R.sup.10 wherein p is 0, 1 or 2 and R.sup.10 is C.sub.1 -C.sub.3 alkyl or C.sub.1 -C.sub.3 haloalkyl, --OSO.sup.2 R.sup.11 wherein R.sup.11 is C.sub.1 -C.sub.3 alkyl, --CO.sub.2 H, --COR.sup.12, --COOR.sup.12 or --NHCOR.sup.12 wherein R.sup.12 is C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 haloalkyl, optionally substituted C.sub.3 -C.sub.6 cycloalkyl, optionally substituted aryl, optionally substituted heteroaryl, (C.sub.1 -C.sub.6)alkoxy-(C.sub.1 -C.sub.6)alkyl or C.sub.1 -C.sub.6 alkylthio, --CONR.sup.13 R.sup.14 or --NR.sup.13 R.sup.14 wherein R.sup.13 and R.sup.14 may be the same or different and are each hydrogen, C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 haloalkyl, optionally substituted C.sub.3 -C.sub.6 cycloalkyl, optionally substituted C.sub.2 -C.sub.6 alkenyl, optionally substituted C.sub.2 -C.sub.6 alkynyl, optionally substituted aryl, optionally substituted heteroaryl, (C.sub.1 -C.sub.6)alkoxy-(C.sub.1 -C.sub.6)alkyl or C.sub.1 -C.sub.6 alkylthio, or R.sup.13 and R.sup.14 together with the N to which they are bound may form a ring having 3-8 members, one or more of which may be O, S or N; and
A is O, S, SO or SO.sub.2 ;
Y is O or S;
Z is a carbon-carbon single bond or S;
or an agriculturally acceptable salt thereof.
15. A method for controlling undesirable vegetation according to claim 14, wherein: R.sup.1 is C.sub.1 -C.sub.3 alkyl or C.sub.1 -C.sub.3 haloalkyl; R.sup.2 is C.sub.1 -C.sub.3 alkyl or C.sub.1 -C.sub.3 haloalkyl; R.sup.3 is hydrogen; and R.sup.5 is hydrogen.
16. A method for controlling undesirable vegetation according to claim 14, wherein R.sup.1 is methyl; R.sup.2 is trifluoromethyl; R.sup.3 is hydrogen; R.sup.4 is cyclopropyl; R.sup.5 is hydrogen; R.sup.6 is hydrogen; R.sup.7 is methyl; R.sup.8 is hydrogen; R.sup.9 is hydrogen and Z is a carbon-carbon single bond.
17. A method for controlling undesirable vegetation according to claim 14 wherein R.sup.1 is methyl; R.sup.2 is trifluoromethyl; R.sup.3 is hydrogen; R.sup.4 is isopropyl; R.sup.5 is hydrogen; R.sup.6 is hydrogen; R.sup.7 is methyl; R.sup.8 is hydrogen; R.sup.9 is hydrogen and Z is a carbon-carbon single bond.
18. A method for controlling undesirable vegetation according to claim 14, wherein R.sup.1 is methyl; R.sup.2 is trifluoromethyl; R.sup.3 is hydrogen; R.sup.4 is ethyl; R.sup.5 is hydrogen; R.sup.6 is hydrogen; R.sup.7 is methyl; R.sup.8 is hydrogen; R.sup.9 is hydrogen and Z is a carbon-carbon single bond.
19. A method for controlling undesirable vegetation according to claim 14, wherein R.sup.1 is methyl; R.sup.2 is trifluoromethyl; R.sup.3 is hydrogen; R.sup.4 is cyclopropyl; R.sup.5 is hydrogen; R.sup.6 is hydrogen; R.sup.7 is chloro; R.sup.8 is hydrogen:, R.sup.9 is hydrogen and Z is a carbon-carbon single bond.

US Referenced Citations (1)

Number	Name	Date	Kind
4008249	Fischer et al.	Feb 1977

Foreign Referenced Citations (3)

Number	Date	Country
0 177 710A	Apr 1986	EPX
36 02 379	Jul 1987	DEX
08245594A	Sep 1996	JPX

Herbicidal substituted pyrazole compounds

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