WO1998028291A1 - Substituted benzothiopyranes salts and their use as herbicides - Google Patents

Abstract

Compounds of Formula (I) are disclosed which are useful for controlling undesired vegetation wherein Q is (Q-1) or (Q-2); and R1-R12, 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).

Description

SUBSTI TUTED BENZOTHIOPYRANES SALTS AND THEI R USE AS HERB IC IDES

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:

1 wherein

X, X¹ and X² are independently O 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 stereoisomers, agricultural compositions containing them and their use for controlling undesirable vegetation:

wherein Q is

Q-1 Q-2

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 C C₃ alkyl; each R³ is CH₃;

R⁴ and R⁵ are each independently H, C_rC₃ alkyl or halogen; R⁶ is C,-C₃ alkyl; R⁷ is C_rC₃ alkyl; R⁸ is H, C_rC₂₅ alkyl or benzyl; R⁹ and R¹⁰ are independently C_rC₂₅ alkyl;

R¹² is H, C ,-C₁₂ alkyl, C,-C₃ alkoxy, N0₂ or CN; m and t are independently 1 , 2 or 3 ; n and p are each independently 0, 1 or 2; and q is O, 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, tt-propyl, z^'-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 "C_j-C;" prefix where i and j are numbers from 1 to 25. For example, C_j-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 la (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.

wherein M is Na

Preferred compounds for reasons of better activity and/or ease of synthesis are: Preferred 1. Compounds of Formula I above wherein:

Q is Q-1. Preferred 2. Compounds of Preferred 1 wherein:

R⁴ and R⁵ are each independently H or C_rC₃ alkyl; n is 2; p is 0; and q is 0, 1 or 2. Preferred 3. Compounds of Preferred 2 wherein: M is

Preferred 4. Compounds of Preferred 2 wherein: M is Li, Na or K. Preferred 5. Compounds of Formula I above wherein:

Q is Q-2. Preferred 6. Compounds of Preferred 5 wherein:

R⁴ and R⁵ are each independently H or C _|-C₃ alkyl; R⁷ is CH₂CH₃; n is 2; p is 0; and q is 0, 1 or 2. Preferred 7. Compounds of Preferred 6 wherein: M is

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-l-benzothiopyran-6-yl)carbonyl]-5,5- dimethyl-1 ,3-cyclohexanedione S,S-di oxide; b) 2-[(2,3-dihydro-5,8-dimethylspiro[4H-l-benzothiopyran-4,2'-[l,3]dioxolan]-6- yl)carbonyl]- 1 ,3-cyclohexanedione S,S-dioxide; c) (2,3-dihydro-5,8-dimethylspiro[4H-l -benzothiopyran-4,2'-[l ,3]dioxolan]-6- yl)(l-ethyl-5-hydroxy-lH-pyrazol-4-yl)methanone S,S-dioxide; and d) 6-[(l-ethyl-5-hydroxy-lH-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 of Q, R'-R'², M, m, n, p, q, and r in the compounds of Formulae 1-11 below are as defined above in the Summary of the Invention. Compounds of Formulae la and lb are subsets of the compounds of Formula I, and all substituents for Formulae la and lb are as defined above for Formula I. For example, compounds of Formula la below are compounds of Formula I wherein Q is Q-1.

la Scheme 1 illustrates the preparation of compounds of Formula la 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 la 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 la 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

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 (Rl and R² are taken together to form -O(CH₂)₂O- optionally substituted with one or two C_j-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

lb

(Rl and R2 are taken together with the carbon to which they are attached to form C(=0))

Scheme 3 illustrates the preparation of a compound of Formula la 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 la. 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 la with aqueous alkali metal hydroxides yields the corresponding alkali metal salt of Formula la. 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

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

Base (e.g., triethylamine)

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-A1. Scheme 5

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 Sulphoxides, John Wiley & Sons).

Scheme 6

5 (n is 0) 5 (n is 1 or 2) oxidizing agent

Scheme 7 illustrates the preparation of acids of Formula 5 (n is 0) whereby a phenyl bromide of Formula 6 (Rl 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 «-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

(R and R² are other than taken together with the carbon to which they are attached to form C(=0) and n is O)

Scheme 8 illustrates the preparation of phenyl bromides of Formula 6 (Rl and R² are taken together to form -O(CH₂)₂O- optionally substituted with one or two C_j-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 7-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

7 (n is O)

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, p 517; H. Gilman, J Am. Chem. Soc. (1955), 77, p 6059. Scheme 9

7

(n is 0) (n is 0)

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 ! Chem. B. (1985), 24(1 1), p. 1 159; 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. 1 1 18; W. S. Johnson, et al., J. Am. Chem. Soc. (1949), 71, p. 1901; J. A. Hirsch, et al., 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-

Bl; J. Dangelo, et al., Tet. Lett. (1991), 32(26), p. 3063; T. Okado, et al., J. Org. Chem.

(1977), 42, p. 1 163; B. E. Maryanoff, et al., J Am. Chem Soc. (1975), 97, p. 2718; E. Er, et al., Helv. Chim. Ada. (1992), 75(7), p. 2265; Y. D. Vankar, et al., 7et. Zett., (1987), 28(5), p. 551 ; C. S. Pak, et al., Tet. Lett. (1991), 32(42), p. 601 1; I. Nishiguchi, et al., Chem. Lett.

(1981), p. 551 ; B. Eistert, et al., Liebigs Ann. Chem. (1962), 659, p. 64; N. K. Hamer, Tet. Lett. (1986), 27(19), p. 2167; M. Sato, et al., Heterocycles (1987), 26(10), p. 261 1 ; 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, et al., U.S. 5,093,503. Compounds of Formula lb 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.

lb

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

Scheme 10

Scheme 1 1 illustrates the preparation of compounds of Formula lb 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

Scheme 12 illustrates the preparation of compounds of Formula lb (Rl and R² are taken together with the carbon to which they are attached to form C(=O)) whereby a compound of Formula lb (Rl and R² are taken together to form -O(CH₂)₂O- optionally substituted with one or two Cj-C₃ alkyl) is stirred in a hydrochloric acid or hydrobromic acid aqueous solution (O.lNto 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

HC1/H₂0 or HBr/H₂0

(Rl and R² are taken together (Rl and R² are taken together with the to form -0(CH₂)2 - optionally carbon to which they are attached to substituted with one or two form (C=0)) Cι-C₃ alkyl)

Esters of Formula 10 can be prepared by reacting a hydroxypyrazole of Formula 1 1 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-A1. Scheme 13

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

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

Without further elaboration, it is believed that one skilled in the art using the preceding description can utilize the present invention to its fullest extent. The following Examples are, therefore, to be construed as merely illustrative, and not limiting of the disclosure in any way whatsoever. Percentages are by weight except for chromatographic solvent mixtures or where otherwise indicated. Parts and percentages for chromatographic solvent mixtures are by volume unless otherwise indicated. The abbreviation "dec" indicates that the compound appeared to decompose on melting. 'H NMR spectra are reported in ppm downfield from tetra ethylsilane; s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet, br s = broad singlet. Example 1 Step A: Preparation of 3-r(2.5-dimefhylphenyl)thio1propanoic 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-dimefhylthiophenol (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 IN HC1 and filtered to yield 112.79 g of the title compound of Step A as a solid melting at 97-98 °C. ^lH NMR (CDC1₃): δ 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-l-benzopyran-4-one

530 mL of concentrated sulfuric acid was added to 24.91 g (0.1 19 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. lΗ NMR (CDCI3): δ 2.3 (s,3Η), 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-dihvdro-5,8-dimethyl-4H- 1 -benzothiopyran-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. 'Η NMR (CDC1₃): δ 2.3 (s,3Η), 2.6 (s,3H), 3.0 (m,2H), 3.2 (m,2H), 7.45 (s,lH). Step D: Preparation of ό-bromo-ΣJ-dihydro-S.S-dimethylspirof^H-l-benzothiopyran- 4.2'-π.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 / 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 IN sodium hydroxide: saturated aqueous ΝaCl (2 x 600 mL) and then with saturated aqueous ΝaCl ( 1 x 600 mL). The organic layer was dried (Νa₂Sθ₄), 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). Η NMR (CDC1₃): δ 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-dimethylspiror4H- 1 -benzothiopyran-4,2'-

[^"1.3]dioxolane1-6-carboxylic 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 «-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 pΗ 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. *Η NMR (Me₂SO- ₆): δ 2.2 (m,5Η), 2.4 (s,3H), 3.0 (m,2H), 4.1-4.2 (m,4H), 7.4 (s,lH).

Step F: Preparation of 2.3-dihydro-5.8-dimethylspiro|^"4H-l-benzothiopyran-4,2'- π.31dioxolanel-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 pΗ 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). Η NMR (Me₂SO-<i6). δ 2.35 (s,3Η), 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- lH-pyrazol-5-yl 2,3-dihydro-5,8-dimethylspiror4H-l- benzothiopyran-4,2'-r 1 ,31dioxolanel-6-carboxylate 1 , 1 -dioxide 1.18 g (3.8 mmol) of the title compound of Step F, 0.99 mL (0.01 1 mol) of oxalyl chloride (purchased from Janssen), and 2 drops of N,N-dimethylformamide were added to 50 L of methylene chloride. The mixture was retluxed 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 G as a semi-solid. ¹Η NMR (CDC1₃): δ 1.4 (t,3Η), 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,lH), 7.5-7.7 (2H).

Step H: Preparation of (2,3-dihydro-5,8-dimethylspiro[4H-l -benzothiopyran-4,2'- ri.31dioxolanl-6-yl)(l-ethyl-5-hydroxy-lH-pyrazol-4-yl)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 pΗ 1 with concentrated hydrochloric acid and extracted with methylene chloride (2 x 50 mL). The combined organic layers were dried (MgSO4), filtered, and evaporated to dryness to yield 0.17 g of the title compound of Step Η as a solid melting at 111 °C (dec). 1Η NMR (CDC1₃): δ 1.46 (t,3Η), 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-dihvdro-5.8-dimethylspiror4H-l-benzothiopyran-4,2'- 3]dioxolanl-6-yl)(l-ethyl-5-hvdroxy-lH-pyrazol-4-yl)methanone S,S- dioxide monopotassium salt 600 mg of the title compound of Step Η, 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-l-cvclohexen-l-yl 2,3-dihydro-5,8-dimethylspiror4H-l- benzothiopyran-4,2'-π ,3]dioxolanel-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 109-1 1 1 °C. 'H NMR (CDC1₃): δ 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-dihydro-5,8-dimethylspiro[4H- 1 -benzothiopyran-4,2'-

[1.31dioxolanl-6-yl)carbonvn-l,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) of triethylamine 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 pΗ 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). ^!Η NMR (CDC1₃): δ 2.0 (m,2Η), 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-IY2,, 3-dihydro-5.8-dimethylspiro[4H-l -benzothiopyran-4,2'-

[1.31dioxolanl-6-yl)carbonyl1-L3-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. 'Η NMR ((CD₃)₂SO): δ 1.75-1.85 (m, 2Η), 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 -benzothiopyran-4,2'- π .31dioxolan]-6-yl⁾carbonyl]-l ,3-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. ^lΗ NMR ((CD₃)₂SO): δ 1.65-1.78 (m, 2Η), 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-rf2.3-dihydro-5,8-dimethylspiror4H-l-benzothiopyran-4,2'- [1.31dioxolanl-6-yl)carbonyl]-L3-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 °C. lΗ NMR ((CD₃)₂SO): δ 1.67-1.8 (m, 2Η), 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-rf2.3-dihvdro-5,8-dimethylspiro[4H-l-benzothiopyran-4,2'-

[1 ,3]dioxolan1-6-yl)carbonyll-l .3-cvcIohexanedione S,S-dioxide benzyldimethylhexadecylammonium salt 1.22 g of benzyldimethylhexadecylammonium chloride monohydrate was dissolved in 3 mL of dichloromethane and then 3.3 mL of IN aqueous ΝaOΗ 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

Rl R² n R⁴ E! R6a _R6b c=o 1 H H H H

C=0 2 H H H H c=o 1 H H H CH₃ c=o 2 H H H CH₃

C=0 1 H H CH₃ CH₃ c=o 2 H H CH₃ CH₃

C=0 1 CH₃ H H H c=o 2 CH₃ H H H

C=0 1 CH₃ H H CH₃ C=0 2 CH₃ H H CH₃ c=o 1 CH₃ H CH₃ CH₃

C=0 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=0 2 CH₃ CH₃ H CH₃ C=0 1 CH₃ CH₃ CH₃ CH₃ C=0 2 CH₃ CH₃ CH₃ CH₃ C=0 1 Cl Cl H H C=0 2 Cl Cl H H C=0 1 Cl Cl H CH₃ C=0 2 CI Cl H CH₃ c=o 1 Cl C! CH₃ CH₃

C=0 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- 0 CH₃ H H H

-OCH₂CH₂0- 1 CH₃ H H H

-OCH₂CH₂0- 2 CH₃ H H H

-OCH₂CH₂0- 0 CH₃ H H CH₃

-OCH₂CH₂0- 1 CH₃ H H CH₃

-OCH₂CH₂0- 2 CH₃ H H CH₃

-OCH₂CH₂0- 0 CH₃ H CH₃ CH₃

-OCH₂CH₂0- 1 CH₃ H CH₃ CH₃

-OCH₂CH₂0- 2 CH₃ H CH₃ CH₃

-OCH₂CH₂0- 0 CH₃ CH₃ H H

-OCH₂CH₂0- 1 CH₃ CH₃ H H

-OCH₂CH₂0- 2 CH₃ CH₃ H H

-OCH₂CH₂0- 0 CH₃ CH₃ H CH₃

-OCH₂CH₂0- 1 CH₃ CH₃ H CH₃

-OCH₂CH₂0- 2 CH₃ CH₃ H CH₃

-OCH₂CH₂0- 0 CH₃ CH₃ CH₃ CH₃

-OCH₂CH₂0- 1 CH₃ CH₃ CH₃ CH₃

-OCH₂CH₂0- 2 CH₃ CH₃ CH₃ CH₃

-OCH₂CH₂0- 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 Cl Cl H CH₃

-OCH₂CH₂0- 2 Cl Cl H CH

-OCH₂CH₂0- 0 Cl C! CH₃ CH₃

-OCH₂CH₂0- 1 Cl CI CH₃ CH₃ ??

-OCH₂CH₂0- 2 Cl Cl CH₃ CH₃

-OCH₂(CH₃)CH₂(CH₃)0- 0 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)0- 0 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- 0 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- 0 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- 0 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- 0 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)0- 0 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- 0 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)0- 0 Cl CI H H

-OCH₂(CH₃ )CH₂(CH₃)0- 1 Cl Cl H H

-OCH₂(CH₃)CH₂(CH₃)0- 2 Cl Cl H H

-OCH₂(CH₃)CH₂(CH₃)0- 0 Cl CI H CH₃

-OCH₂(CH₃)CH₂(CH₃)0- 1 Cl Cl H CH₃

-OCH₂(CH₃)CH₂(CH₃)0- 2 CI Cl H CH₃

-OCH₂(CH₃)CH₂(CH₃)0- 0 Cl Cl CH₃ CH₃

-OCH₂(CH₃)CH₂(CH₃)0- 1 Cl Cl CH₃ CH₃

-OCH₂(CH₃ )C H₂(CH₃ )0- 2 Cl Cl CH₃ CH₃ wherein r is 1 and M is Na

RL Er n El E^ p _R6b

C=0 1 H H H H

CO 2 H H H H

CO 1 H H H CH₃

CO 2 H H H CH₃

CO 1 H H CH₃ CH₃

CO 2 H H CH₃ CH₃

CO 1 CH₃ H H H

CO 2 CH₃ H H H

CO 1 CH₃ H H CH₃

CO 2 CH₃ H H CH₃

CO 1 CH₃ H CH₃ CH₃

CO 2 CH₃ H CH₃ CH₃

CO 1 CH₃ CH₃ H H

CO 2 CH₃ CH₃ H H

CO 1 CH₃ CH₃ H CH₃

CO 2 CH₃ CH₃ H CH₃

CO 1 CH₃ CH₃ CH₃ CH₃

CO 2 CH₃ CH₃ CH₃ CH₃

CO 1 Cl Cl H H

CO 2 Cl Cl H H

CO 1 Cl Cl H CH₃

CO 2 Cl Cl H CH₃

CO 1 Cl Cl CH₃ CH₃

CO 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- 0 CH₃ H H H

-OCH₂CH₂0- 1 CH₃ H H H

-OCH₂CH₂0- 2 CH₃ H H H -OCH₂CH₂0- 0 CH₃ H H CH₃

-OCH₂CH₂0- 1 CH₃ H H CH₃

-OCH₂CH₂0- 2 CH₃ H H CH₃

-OCH₂CH₂0- 0 CH₃ H CH₃ CH₃

-OCH₂CH₂0- 1 CH₃ H CH₃ CH₃

-OCH₂CH₂0- 2 CH₃ H CH₃ CH₃

-OCH₂CH₂0- 0 CH₃ CH₃ H H

-OCH₂CH₂0- 1 CH₃ CH₃ H H

-OCH₂CH₂0- 2 CH₃ CH₃ H H

-OCH₂CH₂0- 0 CH₃ CH₃ H CH₃

-OCH₂CH₂0- 1 CH₃ CH₃ H CH₃

-OCH₂CH₂0- 2 CH₃ CH₃ H CH₃

-OCH₂CH₂0- 0 CH₃ CH₃ CH₃ CH₃

-OCH₂CH₂0- 1 CH₃ CH₃ CH₃ CH₃

-OCH₂CH₂0- 2 CH₃ CH₃ CH₃ CH₃

-OCH₂CH₂0- 0 Cl Cl H H

-OCH₂CH₂0- 1 Cl Cl H H

-OCH₂CH₂0- 2 Cl Cl H H

-OCH₂CH₂0- 0 Cl Cl H CH₃

-OCH₂CH₂0- 1 Cl Cl H CH₃

-OCH₂CH₂0- 2 Cl Cl H CH₃

-OCH₂CH₂0- 0 Cl Cl CH₃ CH₃

-OCH₂CH₂0- 1 Cl Cl CH₃ CH₃

-OCH₂CH₂0- 2 Cl Cl CH₃ CH₃

-OCH₂(CH₃)CH₂(CH₃)0- 0 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- 1 H H H CH₃

-OCH₂(CH₃)CH₂(CH₃)0- 2 H H H CH₃

-OCH₂(CH₃)CH₂(CH₃)0- 0 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- 0 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- 0 CH₃ H H CH₃

-OCH₂(CH₃)CH₂(CH₃)0- 1 CH₃ H H CH₃ II II II II II II II II II II II II II o o o o o o o o o o o o o

J^βto

— to — to — to — to — to — to — |3

n n n n n n n ^ ^ ^ ^ ^ ^

PS PC PS PS PS PS PS PC PS PC PC PC PC PS n n n n n n n n n n n n

PS PS PS

I³ n n n n n n n n n n n n

PS PS PC

pc

PS

CO 2 CH₃ CH₃ H H

CO 1 CH₃ CH₃ H CH₃

CO 2 CH₃ CH₃ H CH₃

CO 1 CH₃ CH₃ CH₃ CH₃

CO 2 CH₃ CH₃ CH₃ CH₃

CO I CI Cl H H

CO 2 Cl Cl H H

CO 1 Cl Cl H CH₃

CO 2 Cl Cl H CH₃

CO 1 Cl CI CH₃ CH₃

CO 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

-OCH₂CH 0- 1 H H CH₃ CH₃

-OCH₂CH₂0- 2 H H CH₃ CH₃

-OCH₂CH₂0- 0 CH₃ H H H

-OCH₂CH₂0- 1 CH₃ H H H

-OCH₂CH₂0- 2 CH₃ H H H

-OCH₂CH₂0- 0 CH₃ H H CH₃

-OCH₂CH₂0- 1 CH₃ H H CH₃

-OCH₂CH₂0- 2 CH₃ H H CH₃

-OCH₂CH₂0- 0 CH₃ H CH₃ CH₃

-OCH₂CH₂0- 1 CH₃ H CH₃ CH₃

-OCH₂CH₂0- 2 CH₃ H CH₃ CH₃

-OCH₂CH₂0- 0 CH₃ CH₃ H H

-OCH₂CH₂0- 1 CH₃ CH₃ H H

-OCH₂CH₂0- 2 CH₃ CH₃ H H

-OCH₂CH₂0- 0 CH₃ CH₃ H CH₃

-OCH₂CH₂0- 1 CH₃ CH₃ H CH₃

-OCH₂CH₂0- 2 CH₃ CH₃ H CH₃

-OCH₂CH₂0- 0 CH₃ CH₃ CH₃ CH₃

-OCH₂CH₂0- 1 CH₃ CH₃ CH₃ CH₃

-OCH₂CH₂0- 2 CH₃ CH₃ CH₃ CH₃ -OCH₂CH₂0- 0 CI Cl H H

-OCH₂CH₂0- 1 Cl Cl H H

-OCH₂CH₂0- 2 Cl CI H H

-OCH₂CH₂0- 0 Cl Cl H CH₃

-OCH₂CH₂0- 1 Cl Cl H CH₃

-OCH₂CH₂0- 2 Cl Cl H CH₃

-OCH₂CH₂0- 0 Cl Cl CH₃ CH₃

-OCH₂CH₂0- 1 Cl Cl CH₃ CH₃

-OCH₂CH₂0- 2 Cl Cl CH₃ CH₃

-OCH₂(CH₃)CH₂(CH₃)0- 0 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- 1 H H H CH₃

-OCH₂(CH₃)CH₂(CH₃)0- 2 H H H CH₃

-OCH₂(CH₃)CH₂(CH₃)0- 0 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- 0 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- 0 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- 0 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- 0 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)0- 0 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- 0 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)0- 0 Cl Cl H H

-OCH₂(CH₃)CH₂(CH₃)0- 1 Cl Cl H H -OCH₂(CH₃)CH₂(CH₃)0- 2 Cl Cl H H

-OCH₂(CH₃)CH₂(CH₃)0- 0 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)0- 0 Cl Cl CH₃ CH₃

-OCH₂(CH₃)CH₂(CH₃)0- 1 Cl Cl CH₃ CH₃

-OCH₂(CH₃)CH₂(CH₃)0- 2 Cl Cl CH₃ CH₃

wherein r is 2 and M is Ca

El R^ n El E Rόa R6b

CO 1 H H H H

CO 2 H H H H

CO 1 H H H CH₃

CO 2 H H H CH₃

CO 1 H H CH₃ CH₃

CO 2 H H CH₃ CH₃

CO 1 CH₃ H H H

CO 2 CH₃ H H H

CO 1 CH₃ H H CH₃

CO 2 CH₃ H H CH₃

CO 1 CH₃ H CH₃ CH₃

CO 2 CH₃ H CH₃ CH₃

CO 1 CH₃ CH₃ H H

CO 2 CH₃ CH₃ H H

CO 1 CH₃ CH₃ H CH₃

CO 2 CH₃ CH₃ H CH₃

CO 1 CH₃ CH₃ CH₃ CH₃

CO 2 CH₃ CH₃ CH₃ CH₃

CO 1 Cl Cl H H

CO 2 Cl CI H H

CO 1 Cl Cl H CH₃

CO 2 Cl Cl H CH₃

CO 1 Cl Cl CH₃ CH₃

CO 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 -OCH₇CH90- 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- 0 CH₃ H H H

-OCH₂CH₂0- I CH₃ H H H

-OCH₂CH₂0- 2 CH₃ H H H

-OCH₂CH₂0- 0 CH₃ H H CH₃

-OCH₂CH₂0- 1 CH₃ H H CH₃

-OCH₂CH₂0- 2 CH₃ H H CH₃

-OCH₂CH₂0- 0 CH₃ H CH₃ CH₃

-OCH₂CH₂0- 1 CH₃ H CH₃ CH₃

-OCH₂CH₂0- 2 CH₃ H CH₃ CH₃

-OCH₂CH₂0- 0 CH₃ CH₃ H H

-OCH₂CH₂0- 1 CH₃ CH₃ H H

-OCH₂CH₂0- 2 CH₃ CH₃ H H

-OCH₂CH₂0- 0 CH₃ CH₃ H CH₃

-OCH₂CH₂0- 1 CH₃ CH₃ H CH₃

-OCH₂CH₂0- 2 CH₃ CH₃ H CH₃

-OCH₂CH₂0- 0 CH₃ CH₃ CH₃ CH₃

-OCH₂CH₂0- 1 CH₃ CH₃ CH₃ CH₃

-OCH₂CH₂0- 2 CH₃ CH₃ CH₃ CH₃

-OCH₂CH₂0- 0 Cl Cl H H

-OCH₂CH₂0- 1 Cl Cl H H

-OCH₂CH₂0- 2 Cl Cl H H

-OCH₂CH₂0- 0 Cl Cl H CH₃

-OCH₂CH₂0- 1 Cl Cl H CH₃

-OCH₂CH₂0- 2 Cl Cl H CH₃

-OCH₂CH₂0- 0 Cl Cl CH₃ CH₃

-0CH₂CH₂0- 1 Cl Cl CH₃ CH₃

-OCH₂CH₂0- 2 Cl Cl CH₃ CH₃

-OCH₂(CH₃)CH₂(CH₃)0- 0 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- 1 H H H CH₃

-OCH₂(CH₃)CH₂(CH₃)0- 2 H H H CH₃ -OCH₂(CH₃)CH₂(CH₃)0- 0 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- 0 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- 0 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- 0 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- 0 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)0- 0 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- 0 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)0- 0 Cl Cl H H

-OCH₂(CH₃)CH₂(CH₃)0- 1 Cl Cl H H

-OCH₂(CH₃)CH₂(CH₃)0- 2 Cl Cl H H

-OCH₂(CH₃)CH₂(CH₃)0- 0 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)0- 0 Cl Cl CH₃ CH₃

-OCH₂(CH₃)CH₂(CH₃)0- 1 Cl Cl CH₃ CH₃

-OCH₂(CH₃)CH₂(CH₃)0- 2 Cl Cl CH₃ CH₃

wherein r is 2 and M is Mε

El Ei n El El R6a _R6b

CO 1 H H H H

CO 2 H H H H

CO 1 H H H CH₃

CO 2 H H H CH₃

CO 1 H H CH₃ CH₃ CO 2 H H CH₃ CH₃

CO 1 CH₃ H H H

CO 2 CH₃ H H H

CO 1 CH₃ H H CH₃

CO 2 CH₃ H H CH₃

CO 1 CH₃ H CH₃ CH₃

CO 2 CH₃ H CH₃ CH₃ c=o 1 CH₃ CH₃ H H

CO 2 CH₃ CH₃ H H

CO 1 CH₃ CH₃ H CH₃

CO 2 CH₃ CH₃ H CH₃

CO 1 CH₃ CH₃ CH₃ CH₃

CO 2 CH₃ CH₃ CH₃ CH₃

CO 1 Cl Cl H H

CO 2 Cl Cl H H

CO 1 Cl Cl H CH₃

CO 2 Cl Cl H CH₃

CO 1 Cl Cl CH₃ CH₃

CO 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- 0 CH₃ H H H

-OCH₂CH₂0- 1 CH₃ H H H

-OCH₂CH₂0- 2 CH₃ H H H

-OCH₂CH₂0- 0 CH₃ H H CH₃

-OCH₂CH₂0- 1 CH₃ H H CH₃

-OCH₂CH₂0- 2 CH₃ H H CH₃

-OCH₂CH₂0- 0 CH₃ H CH₃ CH₃

-OCH₂CH₂0- 1 CH₃ H CH₃ CH₃

-OCH₂CH₂0- 2 CH₃ H CH₃ CH₃

-OCH₂CH₂0- 0 CH₃ CH₃ H H -OCH₂CH₂0- I CH₃ CH₃ H H

-OCH₂CH₂0- 2 CH₃ CH₃ H H

-OCH₂CH₂0- 0 CH₃ CH₃ H CH₃

-OCH₂CH₂0- 1 CH₃ CH₃ H CH₃

-OCH₂CH₂0- 2 CH₃ CH₃ H CH₃

-OCH₂CH₂0- 0 CH₃ CH₃ CH₃ CH₃

-OCH₂CH₂0- 1 CH₃ CH₃ CH₃ CH₃

-OCH₂CH₂0- 2 CH₃ CH₃ CH₃ CH₃

-OCH₂CH₂0- 0 Cl Cl H H

-OCH₂CH₂0- 1 Cl Cl H H

-OCH₂CH₂0- 2 Cl Cl H H

-OCH₂CH₂0- 0 Cl Cl H CH₃

-OCH₂CH₂0- 1 Cl Cl H CH₃

-OCH₂CH₂0- 2 Cl Cl H CH₃

-OCH₂CH₂0- 0 Cl Cl CH₃ CH₃

-OCH₂CH₂0- 1 Cl Cl CH₃ CH₃

-OCH₂CH₂0- 2 Cl Cl CH₃ CH₃

-OCH₂(CH₃)CH₂(CH₃)0- 0 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- 1 H H H CH₃

-OCH₂(CH₃)CH₂(CH₃)0- 2 H H H CH₃

-OCH₂(CH₃)CH₂(CH₃)0- 0 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- 0 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- 0 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- 0 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- 0 CH₃ CH₃ H H

-OCH₂(CH₃)CH₂(CH₃)0- 1 CH₃ CH₃ H H

-OCH₂(CH₃)CH₂(CH₃)0- 2 CH₃ CH₃ H H Ci c n ci Ci c n c n o ci Ci Ci c ci Ci Ci o o II o II o II o II o II o II o II o II o II o II o II o II o II o II o II o II o II o II

to — to — to — to — to — to — to — to — to —

G - G-. nE nE nE nE nE nE nE nE nE nE nE nE _^E _^E _^E E_^ - n ci

■s -s β C Ci Ci Ci Ci Ci Ci C n n n n G E E E E E E

n n n n n n n

E E E E E E E E E E ci c ci ci n n n n ci n n n n n n > ω I en E E E E PE E

-->

E E

_ n n c ci __ n n ci ci n ci c c

E E Cl Cl Cl Cl Cl Cl

E E PC E E E E E 3P E E E E E E E E E X X X X X X X n n n n n n cr - - j i U UJ E (-E EJ E- E> UEJ -_E--•

CD (Z-

H

AH ci ri ri n ci i ri n c ci c c ci c ci ci ci ri n n ri ri n n n

Eυ υE Eu uE PP PC E Eυ υE υE Eυ υE Eυ E E E υE uE Eu υE υE Eυ E E E υE Eυ υE Eυ Eυ υE E E E uE Eυ Eυ

m ci c ci ci cι n ci ci

PS PP E PE P PC E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E PE υ υ υ u u υ υ υ u υ υ

ci d ci ci c n n ci n υ υ υ υ PS PC E E E E E E E E E E E E E E E E E E E E E E E E E O υ υ υ υ υ

rπ C1 C1 C1 C1 C1 C1 C1 C1 C1 C1 C1 C1 C1 C1 C1 C1 C1 C1

U U υ υ -E E E E E E E E E υE Eυ υE Eυ υE Eυ υE υE Eυ υE Eυ uE Eυ Eυ υE υE Eυ Eυ ζ υ υ υ υ u

— π — i o — n o (N O — (N O — (N O — (N O — (N O — (N O — CN O — CN O — (N O — (N

O

-OCH₂CH₂0- 1 Cl Cl CH₃ CH₃

-OCH CH₂0- 2 Cl Cl CH₃ CH₃

-OCH₂(CH₃)CH₂(CH₃)0- 0 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- 1 H H H CH₃

-OCH₂(CH₃)CH₂(CH₃)0- 2 H H H CH₃

-OCH₂(CH₃)CH₂(CH₃)0- 0 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- 0 CH₃ H H H

-OCH₂(CH₃)CH₂(CH₃)0- 1 CH₃ H H H

-OCH₂(CH₃)CH₂(CH )0- 2 CH₃ H H H

-OCH₂(CH₃)CH₂(CH₃)0- 0 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- 0 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- 0 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)0- 0 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- 0 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)0- 0 Cl CI H H

-OCH₂(CH₃)CH₂(CH₃)0- 1 Cl Cl H H

-OCH₂(CH₃)CH₂(CH₃)0- 2 Cl Cl H H

-OCH₂(CH₃)CH₂(CH₃)0- 0 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)0- 0 Cl Cl CH₃ CH₃

-OCH₂(CH₃)CH₂(CH₃)0- 1 Cl Cl CH₃ CH₃

-OCH₂(CH₃)CH₂(CH₃)0- 2 Cl CI CH₃ CH₃ wherein r is 1 and M is (CH^N

El El n El El βόa βόb

CO 1 H H H H

CO 2 H H H H

CO 1 H H H CH₃

CO 2 H H H CH₃

CO 1 H H CH₃ CH₃

CO 2 H H CH₃ CH₃

CO 1 CH₃ H H H

CO 2 CH₃ H H H

CO 1 CH₃ H H CH₃

CO 2 CH₃ H H CH₃

CO 1 CH₃ H CH₃ CH₃

CO 2 CH₃ H CH₃ CH₃

CO 1 CH₃ CH₃ H H

CO 2 CH₃ CH₃ H H

CO 1 CH₃ CH₃ H CH₃

CO 2 CH₃ CH₃ H CH₃

CO 1 CH₃ CH₃ CH₃ CH₃

CO 2 CH₃ CH₃ CH₃ CH₃

CO 1 Cl Cl H H

CO 2 Cl Cl H H

CO 1 Cl Cl H CH₃

CO 2 Cl Cl H CH₃

CO 1 Cl Cl CH₃ CH₃

CO 2 CI CI 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- 0 CH₃ H H H

-OCH₂CH₂0- 1 CH₃ H H H -OCH₂CH₂0- 2 CH₃ H H H

-OCH₂CH₂0- 0 CH₃ H H CH₃

-OCH₂CH₂0- I CH₃ H H CH₃

-OCH₂CH₂0- 2 CH₃ H H CH₃

-OCH₇CH₉O- 0 CH₃ H CH₃ CH₃

-OCH₂CH₂0- 1 CH₃ H CH₃ CH₃

-OCH₂CH₂0- 2 CH₃ H CH₃ CH₃

-OCH₂CH₂0- 0 CH₃ CH₃ H H

-OCH₂CH₂0- 1 CH₃ CH₃ H H

-OCH₂CH₂0- 2 CH₃ CH₃ H H

-OCH₂CH₂0- 0 CH₃ CH₃ H CH₃

-OCH₂CH₂0- 1 CH₃ CH₃ H CH₃

-OCH₂CH₂0- 2 CH₃ CH₃ H CH₃

-OCH₂CH₂0- 0 CH₃ CH₃ CH₃ CH₃

-OCH₂CH₂0- 1 CH₃ CH₃ CH₃ CH₃

-OCH₂CH₂0- 2 CH₃ CH₃ CH₃ CH₃

-OCH₂CH₂0- 0 Cl Cl H H

-OCH₂CH₂0- 1 Cl Cl H H

-OCH₂CH₂0- 2 Cl Cl H H

-OCH₂CH₂0- 0 Cl 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

-OCH₂CH₂0- 2 Cl Cl CH₃ CH₃

-OCH₂(CH₃)CH₂(CH₃)0- 0 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- 1 H H H CH₃

-OCH₂(CH₃)CH₂(CH₃)0- 2 H H H CH₃

-OCH₂(CH₃ )CH₂(CH₃)0- 0 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- 0 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- 0 CH₃ H H CH₃ o II

O

n n n n n n n n

E E E E E E E E E E E E n n n n n n n n n

ON n n

K MM HM HM HM HM > > UJ CO i C ) ω ω ) - ω E E E E E E E E

<_...

o o o o o O O O O O O O O O O O O O O O O O O O o o n n n n n n n n n n o o o o o o o o o o o o o o n n to E to E to E to E E E X PH P-H HM — HH 3H ϊ HM HM HM to to to to to to to to to to to to to to to to to to to E t E to E to E o n n n o o o o o o o o o o o o o o o o o o o o n n n II o II o II o o o o o II o o o o

E E E E o o o o o o o o o o o o to to to to to t to to to to to to to io to to to to to to to to to to to E to E o o o o o o o o o o o o o o o o o o o o o o o o o o

— O to — to to — to — to — to —

O O O O O O O O O O O O O O n n n

E E E E E E E E E E E E Q n n n n n n n n n n

E E E E E E t-

n n n n n n n n n n n n n n

E E E E E u E> u E> u E E

_o - > E E E E E E E E E E E E E E E E E Q Q G Q Q Q E E E E E E

n n n n n _ _ _ n n n n n n -- -- -- n n n _{^ ^ ^} n n n n n n n n

E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E

-OCH2CH20- 2 CH₃ CH₃ CH₃ CH₃

-OCH₂CH₂0- 0 CI Cl H H

-OCH₂CH₂0- 1 Cl Cl H H

-OCH₂CH₂0- 2 Cl Cl H H

-OCH₂CH₂0- 0 Cl CI H CH₃

-OCH₂CH₂0- 1 Cl Cl H CH₃

-OCH₂CH₂0- 2 Cl Cl H CH₃

-OCH₂CH₂0- 0 Cl Cl CH₃ CH₃

-OCH₂CH₂0- 1 Cl Cl CH₃ CH₃

-OCH₂CH₂0- 2 CI Cl CH₃ CH₃

-OCH₂(CH₃)CH₂(CH₃)0- 0 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- 1 H H H CH₃

-OCH₂(CH₃)CH₂(CH₃)0- 2 H H H CH₃

-OCH₂(CH₃)CH₂(CH₃)0- 0 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- 0 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- 0 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- 0 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- 0 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)0- 0 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- 0 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)0- 0 Cl Cl H H

to — to — to — to — to — to — to — to — to — to — |3

_ _ _.-. .--■ --■ .-. --. ---. o n n n n n n n n n n n _{^ ^ !}►—

X X X Q Q Q Q Q Q O O O

UX. UX- UX) UX) UX) UX) UX) UX) UX) UX- UX) UX) X X X X X X P■ *I O O O O O *^■

_{E E} o n n n n n n n n n n n

E E E E E E E E E E E E E E E E E E F n n n n n n n n

E - _^E E- ⁿE ⁿE ^oE ^o n n n n E E_{^ ^}E ⁿE ^oE ^πE ^oE -E-, _ME_H ⁰E ^oE ⁿE E „E „ nE nE nE nE E JO n n E E E E E E E E E

no on on On On On nO on nO On On on On no nO on On On On on on no On on on On n On nO On no on On to E to E to E to E to E to E to E to E to E to E to E t E to E to E to E to E to E to E t E to E to E to E to E to E to E to E to E to E t E E E E E n n n n n n n n n n n n n I ιo 10 n I n n n n n n n n n n n n n n n n n n n to E to E to E to E to E to E to E t E t E t E to E to E to E to E to E to E to E to E to E to E to E to E to E 10 E to E to E to E t E to E to E to E to E to E

O o O O O O o O O O O O O O o O O O O O O O O O O O O O O O O O o

to —

n n n n n n n n n n n O O O O O O O O O O O O O O O n

E E E E E E

I

n n n n n n n n n n n n n n n n n n _^ E E E E E E E E E E E

n n n

E E E E E E E E E E E E E E E E E E _ nE nE nE E E E E n n n

E E E

n n n n n n

E E E E E E E E _^ E nE E nE nE En nE _^E _^E _ n n n n n n n n n n n n

E UE) UE) UE> UE) UE) UE) E E E uE- E) E) U E> u E> u E-

to — to — to — t — to — to — to — to — t — to — 13

n n n n n n n n n n n n n n

E E E E E _{E E E E E E E} Q o n n n n

U E U E⁾ U EJ U E K MM H MM X Ε ) U> U) U⁾ U) U) U) U E) U E E E E E > = FI <

n n n

E E E E E E E E E E E Q G Q Q Q Q

E E E E_ E E E E E E E

E E E T

— to — to — to — 13 t — to — to —

n n n n n o o o o o o n n n n n n n n

E E E E E E E E E E E F I n n n n n n n n n o

E E E E u> E E E E u>

4--.

F n n n n n n n n n n n n n n n n n n

E E E E E E E E

F n n n n n n

E E E E E E E E E E E E E E E PC PC E E E E E E E E E PC

I P U) Ul U)

n n n n n n n _ _ JO n n n n n n _ „ _ n n n n n n „ _ n n n n n n

E E E E E E E E E E E σ^* U E> E) UEl UE) UEl uE> E E E UEl UE) UEl UE) (-EO UE E E E UE UEl UE E UEl El

to — to — to — to —

n n n n n n n n n n n n n n n o o o o o o o

E E E E E E E E E E E E E E E E E E E Q Q n n n n X X X X X X X -

o o o o o n n n n O o

E E E E E E E E E E Q Q G Q Q Q E E E E X X

n E E E E nE nE nE E E E E E E

n n o o o n o o o o o o n n n n n n

E E E E E E E E E E E E E E E E E E E E E E E E E E E

E

to — to — to — to — to — to — to — to — to - 13

Q Q Q Q Q Q E E E E E E E E E E X E E E E E K Ω Ω Ω Ω Ω G Ω Ω G E E

Q Q Q Q G Q E E E E E E E E E E E E E E E E E F n n n n n n n n n

— o to — to —

n n n n n n n n n o o o o o o o o o o o o o o o o o o

S ϊ H-C HM h-C S MH HM MM MM M--M H--M MM >£ MM - E E E E E E E

n n n n n n n n n n E nE nE nE nE nE nE nE nE E E E E E E E E E E E E E E E E E

n n n „ n n n n n n n n n

U E1 UE1 UE1 E E E E E E UE1 UE1 UE1 E E E E E E UE1 UE1 UE1 E E E E E E UE1 UE1 UE1 E E E E E E

n n n n n n _{^ ^ ^} n n n n n n _{^ ^ ^} n n n n n _^ n n n n n n

U El UEl UEl El UEl El E E E UE1 UE1 UE1 UE1 UE1 UE1 E E E UE1 UE1 UE1 UE1 UE1 UE) E E E UE1 UE1 UE1 UE1 UE1 UE1 E E E

TABLE 2

wherein r is 1 and M is Li wherein r is 1 and M is Na

El El n El El El El n El El

CO 1 H H CO 1 H H

CO 2 H H CO 2 H H

CO 1 CH₃ H CO 1 CH₃ H

CO 2 CH₃ H CO 2 CH₃ H

CO 1 CH₃ CH₃ CO 1 CH₃ CH₃

CO 2 CH₃ CH₃ CO 2 CH₃ CH₃

CO 1 Cl Cl CO 1 Cl Cl

CO 2 Cl Cl CO 2 Cl Cl

-OCH₂CH₂0- 0 H H -OCH₂CH₂0- 0 H H

-OCH₂CH₂0- 1 H H -OCH₂CH₂0- 1 H H

-OCH₂CH₂0- 2 H H -OCH₂CH₂0- 2 H H

-OCH₂CH₂0- 0 CH₃ H -OCH₂CH₂0- 0 CH₃ H

-OCH₂CH₂0- 1 CH₃ H -OCH₂CH₂0- 1 CH₃ H

-OCH₂CH₂0- 2 CH₃ H -OCH₂CH₂0- 2 CH₃ H

-OCH₂CH₂0- 0 CH₃ CH₃ -OCH₂CH₂0- 0 CH₃ CH₃

-OCH₂CH₂0- 1 CH₃ CH₃ -OCH₂CH₂0- 1 CH₃ CH₃

-OCH₂CH₂0- 2 CH₃ CH₃ -OCH₂CH₂0- 2 CH₃ CH₃

-OCH₂CH₂0- 0 Cl Cl -OCH₂CH₂0- 0 Cl Cl

-OCH₂CH₂0- 1 Cl Cl -OCH₂CH₂0- 1 CI Cl

-OCH₂CH₂0- 2 Cl Cl -OCH₂CH₂0- 2 Cl Cl

OCH₂(CH₃)CH₂(CH₃)0- 0 H H -OCH₂(CH₃)CH₂(CH₃)0- 0 H H

OCH₂(CH₃)CH₂(CH₃)0- 1 H H -OCH₂(CH₃)CH₂(CH₃)0- 1 H H

OCH₂(CH₃)CH₂(CH₃)0- 2 H H -OCH₂(CH₃)CH₂(CH₃)0- 2 H H

OCH₂(CH₃)CH₂(CH₃)0- 0 CH₃ H -OCH₂(CH₃)CH₂(CH₃)0- 0 CH₃ H

OCH₂(CH₃)CH₂(CH₃)0- 1 CH₃ H -OCH₂(CH₃)CH₂(CH₃)0- 1 CH₃ H

OCH₂(CH₃)CH₂(CH₃)0- 2 CH₃ H -OCH₂(CH₃)CH₂(CH₃)0- 2 CH₃ H

to — to — to —

n n n

E E E E E E E E E G Q G E E E E E E n

E E E Q Q E E E E E n n n

Ul Ul F I NΛ G S E E

OCH₂(CH₃)CH₂(CH₃)0- 0 Cl Cl OCH₂(CH₃)CH₂(CH₃)0- 0 Cl Cl

OCH₂(CH₃)CH₂(CH₃)0- 1 Cl CI OCH₂(CH₃)CH₂(CH₃)0- 1 CI Cl

OCH (CH₃)CH₂(CH₃)0- 2 CI Cl OCH₂(CH₃)CH₂(CH₃)0- 2 CI Cl

wherein r is 2 and M is Vlg wherein r is 1 and M is (CH₃CH₂)₃NH

R^l R² n R⁴ R5 R^l R² n R⁴ R5

CO 1 H H CO 1 H H

CO 2 H H CO 2 H H

CO 1 CH₃ H CO 1 CH₃ H

CO 2 CH₃ H CO 2 CH₃ H

CO 1 CH₃ CH₃ CO 1 CH₃ CH₃

CO 2 CH₃ CH₃ CO 2 CH₃ CH₃

CO 1 Cl Cl CO 1 Cl Cl

CO 2 Cl Cl CO 2 Cl Cl

-OCH₂CH₂0- 0 H H -OCH₂CH₂0- 0 H H

-OCH₂CH₂0- 1 H H -OCH₂CH₂0- 1 H H

-OCH₂CH₂0- 2 H H -OCH₂CH₂0- 2 H H

-OCH₂CH₂0- 0 CH₃ H -OCH₂CH₂0- 0 CH₃ H

-OCH₂CH₂0- 1 CH₃ H -OCH₂CH₂0- 1 CH₃ H

-OCH₂CH₂0- 2 CH₃ H -OCH₂CH₂0- 2 CH₃ H

-OCH₂CH₂0- 0 CH₃ CH₃ -OCH₂CH₂0- 0 CH₃ CH₃

-OCH₂CH₂0- 1 CH₃ CH₃ -OCH₂CH₂0- 1 CH₃ CH₃

-OCH₂CH₂0- 2 CH₃ CH₃ -OCH₂CH₂0- 2 CH₃ CH₃

-OCH₂CH₂0- 0 Cl Cl -OCH₂CH₂0- 0 Cl Cl

-OCH₂CH₂0- 1 Cl Cl -OCH₂CH₂0- 1 Cl Cl

-OCH₂CH₂0- 2 Cl Cl -OCH₂CH₂0- 2 Cl Cl

OCH₂(CH₃)CH₂(CH₃)0- 0 H H -OCH₂(CH₃)CH₂(CH₃)0- 0 H H

OCH₂(CH₃)CH₂(CH₃)0- 1 H H -OCH₂(CH₃)CH₂(CH₃)0- 1 H H

OCH₂(CH₃)CH₂(CH₃)0- 2 H H -OCH₂(CH₃)CH₂(CH₃)0- 2 H H

OCH₂(CH₃)CH₂(CH₃)0- 0 CH₃ H -OCH₂(CH₃)CH₂(CH₃)0- 0 CH₃ H

OCH₂(CH₃)CH₂(CH₃)0- 1 CH₃ H -OCH₂(CH₃)CH₂(CH₃)0- 1 CH₃ H

OCH₂(CH₃)CH₂(CH₃)0- 2 CH₃ H -OCH₂(CH₃)CH₂(CH₃)0- 2 CH₃ H

OCH₂(CH₃)CH₂(CH₃)0- 0 CH₃ CH₃ -OCH₂(CH₃)CH₂(CH₃)0- 0 CH₃ CH₃

OCH₂(CH₃)CH₂(CH₃)0- 1 CH₃ CH₃ -OCH₂(CH₃)CH₂(CH₃)0- 1 CH₃ CH₃

OCH₂(CH₃)CH₂(CH₃)0- 2 CH₃ CH₃ -OCH₂(CH₃)CH₂(CH₃)0- 2 CH₃ CH₃

OCH₂(CH₃)CH₂(CH₃)0- 0 Cl Cl -OCH₂(CH₃)CH₂(CH₃)0- 0 Cl Cl

OCH₂(CH₃)CH₂(CH₃)0- 1 Cl Cl -OCH₂(CH₃)CH₂(CH₃)0- 1 Cl Cl

OCH₂(CH₃)CH₂(CH₃)0- 2 Cl Cl -OCH₂(CH₃)CH₂(CH₃)0- 2 Cl Cl wherein r is 1 and M is wherein r is 1 and M is (CH₃. I4N (C^H^XCH^ CgH^CH^

R¹ R² n R⁴ R5 R¹ R² n R⁴ R⁵

CO 1 H H CO 1 H H

CO 2 H H CO 2 H H

CO 1 CH₃ H CO I CH₃ H

CO 2 CH₃ H CO 2 CH₃ H

CO 1 CH₃ CH₃ CO 1 CH₃ CH₃

CO 2 CH₃ CH₃ CO 2 CH₃ CH₃

CO 1 Cl Cl CO 1 Cl Cl

CO 2 Cl Cl CO 2 Cl Cl

-OCH₂CH₂0- 0 H H -OCH₂CH₂0- 0 H H

-OCH₂CH₂0- 1 H H -OCH₂CH₂0- 1 H H

-OCH₂CH₂0- 2 H H -OCH₂CH₂0- 2 H H

-OCH₂CH₂0- 0 CH₃ H -OCH₂CH₂0- 0 CH₃ H

-OCH₂CH₂0- 1 CH₃ H -OCH₂CH₂0- 1 CH₃ H

-OCH₂CH₂0- 2 CH₃ H -OCH₂CH₂0- 2 CH₃ H

-OCH₂CH₂0- 0 CH₃ CH₃ -OCH₂CH₂0- 0 CH₃ CH₃

-OCH₂CH₂0- 1 CH₃ CH₃ -OCH₂CH₂0- 1 CH₃ CH₃

-OCH₂CH₂0- 2 CH₃ CH₃ -OCH₂CH₂0- 2 CH₃ CH₃

-OCH₂CH₂0- 0 Cl Cl -OCH₂CH₂0- 0 Cl Cl

-OCH₂CH₂0- 1 Cl Cl -OCH₂CH₂0- 1 Cl Cl

-OCH₂CH₂0- 2 Cl Cl -OCH₂CH₂0- 2 Cl Cl

OCH₂(CH₃)CH₂(CH₃)0- 0 H H OCH₂(CH₃)CH₂(CH₃)0- 0 H H

OCH₂(CH₃)CH₂(CH₃)0- 1 H H OCH₂(CH₃)CH₂(CH₃)0- 1 H H

OCH₂(CH₃)CH₂(CH₃)0- 2 H H OCH₂(CH₃)CH₂(CH₃)0- 2 H H

OCH₂(CH₃)CH₂(CH₃)0- 0 CH₃ H OCH₂(CH₃)CH₂(CH₃)0- 0 CH₃ H

OCH₂(CH₃)CH₂(CH₃)0- 1 CH₃ H OCH₂(CH₃)CH₂(CH₃)0- 1 CH₃ H

OCH₂(CH₃)CH₂(CH₃)0- 2 CH₃ H OCH₂(CH₃)CH₂(CH₃)0- 2 CH₃ H

OCH₂(CH₃)CH₂(CH₃)0- 0 CH₃ CH₃ OCH₂(CH₃)CH₂(CH₃)0- 0 CH₃ CH₃

OCH₂(CH₃)CH₂(CH₃)0- 1 CH₃ CH₃ OCH₂(CH₃)CH₂(CH₃)0- 1 CH₃ CH₃

OCH₂(CH₃)CH₂(CH₃)0- 2 CH₃ CH₃ OCH₂(CH₃)CH₂(CH₃)0- 2 CH₃ CH₃

OCH₂(CH₃)CH₂(CH₃)0- 0 Cl Cl OCH₂(CH₃)CH₂(CH₃)0- 0 Cl Cl

OCH₂(CH₃)CH₂(CH₃)0- 1 Cl Cl OCH₂(CH₃)CH₂(CH₃)0- 1 Cl Cl

OCH₂(CH₃)CH₂(CH₃)0- 2 Cl Cl OCH₂(CH₃)CH₂(CH₃)0- 2 Cl Cl

n n _ n n n n

U El El E E E G Q E E E E

E E E E E Q Q E E

U 9l U S) E E PS Q Q G E E E E E E E E E Q G E E F

DJ

-OCH₂CH₂0- ₂ CH₃ H -OCH₂CH₂0- 2 CH₃ H -OCH₂CH 0- 0 CH₃ CH₃ -OCH₂CH₂0- 0 CH₃ CH₃ -OCH₂CH₂0- 1 CH₃ CH₃ -OCH₂CH₂0- 1 CH₃ CH₃ -OCH₂CH₂0- 2 CH₃ CH₃ -OCH₂CH₂0- 2 CH₃ CH₃ -OCH₂CH₂0- 0 Cl Cl -OCH₂CH₂0- 0 CI Cl -OCH₂CH₂0- 1 Cl Cl -OCH₂CH₂0- 1 Cl Cl -OCHoCHO- 2 Cl Cl -OCH₂CH₂0- 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 suspension or solid formulation; alternatively the entire formulation of active ingredient can be encapsulated (or "overcoated"). Encapsulation can control or delay release of the active ingredient. Sprayable formulations can be extended in suitable media and used at spray volumes from about one to several hundred liters per hectare. High-strength compositions are primarily used as intermediates for further formulation.

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

Weight Percent

Active Ingredient Diluent Surfactant

Water-Dispersible and Water-soluble 5-90 0-94 1-15 Granules, Tablets and Powders.

Suspensions, Emulsions, Solutions 5-50 40-95 0-15 (including Emulsifiable Concentrates)

Dusts 1-25 70-99 0-5

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

High Strength Compositions 90-99 0-10 0-2 Typical solid diluents are described in Watkins, et al.. Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey. Typical liquid diluents are described in Marsden, Solvents Guide. 2nd Ed., Interscience, New York, 1950. McCutcheon ^'s Detergents and Emulsifiers Annual, Allured Publ. Corp., Ridgewood, New Jersey, as well as Sisely and Wood, Encyclopedia of Surface Active Agents. Chemical Publ. Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth and the like, or thickeners to increase viscosity.

Surfactants include, for example, polyethoxylated alcohols, polyethoxylated alkylphenols, polyethoxylated sorbitan fatty acid esters, dialkyl sulfosuccinates, alkyl sulfates, alkylbenzene sulfonates, organosilicones, 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 81-96; and Hance et al., Weed Control Handbook. 8th Ed., Blackwell Scientific Publications, Oxford, 1989.

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

Example A High Strength Concentrate

Compound 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-(l-methylethyl)-5-oxo-lH-imidazol-2-yl]-5-methyl-3- pyridinecarboxylic acid (AC 263,222), difenzoquat metilsulfate, diflufenican, dimepiperate, dimethenamid, dimethylarsinic acid and its sodium salt, dinitramine, diphenamid, diquat dibromide, dithiopyr, diuron, DNOC, endothal, EPTC, esprocarb, ethalfluralin, ethametsulfuron-methyl, ethofumesate, ethoxysulfuron, fenoxaprop-ethyl, fenoxaprop-P-ethyl, fenuron, fenuron-TCA, flamprop-methyl, flamprop-M-isopropyl, flamprop-M-methyl, flazasulfuron, fluazifop-butyl, fluazifop-P-butyl, fluchloralin, flumetsulam, flumiclorac-pentyl, flumioxazin, fluometuron, fluoroglycofen-ethyl, flupoxam, flupyrsulfuron-methyl and its sodium salt, fluridone, flurochloridone. tluroxypyr, fluthiacet-methyl, fomesafen, fosamine-ammonium, glufosinate, glufosinate-ammonium, glyphosate, glyphosate-isopropylammonium, glyphosate-sesquisodium, glyphosate-trimesium, halosulfuron-methyl. haloxyfop-etotyl, haloxyfop-methyl, hexazinone, imazamethabenz-methyl, imazamox, imazapyr, imazaquin, imazaquin-ammonium, imazethapyr, imazethapyr-ammonium, imazosulfuron, ioxynil, ioxynil octanoate, ioxynil-sodium, isoproturon, isouron, isoxaben, isoxaflutole, lactofen, lenacil, linuron, maleic hydrazide, MCPA and its dimethylammonium, potassium and sodium salts, MCPA-isoctyl, mecoprop, mecoprop-P, mefenacet, mefluidide, metam-sodium, methabenzthiazuron, methylarsonic acid and its calcium, monoammonium, monosodium and disodium salts, methyl [[[l-[5-[2-chloro-4-(trifluoromethyl)phenoxy]-2- nitrophenyl]-2-methoxyethylidene]amino]oxy]acetate (AKH-7088), methyl 5-[[[[(4,6- dimethyl-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]- 1 -(2-pyridinyl)- lH-pyrazole-4- carboxylate (NC-330), metobenzuron, metolachlor, metosulam, metoxuron, metribuzin, metsulfuron-methyl, molinate, monolinuron, napropamide, naptalam, neburon, mcosulfuron, norflurazon, oryzalin, oxadiazon, oxasulfuron, oxyfluorfen, paraquat dichloride, pebulate, pendimethalin, pentoxazone (KPP-314), perfluidone, phenmedipham, picloram, picloram-potassium, pretilachlor, primisulfuron-methyl, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propyzamide, prosulfuron, pyrazolynate, pyrazosulfuron-ethyl, pyridate, pyriminobac-methyl, pyrithiobac, pyrithiobac-sodium, quinclorac, quizalofop-ethyl, quizalofop-P-ethyl, quizalofop-P-tefuryl, rimsulfuron, sethoxydim, siduron, simazine, sulcotrione (ICIA0051), sulfentrazone, sulfometuron-methyl, TCA, TCA-sodium, tebuthiuron, terbacil, terbuthylazine, terbutryn, thenylchlor, thiafluamide (BAY 1 1390), 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'- [l,3]dioxolan]-6-yl)carbonyl]-l,3-cyclohexanedione 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:

b) 2-[(2,3-dihydro-5,8-dimethylspiro[4H-l-benzothiopyran-4,2'-[l ,3]dioxolan]-6- yl)carbonyl]-l,3-cyclohexanedione SS-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:

c) (2.3-dihydro-5,8-dimethylspiro[4H- l-benzothiopyran-4,2'-[l ,3]dioxolan]-6-yl)(l - ethyl-5-hydroxy-lH-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:

d) (2,3-dihydro-5.8-dimethylspiro[4H- 1 -benzothiopyran-4.2'-[ 1 ,3]dioxolan]-6-yl)(l - ethyl-5-hydroxy-lH-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:

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 El El E⁶, Ml mp (°C

1 Cl Cl H (H₅C₂)₃NH⁺ 140 (dec.)

2 CH₃ CH₃ CH₃ (H₅C₂)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)₃NH⁺ 198-205

*See Index Table C for ^]U NMR data.

INDEX TABLE B

Cmpd Structure mp (°C)

10 (Ex. 1) >260 *

*See Index Table C for *H NMR data.

INDEX TABLE C

Cmpd No. ^JH NMR Data ((CD₃)₂SO solution unless indicated otherwise)³ δ 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). δ 1.65-1.78 ( , 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). δ 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 δ 1.09 (br t, 3H), 2. 17 (s, 3H), 2.4-2.65 (m, 5H), 3.3-3.7 (m. 4H), 4-4.3 (m, 4H), 6.55 (br s, 1 H), 7.1 (br s, I H).

1 1 δ 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, I H), 7. 14 (s, I H).

12 δ 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 δ 1.15-1.24 ( , 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, IH).

14 (CDCl₃) δ 1.17-1.23 (1, 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, IH).

15 δ 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, IH), 7.32 (s, IH). ^{a !}H 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 vulgar e), barnyardgrass (Echinochloa crus-galli), bedstraw (Galium aparine), blackgrass (Alopecurus myosuroides), chickweed (Stellar ia media), cocklebur (Xanthium strumarium), corn (Zea mays), cotton (Gossypium hirsutum), crabgrass (Digitaria sanguinalis), downy brome (Bromus tectorum), giant foxtail (Setaria faberiϊ), lambsquarters (Chenopodium album), momingglory (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 of 0 to 10 where 0 is no effect and 10 is complete control. A dash (-) response means no test result. Table A COMPOUND Table A COMPOUND

Rate 400 g/ha 1 9 13 14 Rate 400 g/ha 1 9 13 14

POSTEMERGENCE PREEMERGENCE

B. signalgrass B. signalgrass

Barley 5 9 - - Barley 0 0 - -

Barnyardgrass 9 9 - - Barnyardgrass 5 9 - -

Bedstraw 9 10 9 9 Bedstraw 5 8 8 9

Blackgrass 7 9 8 8 Blackgrass 2 1 3 2

Chickweed 8 10 - - Chickweed 4 9 - -

Cocklebur 9 9 9 10 Cocklebur 6 8 8 7

Corn 2 2 2 4 Corn 0 0 0 0

Cotton 10 10 - - Cotton 8 10 - -

Crabgrass 7 9 9 10 Crabgrass 8 10 10 10

Downy brome 6 9 - - Downy brome 6 8 - -

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

Lambsquarters 9 9 - - Lambsquarters 10 9 - -

Momingglory 10 10 9 10 Momingglory 6 8 9 8

Nutsedge 2 8 9 8 Nutsedge 3 8 8 10

Rape 10 9 7 9 Rape 9 2 7 9

Redroot pigweed - - 9 9 Redroot pigweed - - 10 10

Rice 9 10 - - Rice 7 9 - -

Sorghum 9 10 - - Sorghum 2 2 - -

Soybean 9 10 10 10 Soybean 6 9 9 9

Sugar beet 10 10 10 10 Sugar beet 10 10 10 10

Velvetleaf 10 10 9 10 Velvetleaf 10 10 10 10

Wheat δ 9 9 8 Wheat 0 5 1 3

Wild buckwheat 6 8 - - Wild buckwheat 6 3 - -

Wild oat 4 8 2 5 Wild oat 0 6 3 1

Table A COMPOUND Table A COMPOUND

Rate 200 g/ha 2 3 4 5 Rate 200 g/ha 2 3 4 5

POSTEMERGENCE PREEMERGENCE

B. signalgrass B. signalgrass

Barley 6 8 9 9 Barley 0 0 0 0

Barnyardgrass 9 9 9 10 Barnyardgrass 9 9 9 9

Bedstraw 9 9 9 10 Bedstraw 8 7 8 8

Blackgrass 6 6 7 9 Blackgrass 0 2 1 0 Chickweed 9 9 9 10 Chickweed 6 7 9 9

Cocklebur 10 10 10 10 Cocklebur 4 4 6 9

Corn 2 3 2 2 Corn 0 0 0 1

Cotton 10 10 10 10 Cotton 0 3 3 2

Crabgrass 9 10 9 10 Crabgrass 10 10 10 10

Downy brome 5 7 7 9 Downy brome 0 0 0 5

Giant foxtail 7 9 9 9 Giant foxtail 0 1 2 3

Lambsquarters 9 9 9 10 Lambsquarters 9 10 10 10

Mo ingglory 9 10 10 10 Momingglory 2 3 3 9

Nutsedge - - - 9 Nutsedge - - - 2

Rape 10 8 6 9 Rape 0 0 0 0

Redroot pigweed - - - - Redroot pigweed - - - -

Rice 9 9 9 10 Rice 8 7 6 8

Sorghum 8 9 9 9 Sorghum 0 0 0 2

Soybean 10 10 10 10 Soybean 4 8 6 7

Sugar beet 10 10 10 10 Sugar beet 9 10 10 10

Velvetleaf 10 10 10 10 Velvetleaf 10 10 10 10

Wheat 8 9 9 9 Wheat 1 0 0 1

Wild buckwheat 7 6 4 2 Wild buckwheat 0 2 4 0

Wild oat 5 7 8 8 Wild oat 1 0 1 3

Table A COMPOUND Table A COMPOUND

Rate 100 g/ha 1 9 13 14 Rate 100 g/ha 1 9 13 14

POSTEMERGENCE PREEMERGENCE

B. signalgrass - - 8 7 B. signalgrass - - 8 4

Barley 4 8 - - Barley 0 0 - -

Barnyardgrass 8 9 - - Barnyardgrass 1 8 - -

Bedstraw 9 9 9 9 Bedstraw 6 2 8 9

Blackgrass 5 5 6 4 Blackgrass 1 0 0 0

Chickweed 7 9 - - Chickweed 3 5 - -

Cocklebur 9 9 9 10 Cocklebur 2 0 8 1

Corn 1 0 1 0 Corn 0 0 0 0

Cotton 10 10 - - Cotton 3 0 - -

Crabgrass 2 9 9 8 Crabgrass 7 8 9 7

Downy brome 5 8 - - Downy brome 0 0 - -

Giant foxtail 3 8 6 7 Giant foxtail 1 1 1 0

Lambsquarters 9 9 - - Lambsquarters 9 9 - -

Mo ingglory 10 10 9 10 Momingglory 5 1 8 4 Nutsedge 2 8 8 6 Nutsedge - 0 1 0

Rape 8 6 5 7 Rape 3 0 0 0

Redroot pigweed - - 9 9 Redroot pigweed - - 10 9

Rice 9 10 - - Rice 7 8 - -

Sorghum 9 8 - - Sorghum 1 2 - -

Soybean 8 10 10 10 Soybean 5 8 9 8

Sugar beet 10 10 10 10 Sugar beet 10 10 10 10

Velvetleaf 10 10 9 10 Velvetleaf 9 10 10 10

Wheat 6 9 8 6 Wheat 0 0 0 0

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

Wild oat 3 3 1 2 Wild oat 0 1 2 0

Table A COMPOUND Table A COMPOUND

Rate 50 g/ha 2 3 4 5 10 Rate 50 g/ha 2 3 4 5 10

POSTEMERGENCE PREEMERGENCE

B. signalgrass B. signalgrass

Barley 5 7 8 8 1 Barley 0 0 0 0 0

Barnyardgrass 9 9 9 9 9 Barnyardgrass 8 7 0 7 5

Bedstraw 7 9 9 9 9 Bedstraw 6 7 7 8 2

Blackgrass 4 5 4 6 3 Blackgrass 0 0 0 0 0

Chickweed 7 9 9 9 10 Chickweed 1 4 5 7 0

Cocklebur 9 10 10 10 9 Cocklebur 0 2 1 1 0

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

Cotton 10 10 10 10 9 Cotton 0 2 2 0 0

Crabgrass 5 9 9 10 9 Crabgrass 1 10 9 9 6

Downy brome 3 3 5 5 0 Downy brome 0 0 0 1 0

Giant foxtail 3 6 6 8 9 Giant foxtail 0 0 1 0 2

Lambsquarters 9 9 9 10 9 Lambsquarters 9 10 10 9 10

Momingglory 9 10 10 10 8 Momingglory 0 0 1 3 0

Nutsedge 8 - - 6 0 Nutsedge - - - 0 0

Rape 6 3 4 6 7 Rape 0 0 0 0 0

Redroot pigweed Redroot pigweed

Rice 9 9 9 10 9 Rice 6 3 3 7 0

Sorghum 4 7 6 6 8 Sorghum 0 0 0 0 0

Soybean 10 10 10 10 8 Soybean 3 5 6 6 0

Sugar beet 9 9 9 10 10 Sugar beet 4 9 9 10 4

Velvetleaf 10 10 10 10 10 Velvetleaf 8 8 9 10 6

Wheat 7 7 8 7 3 Wheat 0 0 0 0 0 Wild buckwheat 7 3 3 0 7 Wild buckwheat 0 0 0 0 0

Wild oat 3 4 7 2 5 Wild oat 0 0 0 0 0

Table A COMPOUNE ) Table A COMPOUND

Rate 400 g/ha 13 14 Rate 100 g/ha 13 14

SPRAYED PADDY SPRAYED PADDY

Barnyardgrass 9 10 Barnyardgrass 9 10

Ducksalad 8 9 Ducksalad 8 7

Rice 9 9 Rice 8 9

S. flatsedge 9 8 S . flatsedge 8 6

TESTB

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), blackgrass (Alopecurus myosuroides), chickweed (Stellaria media), cocklebur (Xanthium strumarium), corn (Zea mays cv. Pioneer 3394), cotton (Gossypium hirsutum), crabgrass (Digitaria sanguinalis), downy brome (Bromus tectorum), giant foxtail (Setariafaberii),johnsongrass (Sorghum hαlpense), lambsquarters (Chenopodium album), momingglory (Ipomoea hederacea), pigweed (Amaranthus retroflexus), rape (Brassica napus), ryegrass (Lolium multiflorum), soybean (Glycine max), speedwell (Veronica persica), sugar beet (Beta vulgaris), velvetleaf (Abutilon theophrasti), wheat (Triticum aestivum), wild buckwheat (Polygonum convolvulus), and wild oat (Avenafatua). 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 ' barnyardgrass 1 ') 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 Table B COMPOUND Table B COMPOUND Rate 250 g/ha 1 Rate 250 g/ha 1 Rate 125 g/ha 1 13 POSTEMERGENCE PREEMERGENCE POSTEMERGENCE

Barley (winter) 15 Barley (winter) 0 Barley (winter) 0

Barnyardgrass 80 Barnyardgrass 95 Barnyardgrass 70

Barnyardgrass 1 70 Bedstraw 80 Barnyardgrass 1 60 40

Bedstraw 90 Blackgrass 0 Bedstraw 90

Blackgrass 40 Chickweed 0 Blackgrass 30

Chickweed 65 Cocklebur 50 Chickweed 65

Cocklebur 90 Corn 1 0 Cocklebur 90

Corn 1 0 Cotton 70 Corn 1 0 -

Cotton 90 Crabgrass 100 Cotton 90

Crabgrass 85 Downy brome 0 Crabgrass 75

Downy brome 25 Giant foxtail 85 Downy brome 20

Ducksalad 45 Italn. ryegrass 0 Ducksalad 30 65

Giant foxtail 50 Johnsongrass 30 Giant foxtail 40

Italn. ryegrass 0 Lambsquarter 90 Italn. ryegrass 0

Johnsongrass - Momingglory 100 Johnsongrass

Lambsquarter 95 Rape 95 Lambsquarter 95

Late watergrass 75 Redroot pigweed Late watergrass 65

Momingglory 90 Soybean 90 Momingglory 90

Rape 95 Speedwell 100 Rape 95

Redroot pigweed 90 Sugar beet 100 Redroot pigweed 90

Rice japonica 60 Velvetleaf 100 Rice japonica 40 0

Soybean 90 Wheat 0 Soybean 80

Speedwell 100 Wild buckwheat 10 Speedwell 95

Sugar beet 100 Wild oat 0 Sugar beet 100

Umbrella sedge 50 Umbrella sedge 40 75

Velvetleaf 100 Velvetleaf 100

Wheat 25 Wheat 0

Wild buckwheat 65 Wild buckwheat 65

Wild oat 0 Wild oat 0 Table B COMPOUND Table B COMPOUND

Rate 125 g/ha 1 Rate 62 g/ha 1 2 3 4 5 10 13

PREEMERGENCE POSTEMERGENCE

Barley (winter) 0 Barley (winter) 10 30 20 30 30 10 -

Barnyardgrass 50 Barnyardgrass 50 95 90 90 90 90 -

Bedstraw 65 Barnyardgrass 1 0 15 35 60 75 10 30

Blackgrass 0 Bedstraw 55 80 80 80 90 80 -

Chickweed 0 Blackgrass 30 30 30 40 35 20 -

Cocklebur 40 Chickweed 50 90 90 - 100 95 -

Corn 1 0 Cocklebur 90 90 90 90 90 90 -

Cotton 40 Corn 1 30 0 35 0 0 0 -

Crabgrass 90 Cotton 100 95 90 90 100 40 -

Downy brome - Crabgrass 75 80 90 90 90 95 -

Giant foxtail 40 Downy brome 25 10 30 30 35 10 -

Italn. ryegrass 0 Ducksalad 0 80 70 70 90 60 50

Johnsongrass 20 Giant foxtail 30 70 60 70 80 100 -

Lambsquarter 90 Italn. ryegrass 0 0 20 30 20 20 -

Momingglory 75 Johnsongrass 55 30 50 70 70 90 -

Rape 30 Lambsquarter 100 100 90 80 90 100 -

Redroot pigweed - Late watergrass 0 - - - - - -

Soybean 70 Momingglory 90 85 90 90 90 90 -

Speedwell 90 Rape 90 40 20 20 50 20 -

Sugar beet 100 Redroot pigweed 80 80 80 85 100 100 -

Velvetleaf 100 Rice japonica 10 0 30 30 50 0 0

Wheat 0 Soybean 90 90 90 90 90 70 -

Wild buckwheat 0 Speedwell 95 70 90 90 80 95 -

Wild oat 0 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

Momingglory 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

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 o - - - - - -

Momingglory 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

Momingglory 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 - - --- - -

Momingglory 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

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

Momingglory 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), barnyardgrass (Echinochloa crus-galli), cocklebur (Xanthium strumarium), common ragweed (Ambrosia elatior), common lambsquarters (Chenopodium album), com (Zea mays), cotton (Gossypium hirsutum), eastem black nightshade (Solanum ptycanthum), fall panicum (Panicum dichotomiflorum), field bindweed (Convolvulus arvensis), Florida beggarweed (Desmodium purpureum), giant foxtail (Setaria faberii), hairy beggarticks (Bidens pilos ), ivyleaf momingglory (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

FI . beggarweed 100 80 Giant foxtail 60 60 20 20 60 90 20 75

H. beggarticks 20 60 10 0 90 100 25 70

I. momingglory 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), alexandergrass (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 momingglory (Ipomoea purpurea), tropical spiderwort (Commelina benghalensis), soybean (Glycine max cv. W20, designated 'Soybean 2') and soybean (Glycine max cv. W4-4, designated 'Soybean 3'), com (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 Table D COMPOUND

Rate 70 g/ha 4 11 15 Rate 35 g/ha 4 11 15

POSTEMERGENCE POSTEMERGENCE

Alexandergrass 90 100 95 Alexandergrass 80 80 60

Apple-of-Peru 100 100 100 Apple-of-Peru 100 100 100

Arrowleaf sida 95 90 65 Arrowleaf sida 85 80 60

B. Signalgrass 75 70 80 B. Signalgrass 70 60 60

Blk nightshade 100 100 100 Blk nightshade 100 100 100

Braz sicklepod 60 10 50 Braz sicklepod 55 10 40

Bristly starbur 85 100 70 Bristly starbur 100 100 25

Capim-Colch 80 80 80 Capim-Colch 75 60 20

Corn 10 10 15 Corn 10 5 5

FI . beggarweed 100 - - Fl . beggarweed 100 - -

H. beggarticks 70 90 100 H. beggarticks 60 80 80

Momingglory 100 80 80 Momingglory 100 80 80

S . amaranth 70 100 100 S . amaranth 40 100 100

S . sandbur 65 80 95 S . sandbur 55 80 85

Soybean 1 100 95 90 Soybean 1 80 80 75

Soybean 2 100 95 80 Soybean 2 100 90 65

Soybean 3 100 95 85 Soybean 3 100 90 85

Tr. Spiderwort 75 100 90 Tr. Spiderwort 70 90 75

Wild poinsettia 100 100 100 Wild poinsettia 100 60 95

Table D COMPOUND Table D COMPOUND

Rate 17 g/ha 4 11 15 Rate 8 g/ha 15

POSTEMERGENCE POSTEMERGENCE

Alexandergrass 85 70 10 Alexandergrass 10

Apple-of-Peru 100 100 95 Apple-of-Peru 80

Arrowleaf sida 85 50 20 Arrowleaf sida 20

B. Signalgrass 60 50 20 B. Signalgrass 10

Blk nightshade 100 100 100 Blk nightshade 100

Braz sicklepod 50 5 20 Braz sicklepod 10

Bristly starbur 100 70 20 Bristly starbur 10

Capim-Colch 55 60 10 Capim-Colch 10

Corn 0 0 5 Corn 0

Fl . beggarweed 100 Fl . beggarweed

H. beggarticks 55 80 50 H. beggarticks 20

Momingglory 85 80 70 Momingglory 50 S . amaranth 70 100 80 S . amaranth 60

S . sandbur 30 80 60 S . sandbur 10

Soybean 1 100 80 65 Soybean 1 35

Soybean 2 80 70 50 Soybean 2 30

Soybean 3 75 85 40 Soybean 3 25

Tr. Spiderwort 60 80 60 Tr. Spiderwort 40

Wild poinsettia 75 0 80 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), blackgrass 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 goatgrass (Aegilops cylindrica), kochia (Kochia scoparia), lambsquarters (Chenopodium album), littleseed canarygrass (Phalaris minor), rape 1 (Brassica napus cv. Westar), rape 2 (Brassica napus cv. Jet Neuf), redroot pigweed (Amaranthus retroβexus), 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-ventϊ) 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 Table E COMPOUND

Rate 62 g/ha 2 4 5 Rate 31 g/ha 1 2 4 5

POSTEMERGENCE POSTEMERGENCE

Annual bluegras - - - Annual bluegras 0 20 - -

Barley (winter) 50 - - Barley (winter) 5 20 - -

Blackgrass 2 45 - - Blackgrass 2 0 50 - -

Blk nightshade - - - Blk nightshade 100 95 - -

Chickweed - - - Chickweed 0 70 - -

Common poppy - - - Common poppy - 20 - -

Deadnettle - - - Deadnettle 90 70 - -

Downy brome - - - Downy brome 10 10 - -

Field violet - - - Field violet 0 100 - -

Galium 2 - - - Galium 2 65 60 - -

Green foxtail 95 - - Green foxtail 10 80 - -

I . Ryegrass 20 - - I . Ryegrass 5 5 - -

Jointed goatgra - - - Jointed goatgra 5 5 - -

Kochia - - - Kochia 35 70 - -

Lambsquarters - - - Lambsquarters 100 90 - -

LS canarygrass - - - LS canarygrass 0 10 - -

Rape 1 50 85 60 Rape 1 30 0 72 40

Rape 2 90 92 60 Rape 2 - 25 70 50

Redroot pigweed - - - Redroot pigweed 85 20 - -

Russian thistle - - - Russian thistle - 30 - -

Scentless chamo - - - Scentless chamo 80 65 - -

Speedwell - - - Speedwell 30 - - -

Spring Barley 65 - - Spring Barley 10 20 - -

Sugar beet - - - Sugar beet 100 100 - -

Sunflower - - - Sunflower 75 50 - -

Veronica hedera - - - Veronica hedera - 85 - -

Wheat 35 - - Wheat - 15 - -

Wheat (spring) 30 - - Wheat (spring) 15 25 - -

Wheat (winter) 55 - - Wheat (winter) 15 35 - -

Wild buckwheat - - - Wild buckwheat 0 30 - -

Wild mustard 100 95 100 Wild mustard 100 100 90 100

Wild oat 1 - - - Wild oat 1 - 0 - -

Wild oat 2 60 - - Wild oat 2 5 60 - -

Windgrass - - - Windgrass 0 20 - - Table E COMPOUND Table E COMPOUND

Rate 16 g/ha 1 2 4 5 Rate 8 g/ha 1 2 4 5

POSTEMERGENCE POSTEMERGENCE

Annual bluegras 0 - - - Annual bluegras 0 2 - -

Barley (winter) 0 15 - - Barley (winter) 0 5 - -

Blackgrass 2 0 35 - - Blackgrass 2 0 5 - -

Blk nightshade 30 - - - Blk nightshade 10 75 - -

Chickweed 0 - - - Chickweed 0 60 - -

Common poppy - - - - Common poppy - 30 - -

Deadnettle 35 - - - Deadnettle 0 50 - -

Downy brome 0 - - - Downy brome 0 0 - -

Field violet 0 - - - Field violet 0 80 - -

Galium 2 10 - - - Galium 2 0 30 - -

Green foxtail 5 65 - - Green foxtail 0 20 - -

I. Ryegrass 5 0 - - I . Ryegrass 0 0 - -

Jointed goatgra 0 - - - Jointed goatgra 0 2 - -

Kochia 0 - - - Kochia 0 60 - -

Lambsquarters 30 - - - Lambsquarters 0 80 - -

LS canarygrass 0 - - - LS canarygrass 0 5 - -

Rape 1 0 10 55 30 Rape 1 5 0 20 20

Rape 2 - 25 20 50 Rape 2 - 10 0 20

Redroot pigweed 60 - - - Redroot pigweed - 0 - -

Russian thistle - - - - Russian thistle - 20 - -

Scentless chamo 70 - - - Scentless chamo - 60 - -

Speedwell 15 - - - Speedwell 0 - - -

Spring Barley 0 20 - - Spring Barley 0 5 - -

Sugar beet 35 - - - Sugar beet 25 85 - -

Sunflower 0 - - - Sunflower 0 30 - -

Veronica hedera - - - - Veronica hedera - 55 - -

Wheat - 4 - - Wheat - - - -

Wheat (spring) 0 25 - - Wheat (spring) 0 10 - -

Wheat (winter) 0 30 - - Wheat (winter) 0 5 - -

Wild buckwheat 0 - - - Wild buckwheat 0 10 - -

Wild mustard 50 80 68 100 Wild mustard 30 60 55 100

Wild oat 1 - - - - Wild oat 1 - 0 - -

Wild oat 2 0 30 - - Wild oat 2 0 - - -

Windgrass 0 - - - Windgrass 0 0 - - Table E COMPOUND Table E COMPOUND

Rate 4 g/ha 1 Rate 4 g/ha 1

POSTEMERGENCE POSTEMERGENCE

Annual bluegras 0 Rape 2 -

Barley (winter) 0 Redroot pigweed 30

Blackgrass 2 0 Russian thistle -

Blk nightshade 0 Scentless chamo 20

Chickweed 0 Speedwell 0

Common poppy - Spring Barley 0

Deadnettle 0 Sugar beet 15

Downy brome 0 Sunflower 0

Field violet 0 Veronica hedera -

Galium 2 0 Wheat -

Green foxtail 0 Wheat (spring) 0

I . Ryegrass 0 Wheat (winter) 0

Jointed goatgra 0 Wild buckwheat 0

Kochia 0 Wild mustard 30

Lambsquarters 0 Wild oat 1 -

LS canarygrass 0 Wild oat 2 0

Rape 1 0 Windgrass 0

TESTF

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 (Heter anther a limosa), early watergrass (Echinochloa oryzoides), junglerice (Echinochloa colonur ), late watergrass (Echinochloa oryzicola), redstem (Ammania species), rice flatsedge (Cyperus iria), smallflower flatsedge (Cyperus difformis) and tighthead sprangletop (Leptochloa fasicularis), were planted into this soil. Plantings and waterings of these crops and weed species were adjusted to produce plants of appropriate size for the test. At the 2-leaf stage, water levels were raised to 3 cm above the soil surface and maintained at this level throughout the test. Chemical treatments were formulated in a non-phytotoxic solvent mixture which included a surfactant and applied directly to the paddy water by pipette, or to the plant foliage by an air pressure-assisted, calibrated belt-conveyer spray system.

Treated plants and controls were maintained in a greenhouse for approximately 21 days, after which all species were compared to controls and visually evaluated. Plant response ratings, summarized in Table 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 Table F COMPOUND Rate 200 g/ha 4 Rate 150 g/ha 4 Paddy / silt loam Paddy / silt loam Barnyardgrass Barnyardgrass Ducksalad 95 Ducksalad 95 E. watergrass E. watergrass Junglerice Junglerice L. watergrass L. watergrass Redstem 95 Redstem 95

Rice flatsedge 95 Rice flatsedge 95 Rice indica l 100 Rice indica 1 90 Rice indica 3 70 Rice indica 3 65 S. flatsedge 98 S. flatsedge 98 T. sprangletop 100 T. sprangletop 100

Table F COMPOUND Table F COMPOUND Table F COMPOUND

Rate 125 g/ha 2 4 5 Rate 100 g/ha 4 Rate 75 g/ha 4 Paddy / silt loam Paddy / silt loam Paddy / silt loam

Barnyardgrass 0 - 60 Barnyardgrass Barnyardgrass

Ducksalad 98 95 90 Ducksalad 90 Ducksalad 95

E. watergrass - - 90 E. watergrass E . watergrass

Junglerice 100 - 65 Junglerice Junglerice

L. watergrass 0 - 35 L. watergrass L. watergrass

Redstem 98 95 100 Redstem 90 Redstem 95

Rice flatsedge 65 95 85 Rice flatsedge 85 Rice flatsedge 85

Rice indica 1 15 90 40 Rice indica 1 65 Rice indica 1 50

Rice indica 3 10 70 45 Rice indica 3 55 Rice indica 3 45

S . flatsedge 100 95 85 S. flatsedge 95 S. flatsedge 95

T. sprangletop 100 95 100 T. sprangletop 100 T. sprangletop 100

Table F COMPOUND Table F COMPOUND Table F COMPOUND Rate 64 g/ha 2 5 Rate 50 g/ha 4 Rate 32 g/ha 2 5 Paddy / silt loam Paddy / silt loam Paddy / silt loam Barnyardgrass 0 15 Barnyardgrass Barnyardgrass 0 0 Ducksalad 98 90 Ducksalad 90 Ducksalad 60 85

E. watergrass - 35 E. watergrass E. watergrass - 20

Junglerice 65 40 Junglerice Junglerice 0 15

L. watergrass 0 20 L. watergrass L. watergrass 0 0

Redstem 98 100 Redstem 75 Redstem 50 75

Rice flatsedge 50 100 Rice flatsedge 80 Rice flatsedge 10 65

Rice indica 1 10 30 Rice indica l 10 Rice indica 1 0 25

Rice indica 3 10 20 Rice indica 3 10 Rice indica 3 0 10

S. flatsedge 100 100 S. flatsedge 90 S. flatsedge 100 65

T. sprangletop 100 98 T. sprangletop 65 T. sprangletop 95 98

Table F COMPOUND Table F COMPOUND Table F COMPOUND

Rate 25 g/ha 4 Rate 16 g/ha 2 5 Rate 8 g/ha 2 5 Paddy / silt loam Paddy / silt loam Paddy / silt loam Barnyardgrass Barnyardgrass 0 0 Barnyardgrass 0 0

Ducksalad 85 Ducksalad 55 45 Ducksalad 0 25 E . watergrass E. watergrass - 15 E. watergrass - 0 Junglerice Junglerice 0 0 Junglerice 0 0 L. watergrass L. watergrass 0 0 L. watergrass 0 0

Redstem 20 Redstem 40 55 Redstem 0 0

Rice flatsedge 65 Rice flatsedge 0 45 Rice flatsedge 0 20

Rice indica 1 10 Rice indica 1 0 0 Rice indica 1 0 0

Rice indica 3 0 Rice indica 3 0 10 Rice indica 3 0 10

S. flatsedge 70 S. flatsedge 50 45 S. flatsedge 0 20

T. sprangletop 20 T. sprangletop 15 85 T. sprangletop 0 85

Claims

CLAIMS What is claimed is:

1. A compound selected from Formula I

wherein Q is

Q-1 Q-2

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 Cj-C₃ alkyl; each R³ is CH₃;

R⁴ and R⁵ are each independently H, C_rC₃ alkyl or halogen; R⁶ is C_rC₃ alkyl; R⁷ is C,-C₃ alkyl;

R⁸ is H, C , -C₂₅ alkyl or benzyl;

R⁹ and R¹⁰ are independently C_rC₂₅ alkyl;

R" is C,-C₂₅ alkyl or

R^{l 2} is H, C,-C₁₂ alkyl, C_rC₃ 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 Q-1 and Rl 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: Q is Q-1.

3. A compound of Claim 2 wherein:

R⁴ and R⁵ are each independently H or Cι-C₃ alkyl; n is 2; p is 0; and q is 0, 1 or 2.

4. A compound of Claim 3 wherein: M is Li, Na, K or

R8 R9— N— RlO

J ^Kt"

5. A compound of Claim 1 wherein: Q is Q-2.

6. A compound of Claim 5 wherein:

R⁴ and R⁵ are each independently H or C_rC₃ alkyl; R⁷ is CH₂CH₃; n is 2; p is 0; and q is 0. 1 or 2.

7. A compound of Claim 6 wherein: M is Li, Na, K or

R8

R9— N— RlO

RU

8. The compound of Formula I which is selected from the group: a) 2-[(3,4-dihydro-5,8-dimethyl-4-oxo-2H-l-benzothiopyran-6-yl)carbonyl]-5,5- dimethyl- 1 ,3-cyclohexanedione S,S-dioxide monolithium salt; b) 2-[(3,4-dihydro-5,8-dimethyl-4-oxo-2H-l-benzothiopyran-6-yl)carbonyl]-5,5- dimethyl-l,3-cyclohexanedione S,S-dioxide monosodium salt; c) 2- [(3 ,4-dihydro-5 , 8 -dimethy l-4-oxo-2H- 1 -benzothiopyran-6-yl)carbony 1] -5 , 5 - dimethyl- 1, 3 -cyclohexanedione S,S-dioxide monopotassium salt; d) 2-[(2,3-dihydro-5,8-dimethylspiro[4H-l-benzothiopyran-4,2'-[l,3]dioxolan]-6- yl)carbonyl]-l,3-cyclohexanedione S,S-dioxide monolithium salt; e) 2-[(2,3-dihydro-5,8-dimethylspiro[4H-l-benzothiopyran-4,2'-[l,3]dioxolan]-6- yl)carbonyl]-l,3-cyclohexanedione S,S-dioxide monosodium salt; f) 2-[(2,3-dihydro-5,8-dimethylspiro[4H-l -benzothiopyran-4,2'-[l ,3]dioxolan]-6- yl)carbonyl]- 1 ,3 -cyclohexanedione S,S-dioxide monopotassium salt; g) (2,3-dihydro-5,8-dimethylspiro[4H-l-benzothiopyran-4,2'-[l,3]dioxolan]-6- yl)(l-ethyl-5-hydroxy-lH-pyrazol-4-yl)methanone S,S-dioxide monolithium salt; h) (2,3-dihydro-5,8-dimethylspiro[4H-l-benzothiopyran-4,2'-[l,3]dioxolan]-6- yl)(l-ethyl-5-hydroxy-lH-pyrazol-4-yl)methanone S,S-dioxide monosodium salt; i) (2,3-dihydro-5,8-dimethylspiro[4H-l-benzothiopyran-4,2'-[l,3]dioxolan]-6- yl)(l-ethyl-5-hydroxy-lH-pyrazol-4-yl)methanone S,S-dioxide monopotassium salt; j) 6-[(l-ethyl-5-hydroxy-lH-pyrazol-4-yl)carbonyl]-2,3-dihydro-5,8-dimethyl-4H- 1 -benzothiopyran-4-one 1 , 1 -dioxide monolithium salt; k) 6-[(l-ethyl-5-hydroxy-lH-pyrazol-4-yl)carbonyl]-2,3-dihydro-5,8-dimethyl-4H-

1 -benzothiopyran-4-one 1 , 1 -dioxide monosodium salt; and 1) 6-[(l-ethyl-5-hydroxy-lH-pyrazol-4-yl)carbonyl]-2,3-dihydro-5,8-dimethyl-4H- 1 -benzothiopyran-4-one 1 , 1 -dioxide 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.