The control of undesired vegetation is extremely important in achieving high crop efficiency. Achievement of selective control of the growth of weeds especially in such useful crops as rice, soybean, sugar beet, corn (maize), potato, wheat, barley, tomato and plantation crops, among others, is very desirable. Unchecked weed growth in such useful crops can cause significant reduction in productivity and thereby result in increased costs to the consumer. The control of undesired vegetation in noncrop areas is also important. Many products are commercially available for these purposes, but the need continues for new compounds which are more effective, less costly, less toxic, environmentally safer or have different modes of action.

Patent application EP 692,482 discloses compounds of Formula i as herbicides: wherein, inter alia, R1 and R2 are independently alkyl, haloalkyl, cycloalkyl, alkenyl, alkynyl or phenyl; R3 is nitro halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio or phenoxy; and nisO, l,2or3.

The tetrazolinones of the present invention are not disclosed in this publication.

SUMMARY OF THE INVENTION This invention is directed to compounds of Formula I including all geometric and stereo isomers, N-oxides, and agriculturally suitable salts thereof as well as agricultural compositions containing them and a method of their use for controlling undesirable vegetation:

wherein A is phenyl or a 5- or 6-membered aromatic heterocyclic ring system containing 1 to 4 heteroatoms independently selected from the group nitrogen, oxygen, and sulfur, and each heterocyclic ring system is optionally substituted by one or more groups selected from halogen, nitro, cyano, C1-C4 alkyl, Cl-C4 haloalkyl, C3-C6 alkenyl, C3-C6 haloalkenyl, C3-C6 alkynyl, C3-C6 haloalkynyl, C1-C4 alkoxy, C1-C4 haloalkoxy, S(O)R4, S(0)20R4, SO2NR5R6, and phenyl optionally substituted on the phenyl ring with C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, 1-2 halogen, cyano or nitro; and when A is a 5- or 6-membered aromatic heterocyclic ring system containing a nitrogen, then A can be bonded through any available carbon or nitrogen atom to the phenyl or pyridyl ring by replacement of a hydrogen on said carbon or nitrogen atom.

W is CH or N; R1 is C1-C6 alkyl, C1-C6 haloalkyl, C3-C7 cycloalkyl, C3-C7 cycloalkenyl, C3-C6 alkenyl, C3-C6 haloalkenyl, C3-C6 alkynyl, C3-C6 haloalkynyl or C1-C6 alkoxy; or R1 is phenyl optionally substituted on the phenyl ring with C1-C3 alkyl, halogen, cyano or nitro; R2 is C1-C6 alkyl, Cl-C6 haloalkyl, C3-C7 cycloalkyl, C3-C7 cycloalkenyl, C3-C6 alkenyl, C3-C6 haloalkenyl, C3-C6 alkynyl, or C3-C6 haloalkynyl; or R2 is phenyl optionally substituted on the phenyl ring with C1-C3 alkyl, halogen, cyano or nitro; or R1 and R2 can be taken together as -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2- -CH2CH2CH2CH2CH2- or -CH2CH2OCH2CH2-; each R3 is independently H, halogen, C1-C4 alkoxy, C1-C4 haloalkoxy, Cl-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkoxyalkyl, C2-C4 alkylthioalkyl, cyano, nitro, NH(C1-C4 alkyl), N(CI-C4 alkyl)2, S(O)R4, S(0)20R4 or SO2NR5R6; R4 is C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 alkenyl, C3-C6 haloalkenyl, C3-C6 alkynyl or C3-C6 haloalkynyl; R5 is H, Cl-C6 alkyl, Cl-C6 haloalkyl, C3-C6 alkenyl or C3-C6 alkynyl;

R6 is H, Cl-C6 alkyl, C1-C6 haloalkyl, C3-C6 alkenyl. C3-C6 alkynyl or C1-C6 alkoxy; or R5 and R6 can be taken together as -CH2CH2-, -CH2CH2CH2-, -CH2CWCWCH2-, -CH2CH2CH2CH2CH2- or-CHoCHrOCHsCH2-; m is O, 1 or 2; and nisO, 1 or2.

In the above recitations, the term "alkyl", used either alone or in compound words such as "alkylthio" or "haloalkyl" includes straight-chain or branched alkyl, such as, methyl, ethyl, n-propyl, i-propyl, or the different butyl, pentyl or hexyl isomers. The term "1-2 alkyl" indicates that one or two of the available positions for that substituent may be alkyl which are independently selected. "Alkenyl" includes straight-chain or branched alkenes such as ethenyl, 1 -propenyl, 2-propenyl, and the different butenyl, pentenyl and hexenyl isomers. "Alkenyl" also includes polyenes such as 1,2-propadienyl and 2,4-hexadienyl. "Alkynyl" includes straight-chain or branched alkynes such as ethynyl, 1-propynyl, 2-propynyl and the different butynyl, pentynyl and hexynyl isomers. "Alkynyl" can also include moieties comprised of multiple triple bonds such as 2,5-hexadiynyl. "Alkoxy" includes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers.

"Alkoxyalkyl" denotes alkoxy substitution on alkyl. Examples of"alkoxyalkyl" include CH30CH2, CH30CH2CH2, CH3CH20CH2, CH3CH2CH2CH20CH2 and CH3CH20CH2CH2. "Alkylthio" includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers. "Alkylthioalkyl" denotes alkylthio substitution on alkyl. Examples of"alkylthioalkyl" include CH3 SCH2, CH3SCH2CH2, CH3CH2SCH2, CH3CH2CH2CH2SCH2 and CH3CH2SCH2CH2. "Cycloalkyl" includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. "Cycloalkenyl" includes groups such as cyclopentenyl and cyclohexenyl as well as groups with more than one double bond such as 1,3- and 1 ,4-cyclohexadienyl. The term "aromatic ring system" denotes fully unsaturated carbocycles and heterocycles in which the polycyclic ring system is aromatic (where aromatic indicates that the Hückel rule is satisfied for the ring system).

The term "aromatic heterocyclic ring system" includes fully aromatic heterocycles and heterocycles in which at least one ring of a polycyclic ring system is aromatic (where aromatic indicates that the Hückel rule is satisfied). The heterocyclic ring systems can be attached through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen. One skilled in the art will appreciate that not all nitrogen containing heterocycles can form N-oxides since the nitrogen requires an available lone pair for oxidation to the oxide; one skilled in the art will recognize those nitrogen containing heterocycles which can form N-oxides. One skilled in the art will also recognize that tertiary amines can form N-oxides. Synthetic methods for the preparation

of N-oxides of heterocycles and tertiary amines are very well known by one skilled in the art including the oxidation of heterocycles and tertiary amines with peroxy acids such as peracetic and m-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethyldioxirane. These methods for the preparation ofrV-oxides have been extensively described and reviewed in the literature, see for example: T. L. Gilchrist in Comprehensive Organic Synthesis, vol. 7, pp 748-750, S. V. Ley, Ed., Pergamon Press; M. Tisler and B. Stanovnik in Comprehensive Heterocyclic Chemistry, vol. 3, pp 18-20, A. J. Boulton and A. McKillop, Eds., Pergamon Press; M. R. Grimmett and B. R. T. Keene in Advances in Heterocyclic Chemistry, vol. 43, pp 149-161, A. R. Katritzky, Ed., Academic Press; M. Tisler and B. Stanovnik in Advances in Heterocyclic Chemistry, vol. 9, pp 285-291, A. R. Katritzky and A. J. Boulton, Eds., Academic Press; and G. W. H. Cheeseman and E. S. G. Werstiuk in Advances in Heterocyclic Chemistry, vol. 22, pp 390-392, A. R. Katritzky and A. J. Boulton, Eds., Academic Press.

The term "halogen", either alone or in compound words such as "haloalkyl", includes fluorine, chlorine, bromine or iodine. The term "1-2 halogen" indicates that one or two of the available positions for that substituent may be halogen which are independently selected. Further, when used in compound words such as "haloalkyl", said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of"haloalkyl" include F3C, C1CH2, CF3CH2 and CF3CCl2. The terms "haloalkenyl", "haloalkynyl", "haloalkoxy", "haloalkylthio", and the like, are defined analogously to the term "haloalkyl". Examples of"haloalkenyl" include (Cl)2C=CHCH2 and CF3CH2CH=CHCH2. Examples of "haloalkynyl" include HC=-CCHCl, CF3C-C, CCl3C-C and FCH2C=-CCH2. Examples of "haloalkoxy" include CF30, CCl3CH2O, HCF2CH2CH2O and CF3CH2O.

The total number of carbon atoms in a substituent group is indicated by the "Ci-Cj" prefix where i andj are numbers from 1 to 7. For example, C1-C3 alkylsulfonyl designates methylsulfonyl through propylsulfonyl; C2 alkoxyalkyl designates CH3OCH2; C3 alkoxyalkyl designates, for example, CH3CH(OCH3), CH3OCH2CH2 or CH3CH2OCH2; and C4 alkoxyalkyl designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including CH3CH2CH2OCH2 and CH3 CH2OCH2CH2. Examples of"alkylcarbonyl" include C(O)CH3, C(O)CH2CH2CH3 and C(O)CH(CH3)2. Examples of "alkoxycarbonyl" include CH30C(=O), CH3 CH2OC(=O), CH3 CH2CH2OC(=O), (CH3)2CHOC(=O) and the different butoxy- or pentoxycarbonyl isomers. In the above recitations, when a compound of Formula I is comprised of one or more heterocyclic rings, all substituents are attached to these rings through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen.

When a compound is substituted with a substituent bearing a subscript that indicates the number of said substituents can exceed 1, said substituents (when they exceed 1) are independently selected from the group of defined substituents. Further, when the subscript indicates a range, e.g. (R)jj, then the number of substituents may be selected from the integers between i and j inclusive.

When a group contains a substituent which can be hydrogen, for example R3 or R5, then, when this substituent is taken as hydrogen, it is recognized that this is equivalent to said group being unsubstituted.

The compounds of this invention thus include compounds of Formula I, geometric and stereoisomers thereof N-oxides thereof and agriculturally suitable salts thereof.

The compound of the invention can exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers.

One skilled in the art will appreciate that one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s). Additionally, the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers. The compounds of the invention may be present as a mixture of stereoisomers, individual stereoisomers, or as an optically active form.

The salts of the compounds of the invention include acid-addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids. The salts of the compounds of the invention also include those formed with organic bases (e.g., pyridine, ammonia, or triethylamine) or inorganic bases (e.g., hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium or barium) when the compound contains an acidic group such as a carboxylic acid or phenol.

Preferred compounds of the invention for reasons of better activity and/or ease of synthesis are: Preferred 1. Compounds of Formula I above, geometric and stereoisomers thereof N-oxides thereof and agriculturally suitable salts thereof wherein A is phenyl, pyridinyl or 1H-pyrazolyl, each optionally substituted by one or more groups selected from halogen, Cl-C4 alkyl, C1-C4 haloalkyl, Cl-C4 alkoxy, and C1-C4 haloalkoxy; and when A is lH- pyrazolyl, then A can be bonded through any available carbon or nitrogen atom of said pyrazole ring to the phenyl or pyridyl ring; R1 is C1-C6 alkyl, C1-C6 haloalkyl or C3-C7 cycloalkyl; R2 is Cl-C6 alkyl, Cl-C6 haloalkyl or C3-C7 cycloalkyl; or

R1 and R2 can be taken together as -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2- or -CH2CH2OCH2CHo-; and each R3 is independently halogen, C1 -C4 alkoxy, C1 -C4 haloalkoxy C1-C4 alkyl or C1-C4 haloalkyl.

Preferred 2. Compounds of Preferred 1 wherein The substituent A and the tetrazolinone ring are attached to adjacent carbon atoms of the phenyl or pyridine ring.

Most preferred is the compound of Preferred 2 which is N,N-diethyl-4,5-dihydro-5-oxo-4-[2- [3 -(trifluoromethyl)- 1 H-pyrazol- 1 - yl]phenyl]- 1 H-tetrazol- 1 -carboxamide.

This invention also relates to herbicidal compositions comprising herbicidally effective amounts of the compounds of the invention and at least one of a surfactant, a solid diluent or a liquid diluent. The preferred compositions of the present invention are those which comprise the above preferred compounds.

This invention also relates to a method for controlling undesired vegetation comprising applying to the locus of the vegetation herbicidally effective amounts of the compounds of the invention (e.g., as a composition described herein). The preferred methods of use are those involving the above preferred compounds.

DETAILS OF THE INVENTION The compounds of Formula I can be prepared by one or more of the following methods and variations as described in Schemes 1-17. The definitions of A, W, R1-R6, m, and n in the compounds of Formulae 1 - 17 below are as defined above in the Summary of the Invention.

Scheme 1 illustrates the preparation of compounds of Formula I whereby a tetrazolinone of Formula 1 is reacted with a carbamyl chloride of Formula 2 in the presence of a suitable acid acceptor agent. Suitable acid acceptor agents include alkali carbonates, alkali bicarbonates, alkyl tertiary amines such as triethylamine, pyridine, and, preferably, 4-dimethylaminopyridine (DMAP). Furthermore, DMAP can be used as a catalyst in the presence of another suitable acid acceptor agent in order to selectively synthesize a compound of Formula I. The reaction is carried out in an inert solvent such as tetrahydrofuran, acetone, chloroform, chlorobenzene or preferably acetonitrile or toluene, and at a temperature range between 0 OC and 110 "C by methods known in the art (or slight modification of these methods); for example, see Yanagi, A. et al. EP 646,577; Goto, T. et al. EP 708,097; Covey, R. A. et al. U.S. Patent 4,618,365.

Scheme I 0 3 R1 ~~~~~~~~~~ ~~~~~ N acid R, > v J t I + CCNX N--- N e.g., DMAP A 2 Alternatively, compounds of Formula I can be prepared whereby a tetrazolinone of Formula 1 in an inert solvent such as toluene or ethyl acetate is reacted with phosgene and a suitable tertiary amine base such as triethylamine, and the product of such reaction is reacted with a secondary amine of Formula 3, optionally in the presence of a suitable base such as pyridine (Scheme 2). This type of reaction can be carried out by methods known in the art (or slight modification of these methods); see, for example, Covey, R.

A. et al. U.S. Patent 5,019,152.

Scheme 2 1. phosgene, triethylamine I R1 H# has 2. NR2 , baste, e.g., pyridine 3 Carbamyl chlorides of Formula 2 are well known in the art; see, for example, Goto, T. et al. EP 711,761, EP 692,482, and EP 695,748.

Scheme 3 illustrates a preferred method for preparing tetrazolinones of Formula 1 whereby an isocyanate of Formula 4 is reacted with refluxing trimethylsilylazide (also known as azidotrimethylsilane), followed by treatment of the product of such reaction with a protic solvent such as water or preferably with methanol, This type of reaction can be carried out by methods known in the art (or slight modification of these methods); see, for example, Tsuge, O. et al. J. Org. Chem. (1980), 45, 5130; Goto, T. et al. EP 695,748 and EP 692,482.

Scheme 3

Many isocyanates of Formula 4 can be prepared by Curtius rearrangement of appropriate acid chlorides of Formula 5 using methods generally known in the art (Scheme 4); see, for example, March, J. Advanced Organic Chemistry, 3rd edition; John Wiley & Sons, 1985; pp 984-985 and 380.

Scheme 4 (R )mX WCCI > 4 e.g., NaN3 A (Curtius Rearrangement) 5 Acid chlorides of Formula 5 can be prepared by reacting an acid of Formula 6 with oxalyl chloride (or thionyl chloride) and optionally a catalytic amount of dimethylformamide (Scheme 5). This chlorination is well known in the art; see, for example, Michaely, W. J. EP 369,803; Goto, T. et al. EP 695,748. Other methods are also well known in the art for converting carboxylic acids to acid chlorides; see, for example, Ogliaruso, M. A. et al. Synthesis of Carboxylic Acids, Esters and Their Derivatives; John Wiley & Sons, 1991, pp 172-174.

Scheme 5 v > oxalyl chloride 5 (R3)mt CQH (optionally a catalytic amount of DMF) A 6 Carboxylic acids of Formula 6 can be prepared as illustrated in Scheme 6, whereby an ester of Formula 7 is saponified (e.g., potassium hydroxide in methanol, then acidified with an acid such as hydrochloric acid) or, alternatively, is acid hydrolyzed (e.g., 5N HC1 in acetic acid) by methods known in the art (or slight modification of these methods); see for example, Ogliaruso, M. A. et al. Synthesis of Carboxylic Acids, Esters and Their Derivatives; John Wiley & Sons, 1991, pp 5-7.

Scheme 6 wherein R7 is C1-C2 alkyl Isocyanates of Formula 4 can also be prepared by treatment of corresponding amines of Formula 8 with phosgene or known phosgene equivalents (e.g., diphosgene or triphosgene) by methods generally known in the art (Scheme 7); see for example, March, J. Advanced Organic Chemistry, 3rd edition; John Wiley & Sons, 1985, p 370; Chem. Rev. (1972), 72, pp 457496; Sandler, R. S. et al. Organic Functional Group Preparations, 2nd edition; Academic Press; Vol. II, pp 152 and 260; Lehman, G. et al.

Preparative Organic Chemistry; John Wiley & Sons, 1972; p 472.

Scheme 7 w 3)m X NH2 phosgene 4 A 8 Amines of Formula 8 can be prepared by reduction of corresponding nitro compounds of Formula 9 (Scheme 8). A wide variety of methods are documented in the chemical literature for carrying out such transformations; see for example, Rorer, M. P.

U.S. Patent 4,511,392; Ohme, R. et al. Preparative Organic Chemistry; John Wiley & Sons, 1972; p 557; Groggins Unit Processes in Organic Chemistry; McGraw-Hill Book Co.: New York, 1947; pp 73-128; March, J. Advanced Organic Chemistry, 3rd edition; John Wiley & Sons, 1985; pp 1103-1104.

Scheme 8 (R3)m NO Reduction 1 > Reduction (R3)1TIM tNOn > 8 A 9 Many nitro compounds of Formula 9a can be prepared as illustrated in Scheme 9 whereby an appropriate nitro compound of Formula 10 in an inert solvent is reacted with a nucleophilic heterocycle of Formula 11 in the presence of a suitable base.

Suitable bases include alkali carbonates such as potassium carbonate, potassium tert- butoxide, and sodium hydride. Suitable solvents include dimethylformamide, 2- butanone, and tetrahydrofuran. The reaction is carried out at a temperature range of about 0 "C to 150 "C, preferably about 80 "C to 120 OC, with dimethylformamide as the solvent and potassium carbonate as the base. Following workup by generally-known methods, the compound of Formula 9a can be purified by recrystallization or flash column chromatography on silica gel by those skilled in the art. Protecting and deprotecting functional groups not compatible with reaction conditions may be necessary for compounds with such functional groups.

Scheme 9 wherein X is F, Cl, Br, CH3S020 or CF3S020 and X is ortho orpara to the N02 group; Nu is an optionally-substituted irnidazole, pyrazole, triazole or tetrazole; and A1 is an optionally-substituted lH-imidazole, lH-pyrazole, lH- 1,2,4-triazole, 4H-1,2,4-triazole or tetrazole and Al is ortho orpara to the N02 group.

Scheme 10 illustrates the preparation of many esters of Formula 7a whereby an appropriate ester of Formula 12 in an inert solvent is reacted with a nucleophilic heterocycle of Formula 13 in the presence of a suitable base. Reaction conditions are as described for Scheme 9.

Scheme 10 wherein X is F, Cl, Br, CH3S020 or CF3S020 and X is ortho orpara to the Co2R7 group; Nu is an optionally-substituted imidazole, pyrazole, triazole or tetrazole; and A1 is an optionally-substituted lH-imidazole, lH-pyrazole, lH-i,2,4-triazole, 4H-l,2,4-triazole or tetrazole and Al is ortho orpara to the Co2R7 group.

Scheme 11 illustrates the preparation of many carboxylic acids of Formula 6 whereby a bromide compound of Formula 13 is treated with n-butyllithium (or magnesium) and the lithium salt (or the Grignard reagent) generated in situ is then reacted with carbon dioxide followed by acidification with an acid such as hydrochloric acid. This conversion is carried out by using methods known in the art (or by slights modification of these methods); see for example, Ogliaruso, M. A. et al. Synthesis of Carboxylic Acids, Esters and Their Derivatives; John Wiley & Sons pp 27-28; Bridges, A. J. et al. J. Org. Chem. (1990), 55, 773; Franke, C. et al. Angew. Chem. Int. Ed.

(1969), 8, 68. Protecting and deprotecting functional groups not compatible with the reaction conditions may be necessary for compounds with such functional groups.

Scheme 11 Some bromo compounds of Formula 13 can be prepared by bromination of the corresponding substituted benzene or pyridine of Formula 14 with bromine or other equivalent reagent in an inert solvent as shown in Scheme 12. This bromination is carried out by general methods known in the art; see for example, Campaigne, E. et al.

J. Heterocycl. Chem. (1969), 6, 517; Gilman, H. J. Am. Chem. Soc. (1955), 77, 6059.

Scheme 12 W Brx or other equivalent (R3)m H brominating agent > 13 A 14 In general, nitro compounds of Formula 9, benzene and pyridine compounds of Formula 14, bromo compounds of Formula 13, and ester compounds of Formula 7 can be prepared by those skilled in the art using methods known in the art (or by obvious modification of these methods); see for example, Rorer, M. P. U.S. Patent 4,511,392; Wolf, A. D. U.S. Patent 4,465,505; Sauers, R. F. U.S. Patent 4,460,401; Denes, R. WO 93/11097; Petersen, C. et al. WO 96/31517; Denes, R. WO 95/09846; Katritzky, A. R. et al. Comprehensive Heterocyclic Chemistry; Pergamon Press; Volumes 2-6.

Protecting and deprotecting functional groups not compatible with the reaction conditions may be necessary for compounds with such functional groups.

Scheme 13 illustrates another preferred method for preparing tetrazolinones of Formula 1 whereby an isocyanate of Formula 4 is reacted with sodium azide and aluminum chloride in an inert solvent such as N,N-dimethylformamide (DMF) followed by addition of water and a mineral acid in excess, such as hydrochloric acid. This type of reaction can be carried out by methods known in the art (or slight modification of these methods); see for example, Horwitz, J. P. et al. J. Am. Chem. Soc. (1959), 81, 3076; Yanagi, A. et al. U.S. Patent 5,530,135; Covey, R. A. et al. U.S. Patent 4,618,365.

Scheme 13 Alternatively, as illustrated in Scheme 14, many tetrazolinones of Formula 1 can be prepared by a multi-step reaction sequence starting from an amino compound of Formula 8. These types of reactions can be carried out by methods known in the art (or slight modification of these methods). Thus, (1) an amino compound of Formula 8 is reacted with carbon disulfide and a tertiary amine base such as triethylamine either neat or preferably in a solvent such as ethanol; (2) the product of such reaction is reacted with an alkylating agent such as methyl iodide to form the corresponding methyl dithiocarbamate (see, for example, Fairfull, A. E. S. J. Chem. Soc. (1955), 796; Knott, E. B. J. Chem. Soc. (1956), 1644); (3) subsequent reaction of this product with sodium azide in a solvent such as water provides the 5-mercaptotetrazole of Formula 15; and (4) reaction of this product in a solvent such as water or ethanol with an alkylene oxide such as propylene oxide and a suitable acid acceptor agent such as sodium hydroxide, followed by acidification with for example, hydrochloric acid, provides a tetrazolinone compound of Formula 1 (see, for example, Goto, T. et al. EP 711,761).

Scheme 14 propylene oxide, NaOH 1 then H+ Scheme 15 illustrates another multi-step reaction sequence for preparing tetrazolinones of Formula 1 from corresponding amines of Formula 8. These types of reactions can also be carried out by methods known in the art (or slight variations of these methods). Thus, (1) an amino compound of Formula 8 is converted to the corresponding methyl dithiocarbamate (see steps 1 and 2 of Scheme 14); (2) subsequent reaction of this product with hydrazine monohydrate in a solvent such as ethanol provides the corresponding 3-thiosemicarbazide; (3) alkylation of this product with, e.g., dimethyl sulfate followed by treatment of the product of such reaction with sodium nitrite in hydrochloric acid provides the corresponding 5-methylthiotetrazole; (4) oxidation of this reagent with a suitable oxidizing agent such as Oxonet' or peracetic acid provides a sulfone of Formula 16; and finally, (5) reaction of this reagent with an inorganic base such as sodium hydroxide in a solvent such as tetrahydrofuran and water, followed by acidification, can provide a compound of Formula 1 (see, for example, Goto, T. et al. EP 692,482).

Scheme 15 h: ICSZCH?I N/ NaOH ~ 1 (R3)m NI 2. H2NNH2H2C LN then then H+ 3. (CH3)2S04; then NaN02 A and aqueous HCI 4. Oxone 16 Many tetrazolinones of Formula 1 can also be prepared as illustrated in Scheme 16 whereby a phenyl carbamate of Formula 17 is reacted in an inert solvent such as dimethylformamide with sodium azide in the presence of aluminum chloride. This type of reaction can be carried out by methods known in the art (or slight modification of these methods); see for example, Goto, T. et al. EP 692,482 and EP 695,748.

Scheme 16 Phenyl carbamates of Formula 17 can be prepared by reaction of an amine of Formula 8 with phenyl chioroformate in pyridine by methods known in the art (or slight modification of these methods); see, for example, Goto, T. et al. EP 692,482 and EP 695,748.

In addition, many tetrazolinones of Formula 1 can be prepared as illustrated in Scheme 17, whereby an appropriate acid chloride of Formula 5 is refluxed with excess trimethylsilylazide, and the product of such reaction is treated with a protic solvent such as water or, preferably with methanol. This type of reaction can be carried out by methods known in the art (or by slight modification of these methods); see, for example, Toselli, M. et al. J. Chem. Soc. Perkin Trans 1, (1992), 1101; Goto, T. et al. EP 695,748 and EP 692,482; Horwitz, J. P. et al. J. Am. Chem. Soc. (1959), 81, 3076.

Scheme 17

It is recognized that some reagents and reaction conditions described above for preparing compounds of Formula I may not be compatible with certain functionalities present in the intermediates. In these instances, the incorporation of protection/deprotection sequences or functional group interconversions into the synthesis will aid in obtaining the desired products. The use and choice of the protecting groups will be apparent to one skilled in chemical synthesis (see, for example, Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 2nd ed.; Wiley: New York, 1991). One skilled in the art will recognize that, in some cases, after the introduction of a given reagent as it is depicted in any individual scheme, it may be necessary to perform additional routine synthetic steps not described in detail to complete the synthesis of compounds of Formula I. One skilled in the art will also recognize that it may be necessary to perform a combination of the steps illustrated in the above schemes in an order other than that implied by the particular sequence presented to prepare the compounds of Formula I.

One skilled in the art will also recognize that compounds of Formula I and the intermediates described herein can be subjected to various electrophilic, nucleophilic, radical, organometallic, oxidation, and reduction reactions to add substituents or modify existing substituents.

Without further elaboration, it is believed that one skilled in the art using the preceding description can utilize the present invention to its fullest extent. The following Examples are, therefore, to be construed as merely illustrative, and not limiting of the disclosure in any way whatsoever. Percentages are by weight except for chromatographic solvent mixtures or where otherwise indicated. Parts and percentages for chromatographic solvent mixtures are by volume unless otherwise indicated.

1H NMR spectra are reported in ppm downfield from tetramethylsilane; s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet, dd = doublet of doublets, dt = doublet of triplets, br s = broad singlet.

EXAMPLE 1 Step A: Preparation of 1-(2-nitrophenyl)-3-(trifluoromethyl)-lH-pvrazole To 135 mL of N,N-dimethylformamide was added 20.2 g (0.149 mol) of 3- (trifluoromethyl)pyrazole (purchased from Maybridge Chemical Co.), 20.0 g (0.142 mol) of l-fluoro-2-nitrobenzene (purchased from Aldrich Chemical Co.) and 20.6 g (0.149 mol) of potassium carbonate. The suspension was stirred and heated under nitrogen for 7.5 h at 80 OC, then cooled to 25 "C and poured into excess water. The aqueous suspension was filtered, and the isolated solid was washed three times with water (70 mL), then suction dried to yield 36.6 g of the title compound of Step A as a solid melting at 52-55"C. lH NMR (CDCl3): 5 6.65 (d, lH), 7.65 (m, 2H) 7.75 (m, 2H), 8.0 (d, 1H).

Step B: Preparation of 2-F3-(trifluoromethvl)- 1 H-pvrazol- 1 -yllbenzenamine A suspension containing 3 1.65 g (0.123 mol) of the title compound of Step A, 274.5 mL of glacial acetic acid and 44.7 mL of water was stirred and heated to 70 OC.

Iron powder (22.7 g; 0.406 mol) was then added portionwise to the suspension at such a rate as to maintain the reaction temperature between 80 °C and 90 °C, Following completion of addition, the suspension was heated at about 85 °C for about 0.5 h, then filtered while hot through a Celitet' pad. After washing the pad with warm glacial acetic acid (about 40 mL at 80 °C), the filtrates were combined, poured into excess cold water and the resulting suspension was filtered. The isolated solid was washed thoroughly four times with water (40 mL), redissolved in dichloromethane and dried over magnesium sulfate, and the filtered solution evaporated to dryness under reduced pressure to yield 23.2 g of the title compound of Step B as a solid melting at 58-61 °C.

1H NMR (CDCl3): 6 4.55 (s, 2H) 6.7 (d, 1H), 6.8 (m, 2H), 7.2 (m, 2H), 7.75 (d, 1H).

Step C Prenaration of 1,4-dihvdro-4-F2-r3 -(trifluoromethvl)- 1 H-vrazol-l- vllphenYll -5H-tetrazol-5 -one 3.0 g (0.0132 mol) of the title compound of Step B was added portionwise to a solution under a nitrogen atmosphere containing 4.9 g (0.0264 mol) of trichloromethyl chloroformate dissolved in 50 mL of ethyl acetate, while maintaining the reaction temperature at about 5 °C with external cooling. After addition was complete, the suspension was refluxed under nitrogen for 7 h, then evaporated to dryness under reduced pressure. The residue was azeotroped with ethyl acetate (twice with about 20 mL at 70 °C) to yield 3.4 g of oil. This oil was added to 3.1 g (0.027 mol) of azidotrimethylsilane (Aldrich). The suspension was refluxed under nitrogen for 20 h, then evaporated to dryness under reduced pressure at about 90 °C to remove excess azidotrimethylsilane. After cooling the residue to 25 °C, 20 mL of methanol was added.

The suspension was stirred about 0.5 h and then concentrated under reduced pressure at about 80 °C. The residue was purified by flash column chromatography on silica gel with hexane:ethyl acetate (7.5:2.5, then 6:4, then 1:1) as eluant to yield 1.46 g of the title compound of Step C as a solid melting at 152-156 °C.

IH NMR ((CD3)2SO): 6 6.95 (d, 1H), 7.7-7.8 (m, 4H) 7.85 (m, 1H) 8.35 (d, 1H) 14.5 (s, 1H).

Step D: Preparation of N,N-diethvl-45-dihvdro-5-oxo-4-r2-r3-(trifluoromethyl!- lH-pvrazol- 1 -yllphenyll- lH-tetrazol- l -carboxamide To a suspension containing 1.35 g (0.0046 mol) of the title compound of Step C in 23 mL of toluene under a nitrogen atmosphere was added 0.67 g (0.00547 mol) of 4- dimethylaminopyridine. After stirring for several minutes, 0.74 g (0.0055 mol) of diethylcarbamyl chloride (Aldrich) was added. The suspension was refluxed for 6 h, stirred at 25 °C overnight, and then added to excess water. The aqueous suspension was

extracted twice with ethyl acetate (30 mL) and the combined organic layers were dried over magnesium sulfate and concentrated under reduced pressure. The residual oil was purified by flash column chromatography on silica gel with hexane:ethyl acetate (8:2 then 1:1) to yield 1.52 g of the title compound of Step D, a compound of this invention, as a solid melting at 94-97 °C, lH NMR (CDCl3): 6 1.25 (m, 6H), 3.3 (m, 2H) 3.55 (m, 2H), 6.7 (d, lH), 7.55-7.7 (m, 4H), 7.8 (d, lH).

EXAMPLE 2 Step A: Preparation of 3 -nitro-2-f3 -(trifluoromethvl- 1 H-pyrazol- 1 -vllpyridine To 66 mL of N,N-dimethylforrnamide was added sequentially 11.1 g (0.07 mol) of 2-chloro-3-nitropyridine (Aldrich), 10.16 g (0.0735 mol) potassium carbonate, and 10.0 g (0.0735 mol) of 3-(trifluoromethyl)pyrazole. The suspension was stirred and heated at 80 °C for 1.5 h, then cooled to 25 °C and poured into excess water. The suspension was filtered, and the isolated solid was suction dried to yield 86.3 g of the title compound of Step A as a solid melting at 60-62 °C.

1H NMR (CDCl3): 6 6.75 (m, lH), 7.5 (m, 1H), 8.15 (m, 1H), 8.4 (m, 1H), 8.65 (m, lH).

Step B: Preparation of 2-f3 -(trifluoromethyl)- lH-pyrazol- 1 -vll-3-pyridinanun.e A suspension containing 5.0 g (0.0194 mol) of the title compound of Step A, 43.3 mL of glacial acetic and 7.1 mL of water was stirred and heated to 70 °C. Iron powder (3.6 g; 0.064 mol) was then added portionwise to the suspension at such a rate as to maintain the reaction temperature between about 80 OC and 90 °C. Following completion of addition, the suspension was heated at 80 OC for about 0.5 h, then filtered while hot through a CeliteX pad. After washing the pad three times with warm glacial acetic acid (30 mL), the filtrates were combined and added to excess cold water. The suspension was filtered, and the isolated solid was washed three times with water (30 mL), then suction dried to yield 3.15 g of the title compound of Step B as a solid melting at 89-92 OC.

1H NMR (CDCl3): 6 5.45 (s, 2H), 6.7 (m, lH), 7.05-7.15 (m, 2H), 7.8 (m, 1H), 8.6 (m, 1H).

Step C: Preparation of 1 ,4-dihvdro4-(3-pyridinyl)-5H-tetrazol-5-one 4.0 g (0.0175 mol) of the title compound of Step B was added portionwise to a solution under a nitrogen atmosphere containing 6.92 g (0.035 mol) of trichloromethyl chloroformate dissolved in 75 mL of ethyl acetate while maintaining the reaction temperature at about 5 °C with external cooling. After addition was complete, the suspension was refluxed for 6 h, stirred 25 OC overnight, and then concentrated under reduced pressure. The residue was azeotroped with ethyl acetate (twice with about 20 mL at 70 °C) to yield 4.45 g of an oil. This oil was added to 4.0 g (0.035 mol) of azidotrimethylsilane (Aldrich). The suspension was refluxed under nitrogen for 24 h

and then concentrated under reduced pressure at about 90 °C to remove excess azidotrimethylsilane. After cooling the residue to 25 OC, about 20 mL of methanol was added. The suspension was stirred about 0.25 h and then concentrated under reduced pressure at 90 "C. An additional 20 mL of methanol was added to the residue and the suspension again concentrated under reduced pressure. The residue was purified by flash column chromatography on silica gel with hexane:ethyl acetate (8:2, then 1:1, then 100% ethyl acetate) to yield a gum. The gum was slurried in hot 1 -chlorobutane (about 10 mL) and the suspension then cooled to 25 °C and filtered to yield 1.13 g of the title compound of Step C as a solid melting at 132-135 °C.

1H NMR (CDC13): 6 6.65 (m, 1H), 7.55 (m, 1H); 8.05 (m, 1H), 8.55 (m, 1H), 8.65 (m, 1H) 12.7-13.1 (brs, 1H).

Step D Preparation of N,N-diethyl-4,5-dihydro-5-oxo-4-[2-[3-(trifluoromethyl)- 1 H-yrazo1- 1 -vll-3-Pvridinvll- 1H-tetrazol-l -carboxamide To a suspension containing 1.0 g (0.0034 mol) of the title compound of Step C in 17 mL of toluene was added 0.5 g (0.0041 mol) of 4-dimethylaminopyridine. After stirring for several minutes, 0.55 g (0.0041 mol) of diethylcarbamyl chloride (Aldrich) was added. The suspension was refluxed for 6 h, stirred at 25 OC overnight, and finally concentrated under reduced pressure. After adding excess water to the residue, the formed suspension was filtered. The isolated solid was washed with water, suction dried, then purified by flash column chromatography on silica gel with hexane:ethyl acetate as eluant (8:2 then 7:3) to yield 0.84 g of the title compound of Step D, a compound ofthis invention, as a solid melting at 126-129 OC.

1H NMR (CDCl3): 6 1.3 (m, 6H), 3.45 (m, 2H), 3.55 (m, 2H), 6.7 (m, 1H), 7.55 (m. 1H), 8.0 (m. 1H), 8.6 (m, 1H), 8.65 (m, 1H).

By the procedures described herein together with methods known in the art, the following compounds of Tables 1 to 4 can be prepared. The following abbreviations are used in the Tables which follow: n = normal, CN = cyano, and NO2 = nitro. The following notations have been used in Tables 1-4: A-1 = (1-methyl-1H-pyrazol-3-yl)- A-2 = (I-ethyl- 1H-pyrazol-3-yl)- A-3 = (1-propyl-IHpyrazol-3-yl)- A-4 = (1,5-dimethyl-1H-pyrazol-3-yl)- A-5 = (4-chloro- 1-methyl- 1H-pyrazol-3-yl)- A-6 = (1H-pyrazol-1-yl)- A-7 = (3-trifluoromethyl-1H-pyrazol-1-yl)- A-8 = (4-chloro-3-trifluoromethyl- lH- pyrazol- 1 -yl)- A-9 = (3-methyl-1H-pyrazol-1-yl)- A-10 = (3,5-dimethyl-1H-pyrazol-1-yl)- A-lI = (3-isoxazolyl)- A-12 = (5-methyl-3-isoxazolyl)- A-13 = (3-methyl-5-isoxazolyl)- A-14 = (5-isoxazolyl)- A-15 = (4-isoxazolyl)- A-16 = (1-methyl-1H-pyrazol-2-yl)- A-17 = (1H-pyrrol-1-yl)- A- 18 = (1-methyl- lH-pyrrol-3-yl)- A-19 = (2-furanyl)- A-20 = (5-methyl-2-filranyl)- A-2 1 = (3-filranyl)- A-22 = (2-thienyl)- A-23 = (3-thienyl)- A-24 = (1-methyl-1H-imidazol-2-yl)- A-25 = ( I-methyl- IH-imidazol-4-yl)- A-26 = (1-methyl-I H-imidazol-5-yl)- A-27 = (2-oxazolyl)- A-28 = (2-methyl-5-oxazolyl)- A-29 = (2-methyl-4-oxazolyl)- A-30 = (4-methyl-2-thiazolyl)- A-31 = (5-methyl-2-thiazolyl)- A-32 = (2-thiazolyl)- A-33 = (2-methyl-5-thiazolyl)- A-34 = (2-methyl-4-thiazolyl)- A-35 = (3-methyl-4-isothiazolyl)- A-36 = (3-methyl-5-isothiazolyl)- A-37 = (5-methyl-3-isothiazolyl)- A-38 = (1H-1,2,4-triazol-1-yl)- A-39 = (l-methyl-1H-1,2,4-triazol-3-yl)- A-40 = (3-methyl-1H-1,2,4-triazol-1-yl)- A-41 = (3-trifluoromethyl-1H-1,2,4-triazol-1- yl)- A-42 = (5-methyl-1H-1,2,4-triazol- l-yl)- A-43 = (4H-1,2,4-triazol-4-yl)- A-44 = (3-methyl-I ,2,4-oxadiazol-5-yl)- A-45 = (5-trifluoromethyl- 1,3,4-oxadiazol-2- yl)- A-46 = (5-methyl-I ,2,4-oxadiazol-3-yl)- A-47 = (4-methyl-3-furazanyl)- A-48 = (3-furazanyl)- A-49 = (1,2,3-thiadiazol-5-yl)- A-50 = (5-methyl- 1,3,4-oxadiazol-2-yl)- A-51 = (5-methyl- 1,2,3-thiadiazol-4-yl)- A-52 = (1,2,3-thiadiazol-4-yl)- A-53 = (3-methyl-l ,2,4-thiadiazol-5-yl)- A-54 = (5-methyl-1,2,4-thiadiazol-3-yl)- A-55 = (5-methyl- 1,3,4-thiadiazol-2-yl)- A-56 = (1-methyl-lH-tetrazol-5-yl)- A-57 = (5-methyl-lH-tetrazol-l-yl)- A-58 = (2-methyl-2H-tetrazol-5-yl)- A-59 = (2-pyridinyl)- A-60 = (6-methyl-2.pyridinyl)- A-61 = (6-trifluoromethyl-2-pyridinyl)- A-62 = (4-pyridinyl)- A-63 = (3-pyridinyl)- A-64 = (6-methyl-3-pyridazinyl)- A-65 = (5-methyl-3-pyridazinyl)- A-66 = (3-pyridazinyl)- A-67 = (4,6-dimethyl-2-pyrimidinyl)- A-68 = (4-methyl-2-pyrimidinyl)- A-69 = (2-pyrimidinyl)- A-70 = (2-methyl-5-pyrimidinyl)- A-71 = (6-methyl-2-pyrazinyl)- A-72 = (2-pyrazinyl)- A-73 = (4,6-dimethyl- 1,3,5-triazin-2-yl)- A-74 = (1,3,5-triazin-2-yl)- A-75 = (3-methyl- 1,2,4-triazin-5-yl)- A-76 = (3-methyl- 1,2,4-triazin-6-yl)- A-77 = (phenyl)- A-78 = (3-trifluoromethylphenyl)- A-79 = (3-methylphenyl)- A-80 = (3-fluorophenyl)- A-81 = (4-trifluoromethylphenyl)- A-82 = (2-methylphenyl)- A-83 = (4-chlorophenyl)- A-84 = (3-methoxyphenyl)- A-85 = (3,5-dichlorophenyl)- A-86 = (3,5-bis(trifluoromethyl)phenyl> A-87 = (3-nitrophenyl)- A-88 = (2,4,6-trimethylphenyl)- A-89 = (5-chloro-2-thienyl)- A-90 = (3-methyl-5-trifluoromethoxy-1H- pyrazol-1 -y1)- A-91 = (3-methyl-5-methoxy-lH- pyrazol- 1 -yl)- A-92 = (1,3,4-oxadiazol-2-yl)- TABLE 1 R1 is CH2CH3 and R2 is cyclohexyl A A A A A A A A A A A A A-1 A-2 A-3 A-4 A-5 A-6 A-7 A-8 A-9 A-10 A-11 A-12 A-13 A-14 A-15 A-16 A-17 A-18 A-19 A-20 A-21 A-22 A-23 A-24 A-25 A-26 A-27 A-28 A-29 A-30 A-31 A-32 A-33 A-34 A-35 A-36 A-37 A-38 A-39 A-40 A-41 A42 A43 A44 A45 A46 A47 A48 A-49 A-50 A-51 A-52 A-53 A-54 A-55 A-56 A-57 A-58 A-59 A-60 A-61 A-62 A-63 A-64 A-65 A-66 A-67 A-68 A-69 A-70 A-71 A-72 A-73 A-74 A-75 A-76 A-77 A-78 A-79 A-80 A-81 A-82 A-83 A-84 A-85 A-86 A-87 A-88 A-89 A-90 A-91 A-92 R1 is CH2CH3 and R2 is cyclopentyl A A A A A A A A A A A A A-1 A-2 A-3 AA A-5 A-6 A-7 A-8 A-9 A-10, A-11 A-12 A-13 A-14 A-15 A-16 A-17 A-18 A-19 A-20 A-21 A-22 A-23 A-24 A-25 A-26 A-27 A-28 A-29 A-30 A-31 A-32 A-33 A-34 A-35 A-36 A-37 A-38 A-39 A-40 A-41 A-42 A-43 A-44 A-45 A-47 A-48 A49 A-50 A-51 A-52 A-53 A-54 A-55 A-56 A-57 A-58 A-59 A-60 A-61 A-62 A-63 A-64 A-65 A-66 A-67 A-68 A-69 A-70 A-71 A-72 A-73 A-74 A-75 A-76 A-77 A-78 A-79 A-80 A-81 A-82 A-83 A-84 A-85 A-86 A-87 A-88 A-89 A-90 A-91 A-92 R1 is CH2CH3 and R2 is cyclopropyl A A A A A A A A A A A A A-1 A-2 A-3 AA A-5 A-6 A-7 A-8 A-9 A-10 A-11 A-12 A-13 A-14 A-15 A-16 A-17 A-18 A-19 A-20 A-21 A-22 A-23 A-24 A-25 A-26 A-27 A-28 A-29 A-30 A-31 A-32 A-33 A-34 A-35 A-36 A-37 A-38 A-39 A-40 AA 1 A-42 A43 A-44 A45 A-46 A-47 A-48 A-49 A-50 A-51 A-52 A-53 A-54 A-55 A-56 A-57 A-58 A-59 A-60 A-61 A-62 A-63 A-64 A-65 A-66 A-67 A-68 A-69 A-70 A-71 A-72 A-73 A-74 A-75 A-76 A-77 A-78 A-79 A-80 A-81 A-82 A-83 A-84 A-85 A-86 A-87 A-88 A-89 A-90 A-91 A-92 R1 is CH2CH3 and R2 is CH2CH3 A A A A A A A A A A A A A-1 A-2 A-3 A4 A-5 A-6 A-7 A-8 A-9 A-10 A-il A-12 A-13 A-14 A-15 A-16 A-17 A-18 A-19 A-20 A-21 A-22 A-23 A-24 A-25 A-26 A-27 A-28 A-29 A-30 A-31 A-32 A-33 A-34 A-35 A-36 A-37 A-38 A-39 A-40 A-41 A-42 A-43 A44 A-45 A-46 A-47 A-48 A-49 A-50 A-51 A-52 A-53 A-54 A-55 A-56 A-57 A-58 A-59 A-60 A-61 A-62 A-63 A-64 A-65 A-66 A-67 A-68 A-69 A-70 A-71 A-72 A-73 A-74 A-75 A-76 A-77 A-78 A-79 A-80 A-81 A-82 A-83 A-84 A-85 A-86 A-87 A-88 A-89 A-90 A-91 A-92 R1 is CH2CH,CH3 and R2 is CH2CH2CH3 A A A A A A A A A A A A A-1 A-2 A-3 A-4 A-5 A-6 A-7 A-8 A-9 A-10 A-11 A-12 A-13 A-14 A-15 A-16 A-17 A-18 A-19 A-20 A-21 A-22 A-23 A-24 A-25 A-26 A-27 A-28 A-29 A-30 A-31 A-32 A-33 A-34 A-35 A-36 A-37 A-38 A-39 A-40 A-41 A-42 A-43 A-44 A-45 A-46 A-47 A-48 A-49 A-50 A-51 A-52 A-53 A-54 A-55 A-56 A-57 A-58 A-59 A-60 A-61 A-62 A-63 A-64 A-65 A-66 A-67 A-68 A-69 A-70 A-71 A-72 A-73 A-74 A-75 A-76 A-77 A-78 A-79 A-80 A-81 A-82 A-83 A-84 A-85 A-86 A-87 A-88 A-89 A-90 A-91 A-92 R1 is CH2CH3 and R2 is CH(CH3)2 A A A A A A A A A A A A A-1 A-2 A-3 AA A-5 A-6 A-7 A-8 A-9 A-10 A-11 A-12 A-13 A-14 A-15 A-16 A-17 A-18 A-19 A-20 A-21 A-22 A-23 A-24 A-25 A-26 A-27 A-28 A-29 A-30 A-31 A-32 A-33 A-34 A-35 A-36 A-37 A-38 A-39 A-40 AA1 A-42 A-43 A-44 A-45 A-46 A-47 A-48 A49 A-50 A-51 A-52 A-53 A-54 A-55 A-56 A-57 A-58 A-59 A-60 A-61 A-62 A-63 A-64 A-65 A-66 A-67 A-68 A-69 A-70 A-71 A-72 A-73 A-74 A-75 A-76 A-77 A-78 A-79 A-80 A-81 A-82 A-83 A-84 A-85 A-86 A-87 A-88 A-89 A-90 A-91 A-92 TABLE 2 W A R3 R1 R2 N A-7 H C2H5 C2H5 N A-7 H C2H5 cyclohexyl N A-59 H C2H5 C2H5 N A-59 H C2H5 cyclohexyl N A-73 H C2H5 C2H5 N A-73 H C2H5 cyclohexyl N A-74 H C2H5 C2H5 N A-74 H C2H5 cyclohexyl N A-78 H C2H5 C2H5 N A-78 H C2H5 cyclohexyl N A-73 H C2H5 cyclopentyl N A-74 H C2H5 cyclobutyl N A-78 H C2H5 cyclopropyl N A-7 4-CH3 C2H5 cyclohexyl N A-7 4-CF3 C2H5 cyclohexyl N A-78 4-CF3 C2H5 cyclohexyl CH A-7 H CH3 CH3 CH A-7 H n-C6H13 CH3 CH A-7 H C2H5 n-C6H13 CH A-7 H CH2CF3 CH3 CH A-7 H CH2CF3 C2H5 CH A-7 H (CH2)5CH2F CH3 CH A-7 H (CH2)5CH2F C2H5 CH A-7 H cycloheptyl CH3 CH A-7 H cycloheptyl C2H5 CH A-7 H -CH2CH2- CH A-7 H -CH2CH2CH2- CH A-7 H -CH2(CH2)2CH2- CH A-7 H -CH2(CH2)3CH2- CH A-7 H -CH2CH2oCH2CH2- CH A-7 H CH2CH=CH2 CH2CH=CH2 CH A-7 H CH2CH=CH(CH2)2CH3 CH3 CH A-7 H C2H5 CH2CH=CH(CH2)2CH3 CH A-7 H CH2CH=C(CI)2 CH3 CH A-7 H C2H5 CH2CH=C(Cl)2 CH A-7 H CH2(CH2)3CH=C(Cl)2 CH3 CH A-7 H CH2C=CH C2H5 CH A-7 H CH3 CH2C#C(CH2)2CH3 CH A-7 H C2H5 CH2C=CCH2F CH A-7 H CH3 OCH3 CH A-7 H CH2CH20CH3 C2H5 CH A-7 H C2H5 CH2O(CH2)2CH3 CH A-7 H C6H5 CH(CH3)2 CH A-7 H C6H5 C2H5 CH A-7 H 4-(CH3)2CH-phenyl CH3 CH A-7 H 4-CH3-phenyl C2H5 CH A-7 H 3-Cl-phenyl CH3 CH A-7 H 2-F-phenyl CH3 CH A-7 H 4-CN-phenyl CH3 CH A-7 H 4-NO2-phenyl CH3 CH A-71 3-C1 C2H5 cyclohexyl CH A-71 6-F C2H5 cyclohexyl CH A-71 4-OCH3 C2H5 cyclohexyl CH A-71 4-OCH(CH3)2 C2H5 cyclohexyl CH A-71 4-OCH2CH(CH3)2 C2H5 cyclohexyl CH A-71 5-Br C2H5 cyclohexyl CH A-71 5-OCH3 C2H5 cyclohexyl CH A-71 4-OCF3 C2H5 cyclohexyl CH A-71 4-OCH2CH2CHF2 C2H5 cyclohexyl CH A-71 6-CH3 C2H5 cyclohexyl CH A-71 4-CH(CH3)2 C2H5 cyclohexyl CH A-71 4-CH2CH(CH3)2 C2H5 cyclohexyl CH A-71 4-CF3 C2H5 cyclohexyl CH A-71 4-CH2CF3 C2H5 cyclohexyl CH A-71 4-CH2(CH2)2CH2F C2H5 cyclohexyl CH A-7 3-Cl C2H5 cyclohexyl CH A-7 6-F C2H5 cyclohexyl CH A-7 5-Br C2H5 cyclohexyl CH A-7 4-OCH3 C2H5 cyclohexyl CH A-7 4-CH(CH3)2 C2H5 cyclohexyl CH A-7 3,4-diCI C2H5 cyclohexyl CH A-7 4-CN C2H5 cyclohexyl TABLE 3 W A R3 R1 R2 CH A-7 H C2H5 cyclohexyl CH A-7 H C2H5 C2H5 CH A-78 H C2H5 cyclohexyl CH A-78 H C2H5 C2H5 N A-7 H C2H5 C2H5 N A-7 H C2H5 cyclohexyl CH A-7 2-Cl C2H5 C2H5 CH A-7 2-Cl C2H5 cyclohexyl TABLE 4 W A R3 R1 R2 N A-7 H C2H5 C2H5 N A-7 H C2H5 cyclohexyl

N A-78 H C2H5 C2H5 N A-78 H C2H5 cyclohexyl CH A-78 H C2H5 C2H5 CH A-78 H C2H5 cyclohexyl FormulationIUtility Compounds of this invention will generally be used as a formulation or composition with an agriculturally suitable carrier comprising at least one of a liquid diluent, a solid diluent or a surfactant. The formulation or composition ingredients are selected to be consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature. Useful formulations include liquids such as solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and/or suspoemulsions) and the like which optionally can be thickened into gels. Useful formulations further include solids such as dusts, powders, granules, pellets, tablets, films, and the like which can be water-dispersible ("wettable") or water-soluble. Active ingredient can be (micro)encapsulated and further formed into a suspension or solid formulation; alternatively the entire formulation of active ingredient can be encapsulated (or "overcoated"). Encapsulation can control or delay release of the active ingredient. Sprayable formulations can be extended in suitable media and used at spray volumes from about one to several hundred liters per hectare. High-strength compositions are primarily used as intermediates for further formulation.

The formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges which add up to 100 percent by weight.

Weight Percent Active Ingredient Diluent Surfactant Water-Dispersible and Water-soluble 5-90 0-94 1-15 Granules, Tablets and Powders.

Suspensions, Emulsions, Solutions 5-50 40-95 0-15 (including Emulsifiable Concentrates) Dusts 1-25 70-99 Granules and Pellets 0.01-99 5-99.99 0-15 High Strength Compositions 999 0-10 Typical solid diluents are described in Watkins, et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950.

McCutcheon 's Detergents and Emulsifiers Annual, Allured Publ. Corp., Ridgewood, New

Jersey, as well as Sisely and Wood, Encvclopedia ofSurface Active Agents, Chemical Publ.

Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth and the like, or thickeners to increase viscosity.

Surfactants include, for example, polyethoxylated alcohols, polyethoxylated alkylphenols, polyethoxylated sorbitan fatty acid esters, dialkyl sulfosuccinates, alkyl sulfates, alkylbenzene sulfonates, organosilicones, N,N-dialkyltaurates, lignin sulfonates, naphthalene sulfonate formaldehyde condensates, polycarboxylates, and polyoxyethylene/polyoxypropylene block copolymers. Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, starch, sugar, silica, talc, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate. Liquid diluents include, for example, water, N,N-dimethylformamide, dimethyl sulfoxide, N-alkylpyrrolidone, ethylene glycol, polypropylene glycol, paraffins, alkylbenzenes, alkylnaphthalenes, oils of olive, castor, linseed, tung, sesame, corn, peanut, cotton-seed, soybean, rape-seed and coconut, fatty acid esters, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone, and alcohols such as methanol, cyclohexanol, decanol and tetrahydrofurfuryl alcohol.

Solutions, including emulsifiable concentrates, can be prepared by simply mixing the ingredients. Dusts and powders can be prepared by blending and, usually, grinding as in a hammer mill or fluid-energy mill. Suspensions are usually prepared by wet-milling; see, for example, U.S. 3,060,084. Granules and pellets can be prepared by spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning, "Agglomeration", Chemical Engineering, December 4, 1967, pp 147-48, Perry's Chemical Engineer 's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and following, and WO 91/13546. Pellets can be prepared as described in U.S. 4,172,714.

Water-dispersible and water-soluble granules can be prepared as taught in U.S. 4,144,050, U.S. 3,920,442 and DE 3,246,493. Tablets can be prepared as taught in U.S. 5,180,587, U.S.

5,232,701 and U.S. 5,208,030. Films can be prepared as taught in GB 2,095,558 and U.S.

3,299,566.

For further information regarding the art of formulation, see U.S. 3,235,361, Col. 6, line 16 through Col. 7, line 19 and Examples 10-41; U.S. 3,309,192, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182; U.S. 2,891,855, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp 81-96; and Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989.

In the following Examples, all percentages are by weight and all formulations are prepared in conventional ways. Compound numbers refer to compounds in Index Tables A and B.

Example A High Strength Concentrate Compound 1 98.5% silica aerogel 0.5% synthetic amorphous fine silica 1.0%.

Example B Wettable Powder Compound 1 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%.

Example C Granule Compound 1 10.0% attapulgite granules (low volatile matter, 0.71/0.30 mm; U.S.S. No. 2-50 sieves) 90.0%.

Example D Extruded Pellet Compound 1 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%.

Test results indicate that the compounds of the present invention are highly active preemergent and postemergent herbicides or plant growth regulants. Many of them have utility for broad-spectrum pre- and/or postemergence weed control in areas where complete control of all vegetation is desired such as around fuel storage tanks, industrial storage areas, parking lots, drive-in theaters, air fields, river banks, irrigation and other waterways, around billboards and highway and railroad structures. Some of the compounds are useful for the control of selected grass and broadleaf weeds with tolerance to important agronomic crops which include but are not limited to alfalfa, barley, cotton, wheat, rape, sugar beets, corn (maize), sorghum, soybeans, rice, oats, peanuts, vegetables, tomato, potato, perennial plantation crops including coffee, cocoa, oil palm, rubber, sugarcane, citrus, grapes, fruit trees, nut trees, banana, plantain, pineapple, hops, tea and forests such as eucalyptus and

conifers (e.g., loblolly pine), and turf species (e.g., Kentucky bluegrass, St. Augustine grass, Kentucky fescue and Bermuda grass). Those skilled in the art will appreciate that not all compounds are equally effective against all weeds. Alternatively, the subject compounds are useful to modify plant growth.

A herbicidally effective amount of the compounds of this invention is determined by a number of factors. These factors include: formulation selected, method of application, amount and type of vegetation present, growing conditions, etc. In general, a herbicidally effective amount of compounds of this invention is 0.001 to 20 kg/ha with a preferred range of 0.004 to 1.0 kg/ha. One skilled in the art can easily determine the herbicidally effective amount necessary for the desired level of weed control.

Compounds of this invention can be used alone or in combination with other commercial herbicides, insecticides or fungicides. Compounds of this invention can also be used in combination with commercial herbicide safeners such as benoxacor, dichlormid and furilazole to increase safety to certain crops. A mixture of one or more of the following herbicides with a compound of this invention may be particularly useful for weed control: acetochlor, acifluorfen and its sodium salt, aclonifen, acrolein (2-propenal), alachlor, ametryn, amidosulfuron, amitrole, ammonium sulfamate, anilofos, asulam, atrazine, azafenidin, azimsulfuron, benazolin, benazolin-ethyl, benfluralin, benfuresate, bensulfuron-methyl, bensulide, bentazone, bifenox, bispyribac and its sodium salt, bromacil, bromoxynil, bromoxynil octanoate, butachlor, butralin, butroxydim (ICIA0500), butylate, caloxydim (BAS 620H), carfentrazone-ethyl, chlomethoxyfen, chloramben, chlorbromuron, chloridazon, chlorimuron-ethyl, chlornitrofen, chlorotoluron, chlorpropham, chlorsulfuron, chlorthal-dimethyl, cinmethylin, cinosulfuron, clethodim, clomazone, clopyralid, clopyralid-olamine, cyanazine, cycloate, cyclosulfamuron, 2,4-D and its butotyl, butyl, isoctyl and isopropyl esters and its dimethylammonium, diolamine and trolamine salts, daimuron, dalapon, dalapon-sodium, dazomet, 2,4-DB and its dimethylammonium, potassium and sodium salts, desmedipham, desmetryn, dicamba and its diglycolammonium, dimethylammonium, potassium and sodium salts, dichlobenil, dichlorprop, diclofop-methyl, 2-[4,5-dihydro-4-methyl-4-( 1 -methylethyl)-5-oxo- lH-imidazol-2-yl]-5-methyl-3- pyridinecarboxylic acid (AC 263,222), difenzoquat metilsulfate, diflufenican, dimepiperate, dimethenamid, dimethylarsinic acid and its sodium salt, dinitramine, diphenamid, diquat dibromide, dithiopyr, diuron, DNOC, endothal, EPTC, esprocarb, ethalfluralin, ethametsulfuron-methyl, ethofumesate, ethoxysulfuron, fenoxaprop-ethyl, fenoxaprop-P-ethyl, fenuron, fenuron-TCA, flamprop-methyl, flamprop-M-isopropyl, flamprop-M-methyl, flazasulfuron, fluazifop-butyl, fluazifop-P-butyl, fluchloralin, flumetsulam, flumiclorac-pentyl, flumioxazin, fluometuron, fluoroglycofen-ethyl, flupoxam, flupyrsulfuron-methyl and its sodium salt, fluridone, flurochloridone, fluroxypyr, fluthiacet-methyl, fomesafen, fosamine-ammonium, glufosinate, glufosinate-ammonium,

glyphosate, glyphosate-isopropylammonium, glyphosate-sesquisodium, glyphosate-trimesium, halosulfuron-methyl, haloxyfop-etotyl, haloxyfop-methyl, hexazinone, imazamethabenz-methyl, imazamox, imazapyr, imazaquin, imazaquin-ammonium, imazethapyr, imazethapyr-ammonium, imazosulfuron, ioxynil, ioxynil octanoate, ioxynil-sodium, isoproturon, isouron, isoxaben, isoxaflutole, lactofen, lenacil, linuron, maleic hydrazide, MCPA and its dimethylammonium, potassium and sodium salts, MCPA-isoctyl, mecoprop, mecoprop-P, mefenacet, mefluidide, metam-sodium, methabenzthiazuron, methylarsonic acid and its calcium, monoammonium, monosodium and disodium salts, methyl [[[1 - [5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrophenylj-2- methoxyethylidene]amino]oxy] acetate (AKH-708 8), methyl 5- [ [ [ [(4,6-dimethyl-2- pyrimidinyl)amino] carbonyl] amino] sulfonyl] -1 -(2 -pyridinyl)- 1 H-pyrazole4-carboxylate (NC-330), metobenzuron, metolachlor, metosulam, metoxuron, metribuzin, metsulfuron-methyl, molinate, monolinuron, napropamide, naptalam, neburon, nicosulfuron, norflurazon, oryzalin, oxadiazon, oxasulfuron, oxyfluorfen, paraquat dichloride, pebulate, pendimethalin, pentoxazone (KPP-314), perfluidone, phenmedipham, picloram, picloram-potassium, pretilachlor, primisulfuron-methyl, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propyzamide, prosulfuron, pyrazolynate, pyrazosulfuron-ethyl, pyridate, pyriminobac-methyl, pyrithiobac, pyrithiobac-sodium, quinclorac, quizalofop-ethyl, quizalofop-P-ethyl, quizalofop-P-tefuryl, rimsulfuron, sethoxydim, siduron, simazine, sulcotrione (1CIA005 1), sulfentrazone, sulfometuron-methyl, TCA, TCA-sodium, tebuthiuron, terbacil, terbuthylazine, terbutryn, thenylchlor, thiafluamide (BAY 11390), thifensulfuron-methyl, thiobencarb, tralkoxydim, tri-allate, triasulfuron, triaziflam, tribenuron-methyl, triclopyr, triclopyr-butotyl, triclopyr-triethylammonium, tridiphane, trifluralin, triflusulfuron-methyl, and vernolate.

The following Tests demonstrate the control efficacy of the compounds of this invention against specific weeds. The weed control afforded by the compounds is not limited, however, to these species. See Index Tables A and B for compound descriptions.

The abbreviation "Ex." stands for "Example" and is followed by a number indicating in which example the compound is prepared.

INDEX TABLE A Cmpd No. W A R1 R2 mp (OC) 1 (Ex. 1) CH | CH2CH3 CH2CH3 94-97 gJ\N CF3 2 (Ex. 2) N N CH2CH3 CH2CH3 126-129 N 7 3 CH H CH2CH3 CH2CH3 oil * I 4 CH O CH2CH3 CH2CH3 oil * \=N 5 CH YCF3 CH2CH3 cyclohexyl oil * aCF3 6 CH N CH2CH3 cyclohexyl oil * gNX ¼CF3 7 CH O CH2CH3 cyclohexyl oil * ao 8 CH j CH2CH3 CH2CH3 95-98 gNX 9 CH NI CH2CH3 cyclohexyl 45-50 N 10 CH N CH2CH3 CH2CH3 116-120 <NJN

11 CH | CH2CH3 cyclohexyl 111-115 rN NJ 12 CH | CH3 phenyl 215-218 N CF3 *See Index Table B for 1H NMR data.

INDEX TABLE B Cmpd No. 1H NMR Data (CDC13 solution unless indicated otherwise)a 3 8 1.1 (m, 3H), 1.3 (m, 3H), 3.05 (m, 2H), 3.45 (m, 2H), 7.4-7.7 (m, 8H).

4 s 1.3 (m, 6H), 3.4 (m, 2H), 3.55 (m, 2H), 6.4 (s, 1H), 7.55-7.7 (m, 3H), 7.85 (m, 1H), 8.25 (s, 111).

5 sl.o-l.s(m, 14H), 3.l(m, 1H), 3.4 (m, 1H), 7.4-7.7 (m, 8H).

6 s 1.0-1.9 (rsi, 14H), 3.2-3.5 (m, 2H), 6.7 (s, 1H), 7.6-7.7 (m, 4H), 7.8 (s, 1H).

7 8 1.1-2.0 (m, 14H), 3.45 (m, 2H), 6.4 (s, 1H), 7.55-7.7 (m, 3H), 7.85 (m, 1H), 8.25 (s, 1H). a 1H NMR data are in ppm downfield from tetramethylsilane. Couplings are designated by (s)-singlet and (m)-multiplet.

BIOLOGICAL EXAMPLES OF THE INVENTION TEST A Seeds of barley (Hordeum vulgare), bedstraw (Galium aparine), blackgrass (Alopecurus myosuroides), broadleaf signalgrass (Brachiaria decumbens), chickweed (Stellaria media), cocklebur (Xanthium strumarium), corn (Zea mays), cotton (Gossypium hirsutum), crabgrass (Digitaria sanguinalis), downy brome (Bromus tectorum), giant foxtail (Setariafaberii), lambsquarters (Chenopodium album), morningglory (Ipomoea hederacea), pigweed (Amaranth us retroflexus), rape (Brassica napus), sorghum (Sorghum bicolor), soybean (Glycine max), sugar beet (Beta vulgaris), velvetleaf (Abutilon theophrasti), wheat (Triticum aestivum), wild buckwheat (Polygonum convolvulus), wild oat (Avenafatua) and purple nutsedge (Cyperus rotundus) tubers were planted and treated preemergence with test chemicals formulated in a non-phytotoxic solvent mixture which included a surfactant.

At the same time, these crop and weed species were also treated with postemergence applications of test chemicals formulated in the same manner. Plants ranged in height from 2 to 18 cm (1- to 4-leaf stage) for postemergence treatments. Plant species in the flood test consisted of rice (Oryza sativa), smallflower flatsedge (Cyperus digormis), duck salad (Heteranthera limosa) and barnyardgrass (Echinochloa crus-galli) grown to the 2-leaf stage for testing. Treated plants and controls were maintained in a greenhouse for twelve to sixteen days, after which all species were compared to controls and visually evaluated. Plant response ratings, summarized in Table A, are based on a scale of O to 10 where 0 is no effect and 10 is complete control. A dash (-) response means no test result.

TABLE A COMPOUND TABLE A COMPOUND Rate 2000 g/ha 1 3 4 Rate 2000 g/ha 1 3 4 POSTEMERGENCE PREEMERGENCE B. signalgrass - - - B. signalgrass - - - Barley 0 0 4 Barley 0 0 3 Barnyardgrass 9 8 9 Barnyardgrass 9 9 10 Bedstraw 5 4 9 Bedstraw 0 0 9 Blackgrass 1 0 6 Blackgrass 7 8 8 Chickweed 5 4 6 Chickweed 0 0 8 Cocklebur 3 0 4 Cocklebur 0 0 0 Corn 6 0 8 Corn 4 5 9 Cotton 8 2 7 Cotton 2 5 2 Crabgrass 8 1 9 Crabgrass 10 9 9 Downy brome 0 0 2 Downy brome 4 7 5 Giant foxtail 7 1 9 Giant foxtail 10 9 9 Lambsquarters 4 1 8 Lambsquarters 4 0 10 Morningglory 5 2 9 Morningglory 0 2 5 Nutsedge - 0 0 Nutsedge 0 - 0 Rape 2 5 5 Rape 0 0 8 Redroot pigweed - - - Redroot pigweed - - - Rice 8 2 8 Rice 5 2 7 Sorghum 7 2 8 Sorghum 8 9 9 Soybean 3 4 8 Soybean 0 2 5 Sugar beet 5 6 5 Sugar beet 4 6 4 Velvetleaf 7 3 7 Velvetleaf 2 0 5 Wheat 0 0 8 Wheat 0 0 5 Wild buckwheat 1 7 0 Wild buckwheat 0 0 3 Wild oat 0 0 0 Wild oat 0 0 0

TABLE A COMPOUND TABLE A COMPOUND Rate 1000 g/ha 5 6 7 8 Rate 1000 g/ha 5 6 7 8 POSTEMERGENCE PREEMERGENCE B. signalgrass - - - 8 B. signalgrass - - - 10 Barley 0 0 4 - Barley 0 0 0 - Barnyardgrass 0 0 6 - Barnyardgrass 0 0 9 - Bedstraw 0 0 7 0 Bedstraw 0 0 0 6 Blackgrass 0 0 0 4 Blackgrass 0 0 6 9 Chickweed 3 0 4 - Chickweed 0 0 0 - Cocklebur 0 0 4 0 Cocklebur 0 0 0 0 Corn 0 0 0 7 Corn 0 0 0 5 Cotton 0 0 4 - Cotton 0 0 3 - Crabgrass 0 0 2 9 Crabgrass 5 0 9 9 Downy brome 0 0 0 - Downy brome 0 0 5 - Giant foxtail 0 0 4 8 Giant foxtail 2 0 9 10 Lambs quarters 0 0 7 - Lambsquarters 0 0 3 - Morningglory 0 0 8 4 Morningglory 0 0 0 0 Nutsedge 0 0 0 0 Nutsedge 0 - 0 0 Rape 0 0 7 1 Rape 0 0 0 7 Redroot pigweed - - - 6 Redroot pigweed - - - 8 Rice 0 0 0 - Rice 0 0 0 - Sorghum 0 0 0 - Sorghum 0 0 0 - Soybean 2 2 5 4 Soybean 0 0 0 4 Sugar beet 0 0 7 0 Sugar beet 0 0 0 5 Velvetleaf 0 0 4 2 Velvetleaf 0 0 0 0 Wheat 0 0 1 0 Wheat 0 0 0 6 Wild buckwheat 0 0 0 - Wild buckwheat 0 0 0 - Wild oat 0 0 3 0 Wild oat 0 0 0 4 TABLE A COMPOUND Rate 1000 g/ha 8 SPRAYED PADDY Barnyardgrass 9 Ducksalad 8 Rice 8 S. flatsedge 9 TABLE A COMPOUND Rate 400 g/ha 1 2 3 4 5 6 7 9 POSTEMERGENCE B. signalgrass - - - - - - - 0 Barley 0 0 0 0 0 0 0 - Barnyardgrass 9 9 7 9 0 0 0 - Bedstraw 0 7 0 6 0 0 - 0 Blackgrass 0 0 0 2 0 0 3 0 Chickweed 0 3 0 0 0 0 0 - Cocklebur 1 3 0 0 0 0 0 0 Corn 1 0 0 6 0 0 0 1 Cotton 4 5 2 6 0 0 1 - Crabgrass 0 1 0 2 0 0 - 0 Downy brome 0 0 0 0 0 0 1 - Giant foxtail 0 2 0 8 0 0 - 0 Lambsquarters 4 6 0 4 0 0 7 - Morningglory 3 3 2 7 0 0 7 7 <BR> <BR> <BR> <BR> Nutsedge - 0 0 0 0 0 0 0 Rape 1 0 0 3 0 0 0 0 Redroot pigweed - - - - - - - 0 Rice 0 0 0 7 0 0 0 - Sorghum 0 0 0 4 0 0 0 - Soybean 2 4 2 7 1 1 5 3 Sugar beet 4 3 4 3 0 0 3 0 Velvetleaf 4 8 0 0 0 0 2 1 Wheat 0 0 0 2 0 0 0 0 Wild buckwheat 0 0 0 0 0 0 0 - Wild oat 0 0 0 0 0 0 0 0 TABLE A COMPOUND Rate 400 g/ha 1 2 3 4 5 6 7 9 PREEMERGENCE B. signalgrass - - - - - - - 0 Barley 0 0 0 0 0 0 0 - Barnyardgrass 9 2 4 6 0 0 0 - Bedstraw 0 0 0 0 0 0 0 0 Blackgrass 0 0 4 3 0 0 3 6 Chickweed 0 0 0 0 0 0 0 - Cocklebur o 0 - 0 0 0 0 0 Corn 0 0 0 0 0 0 0 0 Cotton 0 0 2 0 0 0 0 - Crabgrass 9 4 8 8 0 0 3 5 Downy brome 0 0 3 0 0 0 4 - Giant foxtail 10 2 4 8 0 0 8 8 Lambsquarters 0 0 0 9 0 0 0 - Morningglory 0 2 0 0 0 0 0 0 Nutsedge 0 0 0 0 - - 0 0 Rape 0 0 0 0 0 0 0 0 Redroot pigweed - - - - - - - 0 Rice 4 0 0 0 0 0 0 - Sorghum 0 0 0 0 0 0 - - Soybean 0 0 0 0 0 0 0 0 Sugar beet 0 0 2 0 0 0 0 2 Velvetleaf 0 0 0 0 0 0 0 0 Wheat 0 0 0 0 0 0 0 2 Wild buckwheat 0 0 0 0 0 0 0 - Wild oat 0 0 0 0 0 0 0 3 TABLE A COMPOUND Rate 400 g/ha 9 SPRAYED PADDY Barnyardgrass 0 Ducksalad 4 Rice 0 S. flatsedge 9 TEST B Seeds of barley (Hordeum vulgare), bedstraw (Galium aparine), blackgrass (Alopecurus myosuroides), broadleaf signalgrass (Brachiaria decumbens), chickweed (Stellaria media), cocklebur (Xanthium strumarium), corn (Zea mays), cotton (Gossypium hirsutum), crabgrass (Digitaria sanguinalis), downy brome (Bromus tectorum), giant foxtail (Setariafaberii), lambsquarters (Chenopodium album), morningglory (Ipomoea hederacea), pigweed (Amaranthus retroflexus), rape (Brassica nap us), sorghum (Sorghum bicolor), soybean (Glycine max), sugar beet (Beta vulgaris), velvetleaf (Abutilon theophrasti), wheat (Triticum aestivum), wild buckwheat (Polygonum convolvulus), wild oat (Avenafatua) and

purple nutsedge (Cyperus rotundus) tubers were planted and treated preemergence with test chemicals formulated in a non-phytotoxic solvent mixture which included a surfactant.

At the same time, these crop and weed species were also treated with postemergence applications of test chemicals formulated in the same manner. Plants ranged in height from 2 to 18 cm (1- to 4-leaf stage) for postemergence treatments. Plant species in the flood test consisted of rice (Oryza sativa), smallflower flatsedge (Cyperus difformis), duck salad (Heteranthera limosa) and barnyardgrass (Echinochloa crus-galli) grown to the 2-leaf stage for testing. Treated plants and controls were maintained in a greenhouse for twelve to sixteen days, after which all species were compared to controls and visually evaluated. Plant response ratings, summarized in Table B, are based on a scale of O to 10 where 0 is no effect and 10 is complete control. A dash (-) response means no test result.

TABLE B COMPOUND TABLE B COMPOUND Rate 500 g/ha 8 10 11 12 Rate 500 g/ha 8 10 11 12 Postemergence Preemergence Barnyardgrass 9 4 0 0 Blackgrass 7 4 0 0 Blackgrass 4 3 0 0 Brach. decumben 9 - - 0 Brach. decumben 8 7 0 0 Cocklebur 0 0 0 0 Cocklebur 3 0 0 0 Corn 7 5 0 0 Corn 6 3 0 0 Crabgrass 8 9 0 0 Crabgrass 5 5 0 0 Galium 5 0 0 0 Ducksalad 2 0 2 0 Giant foxtail 9 9 7 0 Galium 0 5 6 0 Morningglory 2 3 4 0 Giant foxtail 7 6 0 0 Nutsedge 0 0 - 0 Morningglory 8 2 7 0 Rape 0 0 0 0 Nutsedge 0 0 0 0 Redroot pigweed 6 0 0 0 Rape 5 3 0 0 Soybean 7 0 0 0 Redroot pigweed 6 4 0 0 Sugar beet 0 0 4 0 Rice 7 4 0 0 Velvetleaf 6 8 - 0 S. Flatsedge 8 3 4 0 Wheat 3 0 0 0 Soybean 7 6 7 0 Wild oats 3 0 0 0 Sugar beet 1 4 0 0 Velvetleaf 4 0 2 0 Wheat 4 0 0 0 Wild oats 0 0 0 0

TEST C Plastic pots were partially filled with silt loam soil. The soil was then saturated with water. Indica Rice (Oryza sativa) seed (designated rice, indica 1) and seedlings (designated rice, indica 3) at the 2 leaf stage, seeds, tubers or plant parts selected from barnyardgrass (Echinochloa crus-galli), ducksalad (Heteranthera limosa), early watergrass (Echinochloa oryzoides), junglerice (Echinochloa colonum), late watergrass (Echinochloa oryzicola), redstem (Ammania species), rice flatsedge (Cyperus iria), smallflower flatsedge (Cyperus difform is) and tighthead sprangletop (Leptochloa fasicularis), were planted into this soil.

Plantings and waterings of these crops and weed species were adjusted to produce plants of appropriate size for the test. At the 2-leaf stage, water levels were raised to 3 cm above the soil surface and maintained at this level throughout the test. Chemical treatments were formulated in a non-phytotoxic solvent mixture which included a surfactant and applied directly to the paddy water by pipette, or to the plant foliage by an air pressure-assisted, calibrated belt-conveyer spray system.

Treated plants and controls were maintained in a greenhouse for approximately 21 days, after which all species were compared to controls and visually evaluated. Plant response ratings, summarized in Table C, are reported on a O to 100 scale where 0 is no effect and 100 is complete control. A dash (-) response means no test result.

TABLE C COMPOUND TABLE C COMPOUND TABLE C COMPOUND Rate 1000 g/ha 1 Rate 750 g/ha 1 Rate 500 g/ha 1 Paddy / silt lo Paddy / silt lo Paddy / silt lo Barnyardgrass 2 80 Barnyardgrass 2 80 Barnyardgrass 2 75 Ducksalad 85 Ducksalad 85 Ducksalad 85 E. watergrass 100 E. watergrass 98 E. watergrass 95 Junglerice 45 Junglerice 40 Junglerice 25 L. watergrass 95 L. watergrass 95 L. watergrass 95 Redstem 98 Redstem 90 Redstem 80 Rice flatsedge 100 Rice flatsedge 100 Rice flatsedge 100 Rice indica 1 85 Rice indica 1 80 Rice indica 1 40 Rice indica 3 80 Rice indica 3 70 Rice indica 3 40 S. flatsedge 95 S. flatsedge 95 S. flatsedge 95 T. sprangletop 100 T. sprangletop 100 T. sprangletop 100 TABLE C COMPOUND TABLE C COMPOUND Rate 250 g/ha 1 Rate 125 g/ha 1 Paddy / silt lo Paddy / silt lo Barnyardgrass 2 45 Barnyardgrass 2 20 Ducksalad 80 E. watergrass 15 Junglerice 20 L. watergrass 60 Redstem 80 Rice flatsedge 95 Rice indica 1 10 Rice indica 3 10 S. flatsedge 95 T. sprangletop 95 Ducksalad 10 E. watergrass 10 Junglerice 10 L. watergrass 20 Redstem 20 Rice flatsedge 85 Rice indica 1 0 Rice indica 3 0 S. flatsedge 80 T. sprangletop 90