MXPA98002601A - Benzisoxazoles and benzisoxazolidinonas heterociclicos herbici - Google Patents

Abstract

New benzisoxazoles and heterocyclic herbicidal benzisoxazolidinones of formula (I) are described, where A is (a), (b), (c), U = N or NR, R = H, alkyl, alkenyl, alkoxycarbonylalkyl, alkoxycarbonylhaloalkyl, benzyl, phenyl or cyanoalkyl, X = CO or CR2, R1 = H, CH2CN, CH2OCH3, alkyl, alkenyl, alkynyl, haloalkyl or amino, R2 = halogen, alkyl, aryl, haloalkyl, alkoxycarbonyl, arylalkyl or substituted haloalkyl; R3 = haloalkyl or alkyl; Y = H, halogen, cyano or haloalkyl, Z = H or halogen

Description

BENZISOXAZOLES AND BENZISOXAZO HETEROCYCLIC IDINONES HERBICIDES Background of the Invention The present invention relates in general to the control of weeds in agriculture, horticulture and other fields, where it is desired to control the growth of unwanted plants. it is related to certain 3- (benzisoxazol-7-yl and 1, 2- (2H) -benzisoxazolidin-3-on-7-yl) -heterocyclic herbicides and certain derivatives and novel intermediates thereof. present invention relates to certain (benziso-xazol-7-yl and 1,2- (2H) -benzisoxazolidin-3-on-7-yl) -heterocyclic herbicides, where the heterocycle is a 2,4- (1H, 3H ) -pyrimidinedione, a 4, 5, 6, 7-tetrahydro-lH-isoindol-l, 3-dione or a 1, 2, 5, 6,6-tetrahydro-l, 3, 5-triazine-2,6-dione. U.S. Patent 5,169,431 describes uracil herbicidal derivatives of the formula: 0? ^ .CF3 where R = alekyl, A and Y = H or halogen and Z = methyl or amino. U.S. Pat. 5,521,147 discloses herbicidal compounds of the formula: where D and E are independently H or alkyl and R is alkyl or amino. SUMMARY OF THE INVENTION It has now been discovered that certain 3- (benzisoxazol-7-yl and (2H) -benzisoxazolidin-3-on-7-yl) -heterocycles wherein the heterocycle is a 2,4- (1H, 3H) pyrim - dinadione, a 4, 5, 6, 7-tetrahydro-lH-isoindol-l, 3-dione or a 1, 2, 5, 6-tetrahydro-l, 3, 5-triazine-2,6-dione have good activity as pre- and post-emersion herbicides, especially on crop weeds such as wheat, corn and soybeans. The compounds are also effective as desiccants, which are useful in the control of total vegetation. This invention also relates to new intermediates useful for preparing the herbicidal compounds. DETAILED DESCRIPTION OF THE INVENTION The new compounds of the present invention have the following generic structure: where A is U = (a) N and X is linked to U by a double bond, or (b) NR and X is linked to U by a single bond; R = H, alkyl, alkenyl, alkoxycarbonylalkyl, (alkoxycarbonyl) alkoalkyl, benzyl, phenyl or cyanoalkyl; X = (a) CO when U is NR or (b) CR2 when U is N; R1 = H, alkyl, haloalkyl or amino; R2 = halogen, alkyl, alkoxy, cyanoalkoxy, phenyl optionally substituted with one or more halogen or alkyl, alkoxycarbonyl, alkoxycarbonylalkoxy, benzyl, benzyloxy or haloalkyl groups; R3 = alkyl or haloalkyl; Y = H, halogen, cyano or haloalkyl; Z = H or halogen. As used in this description, the terms "alkyl", "alkenyl", "alkynyl", "haloalkyl" and "alkoxy" used alone or as part of a larger moiety, include straight or branched carbon chains of 1 to 6 atoms of carbon. "Halogen" refers to fluorine, bromine or chlorine. "THF" means tetrahydrofuran, "DMF" means N, N-dimethylformamide and "DBU" means 1,8-diazabicyclo [5. 4. OJundec-7-ene. Preferred compounds of the present invention include those of the formulas IJE and III: where: R = CH3, CH2CH3 or CH (CH3) 2; R1 = CH3, CHF2 or NH2; R2 = CH3 or phenyl; Y = 4-Cl, 4-Br or 4-CN; Z = 6-F, 6-C1 or 6-H, and R3 = CH3 or CF3. Particularly preferred are compounds of formula I_I or III where: R = CH 3, CH 2 CH 3 or CH (CH 3) 2; R1 = CH3 or NH2; R2 = CH3; Y = 4-Cl or 4-Br; Z = 6-F or 6-H, and R3 = CH3 or CF3. Certain intermediates of the present invention are new. These include compounds of formulas IV and V: wherein R, Y and Z are as defined above for formula I, II or III and S = NH2, NHC02-alkyl or N = C = 0. The compounds of the present invention represented by formula II can be prepared as shown in the following Scheme I. An appropriately substituted chlorophenylcarboxylic acid is nitrated to give nitrobenzoic acid A, which can be converted to benzamide C in two stages, through of the acid chloride B. C undergoes cyclization with DBU to the corresponding (2-al? [uil-7-nitro-substituted) -1, 2 (2H) -benzisoxazolidin-3-one (D). The reduction of the nitro group of D with iron in acetic acid gives the amino intermediate E, as described below in Example 6. Alternatively, when Y or Z are Br (in order to direct the nitration in step a), the catalytic hydrogenation of the nitro group with Pd 10% / C produces a concomitant elimination of Br. Halogenated substituents can possibly be introduced by reaction of E with an N-halosuccinimide. Examples 2-5 provide details of these procedures. The isocyanate group of F is then cyclized with 3-amino-4,4,4-trifluoro-2-butenoate in the presence of an appropriate base in an inert solvent to form the pyrimidinedione ring of G. Examples of suitable bases are they include organic bases, such as triethylamine, pyridine and β, -diethylamine, and inorganic bases, such as sodium hydride and potassium carbonate. Examples of inert solvents which may be used include aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as chloroform and carbon tetrachloride, ethers such as diethyl ether, dioxane and tetrahydrofuran and DMF and dimethyl sulfoxide. The reaction temperature is preferably about 20 ° -80 ° C. The pyrimidinedione ring can then be variously substituted by N-alkylation with an R1-halide (step h of Scheme 1) to give compounds such as II-A, or by N-amination with 1-aminooxysulfo-nil-2 , 4,6-tri ethylbenzene in a suitable solvent, such as THF, in the presence of a suitable base, such as K2C03, to obtain compounds such as II-B. Examples 1, 2 and 3 provide details of this procedure. To obtain compounds of the present invention where the group R3 of II is CH3 more than CF3, the ethyl 3-amino-4,4,4-trifluorocrotonate of the above reaction is substituted with ethyl 3-aminocrotonate. To obtain compounds of the present invention where the group R1 of II is CHF2, the corresponding compound having R1 = H in a mixture of DMF and potassium carbonate at about 120 ° C can be heated, followed by bubbling of chlorodifluoromethane through the reaction mixture for about half an hour. SCHEME 1 bf A, X = OH B, X = C1 ^ C, X = N (R) OH G, Ri = H, R3 = CF3 - E, S = NH2 'C A, Rl =, at < ? uilo F, S = NCO •• is II-B, Ri = NH2 ß _ (a) HN03 / H2SO4, 30-35 ° C; (b) SOCl 2 or oxalyl chloride, heat; (c) NH (R) 0H, Et20, NaHCO3, H20; (d) DBU, CH3CN, heat; (e) Fe, HOAc, H20, 40-50 ° C; (f) ClC02CCl3, toluene, dioxane, heat; (g) CF3C (NH2) = CHC02CH2CH3, NaH, THF, heat; (h) R1X, K2C03, DMSO, heat; (i) 1-aminooxy-sulfonyl-2,4,6-trimethylbenzene, K2CO3, THF. The compounds of the present invention of formula III can be prepared as shown in the following Scheme 2. The choice of starting material depends on whether R2 is phenyl or alkyl. If R2 = phenyl, a 2-halobenzophenone is treated with triethylamine and hydroxylamine hydrochloride to form the corresponding benzophenone oxime H-1. If, on the other hand, R2 = alkyl, a 2-haloacetophenone is treated with an acetone oxime under basic conditions to form the corresponding acetophenone oxime ether H-2. H-2 can be cycled under acidic conditions and H-1 can be cyclized under basic conditions to obtain the corresponding (3-alkyl or 3-substituted phenyl) -1,2 (2H) -benzisoxazole (I.). For the introduction of the heterocyclic ring A in the compounds of the present invention, it is possible to first functionalize I. in the 7-position by treatment with p-butyl-lithium and solid CO 2 to obtain the carboxylic acid K. The rearrangement of K in the presence of triethylamine and diphenylphosphorylazide forms the corresponding t-butyl 1,2 (2H) -benzisoxazolyl carbamate (L). Treatment of L with trifluoroacetic acid gives the aniline M, which in turn reacts with trichloromethylchloroformate to give the isocyanate N. Using methods analogous to those described above for Scheme 1, the cyclization of N provides the pyrimidinedione 0, which can be converted turn in III. where R1 is an amino or alkyl group. Examples 4-6 provide details of this procedure. The construction of the pyrimidinedione ring starting from the anilines E in Scheme 1 and M in Scheme 2 to obtain the compounds of the formulas II and III of the present invention can also be prepared by the methods described in US Pat. 5,169,431, incorporated herein by reference. According to this reference, E can be converted into an alkylcarbamate to give F ', where S = NHC02-alkyl. F 'is treated in general in the same way as F to obtain G, except for the fact that the reaction temperature is preferably about 80 ° -120 ° C when F' is used. In a similar way, M can be converted to O by the formation of an alkylcarbamate intermediate. SCHEME 2 (a) (1) NH20H-HC1, Et3N, (2) tBuOH; (b) EtOH, KOH aq. , to warm; (c) acetone oxime, KOtBu, THF; (d) HCl, EtOH, heat; (e) (1) n-BuLi, THF, (2) C02, -30 at -50 ° C; (f) (1) Et3N, diphenylphosphorylazide, (2) tBuOH, heat; (g) trifluoroacetic acid; (h) C1C02CC13, toluene, 80 ° C; (i) CF3C (NH2) = CHCOCH2CH3, NaH, THF, heat; (j) RXX, K2C03, DMSO, heat; (k) l-aminooxy-sulfonyl-2,4,6-trimethylbenzene, K2CO3, THF. Scheme 3 illustrates a method for the preparation of compounds of the present invention wherein the heterocyclic ring is a tetrahydrophthalimide. Intermediate E, prepared as described above, undergoes condensation with an anhydride P under acidic conditions to obtain IV. Example 7 below provides details of this procedure. To obtain compounds of the present invention which contain a 1, 2, 5, 5,6-tetrahydro-1,3,5-triazine-2,6-dione ring, the above compounds E and M can serve as starting materials, followed of triazineadione ring construction according to methods known in the art (for example, European Patent Application 640 600 Al).

SCHEME 3 SAW The compounds of the present invention can also be prepared according to the procedures shown in the following examples, by methods analogous to those shown in the Examples or by other methods generally known or available to one skilled in the art. Example 1 Synthesis of 3- [4-chloro-2-methyl-1], 2 (2H) -benzisoxazolidin-3-on-7-yl] -1-methyl-6-trifluoromethyl-2,4 (1H, 3H) -pyrimidinedione (Compound 2) Step A N-methyl-N-hydroxy-2 -chloro-3-nitrobenzamide To a stirred solution of 2-chloro-3-nitrobenzoic acid (6.0 grams, 0.031 mol) in toluene (100 ml) was added thionyl chloride (6.8 ml, 0.092 mol). After the addition was complete, the reaction mixture was heated to reflux, where it was stirred for four hours. After this time, the reaction mixture was filtered and concentrated. The concentrate was taken up in ether and added dropwise to an ice-cooled solution of N-methylhydroxylamine hydrochloride (2.6 g, 0.031 mol), sodium bicarbonate (5.5 g, 0.065 mol), water (20 ml). ) and ether (160 ml). After the addition was complete, the reaction mixture was stirred for one hour. After this time, the reaction mixture was diluted with water and the ether layer was separated. The aqueous layer was extracted twice with ether. The ether layer and the combined extracts were dried over magnesium sulfate and concentrated to obtain 6.4 grams of N-methyl-N-hydroxy-2-chloro-3-nitrobenzamide. The NMR spectrum was consistent with the proposed structure. Step B 2-Methyl-7-nitro-1,2 (2H) -benzisoxazolidin-3-one A stirred solution of N-methyl-N-hydroxy-2-chloro-3-nitrobenzamide (6.0 g, 0.026) was heated. moles) and DBU (4.0 g, 0.026 moles) in acetonitrile (63 ml) at reflux for 30 minutes. The reaction mixture was concentrated and the resulting concentrate was partitioned between a mixture of ethyl acetate and water. The mixture was then extracted three times with ethyl acetate. The combined extracts were dried over magnesium sulfate and concentrated. Column chromatography on silica gel using heptane and ethyl acetate 7: 3 gave 3.0 grams of 2-methyl-7-nitro-1,2 (2H) -benzisoxazolidin-3-one. The NMR spectrum was consistent with the proposed structure. Step C 7-Amino-2-methyl-l, 2- (2H) -benzisoxazolidin-3-one A stirred solution of 2-methyl-7-nitro-1,2 (2H) -benzisoxazolidin-3-one was heated ( 3.3 g, 0.02 mol) in acetic acid (100 ml) and water (15 ml) at 40-45 ° C and iron powder (8.0 g, 0.145 mol) was added. After the addition was complete, the reaction mixture was stirred for two hours at 40-45 ° C. The reaction mixture was then diluted with water (150 ml) and methylene chloride (150 ml) and allowed to stand at room temperature for about 18 hours. After this time, the mixture was filtered through diatomaceous earth and the filter cake was washed with methylene chloride. The combined filtrate and washings were placed in a separatory funnel and stirred with a saturated aqueous solution of sodium bicarbonate. The organic layer was dried over magnesium sulfate and concentrated to obtain 7-amino-2-methyl-1,2 (2H) -benzisoxazolidin-3-one. The NMR spectrum was consistent with the proposed structure.

Step D 7-Amino-4-chloro-2-methyl-1,2 (2H) -benzisoxazolidin-3-one A stirred solution of 7-amino-2-methyl-1,2 (2H) -benzisoxazolidin was cooled. -3-one (3.3 g, 0.02 mole) in DMF (60 ml) at -10 ° C and a solution of N-chlorosuccinimide (2.7 g, 0.02 mole) in DMF was added slowly ( 10 mi) -. After the addition was complete, the reaction mixture was heated to room temperature, where it was stirred for about 18 hours. After this time, the reaction mixture was poured into water and the mixture was extracted four times with ether. The combined extracts were dried with magnesium sulfate and concentrated. The concentrate was purified by silica gel column chromatography using heptane and ethyl acetate 1: 1 to obtain 1.4 grams of 7-amino-4-chloro-2-methyl-1,2 (2H) benzisoxazolidin-3. ona, pf 140-141 ° C. The NMR spectrum was consistent with the proposed structure. Step E [4-Chloro-2-methyl-1,2 (2H) -benzisoxazolidin-3-on-7-yl] isocyanate To a stirred mixture of 7-amino-4-chloro-2-methyl-1, 2 ( 2H) -benzisoxazolidin-3-one (1.4 g, 0.007 mol) in dioxane (50 ml) was added trichloromethyl chloroformate (1.2 ml, 0.007 moles). The reaction mixture was heated at reflux for 18 hours and then filtered and concentrated to obtain 1.5 grams of 4-chloro-2-methyl-1,2 (2H) -benziso-xazolidin-3-on-7-. il] isocyanate. Step F 3- [4-Chloro-2-methyl-l, 2 (2H) -benzisoxazolidin-3-on-7-yl] -l-methyl-6-trifluoromethyl-2,4 (1 H, 3 H) -pyrimidinedione ( Compound 2) A solution of sodium hydride (0.3 g, 0.007 mole, 60% in mineral oil) and ethyl 3-amino-4, 4, 4-trifluorocrotonate (1.2 g, 0.004 mole) was stirred and it was cooled to -20 ° C in an ice bath. A solution of 4-chloro-2-methyl-1,2,2 (2H) -benzisoxazolidin-3-on-7-yl] isocyanate (1.5 g, 0.007 mol) in 40 ml of THF was slowly added to this solution. The reaction mixture was then stirred at room temperature for one hour and refluxed for four hours. After this time, the reaction mixture was filtered and concentrated, yielding the sodium salt of 3- [4-chloro-2-methyl-1,2 (2H) -benzisoxazolidin-3-on-7-yl] -6-trifluoromethyl-2, 4 (1H, 3H) -pyrimidinedione, mp 184-187 ° C, as a yellow brown solid. The sodium salt was washed with ether, collected by filtration and then taken up in a solution of methyl iodide (2.8 g, 0.020 mol), potassium carbonate (1.8 g, 0.014 mol) and DMF ( 60 mi). The reaction mixture was stirred at room temperature for approximately 18 hours, poured into water and extracted with ether. The extract was dried with magnesium sulfate and concentrated to give 0.2 grams of Compound 2, m.p. 159-161 ° C. The NMR spectrum was consistent with the proposed structure. Example 2 Synthesis of 3- [4-bromo-2-methyl-1,2- (2H) -benzisoxazolidin-3-on-7-yl] -l-methyl-6-trifluoromethyl-2,4 (1H, 3H) - pyrimidinedione (Compound 5) Step A 7-Amino-2-methyl-1,2 (2H) -benzisoxazolidin-3-one as an intermediate Under a nitrogen atmosphere, a solution of 5-bromo-2-methyl-7- was hydrogenated nitro-l, 2 (2H) -benzisoxa-zolidin-3-one (10.4 g, 0.043 mol) in ethanol (200 ml) in a Parr apparatus in the presence of 10% Palladium on carbon (0.03 grams) in dioxane (0.50 ml). The reaction mixture was filtered and concentrated, after which the residue was dissolved in ethyl acetate and neutralized with sodium bicarbonate. The organic layer was separated and the aqueous layer was extracted twice with ethyl acetate. The organic layer and the combined extracts were dried with magnesium sulfate and concentrated to give 10.0 grams of a reddish brown solid. The solid was subjected to silica gel column chromatography using heptane and ethyl acetate 1: 1, followed by pure ethyl acetate. The starting material was recovered, as determined by the NMR and IR spectra. As a result, the above hydrogenation was repeated using 0.40 g of Palladium 10% on carbon, 200 ml of ethanol and 30 ml of acetic acid. After approximately seven hours of hydrogenation, the reaction mixture was analyzed by TLC, which indicated that the reaction had not been completed. The reaction mixture was allowed to stand for about 18 hours and then an additional 0.30 grams of 10% Palladium on carbon was added to the reaction mixture. The hydrogenation was continued for 2.5 hours. The reaction mixture was then analyzed by TLC, which indicated that the reaction had been completed. The product was isolated from the reaction mixture in the manner indicated above, yielding 6.0 grams of 7-amino-2-methyl-1,2 (2H) -benzisoxazolidin-3-one. The NMR spectrum was consistent with the proposed structure. Step B 7-Amino-4-bromo-2-methyl-1,2 (2H) -benzisoxazolidin-3-one This compound was prepared in the same manner as in Step D, Example 1, using 7-amino- 2-methyl-1,2 (2H) -benzisoxazolidin-3-one (2.2 g, 0.014 mol), DMF (50 ml) and N-bromosuccinimide (2.7 g, 0.015 mol). The yield of 7-amino-4-bromo-2-methyl-1,2,2 (2) -benzisoxazo-lidin-3-one was 2.5 grams. The NMR spectrum was consistent with the proposed structure. Step C [4-Bromo-2-methyl-1,2 (2J?) -benzisoxazolidin-3-on-7-yl] isocyanate This compound was prepared in the same manner as in Step E, Example 1, using 7-amino -4-bromo-2-methyl-1,2 2H) -benzisoxazolidin-3-one (2.2 g, 0.009 mol), toluene (100 ml), trichloromethyl chloroformate (1.8 g, 0.009 mol) and dioxane (30 mi). The yield of [4-bromo-2-methyl-1,2,2 (2J?) -benzisoxazolidin-3-on-7-yl] isocyanate was about 2.4 grams. The IR spectrum was consistent with the proposed structure. Step D 3- [4-Bromo-2-methyl-1,2- (2i?) - benzisoxazolidin-3-yn-7-yl] -l-methyl-6-trifluoromethyl-2,4 (l, 3H) -pyrimidinedione (Compound 5) This compound was prepared in the same manner as in Step F, Example 1, using sodium hydride (0.43 g, 0.011 mol, 60% in mineral oil), 3-amino-4, 4, 4- ethyl trifluoromethacrylate (1.6 g, 0.009 mole), THF (80 ml), [4-bromo-2-methyl-1,2,2 (2-yl) -benzisoxazolidin-3-on-7-yl] isocyanate (2.4 g, 0.009 mole), methyl iodide (1.5 g, 0.011 mole), potassium carbonate (1.5 g, 0.011 mole) and dimethyl sulfoxide (15 ml). The yield of Compound 5 was 0.85 grams, m.p. 201-203, 5 ° C. The NMR spectrum was consistent with the proposed structure. EXAMPLE 3 Synthesis of 3- [4-bromo-2-isopropyl-l, 2 (2H) -benzisoxazolidin-3-on-7-yl] -l-amino-6-trifluoromethyl-2,4 (l, 3H) - pyrimidinedione (Compound 11) A solution of 3- [4-bromo-2-isopro-pyl-1,2 (2H) -benzisoxazolidin-3-on-7-yl] -6-trifluoromethyl-2,4 (1H) was stirred. , 3H) -pyrimidinedione (1.1 g, 0.002 mole), 1-amino-oxysulfonyl-2,4,6-trimethylbenzene (0.5 g, 0.002 mole), potassium carbonate (0.4 g, 0.003 mole) and THF (15 ml) at room temperature for 18 h. The reaction mixture was diluted with water and extracted with ethyl acetate (3 x 50 mL). The combined extracts were dried over magnesium sulfate and concentrated. Chromatography on silica gel using heptane and ethyl acetate gave 0.5 grams of the Compound 11. The NMR spectrum was consistent with the proposed structure.

EXAMPLE 4 Synthesis of 3- [4-chloro-6-fluoro-3-methyl-1,2 (2H) -benzisoxazol-7-yl] -l-methyl-6-trifluoromethyl-2,4 (lff, 3i) - pyrimidinedione (Compound 27) Step A 2- (2-Propyliminooxy) -4-fluoroacetophenone A mixture of potassium t-butoxide (9.0 g, 0.08 mole) and acetone oxime (5.9 g, 0, 08 moles) in THF (50 ml) for one hour. The mixture was added dropwise to a solution of 2,4-difluoroacetophenone (13.7 g, 0.08 mol) in THF (50 ml) over a period of one minute. After the addition was complete, the reaction mixture was stirred for 30 minutes. The reaction mixture was then poured into a saturated aqueous solution of ammonium chloride. The mixture was extracted with ether and the extract was washed with water. The extract was dried with magnesium sulfate and concentrated to a residue. The residue was subjected to silica gel column chromatography using hexane and methylene chloride. The chromatographed product (18.3 g) was recrystallized from hexane, yielding 8.2 grams of 2- (2-propylimino-nooxy) -4-fluoroacetophenone, m.p. 57-58 ° C. The NMR spectrum was consistent with the proposed structure. Step B 6-Fluoro-3-methyl-1,2 (2i?) -benzisoxazole A stirred solution of 2- (2-propyliminooxy) -4-fluoroacetophenone (7.8 g, 0.037 mol), 1 N aqueous HCl was heated. (30 ml) and ethanol (30 ml) at reflux for three hours. After this time, the reaction mixture was poured into water and extracted thoroughly with ether. The combined extracts were washed with water. The organic layer was dried with magnesium sulfate and concentrated to give 5.5 grams of 6-fluoro-3-methyl-1,2 (2H) -benzisoxazole. The NMR spectrum was consistent with the proposed structure. Step C [6-Fluoro-3-methyl-1,2 (2H) -benzisoxazol-7-yl] carboxylic acid A stirred solution of 6-fluoro-3-methyl-1,2 (2tf) -benzisoxazole (5) was cooled. , 5 g, 0.037 mol) in THF (100 ml) in a dry ice-acetone bath and 2.5 M n-butyllithium in hexanes (16 ml, 0.040 mol) was added dropwise, after addition was complete, the reaction mixture was stirred for one hour. The reaction mixture was then exposed to an atmosphere of C02, where it was stirred for three hours. After this time, the reaction mixture was poured into water. The mixture was washed with ether, acidified with hydrochloric acid and then repeatedly extracted with ether. The combined extracts were washed with water, dried with magnesium sulfate and concentrated to obtain 4.5 grams of [6-fluoro-3-methyl-1,2 (2H) -benzisoxazol-7-yl] carboxylic acid. The NMR spectrum was consistent with the proposed structure. Stage D N- (6-fluoro-3-methyl-1,2- (2H) -benzisoxazol-7-yl) carbamic acid t-butyl ester and 7-amino-6-fluoro-3-methyl-1,2 (2i) -benzisoxazole A stirred solution of [6-fluoro-3-methyl-1,2 (2H) -benzisoxazol-7-yl] carboxylic acid (5.3 g, 0.027 mol), diphenylphosphoryl azide (7.4 g, 0.027 mol) and triethylamine (2.7 g, 0.027 mol) in t-butyl alcohol (100 ml) at reflux for about 72 hours. After this time, the reaction mixture was concentrated to a residue. The residue was chromatographed on a silica gel column using hexane and ethyl acetate 9: 1 to 1: 1. Fractions containing N- (6-fluoro-3-methyl-1,2,2- (2i?) -benzisoxazol-7-yl) carbamate t-butyl were combined and concentrated to give 3.7 grams of that product, mp. 121-123 ° C. The fractions containing 7-amino-6-fluoro-3-methyl-1,2,2 (2H) -benzisoxazole were combined and concentrated, obtaining 1.4 grams of that product. The NMR spectra were consistent with the proposed structures. Step E 7-Amino-6-fluoro-3-methyl-1,2 (2H) -benzisoxazole Trifluoroacetic acid (50 ml) was stirred and cooled in an ice-water bath. To this was added N- (6-fluoro-3-methyl-1,2- (2 * 0 -benzisoxazol-7-yl) t-butyl carbamate (3.0 g) After completion of the addition, the mixture was stirred. The reaction mixture was taken up in water and made basic at pH 8 with sodium bicarbonate, then the mixture was thoroughly extracted with methylene chloride, and the combined extracts were washed with water.were dried with magnesium sulfate and concentrated to give 2.1 grams of 7-amino-6-fluoro-3-methyl-1,2 (2-3) -benzisoxazole. The NMR spectrum was consistent with the proposed structure. Step F 7-Amino-4-chloro-6-fluoro-3-methyl-1,2 (2H) -benzisoxazole A solution of 7-amino-6-fluoro-3-methyl-1,2 (2-phenyl) was stirred. ) -benzisoxazole (3.5 g, 0.021 mole) in DMF (50 ml) and a solution of N-chlorosuccinimide (2.8 g, 0.02 mole) in a minimum amount of DMF per drop was added. After the addition was complete, the reaction mixture was stirred for about 18 hours. After this time, the reaction mixture was poured into 10% aqueous lithium chloride and then thoroughly extracted with ether. The combined extracts were washed with 10% aqueous lithium chloride, dried with magnesium sulfate and concentrated to a residue. The residue was chromatographed on a silica gel column using hexane and ethyl acetate 9: 1 to 4: 1 to obtain 2.6 grams of 7-amino-4-chloro-6-fluoro-3-methyl. 1, 2 (2H) -benzisoxazole. The NM spectrum was consistent with the proposed structure. Step G 3- [4-Chloro-6-fluoro-3-methyl-1,2 (22?) -benzisoxazol-7-yl] -6-trifluoromethyl-2,4 (1H, 3H) -pyrimidinedione added trichloromethylchloroformate (2.5 g, 0.013 mol) was added dropwise to a stirred solution of 7-amino-4-chloro-6-fluoro-3-methyl-1,2 (2H) -benzisoxazole (2.6 g, 0.013 mol) in toluene (50 ml). After completion of the addition, the reaction mixture was heated to 80 ° C, where it was stirred for about 18 hours. After this time, the reaction mixture was concentrated to obtain 3- [4-chloro-6-fluoro-3-methyl-1,2 (2H) -benzisoxazol-7-yl] isocyanate. In a separate reaction vessel, sodium hydride (0.8 g, 0.019 mol, 60% in mineral oil) was washed twice with heptane and then taken up in THF (100 mL). The stirred mixture was cooled to -20 ° C and a solution of ethyl 3-amino-4,4,4-trifluorocrotonate (2.5 g, 0.013 mol) in a minimum amount of THF was added dropwise. After completion of the addition, the reaction mixture was stirred for 10 minutes and then a solution of the above isocyanate in a minimum amount of THF was added. The reaction mixture was allowed to warm to room temperature and then heated just below reflux where it was stirred for about 18 hours. After this time, the reaction mixture was concentrated to a residue and water was added. The resulting solution was washed with ether and acidified with concentrated hydrochloric acid. The mixture was thoroughly extracted with ether and the extracts were washed with water. The organic layer was separated, dried with magnesium sulfate and concentrated to a solid residue. The residue was subjected to silica gel column chromatography using hexane and ethyl acetate 9: 1 to 1: 1, obtaining 4.1 grams of 3- [4-chloro-6-fluoro-3-methyl-1, 2]. (2 H) -benzisoxazol-7-yl] -6-trifluoromethyl-2,4 (1 H, 3 H) pyrimidinedione. The spectrum of NMR was consistent with the proposed structure. Step H 3- [4-Chloro-6-fluoro-2-methyl-1,2 (2H) -benzisoxazol-7-yl] -l-methyl-6-trifluoromethyl-2,4 (1H, 3H) - pyrimidinedione (Compound 27) A solution of 3- [4-chloro-6-fluoro-3-methi1-1,2 (2H) -benzisoxazol-7-yl] -6-trifluoromethyl-2,4 (1H) was heated to reflux. , 3H) -pyrimidinedione (3.6 g, 0.010 mole), methyl iodide (2.1 g, 0.014 mole), potassium carbonate (2.0 g, 0.003 mole) and THF (100 ml) and thus stirred for five hours. The reaction mixture was then cooled to room temperature, where it was stirred for about 72 hours. After this time, the reaction mixture was poured into water and thoroughly extracted with ether. The combined extracts were washed with water and a saturated aqueous solution of sodium chloride. The organic layer was separated, dried with magnesium sulfate and concentrated to a residue. The residue was chromatographed on silica gel using hexane and ethyl acetate 9: 1 to 5: 1. The fractions containing product gave 2.0 grams of Compound 27, m.p. 218-219 ° C. The NMR spectrum was consistent with the proposed structure. EXAMPLE 5 Synthesis of 3- [4-chloro-6-fluoro-3-phenyl-1,2 (2H) -benzisoxazol-7-yl] -l-amino-6-trifluoromethyl-2,4 (1-yl, 3 -fr) -pyrimidinedione (Compound 34) 1-Amino-oxysulfonyl-2,4,6-trimethylbenzene (0.5 g, 0.002 mole) was added all at once to a stirred solution of 3- [4-chloro-6 -fluoro-3-phenyl-l, 2 (2H) -benzisoxa-zol-7-yl] -6-trifluoromethyl-2,4 (1H, 3H) -pyrimidinedione (0.8 g, 0.002 mole) and potassium carbonate (0.4 g, 0.003 mol) in THF (50 ml). After the addition was complete, the reaction mixture was stirred at room temperature for approximately 18 hours. After this time, the reaction mixture was filtered and the filtrate was concentrated to a residue. The residue was subjected to silica gel column chromatography using hexane and ethyl acetate 4: 1. The fractions containing product were combined and concentrated, obtaining 0.6 grams of Compound 34, m.p. 171-173 ° C. The NMR spectrum was consistent with the proposed structure.

EXAMPLE 6 Synthesis of 3- [4-chloro-6-fluoro-3-phenyl-1,2 (2H) -benzisoxazol-7-yl] -l-methyl-6-trifluoromethyl-2,4 (l, 3i) - pyrimidinedione (Compound 31) This compound was prepared in the same manner as in Step H, Example 4, using 3- [4-chloro-6-fluoro-3-phenyl-1,2 (2H) -benzisoxazol-7-yl] -6-trifluoromethyl-2,4 (1H, 3H) -pyrimidinedione (0) , 8 g, 0.002 mole), methyl iodide (0.03 g, 0.002 mole), potassium carbonate (0.5 g, 0.004 mole) and THF (50 ml). The yield of Compound 31 was 0.5 grams. The NMR spectrum was consistent with the proposed structure. Example 7 Synthesis of 4,5,6,7-tetrahydro-2- [4-bromo-2-isopropyl-1,2 (2H) -benzisoxazolidin-3-on-7-yl] -líi-isoindol-1,3 (Ii) -dione (Compound 62) A stirred solution of 7-amino-4-bromo-2-isopropyl-l, 2 (2H) -benzisoxazolidin-3-one (0.13 g, 0.0005 mole) and 4,5,6,7-tetrahydro-l, 3-isobenzofurandione (0.072 g, 0.0005 mole) in glacial acetic acid (40 ml) at reflux and stirred well for 18 hours. After this time, the reaction mixture was poured into water and the resulting solution was extracted three times with ether. The combined extracts were dried with magnesium sulfate and concentrated to a residue. This residue was subjected to silica gel column chromatography using methylene chloride, obtaining 0.08 grams of Compound 62, p.f. 115-116 ° C. The NMR spectrum was consistent with the proposed structure.

Table 1: Representative compounds of the present invention Table 2. Empirical formula and characterization data for representative compounds HERBICIDE ACTIVITY The compounds of the present invention were studied for pre- and post-immersion herbicidal activity using a variety of crop and weed plants. The test plants included soybeans (Gly cine max var. Winchester), field corn (Zea mays var. Pioneer 3732), wheat (Triticum aestivum var. Lew), morning glory (Ipomea lacunosa or Ipomea hederacea), mallow (Abutilon theophrasti), green almorejo (Setaria viridis), cañota (Sorghum halepense), foxtail (Aloepecurus myosuroi-des), common chickweed (Stellaria media) and common carp (Xanthiu strumariu L.). For the pre-emersion tests, two disposable fiber beds (8 cm x 15 cm x 25 cm) were filled for each application rate of each candidate herbicide to a depth of 6.5 cm with sandy loam soil sterilized with steam . The soil was leveled and printed with a template to obtain five homogeneously spaced grooves 13 cm long and 0.5 cm deep on each floor. Soybeans, wheat, corn, green almorejo and cannabis seeds were planted in the furrows of the first floor and mauve seeds, day morning glory, common chickweed, cormorant and foxtail were planted in the furrows of the second floor. The five-row template was used to firmly press the seeds into place. A covering floor of equal portions of sand and sandy loam soil was uniformly applied on top of each floor to a depth of approximately 0.5 cm. Floors were prepared for the post-emersion tests in the same way, except for the fact that they were planted 9-14 days before the pre-emersion floors and that they were put in a greenhouse and watered, allowing the seeds to germinate and that the foliage will develop. In both pre- and post-emersion tests, a stock solution of the candidate herbicide was prepared by dissolving 0.27 g of the compound in 20 ml of water / acetone (50/50) containing 0.5% v / v of sorbitan monolaurate. For a rate of application of 3000 g / ha of herbicide, a portion of 10 ml of the stock solution was diluted with water / acetone (50/50) to 45 ml. The following table shows the volumes of stock solution and diluent used to prepare the solutions for the lower rates of application: The pre-emersion floors were initially subjected to a light spray with water. The four floors were placed two to two along a conveyor belt (ie, the two floors pre-emersion, followed by the two floors post-emersion). The conveyor belt was fed under a spray nozzle mounted approximately ten inches above the post-emersion foliage. The pre-emersion floors were raised on the belt in such a way that the surface of the soil was at the same level below the spray nozzle as the foliage roof of the plungers. After starting and stabilizing the spray of the herbicidal solution, the floors were passed under the sprayer at such a rate that it received a covered amount equivalent to 1000 L / ha. At this covered quantity, the application speeds are those shown in the table above for the individual herbicidal solutions. The pre-emersion floors were watered immediately after, placed in a greenhouse and regularly watered on the surface of the soil. The post-emersion floors were immediately placed in the greenhouse, but were not watered until 24 hours after the treatment with the test solution. Then, they were regularly watered at ground level. After 12-17 days, the plants were examined and phytotoxicity data were recorded. In Tables 3 and 4 the data of herbicidal activity are given at selected rates of application for various compounds of the present invention. The test compounds are identified by numbers corresponding to those in Table 1. The phytotoxicity data are taken as a percentage of the control. The percentage of control is determined by a method similar to the titration system from 0 to 100 described in "Research Methods in Weed Science", 2 ^ ed. , B. Truelove, Ed. (Southern Weed Science Society, Auburn University, Auburn, Alabama, 1977). The valuation system is as follows: Rating Description Description Description (% control) of the of the main crop weed categories No effect No reduction No control of or damage in the weeds harvest 10 Light light discoloration Very good control or atrophy bre of weeds Some decoloControl poor ration, atrophy or of the bad loss of herbal support Damages in the harvest Poor poor quality control, but not the long-lasting bad herbs 40 Effect Moderate damage, Moderate control Harvest is deficient Recovers normals Bad mind herbs 50 Sewage damage Detrimental control more durable to moderate, doubtful due to bad herbs 60 Durable damage Control moderaen the harvest, no do of the bad there is recovery herbs 70 Serious Serious Damage and Control Something Support Loss We Satisfied 80 Harvest almost DesControl of satruida, some tisfactorio to how many superbueno of the living weeds 90 Only plan leftControl of very alive, good to good 100 Completely Complete Complete Destruction Effect of Weed Harvesting) Table 3: Pre-emersion herbicidal activity (% control) fifteen The proportion is in kg / hectare. ABUTH is mauve; IPOSS, morning glory; STEME chickweed; XANPE, cadillo; ALOMY, foxtail; SETVI, green almorejo; SORHA, cañota.

Table 4: Post-emersion herbicidal activity (% control) fifteen The proportion is in kg / hectare. ABUTH is mauve; IPOSS, morning glory; STEME chickweed; XANPE, cadillo; ALOMY, foxtail; SETVI, green almorejo; SORHA, cañota.

The herbicidal compositions are prepared by combining herbicidally effective amounts of the active compounds with adjuvants and carriers normally employed in the art to facilitate the dispersion of the active components for the particular utility desired, recognizing the fact that the Formulation and mode of application of a toxicant can affect the activity of the material in a given application. Therefore, for agricultural use the present herbicidal compounds can be formulated as granules of relatively large particle , such as water-soluble or water-dispersible granules, as powder powders, 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. It must be understood that the amounts specified in this description are intended to be only approximate, as if the word "approximately" were placed in front of the indicated quantities. These herbicidal compositions can be applied as sprays diluted in water or as powders or granules to areas where a suppression of vegetation is desired. These formulations may contain from only 0.1%, 0.2% or 0.5% to even 95% or more by weight of active component. The powders are free-flowing mixtures of the active component with finely divided solids, such as talc, natural clays, tripoli, flours such as walnut shells and cottonseed flours and other organic and inorganic solids which act as dispersants and vehicles for the toxicant; these finely divided solids have an average particle of less than about 50 microns. A typical powder formulation useful herein is one that contains 1.0 part or less of the herbicidal compound and 99.0 parts of talc.

Wettable powders, also useful formulations for both pre-emersion and postemersion herbicides, are in the form of finely divided particles which are easily dispersed in water or other dispersant. The wettable powder is applied last to the soil as a dry powder or as an emulsion in water or another liquid. Typical vehicles for wettable powders include fuller's earth, kaolin clays, silicas and other inorganic diluents highly absorbent and easily moistened. Wettable powders are usually prepared so as to contain about 5-80% active component, depending on the absorbency of the vehicle, and usually also contain a small amount of a wetting, dispersing or emulsifying agent to facilitate dispersion. For example, a useful formulation of wettable powder contains 80.0 parts of the herbicidal compound, 17.9 parts of Palmetto clay and 1.0 part of sodium lignosulfonate and 0.3 parts of a sulfonated aliphatic polyester as wetting agents. Frequently, additional wetting agent and / or oil will be added to the tank mix for post-dip application, to facilitate dispersal over the foliage and absorption by the plant. Other formulations useful for herbicidal applications are emulsifiable concentrates (CEs), which are homogeneous liquid dispersible dispersions 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 such as xylene, heavy aromatic naphthas, isophorone or other non-volatile organic solvents. For the herbicidal application, these concentrates are dispersed in water or another liquid vehicle and are normally applied as a spray to the area to be treated. The percentage by weight of the essential active component can vary according to the way in which the composition is to be applied, but, in general, it consists of 0.5 to 95% of the active component by weight with respect to the herbicidal composition. The flowable formulations are similar to the CEs, except for the fact that the active component is suspended in a liquid vehicle, usually water. The flowables, like the CEs, may include a small amount of a surfactant and will typically contain active components in the range of 0.5 to 95%, often 10 to 50%, by weight of the composition. For the application, the fluids can be diluted in water or another liquid vehicle and are normally applied as a spray to the area to be treated. Typical wetting, dispersing or emulsifying agents used in agricultural formulations include, but are not limited to, alkyl and alkylaryl sulfonates and sulfates and their sodium salts, alkylaryl polyether alcohols, sulfated higher alcohols, polyethylene oxides, animal and sulphonated vegetable oils, sulfonated petroleum oils, fatty acid esters and polyhydric alcohols and the ethylene oxide addition products of said esters and the long chain mercaptan addition product and ethylene oxide. Many other types of useful surfactants can be obtained commercially. The surfactants, when used, normally represent 1 to 15% by weight of the composition. Other useful formulations include suspensions of the active component in a relatively non-volatile solvent, such as water, corn oil, kerosene, propylene glycol or other suitable solvents. Still other formulations useful for herbicidal applications include simple solutions of the active component in a solvent in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene or other organic solvents. The granular formulations, where the toxicant is transported in relatively coarse particles, are of particular utility for aerial distribution or for the penetration of awnings for covering the crops. Pressurized sprays, typically aerosols where the active component is dispersed in finely divided form as a result of vaporization of a low boiling point dispersant solvent vehicle, such as fluorinated Freon hydrocarbons, can also be used. The granules soluble in water or dispersible in water are free flowing, non-dusty and easily soluble in water or miscible in water. The soluble or dispersible granular formulations described in US. 3,920,442 are useful herein with the present herbicidal compounds. When used by the farmer in the field, the granular formulations, the emulsifiable concentrates, the flowable concentrates, the solutions, etc., can be diluted with water to obtain an active component concentration in the range of, say, 0, 1% or 0.2% at 1.5% or 2%. The active herbicidal compounds of this invention can be formulated and / or applied with insecticides, fungicides, nematocides, plant growth regulators, fertilizers or other agricultural chemicals and can be used as effective soil sterilants, as well as selective herbicides in agriculture. . By applying an active compound of this invention, whether formulated alone or with other agricultural chemicals, of course, an effective amount and concentration of the active compound is employed.; the amount can be, for example, only about 1 to 250 g / ha, preferably about 4 to 30 g / ha. For field use, where there are losses of herbicide, higher proportions of application can be used (for example, four times the proportions cited above).

The active herbicidal compounds of the present invention can also be used in combination with other herbicides. Such herbicides include, for example, N- (phosphonoethyl) glycine ("glyphosate"); aryloxyalkanoic acids, such as (2,4-dichlorophenoxy) acetic acid ("2,4-D"), (4-chloro-2-methylphenoxy) acetic acid ("MCPA"), acid (+/-) -2- (4-chloro-2-methylphenoxy) propanoic (MCPP); ureas, such as -V / N-dimethyl-W - [4- (1-methylethyl) phenyl] urea ("isoproturon"); imidazolinones, such as 2- [4,5-dihydro-4-methyl-4- (1-methylethyl) -5-oxo-lH-imidazol-2-yl] -3-pyridinecarboxylic acid ("azapir"), a reaction product consisting of (+/-) -2- [4,5-dihydro-4-methyl-4- (1-methylethyl) -5-oxo-1-yl-imidazol-2-yl] -4-methylbenzoic acid and (+/-) -2- [4,5-Dihydro-4-methyl-4- (l-methylethyl) -5-oxo-l, im-imidazol-2-yl] -5-methylbenzoic acid ("imaza-metabenz" ), acid (+/-) -2- [4,5-dihydro-4-methyl-4- (l-methylethyl) -5-oxo-lf-imidazol-2-yl] -5-ethyl-3-pyridinecarbo -xylic ("imazethapyr"), lactide (+/-) - 2- [4,5-dihydro-4-methyl-4- (1-methylethyl) -5-oxo-li-imidazol-2-yl] -3- quinolinecarboxylic ("imazaquin"); Diphenylic ethers, such as 5- [2-chloro-4- (trifluoromethyl) phenoxy] -2-nitrobenzoic acid ("acifluorfen"), 5- (2,4-dichlorophenoxy) -2-nitrobenzoate-methyde ("bifenox") and 5- [2-chloro-4- (trifluoromethyl) phenoxy] -N- (methylsulfonyl) -2-nitrobenzamide ("formasafen"); hydroxybenzonitriles, such as 4-hydroxy-3,5-diiodobenzonitrile ("yoxinil") and 3,5-dibromo-4-hydroxybenzonitrile ("bromoxy-nil"); sulfonylureas, such as 2- [[[[(4-chloro-6-methoxy-2-pyrimidinyl) amino] carbonyl] amino] sulfonyl] benzoic acid ("chlorimuron"), 2-chloro-.V- [[(4 -methoxy-6-methyl-1,3,5-triazin-2-yl) amino] carbonyl] benzenesulfonamide ("chlorosul-furon"), 2- [[[[[(4,6-dimethoxy-2-pyrimidinyl)] ) amino] -carbonyl] amino] sulfonyl] methyl] benzoic acid ("bensulfuron"), 2- [[[[(4,6-dimethoxy-2-pyrimidinyl) amino] carbonyl] amino] sulfonyl] -l-methyl- L-pyrazole-4-carboxylic acid ("pirazosul-furon"), 3- [[[[(4-methoxy-6-methyl-l, 3,5-triazin-2-yl) amino] carbonyl] amino] sulfonyl acid ] -2-thiophenecarboxylic acid ("thifensulfuron") and 2- (2-chloroethoxy) -iV- [[(4-methoxy-6-methyl-1,3,5-triazin-2-yl) amino] carbonyl] benzenesulfonamide ( "triasulfuron"); 2- (4-aryloxyphenoxy) alkanoic acids, such as (+/-) -2- [4- [(6-chloro-2-benzoxazolyl) oxy] -phenoxy] propanoic acid ("fenoxaprop"), acid (+ / -) -2- [4- [[5- (trifluoromethyl) -2-pyridinyl] oxy] phenoxy] propanoic ("flua-zifop"), acid (+/-) - 2- [4- (6-chloro- 2-quinoxalinyl) oxy] phenoxy] propanoic ("quizalofop") and acid (+/-) -2 - [- (2,4-dichlorophenoxy) phenoxy] propanoic ("diclofop"); benzothiadia-zinones, such as 3- (1-methylethyl) -1H-2, 1,3-benzothiadiazin-4 (3H) -one 2,2-dioxide ("bentazone"); 2-chloroaceta-nilides, such as -V-butoxymethyl-2-chloro-2 ', 6'-diethylacetanylide ("butachlor"); arenocarboxylic acids, such as 3,6-dichloro-2-methoxybenzoic acid ("dicamba"), and pyridyloxyacetic acids, such as [(4-amino-3,5-dichloro-6-fluoro-2-pyridinyl) oxy] acetic acid ("fluroxipir"). It is evident that various modifications can be made in the formulation and in the application of the compounds of this invention without departing from the inventive concepts thereof as defined by the claims.

Claims (38)

1. CLAIMS 1. A compound of formula: where A is
2. U = (a) N and X is linked to U by a double bond, or (b) NR and X is linked to U by a single bond; R = H, alkyl, alkenyl, alkoxycarbonylalkyl, (alkoxycarbonyl) haloalkyl, benzyl, phenyl or cyanoalkyl; X = (a) CO when U is NR or (b) CR2 when U is N; R1 = H, alkyl, haloalkyl or amino; R2 = halogen, alkyl, alkoxy, cyanoalkoxy, phenyl optionally substituted with one or more halogen or alkyl, alkoxycarbonyl, alkoxycarbonylalkoxy, benzyl, benzyloxy or haloalkyl groups; R3 - alkyl or haloalkyl; Y = H, halogen, cyano or haloalkyl; Z = H or halogen. 2. A compound of claim 1, wherein U = NR.
3. 3. A compound of claim 2, wherein R is alkyl; R1 is alkyl, haloalkyl or amino; R2 is alkyl or phenyl; R3 is CH3 or CF3, and Y and Z are independently H or halogen.
4. 4. A compound of claim 3, wherein A is
5. 5. A compound of claim 4, wherein R is methyl or isopropyl; R1 is methyl, difluoromethyl or amino; R3 is methyl or trifluoromethyl; And it is H or 4-halo, and Z is H or 6-halo. 6. A compound of claim 5, wherein
6. R1 is methyl or amino; R3 is trifluoromethyl; Y is H or 4-chloro, and Z is H, 6-chloro or 6-fluoro.
7. 7. A compound of claim 5, wherein R1 is difluoromethyl; R3 is methyl; And it is H or 4-halo, and Z is H or 6-halo.
8. 8. A compound of claim 1, wherein U is N.
9. 9. A compound of claim 8, wherein R1 is alkyl, haloalkyl or amino; R2 is alkyl or phenyl; R3 is CH3 or CF3, and Y and Z are independently H or halogen.
10. 10. A compound of claim 9, wherein A is
11. 11. A compound of claim 10, wherein R 1 is methyl, difluoromethyl or amino; R3 is methyl or trifluoromethyl; R2 is alkyl or phenyl; And it is H or 4-halo, and Z is H or 6-halo.
12. 12. A compound of claim 11, wherein R1 is methyl or amino; R3 is trifluoromethyl; Y is H or 4-chloro, and Z is H, 6-chloro or 6-fluoro.
13. 13. A compound of formula: where R = H, alkyl or alkenyl; S = amino, alkoxycarbonylamino or N = C = 0; Y = H, halogen, cyano or haloalkyl, and Z = H or halogen.
14. 14. A compound of formula: where R = H, alkyl or alkenyl; R3 is methyl or trifluoromethyl; Y = H, halogen, cyano or haloalkyl, and Z = H or halogen.
15. 15. A compound of claim 1, wherein U = NR; X = CO; R and R1 = CH3; Y and Z = H, and R3 = CF3.
16. 16. A compound of claim 1, wherein U = NR; X = CO; R and R1 = CH3; Y = 4-Cl; Z = H, and R3 = CF3.
17. 17. A compound of claim 1, wherein U = NR; X = CO, R and R1 = CH3; Y = H; Z = 6-Cl, and R3 = CF3.
18. 18. A compound of claim 1, wherein U = NR; X = CO; R and R1 = CH3; Y = 4-Cl; Z = 6-Cl, and R3 = CF3.
19. 19. A compound of claim 1, wherein U = NR; X = CO; R and R1 = CH3; Y = 4-Br; Z = H, and R3 = CF3.
20. 20. A compound of claim 1, wherein U = NR; X = CO; R and R1 = CH3; Y = H; Z = 5-Br, and R3 = CF3.
21. 21. A compound of claim 1, wherein U = NR; X = CO; R = CH (CH3) 2; R1 = CH3; Y and Z = H, and R3 = CF3.
22. 22. A compound of claim 1, wherein U = NR; X = CO; R = CH (CH3) 2; R1 = CH3; Y = 4-Cl; Z = H, and CF 3 *
23. 23. A compound of claim 1, wherein U = NR; X = CO; R = CH (CH3) 2; R1 = CH3; Y = 4-Cl; Z = 6-Cl, and R3 = CF3.
24. 24. A compound of claim 1, wherein U = NR; X = CO; R = CH (CH3) 2; R1 = CH3; Y = 4-Br; Z = H, and CF 3- ,.
25. 25. A compound of claim 1, wherein U = NR; X = CO; R = CH (CH3) 2; R1 = NH2; Y = 4-Br; Z = H, and R3 = CF.
26. 26. A compound of claim 1, wherein U = NR; X = CO; R = CH3; R1 = NH2; Y = 4-Cl; Z = 6-F, and R3 = CF,
27. 27. A compound of claim 1, wherein U = NR; X = CO; R = CH3; R1 = CH3; Y = 4-Cl; Z = 6-F, and R3 = CF.
28. 28. A compound of claim 1, wherein U = NR; X = CO; R = CH3; R1 = CH3; Y = 4-Cl; Z = 6-F, and R3 = CF.
29. 29. A compound of claim 1, wherein U = NR; X = CO; R = CH (CH3) 2; R1 = CH3; Y = 4-Cl; Z = 6-F, and R3 = CF3.
30. 30. A compound of claim 1, wherein U = NR; X = CO; R = CH3; R1 = CHF2; Y = 4-Cl; Z = F, and R3 = CH3.
31. 31. A method of preparing a compound of claim 4, wherein R1 is alkyl and R3 is trifluoromethyl, which consists of the following steps: (a) letting a compound having the structure where S is NHC02-alkyl or N = C = 0, react with ethyl 3'-amino-4,4,4-trifluorocrotonate in the presence of an appropriate base and an inert solvent to obtain compound G, which has the structure G and (b) let compound G react with an R1-halide.
32. 32. A method of preparing a compound of claim 4, wherein R1 is difluoromethyl and R3 is methyl, which consists of the following steps: (a) letting a compound having the structure where S is NHC02-alkyl or N = C = 0, react with ethyl 3-aminocro-tonate in the presence of an inorganic base and an inert solvent to obtain compound G, which has the structure G and (b) allowing compound G to react with chlorodifluoromethane in the presence of an inorganic base and an inert solvent.
33. 33. A method of preparing a compound of claim 4, wherein R1 is amino and R3 is trifluoromethyl, which consists of the following steps: (a) allowing a compound having the structure where S is N = C = 0 or NHC02-alkyl, react with ethyl 3-amino-4,4,4-trifluorocrotonate in the presence of an inorganic base and an inert solvent to obtain compound G, which has the structure G and (b) allowing compound G to react with 1-aminooxy-sulfo-nyl-2,4,6-trimethylbenzene in the presence of a suitable solvent and a suitable base.
34. 34. A method of preparing the compounds of claim 2, wherein A is which consists of the step ide to allow a compound of claim 13, wherein S is amino, to react with 4,5,6,7-tetrahydro-1,3-isobenzofuranedione in glacial acetic acid.
35. 35. A herbicidal composition consisting of a herbicidally effective amount of a compound of claim 1 and an agriculturally acceptable vehicle therefor.
36. 36. A method of controlling the growth of unwanted plants, consisting of the application to the place where the unwanted plants are growing or in which they are expected to grow from a herbicidally effective amount of a composition of claim 35.
37. 37. A herbicidal composition comprising a herbicidally effective amount of a compound of claim 1 and an herbicidally effective amount of one or more herbicides selected from the group consisting of glyphosate, 2,4-D, MCPA, MCPP, isoproturon, imazapyr, imazametabenz, imazatapir, imazaquín, acifluorfén, bifenox, fomasafén, yoxinil, bromoxynil, chlorimuron, chlorsulfuron, bensulfuron, pirazosulfuron, thifensulfuron, triasulfuron, fenoxaprop, fluazifop, quizalofop, diclofop, bentazone, butachlor, dicamba and fluroxipir.
38. 38. A method of controlling the growth of unwanted plants, consisting of the application to the place where the unwanted plants are growing or in which they are expected to grow, of a herbicidally effective amount of a composition of claim 37.