This invention comprises certain bicyclic imides, their agriculturally-suitable salts and compositions, and methods of their use for weed control in crops. WO 90/9575 (BASF) discloses compounds of Formula i

wherein Ri = halogen, R ₂ = alkyl, etc., R ₃ = H or CH ₃ , X = H or halogen, and

Y = halogen. The compounds of the present invention differ from those disclosed in this reference in that a non-hydrogen, non-alkyl substituent is present on the cyclohexene ring moiety.

JP 3,063,278 (Nissan) discloses compounds of Formula ii

wherein Z is O or S, and Rj is H, alkyl, haloalkyl, etc. The N-phenyl tetrahydrotriazolopyridazines of the present invention differ from the compounds disclosed in JP 3,063,278 in the nature of the substitution on the tetrahydropyridazine

U.S. 4,881,967, U.S. 5,077,401, and U.S. 5,108,483 also disclose related tetrahydrotriazolopyridazines. The compounds of the present invention also differ from the compounds disclosed in these references in the nature of the substitution on the tetrahydropyridazine ring.

SUMMARY OF THE INVENTION This invention pertains to compounds of Formulae I and π, or an agriculturally- suitable salt thereof, for controlling undesirable vegetation:

π

wherein

G is O; S; NH; N(C _r C ₄ alkyl); or N(C _r C ₄ haloalkyl);

R ¹ is hydrogen; halogen; hydroxy; SH; C1-C3 alkoxy; C1-C3 haloalkoxy; C _j -C3 alkylthio; C1-C3 haloalkylthio; C2-C4 alkylcarbonyloxy; or C2-C4 haloalkylcarbonyloxy; R ² is hydrogen; hydroxy; or halogen; or when R ¹ and R ² are bonded to the same carbon atom they can be taken together with the carbon to which they are attached to form C=O; or when R ¹ and R ² are bonded to adjacent atoms they can be taken together with the

O

/ \

— TT CH carbons to which they are attached to form or

Y and Z are each independently H; halogen; C!-C ₂ alkyl; or Cι-C ₂ haloalkyl; n and m are each independently 0; 1; 2; or 3; provided that m + n is 2 or 3; q is 1 or 2; X is CH ₂ ; CH(halogen); CF ₂ ; CHOCH ₂ F; CHOCF ₃ ; CHOCH ₂ CF ₃ ; O; S(O) ₀ _ ₂ ;

NH; N(C _r C ₄ alkyl); or N(C _r C ₄ haloalkyl); Q is selected from the group

Q-l Q-2 Q-3

Q Q-5 Q-6

W is O or S;

R ³ is chlorine or fluorine; R4 is H; C C _s alkyl; C _r C ₈ haloalkyl; halogen; OH; OR ⁹ ; SH; S(O) _p R ⁹ ; COR ⁹ ;

CO ₂ R ⁹ ; C(O)SR ⁹ ; C(O)NRHRl2 _; CHO; CR ⁿ =NOR ¹⁸ ; CH=CR ¹⁹ CO ₂ R ⁹ ; CH ₂ CHR ¹⁹ CO ₂ R ⁹ ; CO ₂ N=CR ¹³ R ¹⁴ ; NO ₂ ; CN; NHSO ₂ R ¹⁵ ; NHSO ₂ NHR ¹⁵ ; NR ⁹ R ²⁰ ; NH ₂ or phenyl optionally substituted with at least one member independently selected from C _j - -i alkyl; p is 0; 1; or 2;

R ⁵ is C _r C ₂ alkyl; C _r C ₂ haloalkyl; OCH ₃ ; SCH ₃ ; OCHF ₂ ; halogen; CN or NO ₂ ; R ⁶ is H; C _r C ₃ alkyl; Ci -C ₃ haloalkyl; or halogen;

R ⁷ is H; C1-C3 alkyl; halogen; i-C^ haloalkyl; cyclopropyl; vinyl; C ₂ alkynyl; CN; C(O)R ²⁰ ; CO ₂ R 0; C(O)NR ²⁰ R ²¹ ; CR^R^CN; CR ¹⁶ R ¹⁷ C(O)R ²⁰ ; CR ¹⁶ R ¹⁷ CO ₂ R ²⁰ ; CR ¹⁶ R ¹⁷ C(O)NR ⁰ R ²¹ ; CHR ¹⁶ OH; CHR ¹⁶ OC(O)R ²⁰ ;

OCHR ¹⁶ OC(O)NR ²⁰ R ²¹ ; or Q is Q-2 and R ⁶ and R ⁷ are taken together with the carbon to which they are attached to form C=O; R ⁸ is C _r C ₆ alkyl; C _r C ₆ haloalkyl; C ₂ -C ₆ alkoxyalkyl; C ₃ -C ₆ alkenyl; or C _r C ₆ alkynyl; R ⁹ is C _r C ₈ alkyl; C ₃ -C ₈ cycloalkyl; C ₃ -C ₈ alkenyl; C ₃ -C ₈ alkynyl; C _r C ₈ haloalkyl; C ₂ -C ₈ alkoxyalkyl; C ₂ -C ₈ alkylthioalkyl; C ₂ -C ₈ alkylsulfmylalkyl; C ₂ -C ₈ alkylsulfonylalkyl; Cι-C ₈ alkylsulfonyl; phenylsulfonyl optionally substituted on the phenyl ring with at least one substituent selected from the group halogen and Cι-C alkyl; C ₄ -C ₈ alkoxyalkoxyalkyl; C -C ₈ cycloalkylalkyl; C ₄ -C ₃ alkenoxyalkyl; C ₄ -C^ alkynoxyalkyl; C ₆ -C ₈ cycloalkoxyalkyl; C ₄ -C ₈ alkenyloxyalkyl; C -C ₈ alkynyloxyalkyl; C ₃ -C^ haloalkoxyalkyl; C ₄ -C ₈ haloalkenoxyalkyl; C ₄ -C ₈ haloalkynoxyalkyl; C ₆ -C ₈ cycloalkylthioalkyl; C ₄ -C ₈ alkenylthioalkyl; C ₄ -C ₈ alkynylthioalkyl; C1-C4 alkyl substituted with phenoxy or benzyloxy, each ring optionally substituted with at least one substituent selected from the group halogen, C _j -C3 alkyl and C1-C3 haloalkyl; C ₄ -C ₈ trialkylsilylalkyl; C ₃ -C ₈ cyanoalkyl; C ₃ -C ₈

halocycloalkyl; C3~C haloalkenyl; C ₅ -C ₈ alkoxyalkenyl; C5-C haloalkoxyalkenyl; C5-C alkylthioalkenyl; C3-C haloalkynyl; C5-C ₈ alkoxy alkynyl; C5-C3 haloalkoxyalkynyl; C ₅ -C ₈ alkylthioalkynyl; C ₂ -Cg alkylcarbonyl; benzyl optionally substituted with at least one substituent selected from the group halogen, C1-C3 alkyl and C1-C3 haloalkyl;

CHR ¹⁶ COR ¹⁰ ; CHR ¹⁶ CO ₂ R ¹⁰ ; CHR ¹⁶ P(O)(OR ¹⁰ ) ₂ ; CHR ¹⁶ P(S)(OR ¹⁰ ) ₂ ; CHR ¹⁶ C(O)NR ⁿ R ¹² ; or CHR ¹⁶ C(O)NH ₂ ; R ¹⁰ is C _r C ₆ alkyl; C ₂ -C ₆ alkenyl; or C ₂ -C ₆ alkynyl; R ¹¹ and R ¹³ are independently hydrogen or C _j -C ₄ alkyl; R ¹² and R ¹⁴ are independently Cj-C alkyl or phenyl optionally substituted with at least one substituent selected from the group halogen, C _j -03 alkyl and C1-C3 haloalkyl; or R ^{1 1} and R ¹² can be taken together to form -(CH ₂ ) ₅ -, -(CH ₂ ) ₄ - or

-CH ₂ CH ₂ OCH ₂ CH ₂ -, each ring thus formed optionally substituted with a substituent selected from the group C1-C3 alkyl, phenyl and benzyl; or

R ¹³ and R ¹⁴ can be taken together with the carbon to which they are attached to form C3-C ₈ cycloalkyl; R ¹⁵ is Cj-C ₄ alkyl or C _r C ₄ haloalkyl; R ¹⁶ and R ¹⁷ are independently H or C*L-C ₄ alkyl; R ¹⁸ is H; C _r C ₆ alkyl; C ₃ -C ₆ alkenyl; or C ₃ -C ₆ alkynyl;

R ¹⁹ is H; C _r C ₄ alkyl; or halogen;

R ²⁰ is H; C _r C ₆ alkyl; C ₃ -C ₆ cycloalkyl; C ₃ -C ₆ alkenyl; C ₃ -C ₆ alkynyl; C ₂ -C ₆ alkoxyalkyl; Cj-Cg haloalkyl; phenyl optionally substituted with at least one substituent selected from the group halogen, Cι-C ₄ alkyl, and C _j - alkoxy; -CH ₂ CO ₂ (C _r C ₄ alkyl); or -CH(CH3)CO ₂ (C _r C ₄ alkyl); and

R ²¹ is H; C _r C ₂ alkyl; or C(O)O(C _r C ₄ alkyl); provided that

(i) R ¹ is other than hydrogen in compounds of Formula I when X is CH ₂ and R ² is hydrogen; and (ii) R ² is other than hydrogen or hydroxy in compounds of Formula II when Q is

Q-l, Q-2, Q-4, or Q-6 and q is 2. For reasons such as ease of synthesis and/or greater herbicidal efficacy, preferred compounds are:

Preferred. 1: Compounds of Formulae I and π, and agriculturally-suitable salts thereof, wherein:

G is O;

R ¹ is hydrogen or halogen; R ² is halogen;

Q is Q-l, Q-2 or Q-6;

R ⁵ is C _r C ₂ haloalkyl; OCH ₃ ; OCHF ₂ ; CN; NO ₂ ; or halogen; R ⁶ is hydrogen; C1-C3 alkyl; C ₂ -C ₃ alkynyl; C ₂ -C ₃ haloalkynyl; or halogen; R ⁷ is H; and

W is O. Preferred 2: Compounds of Preferred 1 wherein:

R ⁴ is halogen; OR ⁹ ; SR ⁹ ; COR ⁹ ; CO ₂ R ⁹ ; C(O)NRUR1 ² ; CH=CHCO ₂ R ⁹ ; NHSO ₂ R ¹⁵ or NHSO ₂ NHR ¹ 5; R ⁵ is halogen;

R ⁶ is hydrogen or C1-C3 alkyl; and

R ⁹ is C ₁ -C ₈ alkyl; C ₃ -C ₈ cycloalkyl; C ₃ -C ₈ alkenyl; C ₃ -C ₈ alkynyl; C _r C ₈ haloalkyl; C2-C ₈ alkoxyalkyl; Cι-C ₄ alkyl substituted with phenoxy or benzyloxy, each ring optionally substituted with at least one substituent selected from the group halogen, C-1-C3 alkyl and C1-C3 haloalkyl; C ₃ -C ₈ haloalkenyl; C ₃ -C ₈ haloalkynyl; C ₂ -C ₈ alkyl carbonyl; benzyl optionally substituted with at least one substituent selected from the group halogen, C1-C3 alkyl and 1-C haloalkyl; CHR ¹⁶ COR ¹⁰ ; CHR ¹⁶ CO ₂ R ¹⁰ ; CHR ¹⁶ P(O)(OR ¹⁰ ) ₂ ; CHR ¹⁶ C(O)NR ^π R ¹² ; or CHR ¹⁶ C(O)NH ₂ .

Preferred 3: Compounds of Preferred 2 wherein: R ¹ is hydrogen or fluorine; R ² is fluorine; X is CH ₂ or O; R ⁵ is chlorine or fluorine;

R ⁹ is C _r C ₆ alkyl; C ₃ -C ₆ alkenyl; C ₃ -C ₆ alkynyl; C _r C ₆ haloalkyl; C ₂ -C ₈ alkoxyalkyl; CH2 substituted with phenoxy or benzyloxy, each ring optionally substituted with at least one substituent selected from the group halogen, C1-C3 alkyl and C1-C3 haloalkyl; C ₃ -C ₈ haloalkenyl; C2~C ₈ alkylcarbonyl; benzyl optionally substituted with at least one substituent selected from the group halogen, C1-C3 alkyl and C1-C3 haloalkyl; CHR ¹⁶ COR ¹⁰ ; CHR ¹⁶ CO ₂ R ¹⁰ ; or CHR ¹⁶ P(O)(OR ¹⁰ ) ₂ . Most preferred are compounds of Preferred 3 selected from the group: 2-[4-chloro-2-fluoro-5-(2-propynyloxy)phenyl]-6-fluorotetrah ydro-lH- [l,2,4]triazolo[l,2-α]pyridazine-l,3(2H)-dione;

2-[4-chloro-2-fluoro-5-(2-propynyloxy)phenyl]-6-fluorodih ydro-lH,5H- pyrazolo[ 1 ,2-α]triazole- 1 ,3(2H)-dione;

2-[4-chloro-2-fluoro-5-(2-propynyloxy)phenyl]-5-fluoro-4,5,6 ,7-tetrahydro-lH- isoindole-l,3(2H)-dione; and

2-[4-chloro-2-fluoro-5-(2-propynyloxy)phenyl]-6,7-dihydro pyrano[3,4-c]- pyrrole- 1 ,3 (2H,4H)-dione. Another embodiment of the invention is an agriculturally suitable composition for controlling the growth of undesired vegetation comprising an effective amount of a compound of Formulae I or π, or an agriculturally-suitable salt thereof, with the substituents as defined above.

A further embodiment of the invention is a method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of Formula I or π, or an agriculturally-suitable salt thereof, with the substituents as defined above.

Further embodiments of the invention are agriculturally suitable compositions and methods for selectively controlling undesired vegetation in the presence of desired crops, especially plantation crops, such as sugarcane, citrus, grapes, coffee, oil palm, cocoa, fruit trees, nut trees, banana, plantain, rubber, pineapple and loblolly pine.

DETAILS OF THE INVENTION Compounds of Formulae I and II may exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers 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 and/or to selectively prepare said stereoisomers. Accordingly, the present invention comprises mixtures, individual stereoisomers, and optically active mixtures of compounds of Formula I as well as agriculturally suitable salts thereof.

The salts of the compounds of the invention include acid-addition salts with inorganic or organic acids such as hydrochloric, nitric, sulfuric, acetic, oxalic, or 4- toluenesulfonic acids. The salts of the compounds of the invention also include those formed which are organic based (e.g., pyridine, ammonia, or triethylamine) or inorganic based (e.g., sodium, potassium, lithium, calcium, magnesium or barium).

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, /-propyl, or the different butyl, pentyl or hexyl isomers. "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 1,3-hexadiene and 2,4,6-heptatriene. "Alkynyl" includes straight-chain or branched alkynes such as ethynyl, 1-propynyl, 3-propynyl and the different butynyl, pentynyl and hexynyl isomers. "Alkynyl" can also include moieties comprised of multiple

triple bonds such as 2,7-octadiyne. "Alkoxy" includes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers. "Alkoxyalkyl" denotes alkoxy substitution on alkyl. Examples of "alkoxyalkyl" include CH ₃ OCH ₂ , CH ₃ OCH ₂ CH ₂ , CH ₃ CH ₂ OCH ₂ , CH ₃ CH ₂ CH ₂ CH ₂ OCH ₂ and CH3CH2OCH2CH2. "Alkenyloxy" includes straight-chain or branched alkenyloxy moieties. Examples of alkenyloxy include H ₂ C=CHCH ₂ O, (CH ₃ ) ₂ C=CHCH ₂ O, (CH ₃ )CH=CHCH ₂ O, (CH ₃ )CH=C(CH ₃ )CH ₂ O and CH ₂ =CHCH ₂ CH ₂ O. "Alkynyloxy" includes straight-chain or branched alkynyloxy moieties. Examples include HG≡CCH ₂ O, CH ₃ C≡CCH ₂ O and CH ₃ C≡CCH ₂ CH ₂ O. "Alkylthio" includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers. "Alkylsulfinyl" includes both enantiomers of an alkylsulfmyl group. For example, CH ₃ S(O), CH ₃ CH ₂ S(O), CH ₃ CH ₂ CH ₂ S(O), (CH ₃ ) ₂ CHS(O) and the different butylsulfinyl, pentylsulfinyl and hexylsulfinyl isomers. Examples of "alkylsulfonyl" include CH ₃ S(O) ₂ , CH3CH ₂ S(O) ₂ , CH ₃ CH ₂ CH ₂ S(O) ₂ , (CH ₃ ) ₂ CHS(O) ₂ and the different butylsulfonyl, pentylsulfonyl and hexylsulfonyl isomers. "Cycloalkyl" includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. The term "cycloalkoxy" includes the same groups linked through an oxygen atom such as cyclopentyloxy and cyclohexyloxy. Examples of "cycloalkylalkyl" include cyclopropylmethyl, cyclohexylethyl, and other cycloalkyl moieties bonded to straight-chain or branched alkyl groups.

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, CICH2, CF3CH2 and CF ₃ CC1 ₂ . Examples of "haloalkenyl" include (C1) ₂ C=CHCH ₂ and CF ₃ CH ₂ CH=CHCH ₂ . Examples of "haloalkynyl" include HC≡CCHCl, CF ₃ C≡C, CC1 ₃ C≡C and FCH ₂ C=CCH ₂ . Examples of "haloalkoxy" include CF ₃ O, CCl ₃ CH ₂ O, CF ₂ HCH ₂ CH ₂ O and CF ₃ CH ₂ O. Examples of "haloalkylthio" include CC1 ₃ S, CF ₃ S, CC1 ₃ CH ₂ S and CH ₂ C1CH ₂ CH ₂ S. 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 8. For example, Cι*-C alkylsulfonyl designates methylsulfonyl through propylsulfonyl; C2 alkoxyalkoxy designates CH ₃ OCH ₂ O; C ₃ alkoxyalkoxy designates, for example, CH ₃ OCH ₂ CH ₂ O or CH ₃ CH OCH ₂ O; and C alkoxyalkoxy designates the various isomers of an alkoxy group substituted with a second alkoxy group containing a total of four carbon atoms, examples including CH ₃ CH ₂ CH ₂ OCH ₂ O, and CH ₃ CH ₂ OCH ₂ CH ₂ O. Examples of "alkoxycarbonyl" include CH ₃ OC(=O), CH ₃ CH ₂ OC(=O), CH ₃ CH ₂ CH ₂ OC(=O), (CH ₃ ) ₂ CHOC(=O) and the different butoxy-, pentoxy- or hexyloxycarbonyl isomers.

The compounds represented by Formulae I and II can be prepared by one or more of the following methods, or variations obvious to one skilled in the art, as described below in Schemes 1-20. The definitions of G, Q, X, W, n, m, p, q and R ¹ through R ²¹ in the compounds of Formula 1-21 below are as defined above in the Summary of the Invention. Compounds of Formulae la-Ip and Formulae ϋa-IIh are within the definition of compounds of Formulae I and π, respectively.

One skilled in the art will recognize that when G is O, some compounds of Formulae I and II have a plane of symmetry. Therefore, the two formulae below are equivalent.

Q = 2-F*4-α-5-(OCH ₂ C=CH)-Ph Q = 2-F-4-α-5-(OCH ₂ C= CH)-Ph

Synthesis of Compounds of Formula I

Condensation of an R ² -substituted 1,4-cyclohexadiene 1,2-dicarboxylic anhydride with aniline in acetic acid (AcOH) at a temperature between room temperature and reflux, gives the dihydrophthalimide of Formula 1, as illustrated in Scheme 1.

Scheme 1

Treatment of the olefin of Formula 1 with borane in an inert solvent such as tetrahydrofuran at a temperature between about -78°C and room temperature followed by addition of aqueous sodium hydroxide and aqueous hydrogen peroxide (preferably 30%) gives the alcohol of Formula la, as illustrated in Scheme 2.

Scheme 2

MCPBA

Alternatively, compounds of Formula la can be obtained by treatment of the olefin of Formula 1 with m-chloroperoxybenzoic acid (MCPBA) in an inert solvent such as dichloromethane to obtain the epoxide illustrated in Scheme 2. Subsequent treatment with a reducing agent such as sodium borohydride affords the alcohol of Formula la.

Compounds of Formula lb (Scheme 3) are made from compounds of Formula la. The R ²² group is a subset of the R ¹ group in compounds of Formula I. For example, treatment of the alcohol of Formula la with diethylaminosulfur trifluoride (DAST) at a temperature between about -78°C and 100°C in an inert solvent such as dichloromethane gives the fluorinated product of Formula lb wherein R ²² = F.

Scheme 3

R ²² = halogen, C-;-C ₃ alkoxy, C- _[ -C ₃ haloalko_< , C ₂ -C ₄ al ylcarbonyloxy, C^C _j haloalkylcarbonylo y

Compounds of Formula la can also be converted to the R ²² = Cl, Br, and I compounds of Formula lb using methods known to those skilled in the art (see March, J., Advanced Organic Chemistry, (1992), 4th Ed., John Wiley and Sons, Inc., pp 382-384). The hydroxy group in compounds of Formula la can be acylated by known methods to

prepare the alkylcarbonyloxy and haloalkylcarbonyloxy derivatives (see March, J., Advanced Organic Chemistry, (1992), 4th Ed., John Wiley and Sons, Inc., pp 346-351). In* addition, the hydroxy or halo group can be converted by known methods to afford the alkoxy and haloalkoxy derivatives (see March, J., Advanced Organic Chemistry, (1992), 4th Ed., John Wiley and Sons, Inc., pp 342-346).

Compounds of Formula lb wherein R ²² = F can also be prepared directly from the unsaturated compound of Formula 1 by the addition of hydrofluoric acid. G. A. Olah and X. Y. Li, Syn. Lett., (1990), 5, 267 and N. Yoneda et al., Chem. Lett., (1984), 7, 1241 describe methods for the addition of HF to double bonds.

For some compounds of Formulae la and lb wherein R ² is other than hydrogen, the R ² substituent is more conveniently introduced along with the R ¹ substituent. This is especially the case when R ¹ and R ² are attached to the same carbon atom. For example, compounds of Formula lb wherein R ¹ and R ² are gem-difluoro (compounds of Formula Id) can be prepared as illustrated in Scheme 4. Oxidation of the alcohol of Formula la wherein R ² is hydrogen with pyridinium chlorochromate (PCC) in an inert solvent, such as dichloromethane, affords the ketone of Formula Ic. Subsequent treatment with DAST in dichloromethane as described above affords the gem-difluoro compound.

Scheme 4

Similarly, as shown in Scheme 5, R ¹ and R ² can be introduced together when they are attached to adjacent carbons. Treatment of the olefin of Formula 1 (where R ² is hydrogen) with NBS or NCS and water in an inert solvent such as DMSO at a temperature between about 0°C and room temperature gives the bromohydrin of Formula Ie. Compounds of Formula If are made from compounds of Formula Ie. Treatment of the alcohol of Formula Ie with DAST at a temperature between about -78°C and 100°C in an inert solvent such as dichloromethane gives the fluorinated product of Formula If. Debromination or dechlorination can be achieved by treatment of Formula If with tributyltinhydride and AIBN at a temperature between about 0°C and 150°C in an inert solvent such as benzene or toluene to give the product of Formula Ig.

Scheme 5

Ig If

Yet another method for preparing compounds of Formula lb is illustrated in Scheme 6. The appropriately substituted phthalic acid esters of Formula 2 can be reduced to form the cyclohexene diester of Formula 3 by hydrogenation over platinum (IV) oxide. Subsequent treatment with acid, such as hydrochloric acid affords the phthalic anhydride of Formula 4. Treatment with an aniline in acetic acid (AcOH) at a temperature between room temperature and reflux as described above, gives the dihydrophthalimide of Formula lb.

4 lb

R ²² = halogen, C1-C3 alkoxy, C1-C3 haloalkoxy, C2* ₄ alkylcarbonyloxy, C^Q _j haloalkylcarbonyloxy

Compounds of Formula I wherein R ² is hydrogen can be prepared by the methods illustrated in Schemes 7-10. Condensation of 3,4,5,6-tetrahydrophthalic anhydride (q ¹ = 2) or its 5-membered ring homolog (q ¹ = 1) with anilines in acetic acid (AcOH) at a temperature between ambient and reflux temperatures gives an imide of Formula 5, as illustrated in Scheme 7.

Scheme 7

Treatment of the imide of Formula 5 with N-bromosuccinimide (ΝBS) in an inert solvent such as carbon tetrachloride at a temperature between ambient and reflux temperatures, in the presence of light, gives the allyl bromide of Formula Ih, as illustrated in Scheme 8.

Scheme 8

Hydrolysis of the bromide of Formula Ih using aqueous dimethyl sulfoxide (DMSO) at a temperature between about room temperature and the reflux temperature of the solvent gives the alcohol of Formula Ii (Scheme 9).

Scheme 9

Compounds of Formula Ij (Scheme 10) can be made from alcohols of Formula Ii.

For example, treatment of the alcohol of Formula Ii with diethylaminosulfur trifluoride (DAST) at a temperature between about -78°C and 100°C in an inert solvent such as dichloromethane gives the fluorinated product of Formula Ij wherein R ²² = F.

Compounds of Formula If can also be converted to compounds of Formula Ij wherein

R ²² = Cl, Br, I, alkylcarbonyloxy and haloalkylcarbonyloxy as described above for compounds of Formula lb. Likewise, compounds of Formula Ij wherein R ²² = alkoxy or haloalkoxy can be derived from the hydroxy (Id) or bromo (Ih) derivatives by known methods (see March, J., Advanced Organic Chemistry, (1992), 4th Ed., John Wiley and

Sons, Inc., pp 382-384, 346-351, 342-346).

Scheme 10

alkylcarbonyloxy, C ₂ -C ₄ haloalkylcarbonyloxy

Compounds of Formula Ik can be prepared by the method illustrated in Scheme 11. Treatment of β-keto esters of Formula 6 with trifluoromethanesulfonic anhydride (triflic anhydride) affords the vinyl triflate of Formula 7 using conditions described in Aldrichimicα Actα, (1983), 16, 15. Carbonylation of the vinyl triflate using carbon monoxide, palladium (II) acetate (Pd(OAc) ) and l,3-bis(diphenylphosphino)propane (dppp) provides the intermediate amide of Formula 8 (see R. E. Dolle et al., J. Chem. Soc, Chem. Commun., (1987), 904; and S. Cacchi et al., Tetrahedron Lett., (1985), 26, 1109 for a discussion of this carbonylation methodology). Cyclization occurs under basic conditions and/or upon heating to give the imide of Formula Be.

Scheme 10

Ik

The β-ketoesters of Formula 6 are known or can be prepared by methods well-known in the art. For example, the ethyl ester of Formula 6 wherein X is S, q ¹ is 2,

and R ¹ and R ² are H is commercially available from Emka-Chemie, Schlusselberg, Germany. When X is a nitrogen-based group, it may be desirable to perform the reactions on a protected form of the nitrogen and introduce the desired X group after formation of the imide ring.

Compounds of Formula I wherein G is S can be prepared as illustrated in Scheme 12. Treatment of the amide-ester of Formula 8 with Lawesson's reagent (2,4-bis(4-methoxyphenyl)- 1 ,3-dithia-2,4-diphosphetane-2,4-disulfide) affords the corresponding thioamide of Formula 9. Cyclization under the conditions described above (base and/or heat) affords the thioimide of Formula E. In instances where heat is necessary to convert the amide to the thioamide using Lawesson's reagent, the cyclized product may be obtained directly.

Scheme 12

alkyl)

Compounds of Formula I wherein n + m = 2 and the R ² -substituent on the cyclopentene ring is not in the allylic position (compounds of Formula In) can be prepared as illustrated in Scheme 13.

Scheme 13

Functional group transformation

11 In

R ²² = halogen, C _j -C alkoxy, CJ-GJ haloalkoxy, G2-C4 alkylcarbonyloxy, C ₂ -C ₄ haloalkylcarbonyloxy

The bromo compound of Formula Im can be prepared by allylic bromination as described above and illustrated in Scheme 8. Treatment of the bromide with a strong base such as l,8-diazabicyclo[5.4.0]undec-7-ene (DBU) leads to elimination of HBr and the formation of the unsaturated compound of Formula 10. Hydroboration using the conditions described above and illustrated in Scheme 2 affords the alcohol of Formula 11. If the ratio of alcohol regioisomers obtained in the hydroboration is undesirable, a larger amount of the desired regioisomer may be obtained by treatment of the olefin with mercuric acetate and water followed by demercuration with sodium borohydride. Conversion of the alcohol to the desired R ²² substituent can be accomplished in a manner analogous to those previously discussed (see above).

Compounds of Formula Io, compounds of Formula I wherein n or m is zero can be prepared as illustrated in Scheme 14. Treatment of the anhydride of Formula 12 with the appropriate aniline in acetic acid (HO Ac) provides the imide of Formula Io. Anhydrides of Formula 12 are known or can be made by well-known methods. For example, the compound of Formula 12 wherein X is S, R ¹ and R ² are H, and q ¹ is 2 is described in

U.S. 4,164,404.

Schema 14

12 Io q ¹ = l or 2

Synthesis of Compounds of Formula II

Treatment of the R ² -substituted tetrahydropyridazine (q = 2) or pyrazoline (q = 1) of Formula 13 with two equivalents of ethyl cyanoformate affords the 1,2-carboxylate of

Formula 14 as illustrated in _^ Scheme 15. The dicarboxylate can be converted to the triazolidinedione of Formula 15 by contact with trimethylaluminum in an inert solvent such as toluene or dichloromethane at a temperature between 0°C and 100°C followed by addition of the aniline H ₂ NQ at a temperature between 0°C and 100°C.

Scheme 15

Treatment of the olefin of Formula 15 with borane in an inert solvent such as tetrahydrofuran at between about -78°C and ambient temperature, followed by the addition of aqueous sodium hydroxide and hydrogen peroxide (preferably 30% aqueous) gives the alcohol of Formula Ha, as illustrated in Scheme 16. Alternatively, the alcohol of Formula Ha when q is 1 can be prepared from 4-hydroxypyrazolidine (see Kumagai, et al., Heterocycles, (1994), 37, 1521-7 for its preparation from epichlorohydrin and hydrazine) using the process described in Scheme 15.

Scheme 16

15 Ha

Functional group transformation

πb hal = halogen

Alcohols of Formula Ha can be converted to the halo-substituted compounds of Formula lib by well-known methods for performing this functional group transformation

(see March, J., Advanced Organic Chemistry, (1992), 4th Ed., John Wiley and Sons, Inc , pp 382-384, 807-809). For example, treatment of the alcohol with diethylaminosulfur trifluoride (DAST) at a temperature between about -78°C and 100°C in an inert solvent such as dichloromethane gives the compound of Formula Hb wherein hal = F. Using the methods described in March above and known to those skilled in the art, compounds of Formula Ila can also be converted to compounds of Formula lib wherein hal = Cl, Br, and I.

For some compounds of Formula lib wherein R ² is other than hydrogen, the R ² substituent is more conveniently introduced along with the R ¹ substituent. When R ¹ and R ² are both chlorine or bromine and attached to adjacent atoms, the halogens can be introduced in the same reaction by treating the olefin of Formula 15 with Br ₂ or Cl ₂ using standard conditions for dihalogenation. When R ¹ and R ² are gem-difluoro, the fluorine atoms can be introduced by treating the corresponding ketone with DAST as described above (see Scheme 4).

Compounds of Formula lib wherein q is 2 (Formula Ed) can also be prepared using the reaction sequence described above starting with the tetrahydropyridazine of

Formula 16 (Scheme 17).

Scheme 17

Functional group transformation

He πd hal = halogen

Compounds of Formulae He, Ilf, and Ilg can be prepared as shown in Scheme 18.

Treatment of the olefin of Formula 17 (where R ² is hydrogen) with NBS or NCS and water in an inert solvent such as DMSO at a temperature between about 0°C and room temperature gives the bromohydrin of Formula He. Treatment of the alcohol of Formula He with DAST at a temperature between about -78°C and 100°C in an inert solvent such as dichloromethane gives the fluorinated product of Formula πf.

Debromination or dechlorination can be done by treatment of Formula πf with tributyltin hydride and AIBN at a temperature between about 0°C and 150°C in an inert solvent such as benzene or toluene to give the product of Formula Ilg.

Scheme 18

17 He (where R ² = H) hal=ClorBr DAST

Compounds of Formula II wherein G is S can be prepared as illustrated in Scheme 19. Treatment of the R ² -substituted tetrahydropyridazine (q = 2) or pyrazoline (q = 1) of Formula 13 with the isothiocyanate derived from Q-NH ₂ affords the thioamide of Formula 18. Cyclization can be accomplished by treatment of the aminoamide with l,l'-carbonyldiimidazole and affords the thiono compound of Formula 19. In some instances, it is desirable to protect the non-acylated nitrogen of the tetrahydropyridazine or pyrazoline prior to contact with the isothiocyanate. The protecting group can be removed prior to cyclization. The thiono compound of Formula 19 can be converted to compounds of Formula II wherein G is S by the methods described above:

Schema 19

19

Compounds of Formula II can also be prepared by methods disclosed in EP-A-75,267 and illustrated in Scheme 20. Treatment of the urazol of Formula 20 with a base, such as sodium methoxide, sodium hydride, or n-butyllithium, in an inert solvent, such as methanol, diethyl ether, or tetrahydrofuran, at a temperature between about 60°C and 160°C, followed by treatment with an alkylating agent of Formula 21 which is substituted at each terminus with a leaving group, affords the desired product. Appropriate leaving groups include chlorine, bromine, methane sulfonate, and ^.-toluene sulfύnate. The R ¹ and R ² groups on the compound of Formula 21 may be substituted on any of the carbon atoms. Alternatively, protected forms of the R ¹ and R ² groups may be incorporated into 21, and then the actual R ¹ and R ² groups can be introduced after cyclization.

Scheme 20

OS0 ₂ (4-CH ₃ -Ph)

The anilines of formula Q-NH ₂ and isothiocyanates of formula Q-NCS used as reactants in the syntheses described above are known or can be prepared by well-known methods. For example, anilines where Q is Q-l, Q-4, and Q-6 can be prepared as described in U.S. 4,902,335, anilines where Q is Q-2 and Q-3 can be prepared as described in U.S. 5,053,071, and anilines where Q is Q-5 can be prepared by well known functional group transformations of known phenyl derivatives.

It is recognized that some reagents and reaction conditions described above for preparing compounds of Formulae I and II may not be compatible with certain functionalities present in the intermediates. In these instances, the incorporation of protection/deprotection sequences or functional group intercon versions 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 also recognize that compounds of Formulae I and II 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 fiillest extent. The following Examples are, therefore, to be construed as merely illustrative, and not limiting of the disclosure in any way whatsoever. *H NMR spectra are reported in ppm downfield from tetramethylsilane; s = singlet, d = doublet, m = multiplet, br s = broad singlet, dm = doublet of multiplets. EXAMPLE 1

Step A: Preparation of 2-f 4-chloro-2-fluoro-5-hvdroxyphenyl'. -4.7-dihvdro- 1 H- isoindole- 1.3C2H.-dione A mixture of 2.79 g (18.6 mmol) of l,4-cyclohexadiene-l,2-dicarboxylic anhydride and 3.00 g (18.6 mmol) of 5-amino-2-chloro-4-fluorophenol in 25 mL of acetic acid was warmed under reflux overnight. The mixture was then cooled to room temperature and concentrated under reduced pressure. The crude product was purified by flash chromatography over silica gel, eluting with a 1 :3 v:v mixture of ethyl acetate and n-hexane to give 4.68 g of the title product of Step A as a yellow solid. -Η NMR (CDC1 ₃ , 300 MHz) 6 3.1 (s, 4H), 5.6 (br s, IH), 5.9 (s, 2H), 6.9 (d, IH), 7.25 (d, IH). Step B: Preparation of 2-(4-chloro-2-fluoro-5-hydroxyphenyl)-4.5.6.7-tetrahydro-5- hydroxy- 1 H-isoindole- 1 ,3 (2H)-dione To a solution of 500 mg (1.61 mmol) of 2-(4-chloro-2-fluoro-5-hydroxyphenyl)- 4,7-dihydro-lH-isoindole-l,3(2H)-dione in 10 mL of tetrahydrofuran (TΗF) was added

1.94 mL of a IM solution of BH3 in THF at 0°C. The mixture was then stirred at the same temperature for 1 h. Then, the mixture was warmed to room temperature. A solution of 3.0 mL of 6N aqueous sodium hydroxide, 1.8 mL of water, and 2.1 mL of 30% aqueous hydrogen peroxide were added subsequently. The mixture was stirred at the same temperature for 4 h. The crude product was diluted with ethyl acetate. The organic layer was washed with water, dried (MgSO ₄ ) and concentrated under reduced pressure. The crude product was purified by flash chromatography over silica gel, eluting with a 1 :2 v:v mixture of ethyl acetate and n-hexane to give 62 mg of the title product of Step B, a compound of the invention, as a yellow oil. *H NMR (CDC1 ₃ , 300 MHz) δ 1.8 (br s, IH), 1.95 (m, 2H), 2.8-2.4 (m, 4H), 4.4 (m, IH), 5.85 (br s, IH), 6.9 (s, IH), 7.5 (s, IH).

EXAMPLE 2 Step A: Preparation of 2-(5-benzyloxy-4-chloro-2-fluorophenyl -5.8-dihydro- 1H- 11.2.41triazolor 1.2-αlpyridazine- 1 ,3(2H)-dione To a solution of 4.8 g of 4-chloro-2-fluoro-5-(phenylmethoxy)benzenamine

(19.1 mmol) in 30 mL of toluene was added 11.5 mL of a 2.0M solution of trimethylaluminum (23.0 mmol) in toluene at room temperature. The mixture was stirred at the same temperature for 10 min. Then, 5.22 g of diethyl l,2,3,6-tetrahydro-l,2- pyridazinedicarboxylate (22.9 mmol) was added at room temperature. The mixture was warmed under reflux overnight. The mixture was then cooled to room temperature and concentrated under reduced pressure. The crude product was purified by flash chromatography over silica gel, eluting with a 1 : 1 v:v mixture of ethyl acetate and rc-hexane to give 6.20 g of the title product of Step A as a yellow solid melting at 165-166°C. ^! Η NMR (CDCI3, 300 MHz) δ 4.2 (s, 4H), 5.1 (s, 2H), 6.0 (s, 2H), 7.0 (d, IH), 7.4 (m, 6H).

Step B: Preparation of 2-(5-benzyloxy-4-chloro-2-fluorophenyl -5.6.7.8-tetrahvdro- 6-hvdroxy- lH-H .2.41triazolor 1.2-α ^" |pyridazine-l .3(2H)-dione To a solution of 500 mg (1.33 mmol) of 2-(5-benzyloxy-4-chloro-2-fluorophenyl)- 5,8-dihydro-lH-[l,2,4]triazolo[l,2-α]pyridazine-l,3(2H)-dio ne in 10 mL of TΗF was added 1.6 mL of a IM solution of BΗ3 in THF at 0°C. The mixture was then stirred at the same temperature for lh. Then, the mixture was warmed to room temperature. A solution of 2.5 mL of 6N aqueous sodium hydroxide, then 1.5 mL of water, and finally 1.7 mL of 30% aqueous hydrogen peroxide were added subsequently. The mixture was stirred at 0°C for 4 h. The crude product was diluted with ethyl acetate. The organic layer was washed with water, dried (MgSO ₄ ) and concentrated under reduced pressure. The crude product was purified by flash chromatography over silica gel, eluting with a 1: 1 v.v mixture of ethyl acetate and n-hexane to give 415 mg of the title product of

Step B as a white solid melting at 138-140°C. *H NMR (CDCI3, 300 MHz) δ 2.0 (m, ^' 2H), 2.2 (s, IH), 3.8 (m, 4H), 4.2 (s, IH), 5.1 (s, 2H), 7.0 (d, IH), 7.4 (m, 6H). Step C: Preparation of 2-(5-benzyloxy-4-chloro-2-fluorophenyl -6-chloro-5.6.7.8- tetrahvdro- lH-f 1.2.41triazolor 1.2-alpyridazine- 1 ,3(2H)-dione A mixture of 212 mg (0.523 mmol) of 2-(5-benzyloxy-4-chloro-2-fluorophenyl)-

5,6,7,8-tetrahydro-6-hydroxy- lH-[ 1 ,2,4]triazolo[ 1 ,2-α]pyridazine- 1 ,3(2H)-dione (0.523 mmol), 76 μL of CC (0.784 mmol), and 206 mg of triphenylphosphine (0.784 mmol) in 8 mL of dichloromethane was warmed under reflux for 2h. The mixture was then concentrated under reduced pressure. The crude product was purified by flash chromatography over silica gel, eluting with a 1: 1 v:v mixture of ethyl acetate and n- hexane to give 200 mg of the title product of Step C, a compound of the invention, as a colorless oil. *Η NMR (CDCI3, 300 MHz) δ 2.3 (m, 2H), 3.5 (m, 2H), 3.9 (m, 2H), 4.4 (m, IH), 5.1 (s, 2H), 7.0 (d, IH), 7.4 (m, 6H).

EXAMPLE 3 Preparation of 5-bromo-2-r4-chloro-2-fluoro-5- 2-propynyloxy phenyll-

4.5.6.7-tetrahvdro-6-hydroxy- 1 H-isoindole- 1.3 f 2H)-dione and 5.6-dibromo-2-r4-chloro-2-fluoro-5-f2-propynyloxy)phenyll-4. 5.6.7- tetrahydro-lH-isoindole-1.3('2H.-dione To a solution of 960 mg (2.89 mmol) of 2-[4-chloro-2-fluoro-5-(2- propynyloxy )phenyl]-4,7-dihydro- 1 H-isoindole- 1 ,3 (2H)-dione in 15 mL of DMS O were added 771 mg (4.33 mmol) of NBS and 1.5 mL of water in sequence at room temperature. The mixture was then stirred at the same temperature for 30 min. The crude product was poured into 100 mL of water. The aqueous layer was extracted with three 100 mL portions of ethyl acetate. The organic layers were washed with water, dried (MgSO ₄ ) and concentrated under reduced pressure. The crude product was purified by flash chromatography over silica gel eluting with a 5:95 v:v mixture of methanol and dichloromethane to give 535 mg of the first title product of Example 3, a compound of the invention, as a white solid melting at 65°C. *Η NMR (CDCI3, 300 MHz) δ 2.5 (m, IH), 2.6-3.4 (m, 5H), 4.35 (m, 2H), 4.8 (s, 2H), 7.0 (d, IH), 7.3 (d, IH). In addition, 76 mg of the second title product of Example 3, a compound of the invention, was isolated as a white solid. *H NMR (CDC1 ₃ , 300 MHz) δ 2.6 (m, IH), 3.2 (d, 2H), 3.6 (2d, 2H), 4.7 (d, 2H), 4.8 (s, 2H), 7.0 (d, IH), 7.3 (d, IH).

EXAMPLE 4 Preparation of 5-bromo-2-r4-chloro-2-fluoro-5-f2-propynyloxy phenyl1-6- ^• fluoro-4.5.6.7-tetrahvdro-lH-isoindole-1.3(2H.-dione

To a solution of 995 mg (2.32 mmol) of 5-bromo-2-[4-chloro-2-fluoro-5-(2- propynyloxy)phenyl]-4,5,6,7-tetrahydro-6-hydroxy-lH-isoindol e-l,3(2H)-dione in 15 mL of dichloromethane was added 430 μL of DAST at 0°C. The mixture was stirred

at the same temperature for lh. The reaction mixture was then poured into 50 mL of cold water. The aqueous layer was extracted with three 50 mL portions of ethyl acetate. The organic layers were dried (MgSO ₄ ) and concentrated under reduced pressure. The crude product was purified by flash chromatography over silica gel eluting with a 1:4 v:v mixture of ethyl acetate and n-hexane to give 626 mg of the title product of Example 4, a compound of the invention, as a white solid melting at 135-136.5°C.

EXAMPLE 5 Preparation of 2-| -chloro-2-fluoro-5-(2-propynyloxy'.phenyll-5-fluoro- 4.5.6.7-tetrahvdro-lH-isoindole-1.3f2H)-dione

A mixture of 526 mg (1.22 mmol) of 5-bromo-2-[4-chloro-2-fluoro-5-(2- propynyloxy)phenyl]-6-fluoro-4,5,6,7-tetrahydro-lH-isoindole -l,3(2H)-dione, 822 mL of n-tributyltin hydride (3.06 mmol), and a catalytic amount of AIBN (2,2'-azobis[2-methylpropanenitrile]) in 20 mL of benzene was warmed under reflux for lh. The mixture was then concentrated under reduced pressure. The crude product was purified by flash chromatography over silica gel eluting with a 1 :4 v:v mixture of ethyl acetate and n-hexane to give 332 mg of the title product of Example 5, a compound of the invention, as a colorless oily film. ^l R NMR (CDC1 ₃ , 300 MHz) δ 1.8-2.0 (m, 2H), 2.3-2.9 (m, 5H), 4.8 (d, 2H), 5.22 (dm, J=50Hz, IH), 7.0 (d, IH), 7.3 (d, IH). By the procedures described herein the compounds of Formula Ip and IHi listed in

Tables 1 to 13 can be prepared. The following abbreviations have been used in Tables 1-13:

n = normal Ph = phenyl Me = methyl i = iso Pr = propyl

Ip Hh

T

TABLE S

Compounds of Formula Ip wherein Q = Q-2; Compounds of Formula Uh wherein Q = Q-2; R ⁵ = Cl; R ⁶ = H; R ⁷ = Me; W = O; R ⁵ = Cl; R ⁶ = H; R ⁷ = Me; W = O;

TAB

Compounds of Formula Ilh wherein Q = Q-5; R ⁶ = R ⁷ = CF ₃

Compounds of this invention will generally be used in formulation with an agriculturally suitable carrier comprising a liquid or solid diluent and/or a surfactant wherein the formulation is consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature. Useful formulations include liquids such as solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and/or suspoemulsions) and the like which optionally can be thickened into gels. Useful formulations further include solids such as dusts, powders, granules, pellets, tablets, films, and ^' the like which can be water-dispersible ("wettable") or water-soluble. Active ingredient can be (micro)encapsulated and further formed into a suspension or solid formulation; alternatively the entire formulation of active ingredient can be encapsulated (or "overcoated"). Encapsulation can control or delay release of the active ingredient.

Sprayable formulations can be extended in suitable media and used at spray volumes from about one to several hundred liters per hectare. High-strength compositions are primarily used as intermediates for further formulation.

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

Weight Percent

Water-Dispersible and Water-soluble 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, N-N-dialkyltaurates, lignin sulfonates, naphthalene sulfonate formaldehyde condensates, polycarboxylates, and polyoxyethylene/polyoxypropylene block copolymers. Solid diluents include, for example, clays such as bentonite, montmorillinite, 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-dimemylformamide, dimethyl sulfoxide, N-alkylpyrrolidone, ethylene glycol, polypropylene glycol, paraffins, alkylbenzenes, alkylnaphthalenes, oils of olive, castor, linseed, tung, sesame, corn, peanut, cotton-seed, soybean, rape-seed and coconut, fatty acid esters, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-

methyl-2-pentanone, and alcohols such as methanol, cyclohexanol, decanol and tetrahydrofurfuryl alcohol.

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

U.S. 4,172,714. Water-dispersible and water-soluble granules can be prepared as taught in U.S. 4,144,050, U.S. 3,920,442 and DE 3,246,493. Tablets can be prepared as taught in U.S. 5,180,587, U.S. 5,232,701 and U.S. 5,208,030. Films can be prepared as taught in GB 2,095,558 and U.S. 3,299,566. For further information regarding the art of formulation, see U.S. 3,235,361,

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

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

High Strength Concentrate

Compound 18 98.5% silica aerogel 0.5% synthetic amorphous fine silica 1.0%. Example B

Wettable Powder

Compound 18 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%.

calcium/magnesium bentonite 59.0%.

Tests results indicate that the compounds of the present invention are highly active preemergent and/or postemergent herbicides and/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, 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 barley, cotton, wheat, rape, sugarbeets, corn, soybeans, rice, and plantation crops such as sugarcane, citrus, grapes, coffee, oil palm, cocoa, fruit trees, nut trees, banana, plantain, rubber, pineapple and loblolly pine. Preferred is the method of using compounds of Formulae I and II such as citrus, sugarcane, coffee, oil palm, rubber, cocoa, grapes, fruit trees, and pineapple.

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. Compounds of this invention can be used alone or in combination with other commercial herbicides, insecticides or fungicides. A mixture of one or more of the following herbicides with a compound of this invention may be particularly useful for weed control. Examples of other herbicides with which compounds of this invention can be formulated are: acetochlor, acifluorfen and its sodium salt, acrolein (2-propenal), alachlor, ametryn, amidosulfuron, amitrole, ammonium sulfamate, anilofos, asulam, atrazine, azimsulfuron, benazolin, benazolin-ethyl, benfluralin, benfuresate, bensulfuron-methyl, bensulide, bentazone, bifenox, bromacil, bromoxynil, bromoxynil octanoate, butachlor, butralin, butylate, chlomethoxyfen, chloramben, chlorbromuron,

chloridazon, chlorimuron-ethyl, chlomitrofen, chlorotoluron, chlorpropham, chlorsulfuron, chlorthal-dimethyl, cinmethylin, cinosulfiiron, 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 dimethylammonium, potassium and sodium salts, dichlobenil, dichlorprop, diclofop-methyl, difenzoquat metilsulfate, diflufenican, dimepiperate, dimethylarsinic acid and its sodium salt, dinitramine, diphenamid, diquat dibromide, dithiopyr, diuron, DNOC, endothal, EPTC, esprocarb, ethalfluralin, ethametsulfiiron-methyl, ethofumesate, ethyl cc ,2-dichloro-5-[4-(difluoromethyl)-4,5-dihydro-3-methyl-5-oxo -lH-l,2,4-triazol-l-yl]-4- fluorobenzenepropanoate (F8426), 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, fluridone, flurochloridone, fluroxypyr, fomesafen, fosamine-ammonium, glufosinate, glufosinate- ammonium, glyphosate, glyphosate-isopropylammonium, glyphosate-sesquisodium, glyphosate-trimesium, halosulfuron-methyl, haloxyfop-etotyl, haloxyfop-methyl, hexazinone, imazamethabenz-methyl, imazapyr, imazaquin, imazaquin-ammonium, imazethapyr, imazethapyr-ammonium, imazosulfuron, ioxynil, ioxynil octanoate, ioxynil-sodium, isoproturon, isouron, isoxaben, lactofen, lenacil, linuron, maleic hydrazide, MCPA and its dimethylammonium, potassium and sodium salts, MCPA-isoctyl, mecoprop, mecoprop-P, mefenacet, mefluidide, metam-sodium, methabenzthiazuron, methyl [[2-chloro-4-fluoro-5-[(tetrahydro-3-oxo- 1H,3H- [l,3,4]thiadiazolo[3,4- ]pyridazin-l-ylidene)amino]phenyl]thioacetate (KIΗ 9201), methylarsonic acid and its calcium, monoammonium, monosodium and disodium salts, methyl [[[l-[5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrophenyl] -2- methoxyethyhdene]amino]oxy]acetate (AKΗ-7088), methyl 5-[[[[(4,6-dimethyl-2- py_ rύdinyl)ami_no]carbonyl]amino]sulfonyl]-l-(2-pyridinyl)-lH- pyrazole-4-carboxylate (NC-330), metobenzuron, metolachlor, metoxuron, metribuzin, metsulfuron-methyl, molinate, monolinuron, napropamide, naptalam, neburon, nicosulfuron, norflurazon, oryzalin, oxadiazon, oxyfluorfen, paraquat dichloride, pebulate, pendimethalin, phenmedipham, picloram, picloram-potassium, pretilachlor, primisulfuron-methyl, prometon, prometryn, propachlor, propanil, propazine, propham, propyzamide, prosulfuron, pyrazolynate, pyrazosulfuron-ethyl, quinclorac, quizalofop-ethyl, quizalofop-P-ethyl, quizalofop-P-tefuryl, rimsulfuron, sethoxydim, siduron, simazine, sulfentrazone, sulfometuron-methyl, TCA, TCA-sodium, tebuthiuron, terbacil, terbuthylazine, terbutryn, thenylchlor, thifensulfuron-methyl, thiobencarb, tralkoxydim,

tri-allate, triasulfuron, tribenuron-methyl, triclopyr, triclopyr-butotyl, triclopyr-triethylammonium, 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 management of resistant weeds.

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 a compound(s) of this invention is applied at rates from about 0.001 to 20 kg/ha with a preferred rate range of 0.004 to 1.0 kg/ha. One skilled in the art can easily determine application rates necessary for the desired level of weed control.

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-C for compound descriptions.

Index Table A

^a This column indicates the stereochemistry of the compound. Trans and cis is the relative orientation between Rl and R ² . ND indicates that the relative stereochemistry was not determined and the compound may be a mixture of diastereomers. A dash (--) indicates that only one diastereomer is possible since at least one of R or R ² is hydrogen. All compounds are racemic.

^b Analysis: Calcd: C 56.87, H 3.75, N 4.74, Cl 11.99, F 6.42; Found: C 51.33, H 4.49, N 3.89, Cl l 1.09, F 5.82.

* See Index Table C for ^! H NMR data.

Index Table B

where q-1 = 0 or 1

^a This column indicates the stereochemistry of the compound. Trans and cis is the relative orientation between R and R ² . A dash (--) indicates that only one diastereomer is possible since at least one of Rl or R ² is hydrogen. All compounds are racemic.

^b Compound contains approximately 47% by weight of the intermediate 2-[4-chloro-2- fluoro-5-hydroxyphenyl]-5,8-dihydro- lH-[ 1 ,2,4]triazolo[ 1 ,2- ]pyridazine- 1 ,3(2H)- dione.

* See Index Table C for ^J Η NMR data.

Index Table C

Cmpd No. IH NMR Data CCDC1 ₃ solution unless otherwise indicated") ³ 4 δ 1.80 (s, IH), 2.00 (m, 2H), 2.46-2.80 (m, 4H), 4.35 (m, IH), 5.9 (s, IH), 6.90 (s, IH), 7.60 (s.lH). δ 1.8 (m, 2H), 2.4 (s, 3H), 2.4-2.8 (m, 4H), 4.3 (m, IH), 7.1 (d, IH) 7.4 (d, IH).

8 δ 2.6 (m, IH), 2.9 (d, 2H), 3.2 (d, 2H), 3.6 (s, 2H), 4.75 (d, 2H), 6.95 (d, IH), 7.3 (d, IH). δ 2.25 (s, 3H), 2.4 (s, 3H), 2.7-3.05 (m, 4H), 3.4 (m, IH), 5.12 (dm, IH), 7.15 (d, IH), 7.4 (d, IH).

10 (in CD ₃ C(=0)CD ₃ ) δ 2.9 (m, 2H), 2.3-2.7 (m, 4H), 2.9 (m, IH), 3.1 (m, IH), 4.3 (m, IH), 4.9 (s, 2H), 7.3 (d, IH), 7.5 (d, IH).

11 δ 2.2 (s, IH), 2.5-3.2 (m, 4H), 4.2 (m, 2H), 5.1 (s, 2H), 6.85 (d, IH), 7.3-7.5 (m, 6H).

12 δ 2.2 (br s, IH), 2.6 (m, IH), 2.6-3.1 (m, 4H), 4.4 (m, IH), 4.8 (d, 2H), 4.95 (dq, J=55Hz, IH), 7.0 (d, IH), 7.3 (d, IH).

13 δ 2.4-3.1 ( , 5H), 3.9-4.4 (m, 2H), 4.7 (s, 2H), 5.0-5.2 (m, IH) 7.0 (d, IH), 7.3 (d, IH).

14 δ 2.1 (s, 3H), 2.6 (m, IH), 2.7-2.95 (m, 4H), 4.8 (s, 2H), 5.1 (dm, J=55Hz, IH), 5.4 (m, IH), 7.0 (d, IH), 7.3 (d, IH).

15 δ 3.0-3.6 (m, 4H), 4.6-4.8 (m, 2H), 5.1 (s, 2H), 6.9 (d, IH), 7.2-7.5 (m, 6H).

18 δ 1.8-2.0 (m, 2H), 2.3-2.9 (m, 5H), 4.8 (d, 2H), 5.22 (dm, J=50Hz, IH), 7.0 (d, IH), 7.3 (d, IH).

19 δ 2.4 (m, 3H), 3.2 (m, 2H), 3.5-3.6 (m, 2H), 4.7 (m, 2H), 7.2 (d, IH), 7.4 (d, IH).

20 δ 2.6-2.7 (m, 2H), 2.9-3.2 (m, 2H), 3.4 (m, IH), 4.3 (m, 2H), 5.9 (s, IH), 6.9 (d, IH), 7.25 (d, IH).

22 δ 2.6 (m, IH), 3.2 (d, 2H), 3.6 (dd, 2H), 4.7 (d, 2H), 4.8 (s, 2H), 7.0

(d, IH), 7.3 (d, IH).

25 δ 2.6 (m, 2H), 2.9-3.4 (m, 3H), 4.3 (m, 2H), 5.1 (s, 2H), 6.9 (d, IH), 7.3-7.5 (m, 6H).

26 δ 1.8-2.6 (m, 6H), 2.7 (br s, IH), 4.8 (m, IH), 5.6 (br s, IH), 6.9 (d, IH), 7.2 (d, IH).

27 δ 2.8 (d, 2H), 3.1 (d, 2H), 3.6 (s, 2H), 6.9 (d, IH), 7.2 (d, IH), 8.1 (s, IH).

28 (in CD ₃ C(=0)CD ₃ ) δ 1.9 (m, 2H), 2.1 (m, IH), 2.3-2.8 (m, 4H), 3.9 (s, 3H), 4.2 (m, IH), 7.2 (d, IH), 7.45 (d, IH).

30 δ 2.6 (m, IH), 3.6 (s, 2H), 3.9-4.0 (m, 2H), 4.1-4.3 (m, 2H), 4.8 (s, 2H), 7.0 (s, IH), 7.6 (s, IH).

31 δ 3.6 (s, 2H), 3.9 (d, 2H), 4.1-4.25 (d, 2H), 5.1 (s, 2H), 6.9 (d, IH), 7.2-7.5 (m, 6H).

32 δ 2.3 (s, 3H), 3.9-4.2 (m, 5H), 4.9 (dm, J=55Hz, IH), 5.9 (s, IH), 7.0 (d, IH), 7.3 (d, IH).

35 (in CD ₃ S(0)CD ₃ ) δ 3.9 (m, 3H), 4.05 (m, 2H), 4.4 ( , IH), 5.2 (s, 2H), 6.2 (d, IH), 7.4-7.6 (m, 6H), 7.8 (d, IH).

36 δ 2.3 (m, 2H), 3.5 (m, 2H), 3.9 (m, 2H), 4.4 (m, IH), 5.1 (s, 2H), 7.0 (d, IH), 7.4 (m, 6H).

37 δ 1.8 (br s, IH), 1.95 (m, 2H), 2.8-2.4 (m, 4H), 4.4 (m, IH), 5.85 (br s, IH), 6.9 (s, IH), 7.5 (s, IH).

^a -Η NMR data are in ppm downfield from tetramethylsilane. Couplings are designated by (s)-singlet, (d)-doublet, (q)-quartet, (m)-multiplet, (br s)-broad singlet, (dq)-doublet of quartets, (dm)-doublet of multiplets.

TEST A

Seeds of barnyardgrass (Echinochloa crus-galli), cocklebur (Xanthium pensylvanicum), crabgrass (Digitaria spp.), downy brome (Bromus tectorum), giant foxtail (Setariafaberii), morningglory (Ipomoea spp.), sorghum (Sorghum bicolor), velvetleaf (Abutilon theophrasti) and wild oat (Avenafatua) were planted into a sandy loam soil and treated preemergence with test chemicals formulated in a non-phytotoxic solvent mixture which includes a surfactant. At the same time, these crop and weed species were also treated postemergence with test chemicals formulated in the same manner.

Plants ranged in height from two to eighteen cm and were in the two to three leaf stage for the postemergence treatment. Treated plants and untreated controls were maintained in a greenhouse for approximately eleven days, after which all treated plants were compared to untreated controls and visually evaluated for injury. Plant response ratings, summarized in Table A, are based on a 0 to 10 scale where 0 is no effect and 10 is complete control. A dash (-) response means no test results.

Seeds of barley (Hordeum vulgare), barnyardgrass (Echinochloa crus-galli), blackgrass (Alopecurus myosuroides), bush bean (Phaseolus vulgaris), cheatgrass (Bromus secalinus), chickweed (Stellaria media), cocklebur (Xanthium pensylvanicum), corn (IZea mays), cotton (Gossypium hirsutum), crabgrass (Digitaria sanguinalis), downy brome (Bromus tectorum), giant foxtail (Setariafaberii), lambsquarters (Chenopodium album), morningglory (Ipomoea hederacea), rape (Brassica napus), rice (Oryza sativa), sicklepod (Cassia tora), 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 includes 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 two to eighteen cm (one to four leaf stage) for postemergence treatments. 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.

TEST C The compounds evaluated in this test were formulated in a non- phytoxic solvent mixture which include a surfactant and applied to the soil surface before plant seedlings emerged (preemergence application), to water that covered the soil surface (flood application), and to plants that were in the one-to-four leaf stage (postemergence application). A sandy loam soil was used for the preemergence and postemergence tests, while a silt loam soil was used in the flood test. Water depth was approximately 2.5 cm for the flood test and was maintained at this level for the duration of the test.

Plant species in the preemergence and postemergence tests consisted of barnyardgrass (Echinochloa crus-galli), barley (Hordeum vulgare), bedstraw (Galium aparine), blackgrass (Alopecurus myosuroides), chickweed (Stellaria media), cocklebur (Xanthium pensylvanicum), corn (Zea mays), cotton (Gossypium hirsutum), crabgrass (Digitaria sanguinalis), downy brome (Bromus tectorum), giant foxtail (Setariafaberii), johnsongrass (Sorghum halpense), lambsquarters (Chenopodium album), morningglory (Ipomoea hederacea), pigweed (Amaranthus retroflexus), rape (Brassica napus), ryegrass (Lolium multiflorum), soybean (Glycine max), speedwell (Veronica persica), sugar beet (Beta vulgaris), velvetleaf (Abutilon theophrasti), wheat (Triticum aestivum), wild buckwheat (Polygonum convolvulus), and wild oat (Avenafatua). All plant species were planted one day before application of the compound for the preemergence portion of this test. Plantings of these species were adjusted to produce plants of appropriate size for the postemergence portion of the test. Plant species in the flood test consisted of rice (Oryza sativa), umbrella sedge (Cyperus difformis), duck salad (Heteranthera limosa), barnyardgrass (Echinochloa crus-galli) and Late watergrass (Echinocloa oryzicola.) grown to the 1 and 2 leaf stage for testing. All plant species were grown using normal greenhouse practices. Visual evaluations of injury expressed on treated plants, when compared to untreated controls, were recorded approximately fourteen to twenty one days after application of the test compound. Plant response ratings, summarized in Table C, were recorded on a 0 to 100 scale where 0 is no effect and 100 is complete control. A dash (-) response means no test result.

TEST D Seeds, rhizomes, or plant parts of alexandergrass (Brachiaria plantaginea), alfalfa (Medicago sativa), annual bluegrass (Poa annua), bermudagrass (Cynodon dactylon), broadleaf signalgrass (Brachiaria platyphylia), common purslane (Portulaca oleracea), common ragweed (Ambrosia artemisiifolia), dallisgrass (Paspalum dilatatum), goosegrass (Eleusine indica), guineagrass (Panicum maximum), itchgrass (Rottboellia cochinchinensis), johnsongrass (Sorghum halepense), large crabgrass (Digitaria sanguinalis), P.J. legume (Pueraria javanica), peanut (Arachis hypoagaea), pitted morningglory (Ipomoea lacunosa), purple nutsedge (Cyperus rotundus), sandbur

(Southern sandbur), smooth crabgrass (Digitaria ischaemum), sourgrass (Panicum Texanum) and yellow nutsedge (Cyperus esculentus) were planted into greenhouse pots containing greenhouse planting medium. Each pot contained only one plant species.

The test compound was formulated in a non-phytotoxic solvent mixture which includes a surfactant and applied preemergence and/or postemergence to the plants. Preemergence appUcations were made within one day of planting the seeds or plant parts. Postemergence applications were applied when the plants were in the two to four leaf stage (three to twenty cm). Untreated control plants and treated plants were placed in the greenhouse and visually evaluated for injury at 14 to 28 days after herbicide application. Plant response ratings, summarized in Table D, are based on a 0 to 100 scale where 0 is no injury and 100 is complete control. A dash (-) response indicates no test result.

TABLE D COMPOUND

Rate 0250 g/ha 1 18

PREEMERGENCE

Alexandergrass 100

Alfalfa Var. 30

Ann Bluegrass

Bermudagrass

Brdlf Sgnlgrass

Cmn Purslane

Cmn Ragweed

Dallisgrass

Goosegrass

Guineagrass

Itchgrass

Johnson grass

Large Crabgrass

P J Legume

Peanuts

Pit Morninglory

Purple Nutsedge

Sandbur

Smooth Crabgras

Sourgrass

Texas Panicum Yellow Nutsedge

TEST E Plant species in the preemergence tests consisted of barnyardgrass (Echinochloa crus-galli), bedstraw (Galium aparine), bluegrass (Poa trivialis), cassia (Cassia tora), cheat grass (Bromus secalinus), cocklebur (Xanthium pensylvanicum), corn (Zea mays), crabgrass (Digitaria sanguinalis), curly indigo (Aeschynomene virginica), giant foxtail (Setariafaberii), ji sonweed (Datura stramonium), johnsongrass (Sorghum halpense), morningglory (Ipomoea hederacea), mustard (Sinapis arvensis), nutsedge (Cyperus rotundus), pig weed (Amaranthus retroflexus), rice (Oryza sativa), sorghum (Sorghum bicolor), soybean (Glycine max), sugar beet (Beta vulgaris), teaweed (Sida Spinosa), velvetleaf (Abutilon theophrasti), wheat (Triticum aestivum) and wild oat (Avenafatua). All plant species were planted one day before application of the compound. Compounds evaluated in this test were formulated in a non-phytotoxic solvent mixture which includes a surfactant and applied to the soil surface before plant seedlings emerged (preemergence application).

All plant species were grown using normal greenhouse practices. Visual evaluations of injury expressed on treated plants, when compared to untreated controls, were recorded approximately fourteen to twenty one days after application of the test compound. Plant response ratings, summarized in Table E, were recorded on a 0 to 10 scale where 0 is no effect and 10 is complete control. A dash (-) response means no test result.

The compounds evaluated in this test were formulated in a non-phytotoxic solvent mixture which includes a surfactant and applied to plants that were in the one-to- four leaf stage (postemergence application).

Plant species in the postemergence tests consisted of alfalfa (Medicago sativa), barnyardgrass (Echinochloa crus-galli), cassia (Cassia tora), cocklebur (Xanthium pensylvanicum), coffee weed (Daubentonia texana pierce), corn (Zea mays), cotton (Gossypium hirsutum), crabgrass (Digitaria sanguinalis), giant foxtail (Setariafaberii), jimsonweed (Datura stramonium), morningglory (Ipomoea hederacea), nutsedge (Cyperus rotundus), rice (Oryza sativa), sorghum (Sorghum bicolor), soybean (Glycine max), velvetleaf (Abutilon theophrasti), wheat (Triticum aestivum) and wild oat (Avena fatua).

All plant species were grown using normal greenhouse practices. Visual evaluations of injury expressed on treated plants, when compared to untreated controls,

were recorded approximately fourteen to twenty one days after application of the test compound. Plant response ratings, summarized in Table F, were recorded on a 0 to 10 scale where 0 is no effect and 10 is complete control. A dash (-) response means no test result.

TEST G Compounds were evaluated under various conditions for their effectiveness in controlling the growth of nutsedge (Cyperus rotundus) in this test. The test compound was applied in a non-phytotoxic solvent (generally water) to nutsedge tubers which had been previously seeded into pots containing a sandy loam soil and allowed to grow for several weeks, these were treated as the post-emergence treatment. Additionally, freshly prepared pots were seeded with tubers. These treatments constituted the preemergence treatment where the covering soil was treated with the compound. In another treatment, the exposed tubers were allowed to contact the sprayed test compound directly. In the final treatment, the soil used to cover the tubers was placed in a bag and treated with the

appropriate amount of the test compound. The contents of the bag were then mixed (incorporated) and placed on the surface of the seeded pots. All treatments were maintained in the greenhouse where visual ratings were made at two and four weeks after application of the test compound. Plant response ratings, summarized in Table G, were recorded on a 0 to 10 scale where 0 is no effect and 10 is complete control. A dash (-) response means no test result.

TABLE G COMPOUND TABLE G COMPOUND Rate 2 g/h 1 Rate 2 g/h 1 Direct Tuber Spray 2 weeks Direct Tuber Spray 4 weeks Nutsedge 0 Nutsedge 2

TEST H This test evaluated the effects of test compounds on monocot weeds grown in association with cereal crops such as rice, wheat or barley. In the current test, compounds were applied to the foliage of barnyardgrass (Echinochloa crus-galli) and Japonica rice (Oriza sativa) or to the surface of pots recently seeded with the test species. All test compounds were first formulated in a non-phytotoxic solvent mixture which includes a surfactant and sprayed over the foliage or soil surface to the test unit. After application of the test compound, the plants were maintained in the greenhouse under standard conditions until such time as they were visually evaluated. Plant response ratings, summarized in Table H, were recorded on a 0 to 10 scale where 0 is no effect and 10 is complete control. A dash (-) response means no test result.

TABLE H COMPOUND TABLE H COMPOUND Rate 2000 g/h 2 Rate 500 g/h 1 PREEMERGENCE POSTEMERGENCE Barnyardgrass 6 Barnyardgrass 7 Japonica Rice 0 Japonica Rice 2 Rice 0 Rice

TABLE H COMPOUND TABLE H COMPOUND Rate -250 g/h 1 Rate 125 g/h 1 PREEMERGENCE POSTEMERGENCE Barnyardgrass 2 Barnyardgrass 0 Japonica Rice 0 Japonica Rice 0 Rice 0 Rice 0

TABLE H COMPOUND Rate 125 g/h 1 PREEMERGENCE Barnyardgrass 0 Japonica Rice 0 Rice 0