WO1999048890A1 - Herbicidal tetrazolinones - Google Patents

Abstract

Compounds of formula (I), geometric and stereoisomers, N-oxides and agriculturally suitable salts thereof, are disclosed which are useful for controlling undesired vegetation wherein Q, R1, R2, x and y 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 TETRAZOLINONES

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 695,748 discloses compounds of Formula i as herbicides:

O o

K. Ν X Ν X Ν

Ν= Ν R² i wherein, ter alia,

R is an optionally substituted 5-membered heterocyclic ring; and

R¹ and R² are independently alkyl, haloalkyl, cycloalkyl, alkenyl, haloalkenyl, alkynyl, alkoxy or phenyl. 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, N-oxides, and agriculturally suitable salts thereof, as well as agricultural compositions containing them and a method of their use for controlling undesirable vegetation: O O

- N N^' \ U /

wherein

Q is a 5- or 6-membered aromatic heterocyclic ring system containing 1 to 3 heteroatoms independently selected from the group consisting of nitrogen, oxygen and sulfur, provided that the heterocyclic ring system contains no more than one oxygen and no more than one sulfur, and each heterocyclic ring system is optionally substituted by 1-3 groups selected from halogen, nitro, cyano, C1-C4 alkyl, C₃-C₇ cycloalkyl, C_rC₄ haloalkyl, C3-C4 alkenyl, C3-C₄ alkynyl, C_rC₄ alkoxy, C_rC₄ haloalkoxy, S(O)_nR⁴, SO₂NR⁵R⁶ or phenyl optionally substituted with C₁-C₄ alkyl, C3-C7 cycloalkyl, Cj-C₄ haloalkyl, halogen, cyano or nitro; and when Q is a 5- or 6-membered aromatic heterocyclic ring system containing a nitrogen, then Q can be bonded through any available carbon or nitrogen atom to the tetrazolinone ring by replacement of a hydrogen on said carbon or nitrogen atom;

R¹ is C_rC₆ alkyl, C_rC₆ haloalkyl, C₃-C₆ alkenyl, C₃-C₆ haloalkenyl, C₃-C₆ alkynyl, C₃-Cg haloalkynyl; or R¹ is C3-C7 cycloalkyl or C3-C7 cycloalkenyl, each optionally substituted with 1-2 R³; each R² is independently C1-C4 alkyl or C1-C4 haloalkyl; each R³ is independently C1-C₄ alkyl or C1-C4 alkoxy;

R⁴ is C_rC₄ alkyl or C_rC₄ haloalkyl;

R⁵ is H or C_rC₄ alkyl;

R⁶ is C_rC₄ alkyl; each n is independently 0, 1 or 2; x is 1, 2 or 3; y is O, 1, 2, 3 or 4; and wherein the dashed lines in the 5-, 6- or 7-membered carbocyclic ring of Formula I shown below

represent one carbon-carbon double bond at any position within the carbocyclic ring.

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, λϊ-propyl, /-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. "Alkenyl" includes straight-chain or branched alkenes such as 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 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, H-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers.

"Cycloalkyl" includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. "Cycloalkenyl" includes, for example, cyclopropenyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl.

The term "halogen", either alone or in compound words such as "haloalkyl", includes fluorine, chlorine, bromine or iodine. 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 CF₃CC1₂. The terms "haloalkenyl", "haloalkynyl", "haloalkoxy", 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. In the above recitations, when a compound of Formula I contains a heterocyclic ring, all substituents are attached to this ring through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen.

Examples of the 5-, 6- or 7-membered carbocyclic ring of Formula I include

and

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

Preferred compounds of this 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

Q is selected from the group lH-pyrrolyl; furanyl; thienyl; lH-pyrazolyl; lH-imidazolyl; isoxazolyl; oxazolyl; isothiazolyl; thiazolyl; lH-lJJ-triazolyl; 2H-l,2,3-triazolyl; lH-lJ,4-triazolyl; 4H-l,2,4-triazolyl; 1,2,3-oxadiazolyl; 1,2,4-oxadiazolyl; 1,2,5-oxadiazolyl; 1,3,4-oxadiazolyl; 1,2,3-thiadiazolyl; 1,2,4-thiadiazolyl; 1,2,5-thiadiazolyl; 1,3,4-thiadiazolyl; lH-tetrazolyl;_ 2H-tetrazolyl; pyridinyl; pyridazinyl; pyrimidinyl; pyrazinyl; 1,3,5-triazinyl; 1,2,4-triazinyl; each heterocyclic group being optionally substituted by 1-3 groups selected from halogen, nitro, cyano, CJ-C₄ alkyl, C3-C7 cycloalkyl, C_]-C₄ haloalkyl, C3-C4 alkenyl, C3-C4 alkynyl, C_rC₄ alkoxy, C_rC₄ haloalkoxy, S(O)_nR⁴, SO₂NR⁵R⁶ or phenyl optionally substituted with C_J-C4 alkyl, C3-C₇ cycloalkyl, C₁-C₄ haloalkyl, halogen, cyano or nitro; and when Q is a 5- or 6-membered aromatic heterocyclic ring system containing a nitrogen, then Q can be bonded through any available carbon or nitrogen atom to the tetrazolinone ring by replacement of a hydrogen on said carbon or nitrogen atom; Preferred 2. Compounds of Preferred 1 wherein

R¹ is C Cg alkyl or C3-C7 cycloalkyl; and wherein the carbon-carbon double bond in the 5-, 6- or 7-membered carbocyclic ring is located as shown in Formula la below

O O (R²)y

1ST

\ /

N= N Rl

la

Preferred 3. Compounds of Preferred 2 wherein

Q is selected from the group IH-pyrrolyl; furanyl; thienyl; lH-pyrazolyl; isoxazolyl; oxazolyl; isothiazolyl; thiazolyl; pyridinyl; and pyrimidinyl; each heterocyclic group being optionally substituted by 1-3 groups selected from halogen, nitro, cyano, C1-C₄ alkyl, C3-C₇ cycloalkyl, C_rC₄ haloalkyl, C3-C4 alkenyl, C₃-C₄ alkynyl, C_rC₄ alkoxy, C_rC₄ haloalkoxy, S(O)_nR⁴, SO₂NR⁵R⁶ or phenyl optionally substituted with C1-C4 alkyl, C3-C7 cycloalkyl, Cj-C4 haloalkyl, halogen, cyano or nitro; and when Q is a 5- or 6-membered aromatic heterocyclic ring system containing a nitrogen, then Q can be bonded through any available carbon or nitrogen atom to the tetrazolinone ring by replacement of a hydrogen on said carbon or nitrogen atom;

Preferred 4. Compounds of Preferred 3 wherein

Q is isoxazole optionally substituted by 1-2 groups selected from halogen, nitro, cyano, C1-C4 alkyl, Cj-C₄ haloalkyl, C3-C4 alkenyl, C3-C4 alkynyl, C_rC₄ alkoxy, C_rC₄ haloalkoxy, S(O)_nR⁴, SO₂NR⁵R6 or phenyl optionally substituted with C1-C4 alkyl, CJ-C4 haloalkyl, halogen, cyano or nitro. Most preferred is the compound of Preferred 4 which is selected from the group consisting of

(a) N-(l-cyclohexen-l-yl)-4-(3,5-dimethyl-4-isoxazolyl)-4,5-dihydro-N-(l- methylethyl)-5-oxo- lH-tetrazole- 1 -carboxamide;

(b) N-(l-cyclohexen-l-yl)-4-(3,5-dimethyl-4-isoxazolyl)-4,5-dihydro-N-ethyl-5-oxo- lH-tetrazole- 1 -carboxamide;

(c) 4-(5-chloro- 1 ,3-dimethyl- lH-pyrazol-4-yl)-N- 1 -cyclohexen- 1 -yl-4,5-dihydro-N- ( 1 -methylethyl)-5-oxo- lH-tetrazole- 1 -carboxamide;

(d) N- 1 -cyclohexen- 1 -yl-N-ethyl-4,5-dihydro-5-oxo-4-( 1 ,3,5-trimethyl- lH-pyrazol- 4-yl)-lH-tetrazole-l-carboxamide;

(e) 4-(5-chloro- 1 -methyl- lH-pyrazol-4-yl)-N- 1 -cyclohexen- 1 -yl-4,5-dihydro-N-( 1 - methylethyl)-5-oxo-lH-tetrazole-l -carboxamide; and

(f) N-l -cyclohexen- l-yl-4-(3-ethyl-5-methyl-4-isoxazolyl)-4,5-dihydro-N-(l- methylethyl)-5-oxo- 1 H-tetrazole- 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 1-13. The definitions of Q, R^R⁶, n, x, and y in the compounds of Formulae 1-15 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 dioxane, 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 1

O 0 i i /' y - (R²)y acid acceptor

I X /_' \ e.g., DMAP

^■ , y

A NH + CA N x

\ /

N I.

Carbamyl chlorides of Formula 2 wherein a carbon-carbon double bond is present within the ring can be synthesized by methods known in the art (or slight modification of these methods); see, for example, Chupp, J.P. J. Het. Chem. (1971), 5, 557-563; Sakairi, N. et al. Tetrahedron Letters (1987), 28, 2871; Nogel, E. et al. Angew. Chem., I.E.E. (1979), 18, 962; Harris, H. C. J et al. Tetrahedron Letters (1995), 36, 4287; and Overman, L. Ace. Chem. Res. (1980), 73, 218-224.

Scheme 2 illustrates the method wherein a ketone of Formula 3 is reacted with an appropriate amine in the presence of a dehydrating agent and the resulting imine intermediate of Formula 4 is treated with phosgene in the presence of a base such as triethylamine to yield the carbamyl chloride of Formula 2a.

Scheme 2

O

Rl

O α- y

^*N

R1ΝH₂ phosgene

KOH or triethylamine molecular sieves

2a

Another synthetic method involves the selective reduction of a ketone of Formula 5 and conversion of the resulting alcohol under Mitsunobu conditions to the azide of Formula 6 (Scheme 3). Reduction to the amine of Formula 7 is followed by alkylation and treatment with phosgene in the presence of a base such as triethylamine to yield the carbamyl chloride of Formula 2b. Scheme 3

O

1. NaBH4, CeCl3

PPh3, NH₃

2. HN3, DEAD, PPh3 MeOH, pyridine

O

R¹

Cl N"

1. R'X, triethylamine

2. phosgene, triethylamine

7 2b

X is a leaving group such as halogen

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 8, optionally in the presence of a suitable base such as pyridine (Scheme 4). 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. Amines of Formula 8 wherein the endocyclic carbon-carbon double bond is adjacent to the amine substituent may exist as their imine tautomers; for example, see the compound of Formula 4. These enamine/imine tautomers are well-documented in the literature.

Scheme 4

O

1. phosgene, Et3N

NH

\ /

N=N

Scheme 5 illustrates a preferred method for preparing tetrazolinones of Formula 1 whereby an isocyanate of Formula 9 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 5

(CH₃)₃SiN3; then e.g., CH3OH Q— NCO »^► 1

9

Many isocyanates of Formula 9 are commercially available. Other isocyanates of Formula 9 can be prepared by treatment of corresponding amines of Formula 10 with phosgene or known phosgene equivalents (e.g., diphosgene or triphosgene) by methods generally known in the art (Scheme 6); 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 6

phosgene

Q— NH₂ — 10

Many amines of Formula 10 are commercially available. Alternatively, amines of Formula 10 can be prepared by reduction of the corresponding nitro compounds of Formula 11 (Scheme 7). 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- 10 Scheme 7

reduction

Q— NO2 10 11

Many nitro compounds of Formula 11 are commercially available or can be synthesized by methods well-established in the art.

Nitro compounds of Formula 11 wherein Q is a heterocyclic ring further substituted with a phenyl ring can be synthesized by known coupling methods reviewed in Kalinin, V. Synthesis (1992), pp 413-432.

Many isocyanates of Formula 9 can be also be prepared by Curtius rearrangement of appropriate acid chlorides of Formula 12 using methods generally known in the art (Scheme 8); see, for example, March, J. Advanced Organic Chemistry, 3rd edition; John Wiley & Sons, 1985; pp 984-985 and 380.

Scheme 8

o

Q— CC1 e.g., NaN3 12 (Curtius Rearrangement)

Acid chlorides of Formula 12 can be prepared by reacting an acid of Formula 13 with oxalyl chloride (or thionyl chloride) and optionally a catalytic amount of dimethylformamide (Scheme 9). 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 9

oxalyl chloride

Q — CO2H 12

(optionally a catalytic amount

13 of DMF)

Carboxylic acids of Formula 13 can be prepared as illustrated in Scheme 10, whereby an ester of Formula 14 is saponified (e.g., potassium hydroxide in methanol, then acidified - with an acid such as hydrochloric acid) or, alternatively, is acid hydrolyzed (e.g., 5 N HCI in acetic acid) by methods known in the art (or slight modification of these methods); see for 11 example, Ogliaruso, M. A. et al. Synthesis of Carboxylic Acids, Esters and Their Derivatives; John Wiley & Sons, 1991, pp 5-7.

Scheme 10

KOH in CH3OH, Q- C02R^{b then H+} ► ₁₃

14 wherein R^b is Cj-C₂ alkyl

Esters of Formula 14 wherein Q is a heterocyclic ring further substituted with a phenyl ring can be synthesized by known coupling methods reviewed in Kalinin, V. Synthesis (1992), pp 413-432.

Scheme 11 illustrates an alternative preparation of many carboxylic acids of Formula 13 whereby a bromide compound of Formula 15 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 slight 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, 113; Franke, C. et al. Angew. Chem. Int. Ed. (1969), 5, 68. Protecting and deprotecting functional groups not compatible with the reaction conditions may be necessary for compounds with such functional groups.

Scheme 11

1. n-BuLi (or Mg)

Q— Br ** 13

2. C0₂

15 3. H+

Many bromo compounds of Formula 15 are commercially available, while others can be prepared by bromination of their corresponding heteroaromatic precursors with bromine or other equivalent reagents in an inert solvent. This type of bromination is carried out by general methods known in the art; see for example, Campaigne, E. et al. J. Heterocyci. Chem. (1969), 6, 517; Gilman, H. J. Am. Chem. Soc. (1955), 77, 6059.

In general, nitro compounds of Formula 11, bromo compounds of Formula 15, and ester compounds of Formula 14 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. 12

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 12 illustrates another method for preparing tetrazolinones of Formula 1 whereby an isocyanate of Formula 9 is reacted with sodium azide and aluminum chloride in an inert solvent such as NN-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 12

AlC , DMF; then 9 + ΝaΝ3 - »» 1

H /H ^"

In addition, many tetrazolinones of Formula 1 can be prepared as illustrated in Scheme 13, whereby an appropriate acid chloride of Formula 12 is refiuxed 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. /. Chem. Soc. Perkin Trans. 1 (1992), 1101; Goto, T. et al. EP 695,748 and EP 692,482; Horwitz, J. et al. J. Am. Chem. Soc. (1959), 81, 3076.

Scheme 13

(CH₃)₃SiN₃

12 ^► 1 then 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 13

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. *H 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 N-( 1 -methylethyl)cyclohexanimine

To a dry flask under a nitrogen atmosphere was added 53 mL of cyclohexanone followed by 8J mL of isopropylamine. The reaction mixture was stirred at room temperature for 10 minutes followed by the addition of 3.1 g of powdered KOH. After stirring overnight at room temperature, 20 mL of anhydrous benzene was added and the reaction mixture was filtered through a thin pad of Celite® diatomaceous filter aid. The filter cake was washed with an additional 20 mL of benzene. The filtrate was concentrated under reduced pressure to give 6.5 g of the title compound of Step A as a liquid, which was used as a starting material in the next step without further purification. Step B: Preparation of 1 -cyclohexen- l-yl(l-methylethyl)carbamic chloride

To a dry flask under a nitrogen atmosphere was added 6.5 g of the title compound of Step A, followed by 8.3 mL of diisopropylethylamine and 45 mL of anhydrous benzene. The flask was cooled to 0 °C and to it was added 25.5 mL of a 20% solution of phosgene in toluene over a period of 10 minutes. After stirring at room temperature for 90 minutes, the reaction mixture was partitioned between benzene/ethyl acetate and water. The benzene/ethyl acetate layer was washed with 35 mL of water, dried over sodium sulfate and concentrated to 14 yield 7.5 g of the title compound of Step B as a liquid which was used as a starting material in Step D without further purification. ^lH NMR (CDC1₃): δ 1.2 (d, 6H), 1.5-2.37 (m, 8H), 4.38 (m, IH), 5.71 (br s, IH). Step C: Preparation of l,4-dihydro-l-[l-phenyl-5-(trifluoromethyl)-lH-pyrazol-4-yl]-

5H-tetrazol-5-one

30 mL of thionyl chloride was added to 6.5 g of l-phenyl-5-(trifluoromethyl)pyrazole- 4-carboxylate (Maybridge) while cooling to 0 °C. After the addition was complete the reaction mixture was refluxed for 18 hours, cooled to room temperature and the excess thionyl chloride was removed under reduced pressure. To this crude acid chloride was added 6J mL of trimethylsilyl azide and the reaction was refluxed for 18 hours. The reaction mixture was then concentrated under reduced pressure and 20 mL of methanol was added. The reaction mixture was stirred at room temperature for 30 minutes, concentrated under reduced pressure and crystallized from hexane to yield 5.2 g of the title compound of Step C as a solid melting at 137-140 °C.

Step D: Preparation of N-( 1 -cyclohexen- 1 -yl)-4,5-dihydro-N-( 1 -methylethyl)-5-oxo-4-

[ 1 -phenyl-5-(trifluoromethyl)- lH-pyrazol-4-yl]- lH-tetrazole- 1 -carboxamide

To 0.6 g of the title compound of Step C was added 15 mL of dioxane, 0J4 g of DMAP, 0.48 g of the title compound of Step B and the reaction was refluxed for 1 hour. The reaction mixture was cooled to room temperature, concentrated under reduced pressure and partitioned between 50 mL of ethyl acetate and 25 mL of saturated aqueous ammonium chloride. The ethyl acetate layer was dried over sodium sulfate, concentrated under reduced pressure and purified using silica gel column chromatography to yield 0.224 g of the title compound of Step D, a compound of this invention, as a solid melting at 105-107 °C.

^JΗ ΝMR (CDCI3): δ 7.94 (s, IH); 7.56-7.50 (m, 5H); 5.69 (m, IH); 4.36 (septet, IH); 2.20 (m, 2 H); 2.03 (m, 2H); 1.63 (m, 2H); 1.53 (m, 2 H); 1.37 (d, 6H).

EXAMPLE 2 Step A: Preparation of 3,5-dimethyl-4-nitroisoxazole

To sulfuric acid (32 mL) cooled to -10 °C in a round bottom flask equipped with an addition funnel and thermometer was added 3,5-dimethylisoxazole (15 g, from Aldrich Chemical Co.) dropwise, keeping the reaction temperature below 5 °C. This was followed by the dropwise addition of HΝO3 (16 mL) and then H₂SO4 (64 mL) at a controlled rate to keep the reaction temp below 5 °C. The reaction was then allowed to warm to room temperature. After 48 , the reaction mixture was poured onto ice and the precipitated solid was collected on a medium frit funnel. The isolated crude product (27 g of a white solid) was used in Step B without further purification.

*H NMR (CDCI3): δ 2.82 (s, 3H), 2.56 (s, 3H). 15

Step B: Preparation of 3,5-dimethyl-4-isoxazolamine

To a solution of 95 g of SnCl₂-2H₂O in 250 mL of HCI cooled to 0 °C was added 20 g of the title compound of Step A. The mixture was allowed to warm to room temperature. After 18 h, the reaction mixture was poured onto ice and quenched to basic pH with 50% aqueous NaOH. The aqueous layer was extracted with ethyl acetate several times, the combined organic layers were dried over MgSO , filtered and concentrated to afford 15J g of a light oil which was used in Step C without further purification.

^}H NMR (CDC1₃): δ 2.5 (br s, 2H), 2.28 (s, 3H), 2.20 (s, 3H). Step C: Preparation of 1 ,4-dihydro- 1 -(3,5-dimethyl-4-isoxazolyl)-5H-tetrazol-5-one

To a solution of 11.5 mL of diphosgene in 100 mL of ethyl acetate cooled to 0 °C was added 5.35 g of the title compound of Step B. The reaction was outfitted with a condenser and heated to reflux (about 80 °C) for 30 minutes. The reaction was then cooled to room temperature and concentrated. IR confirmed the presence of the isocyanate with a N=C=O stretch at 2278 cm^-1. To 6.6 g of this crude isocyanate cooled to 0 °C was added 12J mL of trimethylsilyl azide and the reaction was allowed to warm to room temperature. The reaction was fitted with a condenser and heated to reflux. After 18 h, the reaction was cooled to room temperature and concentrated. The reaction product was diluted with methanol and allowed to stir at room temp for 30 minutes and concentrated. The crude solid (4.9 g) was used in Step D without further purification.

!Η NMR ((CD₃)₂SO): δ 14.7 (br s, 1Η), 2.42 (s, 3Η), 2.20 (s, 3H). Step D: Preparation of N-( 1 -cyclohexen- 1 -yl)-4-(3,5-dimethyl-4-isoxazolyl)-4,5- dihydro-N-( 1 -methylethyl)- 1 H-tetrazole- 1 -carboxamide

To 0.75 g of the title compound of Step C in 40 mL of dioxane at room temperature was added 0.51 g of DMAP followed by the addition of 0.83 g of the title compound of Step B of Example 1. The reaction was heated to reflux for about 2 h and then cooled to room temperature and poured into ice water. The reaction mixture was then extracted with ethyl acetate several times and the combined organic layers were dried over MgSO4, filtered and concentrated. The crude product was purified by column chromatography to afford 0.85 g of the title compound of Step D, a compound of this invention, as an oil that solidified upon standing to a white solid melting at 68-70 °C.

*Η ΝMR (CDCI3): δ 5.69 (m, 1Η); 4.36 (septet, 1Η); 2.43 (s, 3Η); 226 (s, 3H); 2.20 (m, 2H); 2.04 (m, 2H); 1.63 (m, 2H); 1.54 (m, 2H); 1.37 (d, 6H).

EXAMPLE 3 Step A: Preparation of N-ethylcyclohexanimine

To a solution of 5.0 g of cyclohexanone in 10 mL of tetrahydrofuran was added 61.2 ~ mL of ethylamine. The resulting mixture was stirred at room temperature for 15 minutes followed by the addition of 12.2 g of powdered potassium hydroxide. The mixture was 16 stirred at room temperature for 48 h and then filtered over a pad of Celite^® diatomaceous filter aid. The filter cake was rinsed with 20 mL of tetrahydrofuran and 20 mL of benzene. The combined filtrate was dried over magnesium sulfate, filtered and concentrated under reduced pressure to give 9.1 g (72% yield) of the title compound of Step A. The crude material was used directly without further purification.

*H NMR (CDC1₃): δ 3.3 (m, 2H), 2.4-2.3 (m, 4H), 1.9-1.7 (m, 6H), 1.2-0.8 (m, 3H). Step B: Preparation of 1 -cyclohexen- 1 -yl-ethylcarbamic chloride

To a solution of 9J g of the title compound of Step A in 75 mL of benzene at 0 °C was added dropwise 14.0 mL of diisopropylamine. The mixture was stirred for 5 min and 42.3 mL of a 20% solution of phosgene in toluene was added slowly. The reaction mixture was allowed to stir while gradually warmed to RT and maintained for 2 h. It was poured into ice water saturated with ammonium chloride. The mixture was extracted with ethyl acetate (4 x 100 mL). The combined organic layers were dried over magnesium sulfate, filtered and concentrated under vacuum to afford the compound of Step B which was used directly in the next step. ^lH NMR (CDCI3): δ 5.7 (br s, IH), 3.4 (m, 2H), 4.2 (m, IH), 2.4-1 J ( , 8H), 1.2 (m, 3H).

Step C: Preparation of N-( 1 -cyclohexen- 1 -yl)-4-(3 ,5-dimethyl-4-isoxazolyl)-4,5- dihydro-N-ethyl- lH-tetrazole- 1 -carboxamide

To a solution of 7.03 g of the title compound of Step C of Example 2 in 50 mL of dioxane was added 4J4 g of DMAP followed by 7J g of the title compound of Step B. The resulting mixture was heated to reflux for 2 h and then cooled to room temperature and poured into ice water. The mixture was extracted with ethyl acetate (3 x 100 mL), and the combined organic layers were dried over magnesium sulfate, filtered, and concentrated under vacuum. The crude product was purified by flash column chromatography (10:90 ethyl acetate-hexanes) to afford a pale yellow solid which was further purified by recrystallization from hot isopropanol to afford 3.75 g (29% yield) of the title compound of Step C, a compound of this invention, as a white solid melting at 75-77 °C. ^lΗ ΝMR (CDCI3): δ 5.54 (m, 1Η); 3.64 (q, 2Η); 2.43 (s, 3H); 2.26 (s, 3H); 2.24 (m, 2H); 2.01 (m, 2H); 1.71 (m, 2H); 1.55 (m, 2H); 1.27 (t, 3 H).

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 notations have been used in Tables 1-3: 17

Q-l Q-2 CH₃

/A

H3C

Q-3 Q-4 CH3

/A

N-

H₃C

Q-5 CH₃ Q-6

H3C H3C

Q-l Q-8

Q-9 Q-10

H3C—

Cl

Q-ll Q-12 N_^ y\

<

Q-13 Q-14 N^ _/CH₃ 18

Q-15 Q-16

Q-17 OCH3 Q-l 8

Q-19

TABLE 1

R¹ is CH₃ s Q Q 0. Q Q Q

Q-l Q-2 Q-3 Q-4 Q-5 Q-6 Q-7

Q-8 Q-9 Q-10 Q-l l Q-12 Q-13 Q-14

Q-15 Q-16 Q-17 Q-18 Q-19

Rl is CH^CH

Q Q Q. Q Q Q Q

Q-i Q-2 Q-3 Q-4 Q-5 Q-6 Q-7

Q-8 Q-9 Q-10 Q-l l Q-12 Q-13 Q-14

Q-15 Q-16 Q-17 Q-18 Q-19

R¹ is CH(CH

Q Q Q Q 2 Q Q 19

Q-l Q-2 Q-3 Q-4 Q-5 Q-6 Q-7

Q-8 Q-9 Q-10 Q-l l Q-12 Q-13 Q-14

Q-15 Q-16 Q-17 Q-18 Q-19

Rl is cyclopropyl

2 2 2 Q 2 2 Q

Q-l Q-2 Q-3 Q-4 Q-5 Q-6 Q-7

Q-8 Q-9 Q-10 Q-l l Q-12 Q-13 Q-14

Q-15

Q-16 Q-17 Q-18 Q-19

TABLE 2

O o

N N N

\ N= N R I l

Rl is CH₃

2 2 2 2 2 2 Q

Q-i Q-2 Q-3 Q-4 Q-5 Q-6 Q-7

Q-8 Q-9 Q-10 Q-l l Q-12 Q-13 Q-14

Q-15 Q-16 Q-17 Q-18 Q-19

Rl is CH₇CH 3

2 2 2 2 2 2 2

Q-l Q-2 Q-3 Q-4 Q-5 Q-6 Q-7

Q-8 Q-9 Q-10 Q-l l Q-12 Q-13 Q-14

Q-15 Q-16 Q-17 Q-18 Q-19

Rl is CH(CH )₂

2 2 2 2 2 2 Q

Q-l Q-2 Q-3 Q-4 Q-5 Q-6 Q-7

Q-8 Q-9 Q-10 Q-l l Q-12 Q-13 Q-14

Q-15 Q-16 Q-17 Q-18 Q-19

Rl is cyclopropyl

2 Q 2 2 2 2 Q 20

Q-l Q-2 Q-3 Q-4 Q-5 Q-6 Q-7

Q-8 Q-9 Q-10 Q-l l Q-12 Q-13 Q-14

Q-15

Q-16 Q-17 Q-18 Q-19

TABLE 3

R¹ is CH3

Q 2 Q Q Q 2 Q

Q-l Q-2 Q-3 Q-4 Q-5 Q-6 Q-7

Q-8 Q-9 Q-10 Q-l l Q-12 Q-13 Q-14

Q-15 Q-16 Q-17 Q-18 Q-19

Rl is CH2CH3

2 2 2 2 2 2 2

Q-l Q-2 Q-3 Q-4 Q-5 Q-6 Q-7

Q-8 Q-9 Q-10 Q-l l Q-12 Q-13 Q-14

Q-15 Q-16 Q-17 Q-18 Q-19

R^l is CH(CH₃)₂

2 2 2 2 2 Q Q

Q-l Q-2 Q-3 Q-4 Q-5 Q-6 Q-7

Q-8 Q-9 Q-10 Q-l l Q-12 Q-13 Q-14

Q-15 Q-16 Q-17 Q-18 Q-19

Rl is cyclopropyl

2 2 2 2 2 Q 2

Q-l Q-2 Q-3 Q-4 Q-5 Q-6 Q-7

Q-8 Q-9 Q-10 Q-l l Q-12 Q-13 Q-14

Q-15 Q-16 Q-17 Q-18 Q-19

21

TABLE 4

R^{a '} ii if

Y ib N=N Rl

R Rb ^Ri A

CH₂CH₃ CH₃ CH₃ 1 -cyclohexen- 1-yl

CH₃ CH₂CH₃ CH₃ 1 -cyclohexen- 1-yl

CH₂CH₃ CH(CH₃)₂ CH₃ I -cyclohexen- 1-yl

CH₃ cyclopropyl CH₃ I -cyclohexen- 1-yl

CH₂CH₃ CH₂CH₃ CH₃ I -cyclohexen- 1-yl

CH₂CH₃ CH₃ CH₃ 1 -cyclopenten-1-yl

CH₃ CH₂CH₃ CH₃ 1 -cyclopenten-1-yl

CH₂CH₃ CH(CH₃)₂ CH₃ 1 -cyclopenten-1-yl

CH₃ cyclopropyl CH₃ 1 -cyclopenten-1-yl

CH₂CH₃ CH₂CH₃ CH₃ 1 -cyclopenten-1-yl

CH₂CH₃ CH₃ CH₂CH₃ I -cyclohexen- 1-yl

CH₃ CH₂CH₃ CH₂CH₃ I -cyclohexen- 1-yl

CH₂CH₃ CH(CH₃)₂ CH₂CH₃ i -cyclohexen- 1-yl

CH₃ cyclopropyl CH₂CH₃ [-cyclohexen- 1-yl

CH₂CH₃ CH₂CH₃ CH₂CH₃ ; -cyclohexen- 1-yl

CH₂CH₃ CH₃ CH₂CH₃ 1 -cyclopenten-1-yl

CH₃ CH₂CH₃ CH₂CH₃ 1 -cyclopenten-1-yl

CH₂CH₃ CH(CH₃)₂ CH₂CH₃ 1 -cyclopenten-1-yl

CH₃ cyclopropyl CH₂CH₃ 1 -cyclopenten-1-yl

CH₂CH₃ CH₂CH₃ CH₂CH₃ 1 -cyclopenten-1-yl

CH₂CH₃ CH₃ CH(CH₃)₂ -cyclohexen- 1-yl

CH₃ CH₂CH₃ CH(CH₃)₂ -cyclohexen- 1-yl

CH₂CH₃ CH(CH₃)₂ CH(CH₃)₂ -cyclohexen- 1-yl

CH₃ cyclopropyl CH(CH₃)₂ -cyclohexen- 1-yl

CH₂CH₃ CH₂CH₃ CH(CH₃)₂ -cyclohexen- 1-yl

CH₂CH₃ CH₃ CH(CH₃)₂ 1 -cyclopenten-1-yl

CH₃ CH₂CH₃ CH(CH₃)₂ 1 -cyclopenten-1-yl

CH₂CH₃ CH(CH₃)₂ CH(CH₃)₂ 1 -cyclopenten-1-yl 22

CH₃ cyclopropyl CH(CH₃)₂ 1-cyclopenten-l-yl

CH₂CH₃ CH₂CH₃ CH(CH₃)₂ 1-cyclopenten-l-yl

CH₂CH₃ CH₃ cyclopropyl 1 -cyclohexen- 1-yl

CH₃ CH₂CH₃ cyclopropyl 1 -cyclohexen- 1-yl

CH₂CH₃ CH(CH₃)₂ cyclopropyl 1 -cyclohexen- 1-yl

CH₃ cyclopropyl cyclopropyl 1 -cyclohexen- 1-yl

CH₂CH₃ CH₂CH₃ cyclopropyl 1 -cyclohexen- 1-yl

CH₂CH₃ CH₃ cyclopropyl 1-cyclopenten-l-yl

CH₃ CH₂CH₃ cyclopropyl 1-cyclopenten-l-yl

CH₂CH₃ CH(CH₃)₂ cyclopropyl 1-cyclopenten-l-yl

CH₃ cyclopropyl cyclopropyl 1-cyclopenten-l-yl

CH₂CH₃ CH₂CH₃ cyclopropyl 1-cyclopenten-l-yl

CH₂CH₃ CH₃ CH₂CH₂C1 1 -cyclohexen- 1-yl

CH₃ CH₂CH₃ CH₂CH₂C1 1 -cyclohexen- 1-yl

CH₂CH₃ CH(CH₃)₂ CH₂CH₂C1 1 -cyclohexen- 1-yl

CH₃ cyclopropyl CH₂CH₂C1 1 -cyclohexen- 1-yl

CH₂CH₃ CH₂CH₃ CH₂CH₂C1 1 -cyclohexen- 1-yl

CH₂CH₃ CH₃ CH₂CH₂C1 1-cyclopenten-l-yl

CH₃ CH₂CH₃ CH₂CH₂C1 1-cyclopenten-l-yl

CH₂CH₃ CH(CH₃)₂ CH₂CH₂C1 1-cyclopenten-l-yl

CH₃ cyclopropyl CH₂CH₂C1 1-cycloρenten-l-yl

CH₂CH₃ CH₂CH₃ CH₂CH₂C1 1-cyclopenten-l-yl

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 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 23 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, NN-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, NN-dimethylformamide, dimethyl sulfoxide, N-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. 24

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 Table A.

Example A High Strength Concentrate

Compound 1 98.5% silica aerogel 0.5% synthetic amorphous fine silica 1.0%.

Example B Wettable Powder

Compound 2 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 2 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 or equally tolerant to the above crops. 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 26 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-nitrophenyl]-2- methoxyethylidene]amino]oxy]acetate (AKΗ-7088), methyl 5-[[[[(4,6-dimethyl-2- pyrimidinyl)amino]carbonyl]amino]sulfonyl]- 1 -(2-pyridinyl)- lH-pyrazole-4-carboxylate - (NC-330), metobenzuron, metolachlor, metosulam, metoxuron, metribuzin, metsulfuron-methyl, molinate, monolinuron, napropamide, naptalam, neburon, nicosulfuron, 27 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.

In certain instances, combinations with other herbicides having a similar spectrum of control but a different mode of action will be particularly advantageous for preventing the development of resistant weeds.

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

INDEX TABLE A

O

O

N-

\ /

N= N A-

Cmpd No. Rl MP (°C)

1 (Ex. 1) j^'-propyl 105-107

CH3

2 (Ex. 2) ° opyl 68-70

Hc3Cx j^'-pr 28

n-propyl oil*

cyclopropyl oil*

O

H3C

(Ex. 3) ethyl 75-77

O

H3C

/-butyl oil*

O

H3C

methyl oil"

O

H3C

/-propyl oil*

1-C3H7

CH3

-propyl 92-94

N

CH3 29

10 /-propyl 115-117

^

N' CH3

IV /-propyl oil*

C₂H₅

12 /-propyl 86-88

Cl N

N

13 \ A /-propyl oil*

CH3

H3C

Cl

14 /-propyl 111-113

H3C-N

.CH3

N-

15 H3C-N /-propyl 109-110

Cl

N. .CH3

16 H3C— N ethyl 73-78

H3C

,CH₃

N-

17 H3C— N ethyl 98-101

Cl 30

H₃C

/-propyl oil*

N ',/ \\

\ .

19 N

/-propyl 78-80

20 t-C4H9-

/-propyl 72-82

.

N- \

CH₃

N-

21 H₃C— N /-propyl 46-51

Cl

H₃C-

22

ethyl 74-78

N-

H₃C

N

23 I I /-propyl oil*

C₂H₅

.0

24 ^H≠ -

/-propyl oil*

C₂H₅

N-

25 /-propyl oil*

26 /-propyl 73-74

N-

C H₅ 31

H₃C- ^•

27 /-propyl 52-54

N

H3C- _N'

28 /-propyl oil*

H₃C

,CH₃

N-

29 H3C // ethyl 83-85

30

=λ /-propyl oil*

H3CO- CH3

N

^ O

31 /-propyl oil*

C2H5

32 /-propyl 82-85

CH3

H₃C ^3

33 ethyl 118-120

Cl

34 ethyl 101-103

^ ^{^ C1}

CH3 32

Cl

35 7 /-propyl 102-105

N

Cl

CH₃

H₃C CF₃

36 /-propyl 121-127

iJc

37 .. ethyl oil*

N I CH₃

Cl

38 ethyl 90-95

N.

H₃C- y

N

39 ethyl 125-132

N— CH₃

t-G Hα

40 ethyl oil*

• N.

H₃C

N CF₃

H₃C^/°x N

41 \\ // 2-chloroethyl oil*

CH₃

*See Index Table B for lH NMR data.

**1:1 mixture with the 3-ethyl-5-methyloxazole isomer. 33

INDEX TABLE B Cmpd No. H NMR Data (CDCI3 solution unless indicated otherwise)^a

3 δ 5.55 (br s, IH), 3.55 (t, 2H), 2.43 (s, 3H), 2.26 (s, 3H), 2.23 (m, 2H), 2.01 (m, 2H), 1.70 (m, 4H), 1.55 (m, 2H), 0.99 (t, 3H).

4 d 5.50 (br s, IH), 3.01 (m, IH), 2.43 (s, 3H), 2.31 (m, 2H), 2.26 (s, 3H), 2.43 (s, 3H), 2.31 (m, 2H), 2.26 (s, 3H), 2.03 (m, 2H), 1.70 (m, 2H), 1.56 (m, 2H), 0.94 (m, 2H), 0.78 (m, 2H).

6 δ 5.57 (br s, IH), 3.45 (d, IH), 2.43 (s, 3H), 2.26 (s, 3H), 2.22 (m, 2H), 2.01 (m, 3H), 1.70 (m, 2H), 1.55 (m, 2H), 1.00 (d, 6H).

7 δ 5.59 (br s, IH), 3.22 (s, 3H), 2.43 (s, 3H), 2.26 (s, 3H), 2.00 (m, 2H), 1.72 (m, 2H), 1.55 (m, 2H).

8 δ 5.67 (br s, IH), 4.34 (septet, IH), 3.03 (septet, IH), 2.91 (septet, IH), 2.21 (m, 2H), 2.04 (m, 2H), 1.64 (m, 2H), 1.54 ( , 2H), 1.38 (d, 6H), 1.30 (d, 6H), 1.26 (d, 6H).

11 δ 5.68 (br s, IH), 4.35 (septet, IH), 2.64 (q, 2H), 2.42 (s, 3H), 2.20 (m, 2H), 2.04 (m, 2H),

1.63 (m, 2H), 1.54 (m, 2H), 1.37 (d, 6H), 1.22 (t, 3H). 13 δ 1.25 (s, IH), 1.37 (d, 6H), 1.53 (br s, 3H), 1.65 (br s, 2H), 2.05 (br s, 2H), 2.20 (br s, 2H),

2.40 (s, 3H). 4.35 (m, IH), 5.70 (s, IH). 18 δ 1.38 (d, 6H), 1.50 (m, 2H), 1.63 (m, 2H), 2.01 (br s, 2H), 2.20 (br s, 2H), 2.52 (s, 3H),

4.32 ( , IH), 5.62 (br s, IH), 7.40 (s, IH).

23 δ 5.68 (br s, IH), 4.35 (m, IH), 2.75 (q, 2H), 2.63 (q, 2H), 2.21 (m, 2H), 2.04 (m, 2H), 1.64 ( , 2H), 1.54 (m, 2H), 1.37 (d, 6H), 1.29 (t, 3H), 1.23 (t, 3H).

24 δ 5.68 (br s, IH), 4.35 (septet, IH), 2.64 (q, 2H), 2.42 (s, 3H), 2.20 (m, 2H), 2.04 (m, 2H), 1.63 (m, 2H), 1.54 (m, 2H), 1.37 (d, 6H), 1.22 (t, 3H).

25 δ 1.35 (d, 6H), 1.5 (m, 2H), 1.65 (m, 2H), 2.05 (m, 2H), 2.2 (m, 2H), 2.50 (s, 3H), 4.35 (septet, IH), 5.65 (m, IH), 8.93 (s, IH).

28 δ 1.35 (d, 6H), 1.50 (m, 2H), 1.60 (m, 2H), 2.02 (m, 2H), 2.20 (m, 2H), 2.32 (s, 3H), 3.83

(s, 3H), 4.18 (m, IH), 5.63 (m, IH), 6.40 (s, IH).

30 δ 1.34 (d, 6H), 1.52 (m, 2H), 1.63 (m, 2H), 2.05 (m, 2H), 2.18 (m, 2H), 3.79 (s, 3H), 3.93 (s, 3H), 4.38 (m, IH), 5.62 (m, IH), 7.52 (s, IH).

31 δ 5.68 (br s, IH), 4.35 (septet, IH), 2.76 (q, 2H), 2.25 (s, 3H), 2.20 (m, 2H), 2.04 (m, 2H), 1.63 (m, 2H), 1.54 (m, 2H), 1.37 (d, 6H), 1.29 (t, 3H).

37 δ 1.23 (t, 3H), 1.29 (m, 2H), 1.56 (m, 2H), 2.05 (m, 2H), 2.22 (m, 2H), 3.63 (q, 2H), 3.98 (s,

3H), 5.53 (m, IH).

40 δ 1.26 (t, 3H), 1.53 (m, 2H), 1.70 (m, 2H), 2.02 (m, 2H), 2.23 (m, 2H), 3.60 (q, 2H), 4.03 (s, 3H), 5.52 (m, IH), 7.83 (s, IH).

41 δ 5.65 (br s. IH), 3.91 (t, 2H), 3.75 (t, 2H), 2.44 (s, 3H), 2.31 (m, 2H), 2.26 (s, 3H), 2.07- 1.82 (m, 2H), 1.72 (m, 2H), 1.57 (m, 2H). 34

^a iH NMR data are in ppm downfield from tetramethylsilane. Couplings are designated by (s)-singlet, (d)-doublet, (t)-triplet, (q)-quartet, (m)-multiplet, (dd)-doublet of doublets, (dt)-doublet of triplets, (br s)-broad singlet.

TESTA

Seeds of bedstraw (Galium aparine), blackgrass (Alopecurus myosuroides), broadleaf signalgrass (Brachiaria decumbens), cocklebur (Xanthium strumarium), corn (Zea mays), crabgrass (Digitaria sanguinalis), giant foxtail (Setaria faberii), morningglory (Ipomoea hederacea), pigweed (Amaranthus retroβexus), rape (Brassica napus), soybean (Glycine max), sugar beet (Beta vulgaris), velvetleaf (Abutilon theophrastϊ), wheat (Triticum aestivum), wild oat (Avena fatua) 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. A flood test was also conducted with plant species consisting of rice (Oryza sativa), smallflower flatsedge (Cyperus difformis), duck salad (Heteranthera limosa) and barnyardgrass (Echinochloa crus-gallϊ) 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

Rate 500 g/ha 1 2 3 4 5 6 7 8 9 10 11 12 13 19 23 24 41 Postemergence

B. signalgrass 2 9 8 7 8 4 8 0 4 8 0 7 0 8 6 6 4

Barnyardgrass 5 9 9 9 9 9 9 9 7 8 9 9 9 9 9 9 9

Bedstraw 7 8 - 0 8 4 4 2 - - 0 4 4 - 8 0 6

Blackgrass 4 9 8 7 8 7 7 3 9 8 9 7 0 6 8 9 5

Cocklebur 0 5 2 3 3 0 1 2 0 0 0 4 0 5 2 2 4

Corn 0 8 5 6 8 0 7 0 3 7 2 0 2 7 3 2 0

Crabgrass 7 9 9 9 9 9 9 2 8 9 9 6 4 9 6 9 9

Ducksalad 8 9 9 9 8 8 9 4 9 9 9 9 9 9 9 9 9

Giant foxtail 0 8 9 9 9 8 8 2 7 8 7 8 1 9 6 9 9

Morningglory 0 8 9 8 4 3 2 2 4 3 6 1 3 6 10 10 4

Nutsedge 0 - 4 - - - - 0 0 0 - 0 0 2 0 0 0

Rape 3 9 4 3 9 4 6 4 4 8 2 3 0 4 7 2 4

Redroot pigweed 7 8 6 8 8 4 6 0 0 2 3 2 4 7 8 4 5

Rice 0 7 5 7 8 3 5 5 7 7 7 5 0 7 9 9 7

S. Flatsedge 8 9 9 9 9 9 8 8 9 9 9 9 9 9 9 9 9

Soybean 1 8 4 6 6 7 8 3 6 5 7 7 4 8 8 8 4 35

Sugarbeets 4 7 4 0 2 2 1 0 1 0 0 0 0 6 7 2 4

Velvetleaf 0 6 2 0 5 2 5 0 0 2 0 0 0 7 4 3 4

Wheat 0 8 4 6 7 0 5 0 3 6 2 0 0 5 1 0 1

Wild oats 0 8 4 4 7 4 7 0 1 2 0 0 0 5 2 0 2

Table A COMPOUND

Rate 500 g/ha 1 2 3 4 5 6 7 8 9 10 11 12 13 19 23 24 41

Preemergence

B. signalgrass 4 10 8 9 10 8 10 7 7 9 9 10 4 9 9 10 10

Bedstraw 0 5 1 - 9 0 7 0 0 0 3 8 0 4 4 2 2

Blackgrass 1 10 9 9 10 4 5 5 8 9 8 9 6 10 10 10 6

Cocklebur - 6 0 2 1 0 0 - 0 0 0 1 1 - 4 - 0

Corn 0 9 9 7 10 4 9 4 4 9 5 9 3 8 7 7 0

Crabgrass 7 10 10 10 10 10 10 10 10 10 10 10 7 10 10 10 10

Giant foxtail 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10

Morningglory 0 8 0 5 8 0 4 0 0 3 6 2 2 0 6 5 9

Nutsedge 0 8 0 - 3 0 2 0 0 0 0 0

Rape 3 10 8 9 10 0 9 0 7 7 6 8 2 7 8 5 10

Redroot pigweed 7 9 8 8 10 2 8 0 3 5 6 7 3 8 10 6 8

Soybean 0 9 0 7 8 0 7 0 1 0 5 2 2 0 6 8 0

Sugarbeets 6 7 8 9 9 5 5 0 1 7 6 7 2 6 9 7 8

Velvetleaf 0 7 7 5 5 0 7 0 3 3 6 4 0 0 4 6 5

Wheat 0 5 6 6 9 4 8 3 5 3 0 3 0 5 6 6 0

Wild oats 0 9 9 8 10 7 8 4 7 7 7 7 5 8 10 9 8

Table A COMPOUND

Rate 250 g/ha 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 41

Postemergence o

B. signalgrass 0 3 1 1 8 2 5 0 3 8 0 7 0 0 - 6 5 - 6 0 3 2 3 2 2 00

Barnyardgrass 3 9 8 9 8 3 8 5 6 6 9 9 9 4 9 9 9 8 9 5 9 7 9 9 9 00

4 3 7 0 - 2 2 1 - 0 0 4 3 - - - - - 6 - - 6 6 0 5 o

Bedstraw

Blackgrass 0 9 7 4 8 4 5 0 8 8 8 7 0 8 - 9 9 - 6 0 8 7 7 9 4

Cocklebur 0 4 0 3 3 0 0 0 0 0 0 3 0 7 - 0 3 - 4 0 4 0 0 0 4

Corn 0 8 0 1 8 0 5 0 0 6 2 0 0 0 - 7 3 - 4 0 2 5 0 0 0

Crabgrass 6 9 9 9 9 8 9 2 3 4 2 2 2 3 - 9 8 - 8 6 8 6 4 5 5

Ducksalad 8 9 9 9 8 7 8 3 8 9 9 9 8 9 9 10 9 10 9 9 9 9 8 8 9

Giant foxtail 0 8 8 8 9 7 8 0 4 8 4 2 1 8 - 9 8 - - 5 8 3 6 3 8

Morningglory 0 8 2 3 3 2 1 0 2 2 5 1 2 7 - 2 9 - 1 3 6 0 3 10 3

Nutsedge 0 3 0 0 0 - 0 0 0 - 6 3 - 0 0 0 0 0 0 0

Rape 2 5 2 0 7 0 2 1 3 5 2 2 0 5 - 0 7 - 2 6 3 4 6 1 -

Redroot pigweed 7 6 4 5 8 3 3 0 0 1 3 2 4 7 - 0 0 - 7 3 7 3 8 2 2

Rice 0 7 5 6 8 2 5 2 2 6 7 5 0 7 6 7 6 0 7 2 5 3 9 8 5

S . Flatsedge 7 9 9 9 8 8 8 6 9 9 9 9 9 9 9 10 9 10 9 9 9 9 9 9 9 O

Soybean 1 8 4 3 5 6 5 3 3 5 3 3 2 3 - 7 7 - 7 4 5 5 8 8 4

Sugarbeets 3 3 1 0 0 0 0 0 0 0 0 0 0 5 - 0 0 - 3 2 2 0 7 0 3

Velvetleaf 0 4 0 0 4 0 4 0 0 0 0 0 0 0 - 6 7 - 5 0 3 0 4 0 0

Wheat 0 3 0 2 7 0 0 0 2 5 0 0 0 0 - 6 0 - 0 0 2 4 0 0 0

Wild oats 0 1 1 3 7 2 4 0 0 2 0 0 0 0 - 3 0 - 0 2 2 0 1 0 0

Table A COMPOUND

Rate 250 g/ha 1 2 3 4 5 6 7 8 9 10 11 12 13 14 16 17 19 20 21 22 23 24 41

Preemergence

B. signalgrass 0 10 8 9 10 2 10 1 3 9 5 8 4 9 10 6 9 7 10 7 9 8 7

Bedstraw 0 4 0 - - 0 3 0 0 0 - 6 0 0 3 1 2 2 1 4 2 0 2

Blackgrass 0 10 9 8 10 1 5 1 7 9 2 9 4 7 8 6 9 8 9 9 9 8 6

Cocklebur - 4 0 0 0 0 0 0 0 0 0 0 0 0 0 0 - 0 0 0 1 0 0 "0 o

Corn 0 4 5 6 9 3 8 0 4 3 4 8 0 0 6 7 8 4 8 2 3 3 0

Crabgrass 7 10 9 9 10 9 10 9 10 10 10 10 7 9 10 10 10 10 10 10 10 10 7

Giant foxtail 9 10 10 10 10 10 10 10 9 10 10 10 9 10 10 10 10 10 10 10 10 10 10

Morningglory 0 7 0 4 7 0 0 0 0 0 0 0 1 - 6 0 0 0 0 1 3 - 6 δ vO

Nutsedge - 5 0 - - - - 0 0 - 0 0 0 0 0 0 0 0 0 0 0 0 0 00

Rape 0 10 8 7 9 0 8 0 4 7 6 7 0 0 8 7 6 2 7 3 7 2 6

Redroot pigweed 7 9 4 7 9 2 7 0 0 5 3 7 0 4 7 3 7 6 7 8 9 6 7

Soybean 0 9 0 5 8 0 3 0 0 0 2 0 0 0 0 0 0 0 0 3 0 1 0

2 7 6 6 2 8 5 8 6 4 o

Sugarbeets 2 7 7 5 8 5 0 0 7 4 7 0 4

Velvetleaf 0 7 4 0 5 0 6 0 0 1 2 2 0 0 3 0 0 0 0 0 3 5 2 Ϊ--

00 00

Wheat 0 4 3 2 8 0 6 0 1 3 0 0 0 0 2 0 5 0 0 0 4 0 0 o

Wild oats 0 9 8 7 10 3 6 0 4 7 4 3 3 2 8 8 9 3 7 4 8 9 5

Table A COMPOUND

Rate 125 g/ha 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 41

Postemergence

B. signalgrass 0 2 0 0 8 1 4 0 0 2 0 1 0 0 - 6 3 - 4 0 0 1 3 0 1

Barnyardgrass 0 - 7 8 7 3 8 2 0 4 9 9 8 3 9 9 9 5 5 4 9 2 9 9 9

Bedstraw 3 1 7 0 4 0 0 0 0 0 0 2 0 9 - 0 0 - 3 2 3 5 6 0 5

Blackgrass 0 8 6 3 7 3 3 0 5 8 6 4 0 6 - 9 6 - 6 0 8 4 5 5 2

Cocklebur 0 3 0 2 0 0 0 0 0 0 0 3 0 6 - 0 2 - 4 0 4 0 0 0 4

Corn 0 5 0 0 7 0 3 0 0 0 0 0 0 0 - 6 2 - 3 0 0 3 0 0 0 >

Crabgrass 3 9 7 9 9 1 9 1 0 3 1 0 2 2 - 9 6 - 8 2 6 4 4 - 3

Ducksalad 3 9 8 9 8 5 7 2 7 9 8 9 8 8 9 9 9 9 9 9 9 9 3 4 9

Giant foxtail 0 8 6 8 9 2 7 0 0 7 3 0 0 3 - 7 6 - 9 2 8 1 5 3 6

Morningglory 0 8 2 3 3 1 0 0 0 2 1 1 2 6 - 2 8 - 1 2 6 0 2 0 3

Nutsedge 0 1 0 0 0 - 0 0 0 - 2 0 - 0 0 0 0 0 0 0

Rape 2 3 2 0 2 0 2 0 3 3 1 2 0 2 - 0 2 - 2 2 1 3 6 1 2

Redroot pigweed 6 3 0 2 2 1 1 0 0 0 0 2 3 6 - 0 0 - 6 0 6 2 6 2 2

Rice 0 4 2 5 7 0 5 0 0 5 7 2 0 0 2 7 3 0 6 0 4 0 7 4 4

S . Flatsedge 4 9 9 9 8 7 8 2 9 9 8 9 9 9 9 9 9 9 9 9 9 9 4 9 9

Soybean 1 4 4 3 4 5 5 2 3 5 2 3 2 2 - 6 4 - 4 4 4 4 8 8 2

Sugarbeets 0 3 1 0 0 0 0 0 0 0 0 0 0 1 - 0 0 - 3 0 2 0 6 0 2

Velvetleaf 0 1 0 0 4 0 0 0 0 0 0 0 0 0 - 6 5 - 5 0 0 0 0 0 0

Wheat 0 0 0 0 6 0 0 0 0 1 0 0 0 0 - 3 0 - 0 0 2 2 0 0 0

Wild oats 0 0 1 0 5 2 3 0 0 1 0 0 0 0 - 2 0 - 0 0 0 0 1 0 0 π

Table A COMPOUND Rate 125 g/ha 1 2 3 4 5 6 7 8 9 10 11 12 13 14 16 17 19 20 21 22 23 24 41 05 vo Preemergence >o δ B. signalgrass 0 9 6 8 10 2 9 0 3 7 3 6 4 8 8 3 9 4 8 7 8 2 2 <Λ Bedstraw . 00 0 3 0 - 8 0 0 0 0 0 0 2 0 0 0 0 2 0 0 2 2 0 2

38

O C^ CN o σi CN CN O o ro cn O O

O CO o < o O CN CN ro o o rH O O vo r» O O O

CN ro O o σi vo t o >* o o ro ro o >* ro in o o H ro H CN O vo in o ro H O O O

00 o o o σ. o o o VO o vo ro CN o in ro o O CN 00 H O O r CN o cn O O

H CN r^» o σi σ> ro O VO CO o r- ro O vo O CN H m ro o ro n ^■φ H O o in σi ro CN O O co o o m o\ o o O CO o o o O O O O O CN o o O O CO O O O CN O O oo ro O O O CN σi o CN O O o o < t O oo o O o σ> ro i ro VO CN CN 00 I σ\ o o O CN I I > ro m o

H H H o o o σ> o o o in o o o O O CO i o i i i i p σϊ I I I i i o cn i I I I

H H co o ro o o o o ro r- o vo o H t- o r- o CN O o σi ro o H O O σi O o o

H H o o o o o o ro o o ro o O "φ vo n o vo o O VO Λ C~ CN O O O r^» σ> ^ o ro o

H H H co o ^⁾ o O o o vo in o VO CN o ro in i in i I I i i σ> I I I i i o σi i I I I H rH H t- o o σ> o o o o o o o o o o o o co ro CN O H 00 o o o CN CN O cn o o o

H

CN O O VO 00 o o o o o o o o o ro o o o o o O H ro O CN O o ro o σi o o o o

H

00 o r~ o o o o in ro o <tf- o O ro o in <# CN O O CO o o o o o o co ro o o o

H H o o M O O o o CN O O o o O Εf o vo o ro o O O vo H O I H O CN C- CN o o o H H O H ft

CO I ro o o o o CN H O CN O o ro o o o o o O O 00 H O O O O CN r~ o o o

H H § O ° H U r- o o oo σi o o O O O o o o o cn o o o r-t O O o vo o o o O o o ^■φ ro o o o o o o σi oo o O O O o o o o co o o o o o O O o o o i o o o O H o o o i o vo σ\ o o in ^J* ro ro in ro m l ro O o CN O vo r- ro o i CN O O 00 o o o

H o o o σ> o 0 o o o o o o vo o ro o O O o o o H H I O H O O > o o o σi o co o o r~ σ> i in O H _ σ> in 00 VO H ι o in σi r- σ. o i O o o CO ^< o o in

H H

•tf o «»• σi o o vo o ^i O o m O CN O O CN r- o o o o in ro o o o

H CO I o m m o * n o in CN ro o •* vo in o o ro P> CN CN O M O O (Λ H H O O σi ro «tf 01 O ro 01 CO r- r- •* co H 00 O ^■* CN in cn oo P^» O O CN CN CN cn ro CN H O

H o I o r*ι o O ro O o o o o O O H o o o H ro o o o CN VO O " H O O O

T3

OJ Λ CQ OJ 01 A Cl) 00 10 OJ

•H tj m m . 0)

(0 01 β rt <ύ

<n -u o -rl CO -J <u oi u CQ 4-1 0 •H - ^•^0 CQ m

CO in CQ X ft 4J CC CO CN 01 rH 01 CO S-l O T3 X r ft OJ 4J tt

(d 3 CO 0 01 Φ TV OJ 4-> VO a Ό S as ø CO Λ 0 01 <0 CQ OJ J n A Cβ MH 01 01 4-1 β Ol rH πj < <U β rt A (6 rH MH 01 Oi 4-1 4J β OJ H

Oi αi H a Ό o rβ Λ 4 i-i αi o ε 0i rt u 01 OJ Λ β Ό 0 Λ rt Λ 4J

M r-4 01 4-1 •H Q) o OJ 4-> Φ <D -H ι V J4 H 01 O -υ ^•H OJ 0 r-i OJ )H (U 4J a to CD J-I A πs > rt τ) rH OJ 4-1 CQ β CO ϋ X β ■Q M β β CQ U Q) fa A « > Λ rn rt j-i a -α . Oi H <U rH A 4J O O rt o rt υ <a 4J a J U 01 rH

H o 0 >H -rl 0 0 αi 0 ø -co A -H Λ 1. o • rt OJ r-\ 0 0 3 •H 0 3 Λ OJ • 0 3 OJ -β

CQ U u u -ε 2 « S O o > 5 -2

H 04 ft n co to PQ U u U P o Σ 53 « tt « CO O O > S Wild oats 0 0 0 0 4 0 0 0 0 0 0 0 0 0 - 0 0 - 0 0 0 0 0

Table A COMPOUND

Rate 62 g/ha 1 2 3 4 5 6 7 8 9 10 11 12 13 14 16 17 19 20 21 22 23 24 41 VO o

Preemergence i-T oo

B. signalgrass 0 8 4 7 9 0 7 0 1 7 3 6 0 6 8 2 9 0 7 6 4 0 2 oo

V

Bedstraw 0 3 0 - 3 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 oO

Blackgrass 0 8 5 4 8 0 2 0 3 8 0 3 2 3 6 6 6 3 9 5 3 4 0

Cocklebur - 0 0 0 0 - 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

Corn 0 3 0 4 8 0 3 0 0 3 2 4 0 0 2 0 0 0 0 0 0 0 0

Crabgrass 0 9 8 9 9 1 9 9 4 8 8 10 4 7 10 9 9 6 10 9 7 8 3

Giant foxtail 0 10 8 10 10 6 9 7 8 10 9 9 7 10 10 10 10 8 10 9 9 8 9

Morningglory 0 1 0 0 4 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 3

Nutsedge - 3 0 0 - - - 0 - 0 0 0 0 0 0 0 0 0 0 0 0 0 0

Rape 0 4 2 0 5 0 3 0 0 0 0 2 0 0 2 0 2 1 4 0 3 0 3

Redroot pigweed 0 8 0 3 9 0 1 0 0 0 0 3 0 0 5 0 3 2 6 4 6 2 3

Soybean 0 4 0 0 4 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

Sugarbeets 0 6 1 0 - 0 3 0 0 0 0 3 0 0 5 3 4 0 7 0 3 2 2

Velvetleaf 0 4 0 0 0 0 3 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2 0

Wheat 0 3 0 0 6 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

Wild oats 0 4 3 2 8 0 4 0 0 0 0 3 0 0 3 2 3 0 5 0 4 5 0

o H

CΛ vo vo

© in vo

00

40

TEST B

Compounds evaluated in this test were formulated in a non-phytotoxic solvent mixture which included a surfactant and applied to plants that were grown for various periods of time before treatment (postemergence application). A mixture of sandy loam soil and greenhouse potting mix in a 60:40 ratio was used for the postemergence test.

Plantings of these crops and weed species were adjusted to produce plants of appropriate size for the postemergence test. All plant species were grown using normal greenhouse practices. Crop and weed species include arrowleaf sida (Sida rhombifolia), barnyardgrass (Echinochloa crus-galli), cocklebur (Xanthium strumarium), common ragweed (Ambrosia elatior), corn (Zea mays), cotton (Gossypium hirsutum), eastern black nightshade (Solanum ptycanthum), fall panicum (Panicum dichotomiβorum), field bindweed (Convolvulus arvensis), giant foxtail (Setaria faberii), hairy beggarticks (Bidens pilosa), ivyleaf morningglory (Ipomoea hederacea), johnsongrass (Sorghum halepense), ladysthumb smartweed (Polygonum persicaria), lambsquarters (Chenopodium album), large crabgrass (Digitaria sanguinalis), purple nutsedge (Cyperus rotundus), redroot pigweed (Amaranthus retroflexus), soybean (Glycine max), Surinam grass (Brachiaria decumbens), velvetleaf (Abutilon theophrasti) and wild poinsettia (Euphorbia heterophylla).

Treated plants and untreated controls were maintained in a greenhouse for approximately 14 to 21 days, after which all treated plants were compared to untreated controls and visually evaluated. Plant response ratings, summarized in Table B, were based upon a 0 to 100 scale where 0 was no effect and 100 was complete control. A dash response (-) means no test result.

Table B COMPOUND

Rate 280 g/ha 2 7 10 11 12

Preemergence

Arrowleaf sida 40 35 25 25 50

Barnyardgrass 100 100 100 100 95

Cocklebur 0 10 0 0 0

Common ragweed 20 50 20 20 20

Corn 65 50 20 75 25

Cotton 25 50 0 10 20

E . blacknightsh 100 100 80 100 100

Fall panicum 100 100 100 100 95

Field bindweed 0 0 20 0 25

Giant foxtail 100 100 100 100 100

H . beggarticks 0 - 70 - -

I . morningglory 20 25 0 25 65

Johnsongrass 100 70 80 85 100

Ladysthumb 100 100 100 100 - 41

Lambsquarters 100 100 100 80 100 Large crabgrass 100 90 100 100 100 Purple nutsedge - 60 40 0 20 Redroot pigweed 100 100 100 100 100

Soybean 20 60 30 10 20

Surinam grass 100 85 100 70 80

Velvetleaf 50 20 20 30 20

Wild poinsettia 35 50 0 25 10

Table B COMPOUND

Rate 140 g/ha 2 4 5 7 10 11 12

Preemergence

Arrowleaf sida 0 20 50 0 10 10 20

Barnyardgrass 100 100 100 100 100 100 85

Cocklebur 50 0 10 0 0 0 0

Common ragweed 10 30 100 20 20 0 20

Corn 40 10 75 20 15 35 20

Cotton 10 20 80 25 0 10 10

E. blacknightsh 70 - 100 80 80 100 60

Fall panicum 100 100 100 100 100 100 95

Field bindweed 0 0 10 0 0 0 20

Giant foxtail 100 100 100 100 100 100 100

H. beggarticks 60 50 60 0 - - -

I . morningglory 50 0 20 10 0 10 40

Johnsongrass 100 85 100 100 70 60 100

Ladysthumb 100 - 100 100 60 0 -

Lambsquarters 10 - 100 80 80 - 100

Large crabgrass 100 100 100 100 100 85 100

Purple nutsedge 30 0 60 70 20 0 0

Redroot pigweed 50 30 100 100 100 100 90

Soybean 0 40 70 10 20 0 10

Surinam grass 100 85 100 100 100 50 65

Velvetleaf 30 30 75 50 10 30 20

Wild poinsettia 30 10 75 0 0 10 10

Table B COMPOUNT )

Rate 70 g/ha 2 4 5 7 10 11 12

Preemergence

Arrowleaf sida 0 0 20 0 0 0 20

Barnyardgrass 100 100 100 100 90 100 75

Cocklebur 0 0 10 0 0 0 0

Common ragweed 10 0 60 0 10 0 10

Corn 25 10 65 15 10 25 20

Cotton 0 0 50 15 0 0 10

E. blacknightsh 30 0 100 75 20 70 0

Fall panicum 100 100 100 100 100 60 80

Field bindweed 0 0 10 0 0 0 0

Giant foxtail 100 100 100 100 90 85 100

H. beggarticks 20 0 0 0 - - -

I . morningglory 0 0 10 5 0 0 20

Johnsongrass 95 50 100 80 35 35 60

Ladysthumb 20 - 100 100 50 - -

Lambsquarters 10 - 100 100 - 50 50

Large crabgrass 100 80 100 100 85 85 100 42

Purple nutsedge 10 0 60 25 20 0 0 Redroot pigweed 50 0 100 80 75 75 75 Soybean 0 30 35 0 0 0 0 Surinam grass 80 80 100 100 95 25 50 Velvetleaf 20 10 50 40 10 20 10

Wild poinsettia 0 0 40 0 0 0 0

Table B COMPOUND

Rate 35 g/ha 2 4 5 7 10 11 12 Preemergence

Arrowleaf sida 0 0 10 0 0 0 10 Barnyardgrass 70 100 100 100 85 65 65 Cocklebur 0 0 0 0 0 0 0 Common ragweed 0 - 50 0 0 0 20 Corn 25 0 50 10 10 15 10

Cotton 0 0 25 10 0 0 0

E . blacknightsh 0 0 100 35 0 70 0 Fall panicum 100 40 95 100 85 0 65 Field bindweed 0 0 10 0 0 0 0 Giant foxtail 100 70 100 100 75 30 70 H. beggarticks 0 0 0 0 0 - - I . morningglory 0 0 10 0 0 0 0 Johnsongrass 100 20 100 25 25 20 25 Ladysthumb 0 - 20 20 0 0 - Lambsquarters 0 - 50 0 35 30 50

Large crabgrass 85 50 100 80 80 75 80 Purple nutsedge 10 0 40 25 0 0 0 Redroot pigweed 0 - 100 0 30 50 50 Soybean 0 0 10 0 0 0 0 Surinam grass 80 10 80 80 50 10 20 Velvetleaf 0 0 35 30 0 0 0 Wild poinsettia 0 0 10 0 0 0 0

Table B COMPOUND Rate 17 g/ha 2 4 5 7 10 11 12 Preemergence Arrowleaf sida 0 0 0 0 0 0 10 Barnyardgrass 50 75 80 75 25 20 20 Cocklebur 0 0 0 0 0 0 0 Common ragweed 0 0 10 0 0 0 10 Corn 15 0 30 10 0 5 10 Cotton 0 0 20 10 0 0 0

E . blacknightsh 0 0 80 0 0 50 0 Fall panicum 80 0 90 35 10 0 0 Field bindweed 0 0 0 0 0 0 0 Giant foxtail 70 0 90 80 10 10 25 H. beggarticks 0 0 0 0 - - - I . morningglory 0 0 10 0 0 0 0 Johnsongrass 80 0 65 0 10 0 0 Ladysthumb 0 - 0 0 0 - -

Lambsquarters 0 - 0 0 0 - 40 Large crabgrass 70 0 100 60 20 20 40 Purple nutsedge 0 0 25 0 0 0 0 Redroot pigweed

0 0 100 0 0 25 25 43

Soybean 0 0 0 0 o

Surinam grass 0 0 50 50 20

Velvetleaf 0 0 20 0 0

Wild poinsettia 0 0 0 0 0

TEST C

Seeds, tubers, or plant parts of alexandergrass (Brachiaria plantaginea), bermudagrass (Cynodon dactyloή), common purslane (Portulaca oleracea), common ragweed (Ambrosia elatior), common groundsel (Senecio vulgaris), dallisgrass (Paspalum dilatatum), goosegrass (Eleusine indica), guineagrass (Panicum maximum), itchgrass (Rottboellia exaltata), johnsongrass (Sorghum halepense), large crabgrass (Digitaria sanguinalis), pitted morningglory (Ipomoea lacunosa), purple nutsedge (Cyperus rotundus), sandbur (Cenchrus echinatus), sourgrass (Trichachne insularis), Spanishneedles (Bidens bipinnata), sugarcane (Saccharum officinarum), Surinam grass (Brachiaria decumbens) and tall mallow (Malva sylvestris) were planted into greenhouse pots of flats containing greenhouse planting medium. Plant species were grown in separate pots or individual compartments. Preemergence applications were made within one day of planting the seed or plant part. Postemergence applications were applied, to sugarcane, when the plants were in the two to four leaf stage (three to twenty cm). Test chemicals were formulated in a non-phytotoxic solvent mixture which included a surfactant and applied preemergence and postemergence to the plants. Untreated control plants and treated plants were placed in the greenhouse and visually evaluated for injury 13 to 21 days after herbicide application. Plant response ratings, summarized in Table C, are based on a 0 to 100 scale where 0 is no injury and 100 is complete control. A dash (-) response means no test result.

Table C COMPOUND Table C COMPOUND

Rate 500 g/ha 5 Rate 500 g/ha 2 5

Preemergence Postemergence

Alexandergrass

Sugarcane 20 0

Bermudagrass

C. purslane

C. ragweed

Com. groundsel

Dallisgrass

Goosegrass

Guineagrass

Itchgrass

Johnsongrass

Large crabgrass

P. morninglory

Purple nutsedge

Sandbur 44

Sourgrass -

Spanishneedles -

Sugarcane 50

Surinam grass -

Tall Mallow -

Table C COMPOUND Table C COMPOUND

Rate 250 g/ha 2 3 4 5 7 10 Rate 250 g/ha 2 5

Preemergence Postemergence

Alexandergrass 100 100 100 98 98 100 Sugarcane 20 0

Bermudagrass 100 100 100 100 100 100

C. purslane 10 75 0 40 0 30

C . ragweed 80 75 10 100 0 0

Com . groundse1 98 0 98 100 60 0

Dallisgrass 100 100 100 100 100 100

Goosegrass 100 100 100 100 100 100

Guineagrass 100 100 100 100 100 100

Itchgrass 95 75 98 90 70 90

Johnsongrass 85 100 65 90 30 90

Large crabgrass 100 100 100 100 100 100

P . morninglory 40 60 - 50 0 30

Purple nutsedge 20 0 0 50 30 0

Sandbur 100 95 100 95 100 100

Sourgrass 100 100 100 100 100 100

Spanishneedles 60 0 0 80 50 20

Sugarcane - - - 35 - -

Surinam grass 100 100 98 90 100 85

Tall Mallow 75 20 0 50 40 30

Table C COMPOUND Table C COMPOUND

Rate 125 g/ha 2 3 4 5 7 10 Rate 125 g/ha 2 5

Preemergence Postemergence

Alexandergrass 100 100 100 - 80 98 Sugarcane 20 0

Bermudagrass 100 100 100 100 100 100

C . purslane 10 50 0 30 0 0

C . ragweed - - 0 90 0 0

Com. groundsel 100 0 0 100 50 0

Dallisgrass 100 100 100 98 98 98

Goosegrass 100 100 100 100 100 98

Guineagrass 100 100 98 100 90 100

Itchgrass 40 30 80 - 65 75

Johnsongrass 40 65 - - 10 85

Large crabgrass 100 98 100 - 100 100

P . morninglory 30 60 75 - 0 30

Purple nutsedge 10 0 0 35 10 0

Sandbur 90 85 0 75 80 100

Sourgrass 100 100 100 100 100 100

Spanishneedles 30 0 0 - 40 20

Sugarcane - - - 30 - -

Surinam grass 50 100 70 80 80 75

Tall Mallow 40 0 0 0 20 30

Table C COMPOUND ) Table C COMPOUND 45

Rate 64 g/ha 2 3 4 5 7 10 Rate 64 g/ha 2 5

Preemergence Postemergence

Alexandergrass 100 100 98 80 50 85 Sugarcane 30 0

Bermudagrass 100 100 98 80 98 85

C. purslane 0 30 0 0 0 0

C . ragweed - 0 0 50 0 0

Com. groundsel 98 0 0 0 40 0

Dallisgrass 100 90 85 90 80 60

Goosegrass 100 98 100 100 100 90

Guineagrass 100 85 98 100 70 75

Itchgrass 20 30 80 65 60 65

Johnsongrass - 50 - 50 0 75

Large crabgrass 100 98 98 100 100 90

P . morninglory 0 60 60 35 0 0

Purple nutsedge 0 0 0 0 0 0

Sandbur 75 10 0 20 60 90

Sourgrass 100 95 98 100 98 100

Spanishneedles 30 0 0 0 0 10

Sugarcane - - - 0 - -

Surinam grass 70 50 50 40 50 0

Tall Mallow 0 0 0 0 0 30

Claims

46 CLAIMS What is claimed is:

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

wherein

Q is a 5- or 6-membered aromatic heterocyclic ring system containing 1 to 3 heteroatoms independently selected from the group consisting of nitrogen, oxygen and sulfur, provided that the heterocyclic ring system contains no more than one oxygen and no more than one sulfur, and each heterocyclic ring system is optionally substituted by 1-3 groups selected from halogen, nitro, cyano, C_rC₄ alkyl, C₃-C₇ cycloalkyl, C_rC₄ haloalkyl, C₃-C₄ alkenyl, C₃-C₄ alkynyl, C _j -C₄ alkoxy, C ! -C₄ haloalkoxy, S(O)_nR⁴, SO₂ΝR⁵R⁶ or phenyl optionally substituted with C_rC4 alkyl, C3-C7 cycloalkyl, C C haloalkyl, halogen, cyano or nitro; and when Q is a 5- or 6-membered aromatic heterocyclic ring system containing a nitrogen, then Q can be bonded through any available carbon or nitrogen atom to the tetrazolinone ring by replacement of a hydrogen on said carbon or nitrogen atom;

R¹ is C_rC₆ alkyl, C_rC₆ haloalkyl, C₃-C₆ alkenyl, C₃-C₆ haloalkenyl, C₃-C₆ alkynyl, C₃-C₆ haloalkynyl; or R¹ is C3-C₇ cycloalkyl or C3-C7 cycloalkenyl, each optionally substituted with 1-2 R³; each R² is independently C1-C4 alkyl or C1-C4 haloalkyl; each R³ is independently C1-C4 alkyl or C1-C4 alkoxy;

R⁴ is C_rC₄ alkyl or C_rC haloalkyl; R⁵ is H or C,-C₄ alkyl; R⁶ is C_rC₄ alkyl; each n is independently 0, 1 or 2; x is 1, 2 or 3; y is O, 1, 2, 3 or 4; and 47 wherein the dashed lines in the 5-, 6- or 7-membered carbocyclic ring of Formula I shown below

represent one carbon-carbon double bond at any position within the carbocyclic ring.

2. The compounds of Claim 1 wherein

Q is selected from the group IH-pyrrolyl; furanyl; thienyl; lH-pyrazolyl; lH-imidazolyl; isoxazolyl; oxazolyl; isothiazolyl; thiazolyl; lH-l,2,3-triazolyl;

277-1, 2,3-triazolyl; lH-l,2,4-triazolyl; 4H-lJ,4-triazolyl; 1,2,3-oxadiazolyl;

1,2,4-oxadiazolyl; 1,2,5-oxadiazolyl; 1,3,4-oxadiazolyl; 1,2,3-thiadiazolyl;

1,2,4-thiadiazolyl; 1,2,5-thiadiazolyl; 1,3,4-thiadiazolyl; lH-tetrazolyl;

2H-tetrazolyl; pyridinyl; pyridazinyl; pyrimidinyl; pyrazinyl; 1,3,5-triazinyl; 1,2,4-triazinyl; each heterocyclic group being optionally substituted by 1-3 groups selected from halogen, nitro, cyano, C1-C4 alkyl, C1-C₄ haloalkyl, C3-C4 alkenyl, C3-C4 alkynyl, C_rC₄ alkoxy, C_rC₄ haloalkoxy, S(O)_πR⁴, SO₂NR⁵R⁶ or phenyl optionally substituted with C1-C4 alkyl, C1-C4 haloalkyl, halogen, cyano or nitro; and when Q is a 5- or 6-membered aromatic heterocyclic ring system containing a nitrogen, then Q can be bonded through any available carbon or nitrogen atom to the tetrazolinone ring by replacement of a hydrogen on said carbon or nitrogen atom.

3. The compounds of Claim 2 wherein R¹ is CpCg alkyl or C3-C₇ cycloalkyl; and wherein the carbon-carbon double bond in the 5-, 6- or 7-membered carbocyclic ring is located as shown in Formula la below

o o (R²)y

Q

N'

N= N Rl

la 48

4. The compounds of Claim 3 wherein

Q is selected from the group IH-pyrrolyl; furanyl; thienyl; IH-pyrazolyl; isoxazolyl; oxazolyl; isothiazolyl; thiazolyl; pyridinyl; and pyrimidinyl; each heterocyclic group being optionally substituted by 1-3 groups selected from halogen, nitro, cyano, C_rC₄ alkyl, C_rC haloalkyl, C₃-C₄ alkenyl, C3-C4 alkynyl, C_rC₄ alkoxy, C_rC₄ haloalkoxy, S(O)_nR⁴, SO₂NR⁵R⁶ or phenyl optionally substituted with C1-C4 alkyl, C1-C4 haloalkyl, halogen, cyano or nitro; and when Q is a 5- or 6-membered aromatic heterocyclic ring system containing a nitrogen, then Q can be bonded through any available carbon or nitrogen atom to the tetrazolinone ring by replacement of a hydrogen on said carbon or nitrogen atom.

5. The compounds of Claim 4 wherein

Q is isoxazole optionally substituted by 1-2 groups selected from halogen, nitro, cyano, C_rC₄ alkyl, C1-C4 haloalkyl, C3-C₄ alkenyl, C3-C4 alkynyl, C1-C4 alkoxy, C_rC₄ haloalkoxy, S(O)_nR⁴, SO₂NR⁵R⁶ or phenyl optionally substituted with

C_j-C₄ alkyl, C_]-C4 haloalkyl, halogen, cyano or nitro.

6. The compound of Claim 5 which is selected from the group consisting of

(a) N-( 1 -cyclohexen- 1 -yl)-4-(3,5-dimethyl-4-isoxazolyl)-4,5-dihydro-N-( 1 - methyl ethyl)-5-oxo- 1 H-tetrazole- 1 -carboxamide;

(b) N-( 1 -cyclohexen- l-yl)-4-(3,5-dimethyl-4-isoxazolyl)-4,5-dihydro-N-ethyl-5- oxo- lH-tetrazole- 1 -carboxamide;

(c) 4-(5-chloro- 1 ,3 -dimethyl- lH-pyrazol-4-yl)-N- 1 -cyclohexen- 1 -yl-4,5-dihydro-N- ( 1 -methylethyl)-5-oxo- lH-tetrazole- 1 -carboxamide; (d) N- 1 -cyclohexen- 1 -yl-N-ethyl-4,5-dihydro-5-oxo-4-( 1 ,3,5-trimethyl- lH-pyrazol-

4-yl)- lH-tetrazole- 1 -carboxamide;

(e) 4-(5-chloro- 1 -methyl- lH-pyrazol-4-yl)-N- 1 -cyclohexen- 1 -yl-4,5-dihydro-N-( 1 - methylethyl)-5-oxo- lH-tetrazole- 1 -carboxamide; and

(f) N- 1 -cyclohexen- 1 -yl-4-(3-ethyl-5-methyl-4-isoxazolyl)-4,5-dihydro-N-( 1 - methylethyl)-5-oxo- lH-tetrazole- 1 -carboxamide. 49

7. The herbicidal compositions 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.

8. The methods 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.