WO1998025912A1 - Herbicidal heterocyclic amides - Google Patents

Abstract

Compounds for Formula (I), and their N-oxides and agriculturally suitable salts, are disclosed which are useful for controlling undesired vegetation wherein A, W, R?1, R2, R3¿, and m are as defined in the disclosure. Also disclosed are compositions containing the compounds of Formula (I) and a method for controlling undesired vegetation which involves contacting the vegetation or its environment with an effective amount of a compound of Formula (I).

Description

TITLE

HERBICIDAL HETEROCYCLIC AMIDES

BACKGROUND OF THE INVENTION

This invention relates to certain tetrazolinones, their N-oxides, agriculturally suitable salts, compositions thereof, and methods of their use for controlling undesirable vegetation.

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:

i 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 n is O, 1, 2 or 3. 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 stereoisomers, JV-oxides, and agriculturally suitable salts thereof, as well as agricultural compositions containing them and a method of their use for controlling undesirable vegetation:

I

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, C1-C4 haloalkyl, C₃-C₆ alkenyl, C₃-C₆ haloalkenyl, C₃-C₆ alkynyl, C₃-C₆ haloalkynyl, C_rC₄ alkoxy, C_rC₄ haloalkoxy, S(O)_nR⁴, S(O)₂OR⁴, SO2NR⁵R⁶, and phenyl optionally substituted on the phenyl ring with

C1-C3 alkyl, C_rC₃ haloalkyl, C_rC₃ alkoxy, C_rC₃ 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 orN;

R¹ is C_rC₆ alkyl, C_rC₆ haloalkyl, C₃-C₇ cycloalkyl, C₃-C₇ cycloalkenyl, C₃-C₆ alkenyl, C3-C6 haloalkenyl, C₃-C₆ alkynyl, C3-C6 haloalkynyl or Ci-Cg alkoxy; or R¹ is phenyl optionally substituted on the phenyl ring with C1-C3 alkyl, halogen, cyano or nitro;

R² is C_rC₆ alkyl, C_rC₆ haloalkyl, C3-C7 cycloalkyl, C3-C7 cycloalkenyl, C₃-C₆ alkenyl, C3- 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, C_rC haloalkoxy, C1-C4 alkyl, C1-C4 haloalkyl, C -C₄ alkoxyalkyl, C₂-C₄ alkylthioalkyl, cyano, nitro, NH(C_rC₄ alkyl), N(C_rC₄ alkyl)₂, S(O)_nR⁴, S(O)₂OR⁴ or SO₂NR⁵R⁶;

R⁴ is C_rC₆ alkyl, C_rC₆ haloalkyl, C₃-C₆ alkenyl, C₃-C₆ haloalkenyl, C₃-C₆ alkynyl or C3-C6 haloalkynyl; R⁵ is H, C_rC₆ alkyl, C_rC₆ haloalkyl, C₃-C₆ alkenyl or C₃-C₆ alkynyl; R⁶ is H, C_rC₆ alkyl, C _rC₆ haloalkyl, C₃-C₆ alkenyl. C₃-C₆ alkynyl or C_rC₆ alkoxy; or R⁵ and R⁶ can be taken together as -CH₂CH₂-, -CH₂CH₂CH₂-,

-CH₂CH₂CH₂CH₂-, -CH₂CH₂CH₂CH₂CH₂- or -CH₂CH₂OCH₂CH₂-; m is 0, 1 or 2; and n is 0, 1 or 2.

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, z^'-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-ρropenyl, 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, «-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers. "Alkoxyalkyl" denotes alkoxy substitution on alkyl. Examples of "alkoxyalkyl" include CH₃OCH₂, CH₃OCH₂CH₂, CH₃CH₂OCH₂, CH₃CH₂CH₂CH₂OCH₂ and

CH₃CH₂OCH₂CH . "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 CH₃SCH₂, 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 Hlickel 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 Hϋckel 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 JV-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 JV-oxides. One skilled in the art will also recognize that tertiary amines can form N-oxides. Synthetic methods for the preparation of .V-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 w-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as r-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethyldioxirane. These methods for the preparation of -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, C1CH , CF₃CH₂ and CF₃CC1₂. The terms "haloalkenyl", "haloalkynyl", "haloalkoxy", "haloalkylthio", and the like, are defined analogously to the term "haloalkyl". Examples of "haloalkenyl" include (C1)₂C=CHCH₂ and CF₃CH₂CH=CHCH₂. Examples of "haloalkynyl" include HC≡CCHCl, CF₃C≡C, CC1₃C≡C and FCH₂C≡CCH₂. Examples of "haloalkoxy" include CF₃O, CCl₃CH₂O, HCF₂CH₂CH₂O and CF₃CH₂O.

The total number of carbon atoms in a substituent group is indicated by the "Cj-Cj" prefix where i and j 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 CH₃CH₂OCH₂CH₂. Examples of "alkylcarbonyl" include C(O)CH₃, C(O)CH₂CH₂CH₃ and C(O)CH(CH₃)₂. Examples of "alkoxycarbonyl" include CH₃OC(=O), CH₃CH₂OC(=O), CH₃CH₂CH₂OC(=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)_j_;, 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, JV-oxides thereof and agriculturally suitable salts thereof, wherein

A is phenyl, pyridinyl or lH-pyrazolyl, each optionally substituted by one or more groups selected from halogen, Cι-C alkyl, Cj-C₄ haloalkyl, C_j-C₄ alkoxy, and C1-C4 haloalkoxy; and when A is 1H- 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 C_rC₆ alkyl, C_rC₆ haloalkyl or C₃-C₇ cycloalkyl; R² is C_rC₆ alkyl, C_rC₆ haloalkyl or C₃-C₇ cycloalkyl; or R¹ and R² can be taken together as -CH₂CH₂-, -CH₂CH₂CH₂-, -CH₂CH₂CH₂CH₂-, -CH₂CH₂CH₂CH₂CH₂- or -CH₂CH₂OCH₂CH₂-; and each R³ is independently halogen, C1-C₄ alkoxy, C1-C₄ haloalkoxy, C 1 -C₄ alkyl or C _{ -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 NJV-diethyl-4,5-dihydro-5-oxo-4-[2-[3-(trifluoromethyl)-lH-pyrazol-l- y l]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, R'-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 °C 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

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

, base, e.g., pyridine

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

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

oxalyl chloride

(optionally a catalytic amount ofDMF)

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., 5NHC1 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

7 wherein R^ is C j -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 457-496; Sandier, 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

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

Reduction

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 °C, 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

10 9a wherein X is F, Cl, Br, CH3S0₂0 or CF3SO2O and X is ortho o para to the N0₂ group; Nu is an optionally-substituted imidazole, pyrazole, triazole or tetrazole; and A¹ is an optionally-substituted 1 / -imidazole, 1 //-pyrazole, l//-l,2,4-triazole, 4//-l,2,4-triazole or tetrazole and A* is ortho oτpara 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

12 7a wherein X is F, Cl, Br, CH3S0₂0 or CF3S0₂0 and X is ortho or para to the C0₂R⁷ group; Nu is an optionally-substituted imidazole, pyrazole, triazole or tetrazole; and Al is an optionally-substituted 1 -imidazole, l /-pyrazole, l /-l,2,4-triazole, 4 /-l,2,4-triazole or tetrazole and Al is ortho or para to the C0₂R7 group.

Scheme 11 illustrates the preparation of many carboxylic acids of Formula 6 whereby a bromide compound of Formula 13 is treated with «-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

13

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

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 TV^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

AlCh, DMF; then 4 + NaN3 - ► 1

H₂0/H⁺

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 -mercapto tetrazole 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 71 1,761).

Scheme 14

15

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 Oxone® 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

4. Oxone _j g

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

17

Phenyl carbamates of Formula 17 can be prepared by reaction of an amine of

Formula 8 with phenyl chloroformate 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), 1 101 ; 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

(CH₃)₃ SiN₃; 5 »► 1 then, e.g., CH3OH 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. lH 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 l-(2-nitrophenvP-3-(trifluoromethyl)-lH-pyrazole To 135 mL of N^-dimethylformamide was added 20.2 g (0.149 mol) of 3-

(trifTuoromethyl)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 °C, 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.

¹Η NMR (CDC1₃): δ 6.65 (d, 1Η), 7.65 (m, 2Η) 7.75 (m, 2H), 8.0 (d, IH). Step B: Preparation of 2-r3-(trifluoromethyl)- lH-pyrazoI- 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 °C. 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 Celite® 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. IH NMR (CDC1₃): δ 4.55 (s, 2H) 6.7 (d, IH), 6.8 (m, 2H), 7.2 (m, 2H), 7.75 (d, IH). Step C Preparation of L4-dihvdro-4-[2-[3-(trifluoromethyl>lH-pyrazol-l- yllphenyll-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.

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

Step D: Preparation of N V-diethyl-4,5-dihydro-5-oxo-4-r2-r3-(^'trifluoromethyl)- lH-pyrazol- 1 -yllphenyl]- lH-tetrazol- 1 -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.

'H NMR (CDC1₃): δ 1.25 (m, 6H), 3.3 (m, 2H) 3.55 (m, 2H), 6.7 (d, IH), 7.55-7.7 (m, 4H), 7.8 (d, IH).

EXAMPLE 2 Step A: Preparation of 3-nitro-2-[3-f trifluoromethyl)- lH-pyrazol- 1 -yllpyridine To 66 mL of N^V-dimethylformamide was added sequentially 1 1.1 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. H NMR (CDCI3): δ 6.75 (m, IH), 7.5 (m, IH), 8.15 (m, IH), 8.4 (m, IH), 8.65 (m, IH).

Step B: Preparation of 2-f3-(trifluoromethyl)-lH-pyrazol-l-yll-3-pyridmamine

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 °C and 90 °C. Following completion of addition, the suspension was heated at 80 °C for about 0.5 h, then filtered while hot through a Celite® 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 °C. Η NMR (CDCI3): δ 5.45 (s, 2Η), 6.7 (m, IH), 7.05-7.15 (m, 2H), 7.8 (m, IH), 8.6 (m, IH).

Step C: Preparation of L4-dihvdro-4-(3-pyridinv0-5H-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 °C 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 °C, 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. !H NMR (CDC1₃): δ 6.65 (m, IH), 7.55 (m, IH); 8.05 (m, IH), 8.55 (m, IH), 8.65

(m, IH) 12.7-13.1 (br s, IH).

Step D Preparation of N V-diethyl-4,5-dihvdro-5-oxo-4-r2-r3-(trifluoromethyl - lH-pyrazol- 1 -yll-3-pyridinyl]- lH-tetrazol- 1 -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 °C 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 of this invention, as a solid melting at 126-129 °C.

1Η NMR (CDCI3): δ 1.3 (m, 6Η), 3.45 (m, 2H), 3.55 (m, 2H), 6.7 (m, IH), 7.55 (m. IH), 8.0 (m. IH), 8.6 (m, IH), 8.65 (m, IH). 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- l A-25 = ( 1 -methyl- 1 //-imidazol-4-yl)- A-2 A-26 = (1 -methyl- l//-imidazol-5-yl)- A-3 A-27 = (2-oxazolyl)- A-4 A-28 = (2-methyl-5-oxazolyl)- A-5 A-29 = (2-methyl-4-oxazolyl)- A-6 A-30 = (4-methyl-2-thiazolyl)-

A-7 A-31 = (5-methyl-2-thiazolyl)-

A-8 A-32 = (2-thiazolyl)-

A-33 = (2-methyl-5-thiazolyl)-

A-9 A-34 = (2-methyl-4-thiazolyl)-

A-10 A-35 = (3-methyl-4-isothiazolyl)-

A-l l A-36 = (3-methyl-5-isothiazolyl)-

A-12 A-37 = (5-methyl-3-isothiazolyl)-

A-13 A-38 = (l//-l,2,4-triazol-l-yl)-

A-14 A-39 = (1 -methyl- 1 /-1, 2,4-triazol-3-yl)-

A-15 A-40 = (3-methyl-l/ϊ-l,2,4-triazol-l-yl)-

A-16 A-41 = (3-trifluoromethyl- l /-l,2,4-triazol- 1-

A-17 yl)-

A-18 A-42 = (5-methyl-l/ -l,2,4-triazol-l-yl)-

A-19 A-43 = (4//-l,2,4-triazol-4-yl)-

A-20 A-44 = (3-methyl-l,2,4-oxadiazol-5-yl)-

A-21 A-45 = (5-trifluoromethyl-l,3,4-oxadiazol-2-

A-22 yl)-

A-23 A-46 = (5-methyl-l,2,4-oxadiazol-3-yl)-

A-24 A-47 = (4-methyl-3-furazanyl)-

A-48 (3-methyl- l,2,4-trιazιn-5-yl)-

A-49 (3-methyl- l,2,4-tπazιn-6-yl)-

A-50 (phenyl)-

A-51 (3-trifluoromethylphenyl)-

A-52 (3-methylphenyl)-

A-53 (3-fluorophenyl)-

A-54 (4-trifluoromethylphenyl)-

A-55 (2-methylphenyl)-

A-56 (4-chlorophenyl)-

A-57 (3-methoxyphenyl)-

A-58 (3,5-dichlorophenyl)-

A-59 (3,5-_5/5(trifluoromethyl)phenyl)-

A-60 (3-nitrophenyl)-

A-61 (2,4,6-trimethylρhenyl>

A-62 (5-chloro-2-thienyl)-

A-63 (3-methyl-5-trifluoromethoxy-l /-

A-64 pyrazol-1-yl)-

A-65 (3-methyl-5-methoxy-l -

A-66 pyrazol-1-yl)-

A-67 (l,3,4-oxadiazol-2-yl)-

A-68

A-69

A-70

A-71

A-72

A-73

A-74

TABLE

11

TABLE 2

w A l El

N A-7 H C₂H₅ C₂H₅

N A-7 H C₂H₅ cyclohexyl

N A-59 H CH₅ C₂H₅

N A-59 H C₂H₅ cyclohexyl

N A-73 H CH₅ C₂H₅

N A-73 H C₂H₅ cyclohexyl

N A-74 H CH₅ C₂H₅

N A-74 H CH₅ cyclohexyl

N A-78 H C₂H₅ C H₅

N A-78 H CH₅ cyclohexyl

N A-73 H C₂H₅ cyclopentyl

N A-74 H CH₅ cyclobutyl

N A-78 H C₂H₅ cyclopropyl

N A-7 4-CH₃ CH₅ 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 «-C₆H₁₃ CH₃

CH A-7 H CH₅ «-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(C1)₂ CH₃

CH A-7 H C H₅ CH₂CH=C(C1)₂

CH A-7 H CH₂(CH₂)₃CH=C(C1)₂ CH₃

CH A-7 H CH₂C≡CH C₂H₅

CH A-7 H CH₃ CH₂C_≡C(CH₂)₂CH₃

CH A-7 H C H₅ CH₂C≡CCH₂F

CH A-7 H CH₃ OCH3

CH A-7 H CH₂CH₂OCH₃ C₂H₅

CH A-7 H C₂H₅ CH₂0(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 C H₅

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-N0₂-phenyl CH₃

CH A-71 3-C1 C₂H₅ cyclohexyl

CH A-71 6-F C H₅ cyclohexyl

CH A-71 4-OCH3 C H₅ 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 C H₅ cyclohexyl

CH A-71 4-CH₂CF₃ C₂H₅ cyclohexyl CH A-71 4-CH₂(CH₂)₂CH₂F C2H5 cyclohexyl

CH A-7 3-C1 C2H5 cyclohexyl

CH A-7 6-F C2H5 cyclohexyl

CH A-7 5-Br ^C2^H5 cyclohexyl

CH A-7 4-OCH3 C₂H₅ cyclohexyl

CH A-7 4-CH(CH₃)₂ CH₅ cyclohexyl

CH A-7 3,4-diCl C₂H₅ cyclohexyl

CH A-7 4-CN C₂H₅ cyclohexyl

TABLE 3

w A El Ri El

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-C1 ₂H₅ C₂H₅

CH A-7 2-C1 C₂H₅ cyclohexyl

TABLE 4

w A El l

N A-7 H C₂H₅ C₂H₅ N A-7 H C₂H₅ cyclohexyl N A-78 H C H₅ C H₅

N A-78 H C₂H₅ cyclohexyl

CH A-78 H ^C2^H5 C «5

CH A-78 H C₂H₅ cyclohexyl

Formulation/Utility

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 emulsifϊable 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 0-5

Granules and Pellets 0.01-99 5-99.99 0-15

High Strength Compositions 90-99 0-10 0-2

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, Encyclopedia of Surface 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, Λ 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_^V-dimethylformamide, dimethyl sulfoxide, vV-alkylpyrrolidone, ethylene glycol, polypropylene glycol, paraffins, alkylbenzenes, alkylnaphthalenes, oils of olive, castor, linseed, rung, 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. 25-50 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 [[[l-[5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrophenyl]-2- methoxyethylidene]amino]oxy]acetate (AKH-7088), methyl 5-[[[[(4,6-dimethyl-2- pyrimidinyl)amino]carbonyl]amino]sulfonyl]-l-(2-pyridinyl)-lH-pyrazole-4-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 (ICIA0051), 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 Ri El mp (°C) 1 (Ex. 1) CΗ CΗ₂CΗ₃ CH₂CH₃ 94-97

(Ex. 2) N CH₂CH₃ CH₂CH₃ 126-129

CH CH₂CH₃ cyclohexyl oil *

CH CH₂CH₃ cyclohexyl oil *

CH CH₂CH3 cyclohexyl oil

CH₂CH₃ cyclohexyl 45-50

10 CH₂CH₃ CH₂CH₃ 116-120

1 1 CH CH₂CH₃ cyclohexyl 11 1-1 15

N.

N

<

N

12 CH CH₃ phenyl 215-218

^♦See Index Table B for *H NMR data.

INDEX TABLE B

Cmpd No. IH NMR Data (CDC1₃ solution unless indicated otherwise)²¹

3 δ 1.1 (m, 3H), 1.3 (m, 3H), 3.05 (m, 2H), 3.45 (m, 2H), 7.4-7.7 (m, 8H).

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

5 δ 1.0-1.9 (m, 14H), 3.1 (m, IH), 3.4 (m, IH), 7.4-7.7 (m, 8H). 6 δ 1.0-1.9 ( , 14H), 3.2-3.5 (m, 2H), 6.7 (s, IH), 7.6-7.7 (m, 4H), 7.8 (s, IH). δ 1.1-2.0 (m, 14H), 3.45 (m, 2H), 6.4 (s, IH), 7.55-7.7 (m, 3H), 7.85 (m, IH), 8.25 (s, IH).

^a *H 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 vulgar ), 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), momingglory (Ipomoea hederacea), pigweed (Amaranthus retroβexus), 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 difformis), duck salad (Heteranthera limosa) and bamyardgrass (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 0 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

Bamyardgrass 9 8 9 Bamyardgrass 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 o 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

Momingglory 5 2 9 Momingglory 0 2 5

Nutsedge - 0 o 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 -

Bamyardgrass 0 0 6 - Bamyardgrass 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 o o -

Cocklebur 0 0 4 0 Cocklebur o 0 0 0

Corn 0 0 0 7 Corn o 0 0 5

Cotton o 0 4 - Cotton 0 0 3 -

Crabgrass 0 0 2 9 Crabgrass 5 0 9 9

Downy brome o 0 0 - Downy brome 0 o 5 -

Giant foxtail 0 0 4 8 Giant foxtail 2 0 9 10

Lambsquarters o 0 7 - Lambsquarters 0 0 3 -

Momingglory 0 0 8 4 Momingglory 0 0 0 0

Nutsedge 0 0 0 0 Nutsedge 0 - o 0

Rape 0 0 7 1 Rape o o 0 7

Redroot pigweed - - - 6 Redroot pigweed - - - 8

Rice 0 0 0 - Rice 0 0 0 -

Sorghum o 0 0 - Sorghum 0 o o -

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 o o 0

Wheat 0 0 1 0 Wheat 0 0 o 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

Bamyardgrass 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 -

Bamyardgrass 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 o 6 0 0 0 1

Cotton 4 5 2 6 o 0 1 -

Crabgrass 0 1 0 2 o 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 o 0 7 -

Mo ingglory 3 3 2 7 0 0 7 7

Nutsedge - 0 0 0 o 0 0 0

Rape 1 0 0 3 o 0 0 0

Redroot pigweed 0

Rice 0 0 0 7 0 0 0 -

Sorghum 0 0 0 4 o 0 0 -

Soybean 2 4 2 7 1 1 5 3

Sugar beet 4 3 4 3 o 0 3 0

Velvetleaf 4 8 0 0 0 0 2 1

Wheat 0 0 0 2 o 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 0 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 -

Momingglory 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 o 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

Bamyardgrass 0

Ducksalad 4

Rice o

S. flatsedge 9

TESTB

Seeds of barley (Hordeum vulgar e), bedstraw (Galium aparine), blackgrass (Alopecurus myosuroides), broadleaf signalgrass (Brachiaria decumbens), chickweed (Stellaria media), cocklebur (Xanthium strumarium), com (Zea mays), cotton (Gossypium hirsutum), crabgrass (Digitaria sanguinalis), downy brome (Bromus tectorum), giant foxtail (Setariafaberii), lambsquarters (Chenopodium album), momingglory (Ipomoea hederacea), pigweed (Amaranthus 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 difformis), duck salad (Heteranthera limosa) and bamyardgrass (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 0 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

Bamyardgrass 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 Momingglory 2 3 4 0

Giant foxtail 7 6 0 0 Nutsedge o 0 - 0

Momingglory 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 bamyardgrass (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 difformis) 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 0 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 Bamyardgrass 2 80 Bamyardgrass 2 80 Bamyardgrass 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 Bamyardgrass 2 45 Bamyardgrass 2 20 Ducksalad 80 Ducksalad 10

E. watergrass 15 E. watergrass 10

Junglerice 20 Junglerice 10

L. watergrass 60 L. watergrass 20

Redstem 80 Redstem 20

Rice flatsedge 95 Rice flatsedge 85

Rice indica 1 10 Rice indica 1 0

Rice indica 3 10 Rice indica 3 0

S. flatsedge 95 S . flatsedge 80

T. sprangletop 95 T . sprangletop 90

Claims

CLAIMS What is claimed is:

1. A compound selected from Formula I, geometric or stereoisomers thereof, JV-oxides thereof and agriculturally suitable salts thereof,

I 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, -C₄ alkyl, C1-C4 haloalkyl, C₃-C₆ alkenyl, C₃-Cg haloalkenyl, C₃-Cg alkynyl, C3-C6 haloalkynyl, C1-C4 alkoxy, C_rC₄ haloalkoxy, S(O)_nR⁴, S(O)₂OR⁴, SO₂NR⁵R⁶, and phenyl optionally substituted on the phenyl ring with C_]-C₃ alkyl, C!-C₃ haloalkyl, Cj-C₃ alkoxy, Ci-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 C_rC₆ alkyl, C_rC₆ haloalkyl, C₃-C₇ cycloalkyl, C₃-C₇ cycloalkenyl, C₃-C₆ alkenyl, C3-C6 haloalkenyl, C₃-C₆ alkynyl, C₃-Cg haloalkynyl or Cj-C₆ alkoxy; or Rl is phenyl optionally substituted on the phenyl ring with C1-C3 alkyl, halogen, cyano or nitro; R² is C_rC₆ alkyl, C_rC₆ 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 Rl 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, C1-C4 alkyl,

C1-C4 haloalkyl, C₂-C4 alkoxyalkyl, C₂-C4 alkylthioalkyl, cyano, nitro, NH(C_rC₄ alkyl), N(C_rC₄ alkyl)₂, S(O)_nR⁴, S(O)₂OR⁴ or SO₂NR⁵R⁶; R⁴ is C,-C₆ alkyl, C_rC₆ haloalkyl, C₃-C₆ alkenyl, C₃-C₆ haloalkenyl, C₃-C₆ alkynyl or C3-C6 haloalkynyl; R⁵ is H, C_rC₆ alkyl, C_rC₆ haloalkyl, C₃-C₆ alkenyl or C₃-C₆ alkynyl; R⁶ is H, C_rC₆ alkyl, C_rC₆ haloalkyl, C₃-C₆ alkenyl, C₃-C₆ alkynyl or C_rC₆ alkoxy; or R⁵ and R⁶ can be taken together as -CH₂CH₂-, -CH₂CH₂CH₂-, -CH₂CH₂CH₂CH₂-,

-CH₂CH₂CH₂CH₂CH₂- or -CH₂CH₂OCH₂CH₂-; m is 0, 1 or 2; and n is 0, 1 or 2.

2. The compound of Claim 1 wherein

A is phenyl, pyridinyl or lH-pyrazolyl, each optionally substituted by one or more groups selected from halogen, C C4 alkyl, C1-C4 haloalkyl, C1-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 C_rC₆ alkyl, C_rC₆ haloalkyl or C3-C7 cycloalkyl;

R² is C_rC₆ alkyl, C_rC₆ haloalkyl or C₃-C₇ cycloalkyl; or

Rl and R² can be taken together as -CΗ₂CΗ₂-, -CH₂CH₂CH₂-, -CH₂CH₂CH₂CH₂-, -CH₂CH₂CH₂CH₂CH₂- or -CH₂CH₂OCH₂CH₂-; and each R³ is independently halogen, C_j-C alkoxy, C1-C4 haloalkoxy, C1-C4 alkyl or C_rC₄ haloalkyl.

3. The compound of Claim 2 wherein The substituent A and the tetrazolinone ring are attached to adjacent carbon atoms of the phenyl or pyridine ring.

4. The compound of Claim 3 which is N V-diethyl-4,5-dihydro-5-oxo-4-[2-[3-(trifluoromethyl)-lH-pyrazol-l-yl]phenyl]- lH-tetrazol-1-carboxamide.

5. A herbicidal composition comprising a herbicidally effective amount of a compound of Claim 1 and at least one of a surfactant, a solid diluent or a liquid diluent.

6. A method for controlling the growth of undesired vegetation comprising contacting the vegetation or its environment with a herbicidally effective amount of a compound of Claim 1.