TITLE HERBICIDAL OXATRICYCLIC ETHERS CROSS-REFERENCE TO RELATED APPLICATION 5 This is a continuation-in-part of copending application U.S. Serial

No. 07/702,997 filed May 20, 1991.

BACKGROUND OF THE INVENTION This invention relates to certain herbicidal ethers, agriculturally suitable compositions thereof, and a method for their use as broad 10 spectrum preemergent or postemergent herbicides.

New compounds effective for controlling the growth of undesired vegetation are in constant demand. In the most common situation, such compounds are sought to selectively control the growth of weeds in useful crops such as cotton, rice, corn, wheat and soybeans, to name a few. 15 Unchecked weed growth in such crops can cause significant losses, reducing profit to the farmer and increasing costs to the consumer. In other situations, herbicides are desired which will control all plant growth. Examples of areas in which complete control of all vegetation is desired are areas around railroad tracks, storage tanks and industrial 20 storage areas. There are many products commercially available for these purposes, but the search continues for products which are more effective, less costly and environmentally safe.

U.S. 4,670,041 discloses herbicidal compounds of the formula:

* wherein, inter flϋa ^*

Y is (-CR ⁵ R ⁶ -) _n in which n is 0, 1 or 2; and

1

R ⁵ and R ⁶ (in part) form an alkylene group containing 4 or 5 carbon 30 atoms.

U.S. 4,828,603 discloses herbicidal compounds of the formula:

wherein, inter »K» ^*

Xis O, S, NR or CH ₂ ; and Yis (in part) CH2.

SUMMARY OF THE INVENTION This invention pertains to compounds of Formulas I through XV including stereoisomers, suitable compositions containing them and their use as broad spectrum preemergence and postemergence herbicides

XI: XII:

wherein: n is 2, 3 or 4; mis 3, 4 or 5; p is 2 or 3;

R ¹ is straight chain C ₁ -C ₃ alkyl; R ² is H, C C ₄ alkyl, C ₂ -C alkenyl or C ₂ -C ₄ alkynyl; R3 and R ⁴ are independently H, C ₁ -C ₄ alkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl or C _r C ₃ alkyl substituted with OCH ₃ or OCH ₂ CH ₃ ; R ⁵ and R ⁶ are independently H, OCH ₃ or C ₁ -C ₂ alkyl; Qis CH Wor

q and r are independently 0-2;

R7 is H, halogen, C _r C ₃ alkyl, OR ⁸ , SR ⁸ or CN;

R ⁸ is C _r C ₃ alkyl or C C ₃ haloalkyl;

Z is CH ₂ , NR ⁹ , O, S or may be CH and taken to form a double bond with an adjacent carbon; R9 is H or C _r C ₃ alkyl; W is phenyl optionally substituted with 1-3 substituents selected from halogen, C _r C ₃ alkyl, C C ₃ alkoxy, OH, CN, C _r C ₃ haloalkyl, C -C ₃ haloalkoxy, Cι-C ₃ alkylthio, C2-C4 alkenyl and C2-C4 alkynyl; or W is 5-, 6- or 7-membered heterocyclic ring containing 0-2 nitrogens, 0-2 oxygens or 0-2 sulfurs, each ring optionally substituted with 1-2 substituents selected from halogen, CH ₃ and OCH ₃ ; provided that

1) the sum of q and r is 0-2;

2) if the sum of q and r is 0 then Z is CH2; and 3) if W is a heterocycle then the total number of heteroatoms contained within the heterocyclic rings is 3 or less.

Representative examples of the aforementioned heterocycles included in the definition of W include but are not limited to pyrrole, furan, thiophene, tetrahydropyran, tetrahydrofuran, isoxazole, oxazole, pyrazole, imidazole, thiazole, pyridine and pyrazine.

In the above definitions, the term "alkyl", used either alone or in compound words such as "haloalkyl" or "alkylthio", includes straight chain or branched alkyl, e.g., methyl, ethyl, n-propyl, isopropyl or the different butyl isomers.

"Alkoxy", "alkenyl" and "alkynyl" includes straight chain or branched isomers, e.g., ethoxy, n-propyloxy, isopropyloxy, 1-propenyl, 2-propenyl and 3-propenyl.

"Halogen", either alone or in compound words such as "haloalkyl", means 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 CH ₂ CH ₂ F, CF ₂ CF ₃ and CH ₂ CHFC1.

The compounds of the invention which are preferred for either their biological activity and/or ease of synthesis are:

1. Compounds of Formulas I, II, HI, V or VUJ wherein:

W is phenyl optionally substituted by 1-2 substituents selected from F, Cl, Br, CH ₃ and OCH ₃ ; or W is tetrahydropyran, tetrahydrofuran, thiophene, isoxazole, pyridine or pyrazine, each ring optionally substituted with 1-2 substituents selected from F, Cl, Br, CH and OCH ₃ ; Qis CH ₂ or

Q-7 Q-8 Q-9

Q-10 Q-ll Q-12

Q-13 Q-14 -15

R ⁵ and R ⁶ are independently H or C1-C2 alkyl.

2. Compounds of Preferred 1 wherein:

R ² is H, C _r C ₃ alkyl, C -C ₃ alkenyl or C ₂ -C ₃ alkynyl.

Compounds of Preferred 2 wherein:

R ³ is H, C C ₃ alkyl, C3-C ₄ alkenyl or C ₃ -C ₄ alkynyl; R ⁴ is H, C _r C ₃ alkyl, C ₃ -C ₄ alkenyl or C ₃ -C alkynyl.

4. Compounds of Preferred 3 wherein:

Q is CH ₂ W or Q-l, Q-3, Q-4, Q-6, Q-7, -8 or Q-15;

R ^ε and R ⁶ are independently H;

W is phenyl optionally substituted with 1-2 substituents selected from F, Cl, Br and CH ₃ ; tetrahydrofuran; thiophene optionally substituted with Cl or Br; or pyridine.

5. Compounds of Preferred 4 wherein:

R ¹ is CH ₃ or CH ₂ CH ₃ ;

R ² is H, CH ₃ , CH ₂ CH ₃ or allyl; and

R ³ and R ⁴ are H.

6. Compounds of Preferred 5 wherein the formula is Formula I.

7. Compounds of Preferred 5 wherein the formula is Formula H.

8. Compounds of Preferred 5 wherein the formula is Formula HI.

9. Compounds of Preferred 5 wherein the formula is Formula V.

10. Compounds of Preferred 5 wherein the formula is Formula VHL

Compounds of the invention which are specifically preferred for their biological activity and/or ease of synthesis are the compoimds of Preferred 5 which are:

(2α,3β,4aβ,5α,7aβ)-3-[(2-fluorophenyl)methoxy]octahy dro-2,4a- dimethyl-2,5-methanocyclopenta-[b]pyran;

(2α,3β,4aβ,5α,9aβ)-3-[(2,6-d fluorophenyl)methoxy]-decahydro-2- methyl-2,5-methanocyclohepta[b]pyran;

(2α,3β,4aβ,5α,7aβ)-3-[(2-fluorophenyl)methoxy]octahy dro-2- methyl-2,5-methanocyclopenta[b]pyran;

(2α,3β,4aβ,5α,9aβ)-3-[(2-fluorophenyl)methoxy]decahy dro-2- methyl-2,5-methanocyclohepta[b]pyran;

(2α,3β,4aβ,5α,7aβ)-octahydrc-2,4a-c_lmetiιyl-3-(phe nylnιetho-ςr)- 2,5-methanocyclopenta[b]-pyran;

(2α,3β,4aβ,5α,7aβ)-3-[(2-chlorophenyl)methoxy]octahy drc~2,4a- dimethyl-2,5-methanocyclopenta-[b]pyran; and

(2α,3β,4aβ,5α,7aβ)-octahydro-2,4a-dimethyl-3-[(2- niethylphenyl)met^03Qr]-2,5-methanocyclopenta[b]pyran.

Compounds of Formula I-XV that have the QO group svn with respect to the oxygen-containing bridge are usually more herbicidally active than the SOU form. The present invention contemplates all of the

herbicidally active forms resulting from synthesis and from deliberately created mixtures.

Compositions suitable for controlling the growth of undesired vegetation are also contemplated as within the scope of this invention. Such compositions comprise an efifective amount of any of the compounds disclosed herein and at least one of the following: surfactant, solid diluent or liquid diluent.

Methods for controlling the growth of undesired vegetation are similarly considered to be within the scope of the invention. These methods comprise applying to the locus to be protected an efifective amount of any of the compounds disclosed herein. Of particular importance is the method wherein the locus to be protected is rice, corn, soybeans or cereals.

DETAILED DESCRIPTION OF THE INVENTION

The compounds I-XH of the invention are prepared by treating the appropriately substituted oxatricycloalkanol (Ia-XHa wherein Q is H) with a compound of the formula QX in which X is a halogen atom or a mesyloxy or a tosyloxy group or the like. This reaction is carried out, as shown in Scheme 1, in the presence of a strong base, such as an alkali metal hydride, in an inert solvent, such as ethers, aromatic hydrocarbons, dimethylformamide and the like. Suitable temperatures for the reaction are preferably from 20°C to 100°C. The product ethers are recovered and isolated by conventional techniques. ≤£U£____

QX

Ia - XIIa * ^• I - XII base

The alkylating agents QX are prepared in the conventional manners known to those skilled in the art from the alcohols QOH.

The alcohols, QOH, are generally known in the art and are most conveniently prepared through metal hydride (e.g., sodium borohydride) reduction of the corresponding carbonyl compounds or the corresponding ketones which can be derived by Friedel-Crafts type cyclization of

derivatives of phenylalkylcarboxylic acid, phenoxyalkylcarboxylic acids, benzyloxyalkylcarboxylic acids, phenylthioalkylcarboxyhc acids, and benzylthioalkylcarboxylic acids. Details may be found in a) T. Laird in Comprehen-rfyg r an in. Chemistry. D. Barton and W. D. Ollis, ed., Yd, 1, pp. 1165-1168, Pergamon Press, New York (1979); b) M.H. Palmer and N. M. Scollick, J. Chem. Soc. C. (1968), 2833; c) C. E. Dolgliesck and Mann, J. Chem. Soc. (1945), 893; d) C. D. Hurd and S. Hayao, J, Am, Chem, Soc.. (1954), 2S, 4299 and 5056; and e) R.Lesser, Chem. Ber. (1923), jgg, 1642. Alternatively, the compounds of Formulas I-X may be prepared by the coupling procedure described in Scheme 2, which is used in cases where the standard Williamson ether synthesis proves problematic. This procedure uses a Lewis acidic metal oxide wherein the metal can remove the halide ion by forming an insoluble precipitate. For example, silver (I) oxide can be used and the silver halide is the co-product. Alternative metal oxides that may be used are HgO, CaO, MgO. N,N-Dimethyl- formamide and ethereal solvents, such as diethyl ether, tetrahydrofuran, dioxane, or 1,2-dimethoxyethane are the preferred solvents. Other solvents likely to provide good yields include dipolar aprotic solvents like dimethyl sulfoxide, acetone, and N,N'-dimethylpropyleneurea.

Scheme 2

The oxatricycloalkanols Ia-XIla can be obtained generally by the route shown in Scheme 3. This route comprises epoxidation of unsaturated bicyclic alkanols Ib-XQb (Scheme 4) by treatment with a peroxyacid or other epoxidizing agent known in the art, with or without isolation of the intermediate epoxyalkanol, and cyclization by treatment with a protic or Lewis acid in an inert solvent.

Scheme 3

1) Epo-ridize

Ib - XIIb •- Ia - XIIa

2) H ^® or Lewis acid

The unsaturated bicyclic alkanols Ib-XIIb are generally known in the art. They can be prepared directly or from appropriate aldehydes, ketones or carboxylic acids or esters or the like by methods known in the art or obvious modifications thereof.

Scheme 4

Vll

lib: Vlllb:

Illb: IXb

Xllb:

The compounds of ITI-XV of the invention can be prepared by treating the appropriately substituted oxabicycloalkanediols XHIa-XVa with a protic acid, such as methanesulfonic acid or para-toluenesulfonic acid, or with a Lewis acid, such as aluminum trichloride, zinc dichloride, or boron trifluoride, in an inert solvent, such as halogenated hydrocarbons, aromatic hydrocarbons and the like. Suitable temperatures for the reaction are preferably from -78°C to 100°C. The reaction is carried out as shown in Schemes 5-7 and the product ethers are recovered and isolated by conventional techniques.

Scheme 5

(XUIa)

Scheme β

(XlVa)

Scheme 7

(XVa)

Alternatively, some of the compounds XIH-XV can be prepared from the appropriately substituted halooxatricycUc ethers (XQIb-XVb, wherein R ⁵ or R ⁶ is Br or I) as shown in Scheme 8. The halogen atom of XQIb-XVb is replaced by OCH3 by treatment with methanol in the

presence of a silver salt or by treatment with a metal methoxide in a solvent such as methanol or N^-dimethylformamide, optionally in the presence of a catalyst such as a copper salt or a silver salt, or the halogen atom is replaced by an alkyl group by treatment with a metal alkylcuprate or similar reagent in a solvent such as tetrahydrofuran, or the halogen atom is replaced by H by reduction. This reduction can be accomplished by methods known in the art including treatment with a trialkyltin hydride in an inert solvent such as benzene or toluene in the presence of a radical initiator such as benzoyl peroxide, preferably at temperatures of 20°C to 110°C, or treatment with lithium aluminum hydride in an ethereal solvent, such as tetrahydrofuran or 1,2-dimethoxy- ethane, preferably at temperatures of 20°C to 100°C, or treatment with hydrogen gas in the presence of a metal catalyst, such as platinum or palladium, in an inert solvent. Scheme 8

halide displacement

Non-limiting illustrations of the preparation of oxabicyclo- alkanediols XIHa-XVa are shown in Schemes 9 and 10.

The compounds of Formula XTEIa are synthesized as shown in Scheme 9. Readily available haloaryl ethers 1 is subjected to metal- halogen exchange (e.g., by treatment with lithium metal or an alkyllithium) followed by treatment with a haloolefin optionally in the presence of a catalyst such as a cuprous salt to produce adduct _2 (Equation 9a).

Adduct 2 is subjected to the conditions of the Birch reduction (Birch, A. J., Quart. Rev. ( oadaa) 1950469; Watt, G. W., Chem. Rev. 19504fi 318; Birch, A. J.; Smith, M., Quart Rev. (London) 195812 17; Caine, D., Qrgλni -. Reactions 19762S 1) followed by mild acid hydrolysis of the intermediate enol ether to produce dienone _£ (Equation 9b).

Scheme 9

1) Metal-Halogen Exchange

1 2

2

10

WLior WMgX f) fi(R ¹⁰ is H) " ^** XlUa

Dienone 3 is treated with an appropriate Grignard reagent or organolithium reagent R--M.) or with a reducing agent (e.g., sodium borohydride) to produce dienol 4 (Equation 9c).

Dienol 4 s treated with a metal catalyst epoxidizing reagent known in the art (e.g., tert-butylhydroperoxide catalyzed by vanadyl acetylacetonate) followed by acid-catalyzed cyclization to produce hydroxyoxabicycloalkene 5 (Equation 9d).

Compound £ is treated with ozone followed by reductive work-up (e.g., with methyl disulfide) or with osmium tetroxide and sodium periodate to produce aldehyde £ (or the corresponding hemiacetal) (Equation 9e).

Aldehyde £ is treated with two equivalents of a Grignard reagent (WMgX) or of an organolithium reagent (WLd) to produce oxabicycloalkanediol Xlila (Equation 9f).

The compounds of Formula IVa are synthesized as shown in Scheme 10.

Dienone £ is homologated (e.g., with a Wittig reagent) to produce aldehyde 2 (Equation 10a).

Aldehyde Z is optionally converted to the corresponding ester by methods known in the art and optionally alkylated at the α-position -using an alkylating agent (R2X) and general methods known in the art, then treated with organometaUic reagents (R ³ M, R ⁴ M) or with a reducing agent (e.g., lithium aluminum hydride) to produce dienol £ (Equation 10b).

Dienol £ is treated using the methods (or modifications thereof) described in Equations 9d-9f to produce oxabicycloalkanediol XlVa (Equations lOc-lOe).

Scheme 10

&

s

Li or

A non-limiting illustration of the preparation of halooxatricycUc ethers Xlilb-XVb is shown in Scheme 11. Carbonyl compound 11 (β, where R ¹⁰ is R ⁵ and p is p-1) is treated with a Witting reagent to produce hydroxyoxabicycloalkene 12 (Equation 11a).

Treatment of intermediate 2 with a source of electrophiUc halogen such as bromine or H-halosuccinimide in the presence of an acid catalyst produces halooxatricycUc ether Xlllb (Equation lib).

Scheme 11

11 12

NBS

(H ⁺ ) b) 12 — HIb

Alternatively, oxatricycloalkanediols XDIa, where p is 3, can be synthesized as shown in Scheme 12. Oxatricycloalkenones 1& are available by methods, or modifications thereof, known in the art. (See Keay, B.A, J. Chem. Soc. Chem Cn-mm 1987419; DeClercq, P. J.; Van Royen, L. A, Svnth πr mv 1979, 2771.)

Treatment of compound 12 with hydrogen gas in the presence of a metal catalyst produces oxatricycloalkanone 1 (Equation 12a).

Treatment of ketone 14 with a peroxyacid under conditions of the Baeyer-Villiger reaction (Hassal, C. W., Orgaτ_.<. Reactions 1957 £ 73; Lee, S. B.; Ufif, B. C, Quart. Rev. Chem Soc. 196721 29) produces lactone 1£ (Equation 12b).

Treatment of lactone 15 with one equivalent of a reducing agent such as di-iafi-butylaluminum hydride produces hydroxyaldehyde 1£ (Equation 12c).

Treatment of hydroxyaldehyde lβ with at least two equivalents of a Grignard reagent (WMgX) or an organoUthium reagent (WLi) produces oxatricycloalkanediol XLQa (p is 3) (Equation 12d).

Scheme 12

12 14

1£

lfi

WLi WMgX d) 1£ ~* Xllla

The following examples represent the preparation of typical species of the invention. The examples are for illustration and should not be regarded as limiting the invention in any way.

EXAMPLE I fpheBylmethp-sy)-8.5-methanocyclgpei_tarb1pyrai_

Step A: (±)-(lα.3aβ.7aβ)-2.3.3a.4.7.7a-hexahvdro-5.7»-dimethyl- 1H- inden-l-pl A solution of 0.82 g (5.0 mmol) of ja__-2,3,3a,4,7,7a-hexahydro-5,7a- dimethyl-lH-inden-1-one (for a synthesis see FinguelU, F., et al., J.Org. Chem. 1982415056-5064) in 5 mL of ethanol was added dropwise to a suspension of 0.38 g (10 mmol) of sodium borohydride in 5 mL of ethanol maintained at 0-5°C. The mixture was stirred for lh at 0°C, then it was poured into 50 mL of saturated aqueous ammonium chloride solution and extracted twice with 50 mL of diethyl ether. The combined organic extracts were dried over MgS04, filtered, and the solvent removed in vacuo to afford the title compound (0.58 g, 70%), which crystallized to form a white soUd, m.p. 60-69°C. IH NMR: δ 0.96 (s, 3H), 1.4-1.8 (m, 6H), 1.64 (s, 3H), 2.0-2.1 (m, 2H), 2.15 (br, IH), 3.76 (t, IH), 5.54 (m, IH).

¹³ C NMR: 622.8, 23.4, 26.4, 26.9, 29.6, 30.2, 40.3, 40.6, 82.0, 118.0, 130.3.

Si _S P_£: (±)-flaα.2aα.3β.5aα.6aα)-octahvdro-2a.6a-dimethvl-3H- -_ndenor5.6-bTox_ran-3-ol A solution of (±)-lα,3aβ,7aβ)-2,3,3a,4,7,7a-hexahydro-5,7a- dimethyl- lH-inden-1-ol (82 mmol) in 160 mL dichloromethane was cooled to 0°C. Vanadyl acetylacetonate (0.43 g, 1.6 mmol) was added, foUowed by 90% tert-butvl hydroperoxide (13.6 mL, 122 mmol). The cooling bath was removed and the mixture was stirred for 2 h. The mixture was again cooled to 0°C and 160 mL of a 10% aqueous solution of sodium sulfite was added dropwise at 0-10°C. This two-phase mixture was stirred for 30 min at 0°C, then the organic layer was separated and the aqueous layer was extracted with 50 mL of dichloromethane. The organic layers were combined, washed with 100 mL of a saturated aqueous solution of sodium bicarbonate, dried over MgSθ ₄ , filtered, and the solvent evaporated in vacuo. Flash chromatography yielded a residue, which was triturated with hexanes to afford the title compound (4.36 g, 29%) as a white powder, m.p. 83-85°C. ⁱ H NMR: δ 0.96 (s, 3H), 1.32 (s, 3H), 1.5-2.0 (m, 8H), 2.30 (dd, IH), 3.03 (m, IH), 3.09 (d, IH), 3.55 (m, IH).

methanocvclopentarblpvran-3-ol The product of Step B (4.00 g, 22 mmol) was dissolved in 50 mL of dichloromethane. Camphorsulfonic acid (0.36 g, 1.5 mmol) was added and the mixture was stirred overnight at room temperature. The reaction mixture was then poured into 100 mL of diethyl ether, washed with a saturated aqueous solution of sodium bicarbonate, dried over MgS0 ₄ , filtered, and the solvent evaporated in ιa__U__. The residue was subjected to flash chromatography to afford the title compound (1.56 g, 39%) as a colorless oil.

IH NMR: δ 0.77 (s, 3H), 1.10 (s, 3H), 1.4-2.2 (m, 9H), 3.44 (dd, IH), 3.8 (m, 2H).

≤S≤ I): (2α.3β.4aβ.5α.7aβ)-octahvdr-v.2 -t _a -ι.iτnPtbv1-3^phenv1methnτv.- 2.5-methanocvclopentarblpvran 0.12 grams of a sodium hydride 60% dispersion in oil (3.0 mmol), was washed with hexanes, then suspended in 4 mL of dry THF and the mixture was cooled to 0°C. 0.36 g (2.0 mmol) of the product from Step C was dissolved in 4 mL THF and then added dropwise at 0-5°C. The mixture was stirred at 0°C for 30 min, then 0.28 mL of benzyl bromide (2.4 mmol) and 0.03 grams of potassium iodide (0.2 mmol) were added and the mixture was refluxed for 4 hours. Hie mixture was cooled, 0.2 mL of 2-propanol was added, then the mixture was poured into 20 grams of ice and 20 mL of 1.0 ϋ hydrochloric acid and extracted into 40 mL of dichloromethane foUowed by two 20 mL extractions. The combined organic layers were dried over MgSθ , filtered, and the solvent evaporated in vacuo. Flash chromatography afforded the title compound (0.28 g, 52%) as a colorless oil.

IH NMR: δ 0.78 (s, 3H), 1.12 (s, 3H), 1.38 (d, IH), 1.48 (dd, IH), 1.6-2.1 (m, 7H), 3.19 (dd, IH), 3.86 (m, IH), 4.48 (d, IH), 4.73 (d, IH), 7.2-7.4 (m, 5H).

EXAMPLE 2

(-_=)-(5aα.8α.9aβ)-8-Ethvloctahvdro-2-(2-methylphenyl) - 5a.8-eOoxv-6H-l-benzoxepin

Step A: (±)-f2α.4aα.8aB)-2-ethvlhexahvdro-2H-2.4a-epoxvnaphthalen - g(7H)-gBe

To a solution of 10.84 grams of (±M2α,4aα,8aβ)-2-ethyl-l,5,6,8a- tetrahydro-2H-2,4a-epoxynaphthalen-8(7H)-one (synthesized by modification of the methods described by Keay in J. Chem. Soc. Chem.

Onτtιτn 1987419 and by DeClercq and VanRoyen in Svπtlv C^m-n 1979 £ 771, starting with 2-ethylfuran) in 225 mL of ethanol was added 3.4 grams of 5% palladium on carbon. The mixture was treated with hydrogen gas overnight at room temperature and atmospheric pressure.

The catalyst was then filtered off, rinsed with ethanol, and the solvent

was evaporated in vacuo to afford the title compound (10.24 g, 93%) as an oil.

-Η. NMR: δ 0.96 (t, 3H), 1.5-1.9 (m, 7H), 1.9-2.1 (m, 3H), 2.1-2.3 (m, 3H), 2.45 (m, 2H).

£t≤E_B ^* teH5aα,8g.9aβ)-g^tfaylhegahydrp^ 2_3H)_flns

The product of Step A was dissolved in 350 mL of dichloromethane and 27.5 grams of 50% meta-chloroperoxvbenzoic acid (1.5 equivalents) was added. The mixture was stirred for 3 days, then 35 m of a 10% aqueous solution of sodium hydrogen sulfite was added dropwise with cooling to maintain the temperature of the mixture below 30°C. The mixture was stirred for 30 min, then 900 mL dichloromethane was added and the organic layer was separated, washed with 260 mL of a 1.0 ]__ solution of sodiτun hydroxide, dried over MgSθ4 and filtered. The solvent was evaporated in vacuo to afford the title compound (11.08 g, 100%) as a Ught yeUow oil. IH NMR: δ 1.00 (t, 3H), 1.5-2.2 (m, 12H), 2.6-2.9 (m, 2H), 4.50 (dd, IH).

Step C: (±)-exo-4-ethvl-2-hvdro__v-7-oxabicvclor2.2.nheptane-l-buta nal A portion of the product of Step B (2.10 g, 10 mmol) was dissolved in 40 mL of toluene. The solution was cooled to -70°C, then 10 mL of a diisobutylalτuninum hydride solution (1.5 M solution in toluene, 15 mmol) was added dropwise, maintaining the temperature below -60°C. The reaction mixture was stirred for 1 hour at -70°C, then transferred via n-n-nnTfl to a stirred mixture of 50 grams of ice, 40 mL of water and 10 mL of acetic acid. This mixture was stirred for 5 min, then extracted with two 50 mL portions of diethyl ether. The combined ether layers were washed with 50 mL of water, then with 50 mL of saturated aqueous sodium bicarbonate solution. AU of the aqueous layers were combined, saturated with sodium chloride, and extracted with three 50 mL portions of dichloromethane. The dichloromethane layers were combined and washed with two 50 mL portions of saturated aqueous sodium bicarbonate solution. All of the organic layers were dried over MgS0

and filtered, and the solvents were removed in ∑asuQ to afford the title compound (1.30 g, 61%) as an oil. Due to equiUbration between aldehyde and diastereomeric lactol forms, complete spectral characterization of the title compound was difficult. iHNMR Onfcsrflϋa): δ 0.97 (t), 9.77 (s).

Si≤i _ : (t)-«p ^thyl--2-hydre__y-c.-(2-methylphenyl)-7-*g_-abicyclc>- ■2,2,laeptaBe-l-btttaBpl

The product of Step C was dissolved in 15 L of diethyl ether and the solution was cooled to 0°C. Then 8 mL of a solution of ortho-tolvl- magnesium bromide (2 M solution, 16 mmol) was added dropwise, maintaining the temperature of the reaction mixture at 0-5°C. The mixture was stirred for 1 hour at 0°C, then 2 mL of additional ortho- tolylmagnesium bromide (2 M solution, 4 mmol) was added dropwise at 0-5°C. The mixture was stirred for 40 min at 0°C, then 10 mL of a saturated aqueous solution of ammonium chloride was added dropwise. Water and diethyl ether were added to dissolve soUds, the organic layer was separated, and the aqueous layer was extracted with 20 mL of diethyl ether. The combined organic layers were washed with a saturated aqueous solution of sodium bicarbonate, dried over MgSθ4 and filtered. The solvent was removed i vacuo and the soUd residue was triturated with hexanes to afford the title compound (1.19 g, 64%) as a white soUd, mp. 108-119°C.

*H NMR: δ 0.97 (t, 3H), 1.3-2.2 (m, 15H), 2.33 (s, 3H), 3.88 (m, IH), 4.97 (m, IH), 7.1-7.3 (m, 3H), 7.48 (d, IH).

Step E: ■±)-(5aα.8α.9aβ)-8-ethvloctahvdro-2-f2-methvlphenvl)-5 a.8- eposy-gH-l-benzcsep-E

A portion of the product of Step D (0.46 g, 1.5 mmol) and 0.21 grams of zinc chloride (1.5 mmol) were combined in 30 mL of dichloromethane and the mixture was refluxed for 5 hours. The mixture was then cooled, diluted with 60 mL of dichloromethane, and washed with 30 mL of water, then with a saturated aqueous solution of 30 mL of sodium bicarbonate. The organic layer was dried over MgSθ and

filtered and the solvent was removed in vacuo. The residue was subjected to flash chromatography on siUca gel to afford the less polar diastereomer of the title compound (0.06 g, 14%) as an oil, foUowed by the more polar diastereomer of the title compound (0.10 g, 23%) as an oil. ^X H NMR (less polar diastereomer): δ 1.03 (t, 3H), 1.5-1.8 (m, 7H), 1.8-2.0 (m, 5H), 2.12 (m, 2H), 2.31 (s, 3H), 4.12 (m, IH), 5.07 (d, IH), 7.10 (m, 2H), 7.18 (t, IH), 7.42 (d, IH).

^• -K NMR (more polar diastereomer): δ 0.98 (t, 3H), 1.4-1.6 (m, 5H), 1.7- 1.9 (m, 4H), 1.9-2.1 (m, 2H), 2.1-2.2 (m, 2H), 2.24 (m, IH), 2.31 (s, 3H), 3.89 (m, IH), 4.52 (d, IH), 7.1-7.2 (m, 3H), 7.51 (d, IH).

By the general procedures described in Schemes 1-12 and Examples 1-2, or by obvious modifications thereof, the compoimds of Tables 1-15 can be prepared.

GENERAL STRUCTURES FOR TABLES M6

General Structure 1:

General Structure 2:

General Structure 3:

General Structure 4:

General Structure 5:

General Structure 6:

General Structure 7:

General Structure 8:

General Structure 9:

General Structure 10:

General Structure 11:

General Structure 12:

General Structure 13:

General Structure 14:

General Structure 15:

TΔBLE General Structure 1, R ⁵ «-R ⁶ is H, R ¹ is CH ₃

General Structure 1, R ^δ «R ⁶ is H, R ¹ is CH ₃

General Structure 1, R ^δ «R ⁶ is H, R ¹ is CH ₃

General Structure 1, R ⁵ -R ⁶ is H, R ¹ is CH2CH3

General Structure 1, R is OCH ₃ , R ⁶ is H, R ¹ is CH3

TABLE 2 General Structure 2, R ^δ -=R ⁶ is H, R ² is CH ₃

General Structure 2, R ^δ -R ⁶ is H, R ² is CH

£ £

General Structure 2, R ^δ -R ⁶ is H, R ² is CH ₂ CH ₃

General Structure 2, R ^δ is OCH ₃ , R ⁶ is H, R ² is CH3

TABLE 3 General Structure 3, n is 2, R ¹ is CH ₃ , R ² is H

£ E ³ £ fi ³

General Structure 3, n is 2, R ¹ is CH ₃ , R ² is H

General Structure 3, n is 2, R ¹ is CH3, R ² is H

£ E ³ £ E ^a

General Structure 3, n is 2, R ¹ is CH ₃ , R ² is CH3

General Structure 3, n is 2, R ¹ is CH , R ² is CH ₃

E ³

General Structure 3, n is 2, R ¹ is CH3, R ² is CH3

General Structure 3, n is 3, R ¹ is CH ₃ , R ² is H

General Structure 3, n is 3, R ¹ is CH ₃ , R ² is H

£ E ^S £ E ^a

General Structure 3, n is 3, R ¹ is CH ₃ , R ² is H

General Structure 3, n is 3, R ¹ is CH ₃ , R ² is CH ₃

General Structure 3, n is 3, R ^x is CH ₃ , R ² is CH ₃

£ E ^a £ E ^a

General Structure 3, n is 3, R ¹ is CH ₃ , R ² is CH3

General Structure 3, n is 4, R ¹ is CH ₃ , R ² is H

General Structure 3, n is 4, R ¹ is CHg, R- ^~ ι_

General Structure 3, n is 4, R ¹ is CHg, R ² is H

General Structure 3, n is 4, R ¹ is CH ₃ , R ² is CH ₃

£ B ³ £ E ³

CH2(C ₆ H5) H OT^ttetrahydrofuranyl) H

CH2(2-FC ₆ H4) H CH2(2-tetrahydropyranyl) H

CH2(3-FC ₆ H4) H Q-l H

H Q-3 H

CH^^S-F-jC^) H Q-4 H CH ₂ (2,4-F ₂ C ₆ H ₃ ) H Q-6 H CH ₂ (2,5-F ₂ C ₆ H3) H Q-7 H CH ₂ (2,6-F2C ₆ H3) H Q-8 H

CH ₂ (2,4,6-F ₃ C ₆ H2) H Q-15 H

CH-<2-ClC-U ₄ ) H CH^ rCgH^ H

CH23-C1C ₆ H4) H CH ₂ ( ² _» 6-Br2C ₆ H ₃ ) H

CH2(4-αC ₆ H ₄ ) H CH ₂ ⁽² -C ¹ - ⁶ - ^FC 6 ^H 3 ^{) H}

CH ₂ (2,6-C1 ₂ C ₆ H ₃ ) H CH2(2-(OCH ₃ X3 ₆ H4) H

CH2(2-(CH3 C ₆ H ₄ ) H CH^^CNXJ^) H

CH ₂ (3-(CH ₃ )C ₆ H ₄ ) H CH2(2- CF ₃ )C ₆ H4) H

CH2(4-(CH ₃ )C ₆ H ₄ ) H CH ₂ (2-(OCF ₃ X3 ₆ H4) H

CH2(2-pyridyl) H CH2(2-(SCH ₃ )C ₆ H4) H

CH ₂ (2-thienyl) H CH ₂ ⁽² - C ^H« C ^H 2 ^)C 6 ^H 4) ^H

CH ₂ (2-furanyl) H CH2( -(C-CH)C ₆ H4) H

General Structure 3, n is 4, R ¹ is CH ₃ , R ² is CH ₃

General Structure 3, n is 4, R ¹ is CH ₃ , R ² is CH ₃

General Structure 4, is 3, R ³ «R ⁴ is H

General Structure 4, is 3, R «R is CH ³

General Structure 4, in is 3, R ³ -=R ⁴ is CH ₃

fl E ^z fl E ²

CH2(2-tetrahydropyranyl) CH ₃

Q-l CH ₃

Q-3 CH ₃

Q-4 CH ₃

Q-6 CH ₃

Q-7 CH ₃

Q-8 CH ₃

Q-15 CH ₃

CH^BrC _β ^) CH ₃

CH2(2,6-Br2C ₆ H ₃ ) CH ₃

CH ₂ (2-α-6-FC ₆ H3) CH ₃

Ca ₂ {2-(OCH ₃ )C ₆ ϊi ₄ ) CH ₃ CH ₃

CH ₂ ( ² -(CF ₃ )C ₆ H ₄ ) CH ₃

CH2(2-(OCF ₃ )C ₆ H ₄ ) CH ₃

CH2(-MSCH ₃ )C ₆ H ₄ ) CH ₃

CH ₂ (2-(CH-CH ₂ )C ₆ H4) CH ₃

CH^C-CH ^) CH ₃

3 4. General Structure 4, mis 4, R »R isH

General Structure 4, m is 4, R ³ «R ⁴ is H

General Structure 4, m is 4, R ³ «R ⁴ is CH

General Structure 4, m is 4, R ³ _dl ⁴ is CH ₃

£ E ² £ E ²

3 4. General Structure 4, m is 5, R »R is H

TABLES General Structure 6, m is 3, R ³ R ⁴ is H

General Structure 5, m is 3, R 3 «R 4 isH

£ E ¹ £ E ³

General Structure 5, m is 3, R ³ «R ⁴ is CH ₃

General Structure 5, m is 3, R ³ «R ⁴ is CH ₃

£ &£ E ¹

CH ₂ CH ₃ CH2(2-tetrahydropyranyl) CH ₂ ^CH 3

CH2(2-FC ₆ H4) CH ₂ CH ₃

CΑ^3-FC ₆ a ₄ ) CH ₂ CH ₃

CH ₂ ⁴ -FC6H4) CH ₂ CH ₃

CH ₂ (2,3-F2C ₆ H ₃ ) CH ₂ CH ₃

CH ₂ (2,5-F2C ₆ H ₃ ) CH ₂ CH ₃

CH2(2,6-F2C ₆ H ₃ ) CH ₂ CH ₃

CH2(2,4,6-F ₃ C ₆ H2) CH ₂ CH ₃

CH^-CIC^) CH ₂ CH ₃

CH2(3-αC ₆ H4) CH ₂ CH ₃

CH ₂ (4-αC ₆ H4) CH ₂ CH ₃

CH ₂ {2,6-Cl ₂ C ₆ n ₃ ) CH ₂ CH ₃

CH2(2-(CH ₃ )C ₆ H4) CH ₂ CH ₃

CH ₂ ( ³ -<CH ₃ )C ₆ H4) CH ₂ CH ₃

CH2(2-pyridyl) CH ₂ CH ₃

CH2(2-thienyl) CH ₂ CH ₃ CH ₂ CH ₃ CH2CH ₃

General Structure 5, m is 4, R ³ « ^* R ⁴ is H

General Structure 5, m is 4, R ³ «R ⁴ is H

£ E ¹ £ E ^]

General Structure 5, m is 4, R ³ _=R ⁴ is CH ₃

General Structure 5, m is 4, B ^3~ -H ^~ is CH ₃

fl E ³ fl E ³

General Structure 5, m is 5, R ³ «R ⁴ is H

General Structure 6, m is 3, R ¹ is CH ₃

General Structure 6, m is 3, R ¹ is CH ₂ CH ₃

General Structure 6, m is 3, R ¹ is CH ₂ CH ₃

General Structure 6, is 4, R ¹ is CH ₃

E ^a fl E ³

CHzrø _β Hδ) H CH2(2-tβtra_ιydropyranyl) H

CH ₂ (2-FC ₆ H4) H Q-l H

CH20-FC6H4) H Q-3 H

CH^FCβ^ ⁾ H Q-4 H

CH2 ² -3-F2C6H ₃ ) H Q-6 H

CH ₂ (2,4-F2C ₆ H ₃ ) H Q-7 H

CH ₂ (2,5-F ₂ C ₆ H ₃ ) H Q-8 H

CB2(2,β-F2CβH3) H Q-15 H

CH2(2,4,6-F ₃ C ₆ H2) H CH ₂ (2-BrC ₆ H4) H

(m-i2-CxC-H ₄ ) H CH ₂ (2,6-Br2C ₆ H ₃ ) H

CH _j ^-ClC _β ^) H CH ₂ (2-Cl-6-FC ₆ H ₃ ) H

CH^-CIC^) H CH ₂ (2-(OCH ₃ X3 ₆ H4) H

CH2( .6-Cl2C6H ₃ ) H GE ΗGNKtøBψ H

CH ₂ (2-(CH ₃ )C ₆ H4) H CH ₂ (2^CF ₃ XJ ₆ H4) H

CH ₂ (3-(CH ₃ )C ₆ H4) H CH ₂ (2-(OCF ₃ X. ₆ H4) H

CH ₂ (4-(CH ₃ )C ₆ H4) H CH ₂ (2-(SCH ₃ )C ₆ H4) H

CH22-p ridyi) H CH ₂ (2-(CH=CH2)C ₆ H4) H

CH_>(2-thienyl) H CH ₂ (2-(C-CH)C ₆ H4) H GH2(2-tetralιydro_uranyl) H

General Structure 6, m is 4, R is CH ₃

General Structure 6, m is 4, B ¹ is CH ₂ ^CH 3

fl B ³ fl E ³

General Structure 6, m is 4, R ¹ is CH ₂ CH ₃

General Structure 6, m is 5, R is CH ₃

General Structure 7, n is 2, R ¹ is CH ₃ , R ² is H

General Structure 7, n is 2, R ¹ is CH ₃ , R ² is H

General Structure 7, n is 2, R ¹ is CH ₃ , R ² is H

General Structure 7, n is 2, R ¹ is CH ₃ , R ² is CH ₃

General Structure 7, n is 2, R ¹ is CH ₃ , R ² is CH ₃

fl E ³ fl E ³

General Structure 7, n is 2, R ¹ is CH ₃ , R ² is CH ₃

General Structure 7, n is 3, R ¹ is CHg, R ² is H

General Structure 7, nis 3, R ¹ iβ CHg, R ² is H

B ³

General Structure 7, n is 3, R ¹ is CH ₃ , R ² is H

fl B ³ fl B ³

General Structure 7, n is 3, R ¹ is CH ₃ , R ² is CH ₃

General Structure 7, n is 3, R ¹ is CH ₃ , R ² is CH ₃

General Structure 7, n is 3, R ¹ is CH ₃ , R ² is CH ₃

B ³

CH ₂ C«CH CH ₂ C-CH CH ₂ OCH

CΉ ₂ C*CH

CH ₂ C-CH

CH ₂ C»CH

CH ₂ C-CH

CH2CH2OCH ₃

CH ₂ CH2θCH ₃

CH2 H2θCH ₃

CH2CH2θCH ₃

CH ₂ CH2θCH ₃

CH2CH2° H ₃

CH ₂ CH ₂ OCH ₃

CH2CH2θCH ₃

General Structure 7, n is 4, R ¹ is CH ₃ , R ² is H

fl B ³ fl E ³

General Structure 7, nis 4, R!_S CH ₃ , B ² is H

General Structure 7, n is 4, R ¹ is CH ₃ , R ² is H

fl E ³

CH _j ^C _β Hs) CH C-CH

CH ₂ (2-FC6H ₄ ) CH ₂ C-CH

CH ₂ (2,6-F ₂ C ₆ H ₃ ) CH ₂ C!-CH

CH2(2-C1C ₆ H4) CH ₂ OCH

CH2(2-Cl-6-FC ₆ H ₃ ) CH ₂ C-CH

CB- 2-(CB ₃ yC _s B ) ca ₂ c-ca

CH ₂ ( ² -Pyήdyl) CH ₂ ^C - ^CH

Q-l CH ₂ OCH

CH2(C ₆ H5) CH2CH2θCH ₃

CH2(2-FC ₆ H4) CH ₂ CH ₂ OCH ₃

CH ₂ (2,6-F ₂ C ₆ H ₃ ) CH ₂ CH ₂ OCH ₃

CH ₂ (2-σC ₆ H ₄ ) CH ₂ CH ₂ OCH ₃

CH ₂ < ² -Cl-6-FC ₆ H ₃ ) CH2CH2θCH ₃

CH ₂ (2-(CH ₃ )C ₆ H4) CH2CH2OCH3

CH ₂ (2-pyridyl) CH2CH2OCH3

Q-l CH2CH2OCH3

General Structure 7, n is 4, R ¹ is CH ₃ , R ² is CH ₃

General Structure 7, n is 4, R ¹ is CH ₃ , R ² is CH3

General Structure 7, n is 4, R ¹ is CH ₃ , R ² is CH

TABLES q Λ

General Structure 8, m is 3, R « ^* R iβH

General Structure 8, m is 3, B ³ «B ⁴ is H

General Structure 8, m is 3, R ³ -=R ⁴ is CH ₃

General Structure 8, m is 3, R ³ =R ⁴ is CH ₃

fl B ² fl E ^z

CH^tetrahydropyranyl) CH ₃

Q-l CH ₃

0-3 CH ₃

Q-4 CH ₃

Q-6 CH ₃

Q-7 CH ₃

Q-8 CH ₃

Q-15 CH ₃

CH^Σi-BrC^) CH ₃

CHjs(2, ^β -B 2CβH3) CH ₃

CH ₂ (2-(OCH ₃ χ; ₆ H4) CH ₃ CH ₃

CH ₂ (2-(CF ₃ X; ₆ H4) CH ₃

CH ₂ (2-(OCF ₃ X3 ₆ H4) CH ₃

CH ₂ .2-(SCH ₃ X. ₆ H ₄ ) CH ₃

CH ₂ (2-(CH _Ϊ =CH2X36H4) CH ₃

CHj{(2-«_«CH)C ₆ H4) CH ₃

General Structure 8, m is 4, R ³ «R ⁴ is H

General Structure 8, m is 4, R ³ «R ⁴ is H

General Structure 8, m is 4, B ³ -R ⁴ is CH ₃

General Structure 8, m is 4, R ³ -R ⁴ is CH ₃

q Λ

General Structure 8, m is 5, R ^* =R is H

General Structure 9, m is 3, R «-R iβH

fl E ¹ fl E ^J

General Structure 9, m is 3, R ³ «R ⁴ is CH ₃

General Structure 9, m is 3, R ³ «R ⁴ is CH ₃

fl B ¹ fl B ³

General Structure 9, m is 4, R ³ =R ⁴ is H

fl E ¹ fl E ¹

General Structure 9, m is 4, B ³ =R ⁴ is H

General Structure 9, m is 4, R ³ =R ⁴ is CH ₃

fl E ¹ fl B ¹

General Structure 9, m is 4, B ³ aR ⁴ is CH ₃

General Structure 9, m is 5, B ³ «R ⁴ is H

fl B ¹ fl B ¹

TABLE 10 General Structure 10, m is 3, Rl is CHg

General Structure 10, m is 3, R ¹ is CH ₃

fl E ³ fl B ³

General Structure 10, m is 3, R ¹ is CH ₂ CH ₃

General Structure 10, m is 3, B ¹ is CH2CH3

fl E ³ fl E ³

General Structure 10, m is 4, R! is CH ₃

fl E ³ fl E ³

General Structure 10, is 4, R* is CH ₃

General Structure 10, m is 4, R ¹ is CH2CH3

General Structure 10, m is 4, R ¹ is CH2CH ₃

General Structure 10, m is 5, R is CH ₃

General Structure 11, n is 2, R ¹ is CH ₃

fl E ^a fl B ³

General Structure 11, n is 2, R ¹ is CB ₂ CB ₃

General Structure 11, n is 2, R ¹ is CH ₂ CHg

fl E ³ fl E ³

CH2(2-tetrahydropyranyl) CH ₃

Q-l CH ₃

Q-3 CH ₃

Q-4 CH3

Q-6 CH ₃

Q-7 CH ₃

Q-8 CH ₃

Q-15 CH ₃

CH ^BrC^) CH ₃

CH2 2,6-Br2C ₆ H ₃ ) CH ₃

CH2(2- -6-FC ₆ H ₃ ) CH ₃

CH ₂ ( -(OCH ₃ C ₆ H4) CH ₃

CH ₂ ( ² -(CNX. ₆ H4) CH ₃

CH2(2-(CF ₃ 3 ₆ H4) CH ₃

CH ₂ (2-(OCF ₃ X. ₆ H4) CH ₃

CH ₂ < ^SCH ₃ X _-6 H4) CH ₃

CH2(2-(CH«CH2XΪ6H4) CH ₃

CH ₂ ( ² -<C-CH)C ₆ H4) CH ₃

General Structure 11, n is 3, R! is CH ₃

General Structure 11, n is 3, R* is CH ₃

General Structure 11, n is 3, R ¹ is CH2CH3

E ³

General Structure 11, n is 3, R ¹ is CH ₂ CH ₃

General Structure 11, n is 4, R! is CH ₃

fl B ^a fl E ³

CH_>(2-tetrahydropyranyl) H

Q-l H

Q-3 H

Q-4 H

Q-6 H

Q-7 H

Q-8 H

Q-15 H

CH ₂ (2-BrC ₆ H4) H

CH2< ² -6-Br2C ₆ H ₃ ) H

CH ₂ (2- -6-FC ₆ H ₃ ) H

CH ₂ ² -(OCH ₃ X; ₆ H4) H

CH ₂ (2-(CNX. ₆ H ₄ ) H

CH^^OCFs J^ H

CH ₂ (2-(SCH ₃ K! ₆ H4) H

CH ₂ ( ² - CH«CH2)C6H4) H

CH^^C-CHX.^) H

TABLE 12 General Structure 12, m is 3, R ³ «R ⁴ is H

General Structure 12, m is 3, R 3 «R 4 is H

General Structure 12, m is 3, B ³ «=R ⁴ is CH ₃

General Structure 12, m is 3, R ³ =R ⁴ iβ CH ₃

General Structure 12, m is 4, R ³ -R ⁴ is H

General Structure 12, m is 4, R ³ «R ⁴ is H

General Structure 12, m is 4, B ³ «R ⁴ is CH ₃

General Structure 12, m iβ 4, B ³ -B ⁴ is CH ₃

fl B ¹ fl E ³

General Structure 12, m is 5, R ³ «R ⁴ is H

TABLE 13 General Structure 13, p is 2

S_ B ² Ε. B ²

General Structure 13, p is 3

π B ² π B ²

TABLE 14 General Structure 14, R ³ -R ⁴ is H, p iβ 2

General Structure 14, R ³ -R ⁴ is CH ₃ , p is 2

Ε B ² π B ²

General Structure 14, R ³ -R ⁴ iβ H, p iβ 3

E B ² π B ²

General Structure 14, R ³ «R ⁴ is CHg, p iβ 3

TABLE 15 General Structure 15, R ³ «R ⁴ is H, p iβ 2

ffi B ² ffi B ²

General Structure 15, R ³ «R ⁴ is CH ₃ , p iβ 2

General Structure 15, R ³ -R ⁴ iβ H, p iβ 3

General Structure 15, R ³ -R ⁴ iβ CH ₃ , p iβ 3

Formulations

Useful formulations of the compounds of Formula I can be prepared in conventional ways. They include dusts, granules, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates and the like. Many of these may be applied directly to the locus to be protected. Sprayable formulations can be extended in suitable media and used at spray volumes of from a few liters to several hundred liters per hectare. High strength compositions are primarily used as intermediates for further formulation. The formulations, broadly, contain about 0.1% to 99% by weight of active ingredients) and at least one of (a) about 0.1% to 20% surfactants) and (b) about 1% to 99.9% solid or liquid inert diluent(s). More specifically, they will contain these ingredients in the following approximate proportions:

*Active ingredients plus at least one of a surfactant or a diluent equals 100 weight percent.

Lower or higher levels of active ingredient can, of course, be present depending on the intended use and the physical properties of the compound. Higher ratios of surfactant to active ingredient are sometimes desirable, and are achieved by incorporation into the formulation or by tank mixing.

Typical solid diluents are described in Watkins et al., "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books, Caldwell, NewJersey, but other solids, either mined or manufactured, may be used. The more absorptive diluents are preferred for wettable powders and the denser ones for dusts. Typical liquid diluents and solvents are described in Marsden, "Solvents Guide", 2nd Ed., Interscience, New York, 1950. Solubility under 0.1% is preferred for suspension concentrates; solution concentrates are preferably stable against phase separation at 0°C. "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood, NewJersey, as well as Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co., Inc., NewYork, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foaming, caking, corrosion, microbiological growth, etc. The methods of making such compositions are well known.

Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer or fluid energy mill. Suspensions are prepared by wet -milli g (see, for example, Littler, U.S. Patent 3,060,084). Granules and pellets may be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See J.E.Browning, "Agglomeration", flj___ _i _f iβ| Engineering. December 4, 1967, pp. 147ff and "Perry's Chemical Engineer's Handbook", 5th Ed., McGraw-Hill, New York, 1973, pp. 8-59ff. For further information regarding the art of formulation, see for example:

H. M. Loux, U.S. Patent 3,235,361, February 15, 1966, Col. 6, line 16 through Col. 7, line 19 and Examples 10 through 41;

R. W. Luckenbaugh, U.S. Patent 3,309,192, March 14, 1967, 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;

H. Gysin and E. Knusli, U.S. Patent 2,891,855, June 23, 1959, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4;

G. C. Klingman, "Weed Control as a Science", John Wiley & Sons, Inc., New York, 1961, pp. 81-96; and

J. D. Fryer and S. A. Evans, "Weed Control Handbook", 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pp. 101-103.

In the following examples, all parts are by weight unless otherwise indicated.

Wettable Powder (2α,3β,4β,5α,9aβ)-3-[(2-fluorophenyl)methoxy]-decahydro -2- methyl-2,5-methanocyclohepta[b]pyran 60% sodium alkylnaphthalenesulfonate 2% sodium liginsulfonate 2% synthetic amorphous silica 36%

The active ingredient is first sprayed onto the amorphous silica, then the ingredients are blended, hammer-milled imtil all the solids are essentially under 50 microns, reblended, and packaged.

fixλTTipfc fl

Wettab le Powder

(2α,3β,4β,5α,9aβ)-3-[(2-fluorophenyl)methoxy]-decahy dro-2- methyl-2,5-methanocyclohepta[b]pyran 50% sodium alkylnaphthalenesulfonate 2% low viscosity methyl cellulose 2% diatomaceous earth 46%

The active ingredient is first sprayed onto the diatomaceous earth, then the ingredients are blended, coarsely hammer-milled and then air- milled to produce particles essentially all below 10 microns in diameter. The product is reblended before packaging.

F/rflTTip.- . C. Granule

Wettable Powder of Eample B 5% attapulgite granules 95%

A slurry of wettable powder containing 25% solids is sprayed on the surface of attapulgite granules in a double-cone blender. The granules are dried and packaged.

_ ^• --** TΪBΨT P

Emulsifiabl? Concentrate (2α,3β,4β,5α,9aβ)-3-[(2-fluorophenyl)methoxy]-decahydro -2- methyl-2,5-methanocyclohepta[b]pyran 40%

Atlox 3404F 3% Atlox 3404F 3% xylene 54%

The active ingredient and Atlox emulsifiers are dissolved in the solvent, filtered and packaged. Atlox 3403F and 3404F are blends of anionic and ionic emulsifiers from ICI Americas, Inc.

E___amp.e E

Low Strength Granule (2α,3β,4β,5α,9aβ)-3-[(2-fluorophenyl)methoxy]-decahydro -2- methyl-2,5-methanocyclohepta[b]pyran 5% attapulgite granules 95%

(U.S.S. 20-40 mesh)

The active ingredient is dissolved in a solvent and the solution is sprayed upon dedusted granules in a double-cone blender. After spraying of the solution has been completed, the material is warmed to evaporate the solvent. The material is allowed to cool and then packaged.

Example F

Low Strength Granule

(2α,3β,4β,5α,9aβ)-3-[(2-fluorophenyl)methoxy]-decahy dro-2- methyl-2,5-methanocyclohepta[b]pyran 50% wetting agent 1% crude Ugninsulfonate salt 10%

(containing 5-20% of the natural sugars) attapulgite clay 39%

The ingredients are blended and milled to pass through a 100 mesh screen. This material is then added to a fluid bed granulator, the air flow is adjusted to gently fluidize the material, and a fine spray of water is sprayed onto the fluidized material. The fluidization and spraying are continued until granules ofthe desired size range are made, the spraying is stopped, but fluidization is continued, optionally with heat, until the water content is reduced to the desired level, generally less than 1%. The material is then discharged, screened to the desired size range, generally 14-100 mesh (1410-149 microns), and packaged for use.

FϊPW If T

Concentrated Emulsio P

(2α,3β,4β,5α,9aβ)-3-[(2-fluorophenyl)methoxy]-decahy dro-2- methyl-2,5-methanocyclohepta[b]pyran 25% xylene 25%

Atlox 3404F 5%

G1284 5% ethylene glycol 8% water 32% The active ingredient, solvent and emulsifiers are blended together.

This solution is added to a mixture ofthe ethylene glycol and water with stirring.

Solution

(2α,3β,4β,5α,9aβ)-3-[(2-fluorophenyl)methoxy]-decahy dro-2- methyl-2,5-methanocyclohepta[b]pyran 5% water 95%

The compound is added directly to the water with stirring to produce the solution, which may then be packaged for use.

fiτ_nmptø T

Dust (2α,3β,4β,5α,9aβ)-3-[(2-fluorophenyl)methoxy]-decahydro -2- methyl-2,5-methanocyclohepta[b]pyran 10% attapulgite 10%

Pyrophyllite 80%

The active ingredient is sprayed onto the attapulgite and then passed through a hammer-mill to produce particles substantially all below 200 microns. The ground concentrate is then blended with powdered pyrophyllite until homogeneous.

UTILITY

Test results indicate compounds of this invention are active postemergence and, in particular, preemergence herbicides. Many compounds in this invention are useful for the control of selected grass and broadleaf weeds with tolerance to important agronomic crops such as barley (Tfordft..fn Ωilεare), com (Zsa mays), cotton (£fc_s_aα-i!im hmmfriπ , rape (Brassica nagus), rice (Qryza satiza), sorghum ffir *" ^** ™ biεs Q∑), soybean .Glvcine s__-__) _. sugar beet (Beta vulgaris) _τ wheat ⁽ ritifiii flftstiviiTn ⁾ . and to vegetable crops. Grass and broadleaf weed species controlled include, but are not limited to, barnyardgrass fFrhiT-n -Mnfl crus-gaffi). blackgrass (AlopeCTUTlg mvosuroides). crabgrass ⁽ Digitaria spp.), duck salad (Heteranttrera limssa). foxtail <£__t_____S spp.), velvetleaf (Aiutilon theophrasti). and umbrella sedge (Cvperus difformis). Several compounds in this invention are particularly useful for the control of barnyardgrass and selected broadleaf weeds such as duck salad and umbrella sedge in upland and paddy rice.

Effective rates of appUcation for compounds of this invention are determined by a number of factors. These factors include: formulation selected, method of appUcation, amount and type of vegetation present, growing conditions, etc. In general terms, the subject compounds should be appUed at rates from 0.01 to 20 kg/ha with a preferred rate range of 0.03 to 1 kg/ha. One skilled in the art can easily determine efifective appUcation rates necessary for desired level of weed control.

Compounds of this invention may be used alone or in combination with other commercial herbicides, insecticides, or fungicides. The following list exemplifies some ofthe herbicides suitable for use in mixtures. A combination of a compound from this invention with one or more ofthe following herbicides may be particularly useful for weed control.

frttnTPrøl *!"*

acetochlor 2-chloro-N-(ethoxymethyl)-N-(2-ethyl-6- methylphenyDacetamide acifluorfen 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2- nitrobenzoic acid aclonifen 2-cUoro-6-nitro-3-pheno_cybenzenamine acrolein 2-propenal alachlor 2-chIoro-N-(2,6-diethylphenyl)-N-(metho ^* ry- methyDacetamide aUoxydim methyl 2,2-dimethyl-4,6-dioxo-5-[l-[(2-propenyl- oxy)amino butyUdene]cyclohexanecarboxylate ametryn N-ethyl-N-(l-methylethyl)-6-(methylthio)-l,3,5- triazine-2,4-diamine amitrole lH-l,2,4-triazol-3-amine

AMS ammonium sulf amate anilofos S-[2-[(4-chlorophenylXl-methylethyl)amino]-2- oxoethyl] 0,0-dimethylphosphorodithioate flgnlflm methyl [(4-aminophenyl)sulfonylcarbamate atrazine 6-chloro-N-ethyl-N-(l-methylethyl)-l,3,5- triazine-2,4-diamine aziprotryne 4-azido-N-(l-methylethyl)-6-methylthio-l,3,5- triazin-2-amine azoluron N-(l-etiιyl-lH-pyrazol-5-yl)- -phenylurea barban 4-chloro-2-butynyl 3-chlorocarbamate

ethyDbutanamide bromofenoxim 3 ,5-dibromo-4-hydroxybenzaldhyde 0-(2 ,4- dinitrophenyl)oxime bromoxynil 3,5-dibromo-4-hydroxybenzonitrile bromuron N'-(4-bromophenyl)-N,N-dimethylurea buminafos dibutyl [l-(butylamino)cyclohe_cyl]phosphonate butachlor N-(butθMiethyl)-2-chloro-N-(2,6-diethyl- phenyl)acetamide

Common Nam* flhf mm] Nλm

butamifos 0-ethyl O-(5-methyl-2-nitrophenylMlmethyl- propyl)phosphoramidothioate buthidazole 3-[5-(l,l-dimethylethyl)-l,3,4-thiadiazol-2-yl]-4- hydroxy-l-methyl-2-imidazoUdinone butralin 4-(l,l-dimethylethyl)-N-(l-methylpropyl)-2,6- dinitrobenzenamine butylate S-ethyl bis(2-methylpropyl)carbamothioate cacodyUc arid dimethyl arsinic oxide carbetamide (R)-N-ethyl-2-[[(phenylamino)carbonyl]o3cy]- propanamide

CDAA 2-cUoro-N,N-di-2-propenylacetemide CDEC 2-chloroallyl diethyldithiocarbamate chlomethoxyfen 4-(2,4-dichlorophenoxy)-2-methoxy-l-nitro- benzene chloramben 3-amino-2,5-dichlorobenzoic acid chlorbromuron 3-(4-bromo-3-chlorophenyl)-l-methoxy-l- methylurea chlorbufam l-methyl-2-propynl(3-chlorophenyl)carbamate chlorfenac 2,3,6-trichlorobenzeneacetic acid chlorflurecomethyl methyl 2-chloro-9-hydro__y-9H-fluorene-9- carboxylate chloridazon 5-amino-4-chloro-2-phenyl-3(2H)-pyridazinone chlorimuron 2-iπ[(4-chloro-6-metho-ty-2-pyrimidinyl)ethyl- amino]carbonyl]amino]stufonyl]benzoic acid, ethyl ester chlornitrofen l,3,5-trichloro-2-(4-nitropheno3-y)benzene chloropicrin trichloronitromethane chloroxuron N ^' -[4-(4-cMo ^* rophenoxy)phenyl]-N,N-dimethyl- urea

!nτnτnnτ. Nt-m. .

chlorpropham 1-methylethyl 3-chlorophenylcarbamate -lorsulfuron 2<hloro-N-[t(4-metho__y-6-methyl-l,3,5-triazin- 2-yl)ammo]carbonylJbenzenesulfonamide chlorthaldimethyl dimethyl 2,3,5,6-tetrachloro-l,4-benzene- dicarboxylate chlorthiamid 2,6-dichlorobenzene carbothioamide chlortoluron N'-(3-chloro-4-methylphenyl)-N^N-dimethylurea cinmethylin exo-l-methyl-4-(l-methylethyl)-2-[(2-methyl- phenyl)methoxy]-7-oxabicyclo-[2.2.1]heptane clethodim (E,E)-(+)-2-[l-[[(3-chloro-2-propenyl)θ3ty]imino]- pprrooppyyll]]--55--[[22--((eetthhyyl ^" t ^' hio)propyl]-3-hyd_roxy-2- cyc clιoohl exen-1-one clomazone 2-[(2-chlorophenyl)methyl]-4,4-dimethyl-3- isoxazoUdinone cloproxydim (E,E)-2-[l-[[(3-chloro-2-propenyl)oxy)imino]- butyl]-5-[2-(ethylthio)propyl]-3-hydroxy-2- cyclohexen-1-one clopyralid 3,6-dichloro-2-pyridinecarboxyUc acid

CMA calcium salt of MAA cyanazine 2-[[4-chloro-6-(ethylamino)-l,3,5-triazin-2-yl]- amino]-2-methylpropanenitrile cycloate S-ethyl cyclohezylethylcarbamothioate cycloxydim 2-[l-eΛox3 ^* imino)butyl]-3-hydroxy-5-(tetra- hydro-2H-thiopyran-3-yl)-2-cyclohexene-l-one cycluron 3-cyclooctyl-l,l-dimethylurea cyperquat l-methyl-4-phenylpyridinium cyprazine 2-chloro-4-(cyclopropylamino)-6-(isopropyl- amino)-fi-triazine cyprazole N-[5-(2-chloro-l,l-dimethylethyl)-l,3,4- thiadiazol-2-yl]cyclopropanecarboxamide

Chemical Name

cypromid 3',4'-dichlorocyclopropanecarboxaniUde dalapon 2,2-dichloropropanoic arid dazomet tetrahydro-3,5-dimethyl-2H-l,3,5-thiadiazine-2- thione

DCPA dimethyl 2,3,5,6-tetrachloro-l,4-benzene- dicarboxylate desmedipham et^yl [3-[[(phenylamino)carbonyl]ojy]phenyl]- carbamate desmetryn 2-(isopropylamino)-4-(methylamino)-6-(methyl- thio)-fi-triazine diallate S-(2,3-dichloro-2-propenyl)bis(l-methylethyl)- carbamothioate dicamba 3,6-dichloro-2-methoxybenzoic acid dichlobenil 2,6-dichlorobenzonitrile dichlorprop (+)-2-(2,4-dichlorophenoxy)propanoic acid diclofopmethyl (+)-2-[4-(2,4-dichloropheno_cy)pheno3_y]propanoic acid, methyl ester diethatyl N-(chloroacetyl)-N-(2,6-diethylphenyl)glycine difenoxuron N'-[4-(4-methoxyphenoxy)phenyl]-N,N-dimetJιyl- urea difenzoquat l,2-dimethyl-3,5-diphenyl-lH-pyrazoUu ion diflufenican N-(2,4-difluorophenyl)-2-(3-trifluoromethyl- phenoxy)pyridine-3-carboxamide dhnefuron N'-[3-cWoro-4-[5-(l,l-dimethylethyl)-2-oxo-l,3,4- oxadiazol-3(2H)-yl]phenyl]-N^-dimethylurea dimethachlor 2-cUoro-N-(2,6-dimethylphenyl)-N-(2-methory- ethyDacetamide dimethametryn N-d,2-dimethylpropyl)-N'-ethyl-6-(methylthio)- l,3,5-triazine-2,4-diamine

-tv-mnn Nflτn.» (rhftmitffll fliri

dimethipin 2,3-dihydro-5,6-dimethyl-l,4-dithiin 1,1,4,4- tetraoxide dimethylarsinic dunethylarsinic acid dinitramine N ³ ,N ³ -diethyl-2,4-dinitro-6-(t ^* rifluoromethyl)- 1,3-benzenediamine dinoseb 2-(l-methylpropyl)-4,6-dinitrophenol dinoterb 2-(l,l-dimethylethyl)-4,6-dinitrophenol diphenamid N,N-dimethyl-α-phenylbenzeneacetamide dipropetryn 6-(ethylthio)-N,N-bis(l-methylethyl)-l,3,5- triazine-2 ,4-diamine diquat 6,7-dihydrodipyrido[l,2-a:2',l'-c]pyrazinediium ion diuron N'-(3,4-dicMorophenyl)-N,N-dimethylurea DNOC 2-methyl-4,6-dinitrophenol DPX-V9360 2-[[(4 ,6-dimethoxypyri mi di in n --22--yyli): amino- carbo nnyyll]]taminosulfonyl]- -NN^,N4--dc iιnethyl 3-pyridinecarboxamide

DSMA disodium salt of MAA dy ron N-(4-methylphenyl)-N ^' -(l-methyl-l-phenyl- ethyl)urea eglinazine-ethyl N-[4-chloro-6-(ethylamino)-l,3,5-triazin-2- yl]glycine ethyl ester endothall 7-oxabicyclo[2.2. l]heptane-2,3-dicarboxyUc acid

EPTC S-ethyl dipropylcarbamothioate ethalfluralin N-ethyl-N-(2-methyl-2-propenyl)-2,6-dinitro-4- (trifluoromethyl)benzenamine ethidimuron N-[5-(ethylsulfonyl)-l,3,4-thiadiazol-2-yl]-N,N'- dimethylurea ethofumesate (+)-2-ethoxy-2,3-dihydro-3,3-dimethyl-5-benzo- furanyl methanesulfonate

(~!nmrnnτ. «τn-»

fenac 2,3,6-trichlorobenzeneacetic acid fenoprop (+)-2-(2,4,5-tricUorophenoxy)propanoic acid fenoxaprop (+)-2-[4-[(6-chloro-2-benzoxazolyl)oxy]phenoxy]- propanoic acid fenuron N,N-dimethyl- -phenylurea fenuron TCA Salt of fenuron and TCA flamprop-M l-methylethyl N-benzoyl-N-(3-dιloro-4-fluoro- isopropyl phenyl)-D-alanine flamprop-methyl methyl N-benzoyl-N-(3-chloro-4-fluorophenyl)- DLr-alaninate fluazifop (+)-2-[4-[[5-(t ^* rifluoromethyl)-2-pyridinyl]θ-_y]- phenoxyjpropanoic acid fluazifop-P (R)-2-[4-[[5-(trifluoromethyl)-2-pyridinyl]oxy3- phenoxyjpropanoic acid fluchloralin N-(2-chloroethyl)-2,6-dinitro-N-propyl-4- (trifluoromethyDbenzenamine fluometuron N,N-dimethyl- -[3-(trifluoromethyl)phenyl]- urea fluralin N-butyl-N-ethyl-2,6-dinitro-4-(trifluoromethyl)- benzenamine fluorodifen H-nitrophenyl α,α,α-txifluoro-2-nitro-p.-tolyl ether fluoroglycofen carboxymethyl 5-[2-chloro-4-(trifluoromethyl)- phenoxy]-2-nitrobenzoate flurecol-butyl butyl 9-hydroxy-9H-fluoι ^* ene-9-carboxylate fluridone l-methyl-3-phenyl-5-[3-(trifluoromethyl)- phenyl]-4(lH)-pyridinone flurochloridone 3-chloro-4-(chloromethyl)-l-[3-(trifluoromethyl)- phenyl]-2-pyrroUdinone fluroxypyr [(4-amino-3,5-dichloro-6-fluoro-2-pyridinyl)oxy]- acetic acid

£o_m__________ISB___

fomesafen 5-[2-chloro-4-(trifluoromethyl)phenoxy]-N- (methylsulfonyl)-2-nitrobenzamide fosamine- ethyl hydrogen (aminocarbonyl)-phosphonate ammonium ammonium ethyl glufosinate- ammonium 2-amino-4-(hydroxymethylphos- ammonium phinyDbutanoate glyphosate N-(phosphonomethyl)glyrine haloxyfop 2-[4-[[3-cUoro-5-(trifluorometiιyl)-2-pyridinyl]- oxy]pheno3cy]propanoic acid hexaflurate potassium hexafluoroarsenate hexazinone 3-cyclohexyl-6-(dimethylamino)-l-n ethyl-l,3,5- triazine-2,4(lH,3H)-dione imazamethabenz 6-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)- m-tofuic acid, methyl ester and 6-(4-isopropyl- 4-methyl-5-oxo-2-imidazolin-2-yl)-p-toluic acid, methyl ester unazapyr (+)-2-[4,5-dihydro-4-methyl-4-(l-methylethyl)-5- oxo-lH-imidazol-2-yl]-3-pyridinecarboxylic acid imazaquin 2-[4,5-dihydro-4-methyl-4-(l-methylethyl)-5-oxo- lH-imidazol-2-yl]-3-quinolinecarboxyUc acid imazethapyr (+)-2-[4,5-dih^dro-4-methyl-4-(l-methylethyl)-5- oxo-lH-iπudazol-2-yl]-5-ethyl-3-pyridine- carboxyUc acid ioxynil 4-hydroxy-3,5-diiodobenzonitrile isocarbamid N-(2-methylpropyl)-2-oxo-l-imidειzoUdine- carboxamide isopropalin 4-(l-methylethyl)-2,6-dinitro-N^-dipropyl- benzenamine soproturon N-(4-isopropylphenyl)-NJN'-dimethylurea isouron N'-[5-(l,l-dimethylethyl)-3-isoxazolyl]-N^r- dimethylurea

uorome yl enzenam e metha methylcarbamodithioic acid

f-hf m ^nT T Tann ^p

methazole 2-(3,4-dichlorophenyl)-4-methyl-l,2,4- oxadiazoUdine-3,5-dione methoxuron N'-(3-cMorc- -methoxyphenyl)-N,N-dimethyl- urea methoxyphenone (4-methoxy-3-methylphenyiX3-methylphenyl)- methanone methyldymron N-methyl-N'-d-methyl-l-phenylethyD-N- phenylurea metobromuron N'-(4-bromophenyl)-N-methoxy-N-methylurea metolachlo 2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2- methox -l-methylethyl)acetamide metoxuron -(3-cMoro-4-methoxyphenyl)-N,N-diιnethyl- urea metribuzin 4-amino-6-(l,l-dimethylethyl)-3-(methylthio)- l,2,4-triazin-5(4H)-one metsulfuron methy 2-t[[[(4-methoxy-6-methyl-l,3,5-triazin-2- yl)amino]carbonyl]amino]sulfonyl]benzoic acid, methyl ester

MH l,2-dihydro-3,6-pyridazinedione molinate S-ethyl hexahydro-lH-azepine-1-carbothioate monaUde N-(4-chlorophenyl)-2,2-dimethylpentanamide monoUnuron 3-(p.-chlorophenyl)-l-metho ^* sy-l-methylurea monuron N'-(4-chlorophenyl)-N,N-dimethylurea

MSMA monosodium salt of MAA naproaniUde 2-(2-naphthalenyloxy)-N-phenylpropanamide napropamide N,N-diethyl-2-(l-naphthalenyloxy)propanamide naptalam 2-[( l-naphthalenylamino)carbonyl]benzoic acid neburon l-butyl-3-(3,4-dichlorophenyl)-l-methylurea

£2mmsn_2iams Che Tnirnl Nflτn«?

nitralin 4-methylsulfonyl-2,6-dinitro-N^-dipropyl- aniline nitrofen 2,4-dichloro-l-(4-nitrophenoxy)benzene nitrofluorfen 2-cUoro-l- 4-nitropheno ^* ty)-4-(trifluoromethyl)- benzene norea N^-κiimethyl-N'-(oct^vdro-4,7-methano-lH- inden-5-yl)urea 3aα,4α,5α,7α,7aα-isomer norflurazon 4-chloro-5-(methylamino)-2-[3-(trifluoromethyl)- phenyl]-3(2H)-pyridazinone orbencarb S-[2-(chlorophenyl)methyl]diethylcarbamo- thioate oryzalin 4-(dipropylamino)-3,5-dinitrobenzene- sulfonamide oxadiazon 3-[2,4-dichloro-5-(l-methylethoaηr)phenyl]-5- (l,l-dimethylethyl)-l,3,4-oxadiώol-2(3H)-one oxyfluorfen 2-chloro-l-(3-ethoxy-4-nitrophenox ^* )-4- (trifluoromethyDbenzene paraquat l,r-dimethyl-4,4'-dipyridinium ion pebulate S-propyl butylethylcarbamothioate pendimethalin N-(l-ethylpropyl)-3,4-dimethyl-2,6-dinitro- benzenamine perfluidone l,l,l-trifluoro-N-[2-meti .yl-4-(phenylsulfonyl)- phenyljmethanesulfonamide pheniβopham 3-[[(l-methylethoxy)carbonyl3amino]phenyl ethylphenylcarbamate phenmedipham 3-[(methoxycarbonyl)amino]phenyl-(3-methyl- phenyl)carbamate picloram 4-amino-3,5,6-trichloro-2-pyridinecarbosyUc acid piperophos S- [[22--((22--mmeetthhyyll--ll--ppiippeerriiddiinnyyll))--22-- oxoethyl]-0,0- dipropyl phoossppnnoorrooddiitthhiiooaatet

(_nmτnnn nn_ft hf mm] NAP

pretilachlor 2-dιloro-N-(2,6-diethylphenyl)-N-(2-propo3_y- ethyDacetamide procyazine 2-[[4-chloro-6-(cyclopropylamino)-l,3,5-triazine- 2-yl]amino]-2-methylpropanenitrile prodiamine 2,4-dinitro-N3^T3-dipropyl-6-(trifluoromethyl)- 1,3-benzenediamine profluralin N-(cyclopropylmethyl)-2,6-dinitro-N-propyl-4- (trifluoromethyDbenzenamine proglinazine-ethyl N-[4-chloro-6-[(l-methyletibyl)amino]-l,3,5- triazin-2-yl]glycine ethyl ester prometon 6-methoxy-N,N-bis(l-methylethyl)-l,3,5- triazine-2,4-diamine prometryn N,N'-bis(l-methylethyl)-6-(methylthio)-l,3,5- triazine-2,4-diamine pronamide 3,5-dichloro-N-(l,l-dimethyl-2-propynyl)- benz amide propachlor 2-chloro-N-(l-methylethyl)-N-phenylacetamide propanil N-(3 ,4-dichlorophenyl)propanamide propaquizafop 2-[[( l-methylethyUdene)amino]o__y]ethyl 2-[4- [(6-chloro-2-quinoxalinyl)oxy]pnenoxy]- propanoate propazine 6-chloro-N,N'-bis(l-methylethyl)-l,3,5-triazine- 2,4-diamine propham 1-methylethyl phenylcarbamate propyzamide 3,5-dichloro-N-(l,l-dimethyl-2-propynl)- benzamide prosulfalin N-[[4-(dipropylamino)-3,5-dinitrophenyl]- sulfonylj-S.S-diinethylsulfilimine prosulfocarb S-benzyldipropylthiocarbamate prynachlor 2-chloro-N-(l-methyl-2-propynyl)acetaniUde pyrazon 5-amino-4-chloro-2-phenyl-3(2H)-pyridazinone

_{m A} n NflitiB fl hf mm] Nnre*

pyrazosulfuron-ethyl ethyl 5-II[[(4,6-dimethoxy-2-pyrimid_inyl^amino]- carbonyljaminolsiilfonj pyrazole-4-carboxylate pyrazoxyfen 2-[[4-(2,4-dicWorobenzoyl)-l,3-dimethyl-lH- pyrazol-5-yl]oxy]-l-phenylethanone pyridate 0-(6-chloro-3-phenyl-4-pyridazinyl) S-octyl carbonothioate quizalofop ethyl (+)-2-[4-[(6-chlo«>-2-qtιinoxalinyl)o^ ^* ']pheno^]- propanoic acid, ethyl ester secbumeton N-ethyl-6-methoxy- -(l-methylpropyl)-l,3,5- triazine-2,4-diamine setho-cydi 2-[l-(et^o ^* xyimino)butyl]-5-[2-(ethylthio)propyl]- 3-hydroxy-2-cyclohexen-l-one siduron N-(2-methylcyclohexyl)-N'-phenylurea simazine 6-cUoro-N, -diethyl-l,3,5-friazine-2,4-diamine simetryn N, -diethyl-6-(methylthio)-l,3,5-triazine-2,4- diamine sodium chlorate sodium chlorate sodium mono- chloroacetic arid, sodium salt chloroacetate sulfometuron methyl 2-II[[(4,6-dimethyl-2-pyrimidinyl)amino]- carbonyl]amino]sulfonyl]benzoic acid, methyl ester

2,4,5-T (2,4,5-trichlorophenoxy)acetic acid 2,3,6-TBA 2,3,6-trichlorobenzoic acid TCA trichloroacetic arid tebutam 2,2-dimethyl-N-(l-methylethyl)-N-(phenyl- methyDpropanamide tebuthiuron N-[5-(l,l-dimethylethyl)-l,3,4-thiadiazol-2-yl]- N,N-dimethylurea

amino]carbonyl]amino]sulfonyl]-2-thiophene- carboxyUc acid, methyl ester thiameturon-methyl methyl 3-[[[[(4-methoxy-6-methyl-l,3,5-triazin- 2-yl)amino]carbonyl]amino]sulfonyl]2- thiophenecarboxylate thiazafluron N,N'-dimethyl-N-[5-(trifluoromethyl)-l,3,4- thiadiazol-2-yl]urea thiobencarb S-[(4-chlorophenyl)methyl] diethylcarbamo- thioate tiocarbazil S-(phenylmethyl) bis( 1-methylpropyl)- carbamothioate tralkoxydim 2-[l-(ethoxyimino)propyl]-3-hydroxy-5-(2,4,6- trimethylphenyI)-2-cyclohexen-l-one triaUate S-(2,3,3-trichloro-2-propenyl) bis(l-methylethyl)- carbamothioate triasulfuron 2-(2-chloroethoxy)-N-[[(4-methoxy-6-methyl- l,3,5-triazin-2-yl)amino]carbonyl]benzene- sulfonamide tribenuron methyl 2-[[[[N-(4-methoxy-6-methyl-l,3,5-triazine-2-yl)- N-methylamino]-carbonyl]amino]sulfonyl]- benzoic acid, methyl ester

e y aceam e

Selective herbicidal properties of he subject compounds were discovered in greenhouse tests as described below.

TΔBLE_1£ General Structure 1, n is 3, R ¹ is CH ₃ ; R ⁶ is anti, R ⁵ and OQ are BXH. to the oxygen- containing bridge.

Physical/Spectral data

Compound P R6 Q (δin CDCl ₃ )

OCH ₃ H (2-CH ₃ )C ₆ H ₄ oil, NMR: 1.2-2.1 (m, HH),

1.51 (β, 3H), 2.31 (s, 3H), 3.25 (m, IH), 3.25 (s, 3H), 3.45 (m, IH), 4.28 (d, IH), 4.54 (d, IH), 7.17 (m, 3H), 7.30 (m, lH).

H OCH ₃ (2-CH ₃ )C ₆ H ₄ oil, NMR: 1.2-2.2 (m, 11H),

1.51 (s, 3H), 2.30 (s. 3H), 2.92

(m, IH), 3.33 (s, 3H), 3.60 (m,

IH), 4.28 (m, IH), 4.50 (m,

IH), 7.16 (m, 3H), 7.29 (m,

IH).

H OCH ₃ (2-CH ₃ XJ ₆ H ₄ m.p.62-68°C (OQ is anti)

OCH ₃ H (2-CH ₃ X3 ₆ H ₄ oil, NMR: 0.97 (β, 3H), 1.4-2.1

(m, 11H), 1.60 (s, 3H), 2.31 (s, 3H), 3.10 (β, 3H), 3.41 (m, IH), 4.26 (d, IH), 4.54 (d, IH), 7.15 (m, 3H), 7.29 (m, IH).

General -Structure 2, n is 3, R ² is CH ₃ ; R ⁶ is anti, R ⁵ and OQ are asn to the oxygen- containing bridge.

Physical/Spectral data

Compound R° β Q (8in CDCl ₃ )

OCH ₃ H (2-CH8X36H4 ofl, NMR: 1.1-2.2 (m, 11H),

1.60 (s, 3H), 2.30 (s, 3H), 3.2 (m, IH), 3.26 (s, 3H), 3.48 (m, IH), 4.33 (d, IH), 4.55 (d, IH), 7.16 ( , 3H), 7.30 (m, IH).

4 H OCH ₃ (2-CH ₃ .6H4 m.p. 102-103 ^β C.

7 OCH ₃ CH ₃ (2-CH ₃ X3 ₆ H ₄ m.p.65-71 ^β C

General Structure 3, R ¹ is CH ₃ ; OQ is SSL _\ to the oxygen-containing bridge.

Physical/Spectral data

Compound n R ² R ³ Q (8inCDCl ₃ )

16 Et 2-FC6H ₆ oil, NMR: 0.80 (t,3H), (m, 16H), 3.35 (dd, IH), 4.54 (d,lH), 4.70 (d,lH), 6.9-7.3 ( , 3H), 7.49 (dt, IH).

17 CH ₃ CH ₃ (2-CH8 -6H4 oil, NMR: 0(3 (s, 3H), 1.12 (β, 3H), 1.22 (s,3H),1.4(m,2H), 1.6-2.0 (m,7H), 2.34 (s, 3H), 3.15 (dd, IH), 4.46 (d, IH), 4.68 (d, IH), 7.18 (m, 3H), 7.39 (m,lH).

18 CH ₃ CH ₃ CgHδ oil, NMR: 0.77 (s, 3H), 1.11 (s, 3H), 1.24 (s,3H),1.4(m,2H), 1.6-2.0 (m, 7H), 3.14 (dd, IH), 4.47 (d, IH), 4.74 (d, IH), 7.2-7.4 (m, 5H).

19 CH ₃ CH ₃ 2-αC6H ₄ oil, NMR: 0.78 (s, 3H), 1.15 ( s, 3H),

1.23 (s,3H), 1.4 (m, 2H), 1.6-2.0 (m, 7H),

3.24 (dd, IH), 4.55 (d, IH), 4.75 (d,lH), 7.25 (m, 3H), 7.61 (m, IH).

Physical/Spectral data

Compound n R ² R3 Q (6i CDCl ₃ )

26 CH ₃ 2^CH ₃ )C ₆ H ofl, NMR: 0.79 (s, (m, 2H), 1.6-2.1 ( , 7H),2.36(s,3H),3.18 (dd, H), 3.87 (m, IH), 4.46 (d, IH), 4.69 (d,lH),7.18(m,3H), 7.35 (m, IH).

27 CH ₃ C ₆ H ₅ oil, NMR: 0.78(s, 3H), 1.12 (s,3H), 1.4 (m,2H), 1.6-2.1 (m, 7H), 3.20 (dd, IH), 3.87 (m,lH), 4.48 (d, IH), 4.73 (d,lH), 7.2- 7.4(m,5H).

28 CH ₃ 2-FC ₆ H ₄ oil, NMR: 0.79 (s, 3H), 1.10 (s,3H), 1.4 (m,2H), 1.6-2.1 (m, 7H), 3.23 (dd, IH), 3.87 (m, IH), 4.56 (d, IH), 4.74 (d, IH), 6.9- 7.3 (m,3H), 7.48 (dt, IH).

Physical/Spectral data

Compound n R ² R3 Q (δin CDCl ₃ )

29 CH ₃ 2-QC ₆ H ₄ oil, NMR: 0.80 (s, 8H), 1.15 (B, 3H), 1.4 (m, 2H), 1.6-2.2 (m, 7H), 3.28 (dd, lH), 8.88 (m, lH), 4.68 (d, IH), 4.76 (d, lH), 7.25

34 H H 2-ClC ₆ H ₄ oil, NMR: 1.2*. (β, 3H), 1.4-2.0 (m, 14H), 3.48 (dd, IH), 4.26 (m, IH), 4.68 (d, IH), 4.77 (d, lH), 7.1-7.4 (m, 3H), 7.56 (m, IH).

35 4 H H 2-Cl-6-FC ₆ H ₃ m.p.68-70°C 36 4 H H 2,6-F ₂ C6H ₃ ofl, NMR: 1.08 (s, 3H), 1.4-2.0 (m, 14H), 3.39 (dd, IH), 4.20 (m, IH), 4.64 (d, IH), 4.76 (d, IH), 6.87 (m, 2H), 7.25 (m, IH).

Physical/Spectral data

Compound n R ² 3 (δi CDCl ₃ )

37 H 2,3-F ₂ C6H ₃ ofl, NMR: 1.15 (s, 3H), 1.4-2.0 (m, 14H), 8.43 (dd, lH), 4.23 (m, IH), 4.68 (d, lH), 4.74 (d, lH), 7.06 (m, 2H), 7.27 (m, IH).

41 2-FCeH ₄ oil, NMR: 1.10 (8, 3H), 1.3-2.3 (m, 9H), 3.23 (dd, IH), 4.19 (m, IH), 4.66 (d, lH), 4.73 (d, IH), 6.9-7.3 (m, 3H), 7.48 (dt, IH).

43 CH ₃ 2,6-F ₂ C6H ₃ oil, NMR: 0.79 (s, 3H), 1.03 (s, 3H), 1.3- 2.2 (m, 9H), 3.20 (dd, IH), 3.83 (m, IH), 4.55 (d, IH), 4.75 (d, IH), 6.8-6.9 (m, 2H),7.26 (m, IH).

44 CH ₃ H 2-σ, 6-FCeH ₃ oil, NMR: 0.79 (s, 3H), 1.05 (β, 3H), 1.2- 2.2 (m, 9H), 3.19 (dd, IH), 3.83 (m, IH), 4.62 (dd, IH), 4.81 (dd, IH), 6.96 (m, IH), 7.1-7.3 (m, 2H).

General Structure 5, m is 4, R ¹ =R ³ -=R ⁴ iβ CH ₃ ; OQ iβ BSΛ to the oxygen-containing bridge

Physical/Spectral Data

Compound Q (δin CDCl ₃ )

30 2-<ca ₃ )c _ii a ₄ m.p.68-75 ^β C 31 CβH ₅ m.p. 78-79°C 32 2-FC ₆ H ₄ m.p.82-84°C

General Structure 13, R ² is Et; oxygen atoms are svn

Compound W Diastereomer Physical/Spectral Data (δ in CDCI3)

38 3 2-(CH ₃ )C ₆ H less polar oil, NMR: 1.03 (t, 3H), 1.5-1.8 (m,

7H), 1.8-2.0 (m, 5H), 2.12 (m, 2H),

2.31 (s, 3H), 4.12 (m, IH), 5.07 (d,

IH), 7.10 (m, 2H), 7.18 (t, IH), 7.42

(d, IH).

39 2-(CH ₃ X3gH ₄ more polar ofl, NMR: 0.98 (t, 3H), 1.4-1.6 (m,

5H), 1.7-1.9 (m, 4H), 1.9-2.1 (m, 2H),

2.1-2.2 (m, 2H), 2.24 (m, IH), 2.31 (s,

3H), 3.89 (m, IH), 4.52 (d, IH), 7.1-

7.2 (m, 3H), 7.51 (d, lH).

40 C ₆ H ₅ more polar ofl, NMR: 0.98 (t, 3H), 1.4-2.3 (m,

14H), 3.86 (dd, IH), 4.41 (dd, IH),

7.33 (m, 5H).

42 C ₆ H ₅ less polar oil, NMR: 1.04 (t, 3H), 1.4-2.2 (m,

14H), 4.11 (dd, IH), 4.88 (d, IH),

7.30 (m, 5H).

45 C ₆ H ₅ W iβ β ofl, NMR: 1.01 (t, 3H), 1.4-2.3 (m,

12H), 3.87 (dd, lH), 4.31 (m, lH),7.2-7.4 (m, 5H).

Compound P W Diastereomer PhysicalSpectral Data (δ in CDC1 ₃ )

46 2 CH ₅ isα oil, NMR: 1.00 (t, 3H), 1.2-2.4 (m,

12H), 3.83 (dd, IH), 5.05 ( , IH), 7.2-7.4 (m,6H).

47 2 2-FC ₆ H ₄ Wiββ oii, NMR: 1.02 (t, 3H), 1.4-1.7 ( ,

5H), 1.7-2.1 (m, 6H), 2.24 (dd, IH), 3.88 (d, IH), 4.67 (d, IH), 6.98 (dd, IH), 7.13 (t, IH), 7.2 (m, IH), 7.54 (6, IH).

TESLΔ

Seeds of barley fTTrnihmin xulgarfi), barnyardgrass (Echinoshka cπιs_£fllli), bedstraw ( flli m asa∑ o), blackgrass ⁽ Alopecurus mvosuroides ⁾ . cheatgrass (E∑__mUfi fi£2flliniia), chickweed (Stellaria media), cocklebur πfawtt tu pgngyJϊflnicji ), corn (Zsa mass), cotton ⁽ GoBsvpium hirmifrim). crabgrass φjgitaria spp.), giant foxtail (Ssiaria fafcfi∑ii), lambsquarters f- fTimffldil?™ album), mdrningglory ⁽ Ipomoea hederacea ⁾ . rape ⁽ Brassica najais), rice ⁽ Orvza aa&∑a , sorghum (gfi∑glmffi bicolor). soybean (Glvcine max), sugar beet (B≤ta vulparis ⁾ . velvetleaf (Abutilon theophrasti). wheat π itim-m flfiaϋoim), wild buckwheat

^(" Pnlvgnniirn convolvulus), and wild oat (Δ∑&πa fatua) and purple nuteedge preemergence with test chemicals dissolved in a non-phytotoxic solvent. At the same time, these crop and weed species were also treated with postemergence applications of test compounds. 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.

Table A COMPOUND

Rate (200 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 25 26 27 28 29

POSTEMERGENCE

Barley 0 0 0 0 0 0 0 0 0 0 2 0 3 0 0 3 0 2 3 0 0 0 0 0 0 0 0 2 2

Barnyardgrass 0 0 0 0 0 0 0 0 2 7 1 0 3 0 - - 0 0 0 2 2 0 0 7 9 9 9 9 9

Bedstraw - - - - - - - 0 0 0 0 0 0 0 0 0 0 0 3 0 3 0 0 2 2 2 0 0 2

Blackgrass - - - - - - - 2 2 0 2 0 2 2 0 3 7 - 6 4 7 7 2 3 3 2 4 0 0

Cheatgrass 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 2 0 3 3 3 0 2 0 0 0 3 2 0 0

Chickweed - - - - - - - 4 - 2 0 0 2 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

Cocklebur 1 0 1 0 0 0 1 - - - - - - - - - - - - - - - - 2 2 1 - 2 1

Corn 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 1 2 1

Cotton 0 0 0 0 0 2 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2 2

Crabgrass 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2 3 0 0 0 0 0 2 8 0 0 0 0

Giant foxtail 0 5 0 0 0 2 0 0 0 0 2 2 0 0 0 0 0 0 0 0 2 0 0 0 1 0 2 3 0

Lambsquarters - - - - - - - 3 0 2 0 0 0 - 0 0 - 4 4 3 0 4 - 0 0 0 0 0 0

Morningglory 0 0 0 0 1 0 0 0 0 0 0 0 0 0 1 0 0 0 0 0 1 0 0 0 0 0 0 0 0

Nut sedge 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 - 0

Rape - - - - - - - 0 0 2 0 3 4 0 3 3 0 0 2 0 2 2 2 2 2 2 2 0 0

Rice 0 0 0 0 0 0 0 0 0 0 0 0 2 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

Sorghum 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 1 4 1

Soybean 0 0 0 0 0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 0 0 0 0 1 1 0

Sugar beet 0 0 0 0 0 0 0 1 1 3 5 2 6 3 7 5 0 2 2 0 3 2 2 4 4 5 3 4 3

Velvetleaf 4 0 0 0 0 0 0 0 0 0 0 1 2 0 0 0 - - - 0 - 0 0 5 5 4 1 5 2

Wheat 0 0 0 0 0 0 0 0 0 0 2 0 2 3 0 2 0 0 0 0 2 0 0 2 0 0 2 2 0

Wild buckwheat - - - - - - - 2 3 0 2 0 2 0 0 0 0 0 0 0 0 0 0 2 2 0 0 0 0

Wild oat 0 0 0 0 0 0 0 0 0 0 0 0 0 2 0 0 0 3 2 0 3 0 0 2 2 0 2 2 0

Table A COMPOUND

Rate (200 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 25 2627 28 29

PREEMERGENCE

Barley 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2 0 0 0 0 0 0 0 0 2 2 2 2 2 0

Barnyardgrass 9 1 8 0 0 9 0 7 8 10 2 9 10 0 0 0 0 7 2 4 8 1 0 10 10 10 10 10 10

Bedstraw - - - - - - - 0 - 0 0 0 0 0 3 0 0 0 0 0 0 0 0 0 0 0 0 0 0

Blackgrass - - - - - - - 2 0 3 0 2 4 0 3 2 0 2 0 2 0 0 0 4 9 6 6 2 6

Cheatgrass 0 0 0 0 0 0 0 0 2 2 0 0 6 0 4 2 0 0 0 0 0 0 0 5 2 4 3 4 3

Chickweed - - - - - - - 0 0 0 0 0 4 0 0 6 0 4 0 0 0 0 0 2 0 2 3 0 4

Cocklebur - 0 0 0 - - 0 - - - - - - - - - - - - - - - - - 1 0 0 1 0

Corn 0 0 0 0 0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 0 1 2 1 3 5 3

Cotton 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

Crabgrass 8 4 9 0 0 3 0 2 7 8 0 3 9 0 0 0 0 0 0 2 0 0 0 9 9 910 10 9

Giant foxtail 9 6 9 0 0 8 0 3 5 6 3 6 8 0 0 0 0 3 5 2 0 2 0 8 9 10 10 10 10

Lambsquarters - - - - - - - 0 - 3 0 0 0 0 0 0 0 3 0 6 0 0 0 0 0 0 3 0 0

Morningglory 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 - 0 0 0 0 0 0 0 - 0 0

Nutsedge 0 0 - 0 0 9 0 0 0 3 0 0 0 0 0 0 0 - 0 0 0 0 0 4 0 - 0 - 0

Rape - - - - - - - 0 0 0 2 0 0 0 2 2 0 0 0 0 0 0 0 3 2 2 2 2 0

Rice 0 0 0 0 0 0 0 0 0 0 0 2 0 0 0 0 0 0 0 0 0 0 0 3 0 0 2 2 0

Sorghum 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2 2 2 1 1 0

Soybean 0 0 0 0 0 0 0 0 0 0 0 0 2 0 0 0 0 0 0 0 0 0 0 1 0 0 0 2 0

Sugar beet 0 0 0 0 0 0 0 0 4 1 2 2 2 2 4 3 0 0 0 0 0 0 0 3 3 2 4 3 2

Velvetleaf 1 0 0 0 0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 2 0 0 2 2 1 4 2

Wheat 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2 0 0 0 0 0 0 0 0 2 0 0 3 2 2

Wild buckwheat - - - - - - - 0 6 2 0 0 0 2 3 0 0 0 0 0 0 0 0 0 0 0 0 0 0

Wild oat 0 0 0 0 0 0 0 0 0 0 0 0 2 0 0 0 0 0 0 0 3 0 0 2 2 2 4 5 4

Table A COMPOUND

Rate (200 g/ha) 30 31 32 33 34 35 36 37 38 39 40 41 43 44 45 46 47

PREEMERGENCE

Barley 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

Barnyardgrass 0 7 2 0 10 9 10 10 0 4 10 10 7 0 1

Bedstraw 0 0 2 0 0 0 2 0 0 0 0 0 0

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

Cheatgrass 1 3 2 - 0 0 4 2 0 0 5 0 7 0 3

Chickweed 0 0 0 - 0 0 0 2 0 0 5 2 0 0 0

Cocklebur 0 - 0 0 0 0 0

Corn 0 0 0 0 0 0 2 0 0 1 0 0 3 6

Cotton 0 0 0 0 0 0 0 0 0 0 0 0 0 0

Crabgrass 2 2 0 0 9 9 9 0 7 10 8 9 0

Giant foxtail 8 9 8 5 8 8 9 9 0 8 7 7 5 1 8

Lambsquarters 0 0 0 3 0 2 3 0 0 5 2 2 0 0 0

Morningglory 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

Nutsedge 0 0 0 0 0 0 0 0 2 0 0 0 0 0

Rape 0 0 0 0 0 0 0 0 0 0 3 0 0 0 0 0

Rice 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

Sorghum 0 0 0 0 0 3 2 0 0 5 3 1 0 0 0 0

Soybean 0 0 0 0 0 0 0 0 0 0 4 0 0 0 0 1

Sugar beet 0 0 0 0 0 0 0 0 0 0 4 0 0 0 0 0

Velvetleaf 0 0 0 0 0 6 3 0 0 2 8 5 2 0 0 0

Wheat 0 0 0 0 0 0 0 0 0 2 2 2 0 0 0 0

Wild buckwheat 0 0 0 0 0 0 0 2 2 0 0 0

Wild oat 0 2 2 0 0 0 8 0 0 0 4 7 0 0 0

Table A COMPOUND

Rate (50 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 25 26 27 28 29

POSTEMERGENCE

Barley 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2 0 0 0 0 0 0 0 0 0 0

Barnyardgrass 0 0 0 0 0 0 0 0 0 0 0 0 1 0 - - 0 0 0 0 0 0 0 0 2 4 3 5 1

Bedstraw - - - - - - - 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

Blackgrass - - - - - - - 0 0 0 0 0 2 0 0 0 6 8 - - 2 7 2 2 2 0 2 2 0

Cheatgrass 0 0 0 0 0 0 0 0 0 0 0 0 0 - 0 0 0 3 3 0 0 0 0 0 0 0 0 0 0

Chickweed - - - - - - - - 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

Cocklebur o i O O O O - - - - - - - - - - - - - - - - - - 0 1 - 0

Corn 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

Cotton 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

Crabgrass 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

Giant foxtail 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 00 00

Lambsquarters - - - - - - - 0 0 - 0 0 0 0 0 0 0 - 0 2 0 0 0 0 0 0 0 0 0

Morningglory 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Nutsedge - 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

Rape - - - - - - - 0 0 3 0 0 0 0 3 2 0 0 0 0 0 0 0 0 0 0 0 0 0

Rice 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

Sorghum 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

Soybean 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

Sugar beet 0 0 0 0 0 0 0 0 0 3 4 4 5 3 4 4 0 0 0 0 4 1 0 2 3 4 3 3 33 22

Velvetleaf 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 - - - - 2 0 1 0 0 11 00

Wheat 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 00 00

Wild buckwheat - - - - - - - 0 2 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0" " 0 " 0

Wild oat 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2 0 2 0 0 0 0 0 0 0 0

Table A COMPOUND

Rate (50 g/ha) 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 1617 18 19 20 21 22 23242526 27 28 29

PREEMERGENCE

Barley 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

Barnyardgrass 0 0 0 0 0 0 0 1 2 3 0 0 0 0 0 0 0 0 0 0 0 0 0 8 10 10 10 10 10

Bedstraw - - - - - - - 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

Blackgrass - - - - - - - 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2 0 0 0 2

Cheatgrass 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2 0 0 0 0 -

Chickweed - - - - - - - 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

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

Corn 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

Cotton 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

Crabgrass 6 0 0 0 0 2 0 0 2 2 0 0 0 0 0 0 0 0 0 2 0 0 0 5 8 2 5 8 5

Giant foxtail 0 0 5 0 0 4 0 0 0 2 0 0 0 0 0 0 0 0 3 2 0 0 0 6 7 8 9 10 9

Lambsquarters - - - - - - - 0 2 2 0 0 0 0 0 0 0 3 0 3 0 0 0 0 0 0 0 0 0

Morningglory 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

Nutsedge 0 0 - 0 0 0 0 0 0 0 0 0 0 0 0 0 - 0 - 0 0 0 0 - 0 0 0 0 0

Rape - - - - - - - 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2 0 0 2 0 0

Rice 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

Sorghum 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

Soybean 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

Sugar beet 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2 2 0 0 0 0 0 0 0 2 2 0 2 2 2

Velvetleaf 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 0 2 0

Wheat 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

Wild buckwheat - - - - - - - 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

Wild oat 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2 0 0 0 0 0 2 3 2

EST B

The compounds evaluated in this test were formulated in a non- phytoxic solvent and applied to the soil surface before plant seedlings emerged (preemergence appUcation), to water that covered the soil surface (paddy appUcation), and to plants that were in the one-to-four leaf stage (postemergence appUcation). A sandy loam soil was used for the preemergence and postemergence tests, while a silt loam soil was used in the paddy test. Water depth was approximately 2.5 cm for the paddy test and was maintained at this level for the duration of he test. Plant species in the preemergence and postemergence tests consisted of barley rwdwmn xulga∑s), bedstraw ⁽ Ci-»M---ι- aga∑ins), blackgrass ⁽ Alopecurus mXfiSlirfiidss), chickweed ⁽ Stellaria media), corn (Zfia maϊS), cotton fi p pjηm h mtrlim), crabgrass ⁽ Digitaria PflTirπinalip), downy brome (Brcmus tsεtøum), giant foxtail (Seiaάfi faksrii), lambsquarters ⁽ fihfnftlffldi.iτn album), morningglory ⁽ Ipomoea hsda∑aεsa), pigweed ⁽ AτnarnnthuBretrofle_-UB.. rape (Brassica nflpjis), xyegrass ⁽ T^l ^mm nmJ&flffiQim). sorghum ffføi-gtfflm h Ωlcr), soybean (Glvcine max), speedwell (Veronica persica). sugar beet (Beta vulgaris). velvetleaf (Abtttiloa theophraBti). wheat ⁽ Tri-him™ AfiSϋ∑u ), wild hnclr-DσhAfl* and wild oat (Avena fatua). All plant species were planted one day before appUcation ofthe compound for the preemergence portion of this test. Plantings of these species were adjusted to produce plants of appropriate size for the postemergence portion ofthe test. Plant species in the paddy test consisted of barnyardgrass (Oryza aaiά∑a , umbrella sedge (Cvperus d fformig) and duck salad (Heteranthera ϋmfififi).

AU plant species were grown using normal greenhouse practices. Visual evaluations of iiyury expressed on treated plants, when compared to untreated controls, were recorded approximately fourteen to twenty one days after appUcation ofthe test compound. Plant response ratings, summarized in Table B, 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 B COMPOUND

Rate (250 g/ha) 25 2627 28 29 3640 41 43 PREEMERGENCE

Barley Igri 0 0 0 0 0 0 2 1 2

Bedstraw 0 4 3 0 3 7 2 - 9

Blackgrass 10 8 8 10 7 10 10 10 10 Chickweed 6 8 8 7 5 9 9 7 9

Corn 2 0 2 2 0 2 0 6 6

Cotton 0 3 0 0 0 0 0 2 7

Crabgrass 10 9 10 10 10 10 10 10 10

Downy brome 3 0 3 6 0 4 9 6 6

Duck salad _ _ _ _ _ _ _ _ _

Giant foxtail 10 9 9 10 9 10 7 10 10

Lambsquarters 7 8 6 7 0 8 9 9 9

Morningglory 3 0 2 2 0 6 0 0 0 ^"

Pigweed 0 0 7 6 7 4 4 8 7

Rape 0 0 0 0 0 3 0 5 0

Ryegrass 10 10 6 10 6 9 10 9 10

Sorghum 4 2 5 4 0 6 4 2 3

Soybean 2 - 0 0 - 0 0 0 4

Speedwell 5 7 6 7 3 6 9 8 6

Sugar beet 0 0 4 4 3 6 6 7 4

Velvetleaf 5 8 3 7 4 5 2 8 8

Wheat 3 0 3 0 3 0 0 2 5

Wild buckwheat 0 5 6 5 3 9 0 9 8

Wild oat 0 3 3 6 3 5 4 5 5

Barnyardgrass _ _ _ _ _ _ _ _ _

Rice Japonica _ _ _ _ _ _ _ _ _

Umbrella sedge _ _ _ _ _ _ _ _ _

Table B COMPOUND

Rate (125 g/ha) 25 26 27 28 29 36 40 41

POSTEMERGENCE

Barley Igri 0 0 0 0 0 0 2 0

Bedstraw 2 0 0 0 0 0 0 3

Blackgrass 8 2 7 4 1 9 4 9

Chickweed 0 2 3 0 0 2 0 4

Corn 0 0 0 0 0 0 0 0

Cotton 0 0 0 0 0 0 0 0

Crabgrass 3 2 0 3 0 4 0 5

Downy brome 0 0 2 0 1 0 0 0

Duck salad 0 0 1 6 0 0 3 2 t.

Giant foxtail 3 4 6 6 3 6 3 3

Lambsquarters 1 0 2 2 0 6 0 8

Morningglory 3 0 0 0 0 0 0 0

Pigweed 3 0 0 0 0 2 0 0

Rape 0 0 0 0 0 0 0 0

Ryegrass 4 2 1 2 0 0 4 6

Sorghum 0 0 0 0 0 2 2 2

Soybean 0 0 0 2 0 0 0 0

Speedwell 2 2 0 0 0 5 0 3

Sugar beet 2 0 0 0 0 0 0 0

Velvetleaf 3 3 0 0 0 4 0 2

Wheat 0 0 0 0 0 0 2 3

Wild buckwheat 2 0 0 0 0 7 - 7

Wild oat 0 0 0 0 0 0 0 0

Barnyardgrass 9 9 9 9 9 10 9 10

Rice Japonica 0 0 2 0 0 1 7 7

Umbrella sedge 7 9 9 9 9 2 9 8

Table B COMPOUND

Rate (125 g/ha) 25 2627 28 29 3640 41

PREEMERGENCE

Barley Igri 0 0 0 0 0 0 0 0

Bedstraw 0 0 0 0 0 5 0 0

Blackgrass 10 7 7 10 5 10 10 10

Chickweed 4 7 7 6 3 0 4 5

Corn 0 0 0 0 0 0 0 2

Cotton 0 2 0 0 0 0 0 0

Crabgrass 9 8 10 10 8 8 8 10

Downy brome 0 0 2 5 0 0 4 4

Duck salad _ _ _ _ _ _ _ _

Giant foxtail 9 9 8 10 9 8 6 10

Lambsquarters 5 3 5 6 0 4 - 8

Morningglory 2 0 0 2 0 4 0 0

Pigweed 0 0 2 3 5 1 4 8

Rape 0 0 0 0 0 0 0 4

Ryegrass 7 7 5 10 4 9 8 7

Sorghum 2 0 3 2 0 4 1 2

Soybean 0 - 0 0 0 0 0 0

Speedwell 3 3 2 5 0 5 4 5

Sugar beet 0 0 3 3 2 3 0 3

Velvetleaf 2 3 2 5 2 3 2 7

Wheat 3 0 0 0 0 0 0 0

Wild buckwheat 0 3 4 3 0 5 0 5

Wild oat 0 0 0 4 0 3 4 3

Barnyardgrass _ _ _ _ _ _ _ _

Rice Japonica _ _ _ _ _ _ _ _

Umbrella sedge _ _ _ _ _ _ _ _

Table B COMPOUND

Rate (62 g/ha) 25 2627 28 29 36 40 41 43 PREEMERGENCE

Barley Igri 0 0 0 0 0 0 0 0 0

Bedstraw 0 0 0 0 0 2 0 0 2

Blackgrass 8 4 6 8 4 10 8 10 6

Chickweed 3 4 6 5 2 0 0 5 2

Corn 0 0 0 0 0 0 0 0 3

Cotton 0 0 0 0 0 0 0 0 4

Crabgrass 9 5 9 10 8 8 6 10 9

Downy brome 0 0 0 3 0 0 4 0 4

Duck salad _ _ _ _ _ _ _ _ _

Giant foxtail 8 6 7 10 8 7 3 10 8

Lambsquarters 4 3 4 2 0 4 - 8 8

Morningglory 0 0 0 0 0 0 0 0 0

Pigweed 0 0 2 0 2 0 2 6 3

Rape 0 0 0 0 0 0 0 4 0

Ryegrass 6 4 4 6 3 2 8 3 4

Sorghum 0 0 2 0 0 2 0 0 0

Soybean 0 0 0 0 0 0 0 0 0

Speedwell 0 0 0 3 0 2 0 3 6

Sugar beet 0 0 0 0 0 3 0 2 4

Velvetleaf 0 2 0 2 2 3 0 5 6

Wheat 0 0 0 0 0 0 0 0 2

Wild buckwheat 0 0 4 0 0 4 0 3 0

Wild oat 0 0 0 0 0 0 0 2 0

Barnyardgrass _ _ _ _ _ _ _ _ _

Rice Japonica _ _ _ _ _ _ _ _ _

Umbrella sedge _ _ _ _ _ _ _ _ _

Table B COMPOUND

Rate (31 g/ha) 25 2627 28 29 36 40 41 POSTEMERGENCE

Barley Igri 0 0 0 0 0 0 0 0

Bedstraw 0 0 0 0 0 0 0 0

Blackgrass 2 0 2 0 0 0 0 4

Chickweed 0 0 0 0 0 0 0 0

Corn 0 0 0 0 0 0 0 0

Cotton 0 0 0 0 0 0 0 0

Crabgrass 0 0 0 0 0 0 0 0

Downy brome 0 0 0 0 0 0 0 0

Duck salad 0 0 0 0 0 0 0 0

Giant foxtail 0 0 0 3 0 0 0 0

Lambsquarters 0 0 0 0 0 2 0 8

Morningglory 0 0 0 0 0 0 0 0

Pigweed 0 0 0 0 0 0 0 0

Rape 0 0 0 0 0 0 0 0

Ryegrass 0 0 0 0 0 0 0 0

Sorghum 0 0 0 0 0 0 0 0

Soybean 0 0 0 0 0 0 0 0

Speedwell 0 0 0 0 0 3 0 0

Sugar beet 0 0 0 0 0 0 0 0

Velvetleaf 0 0 0 0 0 0 0 0

Wheat 0 0 0 0 0 0 0 0

Wild buckwheat 0 0 0 0 0 3 0 5

Wild oat 0 0 0 0 0 0 0 0

Barnyardgrass 9 9 9 9 7 9 6 9

Rice Japonica 0 0 0 0 0 0 1 3

Umbrella sedge 0 0 8 8 0 0 6 7

Table B COMPOUND

Rate (31 g/ha) 25 2627 28 29 3640 41

PREEMERGENCE

Barley Igri 0 0 0 0 0 0 0 0

Bedstraw 0 0 0 0 0 0 0 0

Blackgrass 6 3 4 5 3 5 1 9

Chickweed 0 0 4 4 0 0 0 2

Corn 0 0 0 0 0 0 0 0

Cotton 0 0 0 0 0 0 0 0

Crabgrass 8 - 8 9 5 7 2 9

Downy brome 0 0 0 0 0 0 0 0

Duck salad _ _ _ _ _ _ _ _

Giant foxtail 6 4 7 8 6 7 0 8

Lambsquarters 3 3 3 0 0 2 8 7

Morningglory 0 0 0 0 0 0 0 0

Pigweed 0 0 0 0 0 0 2 4

Rape 0 0 0 0 0 0 0 0

Ryegrass 4 3 4 4 0 0 0 3

Sorghum 0 0 0 0 0 2 0 0

Soybean 0 0 0 0 0 0 0 0

Speedwell 0 0 0 0 0 3 0 0

Sugar beet 0 0 0 0 0 3 0 0

Velvetleaf 0 0 0 0 0 3 0 3

Wheat 0 0 0 0 0 0 0 0

Wild buckwheat 0 0 3 0 0 - 0 0

Wild oat 0 0 0 0 0 0 0 0

Barnyardgrass _ _ _ _ _ _ _ _

Rice Japonica _ _ _ _ _ _ _ _

Umbrella sedge _ _ _ _ _ _ _ _

Table B COMPOUND

Rate (16 g/ha) 25 26 27 28 29 36 43 POSTEMERGENCE

Barley Igri 0 0 0 0 0 0 -

Bedstraw 0 0 0 0 0 0 -

Blackgrass 0 0 0 0 0 0 -

Chickweed 0 0 0 0 0 0 -

Corn 0 0 0 0 0 0 -

Cotton 0 0 0 0 0 0 -

Crabgrass 0 0 0 0 0 0 -

Downy brome 0 0 0 0 0 0 -

Duck salad 0 0 0 0 0 0 0

Giant foxtail 0 0 0 0 0 0 -

Lambsquarters 0 0 0 0 0 0 -

Morningglory 0 0 0 0 0 0 -

Pigweed 0 0 0 0 0 0 -

Rape 0 0 0 0 0 0 -

Ryegrass 0 0 0 0 0 0 -

Sorghum 0 0 0 0 0 0 -

Soybean 0 0 0 0 0 0 -

Speedwell 0 0 0 0 0 3 -

Sugar beet 0 0 0 0 0 0 -

Velvetleaf 0 0 0 0 0 0 -

Wheat 0 0 0 0 0 0 -

Wild buckwheat 0 0 0 0 0 0 -

Wild oat 0 0 0 0 0 0 -

Barnyardgrass 9 7 7 9 0 9 8

Rice Japonica 0 0 0 0 0 0 1

Umbrella sedge 0 0 0 7 0 0 0

Table B COMPOUND

Rate (16 g/ha) 25 26 27 28 29 36 43

PREEMERGENCE

Barley Igri 0 0 0 0 0 0 0

Bedstraw 0 0 0 0 0 0 0

Blackgrass 3 0 3 4 3 4 0

Chickweed 0 0 0 3 0 0 0

Corn 0 0 0 0 0 0 0

Cotton 0 0 0 0 0 0 0

Crabgrass 6 2 5 7 5 5 5

Downy brome 0 0 0 0 0 0 0

Duck salad _ _ _ _ _ _ _ J

Giant foxtail 4 2 5 5 5 3 4

Lambsquarters 0 3 0 0 0 0 7

Morningglory 0 0 0 0 0 0 0

Pigweed 0 0 0 0 0 0 0

Rape 0 0 0 0 0 0 0

Ryegrass 3 0 3 3 0 0 3

Sorghum 0 0 0 0 0 0 0

Soybean 0 0 0 0 0 0 0

Speedwell 0 0 0 0 0 0 2

Sugar beet 0 0 0 0 0 0 2

Velvetleaf 0 0 0 0 0 0 3

Wheat 0 0 0 0 0 0 0

Wild buckwheat 0 0 3 0 0 - 0

Wild oat 0 0 0 0 0 0 0

Barnyardgrass _ _ _ _ _ _ _

Rice Japonica _ _ _ _ _ _ _

Umbrella sedge _ _ _ _ _ _ _

ES Q

Plastic pots were partiaUy fiUed with silt loam soil. The soil was then saturated with water. Japonica rice (Oryza fiatixa) seedlings at the 2.0 to 2.5 leaf stage, seeds selected from barnyardgrass πfohinnrfiina s∑siBz gaUi), duck salad (Heteranthera JUOQBS), umbreUa sedge ⁽ Cvperus diffiαmis) _. and tubers selected from arrowhead (Sagittaria spp.), and waterchestnut (Eleocharis spp.), were planted into this soil. After planting, water levels were raised to 3 cm above the soil surface and maintained at this level throughout the test. The compounds indicated were formulated in a non-phytotoxic solvent and appUed directly to the paddy water. Treated plants and controls were maintained in a greenhouse for approximately 21 days, after which aU species were compared to controls and visually evaluated. Plant response ratings, summarized in Table C, are reported on a 0 to 10 scale where 0 is no effect and 10 is complete control. A dash (-) response means no test result.

Rate (250 g/ha) 25 27 28 PADDY

TESLΏ.

Plastic pots were partially fiUed with silt loam soil. The soil was then flooded with water, Japonica rice (Oryza aaftxa) sprouted seeds and 1.5 leaf transplants were planted in the soil. Seeds of barnyardgrass (jRnh.nnctilnfl mta-yalli. were planted in saturated soil and plants grown to the 1 leaf, 2 leaf and 3 leaf stages for testing. At testing, the water level for aU plantings was raised to 2 cm above the soil surface. The compounds indicated were formulated in a non-phytotoxic solvent and appUed directly to the paddy water. Treated plants and controls were maintained in a greenhouse for approximately 21 days, after which all species were compared to controls and visually evaluated. Plant response ratings, summarized in Table D are reported on a 0 to 10 scale where 0 is no effect and 10 is complete control. A dash (-) response means no test result.

Table D COMPOUND

Rate (1000 g/ha) 26 27 28 29 36 PADDY

1-LF B.Y.Grass 10 10 10 10 10

2-LF B.Y.Grass 10 10 10 10 10

3-lf B.Y.Grass 10 10 10 10 9

Jap Direct Seed 9 9 9 7 9

Jap Rice Eff 6 8 5 3 0

Rate (500 g/ha) 25 26 27 28 29 36 43

PADDY

1-LF B.Y.Grass 10 10 10 10 10 10 -

2-LF B.Y.Grass 10 10 10 10 9 9 10

3-lf B.Y.Grass 9 9 10 10 10 8 10

Jap Direct Seed 6 7 8 8 6 6 10

Jap Rice Eff 4 2 5 5 0 0 4

Rate (250 g/ha) 25 26 27 28 29 36 43

PADDY

1-LF B.Y.Grass 10 10 10 10 10 10 -

2-LF B.Y.Grass 9 10 10 10 10 9 10

3-lf B.Y.Grass 8 9 10 10 10 7 10

Jap Direct Seed 4 7 5 5 4 5 10

Jap Rice Eff 5 2 0 3 0 0 2

Table D COMPOUND

Rate (125 g/ha) 25 26 27 28 29 36 41 43

PADDY

1-LF B.Y.Grass 9 10 10 10 10 10 - -

2-LF B.Y.Grass 6 6 10 10 9 9 8 10

3-lf B.Y.Grass 6 6 9 10 7 7 9 9

Jap Direct Seed 2 2 1 2 2 1 8 8

Jap Rice Eff 0 0 1 0 0 0 1 2

Rate (64 g/ha) 25 2627 28 293641 43

PADDY

1-LF B.Y.Grass

2-LF B.Y.Grass

3-lf B.Y.Grass

Jap Direct Seed

Jap Rice Eff 0 0 0 0 0 0 0

Rate (32 g/ha) 25 41 43

PADDY

1-LF B.Y.Grass 9 - -

2-LF B.Y.Grass 3 4 8

3-lf B.Y.Grass 2 3 6

Jap Direct Seed 0 0 5

Jap Rice Eff 0 0 1

Rate (16 g/ha) 41

PADDY

2-LF B.Y.Grass 3

3-lf B.Y.Grass 0

Jap Direct Seed 0

Jap Rice Eff 1

TESTE

Seeds of barnyardgrass πft-1.iτι<v .1n» <-τ-πH-yn1Ti_ _r corn (Zsa mays) _. cotton (Grøgypjum hi∑sutam), crabgrass jgitaria spp.), fall panicum

■ P _q τ..m.rn <«ffTm1nττ._ lnτιιτι_ . _| giant foxtail (ggtaxia fahfiEU), gTββn foxtail (Setaria YJyidJB), Johnson grass fSf grhiim hals sofis), signalgrass

(Brachiaria platvphvUa) _r soybean (QlyαilS max) and wild proso (PnηπiTTn -r lion iiTw. were planted into a silt loam soil. The compounds indicated were dissolved in a non-phytotoxic solvent, and then appUed to the soil surface within one day after the seeds were planted. Treated plants and untreated controls were maintained in the greenhouse approximately 21 days, then treated plants were compared to -untreated controls and visually evaluated. Plant response ratings, summarized in Table £, are reported on a 0 to 10 scale where 0 is no effect and 10 is complete control.

TEST F

Compounds evaluated in this test were formulated in a non- phytoxic solvent and appUed to the soil surface before plant seedlings emerged (preemergence appUcation) and to plants that were in the one-to- four leaf stage (postemergence appUcation). A sandy loam soil was used for the preemergence test while a mixture of sandy loam soil and greenhouse potting mix in a 60:40 ratio was used for the postemergence test. Test compounds were appUed within approximately one day after planting seeds for the preemergence test. Plantings of these crops and weed species were adjusted to produce plants of appropriate size for the postemergence test. AU plant species were grown using normal greenhouse practices. Crop and weed species include winter barley ■ Hn «_fti τn vulpare cv. Igri'), blackgrass (Alopecurus mvosuroides). chickweed (SteUaria media), downy brome (Bromus -tøtø-um), field violet (Viola a∑∑e&sis). gaUum (fialium asaims), green foxtail (Ssfcaiia ∑ iϋs), kochia ⁽ Kn ia scoparia). lambsquarters Persian speedweU (Veronica pers a), rape ⁽ Brassica αasus cv. 'Jet Neuf ), ryegrass ^f T ^* *li ττi mulJaflOD-m). sugar beet (£≤ta vulparis cv. S1'), sunflower (HeUanthus «τι ι__iB cv. "Russian Giant'), spring wheat (Tritinim nfi iviiπ. cv. ΕRA'), winter wheat rTri-ti ^* a ^pg ti n-m cv.

Talent'), wild buckwheat TftlYgOTl.im convolvulus), wild mustard (Smapis arvengiB). wild oat (Δ∑enfl fja lfl), and wild radish ⁽ Raphanus a -ianiHtniTT V Blackgrass and wild oat were treated postemergence at two growth stages. The first stage (1) was when the plants had two to three leaves. The second stage (2) was when the plants had approximately four leaves or in the initial stages of tiUering. Treated plants and untreated controls were maintained in a greenhouse for approximately 21 to 28 days, after which aU treated plants were compared to untreated controls and visually evaluated. Plant response ratings, summarized in Table F, are based upon a 0 to 10 scale where 0 is no effect and 10 is complete control. A dash response (-) means no test result.