Login| Sign Up| Help| Contact|

Patent Searching and Data


Title:
SUBSTITUTED BENZOTHIOPYRANES SALTS AND THEIR USE AS HERBICIDES
Document Type and Number:
WIPO Patent Application WO/1998/028291
Kind Code:
A1
Abstract:
Compounds of Formula (I) are disclosed which are useful for controlling undesired vegetation wherein Q is (Q-1) or (Q-2); and R?1�-R?12�, M, m, n, p, q, r, and t are as defined in the disclosure. Also disclosed are compositions containing the compounds of Formula (I) and a method for controlling undesired vegetation which involves contacting the vegetation or its environment with an effective amount of a compound of Formula (I).

Inventors:
TSENG CHI-PING (US)
Application Number:
PCT/US1997/023469
Publication Date:
July 02, 1998
Filing Date:
December 17, 1997
Export Citation:
Click for automatic bibliography generation   Help
Assignee:
DU PONT (US)
TSENG CHI PING (US)
International Classes:
A01N43/18; A01N43/56; A01N43/90; C07D335/06; C07D409/06; C07D495/10; (IPC1-7): C07D335/06; A01N43/18; A01N43/56; A01N43/90; C07D409/06; C07D495/10
Foreign References:
EP0712853A11996-05-22
US5480858A1996-01-02
Attorney, Agent or Firm:
Katz, Elliott A. (Legal Patent Records Center 1007 Market Stree, Wilmington DE, US)
Download PDF:
Claims:
CLAIMS What is claimed is:
1. A compound selected from Formula I wherein Qis M is Li, Na, K, Ca, Mg, Co, Ni, Cu or Zn; or M is r is 1 when M is Li, Na, K or r is 2 when M is Ca, Mg, Co, Ni, Cu or Zn; R1 and R2 are taken together with the carbon to which they are attached to form C(=O) or R1 and R2 are taken together to form OCH2CH2O optionally substituted with one to two ClC3 alkyl; each R3 is CH3; R4 and R5 are each independently H, ClC3 alkyl or halogen; R6 is ClC3 alkyl; R7 is C1C3 alkyl; R8 is H, C1C25 alkyl or benzyl; R9 and R10 are independently C1C25 alkyl; R1 I is C1C25 alkyl or R12 is H, C1C12 alkyl, C1C3 alkoxy, NO2 or CN; m and t are independently 1, 2 or 3; n and p are each independently 0, 1 or 2; and q is 0, 1, 2, 3 or 4; provided that when Q is Q1 and R1 and R2 are taken together with the carbon to which they are attached to form C(=O), then n is 1 or 2.
2. A compound of Claim 1 wherein: QisQ1.
3. A compound of Claim 2 wherein: R4 and R5 are each independently H or C1C3 alkyl; nis2; pis 0; and qisO, 1 or2.
4. A compound of Claim 3 wherein: Mis Li, Na, K or.
5. A compound of Claim 1 wherein: Q is Q2.
6. A compound of Claim 5 wherein: R4 and R5 are each independently H or C1C3 alkyl; R7 is CH2CH3; n is 2; p is 0; and q is 0. 1 or 2.
7. A compound of Claim 6 wherein: Mis Li, NaKor.
8. The compound of Formula I which is selected from the group: a) 2[(3,4dihydro5,8dimethyl4oxo2H 1 benzothiopyran6yl)carbonyl]5,5 dimethyl1,3cyclohexanedione S,Sdioxide monolithium salt; b) 2[(3,4dihydro5,8dimethyl4oxo2H 1 benzothiopyran6yl)carbonyl]5,5 dimethyl 1,3 cyclohexanedione S,Sdioxide monosodium salt; c) 2[(3,4dihydro5,8dimethyl4oxo2H1benzothiopyran6yl)carbonyl]5,5 dimethyl 1,3cyclohexanedione S,Sdioxide monopotassium salt; d) 2[(2,3dihydro5,8dimethylspiro[4H1benzothiopyran4,2'[1,3]dioxolan]6 yl)carbonyl]1,3cyclohexanedione S,Sdioxide monolithium salt; e) 2[(2,3dihydro5,8dimethylspiro[4H 1 benzothiopyran4,2'[1 ,3]dioxolan]6 yl)carbonyl]1,3cyclohexanedione S,Sdioxide monosodium salt; f) 2[(2,3dihydro5,8dimethylspiro[4H1benzothiopyran4,2'[1,3]dioxolan]6 yl)carbonyl]1,3 cyclohexanedione S,Sdioxide monopotassium salt; g) (2,3dihydro5,8dimethylspiro[4H1benzothiopyran4,2'[1,3]dioxolan]6 yl)(lethyl5 hydroxyl Hpyrazol4yl)methanone S,Sdioxide monolithium salt; h) (2,3dihydro5,8dimethylspiro[4H 1 benzothiopyran4,2'[1 ,3]dioxolan]6 yl)(1ethyl5hydroxy1Hpyrazol4yl)methanone S,Sdioxide monosodium salt; i) (2,3dihydro5,8dimethylspiro[4H1benzothiopyran4,2'[1,3]dioxolan]6 yl)(1 ethyl5hydroxy 1 Hpyrazol4yl)methanone S,Sdioxide monopotassium salt; j) 6[(1ethyl5hydroxy1Hpyrazol4yl)carbonyl]2,3dihydro5,8dimethyl4H 1benzothiopyran4one 1,1dioxide monolithium salt; k) 6[(1ethyl5hydroxy1Hpyrazol4yl)carbonyl]2,3dihydro5,8dimethyl4H 1 benzothiopyran4one 1,1dioxide monosodium salt; and 1) 6[(1 ethyl5hydroxy l Hpyrazol4yl)carbonyl]2,3 dihydro5,8dimethyl4H lbenzothiopyran4one l,1dioxide monopotassium salt.
9. A herbicidal composition comprising a herbicidally effective amount of a compound of Claim 1 and at least one of a surfactant, a solid diluent or a liquid diluent.
10. A method for controlling the growth of undesired vegetation comprising contacting the vegetation or its environment with a herbicidally effective amount of a compound of Claim 1.
Description:
SUBSTITUTED BENZOTHIOPYRANES SALTS AND THEIR USE AS HERBICIDES BACKGROUND OF THE INVENTION This invention relates to certain salts, compositions of said salts, and methods of their use for controlling undesirable vegetation.

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

EP 283,261 discloses heterocycles of Formula i as herbicides: wherein X, X1 and X2 are independently 0 or S; R1 is a monocyclic or fused-bicyclic heterocyclic group optionally substituted by one or more groups selected from oxo, mercapto, halo, nitro, cyano, amino, mono- or dialkylamino, amido, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, haloalkoxy, aryl, hydroxy, alkoxy, alkoxycarbonyl, alkylcarbonyl, mono- or dialkylcarbamoyl, alkylthio, alkylsulfinyl, alkylsulfonyl, sufonamido, alkylcarbonyloxy, alkylcarbonylamino or heterocyclyl; and Y is, inter alia, C2-C4 alkylene.

The salts of the present invention are not disclosed in this reference.

SUMMARY OF THE INVENTION This invention is directed to compounds of Formula I including all geometric and stereo isomers, agricultural compositions containing them and their use for controlling undesirable vegetation:

wherein Qis M is Li, Na, K, Ca, Mg, Co, Ni, Cu or Zn; or M is r is 1 when M is Li, Na, K or r is 2 when M is Ca, Mg, Co, Ni, Cu or Zn; R1 and R2 are taken together with the carbon to which they are attached to form C(=O) or R1 and R2 are taken together to form -OCH2CH2O- optionally substituted with one to two Cl-C3 alkyl; each R3 is CH3; R4 and R5 are each independently H, C1 -C3 alkyl or halogen; R6 is Cl-C3 alkyl; R7 is C1-C3 alkyl; R8 is H, C1-C25 alkyl or benzyl; R9 and R10 are independently C1-C25 alkyl;

R1 l is C1-C25 alkyl or R12 is H, Cl-Cz, alkyl, Cl-C3 alkoxy, NO9 or CN; m and t are independently 1, 2 or 3; n and p are each independently 0, 1 or 2; and qisO, 1,2, 3 or 4; provided that when Q is Q-1 and R1 and R2 are taken together with the carbon to which they are attached to form C(=O), then n is 1 or 2.

In the above recitations, the term "alkyl", used either alone or in compound words such as "alkylthio" or "haloalkyl" includes straight-chain or branched alkyl, such as, methyl, ethyl, n-propyl, i-propyl, or the different butyl, pentyl or hexyl isomers. "Alkoxy" includes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers.

The term "halogen", either alone or in compound words such as "haloalkyl", includes fluorine, chlorine, bromine or iodine.

The total number of carbon atoms in a substituent group is indicated by the "Cj-Cj" prefix where i andj are numbers from 1 to 25. For example, C1-C3 alkyl designates methyl through propyl.

When a compound is substituted with a substituent bearing a subscript that indicates the number of said substituents can exceed 1, said substituents (when they exceed 1) are independently selected from the group of defined substituents.

When a group contains a substituent which can be hydrogen, for example R12, then, when this substituent is taken as hydrogen, it is recognized that this is equivalent to said group being unsubstituted.

Compounds of this invention can exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers. One skilled in the art will appreciate that one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s). Additionally, the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers. Accordingly, the present invention comprises compounds selected from Formula I and agriculturally suitable salts thereof. The compounds of the invention may be present as a mixture of stereoisomers, individual stereoisomers, or as an optically active form.

Some compounds of this invention can exist as one or more tautomers. One skilled in the art will recognize, for example, that compounds of Formula Ia (Formula I where Q is

Q-1) can also exist as other tautomers as shown below. One skilled in the art will recognize that said tautomers often exist in equilibrium with each other. As these tautomers interconvert under environmental and physiological conditions, they provide the same useful biological effects. The present invention includes mixtures of such tautomers as well as the individual tautomers of compounds of Formula I. + R1 R2 (R3)< < ; (R6)q (°)n RS 7 Ia ¼ wherein M is Na Rl R2 R4 Na+ R1 R2 R4 o Na O (R3,,- A AS >< AS R3 R3 Preferred compounds for reasons of better activity and/or ease of synthesis are: Preferred 1. Compounds of Formula I above wherein: QisQ-1.

Preferred 2. Compounds of Preferred 1 wherein: R4 and R5 are each independently H or Cl-C3 alkyl; nis2; p is 0; and qisO, 1 or2.

Preferred 3. Compounds of Preferred 2 wherein: Mis Preferred 4. Compounds of Preferred 2 wherein: M is Li, Na or K.

Preferred 5. Compounds of Formula I above wherein: QisQ-2.

Preferred 6. Compounds of Preferred 5 wherein: R4 and R5 are each independently H or C1-C3 alkyl; R7 is CH2CH3; n is 2; p is 0; and qisO, 1 or2.

Preferred 7. Compounds of Preferred 6 wherein: Mis Preferred 8. Compounds of Preferred 6 wherein: M is Li, Na or K.

Most preferred are the compounds of Formula I selected from the group of the lithium, sodium, and potassium salts of: a) 2-[(3,4-dihydro-5,8-dimethyl-4-oxo-2H-1-benzothiopyran-6-yl) carbonyl]-5,5 dimethyl- 1,3 -cyclohexanedione S,S-dioxide; b) 2-[(2,3-dihydro-5,8-dimethylspiro[4H-1-benzothiopyran-4,2'-[ 1,3]dioxolan]-6- yl)carbonyl]-1,3-cyclohexanedione S,S-dioxide; c) (2,3-dihydro-5,8-dimethylspiro[4H-1-benzothiopyran-4,2'-[1,3 ]dioxolan]-6- yl)( 1 -ethyl-5-hydroxy- 1 H-pyrazol-4-yl)methanone S,S-dioxide; and d) 6-[(1-ethyl-5-hydroxy-1H-pyrazol-4-yl)carbonyl]-2,3-dihydro- 5,8-dimethyl-4H- 1 -benzothiopyran-4-one 1,1-dioxide.

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

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

DETAILS OF THE INVENTION The compounds of Formula I can be prepared by one or more of the following methods and variations as described in Schemes 1-13. The definitions ofQ, R1-R12, M, m, n, p, q, and r in the compounds of Formulae 1-1 1 below are as defined above in the Summary of the

Invention. Compounds of Formulae Ia and Ib are subsets of the compounds of Formula I, and all substituents for Formulae Ia and Ib are as defined above for Formula I. For example, compounds of Formula Ia below are compounds of Formula I wherein Q is Q-1.

Scheme 1 illustrates the preparation of compounds of Formula Ia whereby an enol of Formula 1 is treated with an alkali metal alkoxide in an alcoholic solvent such as methanol or ethanol. When M is Ca or Mg, compounds of Formula Ia may be prepared by the treatment of an enol of Formula 1 with a calcium or magnesium alkoxide. When M is a quaternary ammonium salt, compounds of Formula Ia may be prepared by the treatment of an enol of Formula 1 with a suitable quaternary ammonium halide salt and a base. This conversion is carried out by methods are known in the art (or by slight modification of these methods).

Scheme 1 R1 R2 R4 0 OH alkali Ca alkoxide or nary alkoxide or (R3) (R6)q la salt °4 base quaternary ammonium (°)n salt and base Scheme 2 illustrates the preparation of compounds of Formula lb (R1 and R2 are taken together with the carbon to which they are attached to form C(=O)) whereby a compound of Formula la(R1 and R2 are taken together to form -O(CH2)20- optionally substituted with one or two C1 -C3 alkyl) is stirred in hydrochloric acid or hydrobromic acid aqueous solution (0.1 N to 12 N) at temperatures between 0 "C and 100 "C for a period of time ranging from 30 minutes to 3 days. This conversion is carried out by methods known in the art (or by slight modification of these methods): for example; see P. A. Grieco, et al., J: Am. Chem.

Soc. (1977), 99, p 5773; P. A. Grieco, et al., j Org. Chem. (1978), 43, p 4178.

Scheme 2 la (R1 and R2 are taken together to form -O(CH2)20- optionally substituted with one or two C1-C3 alkyl) ib (R1 and R2 are taken together with the carbon to which they are attached to form C(=O)) Scheme 3 illustrates the preparation of a compound of Formula 1 a whereby an enol ester of Formula 2 is reacted with a base such as triethylamine in the presence of a catalytic amount of a cyanide source (e.g., acetone cyanohydrin or potassium cyanide)); standard acidic workup procedures then yield the compound of Formula 1 a. Alternatively, the triethylammonium salt of 1 a can be isolated directly; this method is preferred for compounds which may be sensitive to the acidic workup conditions. Treatment of the triethylammonium salt of 1 a with aqueous alkali metal hydroxides yields the corresponding alkali metal salt of Formula Ia. The cyanide-catalyzed rearrangement is carried out by general methods known in the art; see for example, W. J. Michaely, EP 0369803-A1; D.

Cartwright, et al., EP 0283261-B1.

Scheme 3 o /S 0 osY (R6)q Base (e.g., triethylamine) 3)Pt Base (e.g., triethylamine) Ia (°)n R5 Cyanide source in catalytic 2 amount (e.g., acetone cyano- hydrin or potassium cyanide) Enol esters of Formula 2 can be prepared by reacting a dicarbonyl compound of Formula 3 with an acid chloride of Formula 4 in the presence of a slight molar excess of a base such as triethylamine in an inert organic solvent such as acetonitrile, methylene chloride or toluene at temperatures between 0 "C and 110 "C (Scheme 4). This type of coupling is carried out by general methods known in the art (or by slight modification of these methods): for example, see W. J. Michaely, EP 0369803-A1; D. Cartwright, et al., EP 0283261-B1.

Scheme 4 0 R4 0 (R6)q + (R3))CI 0 (O) R5 3 4 Base (e.g., triethylamine) 2 The acid chlorides of Formula 4 can be prepared by reacting an acid of Formula 5 with oxalyl chloride (or thionyl chloride) and a catalytic amount of N,N-dimethylformamide (DMF) (Scheme 5). This chlorination is well known in the art; see for example, W. J.

Michaely, EP 0369803-Al.

Scheme 5 Rl Rn IR4 R R R4 or ;:":% OH oxalyl chloride or < 2R)0Cl chloride (R3)p thionyl (R3)p (R3)Pt J catalytic amount S R5 RS of DMF (O)n 5 4 Alternatively, compounds of Formula 2 can be prepared directly from the acids of Formula 5 by treatment with an alkyl chloroformate, followed by reaction of the formed intermediate mixed anhydrides with the dicarbonyl compounds of Formula 3.

Scheme 6 illustrates the preparation of acids of Formula 5 (n is 1 or 2) whereby an acid of Formula 5 (n is 0) is reacted with a oxidizing reagent such as peroxyacetic acid, m-chloroperoxybenzoic acid, potassium peroxymonosulfate or hydrogen peroxide. The reaction may be buffered with a base such as sodium acetate or sodium carbonate. The oxidation is carried out by general methods known in the art (see for example, B. M. Trost, et al., J. Org. Chem. (1988), 53, 532; B. M. Trost, et al., Tetrahedron Lett. (1981), 21, 1287; S. Patai, et al., The Chemistry ofSulphones and Suiphoxides, John Wiley & Sons).

Scheme 6 5 (n is 0) o 5 (nits 1 or2) oxidizing agent Scheme 7 illustrates the preparation of acids of Formula 5 (n is 0) whereby a phenyl bromide of Formula 6 (R1 and R2 are other than taken together with the carbon to which they are attached to form C(=O) and n is 0) is treated with n-butyllithium (or magnesium), and the lithium salt (or the Grignard reagent) generated in situ is then reacted with carbon dioxide followed by acidification with an acid such as hydrochloric acid. This conversion is carried out by general methods known in the art; see for example, M. A. Ogliaruso et al., Synthesis of Carboxylic Acids, Esters and Their Derivatives, pp 27-28, John Wiley & Sons A. J.

Bridges, et al., J. Org. Chem. (1990), 55 (2), 773; C. Franke, et al., Angew. Chem. Int. Ed.

(1969), 8, 68. In some instances, the incorporation of protection/deprotection sequences or functional group interconversions into the synthesis will aid in obtaining the desired products. The use and choice of the protecting groups will be apparent to one skilled in

chemical synthesis (see, for example. Green T. W.; Wuts, P. G. M., Protective Groups in Organic Synthesis, 2nd ed.; Wiley: New York, 1991).

Scheme 7 Rl R2 R4 I) n-BuLi (or Mg) C07 t 5 (n is 0) tS/R5 3) H30+ 6 6 (R1 and R2 are other than taken together with the carbon to which they are attached to forrn C(=O) and n is O) Scheme 8 illustrates the preparation of phenyl bromides of Formula 6 (R1 and R2 are taken together to form -O(CH2)2O- optionally substituted with one or two Cl-C3 alkyl and n is 0) whereby a ketone of Formula 7 (n is 0) is reacted with HO(CH2)2OH in the presence of a protic acid catalyst such as p-toluenesulfonic acid (or a Lewis acid such as BF3) in an inert organic solvent such as toluene. This conversion is carried out by general methods known in the art; see for example, T. W. Greene, et al., Protective Groups in Organic Synthesis (Second Edition), pp 175-221, John Wiley & Sons, Inc.

Scheme 8 O R4 HOCH2CH2OH optionally Br substituted with one or (R3)y½ two Cl-C3 optionally (Om substituted with one or (catalytic amount of acid) (°)n R5 7 (n is 0) Some compounds of Formula 7 (n is 0) can also be prepared by reacting a substituted benzene of Formula 8 (n is 0) with bromine in an inert organic solvent (Scheme 9). This bromination is carried out by general methods known in the art. See E. Campaigne, et al., J Heterocycl. Chem. (1969)6, 6, p 517; H. Gilman, J; Am. Chem. Soc. (1955), 77, p 6059.

Scheme 9 (n is O) (n is O) The ketones of Formula 7 can also be prepared by general methods known in the art (or by slight modification of these methods); see, for example, W. Flemming, et al., Chem.

Ber. (1925), 58, 1612; I. W. J. Still, et al., Can. J Chem. (1976), 54, 453-470; V. J.

Traynelis, et al., J Org. Chem. (1961), 26, 2728; I. Nasuno, et al., WO 94/08988; F. Camps, et al., J. Heterocycl. Chem. (1985), 22(5), p. 1421; T. S. Rao, et al., Indian J: Chem. B.

(1985), 24(11), p. 1159; S. Ghosh, et al., Tetrahedron (1989), 45(5), p. 1441; A. Danan, et al., Synthesis-Stuttgart (1991), (10), p. 879; P. Magnus, et al., J. Chem. Soc. Chem. Comm.

(1991), (7), p. 544; A. Padwa, et al., J: Org. Chem. (1989), 54(12), p. 2862; S. A. Ali, et al., J: Org. Chem. (1979), 44, p. 4213; J. Blake, et al., J. Am. Chem. Soc. (1966), 88, p. 4061; M. Mori, et al., J: Chem. Soc. Chem. Comm. (1990), (18), p. 1222; S. Kano, et al., J. Chem.

Soc., Perkin. Trans. 1 (1980), p. 2105; A. F. Bekhli, et al., Khim Geterotsikl. Soedin. (1975), p. 1118; W. S. Johnson, et al., J. Am. Chem. Soc. (1949), 71, p. 1901; J. A. Hirsch, etal.,J Org. Chem. (1974), 39(14), p. 2044; F. G. Mann, et al., J. Chem. Soc. (1957), p. 4166; A. C. Jain, et al., Indian. J. Chem. B (1987), 26(2), p. 136; G. Ariamala, et al., Tet. Lett.

(1988), 29(28), p. 3487; B. Loubinoux, et al., Tet. Lett. (1992), 33(16), p. 2145; S. Cabiddu, et al., j Organomet. Chem. (1989), 366(1-2), p. 1; R. HasenKamp, et al., Chem. Ber. (1980), 113, p. 1708; D. A. Pulman, et al., j Chem. Soc. Perkin. Trans. 1 (1973), p. 410; W. C. Lumma, et al., j Org. Chem. (1969), 34, p. 1566; P. D. Clark, et al., Can. J. Chem.

(1982), 60(3), p. 243.

Compounds of Formula 8 can be prepared by one skilled in the art by using the reactions and techniques known in the art. The dicarbonyl compounds of Formula 3 are either commercially available or can be prepared by general methods known in the art (or by slight modification of these methods): for example, see D. Cartwright, et al., EP 0283261- B1; J. Dangelo, et al., Tet. Lett. (1991), 32(26), p. 3063; T. Okado, et al., J; Org. Chem.

(1977), 42, p. 1163; B. E. Maryanoff, et al., J. Am. Chem Soc. (1975), 97, p. 2718; E. Er, et al., Helv. Chim. Acta. (1992), 75(7), p. 2265; Y. D. Vankar, et al., Tet. Lett., (1987), 28(5), p. 551; C. S. Pak, et al., Tet. Lett. (1991), 32(42), p. 6011; I. Nishiguchi, et al., Chem. Lett.

(1981), p. 551; B. Eistert, et al., LiebigsAnn. Chem. (1962), 659, p. 64; N. K. Hamer, Tet.

Lett. (1986), 27(19), p. 2167; M. Sato, et al., Heterocycles (1987), 26(10), p. 2611; A. Murray, et al., Tet. Lett. (1995), 36(2), p. 291; K. S. Kochhar, et al., Tet. Lett. (1984), 25(18), p. 1871; M. Sato, et al., Tetrahedron (1991), 47(30), p. 5689; M. Sato, et al., Chem.

Pharm. Bull. (1990), 38(1), p. 94; T. Meal, U.S. 4,931,570; T. Muel, metal., U.S. 5,093,503.

Compounds of Formula Ib can be readily prepared by one skilled in the art by using the reactions and techniques described in Schemes 10-13 of this section as well as by following the specific procedures given in Example 1.

Scheme 10 illustrates the preparation of compounds of Formula Ib from compounds of Formula 9. Reaction conditions are as described for Scheme 1.

Scheme 10 R1 R2 R4 OH alkali alkoxide or (R3)p N-R7 Ib quaternary anamonium (O) R5 H salt and base 9 Scheme 11 illustrates the preparation of compounds of Formula Ib whereby an ester of Formula 10 is reacted with a base such as triethylamine in the presence of a catalytic amount of cyanide source (e.g., acetone cyanohydrin or potassium cyanide). This rearrangement is carried out by methods known in the art; see for example, W. J. Michaely, EP 0369803-A1.

Scheme 11 R7 R4 S R4 0 R3)+ | Base (e.g., triethylamine) SSv > lb (°)n R5 Cyanide source in catalytic 10 amount (e.g., acetone cyano- hydrin or potassium cyanide) Scheme 12 illustrates the preparation of compounds of Formula Ib (R1 and R2 are taken together with the carbon to which they are attached to form C(=O)) whereby a compound of Formula Ib (R1 and R2 are taken together to form -O(CH2)2O- optionally substituted with one or two C1 -C3 alkyl) is stirred in a hydrochloric acid or hydrobromic acid aqueous solution (0. iN to 12N) at temperatures between 0 °C and 100 °C for a period of time ranging from 30 minutes to 3 days. This conversion is carried out by methods known in the art (or by slight modification of these methods): for example; see P. A. Grieco, et al., J: Am.

Chem. Soc. (1977), 99, p 5773; P. A. Grieco, et al, J. Am. Chem. Soc. (1978), 43, p 4178.

Scheme 12 (R 1 and RZ are taken together to form -O(CH2hO- optionally substituted with one or two Cl-C3 alkyl) (Rl and RZ are taken together with the carbon to which they are attached to form (C=O)) Esters of Formula 10 can be prepared by reacting a hydroxypyrazole of Formula 11 with an acid chloride of Formula 4 in the presence of a slight molar excess of a base such as triethylamine in an inert organic solvent such as acetonitrile, dichloromethane or toluene at temperatures between 0 °C and 110 °C (Scheme 13). This type of coupling is carried out by methods known in the art; see for example, W. J. Michaely, EP 0369803-Al.

Scheme 13 H (N base 4 + HO N (e.g., triethylamine) 10 R7 II It is recognized that some reagents and reaction conditions described above for preparing compounds of Formula I may not be compatible with certain functionalities present in the intermediates. In these instances, the incorporation of protection/deprotection sequences or functional group interconversions into the synthesis will aid in obtaining the desired products. The use and choice of the protecting groups will be apparent to one skilled in chemical synthesis (see, for example, Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 2nd ed.; Wiley: New York, 1991). One skilled in the art will recognize that, in some cases, after the introduction of a given reagent as it is depicted in any individual scheme, it may be necessary to perform additional routine synthetic steps not described in detail to complete the synthesis of compounds of Formula I. One skilled in the art will also recognize that it may be necessary to perform a combination of the steps illustrated in the above schemes in an order other than that implied by the particular sequence presented to prepare the compounds of Formula I.

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

Without further elaboration, it is believed that one skilled in the art using the preceding description can utilize the present invention to its fullest extent. The following Examples are, therefore, to be construed as merely illustrative, and not limiting of the disclosure in any way whatsoever. Percentages are by weight except for chromatographic solvent mixtures or where otherwise indicated. Parts and percentages for chromatographic solvent mixtures are by volume unless otherwise indicated. The abbreviation "dec" indicates that the compound appeared to decompose on melting. 1H NMR spectra are reported in ppm downfield from tetramethylsilane; s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet, br s = broad singlet.

Example I Step A: Preparation of 3-[(2,5-dimethylphenyl)thio]propanoic acid 43.4 g (1.086 mol) of sodium hydroxide was added to 230 mL of water, 75.0 g (0.543 mol) of 2.5-dimethyithiophenol (purchased from Aldrich Chemical Company) was then added and the mixture was cooled to about 10 "C. 91.30 g (0.597 mol) of 3-bromopropionic acid (purchased from Aldrich Chemical Company) was added in portions while keeping the temperature below 25 "C. The mixture was warmed to room temperature, stirred for 2 h under nitrogen, and was then washed with diethyl ether (3 x 500 mL). The aqueous layer was acidified with 1N HC1 and filtered to yield 112.79 g of the title compound of Step A as a solid melting at 97-98 "C. 1H NMR (CDC13): 6 2.3 (s,3H), 2.34 (s,3H), 2.68 (t,2H), 3.1 (t,2H), 6.9 (d,lH), 7.06-7.14 (2H).

Step B: Preparation of 2,3-dihydro-5,8-dimethyl-4H-1-benzopyran-4-one 530 mL of concentrated sulfuric acid was added to 24.91 g (0.119 mol) of the title compound of Step A while being cooled with an acetone/ice bath. The ice bath was removed, the mixture was stirred for 1 h and was then poured over crushed ice. The aqueous mixture was extracted with a 1: 9 mixture of diethyl ether: hexane (6 x 500 mL), dried (MgSO4), filtered, and evaporated to dryness to yield 11.75 g of the title compound of Step B as an oil. 1H NMR (CDC13): 6 2.3 (s,3H), 2.6 (s,3H), 2.97 (m,2H), 3.2 (m,2H), 6.9-7.1 (2H).

Step C: Preparation of 6-bromo-2,3 -dihvdrn-5 8 -dimethyl-4H- 1 -benzothi oi'yran-4- one A solution of 4.07 g (0.021 mol) of the title compound of Step B in 25 mL of methylene chloride was added dropwise to a mixture of 7.07 g (0.053 mol) of aluminum chloride (purchased from Aldrich Chemical Company) and 25 mL of methylene chloride.

The suspension was stirred for approximately 15 minutes, 1.14 mL (0.022 mol) of bromine (purchased from Janssen) was added dropwise, and the mixture was refluxed for 10 minutes.

The warm mixture was poured into 10 mL of concentrated hydrochloric acid containing 75 g of ice, stirred for 10 minutes, diluted with 50 mL of water, and then extracted with diethyl ether (2 x 200 mL). The combined organic layers were washed with water (2 x 200 mL), dried (Na2SO4), filtered, and evaporated to dryness. The crude product was chromatographed over silica gel eluting with a mixture of ethyl acetate : hexane (5% : 95%) to yield 2.62 g of the title compound of Step C as a solid melting at 87-88 "C. 1H NMR (CDCI3): 6 2.3 (s,3H), 2.6 (s,3H), 3.0 (m,2H), 3.2 (m,2H), 7.45 (s,lH).

Step D: Preparation of 6-bromo-2,3-dihydro-5,8-dimethylspiro[4H-1 -benzothiopyran- 4,2'-[1.31dioxolanel 26.06 g (0.096 mol) of the title compound of Step C, 250 mL of ethylene glycol, 170 mL of trimethyl orthoformate (purchased from Aldrich Chemical Company), and 0.06 g of p-toluenesulfonic acid monohydrate were stirred together at 80 °C under nitrogen overnight.

The mixture was diluted with 400 mL of diethyl ether. The resulting mixture was washed with a 1:1 mixture of 1 AT sodium hydroxide: saturated aqueous NaCl (2 x 600 mL) and then with saturated aqueous NaCI (1 x 600 mL). The organic layer was dried (Na2SO4), filtered, and evaporated to dryness. The crude product was chromatographed over silica gel eluting with a mixture of ethyl acetate : hexane (1 : 9) to yield 24.73 g of the title compound of Step D as a solid melting at 97 °C (dec). 1H NMR (CDCl3): 6 2.2 (s,3H), 2.3 (m.2H), 2.4 (s,3H), 3.0 (m,2H), 4.15 (m,2H), 4.3 (m,2H), 7.3 (s,lH).

Step E: Preparation of 2,3-dihydro-5,8-dimethylspiro[4H-1-benzothiopyran-4,2'- 1,3 ldioxolanel-6-carboxvlic acid 24.73 g (0.078 mol) of the title compound of Step D was added to 150 mL of tetrahydrofuran. The solution was cooled to about -70 " under nitrogen and 37.68 mL (0.094 mol) of 2.5M n-butyllithium in hexane was added dropwise while keeping the temperature below -65 °C, After stirring for 1 h, carbon dioxide was bubbled into the mixture for 2 h.

The mixture was allowed to warm to room temperature, 300 mL of hexanes were added, and the resulting mixture was filtered. The resulting solid was added to a mixture of water: methylene chloride (400 mL : 400 mL), cooled to about 0 °C, and acidified to pH 1 with concentrated hydrochloric acid. The layers were separated and the aqueous layer was extracted with diethyl ether (2 x 300 mL). The combined organic layers were dried (MgSO4), filtered, and evaporated to dryness to yield 4.73 g of the title compound of Step E as a solid melting at 207-208 °C. 1H NMR (Me2SO-d6): 6 2.2 (m,5H), 2.4 (s,3H), 3.0 (m,2H), 4.1-4.2 (m,4H), 7.4 (s,lH).

Step F: Preparation of 23 -dihydro-S 8-dimethylsrnro [4H- 1 -benzothiopyranA2'- [1,3]dioxolane]-6-carboxylic acid 1,1-dioxide 4.73 g (0.017 mol) of the title compound of Step E and 2.08 g (0.025 mol) of sodium acetate were added to 85 mL of methanol. The solution was cooled to about 0 °C, and a solution of 17.66 g (0.029 mol) of OXONE# (purchased from Aldrich Chemical Company) in 85 mL of water was added dropwise while keeping the temperature below 6 °C. The mixture was warmed to room temperature and stirred under nitrogen overnight. The mixture was diluted with 50 mL of water, cooled to about 0 °C, acidified to around pH 2 with concentrated hydrochloric acid, and then extracted with chloroform (3 x 150 mL). The combined organic layers were dried (MgSO4), filtered, and evaporated to dryness. The residue was triturated in diethyl ether: hexane (1: 9) which was decanted to yield 4.18 g of the title compound of Step F as a solid melting at 185 °C (dec). 1H NMR (Me2SO-d6): 6 2.35 (s,3H), 2.5 (m,2H), 2.6 (s,3H), 3.5 (m,2H), 4.16 (m,2H), 4.2 (m,2H), 7.6 (s,lH).

Step G: Preparation of 1-ethyl-i H-pvrazol-5-yl 2,3-dihydro-5,8-dimethylspiro[4H-1- benzothiopyran-4,2'-[1,3]dioxolane]-6-carboxylate 1,1-dioxide 1.18 g (3.8 mmol) of the title compound of Step F, 0.99 mL (0.011 mol) of oxalyl chloride (purchased from Janssen), and 2 drops of N,N-dimethylformamide were added to 50

mL of methylene chloride. The mixture was refluxed under nitrogen for 2 h, and was then evaporated to dryness. 50 mL of methylene chloride was added to the residue and the resulting mixture was evaporated to dryness. Another 50 mL of methylene chloride was added to the residue, and the solution was cooled to about 0 °C. 0.51 g (4.5 mmol) of 1 - ethyl-lH-pyrazol-5-ol was added followed by 1.63 mL (0.012 mol) of triethylamine, and the mixture was stirred overnight while warming to room temperature. The mixture was evaporated to dryness and the crude product was chromatographed eluting with a mixture of ethyl acetate : hexane (6 : 4) to yield 0.24 g of the title compound of Step Gas a semi-solid. lH NMR (CDCl3): 6 1.4 (t,3H), 2.5 (s,3H), 2.6 (m,2H), 2.8 (s,3H), 3.5 (m,2H), 4.1-4.4 (m,6H), 6.26 (s,l H), 7.5-7.7 (2H). <BR> <BR> <BR> <P>Step H: Preparation of (2,3 -dihvdro-5, 8-dimethvlspiro r4H-1 -benzothiopyran-4,2'- <BR> <BR> <BR> <BR> <BR> <BR> <BR> 11,3 3]dioxolan]-6-yl)(1-ethyl-5-hydroxy- 1 H-pvrazolA-vl)methanone S.S- dioxide 0.24 g (0.59 mmol) of the title compound of Step G, 0.25 drops of acetone cyanohydrin (purchased from Aldrich Chemical Company), and 0.14 mL (1.0 mmol) of triethylamine were added to 25 mL of acetonitrile and the mixture was allowed to stir at room temperature under nitrogen for 1.5 h. About 0.06 g of potassium cyanide was added to the mixture which then was stirred at room temperature overnight. The mixture was evaporated to dryness and water was added to the residue. The resulting mixture was acidified to pH 1 with concentrated hydrochloric acid and extracted with methylene chloride (2 x 50 mL). The combined organic layers were dried (MgS04), filtered, and evaporated to dryness to yield 0.17 g of the title compound of Step H as a solid melting at 111 °C (dec).

IH NMR (CDC13): 6 1.46 (t,3H), 2.3 (s,3H), 2.6 (m,2H), 2.8 (s,3H), 3.5 (m,2H), 4.1 (q,2H), 4.2-4.3 (m,4H), 7.3 (2H).

Step I: Preparation of (2 3-dihydro-S 8-dimethylspiro[4H-1-benzothiopyran-4.2'- [1 .3ldioxolanl-6-vl)(l-ethvl-5-hvdroxv- lH-pvrazol-4-ylEmethanone S, S- dioxide monopotassium salt 600 mg of the title compound of Step H, 105 mg of potassium methoxide, and 40 mL of methanol were added to a flask and the resulting mixture was stirred at room temperature overnight under a nitrogen atmosphere. The reaction mixture was then concentrated under reduced pressure and the residue was triturated with ether. The resulting solid was collected by filtration and dried under vacuum overnight to yield 630 mg of the title compound of Step I, a compound of this invention, as a solid melting at >260 °C.

Example 2 Step A: Preparation of 3-oxo-1-cyclohexen-1-yl 2,3-dihydro-5,8-dimethylspiro[4H-1- benzothiopyran-4,2'-[1,3]dioxolane]-6-carboxylate 1,1-dioxide 3.0 g (9.6 mmol) of the title compound of Step F in Example 1, 2.5 mL (0.029 mol) of oxalyl chloride (purchased from Janssen), and 2 drops of N,N-dimethylformamide were

added to 100 mL of methylene chloride. The mixture was refluxed under nitrogen for 2 h, and was then evaporated to dryness. 100 mL of methylene chloride was added to the residue and evaporated to dryness. Another 100 mL of methylene chloride was added to the residue, and the solution was cooled to about 0 °C. 1.19 g (0.0106 mol) of 1,3-cyclohexanedione (purchased from Aldrich Chemical Company) was added followed by 4.15 mL (0.030 mol) of triethylamine, and the mixture was stirred overnight while warming to room temperature.

The mixture was evaporated to dryness and the crude product was chromatographed over silica gel eluting with a mixture of ethyl acetate : hexane (1:1) to yield 1.33 g of the title compound of Step A as a solid melting at 109-111 OC. 1H NMR (CDC13): 6 2.1 (m,2H), 2.5 (m,5H), 2.6 (m,2H), 2.7 (m,2H), 2.8 (s,3H), 3.5 (m,2H), 4.2 (m,2H), 4.3 (m,2H), 6.0 (s,lH), 7.7 (s,lH).

Step B: Preparation of 2-r(2.3-dihvdro-5.8-dimethvlsiroC4H-l -benzothiopvran-4,2'- [1 .3ldioxolanl-6-vl)carbonvll- 1 .3-cvclohexanedione S. S-dioxide 1.33 g (3.3 mmol) of the title compound of Step A, 1 drop of acetone cyanohydrin (purchased from Aldrich Chemical Company), and 0.80 mL (5.7 mmol) oftriethylamine were added to 50 mL of acetonitrile and the mixture was allowed to stir for 1.5 h. About 0.06 g of potassium cyanide was added to the mixture which was then stirred overnight at room temperature under nitrogen. Another 0.03 g of potassium cyanide was added to the mixture which was then stirred for 3 h. The mixture was then evaporated to dryness, water was added to the residue, and the aqueous mixture was acidified to pH 1 with concentrated hydrochloric acid and filtered. The solid residue was dissolved in methylene chloride and the resulting solution was dried (MgSO4), filtered, and evaporated to dryness to yield 1.09 g of the title compound of Step B, a compound of the invention, as a solid melting at 130 °C (dec.). 1H NMR (CDCl3): 6 2.0 (m,2H), 2.2 (s,3H), 2.6 (m,6H), 2.7 (s,3H), 3.5 (m,2H), 4.14 (m,2H), 4.26 (m,2H), 6.9 (1H).

Step C: Preparation of 2-[(2,3-dihydro-5,8-dimethylspiro[4H-1-benzothiopyran-4,2'- [1,3]dioxolan]-6-yl)carbonyl]-1,3-cyclohexanedione S,S-dioxide monolithium salt 8.0 g of the title compound of Step B, 760 mg of lithium methoxide, and 560 mL of methanol were added to a flask and the resulting mixture was stirred at room temperature for 3 days under a nitrogen atmosphere. The reaction mixture was then concentrated under reduced pressure and the residue was triturated with ether. The resulting solid was collected by filtration and dried under vacuum to yield 7.0 g of the title compound of Step C, a compound of this invention, as a solid melting at 266-267 °C. 1H NMR ((CD3)2SO): 6 1.75-1.85 (m, 2H), 2.08 (s, 3H), 2.2-2.35 (m, 4H), 2.4-2.6 (m, 5H), 3.42-3.54 (m, 2H), 4.05- 4.25 (m, 4H), 6.83 (s, 1H).

Example 3 Step A: Preparation of 2-[(2,3-dihydro-5,8-dimethylspiro[4H- 1 -benzothiopvran-4*2'- 11,3 Idioxolanl-6-vl)carbonvll- 1 ,j-cvclohexanedione S. S-dioxide monopotassium salt 6.0 g of the title compound of Step B of Example 2, 1.06 g of potassium methoxide, and 420 mL of methanol were added to a flask and the resulting mixture was stirred at room temperature overnight under a nitrogen atmosphere. The reaction mixture was then concentrated under reduced pressure and the residue was triturated with ether. The resulting solid was collected by filtration, washed further with ether, and dried under vacuum to yield 6.56 g of the title compound of Step A, a compound of this invention, as a solid melting at >215 °C. 111 NMR ((CD3)2SO): 6 1.65-1.78 (m, 2H), 2.0-2.15 (m, 7H), 2.4-2.53 (m, 5H), 3.4-3.5 (m, 2H), 4.05-4.25 (m, 4H), 6.76 (s, 1H).

Example 4 Step A: Preparation of 2-[(2,3-dihydro-5,8-dimethylspiro[4H-1 -benzothiopvran4,2'- r1.3 Idioxolanl-6-vl)carbonvll- 1 3 -cyclohexanedione S, S-dioxide monosodium salt 580 mg of sodium metal was added to 700 mL of methanol and the reaction was stirred at room temperature until the complete disappearance of the sodium metal. To this solution was added 10.0 g of the title compound of Step B of Example 2, and the resulting mixture was stirred at room temperature overnight under a nitrogen atmosphere. The reaction mixture was then concentrated under reduced pressure and the residue was triturated with ether. The resulting solid was collected by filtration, washed further with ether, and dried under vacuum to yield 10.5 g of the title compound of Step A, a compound of this invention, as a solid melting at >215 OC. 1H NMR ((CD3)2SO): 6 1.67-1.8 (m, 2H), 2.0-2.2 (m, 7H), 2.4-2.57 (m, 5H), 3.4-3.5 (m, 2H), 4.05-4.25 (m, 4H), 6.76 (s, 1H).

Example 5 Step A: Preparation of 2-[(2,3-dihydro-5,8-dimethylspiro[4H-1 -benzothiopyran-4.2'- [1 ,3ldioxolanl-6-vl3carbonyll-l 3-cyclohexanedione S, S-dioxide benzvldimethvlhexadecvlammonium salt 1.22 g of benzyldimethylhexadecylammonium chloride monohydrate was dissolved in 3 mL of dichloromethane and then 3.3 mL of 1N aqueous NaOH was added and the mixture was thoroughly stirred. In a separate vial, 1.25 g of the title compound of Step B of Example 2 was dissolved in 3 mL of dichloromethane, and this solution was added to the contents of the previously prepared ammonium salt solution. After thorough mixing, the mixture was transferred to a separatory funnel and the organic layer was separated. The aqueous layer was extracted three times with 3 mL portions of dichloromethane and the combined organic layers were washed with water and dried over molecular sieves for 4 hours. The sieves were removed by filtration and the solution was concentrated under

reduced pressure to provide the title compound of Step A, a compound of this invention, as a tan solid (45% yield).

By the procedures described herein together with methods known in the art, the following compounds of Tables 1 and 2 can be prepared.

TABLE 1 wherein r is 1 and M is Li R1 R2 n R4 R5 R6a R6b C=O 1 H H H H C=O 2 H H H H C=O 1 H H H CH3 C=O 2 H H H CH3 CO 1 H H CH3 CH3 C=O 2 H H CH3 CH3 C=O 1 CH3 H H H C=O 2 CH3 H H H C=O 1 CH3 H H CH3 C=O 2 CH3 H H CH3 C=O 1 CH3 H CH3 CH3 C=O 2 CH3 H CH3 CH3 C=O 1 CH3 CH3 H H C=O 2 CH3 CH3 H H C=O 1 CH3 CH3 H CH3 C=O 2 CH3 CH3 H CH3 C=O I CH3 CH3 CH3 CH3 C=O 2 CH3 CH3 CH3 CH3 C=O 1 Cl Cl H H CO 2 Cl Cl H H C=O 1 Cl Cl H CH3 C=O 2 CI Cl H CH3 CO I Cl CI CH3 CH3 C=O 2 CI CI CH3 CH3 -OCH2CH2O- 0 H H H H -OCH2CH2O- I H H H H -OCH2CH2O- 2 H H H H -OCH2CH20- 0 H H H CH3 -OCH2CH20- I H H H CH3 -OCH2CH20- 2 H H H CH3 -OCH2CH20- 0 H H CH3 CH3 -OCH2CH2O- 1 H H CH3 CH3 -OCH2CH20- 2 H H CH3 CH3 -OCH2CH20- O CH3 H H H -OCH2CH20- 1 CH3 H H H -OCH2CH20- 2 CH3 H H H -OCH2CH20- O CH3 H H CH3 -OCH2CH20- 1 CH3 H H CH3 -OCH2CH20- 2 CH3 H H CH3 -OCH2CH20- O CH3 H CH3 CH3 -OCH2CH20- 1 CH3 H CH3 CH3 -OCH2CH20- 2 CH3 H CH3 CH3 -OCH2CH20- O CH3 CH3 H H -OCH2CH20- 1 CH3 CH3 H H -OCH2CH20- 2 CH3 CH3 H H -OCH2CH20- O CH3 CH3 H CH3 -OCH2CH2O- 1 CH3 CH3 H CH3 -OCH2CH20- 2 CH3 CH3 H CH3 -OCH2CH20- O CH3 CH3 CH3 CH3 -OCH2CH20- 1 CH3 CH3 CH3 CH3 -OCH2CH20- 2 CH3 CH3 CH3 CH3 -OCH2CH20- O Cl Cl H H -OCH2CH20- 1 Cl Cl H H -OCH2CH20- 2 Cl Cl H H -OCH2CH20- 0 CI Cl H CH3 -OCH2CH20- 1 Cl Cl H CH3 -OCH2CH20- 2 Cl Cl H CH3 -OCH2CH20- 0 Cl CI CH3 CH3 -OCH2CH20- 1 CI CI CH3 CH3 -OCH2CH2O- 2 CI CI CH3 CH3 -OCH2(CH3)CH2(CH3)O- O H 11 H H -OCH2(CH3)CH2(CH3)O- 1 H H H H -OCH2(CH3)CH2(CH3)o- 2 H H H H -OCH2(CH3)CH2(CH3)0- O H H H CH3 -OCH2(CH3)CH2(CH3)O- I H H H CH3 -OCH2(CH3)CH2(CH3)O- 2 H H H CH3 -OCH2(CH3)CH2(CH3)O- O H H CH3 CH3 -OCH2(CH3)CH2(CH3)0- 1 H H CH3 CH3 -OCH2(CH3)CH2(CH3)0- 2 H H CH3 CH3 -OCH2(CH3)CH2(CH3)0- O CH3 H H H -OCH2(CH3)CH2(CH3)0- 1 CH3 H H H -OCH2(CH3)CH2(CH3)0- 2 CH3 H H H -OCH2(CH3)CH2(CH3)O- O CH3 H H CH3 -OCH2(CH3)CH2(CH3)0- 1 CH3 H H CH3 -OCH2(CH3)CH2(CH3)0- 2 CH3 H H CH3 -OCH2(CH3)CH2(CH3)0- O CH3 H CH3 CH3 -OCH2(CH3)CH2(CH3)0- 1 CH3 H CH3 CH3 -OCH2(CH3)CH2(CH3)0- 2 CH3 H CH3 CH3 -OCH2(CH3)CH2(CH3)O- O CH3 CH3 H H -OCH2(CH3)CH2(CH3)0- 1 CH3 CH3 H H -OCH2(CH3)CH2(CH3)0- 2 CH3 CH3 H H -OCH2(CH3)CH2(CH3)O- O CH3 CH3 H CH3 -OCH2(CH3)CH2(CH3)0- 1 CH3 CH3 H CH3 -OCH2(CH3)CH2(CH3)0- 2 CH3 CH3 H CH3 -OCH2(CH3)CH2(CH3)O- O CH3 CH3 CH3 CH3 -OCH2(CH3)CH2(CH3)0- 1 CH3 CH3 CH3 CH3 -OCH2(CH3)CH2(CH3)0- 2 CH3 CH3 CH3 CH3 -OCH2(CH3)CH2(CH3)O- O Cl CI H H -OCH2(CH3)CH2(CH3)O- 1 Cl Cl H H -OCH2(CH3)CH2(CH3)O- 2 Cl Cl H H -OCH2(CH3)CH2(CH3)0- O Cl Cl H CH3 -OCH2(CH3)CH2(CH3)0- 1 Cl Cl H CH3 -OCH2(CH3)CH2(CH3)0- 2 Cl Cl H CH3 -OCH2(CH3)CH2(CH3)O- O Cl Cl CH3 CH3 -OCH2(CH3)CH2(CH3)0- 1 Cl Cl CH3 CH3 -OCH2(CH3)CH2(CH3)O- 2 CI CI CH3 CH3 wherein r is I and M is Na R1 R2 n R4 R5 R6a R6b C=O I H H H H C-O 2 H H H H CO I H H H CH3 CO 2 H H H CH3 C=O I H H CH3 CH3 C=O 2 H H CH3 CH3 C=O I CH3 H H H C=O 2 CH3 H H H C=O 1 CH3 H H CH3 C=O 2 CH3 H H CH3 C=O 1 CH3 H CH3 CH3 C=O 2 CH3 H CH3 CH3 C=O 1 CH3 CH3 H H C=O 2 CH3 CH3 H H C=O 1 CH3 CH3 H CH3 C=O 2 CH3 CH3 H CH3 C=O 1 CH3 CH3 CH3 CH3 C=O 2 CH3 CH3 CH3 CH3 C=O 1 Cl CI H H C=O 2 Cl Cl H H C=O 1 Cl Cl H CH3 C=O 2 Cl Cl H CH3 C=O 1 Cl Cl CH3 CH3 C=O 2 Cl Cl CH3 CH3 -OCH2CH20- 0 H H H H -OCH2CH20- 1 H H H H -OCH2CH20- 2 H H H H -OCH2CH20- 0 H H H CH3 -OCH2CH20- 1 H H H CH3 -OCH2CH20- 2 H H H CH3 -OCH2CH20- 0 H H CH3 CH3 -OCH2CH20- I H H CH3 CH3 -OCH2CH20- 2 H H CH3 CH3 -OCH2CH20- O CH3 H H H -OCH2CH20- I CH3 H H H -OCH2CH20- 2 CH3 H H H -OCH2CH2O- O CH3 H H CH3 -OCH2CH2O- I CH3 H H CH3 -OCH2CH2O- 2 CH3 H H CH3 -OCH2CH20- O CH3 H CH3 CH3 -OCH2CH2O- I CH3 H CH3 CH3 -OCH2CH2O- 2 CH3 H CH3 CH3 -OCH2CH20- O CH3 CH3 H H -OCH2CH20- 1 CH3 CH3 H H -OCH2CH20- 2 CH3 CH3 H H -OCH2CH2O- O CH3 CH3 H CH3 -OCH2CH20- 1 CH3 CH3 H CH3 -OCH2CH20- 2 CH3 CH3 H CH3 -OCH2CH20- O CH3 CH3 CH3 CH3 -OCH2CH20- 1 CH3 CH3 CH3 CH3 -OCH2CH20- 2 CH3 CH3 CH3 CH3 -OCH2CH2O- 0 Cl Cl H H -OCH2CH2O- 1 Cl Cl H H -OCH2CH2O- 2 Cl Cl H H -OCH2CH20- 0 Cl Cl H CH3 -OCH2CH20- 1 Cl Cl H CH3 -OCH2CH20- 2 Cl Cl H CH3 -OCH2CH2O- 0 Cl Cl CH3 CH3 -OCH2CH2O- 1 Cl Cl CH3 CH3 -OCH2CH2O- 2 Cl Cl CH3 CH3 -OCH2(CH3)CH2(CH3)O- 0 H H H H -OCH2(CH3)CH2(CH3)0- 1 H H H H -OCH2(CH3)CH2(CH3)O- 2 H H H H -OCH2(CH3)CH2(CH3)0- O H H H CH3 -OCH2(CH3)CH2(CH3)0- 1 H H H CH3 -OCH2(CH3)CH2(CH3)0- 2 H H H CH3 -OCH2(CH3)CH2(CH3)o- O H H CH3 CH3 -OCH2(CH3)CH2(CH3)0- I H H CH3 CH3 -OCH2(CH3)CH2(CH3)0- 2 H H CH3 CH3 -OCH2(CH3)CH2(CH3)0- O CH3 H H H -OCH2(CH3)CH2(CH3)0- 1 CH3 H H H -OCH2(CH3)CH2(CH3)O- 2 CH3 H H H -OCH2(CH3)CH2(CH3)0- O CH3 H H CH3 -OCH2(CH3)CH2(CH3)0- 1 CH3 H H CH3 -OCH2(CH3)CH2(CH3)O- 2 CH3 H H CH3 -OCH2(CH3)CH2(CH3)O- O CH3 H CH3 CH3 -OCH2(CH3)CH2(CH3)O- I CH3 H CH3 CH3 -OCH2(CH3)CH2(CH3)O- 2 CH3 H CH3 CH3 -OCH2(CH3)CH2(CH3)0- O CH3 CH3 H H -OCH2(CH3)CH2(CH3)0- I CH3 CH3 H H -OCH2(CH3)CH2(CH3)o- 2 CH3 CH3 H H -OCH2(CH3)CH2(CH3)O- O CH3 CH3 H CH3 -OCH2(CH3)CH2(CH3)O- 1 CH3 CH3 H CH3 -OCH2(CH3)CH2(CH3)0- 2 CH3 CH3 H CH3 -OCH2(CH3)CH2(CH3)0- O CH3 CH3 CH3 CH3 -OCH2(CH3)CH2(CH3)O- 1 CH3 CH3 CH3 CH3 -OCH2(CH3)CH2(CH3)O- 2 CH3 CH3 CH3 CH3 -OCH2(CH3)CH2(CH3)O- 0 Cl Cl H H -OCH2(CH3)CH2(CH3)O- 1 Cl Cl H H -OCH2(CH3)CH2(CH3)0- 2 Cl Cl H H -OCH2(CH3)CH2(CH3)O- 0 Cl Cl H CH3 -OCH2(CH3)CH2(CH3)O- 1 Cl Cl H CH3 -OCH2(CH3)CH2(CH3)O- 2 Cl Cl H CH3 -OCH2(CH3)CH2(CH3)0- O Cl Cl CR3 CH3 -OCH2(CH3)CH2(CH3)0- 1 Cl Cl CH3 CH3 -OCH2(CH3)CH2(CH3)O- 2 Cl Cl CH3 CH3 wherein r is 1 and M is K R1 R2 n R4 R5 R6a R6b C=O 1 H H H H C=O 2 H H H H C=O 1 H H H CH3 C=O 2 H H H CH3 C=O 1 H H CH3 CH3 C--O 2 H H CH3 CH3 C=O 1 CH3 H H H C=O 2 CH3 H H H C=O 1 CH3 H H CH3 C=O 2 CH3 H H CH3 C=O I CH3 H CH3 CH3 C=O 2 CH3 H CH3 CH3 C=O 1 CH3 CH3 H H CO 2 CH3 CH3 H H C-O I CH3 CH3 H CH3 C-O 2 CH3 CH3 H CH3 C=O I CH3 CH3 CH3 CH3 C=O 2 CH3 CH3 CH3 CH3 C=O I CI CI H H CO 2 Cl Cl H H C=C I Cl Cl H CH3 C=O 2 Cl Cl H CH3 C=O 1 Cl Cl CH3 CH3 C=C 2 Cl Cl CH3 CH3 -OCH2CH20- 0 H H H H -OCH2CH20- 1 H H H H -OCH2CH20- 2 H H H H -OCH2CH2O- 0 H H H CH3 -OCH2CH20- 1 H H H CH3 -OCH2CH20- 2 H H H CH3 -OCH2CH20- 0 H H CH3 CH3 -OCH2CH20- 1 H H CH3 CH3 -OCH2CH20- 2 H H CH3 CH3 -OCH2CH20- O CH3 H H H -OCH2CH20- I CH3 H H H -OCH2CH20- 2 CH3 H H H -OCH2CH20- O CH3 H H CH3 -OCH2CH20- I CH3 H H CH3 -OCH2CH20- 2 CH3 H H CH3 -OCH2CH20- O CH3 H CH3 CH3 -OCH2CH20- 1 CH3 H CH3 CH3 -OCH2CH2O- 2 CH3 H CH3 CH3 -OCH2CH20- O CH3 CH3 H H -OCH2CH2O- I CH3 CH3 H H -OCH2CH20- 2 CH3 CH3 H H -OCH2CH20- O CH3 CH3 H CH3 -OCH2CH20- I CH3 CH3 H CH3 -OCH2CH20- 2 CH3 CH3 H CH3 -OCH2CH20- O CH3 CH3 CH3 CH3 -OCH2CH20- I CH3 CH3 CH3 CH3 -OCH2CH20- 2 CH3 CH3 CH3 CH3 -OCH2CH2O- 0 Cl Cl H H -OCH9CH20- I CI Cl H H -OCH2CH2O- 2 CI CI H H -OCH2CH20- 0 CI CI H CH3 -OCH2CH2O- I CI CI H CH3 -OCH2CH20- 2 Cl CI H CH3 -OCH2CH20- 0 Cl Cl CH3 CH3 -OCH2CH20- I Cl CI CH3 CH3 -OCH2CH20- 2 Cl Cl CH3 CH3 -OCH2(CH3)CH2(CH3)o- O H H H H -OCH2(CH3)CH2(CH3)O- 1 H H H H -OCH2(CH3)CH2(CH3)0- 2 H H H H -OCH2(CH3)CH2(CH3)0- O H H H CH3 -OCH2(CH3)CH2(CH3)0- 1 H H H CH3 -OCH2(CH3)CH2(CH3)O- 2 H H H CH3 -OCH2(CH3)CH2(CH3)0- O H H CH3 CH3 -OCH2(CH3)CH2(CH3)O- 1 H H CH3 CH3 -OCH2(CH3)CH2(CH3)0- 2 H H CH3 CH3 -OCH2(CH3)CH2(CH3)0- O CH3 H H H -OCH2(CH3)CH2(CH3)O- 1 CH3 H H H -OCH2(CH3)CH2(CH3)O- 2 CH3 H H H -OCH2(CH3)CH2(CH3)O- O CH3 H H CH3 -OCH2(CH3)CH2(CH3)O- 1 CH3 H H CH3 -OCH2(CH3)CH2(CH3)O- 2 CH3 H H CH3 -OCH2(CH3)CH2(CH3)0- O CH3 H CH3 CH3 -OCH2(CH3)CH2(CH3)O- 1 CH3 H CH3 CH3 -OCH2(CH3)CH2(CH3)O- 2 CH3 H CH3 CH3 -OCH2(CH3)CH2(CH3)O- O CH3 CH3 H H -OCH2(CH3)CH2(CH3)O- 1 CH3 CH3 H H -OCH2(CH3)CH2(CH3)O- 2 CH3 CH3 H H -OCH2(CH3)CH2(CH3)0- O CH3 CH3 H CH3 -OCH2(CH3)CH2(CH3)o- 1 CH3 CH3 H CH3 -OCH2(CH3)CH2(CH3)0- 2 CH3 CH3 H CH3 -OCH2(CH3)CH2(CH3)O- O CH3 CH3 CH3 CH3 -OCH2(CH3)CH2(CH3)O- I CH3 CH3 CH3 CH3 -OCH2(CH3)CH2(CH3)O- 2 CH3 CH3 CH3 CH3 -OCH2(CH3)CH2(CH3)0- O Cl Cl H H -OCH2(CH3)CH2(CH3)0- 1 CI CI H H -OCH2(CH3)CH2(CH3)0- 2 CI Cl H H -OCH2(CH3)CH2(CH3)O- 0 Cl Cl H CH3 -OCH2(CH3)CH2(CH3)0- I Cl CI H CH3 -OCH2(CH3)CH2(CH3)0- 2 Cl CI H CH3 -OCH2(CH3)CH2(CH3)0- O Cl CI CH3 CH3 -OCH2(CH3)CH2(CH3)O- 1 Cl Cl CH3 CH3 -OCH2(CH3)CH2(CH3)0- 2 Cl CI CH3 CH3 wherein r is 2 and M is Ca R1 R2 n R4 R5 R6a R6b C=O 1 H H H H C=O 2 H H H H C--O 1 H H H CH3 C=O 2 H H H CH3 C=O I H H CH3 CH3 C=O 2 H H CH3 CH3 C=O 1 CH3 H H H C=O 2 CH3 H H H C=O 1 CH3 H H CH3 C=O 2 CH3 H H CH3 C=O 1 CH3 H CH3 CH3 C=O 2 CH3 H CH3 CH3 C=O 1 CH3 CH3 H H CO 2 CH3 CH3 H H C=O 1 CH3 CH3 H CH3 C=O 2 CH3 CH3 H CH3 C=O 1 CH3 CH3 CH3 CH3 C=O 2 CH3 CH3 CH3 CH3 C=O 1 CI Cl H H C=O 2 Cl Cl H H C=O 1 Cl Cl H CH3 C=O 2 Cl Cl H CH3 C=O 1 Cl Cl CH3 CH3 C=O 2 Cl Cl CH3 CH3 -OCH2CH20- 0 H H H H -OCH2CH20- 1 H H H H -OCH2CH20- 2 H H H H -OCH2CH20- 0 H H H CH3 -OCH2CH20- I H H H CH3 -OCH2CH2O- 2 H H H CH3 -OCH2CH2O- 0 H H CH3 CH3 -OCH2CH20- I H H CH3 CH3 -OCH2CH20- 2 H H CH3 CH3 -OCH2CH20- O CH3 H H H -OCH2CH20- I CH3 H H H -OCH2CH20- 2 CH3 H H H -OCH2CH20- O CH3 H H CH3 -OCH2CH20- 1 CH3 H H CH3 -OCH2CH20- 2 CH3 H H CH3 -OCH2CH20- O CH3 H CH3 CH3 -OCH2CH20- 1 CH3 H CH3 CH3 -OCH2CH20- 2 CH3 H CH3 CH3 -OCH2CH20- O CH3 CH3 H H -OCH2CH20- 1 CH3 CH3 H H -OCH2CH20- 2 CH3 CH3 H H -OCH2CH20- O CH3 CH3 H CH3 -OCH2CH20- 1 CH3 CH3 H CH3 -OCH2CH20- 2 CH3 CH3 H CH3 -OCH2CH20- O CH3 CH3 CH3 CH3 -OCH2CH20- 1 CH3 CH3 CH3 CH3 -OCH2CH20- 2 CH3 CH3 CH3 CH3 -OCH2CH20- 0 Cl CI H H -OCH2CH2O- 1 Cl Cl H H -OCH2CH2O- 2 Cl Cl H H -OCH2CH2O- 0 Cl Cl H CH3 -OCH2CH20- I Cl CI H CH3 -OCH2CH20- 2 Cl Cl H CH3 -OCH2CH20- 0 Cl CI CH3 CH3 -OCH2CH20- 1 Cl CI CH3 CH3 -OCH2CH2O- 2 Cl Cl CH3 CH3 -OCH2(CH3)CH2(CH3)O- O H H H H -OCH2(CH3)CH2(CH3)0- 1 H H H H -OCH2(CH3)CH2(CH3)0- 2 H H H H -OCH2(CH3)CH2(CH3)0- 0 H H H CH3 -OCH2(CH3)CH2(CH3)0- I H H H CH3 -OCH2(CH3)CH2(CH3)0- 2 H H H CH3 -OCH2(CH3)CH2(CH3)O- O H H CH3 CH3 -OCH2(CH3)CH2(CH3)O- 1 H H CH3 CH3 -OCH2(CH3)CH2(CH3)O- 2 H H CH3 CH3 -OCH2(CH3)CH2(CH3)O- O CH3 H H H -OCH2(CH3)CH2(CH3)O- I CH3 H H H -OCH2(CH3)CH2(CH3)0- 2 CH3 H H H -OCH2(CH3)CH2(CH3)0- O CH3 H H CH3 -OCH2(CH3)CH2(CH3)0- I CH3 H H CH3 -OCH2(CH3)CH2(CH3)O- 2 CH3 H H CH3 -OCH2(CH3)CH2(CH3)0- O CH3 H CH3 CH3 -OCH2(CH3)CH2(CH3)o- 1 CH3 H CH3 CH3 -OCH2(CH3)CH2(CH3)0- 2 CH3 H CH3 CH3 -OCH2(CH3)CH2(CH3)0- O CH3 CH3 H H -OCH2(CH3)CH2(CH3)O- 1 CH3 CH3 H H -OCH2(CH3)CH2(CH3)O- 2 CH3 CH3 H H -OCH2(CH3)CH2(CH3)O- O CH3 CH3 H CH3 -OCH2(CH3)CH2(CH3)0- 1 CH3 CH3 H CH3 -OCH2(CH3)CH2(CH3)0- 2 CH3 CH3 H CH3 -OCH2(CH3)CH2(CH3)0- O CH3 CH3 CH3 CH3 -OCH2(CH3)CH2(CH3)0- 1 CH3 CH3 CH3 CH3 -OCH2(CH3)CH2(CH3)O- 2 CH3 CH3 CH3 CH3 -OCH2(CH3)CH2(CH3)0- O Cl Cl H H -OCH2(CH3)CH2(CH3)O- 1 Cl Cl H H -OCH2(CH3)CH2(CH3)0- 2 Cl Cl H H -OCH2(CH3)CH2(CH3)O- O Cl Cl H CH3 -OCH2(CH3)CH2(CH3)O- 1 Cl Cl H CH3 -OCH2(CH3)CH2(CH3)O- 2 Cl Cl H CH3 -OCH2(CH3)CH2(CH3)O- 0 Cl Cl CH3 CH3 -OCH2(CH3)CH2(CH3)O- 1 Cl Cl CH3 CH3 -OCH2(CH3)CH2(CH3)O- 2 Cl Cl CH3 CH3 wherein r is 2 and M is Mg R1 R2 n R4 R5 R6a R6b C=O 1 H H H H C--O 2 H H H H C=O 1 H H H CH3 C=O 2 H H H CH3 C=O I H H CH3 CH3 C=O 2 H H CH3 CH3 C=O I CH3 H H H C=O 2 CH3 H H H C=O 1 CH3 H H CH3 C=O 2 CH3 H H CH3 C=O 1 CH3 H CH3 CH3 C=O 2 CH3 H CH3 CH3 C=O 1 CH3 CH3 H H C=O 2 CH3 CH3 H H C=O 1 CH3 CH3 H CH3 C=O 2 CH3 CH3 H CH3 C=O 1 CH3 CH3 CH3 CH3 C=O 2 CH3 CH3 CH3 CH3 C=O I Cl Cl H H C=O 2 Cl Cl H H C=O 1 Cl Cl H CH3 C=O 2 Cl Cl H CH3 C=O 1 Cl Cl CH3 CH3 C=O 2 Cl Cl CH3 CH3 -OCH2CH20- 0 H H H H -OCH2CH20- 1 H H H H -OCH2CH20- 2 H H H H -OCH2CH20- 0 H H H CH3 -OCH2CH20- 1 H H H CH3 -OCH2CH20- 2 H H H CH3 -OCH2CH20- 0 H H CH3 CH3 -OCH2CH20- 1 H H CH3 CH3 -OCH2CH20- 2 H H CH3 CH3 -OCH2CH20- O CH3 H H H -OCH2CH20- 1 CH3 H H H -OCH2CH20- 2 CH3 H H H -OCH2CH20- O CH3 H H CH3 -OCH2CH20- 1 CH3 H H CH3 -OCH2CH20- 2 CH3 H H CH3 -OCH2CH20- O CH3 H CH3 CH3 -OCH2CH20- 1 CH3 H CH3 CH3 -OCH2CH20- 2 CH3 H CH3 CH3 -OCH2CH20- O CH3 CH3 H H -OCH2CH2O- I CH3 CH3 H H -OCH2CH2O- 2 CH3 CH3 H H -OCH2CH2O- O CH3 CH3 H CH3 -OCH2CH20- I CH3 CH3 H CH3 -OCH9CH20- 2 CH3 CH3 H CH3 -OCH2CH20- O CH3 CH3 CH3 CH3 -OCR2CH2O- I CH3 CH3 CH3 CH3 -OCH2CH20- 2 CH3 CH3 CH3 CH3 -OCH2CH20- 0 Cl Cl H H -OCH2CH20- I Cl Cl H H -OCH2CH2O- 2 Cl Cl H H -OCH2CH2O- 0 Cl Cl H CH3 -OCH2CH2O- 1 Cl Cl H CH3 -OCH2CH2O- 2 Cl Cl H CH3 -OCH2CH2O- 0 Cl Cl CH3 CH3 -OCH2CH2O- 1 Cl Cl CH3 CH3 -OCH2CH2O- 2 Cl Cl CH3 CH3 -OCH2(CH3)CH2(CH3)0- O H H H H -OCH2(CH3)CH2(CH3)0- 1 H H H H -OCH2(CH3)CH2(CH3)0- 2 H H H H -OCH2(CH3)CH2(CH3)0- O H H H CH3 -OCH2(CH3)CH2(CH3)0- 1 H H H CH3 -OCH2(CH3)CH2(CH3)0- 2 H H H CH3 -OCH2(CH3)CH2(CH3)0- O H H CH3 CH3 -OCH2(CH3)CH2(CH3)0- 1 H H CH3 CH3 -OCH2(CH3)CH2(CH3)0- 2 H H CH3 CH3 -OCH2(CH3)CH2(CH3)0- O CH3 H H H -OCH2(CH3)CH2(CH3)0- I CH3 H H H -OCH2(CH3)CH2(CH3)0- 2 CH3 H H H -OCH2(CH3)CH2(CH3)0- O CH3 H H CH3 -OCH2(CH3)CH2(CH3)0- I CH3 H H CH3 -OCH2(CH3)CH2(CH3)0- 2 CH3 H H CH3 -OCH2(CH3)CH2(CH3)0- O CH3 H CH3 CH3 -OCH2(CH3)CH2(CH3)0- 1 CH3 H CH3 CH3 -OCH2(CH3)CH2(CH3)0- 2 CH3 H CH3 CH3 -OCH2(CH3)CH2(CH3)0- O CH3 CH3 H H -OCH2(CH3)CH2(CH3)0- I CH3 CH3 H H -OCH2(CH3)CH2(CH3)0- 2 CH3 CH3 H H -OCH2(CH3)CH2(CH3)O- O CH3 CH3 H CH3 -OCH2(CH3)CH2(CH3)O- I CH3 CH3 H CH3 -OCH2(CH3)CH2(CH3)O- 2 CH3 CH3 II CH3 -OCH2(CH3)CH2(CH3)O- O CH3 CH3 CH3 CH3 -OCH2(CH3)CH2(CH3)o- I CH3 CH3 CH3 CH3 -OCH2(CH3)CH2(CH3)0- 2 CH3 CH3 CH3 CH3 -OCH2(CH3)CH2(CH3)O- O Cl CI H H -OCH2(CH3)CH2(CH3)O- I Cl CI H H -OCH2(CH3)CH2(CH3)O- 2 Cl Cl H H -OCH2(CH3)CH2(CH3)O- 0 Cl Cl H CH3 -OCH2(CH3)CH2(CH3)0- I Cl Cl H CH3 -OCH2(CH3)CH2(CH3)0- 2 Cl Cl H CH3 -OCH2(CH3)CH2(CH3)O- 0 Cl Cl CH3 CH3 -OCH2(CH3)CH2(CH3)O- 1 Cl Cl CH3 CH3 -OCH2(CH3)CH2(CH3)O- 2 Cl Cl CH3 CH3 wherein r is 1 and M is (CH3CH2)3NH R1 R2 n @ R4 R5 R6a R6b CO 1 H H H H C=O 2 H H H H C=O 1 H H H CH3 C=O 2 H H H CH3 C=O 1 H H CH3 CH3 C=O 2 H H CH3 CH3 C=O 1 CH3 H H H C=O 2 CH3 H H H C=O 1 CH3 H H CH3 C=O 2 CH3 H H CH3 C=O I CH3 H CH3 CH3 C=O 2 CH3 H CH3 CH3 C=O 1 CH3 CH3 H H C=O 2 CH3 CH3 H H C=O 1 CH3 CH3 H CH3 C=O 2 CH3 CH3 H CH3 C=O 1 CH3 CH3 CH3 CH3 C=O 2 CH3 CH3 CH3 CH3 C=O I Cl Cl H H C=O 2 Cl Cl H H C=O I CI CI H CH3 C=O 2 CI CI H CH3 C=O I CI CI CH3 CH3 C=O 2 Cl CI CH3 CH3 -OCH2CH2O- 0 H H H H -OCH2CH2O- I H H H H -OCH2CH20- 2 H H H H -OCH2CH20- 0 H H H CH3 -OCH2CH20- 1 H H H CH3 -OCH2CH20- 2 H H H CH3 -OCH2CH20- 0 H H CH3 CH3 -OCH2CH20- 1 H H CH3 CH3 -OCH2CH20- 2 H H CH3 CH3 -OCH2CH20- O CH3 H H H -OCH2CH20- 1 CH3 H H H -OCH2CH20- 2 CH3 H H H -OCH2CH20- O CH3 H H CH3 -OCH2CH20- 1 CH3 H H CH3 -OCH2CH20- 2 CH3 H H CH3 -OCH2CH20- O CH3 H CH3 CH3 -OCH2CH20- 1 CH3 H CH3 CH3 -OCH2CH20- 2 CH3 H CH3 CH3 -OCH2CH2O- O CH3 CH3 H H -OCH2CH20- 1 CH3 CH3 H H -OCH2CH20- 2 CH3 CH3 H H -OCH2CH20- O CH3 CH3 H CH3 -OCH2CH20- 1 CH3 CH3 H CH3 -OCH2CH20- 2 CH3 CH3 H CH3 -OCH2CH20- O CH3 CH3 CH3 CH3 -OCH2CH20- 1 CH3 CH3 CH3 CH3 -OCH2CH20- 2 CH3 CH3 CH3 CH3 -OCH2CH2O- 0 Cl Cl H H -OCH2CH20- 1 Cl Cl H H -OCH2CH20- 2 Cl Cl H H -OCH2CH20- 0 CI Cl H CH3 -OCH2CH20- 1 CI Cl H CH3 -OCH2CH20- 2 CI Cl H CH3 -OCH2CH20- 0 CI Cl CH3 CH3 -OCHoCH20- I CI CI CH3 CH3 -OCH2CH2O- 2 Cl CI CH3 CH3 -OCH,(CH3)CH2(CH3)0- O H H H H -OCH2(CH3)CH2(CH3)O- 1 H H H H -OCH2(CH3)CH2(CH3)O- 2 H H H H -OCH2(CH3)CH2(CH3)O- 0 H H H CH3 -OCH2(CH3)CH2(CH3)O- I H H H CH3 -OCH2(CH3)CH2(CH3)0- 2 H H H CH3 -OCH2(CH3)CH2(CH3)0- O H H CH3 CH3 -OCH2(CH3)CH2(CH3)0- 1 H H CH3 CH3 -OCH2(CH3)CH2(CH3)O- 2 H H CH3 CH3 -OCH2(CH3)CH2(CH3)O- O CH3 H H H -OCH2(CH3)CH2(CH3)0- 1 CH3 H H H -OCH2(CH3)CH2(CH3)o- 2 CH3 H H H -OCH2(CH3)CH2(CH3)0- O CH3 H H CH3 -OCH2(CH3)CH2(CH3)O- 1 CH3 H H CH3 -OCH2(CH3)CH2(CH3)0- 2 CH3 H H CH3 -OCH2(CH3)CH2(CH3)0- O CH3 H CH3 CH3 -OCH2(CH3)CH2(CH3)0- 1 CH3 H CH3 CH3 -OCH2(CH3)CH2(CH3)0- 2 CH3 H CH3 CH3 -OCH2(CH3)CH2(CH3)0- O CH3 CH3 H H -OCH2(CH3)CH2(CH3)0- 1 CH3 CH3 H H -OCH2(CH3)CH2(CH3)0- 2 CH3 CH3 H H -OCH2(CH3)CH2(CH3)o- O CH3 CH3 H CH3 -OCH2(CH3)CH2(CH3)0- I CH3 CH3 H CH3 -OCH2(CH3)CH2(CH3)0- 2 CH3 CH3 H CH3 -OCH2(CH3)CH2(CH3)0- O CH3 CH3 CH3 CH3 -OCH2(CH3)CH2(CH3)0- 1 CH3 CH3 CH3 CH3 -OCH2(CH3)CH2(CH3)0- 2 CH3 CH3 CH3 CH3 -OCH2(CH3)CH2(CH3)O- 0 Cl Cl H H -OCH2(CH3)CH2(CH3)O- 1 Cl Cl H H -OCH2(CH3)CH2(CH3)O- 2 Cl Cl H H -OCH2(CH3)CH2(CH3)0- O Cl Cl H CH3 -OCH2(CH3)CH2(CH3)O- 1 Cl Cl H CH3 -OCH2(CH3)CH2(CH3)0- 2 Cl Cl H CH3 -OCH2(CH3)CH2(CH3)O- 0 Cl Cl CH3 CH3 -OCH2(CH3)CH2(CH3)O- 1 Cl Cl CH3 CH3 -OCH2(CH3)CH2(CH3)0- 2 Cl CI CH3 CH3 wherein r is 1 and M is (CH3)4N R1 R2 n R4 R5 R6a 46b C--O I H H H H C=O 2 H H H H C=O 1 H H H CH3 C=O 2 H H H CH3 C=O I H H CH3 CH3 C=O 2 H H CH3 CH3 C=O 1 CH3 H H H C=O 2 CH3 H H H C=O 1 CH3 H H CH3 C=O 2 CH3 H H CH3 C=O 1 CH3 H CH3 CH3 C=O 2 CH3 H CH3 CH3 C=O 1 CH3 CH3 H H C=O 2 CH3 CH3 H H C=O 1 CH3 CH3 H CH3 C=O 2 CH3 CH3 H CH3 C=O 1 CH3 CH3 CH3 CH3 C=O 2 CH3 CH3 CH3 CH3 C=O 1 Cl Cl H H C=O 2 Cl Cl H H C=O 1 Cl Cl H CH3 C=O 2 Cl Cl H CH3 C=O 1 Cl Cl CH3 CH3 C=O 2 CI Cl CH3 CH3 -OCH2CH2O- 0 H H H H -OCH2CH20- 1 H H H H -OCH2CH20- 2 H H H H -OCH2CH20- 0 H H H CH3 -OCH2CH20- 1 H H H CH3 -OCH2CH20- 2 H H H CH3 -OCH2CH20- 0 H H CH3 CH3 -OCH2CH20- 1 H H CH3 CH3 -OCH2CH20- 2 H H CH3 CH3 -OCH2CH20- O CH3 H H H -OCH2CH20- 1 CH3 H H H -OCH2CH2O- 2 CH3 H H H -OCH,CH20- O CH3 H H CH3 -OCH2CH2O- 1 CH3 H H CH3 -OCH2CH2O- 2 CH3 H H CH3 -OCH2CH2O- O CH3 H CH3 CH3 -OCH2CH2O- I CH3 H CH3 CH3 -OCH2CH2O- 2 CH3 H CH3 CH3 -OCH2CH20- O CH3 CH3 H H -OCH2CH20- I CH3 CH3 H H -OCH2CH20- 2 CH3 CH3 H H -OCH2CH20- O CH3 CH3 H CH3 -OCH2CH20- 1 CH3 CH3 H CH3 -OCH2CH20- 2 CH3 CH3 H CH3 -OCH2CH20- O CH3 CH3 CH3 CH3 -OCH2CH20- I CH3 CH3 CH3 CH3 -OCH2CH20- 2 CH3 CH3 CH3 CH3 -OCH2CH2O- 0 Cl Cl H H -OCH2CH2O- 1 Cl Cl H H -OCH2CH20- 2 Cl Cl H H -OCH2CH20- 0 Ci Cl H CH3 -OCH2CH20- 1 Cl Cl H CH3 -OCH2CH20- 2 Cl Cl H CH3 -OCH2CH20- 0 Cl Cl CH3 CH3 -OCH2CH20- 1 Cl CI CH3 CH3 -OCH2CH2O- 2 Cl Cl CH3 CH3 -OCH2(CH3)CH2(CH3)0- O H H H H -OCH2(CH3)CH2(CH3)O- 1 H H H H -OCH2(CH3)CH2(CH3)O- 2 H H H H -OCH2(CH3)CH2(CH3)0- O H H H CH3 -OCH2(CH3)CH2(CH3)O- 1 H H H CH3 -OCH2(CH3)CH2(CH3)O- 2 H H H CH3 -OCH2(CH3)CH2(CH3)0- O H H CH3 CH3 -OCH2(CH3)CH2(CH3)0- 1 H H CH3 CH3 -OCH2(CH3)CH2(CH3)0- 2 H H CH3 CH3 -OCH2(CH3)CH2(CH3)O- O CH3 H H H -OCH2(CH3)CH2(CH3)O- 1 CH3 H H H -OCH2(CH3)CH2(CH3)O- 2 CH3 H H H -OCH2(CH3)CH2(CH3)O- O CH3 H H CH3 -OCH2(CH3)CH2(CH3)O- 1 CH3 H H CH3 -OCH2(CH3)CH2(CH3)O- ' CH3 H H CH3 -OCH2(CH3)CH2(CH3)O- O CH3 H CH3 CH3 -OCH2(CH3)CH2(CH3)0- I CH3 H CH3 CH3 -OCH2(CH3)CH2(CH3)0- 2 CH3 H CH3 CH3 -OCH2(CH3)CH2(CH3)0- O CH3 CH3 H H -OCH2(CH3)CH2(CH3)O- I CH3 CH3 H H -OCH2(CH3)CH2(CH3)0- 2 CH3 CH3 H H -OCH2(CH3)CH2(CH3)0- O CH3 CH3 H CH3 -OCH2(CH3)CH2(CH3)0- 1 CH3 CH3 H CH3 -OCH2(CH3)CH2(CH3)O- 2 CH3 CH3 H CH3 -OCH2(CH3)CH2(CH3)0- O CH3 CH3 CH3 CH3 -OCH2(CH3)CH2(CH3)O- 1 CH3 CH3 CH3 CH3 -OCH2(CH3)CH2(CH3)0- 2 CH3 CH3 CH3 CH3 -OCH2(CH3)CH2(CH3)0- O Cl Cl H H -OCH2(CH3)CH2(CH3)0- 1 Cl Cl H H -OCH2(CH3)CH2(CH3)O- 2 Cl Cl H H -OCH2(CH3)CH2(CH3)O- 0 Cl Cl H CH3 -OCH2(CH3)CH2(CH3)O- 1 Cl Cl H CH3 -OCH2(CH3)CH2(CH3)O- 2 Cl Cl H CH3 -OCH2(CH3)CH2(CH3)0- 0 Cl Cl CH3 CH3 -OCH2(CH3)CH2(CH3)O- 1 Cl Cl CH3 CH3 -OCH2(CH3)CH2(CH3)O- 2 Cl Cl CH3 CH3 wherein r is 1 and M is (C16H33)(CH3)2(C6H5CH2)N R1 R2 n R4 R5 R6a R6b C=O 1 H H H H C=O 2 H H H H C=O 1 H H H CH3 C=O 2 H H H CH3 C=O 1 H H CH3 CH3 C=O 2 H H CH3 CH3 C--O 1 CH3 H H H CO 2 CH3 H H H C=O 1 CH3 H H CH3 C=O 2 CH3 H H CH3 C=O 1 CH3 H CH3 CH3 CO 2 CH3 H CH3 CH3 C=O I CH3 CH3 H H C=O 2 CH3 CH3 H H C=O I CH3 CH3 H CH3 C=O 2 CH3 CH3 H CH3 C=O I CH3 CH3 CH3 CH3 C=O 2 CH3 CH3 CH3 CH3 C=O I Cl CI H H C=O 2 Cl Cl H H C=O 1 Cl Cl H CH3 C=O 2 Cl Cl H CH3 C=O 1 Cl Cl CH3 CH3 C=O 2 Cl Cl CH3 CH3 -OCH2CH2O- 0 H H H H -OCH2CH20- 1 H H H H -OCH2CH20- 2 H H H H -OCH2CH20- 0 H H H CH3 -OCH2CH20- 1 H H H CH3 -OCH2CH20- 2 H H H CH3 -OCH2CH20- 0 H H CH3 CH3 -OCH2CH2O- 1 H H CH3 CH3 -OCH2CH20- 2 H H CH3 CH3 -OCH2CH20- O CH3 H H H -OCH2CH20- 1 CH3 H H H -OCH2CH20- 2 CH3 H H H -OCH2CH20- O CH3 H H CH3 -OCH2CH20- 1 CH3 H H CH3 -OCH2CH2O- 2 CH3 H H CH3 -OCH2CH20- O CH3 H CH3 CH3 -OCH2CH20- 1 CH3 H CH3 CH3 -OCH2CH20- 2 CH3 H CH3 CH3 -OCH2CH20- O CH3 CH3 H H -OCH2CH20- I CH3 CH3 H H -OCH2CH20- 2 CH3 CH3 H H -OCH2CH20- O CH3 CH3 H CH3 -OCH2CH20- I CH3 CH3 H CH3 -OCH2CH20- 2 CH3 CH3 H CH3 -OCH2CH20- O CH3 CH3 CH3 CH3 -OCH2CH20- 1 CH3 CH3 CH3 CH3 -OCH2CH2O- 2 CH3 CH3 CH3 CH3 -OCH2CH2O- O CI CI H H -OCH2CH2O- I CI CI H H -OCH2CH2O- 2 CI CI H H -OCH9CH20- 0 Cl Cl H CH3 -OCH2CH2O- 1 Cl Cl H CH3 -OCH2CH20- 2 Cl Cl H CH3 -OCH2CH20- 0 Cl Cl CH3 CH3 -OCH2CH20- I Cl Cl CH3 CH3 -OCH2CH2O- 2 Cl Cl CH3 CH3 -OCH2(CH3)CH2(CH3)0- O H H H H -OCH2(CH3)CH2(CH3)0- 1 H H H H -OCH2(CH3)CH2(CH3)0- 2 H H H H -OCH2(CH3)CH2(CH3)0- O H H H CH3 -OCH2(CH3)CH2(CH3)0- I H H H CH3 -OCH2(CH3)CH2(CH3)O- 2 H H H CH3 -OCH2(CH3)CH2(CH3)O- O H H CH3 CH3 -OCH2(CH3)CH2(CH3)0- 1 H H CH3 CH3 -OCH2(CH3)CH2(CH3)O- 2 H H CH3 CH3 -OCH2(CH3)CH2(CH3)O- O CH3 H H H -OCH2(CH3)CH2(CH3)0- 1 CH3 H H H -OCH2(CH3)CH2(CH3)0- 2 CH3 H H H -OCH2(CH3)CH2(CH3)0- O CH3 H H CH3 -OCH2(CH3)CH2(CH3)O- 1 CH3 H H CH3 -OCH2(CH3)CH2(CH3)o- 2 CH3 H H CH3 -OCH2(CH3)CH2(CH3)0- O CH3 H CH3 CH3 -OCH2(CH3)CH2(CH3)O- 1 CH3 H CH3 CH3 -OCH2(CH3)CH2(CH3)O- 2 CH3 H CH3 CH3 -OCH2(CH3)CH2(CH3)0- O CH3 CH3 H H -oCH2(CH3)CH2(CH3)o- 1 CH3 CH3 H H -OCH2(CH3)CH2(CH3)O- 2 CH3 CH3 H H -OCH2(CH3)CH2(CH3)0- O CH3 CH3 H CH3 -OCH2(CH3)CH2(CH3)0- I CH3 CH3 H CH3 -OCH2(CH3)CH2(CH3)0- 2 CH3 CH3 H CH3 -OCH2(CH3)CH2(CH3)0- O CH3 CH3 CH3 CH3 -oCH2(CH3)CH2(CH3)o- I CH3 CH3 CH3 CH3 -OCH2(CH3)CH2(CH3)O- 2 CH3 CH3 CH3 CH3 -OCH2(CH3)CH2(CH3)O- 0 Cl Cl H H -OCH2(CH3)CH2(CH3)O- 1 Cl Cl H H <BR> <BR> <BR> -OCH2(CH3)CH2(CH3)O- 9 Cl CI H H -OCH2(CH3)CH2(CH3)O- 0 Cl Cl H CH3 -OCH2(CH3)CH2(CH3)0- I Cl Cl H CH3 -OCH2(CH3)CH2(CH3)O- 2 Cl Cl H CH3 -OCH2(CH3)CH2(CH3)O- 0 Cl Cl CH3 CH3 -OCH2(CH3)CH2(CH3)0- I CI Cl CH3 CH3 -OCH2(CH3)CH2(CH3)0- 2 CI Cl CH3 CH3 wherein r is 2 and M is Co R1 R2 n R4 R5 R6a R6b C=C 1 H H H H C=C 2 H H H H C=C 1 H H H CH3 C=C 2 H H H CH3 C=C 1 H H CH3 CH3 C=O 2 H H CH3 CH3 C=O 1 CH3 H H H C=O 2 CH3 H H H C=O 1 CH3 H H CH3 C=C 2 CH3 H H CH3 C=O 1 CH3 H CH3 CH3 C=C 2 CH3 H CH3 CH3 C=C I CH3 CH3 H H C=O 2 CH3 CH3 H H C=O I CH3 CH3 H CH3 C=O 2 CH3 CH3 H CH3 C=O 1 CH3 CH3 CH3 CH3 C=O 2 CH3 CH3 CH3 CH3 C=O 1 Cl Cl H H C=O 2 Cl Cl H H C=O 1 Cl Cl H CH3 C=O 2 Cl Cl H CH3 C=O 1 Cl Cl CH3 CH3 C=O 2 Cl Cl CH3 CH3 -OCH2CH20- 0 H H H H -OCH2CH20- 1 H H H H -OCH2CH20- 2 H H H H -OCH2CH2O- 0 H H H CH3 -OCH2CH2O- I H H H CH3 -OCH2CH2O- 2 H H H CH3 -OCH2CH2O- 0 H H CH3 CH3 -OCH2CH2O- 1 H H CH3 CH3 -OCH2CH20- 2 H H CH3 CH3 -OCH2CH20- O CH3 H H H -OCH2CH2O- I CH3 H H H -OCH2CH2O- 2 CH3 H H H -OCH2CH20- O CH3 H H CH3 -OCH2CH20- 1 CH3 H H CH3 -OCH2CH20- 2 CH3 H H CH3 -OCH2CH20- O CH3 H CH3 CH3 -OCH2CH20- 1 CH3 H CH3 CH3 -OCH2CH20- 2 CH3 H CH3 CH3 -OCH2CH20- O CH3 CH3 H H -OCH2CH20- 1 CH3 CH3 H H -OCH2CH20- 2 CH3 CH3 H H -OCH2CH2O- O CH3 CH3 H CH3 -OCH2CH2O- 1 CH3 CH3 H CH3 -OCH2CH20- 2 CH3 CH3 H CH3 -OCH2CH20- O CH3 CH3 CH3 CH3 -OCH2CH20- 1 CH3 CH3 CH3 CH3 -OCH2CH2O- 2 CH3 CH3 CH3 CH3 -OCH2CH2O- 0 Cl Cl H H -OCH2CH2O- 1 Cl Cl H H -OCH2CH2O- 2 Cl Cl H H -OCH2CH2O- 0 Cl Cl H CH3 -OCH2CH2O- 1 Cl Cl H CH3 -OCH2CH2O- 2 Cl Cl H CH3 -OCH2CH20- 0 Cl Cl CH3 CH3 -OCH2CH20- 1 Cl CI CH3 CH3 -OCH2CH20- 2 Cl CI CH3 CH3 wherein r is 2 and M is Ni RI R2 n R4 R5 R6a R6b C=O I H H H H C=O 2 H H H H C=O I H H H CH3 C=O 2 H H H CH3 C=O I H H CH3 CH3 C=O 2 H H CH3 CH3 C=C 1 CH3 H H H C=C 2 CH3 H H H C=C I CH3 H H CH3 C=C 2 CH3 H H CH3 C=C 1 CH3 H CH3 CH3 C=C 2 CH3 H CH3 CH3 C=C 1 CH3 CH3 H H C=C 2 CH3 CH3 H H C=O 1 CH3 CH3 H CH3 C=C 2 CH3 CH3 H CH3 C=O 1 CH3 CH3 CH3 CH3 C=O 2 CH3 CH3 CH3 CH3 C=O 1 Cl Cl H H C=O 2 Cl Cl H H C=O 1 Cl Cl H CH3 C=O 2 Cl Cl H CH3 C=O 1 Cl Cl CH3 CH3 C=O 2 Cl Cl CH3 CH3 -OCH2CH20- 0 H H H H -OCH2CH20- 1 H H H H -OCH2CH20- 2 H H H H -OCH2CH20- 0 H H H CH3 -OCH2CH20- 1 H H H CH3 -OCH2CH20- 2 H H H CH3 -OCH2CH20- 0 H H CH3 CH3 -OCH2CH20- I H H CH3 CH3 -OCH2CH20- 2 H H CH3 CH3 -OCH2CH20- O CH3 H H H -OCH2CH20- I CH3 H H H -OCH2CH20- 2 CH3 H H H -OCH2CH2O- O CH3 H H CH3 -OCH2CH2O- I CH3 H H CH3 -OCH2CH2O- 2 CH3 H H CH3 -OCH2CH2O- O CH3 H CH3 CH3 -OCH2CH20- I CH3 H CH3 CH3 -OCH2CH20- 2 CH3 H CH3 CH3 -OCH2CH20- O CH3 CH3 H H -OCH2CH20- I CH3 CH3 H H -OCH2CH20- 2 CH3 CH3 H H -OCH2CH20- O CH3 CH3 H CH3 -OCH2CH20- 1 CH3 CH3 H CH3 -OCH2CH20- 2 CH3 CH3 H CH3 -OCH2CH20- O CH3 CH3 CH3 CH3 -OCH2CH20- 1 CH3 CH3 CH3 CH3 -OCH2CH20- 2 CH3 CH3 CH3 CH3 -OCH2CH2O- 0 Cl Cl H H -OCH2CH20- I Cl Cl H H -OCH2CH20- 2 Cl Cl H H -OCH2CH2O- 0 Cl Cl H CH3 -OCH2CH2O- 1 Cl Cl H CH3 -OCH2CH2O- 2 Cl Cl H CH3 -OCH2CH2O- 0 Cl Cl CH3 CH3 -OCH2CH20- 1 Cl Cl CH3 CH3 -OCH2CH20- 2 Cl Cl CH3 CH3 wherein r is 2 and M is Cu R1 R2 n R4 R5 R6a R6b C=C 1 H H H H C=C 2 H H H H C=C I H H H CH3 C=C 2 H H H CH3 C=C 1 H H CH3 CH3 C=C 2 H H CH3 CH3 C=O 1 CH3 H H H C=O 2 CH3 H H H C=O I CH3 H H CH3 C=O 2 CH3 H H CH3 C=O 1 CH3 H CH3 CH3 C=O 2 CH3 H CH3 CH3 C=O I CH3 CH3 H H C=O 2 CH3 CH3 H H C=O I CH3 CH3 H CH3 C=O 2 CH3 CH3 H CH3 C=O I CH3 CH3 CH3 CH3 C=O 2 CH3 CH3 CH3 CH3 C=O 1 Cl Cl H H C=O 2 Cl Cl H H C=O 1 Cl Cl H CH3 C=O 2 Cl Cl H CH3 C=O 1 Cl Cl CH3 CH3 C=O 2 Cl Cl CH3 CH3 -OCH2CH20- 0 H H H H -OCH2CH20- 1 H H H H -OCH2CH20- 2 H H H H -OCH2CH20- 0 H H H CH3 -OCH2CH20- 1 H H H CH3 -OCH2CH20- 2 H H H CH3 -OCH2CH20- 0 H H CH3 CH3 -OCH2CH20- 1 H H CH3 CH3 -OCH2CH20- 2 H H CH3 CH3 -OCH2CH20- O CH3 H H H -OCH2CH20- 1 CH3 H H H -OCH2CH20- 2 CH3 H H H -OCH2CH20- O CH3 H H CH3 -OCH2CH20- 1 CH3 H H CH3 -OCH2CH20- 2 CH3 H H CH3 -OCH2CH20- O CH3 H CH3 CH3 -OCH2CH20- 1 CH3 H CH3 CH3 -OCH2CH20- 2 CH3 H CH3 CH3 -OCH2CH20- O CH3 CH3 H H -OCH2CH20- 1 CH3 CH3 H H -OCH2CH20- 2 CH3 CH3 H H -OCH2CH20- O CH3 CH3 H CH3 -OCH2CH20- I CH3 CH3 H CH3 -OCH2CH2O- 2 CH3 CH3 H CH3 -OCH2CH2O- O CH3 CH3 CH3 CH3 -OCH2CH20- 1 CH3 CH3 CH3 CH3 -OCH2CH20- 2 CH3 CH3 CH3 CH3 -OCH2CH2O- 0 Cl Cl H H -OCH2CH20- I Cl CI H H -OCH2CH2O- 2 CI CI H H -OCH2CH2O- 0 Cl Cl H CH3 -OCH2CH20- 1 Cl CI H CH3 -OCH2CH20- 2 Cl CI H CH3 -OCH2CH20- 0 CI Cl CH3 CH3 -OCH2CH2O- 1 Cl Cl CH3 CH3 -OCH2CH2O- 2 Cl Cl CH3 CH3 wherein r is 2 and M is Zn R1 R2 n R4 R5 R6a R6b C=C 1 H H H H C=O 2 H H H H C=C 1 H H H CH3 C=O 2 H H H CH3 C=C 1 H H CH3 CH3 C=C 2 H H CH3 CH3 C=O 1 CH3 H H H C=O 2 CH3 H H H C=C 1 CH3 H H CH3 C=O 2 CH3 H H CH3 C=C 1 CH3 H CH3 CH3 C=C 2 CH3 H CH3 CH3 C=C 1 CH3 CH3 H H C=C 2 CH3 CH3 H H C=O 1 CH3 CH3 H CH3 C=O 2 CH3 CH3 H CH3 C=O I CH3 CH3 CH3 CH3 C=O 2 CH3 CH3 CH3 CH3 C=O 1 Cl Cl H H C=O 2 Cl Cl H H C=O 1 Cl Cl H CH3 C=O 2 Cl Cl H CH3 C=O 1 Cl Cl CH3 CH3 C=O 2 Cl Cl CH3 CH3 -OCH2CH2O- 0 H H H H -OCH2CH2O- 1 H H H H -OCH2CH2O- R H H H -OCH2CH2O- 0 H H H CH3 -OCH2CH2O- I H H H CH3 -OCH2CH20- 2 H H H CH3 -OCH2CH20- 0 H H CH3 CH3 -OCH2CH20- I H H CH3 CH3 -OCH2CH20- 2 H H CH3 CH3 -OCH2CH20- O CH3 H H H -OCH2CH20- 1 CH3 H H H -OCH2CH2O- 2 CH3 H H H -OCH2CH20- O CH3 H H CH3 -OCH2CH20- 1 CH3 H H CH3 -OCH2CH20- 2 CH3 H H CH3 -OCH2CH20- O CH3 H CH3 CH3 -OCH2CH20- 1 CH3 H CH3 CH3 -OCH2CH2O- 2 CH3 H CH3 CH3 -OCH2CH20- O CH3 CH3 H H -OCH2CH20- 1 CH3 CH3 H H -OCH2CH20- 2 CH3 CH3 H H -OCH2CH20- O CH3 CH3 H CH3 -OCH2CH2O- 1 CH3 CH3 H CH3 -OCH2CH20- 2 CH3 CH3 H CH3 -OCH2CH20- O CH3 CH3 CH3 CH3 -OCH2CH20- 1 CH3 CH3 CH3 CH3 -OCH2CH20- 2 CH3 CH3 CH3 CH3 -OCH2CH2O- 0 Cl Cl H H -OCH2CH20- 1 Cl Cl H H -OCH2CH2O- 2 Cl Cl H H -OCH2CH20- 0 CI CI H CH3 -OCH2CH20- 1 Cl CI H CH3 -OCH2CH2O- 2 Cl Cl H CH3 -OCH2CH20- 0 Cl Cl CH3 CH3 -OCH2CH20- 1 CI Cl CH3 CH3 -OCH2CH2O- 2 Cl CI CH3 CH3 TABLE 2 wherein r is 1 and M is Li R1 R2 n R4 R5 C=O 1 H H C=O 2 H H C=O 1 CH3 H C=O 2 CH3 H C=O 1 CH3 CH3 C=O 2 CH3 CH3 C=O 1 Cl Cl C=O 2 Cl Cl -OCH2CH20- 0 H H -OCH2CH20- 1 H H -OCH2CH20- 2 H H -OCH2CH20- O CH3 H -OCH2CH20- 1 CH3 H -OCH2CH20- 2 CH3 H -OCH2CH20- 0 CH3 CH3 -OCH2CH20- I CH3 CH3 -OCH2CH2O- 2 CH3 CH3 -OCH2CH2O- 0 Cl Cl -OCH2CH2O- 1 Cl Cl -OCH2CH2O- 2 Cl Cl -OCH2(CH3)CH2(CH3)O- O H H -OCH2(CH3)CH2(CH3)O- I H H -OCH2(CH3)CH2(CH3)O- 2 H H -OCH2(CH3)CH2(CH3)O- O CH3 H -OCH2(CH3)CH2(CH3)O- I CH3 H -OCH2(CH3)CH2(CH3)O- 2 CH3 H wherein r is 1 and M is Na R1 R2 n R4 R5 C=O 1 H H C=O 2 H H C=O 1 CH3 H C=O 2 CH3 H C=O 1 CH3 CH3 C=O 2 CH3 CH3 C=O 1 Cl Cl C=O 2 Cl Cl -OCH2CH20- O H H -OCH2CH20- 1 H H -OCH2CH20- 2 H H -OCH2CH20- 0 CH3 H -OCH2CH20- 1 CH3 H -OCH2CH20- 2 CH3 H -OCH2CH2O- 0 CH3 CH3 -OCH2CH20- 1 CH3 CH3 -OCH2CH20- 2 CH3 CH3 -OCH2CH2O- 0 Cl Cl -OCH2CH20- 1 CI Cl -OCH2CH2O- 2 Cl Cl -OCH2(CH3)CH2(CH3)O- 0 H H -OCH2(CH3)CH2(CH3)O- 1 H H -OCH2(CH3)CH2(CH3)O- 2 H H -OCH2(CH3)CH2(CH3)O- 0 CH3 H -OCH2(CH3)CH2(CH3)O- 1 CH3 H -OCH2(CH3)CH2(CH3)0- 2 CH3 H -OCH2(CH3)CH2(CH3)O- 0 CH3 CH3 -OCH2(CH3)CH2(CH3)O- 1 CH3 CH3 -OCH2(CH3)CH2(CH3)O- 2 CH3 CH3 -OCH2(CH3)CH2(CH3)O- O CI CI -OCH2(CH3)CH2(CH3)O- 1 Cl Cl -OCH2(CH3)CH2(CH3)O- 2 Cl Cl -OCH2(CH3)CH2(CH3)O- 0 CH3 CH3 -OCH2(CH3)CH2(CH3)O- 1 CH3 CH3 -OCH2(CH3)CH2(CH3)O- 2 CH3 CH3 -OCH2(CH3)CH2(CH3)O- 0 Cl Cl -OCH2(CH3)CH2(CH3)O- I CI Cl -OCH2(CH3)CH2(CH3)0- 2 CI CI wherein r is 1 and M is K R1 R2 n R4 R5 C=O 1 H H C=O 2 H H C=O 1 CH3 H C=O 2 CH3 H C=O 1 CH3 CH3 C=O 2 CH3 CH3 C=O 1 Cl Cl C=O 2 Cl Cl -OCH2CH20- 0 H H -OCH2CH20- I H H -OCH2CH20- 2 H H -OCH2CH2O- O CH3 H -OCH2CH20- 1 CH3 H -OCH2CH20- 2 CH3 H -OCH2CH20- 0 CH3 CH3 -OCH2CH20- 1 CH3 CH3 -OCH2CH20- 2 CH3 CH3 -OCH2CH2O- 0 Cl Cl -OCH2CH20- I Cl Cl -OCH2CH20- 2 Cl Cl -OCH2(CH3)CH2(CH3)0- O H H -OCH2(CH3)CH2(CH3)0- I H H -OCH2(CH3)CH2(CH3)0- 2 H H -OCH2(CH3)CH2(CH3)0- O CH3 H -OCH2(CH3)CH2(CH3)O- I CH3 H -OCH2(CH3)CH2(CH3)O- 2 CH3 H -OCH2(CH3)CH2(CH3)O- 0 CH3 CH3 -OCH2(CH3)CH2(CH3)O- I CH3 CH3 -OCH2(CH3)CH2(CH3)0- 2 CH3 CH3 wherein r is 2 and M is Ca R1 R2 n R4 R5 C=O I H H C=O 2 H H C=O 1 CH3 H C=O 2 CH3 H C=O 1 CH3 CH3 C=O 2 CH3 CH3 C=O 1 Cl Cl C=O 2 Cl Cl -OCH2CH20- 0 H H -OCH2CH20- 1 H H -OCH2CH20- 2 H H -OCH2CH20- 0 CH3 H -OCH2CH20- I CH3 H -OCH2CH20- 2 CH3 H -OCH2CH20- 0 CH3 CH3 -OCH2CH2O- 1 CH3 CH3 -OCH2CH20- 2 CH3 CH3 -OCH2CH2O- 0 Cl Cl -OCH2CH2O- 1 Cl Cl -OCH2CH2O- 2 Cl Cl -OCH2(CH3)CH2(CH3)0- O H H -OCH2(CH3)CH2(CH3)0- I H H -OCH2(CH3)CH2(CH3)0- 2 H H -OCH2(CH3)CH2(CH3)0- 0 CH3 H -OCH2(CH3)CH2(CH3)0- I CH3 H -OCH2(CH3)CH2(CH3)0- 2 CH3 H -OCH2(CH3)CH2(CH3)O- 0 CH3 CH3 -OCH2(CH3)CH2(CH3)0- I CH3 CH3 -OCH2(CH3)CH2(CH3)O- 2 CH3 CH3 -OCH2(CH3)CH2(CH3)O- O CI CI -OCH2(CH3)CH2(CH3)O- 1 Cl Cl -OCH2(CH3)CH2(CH3)O- 2 CI CI -OCH2(CH3)CH2(CH3)O- O CI CI -OCH2(CH3)CH2(CH3)O- I CI CI -OCH2(CH3)CH2(CH3)O- 2 Cl Cl wherein r is 2 and M is Mg R1 R2 n R4 R5 C=O I H H C=O 2 H H C=O I CH3 H C=O 2 CH3 H C=O I CH3 CH3 C=C 2 CH3 CH3 C=C I Cl Cl C=C 2 Cl Cl -OCH2CH20- 0 H H -OCH2CH2O- 1 H H -OCH2CH20- 2 H H -OCH2CH20- O CH3 H -OCH2CH20- 1 CH3 H -OCH2CH20- 2 CH3 H -OCH2CH20- 0 CH3 CH3 -OCH2CH20- 1 CH3 CH3 -OCH2CH20- 2 CH3 CH3 -OCH2CH20- 0 Cl Cl -OCH2CH2O- 1 Cl Cl -OCH2CH2O- 2 Cl Cl -OCH2(CH3)CH2(CH3)0- O H H -OCH2(CH3)CH2(CH3)0- 1 H H -OCH2(CH3)CH2(CH3)0- 2 H H -OCH2(CH3)CH2(CH3)O- O CH3 H -OCH2(CH3)CH2(CH3)0- I CH3 H -OCH2(CH3)CH2(CH3)0- 2 CH3 H -OCH2(CH3)CH2(CH3)0- O CH3 CH3 -OCH2(CH3)CH2(CH3)o- I CH3 CH3 -OCH2(CH3)CH2(CH3)O- 2 CH3 CH3 -OCH2(CH3)CH2(CH3)0- O Cl CI -OCH2(CH3)CH2(CH3)O- 1 Cl Cl -OCH2(CH3)CH2(CH3)O- 2 Cl Cl wherein r is 1 and M is (CH3CH2)3NH R1 R2 n R4 R5 C=O 1 H H C=O 2 H H C=C I CH3 H C=C 2 CH3 H C=O I CH3 CH3 C=C 2 CH3 CH3 C=O 1 Cl Cl C=C 2 Cl Cl -OCH2CH20- 0 H H -OCH2CH20- 1 H H -OCH2CH20- 2 H H -OCH2CH20- 0 CH3 H -OCH2CH20- 1 CH3 H -OCH2CH20- 2 CH3 H -OCH2CH20- 0 CH3 CH3 -OCH2CH20- 1 CH3 CH3 -OCH2CH20- 2 CH3 CH3 -OCH2CH2O- 0 Cl Cl -OCH2CH2O- 1 Cl Cl -OCH2CH2O- 2 Cl Cl -OCH2(CH3)CH2(CH3)O- O H H -OCH2(CH3)CH2(CH3)O- I H H -OCH2(CH3)CH2(CH3)O- 2 H H -OCH2(CH3)CH2(CH3)0- 0 CH3 H -OCH2(CH3)CH2(CH3)0- 1 CH3 H -OCH2(CH3)CH2(CH3)O- 2 CH3 H -OCH2(CH3)CH2(CH3)0- 0 CH3 CH3 -OCH2(CH3)CH2(CH3)0- 1 CH3 CH3 -OCH2(CH3)CH2(CH3)O- 2 CH3 CH3 -OCH2(CH3)CH2(CH3)0- 0 Cl Cl -OCH2(CH3)CH2(CH3)0- I Cl Cl -OCH2(CH3)CH2(CH3)O- 2 Cl Cl wherein r is I and M is wherein r is 1 and M is (CH3)4N (C16H33)(CH3)2(C6H5CH2)N R1 R2 n R4 R5 C=C I H H C=C 2 H H C=C 1 CH3 H C=C 2 CH3 H C=C 1 CH3 CH3 C=C 2 CH3 CH3 C=C 1 Cl Cl C=O 2 Cl Cl -OCH2CH20- 0 H H -OCH2CH20- 1 H H -OCH2CH20- 2 H H -OCH2CH20- O CH3 H -OCH2CH20- 1 CH3 H -OCH2CH2O- 2 CH3 H -OCH2CH20- 0 CH3 CH3 -OCH2CH20- 1 CH3 CH3 -OCH2CH20- 2 CH3 CH3 -OCH2CH2O- 0 Cl Cl -OCH2CH20- 1 Cl Cl -OCH2CH20- 2 Cl Cl -OCH2(CH3)CH2(CH3)0- 0 H H -OCH2(CH3)CH2(CH3)0- 1 H H -OCH2(CH3)CH2(CH3)0- 2 H H -OCH2(CH3)CH2(CH3)0- O CH3 H -OCH2(CH3)CH2(CH3)O- I CH3 H -OCH2(CH3)CH2(CH3)O- 2 CH3 H -OCH2(CH3)CH2(CH3)0- O CH3 CH3 -OCH2(CH3)CH2(CH3)0- I CH3 CH3 -OCH2(CH3)CH2(CH3)O- 2 CH3 CH3 -OCH2(CH3)CH2(CH3)O- 0 Cl Cl -OCH2(CH3)CH2(CH3)0- I Cl Cl -OCH2(CH3)CH2(CH3)O- 2 Cl Cl R1 R2 n R4 R5 C=O I H H C=C 2 H H C=O I CH3 H C=O 2 CH3 H C=C I CH3 CH3 C=C 2 CH3 CH3 C=O 1 Cl Cl C=C 2 Cl Cl -OCH2CH20- 0 H H -OCH2CH2O- 1 H H -OCH2CH20- 2 H H -OCH2CH2O- 0 CH3 H -OCH2CH20- 1 CH3 H -OCH2CH2O- 2 CH3 H -OCH2CH20- 0 CH3 CH3 -OCH2CH20- 1 CH3 CH3 -OCH2CH20- 2 CH3 CH3 -OCH2CH2O- 0 Cl Cl -OCH2CH20- 1 Cl Cl -OCH2CH20- 2 Cl Cl -OCH2(CH3)CH2(CH3)O- O H H -OCH2(CH3)CH2(CH3)O- 1 H H -OCH2(CH3)CH2(CH3)O- 2 H H -OCH2(CH3)CH2(CH3)0- 0 CH3 H -OCH2(CH3)CH2(CH3)O- 1 CH3 H -OCH2(CH3)CH2(CH3)O- 2 CH3 H -OCH2(CH3)CH2(CH3)O- 0 CH3 CH3 -OCH2(CH3)CH2(CH3)0- I CH3 CH3 -OCH2(CH3)CH2(CH3)O- 2 CH3 CH3 -OCH2(CH3)CH2(CH3)O- 0 Cl Cl -OCH2(CH3)CH2(CH3)0- 1 CI Cl -OCH2(CH3)CH2(CH3)O- 2 Cl Cl wherein r is 2 and M is Co R1 R2 n R4 R5 C=O I H H C=C 2 H H C=O I CH3 H C=O 2 CH3 H C=O I CH3 CR3 C=O 2 CH3 CR3 C=O 1 Cl Cl C=O 2 Cl Cl -OCH2CH20- 0 H H -OCH2CH20- 1 H H -OCH2CH20- 2 H H -OCH2CH20- O CH3 H -OCH2CH20- 1 CH3 H -OCH2CH20- 2 CH3 H -OCH2CH20- 0 CH3 CH3 -OCH2CH20- 1 CH3 CR3 -OCH2CH20- 2 CH3 CR3 -OCH2CH2O- 0 Cl Cl -OCH2CH2O- 1 Cl Cl -OCH2CH2O- 2 Cl Cl wherein r is 2 and M is Ni R1 R2 n R4 R5 C=O I H H C=O 2 H H C=O I CH3 H C=O 2 CH3 H C=O 1 CH3 CH3 C=O 2 CH3 CH3 C=O 1 Cl Cl C=O 2 Cl Cl -OCH2CH20- 0 H H -OCH2CH20- 1 H H -OCH2CH20- 2 H H -OCH2CH20- 0 CH3 H -OCH2CH20- 1 CH3 H -OCH2CH20- 2 CH3 H -OCH2CH20- 0 CH3 CH3 -OCH2CH20- 1 CH3 CH3 -OCH2CH20- 2 CH3 CH3 -OCH2CH20- 0 Cl Cl -OCH2CH20- I Cl Cl -OCH2CH2O- 2 Cl Cl wherein r is 2 and M is Cu R1 R2 n R4 R5 C=O 1 H H C=O 2 H H C=O I CH3 H C=O 2 CH3 H C=O I CH3 CH3 C=O 2 CH3 CH3 C=O 1 Cl Cl C=O 2 Cl Cl -OCH2CH20- 0 H H -OCH2CH20- I H H -OCH2CH2O- 2 H H -OCH2CH20- O CH3 H -OCH2CH20- I CH3 H wherein r is 2 and M is Zn R1 R2 n R4 R5 C=O 1 H H C=O 2 H H C=O 1 CH3 H C=O 2 CH3 H C=O 1 CH3 CH3 C=O 2 CH3 CH3 C=O 1 Cl Cl C=O 2 Cl Cl -OCH2CH20- 0 H H -OCH2CH20- I H H -OCH2CH2O- 2 H H -OCH2CH20- 0 CH3 H -OCH2CH20- I CH3 H

-OCH2CH20- 2 CH3 H -OCH2CH2O- O CH3 CH3 -OCH2CH2O- I CH3 CH3 -OCH2CH20- 2 CH3 CH3 -OCH2CH,O- O CI Cl -OCH2CH20- I Cl Cl -OCH2CH2O- 2 Cl Cl -CCR2CR2C- 2 CH3 H -OCH2CH20- 0 CH3 CH3 -OCH2CH20- I CH3 CH3 -OCH2CH2O- 2 CH3 CH3 -OCHoCH20- 0 Cl CI -OCH2CH20- I Cl Cl -OCH2CH2O- 2 Cl Cl Formulation/Utility Compounds of this invention will generally be used as a formulation or composition with an agriculturally suitable carrier comprising at least one of a liquid diluent, a solid diluent or a surfactant. The formulation or composition ingredients are selected to be consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature. Useful formulations include liquids such as solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and/or suspoemulsions) and the like which optionally can be thickened into gels. Useful formulations further include solids such as dusts, powders, granules, pellets, tablets, films, and the like which can be water-dispersible ("wettable") or water-soluble. Active ingredient can be (micro)encapsulated and further formed into a suspenslon or solid formulation; alternatively the entire formulation of active ingredient can be encapsulated (or "overcoated"). Encapsulation can control or delay release of the active ingredient. Sprayable formulations can be extended in suitable media and used at spray volumes from about one to several hundred liters per hectare. High-strength compositions are primarily used as intermediates for further formulation.

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

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

Suspensions, Emulsions, Solutions 5-50 40-95 0-15 (including Emulsifiable Concentrates) Dusts 1-25 70-99 0-5 Granules and Pellets 0.01-99 5-99.99 0-15 High Strength Compositions 90-99 0-10 0-2

Typical solid diluents are described in Watkins, et al.. Hbmclhook of Insecticide Dust Diluents and ('farriers, 2nd Ed.. Dorland Books, Caldwell, New Jersey. Typical liquid diluents are described in Marsden. Solvents Guide, 2nod Ed., Interscience. New York, 1950. kicCutcheon s Detergents and Emulsifiers Annual, Allured Publ. Corp., Ridgewood, New Jersey, as well as Sisely and Wood, Encyclopedia ofSurjace Active Agents. Chemical Publ.

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

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

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

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

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

3,299,566.

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

pp 8 1 -96, and Glance 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 Hih Strength Concentrate Compound 3 98.5% silica aerogel 0.5% synthetic amorphous fine silica 1.0%.

Example B Wettable Powder Compound 4 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%.

Example C Granule Compound 10 10.0% attapulgite granules (low volatile matter, 0.71/0.30 mm; U.S.S. No. 25-50 sieves) 90.0%.

Example D Extruded Pellet Compound 11 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%.

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

plantation crops including coffee. cocoa, oil palm, rubber, sugarcane. citrus, grapes, fruit trees, nut trees, banana, plantain. pineapple, hops tea and forests such as eucalyptus and conifers (e.g. loblolly pine). and turf species (e.g., Kentucky bluegrass, St. Augustine grass, Kentucky fescue and Bermuda grass). Those skilled in the art will appreciate that not all compounds are equally effective against all weeds. Alternatively, the subject compounds are useful to modify plant growth.

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

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

flupyrsuifuron-methyl and its sodium salt, fiuridone flurochloridone fluroxypyr, futhiacet-methyl, fomesafen, fbsamine-ammonium, glufosinate, glufosinate-ammonium, glyphosate glyphosate-isopropylammonium, glyphosate-sesquisodium, glyphosate-trimesium, halosulfuron-methy 1, haloxyfop-etotyl haloxyfop-methyl, hexazinone, imazamethabenz-rnethyl, imazamox, imazapyr, imazaquin, imazaquin-ammonium, imazethapyr, imazethapyr-ammonium, imazosulfuron, ioxynil, ioxynil octanoate, ioxynil-sodium, isoproturon, isouron isoxaben, isoxaflutole, lactofen, lenacil, linuron, maleic hydrazide, MCPA and its dimethylammonium, potassium and sodium salts, MCPA-isoctyl, mecoprop, mecoprop-P, mefenacet, mefluidide, metam-sodium, methabenzthiazuron, methylarsonic acid and its calcium, monoammonium, monosodium and disodium salts, methyl [[[1-[5-[2-chloro-4-(trifluoromethyl)phenoxy]-2- nitrophenyl]-2-methoxyethylidene]amino]oxy]acetate (AKH-708 8), methyl 5-[[[[(4,6- dimethyl-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]- 1 -(2-pyridinyl)- lH-pyrazole-4- carboxylate (NC-330), metobenzuron, metolachlor, metosulam, metoxuron, metribuzin, metsulfuron-methyl, molinate, monolinuron, napropamide, naptalam, neburon, nicosulfuron, norflurazon, oryzalin, oxadiazon, oxasulfuron, oxyfluorfen, paraquat dichloride, pebulate, pendimethalin, pentoxazone (KPP-3 14), perfluidone, phenmedipham, picloram, picloram-potassium, pretilachlor, primisulfuron-methyl, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propyzamide, prosulfuron, pyrazolynate, pyrazosulfuron-ethyl, pyridate, pyriminobac-methyl, pyrithiobac, pyrithiobac-sodium, quinclorac, quizalofop-ethyl, quizalofop-P-ethyl, quizalofop-P-tefuryl, rimsulfuron, sethoxydim, siduron, simazine, sulcotrione (1C1A005 1), sulfentrazone, sulfometuron-methyl, TCA, TCA-sodium, tebuthiuron, terbacil, terbuthylazine, terbutryn, thenylchlor, thiafluamide (BAY 11390), thifensulfuron-methyl, thiobencarb, tralkoxydim, tri-allate, triasulfuron, triaziflam, tribenuron-methyl, triclopyr, triclopyr-butotyl, triclopyr-triethylammonium, tridiphane, trifluralin, triflusulfuron-methyl, and vernolate.

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

Preferred for better control of undesired vegetation in corn (e.g., lower use rate, broader spectrum of weeds controlled, or enhanced crop safety) or for preventing the development of resistant weeds in corn are mixtures of a compound of this invention with one or more of the herbicides selected from the group thifensulfuron-methyl, rimsulfuron, nicosulfuron, primisulfuron, atrazine, terbuthylazine, 2,4-D, dicamba, bromoxynil, imazethapyr, clopyralid, prosulfuron, glyphosate, glyphosate-trimesium, glufosinate, fluthiacet-methyl, quizalofop-P-ethyl, bentazone, flumetsulam, halosulfuron, sethoxydim, and flumiclorac-pentyl.

Specifically preferred mixtures for use in corn are selected from the group: a) Preparation of 2-[(2,3-dihydro-5,8-dimethylspiro [4H- 1 -benzothiopyran-4,2'- [1,3]dioxolan]-6-yl)carbonyl]-1,3-cyclohexanedione S,S-dioxide monosodium salt (mixture partner A, generally applied at a rate of 4 to 280 g/ha, preferably applied at a rate of 8 to 70 g/ha) in combination with: Preferred Preferred Ratio Use Rate Use Rate Combination Ratio Range Range Range of Range Number Mixture Partner B of A:B of A:B B (g/ha) of B (g/ha) 1 rimsulfuron 1:5-300:1 1:1-70:1 1-20 1-10 2 thifensulfuron-methyl 1:2-300:1 1:1-70:1 1-10 1-5 3 nicosulfuron 1:10-300:1 1:1-70:1 1-50 1-10 4 rimsulfuron 1:5-300:1 1:1-70:1 1-20 1-10 in combination with nicosulfuron 1:10-300:1 1:1-70:1 1-50 1-10 5 rimsulfuron 1:5-300:1 1:1-70:1 1-20 1-10 in combination with thiefensulfuron-methyl 1:2-300:1 1:1-70:1 1-10 1-5 6 prosulfuron 1:10-300:1 2:1-70:1 1-50 1-10 7 prosulfuron 1:10-300:1 2:1-70:1 1-50 1-10 in combination with primisulfuron 1:10-300:1 2:1-70:1 1-50 1-10 8 atrazine 1:500-3:1 1:25-1:1 100-2000 100-500 9 terbuthylazine 1:500-3:1 1:25-1:1 100-2000 100-500 10 dicamba 1:125-30:1 1:5-7:1 10-500 10-100 11 2,4-D 1:250-6:1 1:25-1:1 50-1000 50-500 12 bromoxynil 1:250-6:1 1:25-1:1 50-1000 50-500 13 imazethapyr 1:25-300:1 1:2-14:1 1-100 5-50 14 glyphosate 1:250-6:1 1:25-1:1 50-1000 50-500 15 glufosinate 1:250-6:1 1:25-1:1 50-1000 50-500 16 glyphosate-trimesium 1:250-6:1 1:25-1:1 50-1000 50-500

b) 2-[(2,3-dihydro-5,8-dimethylspiro[4H-1-benzothiopyran-4,2'-[ 1,3]dioxolan]-6- yl)carbonyl]-1,3-cyclohexanedione S,S-dioxide monopotassium salt (mixture partner A, generally applied at a rate of 4 to 280 g/ha, preferably applied at a rate of 8 to 70 g/ha) in combination with: Preferred Preferred Ratio Use Rate Use Rate Combination Ratio Range Range Range of Range Number Mixture Partner B of A:B of A:B B (g/ha) of B (g/ha) I rimsulfuron 1:5-300:1 1:1-70:1 1-20 1-10 2 thifensulfaron-methyl 1:2-300:1 1:1-70:1 1-10 1-5 3 nicosulfuron 1:10-300:1 1:1-70:1 1-50 1-10 4 rimsulfuron 1:5-300:1 1:1-70:1 1-20 1-10 in combination with nicosulfuron 1:10-300:1 1:1-70:1 1-50 1-10 5 rimsulfuron 1:5-300:1 1:1-70:1 1-20 1-10 in combination with thifensulfuron-methyl 1:2-300:1 1:1-70:1 1-10 1-5 6 prosulfuron 1:10-300:1 2:1-70:1 1-50 1-10 7 prosulfuron 1:10-300:1 2:1-70:1 1-50 1-10 in combination with primisulfuron 1:10-300:1 2:1-70:1 1-50 1-10 8 atrazine 1:500-3:1 1:25-1:1 100-2000 100-500 9 terbuthylazine 1:500-3:1 1:25-1:1 100-2000 100-500 10 dicamba 1:125-30:1 1:5-7:1 10-500 10-100 11 2,4-D 1:250-6:1 1:25-1:1 50-1000 50-500 12 bromoxynil 1:250-6:1 1:25-1:1 50-1000 50-500 13 imazethapyr 1:25-300:1 1:2-14:1 1-100 5-50 14 glyphosate 1:250-6:1 1:25-1:1 50- 1000 50-500 15 glufosinate 1:250-6:1 1:25-1:1 50-1000 50-500 16 glyphosate-trimesium 1:250-6:1 1:25-1:1 50-1000 50-500

c) (2,3-dihydro-5,8-dimethylspiro[4H-1-benzothiopyran-4,2'-[1,3 ]dioxolan]-6-yl)(1- ethyl-5-hydroxy-l H-pyrazol-4-yl)methanone S, S-dioxide monopotassium salt (mixture partner A, generally applied at a rate of 4 to 280 g/ha, preferably applied at a rate of 8 to 70 g/ha) in combination with: Preferred Preferred Ratio Use Rate Use Rate Combination Ratio Range Range Range of Range Number Mixture Partner B of A:B of A:B B (g/ha) of B (glha) 1 rimsulfuron 1:5-300:1 1:1-70:1 1-20 1-10 2 thifensulfuron-methyl 1:2-300:1 1:1-70:1 1-10 1-5 3 nicosulfuron 1:10-300:1 1:1-70:1 1-50 1-10 4 rimsulfuron 1:5-300:1 1 1: 1-70: 1-20 1-10 in combination with nicosulfuron 1:10-300:1 1:1-70:1 1-50 1-10 5 rimsulfuron 1:5-300:1 1:1-70:1 1-20 1-10 in combination with thitensulfuron-methyl 1:2-300:1 1:1-70:1 1 - 10 1-5 6 prosulfuron 1:10-300:1 2:1-70:1 1-50 1-10 7 prosulfuron 1:10-300:1 2:1-70:1 1-50 1-10 in combination with primisulfuron 1:10-300:1 2:1-70:1 1-50 1-10 8 atrazine 1:500-3:1 1:25-1:1 100-2000 100-500 9 terbuthylazine 1:500-3:1 1:25-1:1 100-2000 100-500 10 dicamba 1:125-30:1 1:5-7:1 10-500 10-100 11 2,4-D 1:250-6:1 1:25-1:1 50-1000 50-500 12 bromoxynil 1:250-6:1 1:25-1:1 50-1000 50-500 13 imazethapyr 1:25-300:1 1:2-14:1 1-100 5-50 14 glyphosate 1:250-6:1 1:25-1:1 50-1000 50-500 15 glufosinate 1:250-6:1 1:25-1:1 50-1000 50-500 16 glyphosate-trimesium 1:250-6:1 1:25-1:1 50-1000 50-500

d) (2,3-dihydro-5,8-dimethylspiro[4H-1-benzothiopyran-4,2'-[1,3 ]dioxolan]-6-yl)(1- ethyl-5-hydroxy- l H-pyrazol-4-yl)methanone SS-dioxide monosodium salt (mixture partner A, generally applied at a rate of 4 to 280 g/ha. preferably applied at a rate of 8 to 70 g/ha) in combination with: Preferred Preferred Ratio Use Rate Use Rate Combination Ratio Range Range Range of Range Number Mixture Partner B of A:B of A:B B (g"ha) of B (g/ha) 1 rimsulfuron 1:5-300:1 1:1-70:1 1-20 1-10 2 thifensulfuron-methyl 1:2-300:1 1:1-70:1 1-10 1-5 3 nicosulfuron 1:10-300:1 1:1-70:1 1-50 1-10 4 rimsulfuron 1:5-300:1 1:1-70:1 1-20 1-10 in combination with nicosulfuron 1:10-300:1 1 1:1 -70: 1-50 1-10 5 rimsulfuron 1:5-300:1 1:1-70:1 1-20 1-10 in combination with thifensulluron-methyl 1:2-300:1 1:1-70:1 1 - 10 1-5 6 prosulfuron 1:10-300:1 2:1-70:1 1-50 1-10 7 prosulfuron 1:10-300:1 2:1-70:1 1-50 1-10 in combination with primisulfuron 1:10-300:1 2:1-70:1 1-50 1-10 8 atrazine 1:500-3:1 1:25-1:1 100-2000 100-500 9 terbuthylazine 1:500-3:1 1:25-1:1 100-2000 100-500 10 dicamba 1:125-30:1 1:5-7:1 10-500 10-100 11 2,4-D 1:250-6:1 1:25-1:1 50- 1000 50-500 12 bromoxynil 1:250-6:1 1:25-1:1 50- 1000 50-500 13 | imazethapyr 1:25-300:1 1:2-14:1 1-100 5-50 14 glyphosate 1:250-6:1 1:25-1:1 50-1000 50-500 15 glufosinate 1:250-6:1 1:25-1:1 50-1000 50-500 16 glyphosate-trimesium 1:250-6:1 1:25-1:1 50-1000 50-500

A herbicidally effective amount of the compounds of this invention is determined by a number of factors. These factors include: formulation selected, method of application, amount and type of vegetation present, growing conditions, etc. In general, a herbicidally effective amount of compounds of this invention is 0.001 to 20 kg/ha with a preferred range

of 0.004 to 1.0 kg/ha. One skilled in the art can easily determine the herbicidally effective amount necessary for the desired level of weed control.

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. The abbreviation "dec." indicates that the compound appreared to decompose on melting. The abbreviation "Ex." stands for "Example" and is followed by a number indicating in which example the compound is prepared. An "-" indicates that a melting point is not available.

INDEX TABLE A Cmpd R4 R5 R6 M+ mp(°C) 1 Cl Cl H (H5C2)3NH+ 140 (dec.) 2 CH3 CH3 CH3 (Hsc2)3NH+ 115 (dec.) 3 (Ex. 4) CH3 CH3 H Na+ >215* 4 (Ex. 3) CH3 CH3 H K+ >215* 5 (Ex. 2) CH3 CH3 H Li+ 266-267 * 6 (Ex. 5) CH3 CH3 H (C16H33)(CH3)2(C6H5CH2)N+ - 7 CH3 CH3 H (CH3)3(C6H5CH2)N+ - 8 CH3 CH3 H ((CH3)3CCH2(CH3)2C-4-C6H4- - (OCH2CH2)2)(CH3)2- (C6H5CH2)N+ 9 CH3 CH3 H (H5C2)3NHt 198-205 *See Index Table C for 1H NMR data.

INDEX TABLE B Cmpd Structure mp(°C) 10(Ex.1) ((Tho CH3 O O K >260* C2Hg V CH3 02cR 11 (¼) Cli3 O O Na >250 ,C2t-15 5 N CH3 12 (Do CH3 O O Na C e eN CH3 (O) 23 13 roc CH3 280-285 13 H3Cfa ONaf °,X <> (02 CH3 14 H3C CH3 130-140 3 Oy CH3 15 o CH3 O ONa >250* O CH3 O ONa 2 CH3 (0)2 CH3 *See Index Table C for 1H NMR data.

INDEX TABLE C Cmpd No. 1H NMR Data ((CD3)2SO solution unless indicated otherwise)a 3 # 1.67-1.8(m, 2H), 2.0-2.2(m, 7H), 2.4-2.57(m, 5H), 3.4-3.5(m, 2H), 4.05-4.25 (m, 4H), 6.76 (s, 1H).

4 # 1.65-1.78 (m, 2H), 2.0-2.15 (m, 7H), 2.4-2.53 (m, 5H), 3.4-3.5 (m, 2H), 4.05-4.25 (m, 4H), 6.76 (s, IH).

5 # 1.75-1.85 (m, 2H), 2.08 (s, 3H), 2.2-2.35 (m, 4H), 2.4-2.6 (m, 5H), 3.42- 3.54 (m, 2H), 4.05-4.25 (m, 4H), 6.83 (s, 1H).

10 6 1.09 (br t, 311)2.17 (s, 3H), 2.4-2.65 (m, 511)3.3-3.7 (m. 4H), 4-4.3 (m, 4H), 6.55 (br s, IH), 7.1 (br s, IH).

11 # 1.13(t, 3H), 2.19(s, 3H), 2.4-2.55(m, 2H), 2.6(s, 3H), 3.4-3.7(m, 4H), 4-4.3 (m, 4H), 6.65 (br s. IH), 7.14 (s, IH).

12 # 2.17(s, 3H), 2.4-2.55(m, 2H), 2.59(s, 3H), 3.17(s, 3H), 3.49(m, 2H), 4.1-4.3 (m, 4H), 6.6 (br s, IH), 7.1 (br s, IH).

13 # 1.15-1.24(m, 6H), 1.65-1.75(t, 2H), 2.10-2.20(m, 3H), 2.25(s, 3H), 3.30-3.45 (m, 2H), 2.50-2.55 (m, 4H), 3.35-3.45 (m, 2H), 4.50-4.60 (m, 2H), 6.76 (s, 1H).

14 (CDC13) b 1.17-1.23 (t, 9H), 1.29-1.31 (d, 6H), 1.90-1.95 (t, 2H), 2.40 (s, 3H), 2.43-2.5 (t, 4H), 2.60-2.65 (t, 2H), 2.69 (s, 3H), 2.90-3.03 (q, 6H), 3.40-3.45 (t, 2H), 4.40-4.45 (m, 2H), 6.91 (s, 1H).

15 5 1.13 (t, 3H), 2.32 (s, 3H), 2.62 (s, 3H), 3.19 (m, 2H), 3.6 (m, 2H), 3.93 (m, 2H), 6.8 (br s, 1H), 7.32 (s, 1H). a 1H NMR data are in ppm downfield from tetramethylsilane. Couplings are designated by (s)-singlet, (d)-doublet, (t)-triplet, (q)-quartet, (m)-multiplet, and (br)-broad.

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

At the same time, these crop and weed species were also treated with postemergence applications of test chemicals formulated in the same manner. Plants ranged in height from 2 to 18 cm (1 - to 4-leaf stage) for postemergence treatments. Treated plants and controls were maintained in a greenhouse for twelve to sixteen days, after which all species were compared to controls and visually evaluated. Plant response ratings, summarized in Table B, are based on a scale of0 to 10 where 0 is no effect and 10 is complete control. A dash (-) response means no test result.

Table A COMPOUND Rate 400 g/ha 1 9 13 14 POSTEMERGENCE B. signalgrass - - 9 9 Barley 5 9 - - Barnyardgrass 9 9 - - Bedstraw 9 10 9 9 Blackgrass 7 9 8 8 Chickweed 8 10 - - Cocklebur 9 9 9 10 Corn 2 2 2 4 Cotton 10 10 - - Crabgrass 7 9 9 10 Downy brome 6 9 - - Giant foxtail 5 9 8 9 Lambsquarters 9 9 - - Morningglory 10 10 9 10 Nutsedge 2 8 9 8 Rape 10 9 7 9 Redroot pigweed - - 9 9 Rice 9 10 - - Sorghum 9 10 - - Soybean 9 10 10 10 Sugar beet 10 10 10 10 Velvetleaf 10 10 9 10 Wheat 8 9 9 8 Wild buckwheat 6 8 - - Wild oat 4 8 2 5 Table A COMPOUND Rate 200 g/ha 2 3 4 5 POSTEMERGENCE B. signalgrass - - - - Barley 6 8 9 9 Barnyardgrass 9 9 9 10 Bedstraw 9 9 9 10 Blackgrass 6 6 7 9 Table A COMPOUND Rate 400 g/ha 1 9 13 14 PREEMERGENCE B. signalgrass - - 9 9 Barley 0 0 - - Barnyardgrass 5 9 - - Bedstraw 5 8 8 9 Blackgrass 2 1 3 2 Chickweed 4 9 - - Cocklebur 6 8 8 7 Corn 0 0 0 0 Cotton 8 10 - - Crabgrass 8 10 10 10 Downy brome 6 8 - - Giant foxtail 2 3 6 2 Lambsquarters 10 9 - - Morningglory 6 8 9 8 Nutsedge 3 8 8 10 Rape 9 2 7 9 Redroot pigweed - - 10 10 Rice 7 9 - - Sorghum 2 2 - - Soybean 6 9 9 9 Sugar beet 10 10 10 10 Velvetleaf 10 10 10 10 Wheat 0 5 1 3 Wild buckwheat 6 3 - - Wild oat 0 6 3 1 Table A COMPOUND Rate 200 g/ha 2 3 4 5 PREEMERGENCE B. signalgrass - - - - Barley 0 0 0 0 Barnyardgrass 9 9 9 9 Bedstraw 8 7 8 8 Blackgrass 0 2 1 0 Chickweed 9 9 9 10 Cocklebur 10 10 10 10 Corn 2 3 2 2 Cotton 10 10 10 10 Crabgrass 9 10 9 10 Downy brome 5 7 7 9 Giant foxtail 7 9 9 9 Lambsquarters 9 9 9 10 Morningglory 9 10 10 10 Nutsedge - - - 9 Rape 10 8 6 9 Redroot pigweed - - - - Rice 9 9 9 10 Sorghum 8 9 9 9 Soybean 10 10 10 10 Sugar beet 10 10 10 10 Velvetleaf 10 10 10 10 Wheat 8 9 9 9 Wild buckwheat 7 6 4 2 Wild oat 5 7 8 8 Table A COMPOUND Rate 100 g/ha 1 9 13 14 POSTEMERGENCE B. signalgrass - - 8 7 Barley 4 8 - - Barnyardgrass 8 9 - - Bedstraw 9 9 9 9 Blackgrass 5 5 6 4 Chickweed 7 9 - - Cocklebur 9 9 9 10 Corn 1 0 1 0 Cotton 10 10 - - Crabgrass 2 9 9 8 Downy brome 5 8 - - Giant foxtail 3 8 6 7 Lambsquarters 9 9 - - Morningglory 10 10 9 10 Chickweed 6 7 9 9 Cocklebur 4 4 6 9 Corn 0 0 0 1 Cotton 0 3 3 2 Crabgrass 10 10 10 10 Downy brome 0 0 0 5 Giant foxtail 0 1 2 3 Lambsquarters 9 10 10 10 Morningglory 2 3 3 9 Nutsedge - - - 2 Rape 0 0 0 0 Redroot pigweed - - - - Rice 8 7 6 8 Sorghum 0 0 0 2 Soybean 4 8 6 7 Sugar beet 9 10 10 10 Velvetleaf 10 10 10 10 Wheat 1 0 0 1 Wild buckwheat 0 2 4 0 Wild oat 1 0 1 3 Table A COMPOUND Rate 100 g/ha 1 9 13 14 PREEMERGENCE B. signalgrass - - 8 4 Barley 0 0 - - Barnyardgrass 1 8 - - Bedstraw 6 2 8 9 Blackgrass 1 0 0 0 Chickweed 3 5 - - Cocklebur 2 0 8 1 Corn 0 0 0 0 Cotton 3 0 - - Crabgrass 7 8 9 7 Downy brome 0 0 - - Giant foxtail 1 1 1 0 Lambsquarters 9 9 - - Morningglory 5 1 8 4 Nutsedge 2 8 8 6 Rape 8 6 5 7 Redroot pigweed - - 9 9 Rice 9 10 - - Sorghum 9 8 - - Soybean 8 10 10 10 Sugar beet 10 10 10 10 Velvetleaf 10 10 9 10 Wheat 6 9 8 6 Wild buckwheat 6 6 - - Wild oat 3 3 1 2 Table A COMPOUND Rate 50 g/ha 2 3 4 5 10 POSTEMERGENCE B. signalgrass Barley 5 7 8 8 1 Barnyardgrass 9 9 9 9 9 Bedstraw 7 9 9 9 9 Blackgrass 4 5 4 6 3 Chickweed 7 9 9 9 10 Cocklebur 9 10 10 10 9 Corn 1 1 2 1 1 Cotton 10 10 10 10 9 Crabgrass 5 9 9 10 9 Downy brome 3 3 5 5 0 Giant foxtail 3 6 6 8 9 Lambsquarters 9 9 9 10 9 Morningglory 9 10 10 10 8 Nutsedge 8 - - 6 0 Rape 6 3 4 6 7 Redroot pigweed Rice 9 9 9 10 9 Sorghum 4 7 6 6 8 Soybean 10 10 10 10 8 Sugar beet 9 9 9 10 10 Velvetleaf 10 10 10 10 10 Wheat 7 7 8 7 3 Nutsedge - 0 1 0 Rape 3 0 0 0 Redroot pigweed - - 10 9 Rice 7 8 - - Sorghum 1 2 - - Soybean 5 8 9 8 Sugar beet 10 10 10 10 Velvetleaf 9 10 10 10 Wheat O 0 0 0 Wild buckwheat 2 0 - - Wild oat 0 1 2 0 Table A COMPOUND Rate 50 g/ha 2 3 4 5 10 PREEMERGENCE B. signalgrass Barley 0 0 0 0 0 Barnyardgrass 8 7 0 7 5 Bedstraw 6 7 7 8 2 Blackgrass 0 0 0 0 0 Chickweed 1 4 5 7 0 Cocklebur 0 2 1 1 0 Corn 0 0 0 0 0 Cotton 0 2 2 0 0 Crabgrass 1 10 9 9 6 Downy brome 0 0 0 1 0 Giant foxtail 0 0 1 0 2 Lambsquarters 9 10 10 9 10 Morningglory 0 0 1 3 0 Nutsedge - - - 0 0 Rape 0 0 0 0 0 Redroot pigweed Rice 6 3 3 7 0 Sorghum 0 0 0 0 0 Soybean 3 5 6 6 0 Sugar beet 4 9 9 10 4 Velvetleaf 8 8 9 10 6 Wheat o 0 0 0 0

Wild buckwheat 7 3 3 0 7 Wild oat 3 4 7 2 5 Table A COMPOUND Rate 400 g/ha 13 14 SPRAYED PADDY Barnyardgrass 9 10 Ducksalad 8 9 Rice 9 9 S. flatsedge 9 8 Wild buckwheat 0 0 0 0 0 Wild oat 0 0 0 0 0 Table A COMPOUND Rate 100 g/ha 13 14 SPRAYED PADDY Barnyardgrass 9 10 Ducksalad 8 7 Rice 8 9 S. flatsedge 8 6 TEST B The compounds evaluated in this test were formulated in a non-phytotoxic solvent mixture which included 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 1- to 4-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), black grass (A lopecurus myosuroides), chickweed (Stellaria media), cocklebur (Xanthium strumarium), corn (Zea mays cv. Pioneer 3394), cotton (Gossypium hirsutum), crab grass (Digitaria sanguinalis), downy brome (Bromus tectorum), giant foxtail (Setariafaberii), johnsongrass (Sorghum halpense), lambsquarters (Chenopodium album), morningglory (Ipomoea hederacea), pigweed (Amaranthus retroflexus), rape (Brassica napus), rye grass (Lolium multiflorum), soybean (Glycine max), speedwell (Veronicapersica), sugar beet (Beta vulgaris), velvetleaf (Abutilon theophrasti), wheat (Triticum aestivum), wild buckwheat (Polygonum convolvulus), and wild oat (Avenafatua).

Plant species in the flood test consisted of rice (Oryza sativa), umbrella sedge (Cyperus difformis), duck salad (Heteranthera limosa), barnyardgrass (Echinochloa crus-galli, designated as 'barnyardgrassl') and late watergrass (Echinochloa oryzicola) grown to the 2- leaf stage for testing.

All plant species were planted one day before application of the formulated 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. 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 B, 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.

Table B COMPOUND Rate 250 g/ha 1 POSTEMERGENCE Barley (winter) 15 Barnyardgrass 80 Barnyardgrass 1 70 Bedstraw 90 Blackgrass 40 Chickweed 65 Cocklebur 90 Corn 1 0 Cotton 90 Crabgrass 85 Downy brome 25 Ducksalad 45 Giant foxtail 50 Italn. ryegrass 0 Johnsongrass - Lambs quarter 95 Late watergrass 75 Morningglory 90 Rape 95 Redroot pigweed 90 Rice japonica 60 Soybean 90 Speedwell 100 Sugar beet 100 Umbrella sedge 50 Velvetleaf 100 Wheat 25 Wild buckwheat 65 Wild oat 0 Table B COMPOUND Rate 250 g/ha 1 PREEMERGENCE Barley (winter) 0 Barnyardgrass 95 Bedstraw 80 Blackgrass 0 Chickweed 0 Cocklebur 50 Corn 1 0 Cotton 70 Crabgrass 100 Downy brome 0 Giant foxtail 85 Italn. ryegrass 0 Johnsongrass 30 Lambsquarter 90 Morningglory 100 Rape 95 Redroot pigweed - Soybean 90 Speedwell 100 Sugar beet 100 Velvetleaf 100 Wheat O Wild buckwheat 10 Wild oat 0 Table B COMPOUND Rate 125 g/ha 1 13 POSTEMERGENCE Barley (winter) 0 - Barnyardgrass 70 - Barnyardgrass 1 60 40 Bedstraw 90 - Blackgrass 30 - Chickweed 65 - Cocklebur 90 - Corn 1 0 - Cotton 90 - Crabgrass 75 - Downy brome 20 - Ducksalad 30 65 Giant foxtail 40 - Italn. ryegrass 0 - Johnsongrass - - Lambs quarter 95 - Late watergrass 65 - Morningglory 90 - Rape 95 - Redroot pigweed 90 - Rice japonica 40 0 Soybean 80 - Speedwell 95 - Sugar beet 100 - Umbrella sedge 40 75 Velvetleaf 100 - Wheat 0 - Wild buckwheat 65 - Wild oat 0 -

Table B COMPOUND Rate 125 g/ha 1 PREEMERGENCE Barley (winter) 0 Barnyardgrass 50 Bedstraw 65 Blackgrass 0 Chickweed 0 Cocklebur 40 Corn 1 0 Cotton 40 Crabgrass 90 Downy brome - Giant foxtail 40 Italn. ryegrass 0 Johnsongrass 20 Lambs quarter 90 Morningglory 75 Rape 30 Redroot pigweed - Soybean 70 Speedwell 90 Sugar beet 100 Velvetleaf 100 Wheat 0 Wild buckwheat 0 Wild oat 0 Table B COMPOUND Rate 62 g/ha 1 2 3 4 5 10 13 POSTEMERGENCE Barley (winter) 10 30 20 30 30 10 - Barnyardgrass 50 95 90 90 90 90 - Barnyardgrass 1 0 15 35 60 75 10 30 Bedstraw 55 80 80 80 90 80 - Blackgrass 30 30 30 40 35 20 - Chickweed 50 90 90 - 100 95 - Cocklebur 90 90 90 90 90 90 - Corn 1 30 0 35 0 0 0 - Cotton 100 95 90 90 100 40 - Crabgrass 75 80 90 90 90 95 - Downy brome 25 10 30 30 35 10 - Ducksalad 0 80 70 70 90 60 50 Giant foxtail 30 70 60 70 80 100 - Italn. ryegrass 0 0 20 30 20 20 - Johnsongrass 55 30 50 70 70 90 - Lambsquarter 100 100 90 80 90 100 - Late watergrass 0 - - - - - - Morningglory 90 85 90 90 90 90 - Rape 90 40 20 20 50 20 - Redroot pigweed 80 80 80 85 100 100 - Rice japonica 10 0 30 30 50 0 0 Soybean 90 90 90 90 90 70 - Speedwell 95 70 90 90 80 95 - Sugar beet 100 70 - 90 100 100 - Umbrella sedge 0 70 70 60 70 40 55 Velvetleaf 95 100 90 90 100 95 - Wheat 30 10 40 40 50 0 - Wild buckwheat 35 30 20 30 20 70 - Wild oat 0 30 30 30 25 30 -

Table B COMPOUND Rate 62 g/ha 1 2 3 4 5 10 PREEMERGENCE Barley (winter) 0 0 0 0 0 0 Barnyardgrass 0 40 20 35 50 0 Bedstraw 10 20 80 40 90 70 Blackgrass 0 10 0 0 0 0 Chickweed 0 65 70 80 65 60 Cocklebur 20 - 50 35 50 100 Corn 1 0 0 20 0 0 0 Cotton 30 0 10 40 40 0 Crabgrass 40 90 80 85 85 100 Downy brome 0 0 0 20 0 0 Giant foxtail 20 10 35 30 15 30 Italn. ryegrass 0 0 0 0 0 0 Johnsongrass 0 0 0 20 0 0 Lambsquarter 95 90 90 90 95 100 Morningglory 50 50 30 40 60 0 Rape 0 10 0 0 0 0 Redroot pigweed 75 40 30 60 30 30 Soybean 40 10 10 40 50 0 Speedwell 95 40 80 60 50 - Sugar beet 100 50 70 90 100 40 Velvetleaf 90 90 100 100 100 100 Wheat 0 10 0 0 0 0 Wild buckwheat 0 10 0 30 0 0 Wild oat 0 10 0 0 0 0 Table B COMPOUND Rate 31 g/ha 1 2 3 4 5 10 13 POSTEMERGENCE Barley (winter) 10 10 10 20 15 0 Barnyardgrass 40 90 90 90 90 90 Barnyardgrass 1 0 10 30 35 50 10 20 Bedstraw 45 70 70 80 80 70 Blackgrass 30 20 20 30 25 10 Chickweed 10 90 90 90 100 90 Cocklebur 90 90 90 90 90 90 Corn 1 0 0 10 0 0 0 - Cotton 90 90 90 90 90 30 - Crabgrass 60 70 85 90 90 90 - Downy brome 0 0 10 0 25 0 - Ducksalad 0 70 50 50 80 20 0 Giant foxtail 20 30 50 60 60 95 - Italn. ryegrass 0 0 10 10 10 10 - Johnsongrass 45 20 40 50 40 40 - Lambsquarter 95 95 90 80 90 100 - Late watergrass 0 - - - - - - Morningglory 90 70 90 90 90 - - Rape 90 0 0 0 40 0 - Redroot pigweed 80 50 80 80 90 95 - Rice japonica 10 0 30 20 20 0 0 Soybean 90 90 80 90 90 50 - Speedwell 70 70 80 80 80 90 - Sugar beet 100 70 90 90 100 100 - Umbrella sedge 0 60 60 60 50 30 20 Velvetleaf 95 90 90 90 100 95 - Wheat 25 0 30 30 35 0 - Wild buckwheat 30 20 20 20 10 70 - Wild oat 0 20 10 10 0 20 - Table B COMPOUND Rate 31 g/ha 1 2 3 4 5 10 PREEMERGENCE Barley (winter) 0 0 0 0 0 0 Barnyardgrass 0 0 10 0 30 0 Bedstraw 10 10 30 40 0 20 Blackgrass 0 0 0 0 0 0 Chickweed 0 10 70 70 0 50 Cocklebur 10 0 10 10 20 70 Corn 1 0 0 0 0 0 0 Cotton 10 0 0 20 20 0 Crabgrass 20 70 60 50 70 100 Downy brome 0 0 0 0 0 0 Giant foxtail 0 0 10 0 0 20 Italn. ryegrass 0 0 0 0 0 0 Johnsongrass 0 0 0 0 0 0 Lambsquarter 95 90 90 90 80 95 Morningglory 10 50 0 20 0 0 Rape 0 0 0 0 0 0 Redroot pigweed 20 0 20 30 - 30 Soybean 10 0 0 20 30 0 Speedwell 95 20 80 0 50 - Sugar beet 100 20 60 70 100 0 Velvetleaf 0 90 70 95 100 50 Wheat 0 0 0 0 0 0 Wild buckwheat 0 0 0 0 0 0 Wild oat 0 0 0 0 0 0 Table B COMPOUND Rate 16 g/ha 1 2 3 4 5 10 13 POSTEMERGENCE Barley (winter) 10 0 0 0 10 0 - Barnyardgrass 20 90 90 90 90 90 - Barnyardgrass 1 0 0 20 20 20 0 15 Bedstraw 40 40 60 70 70 70 - Blackgrass 10 0 10 30 0 0 - Chickweed 10 80 90 80 90 90 - Cocklebur 90 90 90 90 90 80 - Corn 1 0 0 0 0 0 0 - Cotton 90 80 80 80 90 - - Crabgrass 40 40 80 80 90 90 - Downy brome 0 0 0 0 10 0 - Ducksalad 0 40 20 0 70 0 0 Giant foxtail 10 20 40 40 60 70 - Italn. ryegrass 0 0 0 0 0 0 - Johnsongrass 35 0 30 40 20 30 - Lambsquarter 90 80 80 70 90 95 - Late watergrass 0 - - - - - - Morningglory 90 70 90 90 90 90 - Rape 70 0 0 0 0 0 - Redroot pigweed 60 40 80 70 80 90 - Rice japonica 0 0 10 0 0 0 0 Soybean 80 90 80 90 90 50 - Speedwell 40 - 60 80 60 80 Sugar beet 100 60 90 90 100 100 Umbrella sedge 0 40 40 20 35 0 0 Velvetleaf 90 90 90 90 100 95 Wheat 0 0 20 20 20 0 Wild buckwheat 20 10 10 10 10 30 Wild oat 0 0 0 0 0 10 Table B COMPOUND Rate 16 g/ha 1 2 3 4 5 10 PREEMERGENCE Barley (winter) 0 0 0 0 0 0 Barnyardgrass 0 0 0 0 10 0 Bedstraw 0 0 0 30 0 20 Blackgrass 0 0 0 0 0 0 Chickweed 0 0 60 30 0 0 Cocklebur 0 0 0 0 10 0 Corn 1 0 0 0 0 0 0 Cotton 0 0 0 10 0 0 Crabgrass 0 10 0 30 40 95 Downy brome 0 0 0 0 0 0 Giant foxtail 0 0 0 0 0 0 Italn. ryegrass 0 0 0 0 0 0 Johnsongrass 0 0 0 0 0 0 Lambsquarter 95 90 80 90 70 95 Morningglory 0 10 0 0 0 0 Rape 0 0 0 0 0 0 Redroot pigweed 0 0 0 20 0 10 Soybean 10 0 0 0 10 0 Speedwell 0 0 70 0 - - Sugar beet 100 0 0 60 40 0 Velvetleaf 0 80 40 10 70 0 Wheat 0 0 0 0 0 0 Wild buckwheat 0 0 0 0 0 0 Wild oat 0 0 0 0 0 0

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

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

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

Table C COMPOUND Rate 35 g/ha 3 4 5 9 10 11 14 15 POSTEMERGENCE A. blacknightsh - - - - 100 - - - Arrowleaf sida 50 20 80 90 10 60 60 20 Barnyardgrass 95 95 95 65 90 100 85 95 Cocklebur 95 95 95 100 95 100 85 85 Common ragweed 100 90 100 85 90 100 80 65 Corn 1 0 0 0 0 0 0 0 0 Cotton 95 95 100 90 80 95 100 60 E. blacknightsh 100 100 100 100 - 100 100 100 Fall panicum 80 80 60 25 95 100 80 70 Field bindweed 85 90 80 60 70 60 80 20 Fl. beggarweed 100 80 - - - - - -

Giant foxtail 60 60 20 20 60 90 20 75 H. beggarticks 20 60 10 0 90 100 25 70 I. morningglory 100 85 100 80 80 85 95 50 Johnsongrass 5 5 0 0 0 60 10 15 Ladysthumb 100 100 100 100 100 100 100 100 Lambsquarters 90 95 100 70 95 100 100 95 Large crabgrass 80 80 80 60 80 80 75 25 Purple nutsedge 80 30 20 0 0 5 0 0 Redroot pigweed 90 95 90 65 90 90 70 85 Soybean 1 95 95 100 100 80 90 95 40 Surinam grass 60 60 60 25 40 60 25 20 Velvetleaf 100 100 100 100 95 100 100 90 Wild poinsettia 100 90 100 65 5 60 95 80 TEST D Compounds evaluated in this test were formulated in a non-phytotoxic solvent mixture which included a surfactant and applied to plants that were grown for various periods of time before treatment (postemergence application). A mixture of sandy loam soil and greenhouse potting mix in a 60:40 ratio was used for the postemergence test. Test compounds were applied 13 days after the last postemergence planting.

Plantings of these crops and weed species were adjusted to produce plants of appropriate size for the postemergence test. All plant species were grown using normal greenhouse practices. Crop and weed species include bristly starbur (Acanthospermun hispidum), alexander grass (Brachiaria plantaginea), American black nightshade (Solanum americanum), apple-of-Peru (Nicandra physaloides), arrowleaf sida (Sida rhombifolia), broadleaf signalgrass (Brachiaria platyphylla), Brazilian sicklepod (Cassia tora Brazilian), capim-colchao (Digitaria horizontalis), soybean (Glycine max cv. Cristalina, designated 'Soybean 1'), Florida beggarweed (Desmodium purpureum), hairy beggarticks (Bidens pilosa), slender amaranth (Amaranthus viridis), southern sandbur (Cenchrus echinatus), tall morningglory (Ipomoea purpurea), tropical spiderwort (Commelina benghalensis), soybean (Glycine max cv. W20, designated 'Soybean 2') and soybean (Glycine max cv. W4-4, designated 'Soybean 3'), corn (Zea mays) and wild pointsettia (Eupohorbia heterophylla).

Treated plants and untreated controls were maintained in a greenhouse for approximately 13 days, after which all treated plants were compared to untreated controls and visually evaluated. Plant response ratings, summarized in Table D, are based upon a 0 to 100 scale where 0 is no effect and 100 is complete control.

Table D COMPOUND Rate 70 g/ha 4 11 15 POSTEMERGENCE Alexandergrass 90 100 95 Apple-of-Peru 100 100 100 Arrowleaf sida 95 90 65 B. Signalgrass 75 70 80 Blk nightshade 100 100 100 Braz sicklepod 60 10 50 Bristly starbur 85 100 70 Capim-Colch 80 80 80 Corn 10 10 15 Fl. beggarweed 100 - - H. beggarticks 70 90 100 Morningglory 100 80 80 S. amaranth 70 100 100 S. sandbur 65 80 95 Soybean 1 100 95 90 Soybean 2 100 95 80 Soybean 3 100 95 85 Tr. Spiderwort 75 100 90 Wild poinsettia 100 100 100 Table D COMPOUND Rate 17 g/ha 4 11 15 POSTEMERGENCE Alexandergrass 85 70 10 Apple-of-Peru 100 100 95 Arrowleaf sida 85 50 20 B. Signalgrass 60 50 20 Blk nightshade 100 100 100 Braz sicklepod 50 5 20 Bristly starbur 100 70 20 Capim-Colch 55 60 10 Corn 0 0 5 Fl. beggarweed 100 - - H. beggarticks 55 80 50 Morningglory 85 80 70 Table D COMPOUND Rate 35 g/ha 4 11 15 POSTEMERGENCE Alexandergrass 80 80 60 Apple-of-Peru 100 100 100 Arrowleaf sida 85 80 60 B. Signalgrass 70 60 60 Blk nightshade 100 100 100 Braz sicklepod 55 10 40 Bristly starbur 100 100 25 Capim-Colch 75 60 20 Corn 10 5 5 Fl. beggarweed 100 - - H. beggarticks 60 80 80 Morningglory 100 80 80 S. amaranth 40 100 100 S. sandbur 55 80 85 Soybean 1 80 80 75 Soybean 2 100 90 65 Soybean 3 100 90 85 Tr. Spiderwort 70 90 75 Wild poinsettia 100 60 95 Table D COMPOUND Rate 8 g/ha 15 POSTEMERGENCE Alexandergrass 10 Apple-of-Peru 80 Arrowleaf sida 20 B. Signalgrass 10 Blk nightshade 100 Braz sicklepod 10 Bristly starbur 10 Capim-Colch 10 Corn o Fl. beggarweed - H. beggarticks 20 Morningglory 50

S. amaranth 70 100 80 S. sandbur 30 80 60 Soybean 1 100 80 65 Soybean 2 80 70 50 Soybean 3 75 85 40 Tr. Spiderwort 60 80 60 Wild poinsettia 75 0 80 S. amaranth 60 S. sandbur 10 Soybean 1 35 Soybean 2 30 Soybean 3 25 Tr. Spiderwort 40 Wild poinsettia 60 TEST E Compounds evaluated in this test were formulated in a non-phytotoxic solvent mixture which included a surfactant and applied to plants that were in the 1- to 4-leaf stage (postemergence application). A mixture of sandy loam soil and greenhouse potting mix in a 60:40 ratio was used for the postemergence test.

Plantings of these crops and weed species were adjusted to produce plants of appropriate size for the postemergence test. All plant species were grown using normal greenhouse practices. Crop and weed species include annual bluegrass (Poa annua), black grass 2 (Alopecurus myosuroides), black nightshade (Solanum nigra), chickweed (Stellaria media), common poppy (Papaver rhoeas), deadnettle (Lamium amplexicaule), downy brome (Bromus tectorum), field violet (Viola arvensis), galium 2 (Galium aparine), green foxtail (Setaria viridis), jointed goat grasps (Aegilops cylindrica), kochia (Kochia scoparia), lambs quarters (Chenopodium album), littleseed canarygrass (Phalaris minor), rape 1 (Brassica nap us cv. Westar), rape 2 (Brassica nap us cv. Jet Neuf), redroot pigweed (Amaranthus retroflexus), Russian thistle (Salsola kali), Italian ryegrass (Lolium multiflorum), scentless chamomile (Matricaria inodora), spring barley (Hordeum vulgare), sugar beet (Beta vulgaris), sunflower (Helianthus annuus), ivyleaf speedwell (Veronica hederaefolia), winter wheat (Triticum aestivum cv. cymmit, designated 'wheat'), spring wheat (Triticum aestivum), winter wheat (Triticum aestivum designated 'wheat (winter)'), wild buckwheat (Polygonum convolvulus), wild mustard (Sinapis arvensis), wild oat (Avena fatua) 1 to 2 leaf designated 'Wild oat 1' and 2 to 3 leaf designated 'Wild oat 2', windgrass (Apera spica-venti) and winter barley (Hordeum vulgare).

Treated plants and untreated controls were maintained in a greenhouse for approximately 21 to 28 days, after which all treated plants were compared to untreated controls and visually evaluated. Plant response ratings, summarized in Table E, are based upon a 0 to 100 scale where 0 is no effect and 100 is complete control. A dash response (-) means no test result. Table E COMPOUND Rate 62 g/ha 2 4 5 POSTEMERGENCE Annual bluegras - - - Barley (winter) 50 - - Blackgrass 2 45 - - Blk nightshade - - - Chickweed - - - Common poppy - - - Deadnettle - - - Downy brome - - - Field violet - - - Galium 2 - - - Green foxtail 95 - - I. Ryegrass 20 - - Jointed goatgra - - - Kochia - - - Lambsquarters - - - LS canarygrass - - - Rape 1 50 85 60 Rape 2 90 92 60 Redroot pigweed - - - Russian thistle - - - Scentless chamo - - - Speedwell - - - Spring Barley 65 - - Sugar beet - - - Sunflower - - - Veronica hedera - - - Wheat 35 - - Wheat (spring) 30 - - Wheat (winter) 55 - - Wild buckwheat - - - Wild mustard 100 95 100 Wild oat 1 - - - Wild oat 2 60 - - Windgrass - - - Table E COMPOUND Rate 31 g/ha 1 2 4 5 POSTEMERGENCE Annual bluegras 0 20 - - Barley (winter) 5 20 - - Blackgrass 2 0 50 - - Blk nightshade 100 95 - - Chickweed 0 70 - - Common poppy - 20 - - Deadnettle 90 70 - - Downy brome 10 10 - - Field violet 0 100 - - Galium 2 65 60 - - Green foxtail 10 80 - - I. Ryegrass 5 5 - - Jointed goatgra 5 5 - - Kochia 35 70 - - Lambsquarters 100 90 - - LS canarygrass 0 10 - - Rape 1 30 0 72 40 Rape 2 - 25 70 50 Redroot pigweed 85 20 - - Russian thistle - 30 - - Scentless chamo 80 65 - - Speedwell 30 - - - Spring Barley 10 20 - - Sugar beet 100 100 - - Sunflower 75 50 - - Veronica hedera - 85 - - Wheat - 15 - - Wheat (spring) 15 25 - - Wheat (winter) 15 35 - - Wild buckwheat 0 30 - - Wild mustard 100 100 90 100 Wild oat 1 - 0 - - Wild oat 2 5 60 - - Windgrass 0 20 - - Table E COMPOUND Rate 16 g/ha 1 2 4 5 POSTEMERGENCE Annual bluegras 0 - - - Barley (winter) 0 15 - - Blackgrass 2 0 35 - - Blk nightshade 30 - - - Chickweed 0 - - - Common poppy - - - - Deadnettle 35 - - - Downy brome 0 - - - Field violet 0 - - - Galium 2 10 - - - Green foxtail 5 65 - - I. Ryegrass 5 0 - - Jointed goatgra 0 - - - Kochia 0 - - - Lambsquarters 30 - - - LS canarygrass 0 - - - Rape 1 0 10 55 30 Rape 2 - 25 20 50 Redroot pigweed 60 - - - Russian thistle - - - - Scentless chamo 70 - - - Speedwell 15 - - - Spring Barley 0 20 - - Sugar beet 35 - - - Sunflower 0 - - - Veronica hedera - - - - Wheat - 4 - - Wheat (spring) 0 25 - - Wheat (winter) 0 30 - - Wild buckwheat 0 - - - Wild mustard 50 80 68 100 Wild oat 1 - - - - Wild oat 2 0 30 - - Windgrass ° - ~ ~ Table E COMPOUND Rate 8 g/ha 1 2 4 5 POSTEMERGENCE Annual bluegras 0 2 - - Barley (winter) 0 5 - - Blackgrass 2 0 5 - - Blk nightshade 10 75 - - Chickweed 0 60 - - Common poppy - 30 - - Deadnettle 0 50 - - Downy brome 0 0 - - Field violet 0 80 - - Galium 2 0 30 - - Green foxtail 0 20 - - I. Ryegrass 0 0 - - Jointed goatgra 0 2 - - Kochia 0 60 - - Lambsquarters 0 80 - - LS canarygrass 0 5 - - Rape 1 5 0 20 20 Rape 2 - 10 0 20 Redroot pigweed - 0 - - Russian thistle - 20 - - Scentless chamo - 60 - - Speedwell 0 - - - Spring Barley 0 5 - - Sugar beet 25 85 - - Sunflower 0 30 - - Veronica hedera - 55 - - Wheat - - - - Wheat (spring) 0 10 - - Wheat (winter) 0 5 - - Wild buckwheat 0 10 - - Wild mustard 30 60 55 100 Wild oat 1 - 0 - - Wild oat 2 0 - - - Windgrass 0 0 - - Table E COMPOUND Rate 4 g/ha 1 POSTEMERGENCE Annual bluegras 0 Barley (winter) 0 Blackgrass 2 0 Blk nightshade 0 Chickweed 0 Common poppy - Deadnettle 0 Downy brome 0 Field violet 0 Galium 2 0 Green foxtail 0 I. Ryegrass 0 Jointed goatgra 0 Kochia 0 Lambsquarters 0 LS canarygrass 0 Rape 1 0 Table E COMPOUND Rate 4 g/ha 1 POSTEMERGENCE Rape 2 Redroot pigweed 30 Russian thistle - Scentless chamo 20 Speedwell 0 Spring Barley 0 Sugar beet 15 Sunflower 0 Veronica hedera - Wheat Wheat (spring) 0 Wheat (winter) 0 Wild buckwheat 0 Wild mustard 30 Wild oat 1 Wild oat 2 0 Windgrass 0

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

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

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

Table F COMPOUND Rate 200 g/ha 4 Paddy / silt loam Barnyardgrass - Ducksalad 95 E. watergrass - Junglerice - L. watergrass - Redstem 95 Rice flatsedge 95 Rice indica 1 100 Rice indica 3 70 S. flatsedge 98 T. sprangletop 100 Table F COMPOUND Rate 150 g/ha 4 Paddy / silt loam Barnyardgrass - Ducksalad 95 E. watergrass - Junglerice - L. watergrass - Redstem 95 Rice flatsedge 95 Rice indica 1 90 Rice indica 3 65 S. flatsedge 98 T. sprangletop 100 Table F COMPOUND Rate 125 g/ha 2 4 5 Paddy / silt loam Barnyardgrass 0 - 60 Ducksalad 98 95 90 E. watergrass - - 90 Junglerice 100 - 65 L. watergrass 0 - 35 Redstem 98 95 100 Rice flatsedge 65 95 85 Rice indica 1 15 90 40 Rice indica 3 10 70 45 S. flatsedge 100 95 85 T. sprangletop 100 95 100 Table F COMPOUND Rate 100 g/ha 4 Paddy / silt loam Barnyardgrass - Ducksalad 90 E. watergrass - Junglerice - L. watergrass - Redstem 90 Rice flatsedge 85 Rice indica 1 65 Rice indica 3 55 S. flatsedge 95 T. sprangletop 100 Table F COMPOUND Rate 75 g/ha 4 Paddy / silt loam Barnyardgrass - Ducksalad 95 E. watergrass - Junglerice - L. watergrass - Redstem 95 Rice flatsedge 85 Rice indica 1 50 Rice indica 3 45 S. flatsedge 95 T. sprangletop 100 Table F COMPOUND Rate 64 g/ha 2 5 Paddy / silt loam Barnyardgrass 0 15 Table F COMPOUND Rate 50 g/ha 4 Paddy / silt loam Barnyardgrass - Table F COMPOUND Rate 32 g/ha 2 5 Paddy / silt loam Barnyardgrass 0 0

Ducksalad 98 90 E. watergrass - 35 Junglerice 65 40 L. watergrass 0 20 Redstem 98 100 Rice flatsedge 50 100 Rice indica 1 10 30 Rice indica 3 10 20 S. flatsedge 100 100 T. sprangletop 100 98 Ducksalad 90 E. watergrass - Junglerice L. watergrass - Redstem 75 Rice flatsedge 80 Rice indica 1 10 Rice indica 3 10 S. flatsedge 90 T. sprangletop 65 Ducksalad 60 85 E. watergrass - 20 Junglerice 0 15 L. watergrass 0 0 Redstem 50 75 Rice flatsedge 10 65 Rice indica 1 0 25 Rice indica 3 0 10 S. flatsedge 100 65 T. sprangletop 95 98 Table F COMPOUND Rate 25 g/ha 4 Paddy / silt loam Barnyardgrass - Ducksalad 85 E. watergrass - Junglerice - L. watergrass - Redstem 20 Rice flatsedge 65 Rice indica 1 10 Rice indica 3 0 S. flatsedge 70 T. sprangletop 20 Table F COMPOUND Rate 16 g/ha 2 5 Paddy / silt loam Barnyardgrass 0 0 Ducksalad 55 45 E. watergrass - 15 Junglerice 0 0 L. watergrass 0 0 Redstem 40 55 Rice flatsedge 0 45 Rice indica 1 0 0 Rice indica 3 0 10 S. flatsedge 50 45 T. sprangletop 15 85 Table F COMPOUND Rate 8 g/ha 2 5 Paddy / silt loam Barnyardgrass 0 0 Ducksalad 0 25 E. watergrass - 0 Junglerice 0 0 L. watergrass 0 0 Redstem 0 0 Rice flatsedge 0 20 Rice indica 1 0 0 Rice indica 3 0 10 S. flatsedge 0 20 T. sprangletop 0 85