HERBICIDAL SUBSTITUTED-THIOPHENE, FURAN AND PYRROLE SULFONAMIDES

Abstract: Novel sulfonamide derivatives of the formula where E is a bridge of 3 or 4 atoms including 0-2 oxygen, sulfur or nitrogen heteroatoms and at least one carbon atom; G is O, S, NH or NCH₃; W is O or S; R is H or CH₃; and A is a substituted nono or bicyclic heterocyclic residue, especially a pyrimidine or triazine residue; exhibit potent herbicidal activity; many also exhibit a plant growth regulant effect. The novel compounds may be made by a variety of synthetic routes, e. g. by reacting the appropriate sulfonyl isocyanate or isothiocyanate of formula JSO₂NCW with an appropriate heterocyclic amine of formula H-A.

Description: The invention relates to novel N-(heterocyclicaminocarbonyl) substituted thiophene, furan and pyrrolesulfonamides which are useful as herbicides, and their method-of-use as general pre-emergence or post-emergence herbicides or plant growth regulants. In U.S. Patent 4,127,405, issued November 28, 1978 to Levitt, herbicidal benzene- and thiophenesulfonylureas are disclosed. U.S. Patent 4,398,939, issued August 16, 1983 to Levitt discloses herbicidal thiophenesulfonylureas substituted by alkyl, OCH₃, NO₂, halogen, or sulfamoyl groups. European Patent Application (EP-A)-30,142, published June 10, 1981 teaches herbicidal thiophenesulfonylureas bearing ortho -carboxylic acid ester groups as well as other derivatives of carboxylic acids. European Patent Application (EP-A)-64,804, published November 17, 1982, discloses herbicidal thiophenesulfonylureas bearing ortho -alkylsulfonyl groups. U.S. Patent 4,391,627, issued July 5, 1983 to Levitt discloses benzothiophenesulfonylureas. European Patent Application (EP-A)-79,683, published May 25, 1983, teaches herbicidal sulfonylureas including those of the general formulae: wherein Q is O, S or SO₂; R₂ is H or C₁-C₃ alkyl; R₃ is H or CH₃; and R₄ is H or CH₃. EPA-107,979, published May 9, 1984, teaches herbicidal sulfonylureas including those of general Formulae III-VI: wherein n is O, 1 or 2; G is O or NR"; and R" is alkyl. Still further herbicidal sulfonylureas are disclosed in our EP-A-45,196 and EP-A-70,698. Summary of the Invention This invention relates to novel compounds of Formula I, suitable agricultural compositions containing them and their method-of-use as general pre-emergence and/or post-emergence herbicides or plant growth regulants. wherein J is E is a bridge of 3 to 4 atoms. containing 0-2 heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen and also containing 1 to 4 atoms of carbon, said bridge together with the two carbon attachment sites forming a non-aromatic 5 to 6 membered carbocyclic ring, an aromatic 5 to 6 membered heterocyclic ring, or a non-aromatic 5 to 6 membered heterocyclic ring, with the proviso that two oxygen atoms must be separated by at least one atom of carbon and that oxygen and sulfur are only linked to each other if the sulfur is in the form of -SO- or -SO₂-; G is O, S or N-R; W is O or S; R is H or CH₃; R'₁ is H, CH₃ or Cl when G is S and is H when G is O or N-R; R₁ is H, CH₃, OCH₃, Cl, Br, SCH₃, SO₂CH₃ or NO₂; and wherein X is H, C₁-C₄ alkyl, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, C₁-C₄ haloalkyl, C₁-C₄ haloalkylthio,C₁-C₄ alkythio, halogen, C₂-C₅ alkoxyalkoxy, amino, C₁-C₃ alkylamino or di(C₁-C₃ alkyl)amino; Y is H, C₁-C₄ alkyl, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, C₁-C₄ haloalkylthio C₁-C₄ alkylthio, halogen, C₂-C₅ alkoxyalkyl, C₂-C₅ alkoxyalkoxy, amino, C₁-C₃ alkylamino di(C₁-C₃ alkyl)amino, C₃-C₄ alkenyloxy, C₃-C₄ alkylnyloxy, C₂-C₅ alkylthioalkyl, C₁-C₄ haloalkyl, C₃-C₅ cycloalkyl, C₂-C₄ alkynyl; W is O or S; m is 2 or 3; R a is H or CH₃; R b is C₁-C₂ alkyl; R c is C₁-C₂ alkyl; Z is CH, N, CCH₃, CC₂H₅, CCl or CBr; Y₁ is O or CH₂; X₁ is CH₃, OCH₃, OC₂H₅ or OCF₂H; X₂ is CH₃, C₂H₅ or CH₂CF₃; Y₂ is OCH₃, OC₂H₅, SCH₃, SC₂H₅, OCF₂H, SCF₂H, CH₃ or CH₂CH₃; X₃ is CH₃ or OCH₃; and Y₃ is H or CH₃; provided that a) when W is S, then R is H, A is A-1, Z is CH or N, and Y is CH₃, OCH₃, OC₂H₅, CH₂OCH₃, C₂H₅, CF₃, SCH₃, OCH₂CH=CH₂, OCH₂C≡CH, OCH₂CH₂OCH₃, CH(OCH₃)₂, OCH₂CF₃ c) when X is Cl, F or Br, then Z is CH and Y is OCH₃, OC₂H₅, NH₂, NHCH₃ N(CH₃)₂ or OCF₂H; g) when X or Y is OCF₂H, then Z is CH; and their agriculturally suitable salts. Other compounds of the present invention have the formula wherein J is R is H or CH₃; R₁' is H, CH₃ or Cl; R₁ is H, CH₃, OCH₃, Cl, Br, SCH₃, SO₂CH₃, or NO₂; R₂ is H, Cl or C₁-C₄ alkyl; R₃ is H, Cl or C₁-C₄ alkyl; R₄ is H or C₁-C₄ alkyl; R₅ is H or CH₃; R₆ is H, R₈, SR₈, SO₂R₈, OR₈, C(O)R₈, CO₂R₈, NR₈R₄, CN or Si(CH₃)₂R₉; R₇ is H, C₁-C₆ alkyl, Cl, Br, CN, NO₂, SR₉, SO₂R₉, CO₂R₉ or C(O)R₉; R₈ is C₁-C₆ alkyl, C₂-C₆ alkenyl, or C₂-C₆ alkynyl, each optionally substituted by one or more halogens and/or R₁₁, C₂-C₆ epoxyalkyl, C₃-C₆ cycloalkyl, C₄-C₇ cycloalkylaklyl. R₉ is C₁-C₄ alkyl, R₁₀ is H, F, Cl Br, CH₃, OCH₃, CN, NO₂, SCH₃, SO₂CH₃ or CF₃; R₁₁ is OR₁₂, OC(O)R₁₂, OC(O)NR₉R₁₂, OSO₂R₁₂, OSi(CH₃)₂R₉, Si(CH₃)₂R₉, SR₁₂, SOR₁₂, SO₂R₁₂, SCN, CN, NO₂, C(O)R₁₂, C(O)OR₁₂, C(O)NR₄R₁₂, or L. R₁₂ is H, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkynyl; C₂-C₆ alkynyl, C₃-C₆ cycloalkyl or n is O or 1; Q is O, S, SO, SO₂, CH₂ or CHCH₃; and G is O, S or NR; L is a 5 or 6 membered aromatic heterocycle, a 5-6-membered dihydroaromatic heterocycle or a 5- or 6-membered tetrahydroaromatic heterocycle each containing 1-4 heteroatoms selected from the group consisting of 0-1 oxygen atoms, 0-1 sulfur atoms and 0-4 nitrogen atoms, also each optionally substituted with 1-4 CH₃, 1-2 OCH₃, 1 SCH₃, 1 Cl, 1 N(CH₃)₂or 1 CN or L is a 5- or 6-membered lactone, lactam or cycloalkanone optionally substituted with 1-4 CH₃ groups; W is O or S; R₁, R₁' and A are as defined above; said provisos a), c) and g) as defined above apply; and provided further that b) the total number of carbon atoms in R₂ and R₃ is less than or equal to 4; d) when J is J₁ or J₂, then R₂ and R₃ are other than Cl; e) the total number of carbon atoms in R₄ and R₅ is less than or equal to 4; and f) when J is J₅, J₆, J₇ or J₈ and n = O, then R₄ is H; and their agriculturally suitable salts. In the above formula, preferably J is R is H or CH₃; R₁ is H, CH₃, OCH₃, Cl or Br; R₂ is H, Cl or C₁-C₄ alkyl; R₃ is H, Cl or C₁-C₄ alkyl; R₄ is H or C₁-C₄ alkyl; R₅ is H or CH₃; R₆ is H or C₁-C₄ alkyl; Q is O, S, SO, SO₂, CH₂ or CHCH₃; n is 0 or 1; X is CH₃, OCH₃, OCH₂CH₃, Cl, F, Br, CH₂F, OCF₂H or CF₃; Y is H, CH₃, OCH₃, OC₂H₅, CH₂OCH₃, NH₂, NHCH₃, N(CH₃)₂, C₂H₅, CF₃, SCH₃, OCH₂CH=CH₂, OCH₂C≡CH, OCH₂CF₃, CN, N₃, OCH₂CH₂OCH₃, CH₂SCH₃, CR a (WCH₃)₂, CR a (WCH₂CH₃)₂, or WCF₂T wherein W is O or S, R a is H or CH₃ and T is H, CHClF, CHBrF or CHFCF₃; Z is CH, N, CCH₃, CC₂H₅, CCl or CBr; Y₁ is O or CH₂; X₁ is CH₃, OCH₃, OC₂H₅ or OCF₂H; X₂ is CH₃, C₂H₅ or CH₂CF₃; Y₂ is OCH₃, OC₂H₅, SCH₃, SC₂H₅, CH₃ or CH₂CH₃; and X₃ is CH₃ or OCH₃, Preferred for reasons of their higher herbicidal activity, greater plant growth regulant activity or more favorable ease of synthesis are: 1) Compounds of Formula I wherein R is H, W is O, and G is O or S. 2) Compounds of Formula I wherein J is J₁-J₂₂, defined above. 3) Compounds of Preferred 2 wherein R is H, W is O, and G is O or S. 4) Compounds of Preferred 3 wherein A is A-1; X is CH₃, OCH₃, Cl, Br, OCH₂CF₃ or OCF₂H; Y is C₁-C₃ alkyl, cyclopropyl, C≡CH, OCH₃, OC₂H₅, CH₂OCH₃, NH₂, NHCH₃, N(CH₃)₂, C₂H₅, CF₃, SCH₃, OCH₂CH=CH₂, OCH₂C≡CH, OCH₂CH₂OCH₃, CR(OCH₃)₂, CR₅(OCH₂CH₃)₂ or OCF₂H; and Z is CH or N. 5) Compounds of Preferred 4 wherein R₁ is H, Cl, Br or CH₃; R₂, R₃ and R₄ are H or C₁-C₃ alkyl; R₆ is H, R₈, C(O)R₈ or CO₂R₈; R₇ is Cl, Br, CO₂CH₃ or CO₂CH₂CH₃; R₈ is C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₃-C₆ cycloalkyl or C₄-C₇ cycloalkylalkyl and R₁₁ is OCH₃, OCH₂CH₃, CN, CO₂(C₁-C₄ alkyl), OH or C(O)CH₃. 6) Compounds of Preferred 5 wherein G is S, Y is CH₃ or OCH₃ and X is CH₃, OCH₃, Cl or Br. 7) Compounds of Preferred 6 where J is J₁. 8) Compounds of Preferred 6 where J is J₃. 9) Compounds of Preferred 6 where J is J₅. 10) Compounds of Preferred 6 where J is J₇. 11) Compounds of Preferred 6 where J is J₉. 12) Compounds of Preferred 6 where J is J₁₁. 13) Compounds of Preferred 6 where J is J₁₃. Specifically Preferred for reasons of their highest herbicidal activity, greatest plant growth regulant activity and/or most favorable ease of synthesis are: N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-6,7-dihydro-5H-thieno[3,2-B]thiopyran-3-sulfonamide, 4,4-dioxide, m.p. 224-225.5°C. N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-6,7-dihydro-5H-thieno[3,2-B]thiopyran-3-sulfonamide, 4,4-dioxide, m.p. 228-230°C. N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-5,6-dihydro-5-methylthieno[3,2-B]-thiophene-3-sulfonamide-4,4-dioxide, m.p. 186-187°C. N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-5,6-dihydro-5-methythieno[3,2-B]-thiophene-3-sulfonamide-4,4-dioxide, m.p. 192-193°C. N-[(4-chloro-6-methoxypyrimidin-2-yl)aminocarbonyl]-5,6-dihydro-5-methylthieno[3,2-B]-thiophene-3-sulfonamide-4,4-dioxide, m.p. 203-204°C. DETAILED DESCRIPTION OF THE INVENTION Synthesis The following discussion represents a general outline for the preparation of the compounds of this invention. All of the syntheses described below are multistep with one or more methods being taught for each step. This allows for a wide variety of possible synthetic pathways to prepare a particular compound of Formula 1. The proper choice of the synthetic pathway and the best ordering of the reaction sequences for each individual compound will be knovn to one skilled in the art. The compounds of Formula I can be prepared by one or more of the methods described below in Equations 1 to 6. As shown in Equation 1, many of the compounds of Formula I can be prepared by reacting a sulfonylisocyanate (W = 0) or a sulfonylisothiocyanate (W = S) of Formula II with an appropriate heterocyclic amine of Formula III. R, A and W are as previously defined. Equation 1 The reaction is carried out at 25° to 100°C in an inert, aprotic solvent such as methylene chloride or xylene for 0.5 to 24 hours as taught in U.S. Patent 4,127,405. Many of the compounds of Formula I, where W is S and R is H, (Ia) can be prepared by reacting the appropriate sulfonamide of Formula IV with a heterocyclic isothiocyanate of Formula V, as shown in Equation 2. Equation 2 The reaction is carried out at 25° to 80°C in an inert, aprotic solvent such as acetone or acetonitrile in the presence of a base such as potassium carbonate for 0.5 to 24 hours. The required heterocyclic isothiocyanates V are prepared from the corresponding amines III as taught in EPO Publication 35,893. Many of the compounds of Formula I, where W is O (Ib) and J is other than J₅, J₆, J₉ and J₁₀, can be prepared by reacting the sulfonamides of Formula IV with an appropriate methylcarbamate of Formula VI in the presence of an equimolar amount of trimethylaluminum, as shown in Equation 3. Equation 3 The reaction is carried out at 25° to 40°C in a solvent such as methylene chloride for 10 to 96 hours under an inert atmosphere as taught in EPO Publication 82,681. The required carbamates VI are prepared by reacting the corresponding amines III with dimethylcarbonate or methyl chloroformate in the presence of a strong base. Alternatively, many of the compounds of Formula Ib, can be prepared by reacting a sulfonylcarbamate of Formula VII with an appropriate amine of Formula III, as shown in Equation 4. Equation 4 The reaction is carried out at 50° to 100°C in a solvent such as dioxane for 0.5 to 24 hours as taught in EPO publication No. 44,807. The required carbamates VII are prepared by reacting the corresponding sulfonamides IV vith diphenylcarbonate in the presence of a strong base, such as sodium hydride. Compounds of Formula Ib can also be prepared, as shown in Equation 5, by reacting a heterocyclic carbamate of Formula VIII with an appropriate sulfonamide of Formula IV. Equation 5 The reaction is carried out at 0° to 50°C in a solvent such as acetonitrile or dioxane in the presence of a non-nucleophilic base such as DBU for 0.2 to 24 hours. The required phenylcarbamate VIII are prepared by reacting the corresponding heterocyclic amines III with diphenylcarbonate or phenylchloroformate in the presence of a strong base, such as sodium hydride. Many of the compounds of Formula Ib, particularly when G is NH or NCH₃ can be prepared by reacting the bicyclic heterocycles IX with a sulfamoyl chloride X as shown in Equation 6. Equation 6 The reaction is carried out at -78°C to 80°C in a solvent such as tetrahydrofuran or nitroethane for 1 to 48 hours alone or in the presence of a Friedel-Crafts catalyst as taught in U.S. 4,368,067 and 4,473,394. The sulfamoyl chloride intermediates X are prepared by reacting the heterocyclic amines III with chlorosulfonylisocyanate by methods taught in U.S. 4,401,816. The intermediate sulfonylisocyanates (W = 0) and sulfonylisothiocyanates (W = S) of Formula II from Equation 1 can be prepared as shown in Equations 7, 8 and 9. As shown in Equation 7, many of the sulfonylisocyanates of Formula IIa where J is other than J₃ and J₄ can be prepared by the reaction of sulfonamides of Formula IV with phosgene, in the presence of n -butylisocyanate and a tertiary amine catalyst, at reflux in a solvent such as xylene by the method of U.S. Patent 4,238,621. Equation 7 The sulfonylisocyanates can also be prepared from the sulfonamides by a two step procedure involving (a) reacting the sulfonamides with n -butylisocyanate in the presence of a base such as K₂CO₃ at reflux in an inert solvent such as 2-butanone forming a n -butylsulfonylurea; and (b) reacting this compound with phosgene and a tertiary amine catalyst at reflux in xylene solvent. The method is similar to a procedure taught by Ulrich and Sayigh, Newer Methods of Preparative Organic Chemistry, Vol. VI, p. 223-241, Academic Press, New York and London, W. Foerst Ed. Alternatively, as shown in Equation 8, many of the sulfonylisocyanates of Formula IIa can be prepared by reacting the corresponding sulfonyl chlorides VIII with cyanic acid salts. Equation 8 The reaction is carried out at 25° to 100°C in an inert aprotic solvent such as acetonitrile for 0.5-24 hours in the presence of phosphorus pentoxide and an alkali metal salt such as lithium iodide according to the teachings of Japanese Patent No. 76/26,816 ( Chem. Abst. , 85:77892e (1976)). Many of the sulfonylisothiocyanates of Formula IIb where J is other than J₃ and J₄ can be prepared, as shown in Equation 9, by contacting the sulfonamides of Formula IV with carbon disulfide in the presence of two equivalents of a strong base. The resulting salt is then reacted with phosgene according to the teachings of K. Hartke, Arch. Pharm. , 299 , 174 (1966). Equation 9 The sulfonamides of Formula IV of Equations 2, 3, 5, 7 and 9 are important intermediates for the preparation of the compounds of this invention. The syntheses of the required sulfonamide intermediates are described in Equations 10 to 15. As shown in Equation 10, sulfonamides of Formula IV can be prepared from the corresponding sulfonyl chlorides of Formula XI by contacting with either anhydrous or aqueous ammonia. Equation 10 The preparation of sulfonamides from sulfonyl chlorides is widely reported in the literature, for reviews see: F. Hawking and J. S. Lawrence, "The Sulfonamides," H. K. Lewis and Co., London, 1950 and E. H. Northey, "The Sulfonamides and Allied Compounds," Reinhold Publishing Corp., New York, 1948. Alternatively, many sulfonamides IV can be prepared by dealkylation of their corresponding N- t -butyl sulfonamides XII as shown in Equation 11. Equation 11 The reaction is carried out by contacting the N- t -butyl sulfonamide XII with a strong acid such as trifluoroacetic acid or methanolic HCl at 25° to 50°C for 0.5 to 24 hours. The N-t-butyl sulfonamides XII are readily prepared by reacting sulfonylchlorides XI with t -butylamine and are useful either as an aid in purification, to enhance solubility for subsequent reactions such as Equation 12 below or to protect the sulfonamide function from competing with reactions at other parts of the molecule. Many of the unsaturated sulfonamides of Formula IVa and IVb can be prepared from the corresponding saturated sulfonamides of Formula IVc and IVd by the two-step procedure shown in Equation 12. G₁-G₂ is CO-O, SO₂-NR₆, CO-NR₄ or O-SO₂ and R" is H or C(CH₃)₃. Equation 12 The first step involves α-bromination by N-bromosuccinimide to give a monobromide which is subsequently dehydrobrominated in a second step by reaction with a suitable base such as triethylamine or potassium- t -butoxide in an inert solvent such as THF. This method has been used to prepare isocoumarins from 3,4-dihydroisocoumarins, see R. Barry, Chem. Rev. , 64 , 229 (1964). In cases where R₁ or R₁' is a methyl function, competitive bromination at this site may occur resulting in a mixture. The desired bromide may be separated at this stage, or after treatment with the base, by standard methods. Many of the sulfonamides of Formula IVe and IVf can be prepared from sulfonamides of Formula IVg and IVh, respectively by dehalogenation as shown in Equation 13. G₁-G₂-G₃ is Q-CR₂R₃-CH₂, CO-CR₂R₃-CH₂, CO-O-CR₄R₅, SO₂-NR₆-CHR₅, CO-NR₄-CHR₅ or O-SO₂-CHR₅; R₁ and R' are Cl or Br and R" is H or C(CH₃)₃. Equation 13 A typical dehalogenation method involves contacting the halo compound with zinc in aqueous acetic acid at 25° to 100°C for 0.5 to 24 hours. A variety of dehalogenation methods are known, for example, see H. D. Hartough, Thiophene and Derivatives , Vol. III of The Chemistry of Heterocyclic Compounds , Interscience, New York, 1952. Additionally, as shown in Equation 14, many of the sulfonamides of Formula IVi and IVj can be prepared by oxidation of sulfonamides of Formula IVk and IVl, respectively. m is 1 or 2. R₁ is not SCH₃ and R" is H or C(CH₃)₃. Equation 14 The oxidation of sulfides to sulfoxides and sulfones are widely reported in the literature, for an overview see: "Organic Chemistry of Sulfur", Plenum Press, New York, 1977, S. Oae Ed. Many of the sulfonamides of Formula IVm and IVn can be prepared by functionalization of the corresponding N-unsubstituted sulfonamides of Formula IVo and IVp, respectively, as shown in Equation 15. G₁-G₂ is (CH₂) n -CHR₅ or CH=CR₅, R" is H or C(CH₃)₃ and X is Cl, Br, I or other readily displaceable groups. Equation 15 The reaction is carried out by contacting the sulfonamides IVo or IVp with the appropriate electrophile in the presence of a suitable base such as K₂CO₃ in an inert, polar solvent such as DMF at 0° to 100°C for 0.5 to 24 hours. In some instances the R₆ function can also be introduced by Michael addition of IVo or IVp to the appropriate Michael acceptor as known to one skilled in the art. While many of the R₆ groups can be introduced directly, as described above, some of the R₆ groups may best be prepared by standard functional group manipulations upon compounds of Formula IVm or IVn containing an appropriate R₆ group precursor as will be known to one skilled in the art. Some examples of these manipulations are the preparation of IVm or IVn where R₆ contains an epoxide by the expoxidation of IVm or IVn where R₆ contains a carbon-carbon double bond, the preparation of IVm or IVn where R₆ contains a sulfone by the oxidation of IVm or IVn where R₆ contains a thioether function, the preparation of IVm or IVn where R₆ contains OC(O)CH₃ by acetylation of IVm or IVn where R₆ contains OH, or the preparation of IVm or IVn where R₆ contains NH₂ by the reduction of IVm or IVn where R₆ contains NO₂. The sulfonyl chlorides of Formula XI of Equations 8 and 10 can be prepared by methods outlined in Equations 16 to 18. As shown in Equation 16, many of the sulfonyl chlorides of Formula XIa and XIb can be prepared from thiophenes of Formula XIIIa and XIIIb, respectively by direct chlorosulfonation. R₁ is not H. Equation 16 Direct chlorosulfonation can be carried out by standard methods such as those cited by Hartough ( loc. cit. ) for the preparation of thiophene sulfonylchlorides. For compounds of Formula XIIIa, R₁ cannot be hydrogen in order to avoid chlorosulfonation at the more reactive 2-position of the heterocyclic ring. For compounds of Formula IXb, mixtures may result when R₁' is hydrogen due to competitive chlorosulfonation at the 5-position of the heterocyclic ring. These isomers can be separated by standard fractional crystallization, fractional distillation or chromatographic methods. When G is NH or NCH₃, direct ring sulfonation with pyridine-sulfur trioxide complex may be preferable as known to one skilled in the art. The resulting sulfonic acid can be converted to the sulfonyl chlorides by standard methods. Alternatively, many of the sulfonyl chlorides of Formula XIa and XIb can be prepared from compounds of Formula XIIIa and XIIIb by the four step sequence shown in Equation 17. Equation 17 Nitration of compounds can be carried out by standard methods such as those cited by Hartough ( loc. cit. ) for the thiophene ring system. The same regioselectivity in nitration is observed as described for the chlorosulfonation of XIIIa and XIIIb (vide supra). The reduction of the intermediate nitro compounds to amines can be carried out by any of several methods as described in Preparative Organic Chemistry , 4th Edition, p. 557-563, John Wiley and Sons, New York and London, G. Hilgetag and A. Martini Ed. Diazotization of the amines with sodium nitrite in HCl, followed by reaction of the diazonium salt with sulfur dioxide and cupric chloride in acetic acid analogous to the teachings of Yale and Sowinski, J. Org. C hem. , 25 , 1824 (1960) provides the desired sulfonyl chlorides. Alternatively, the sulfonyl chlorides can be prepared by a modification of the above procedure whereby the diazotization reaction is carried out in dilute sulfuric acid and the resulting diazonium salt is reacted with sulfur dioxide, HCl and cupric chloride in a cosolvent mixture consisting of acetic acid-water (1:1) and an immiscible, inert solvent such as 1-chlorobutane or methylene chloride at 0°-40°C for 1 to 24 hours. Sulfonyl chlorides of Formula XIc and XId can also be prepared from the bromothiophenes XIIIc and XIIId by the three-step sequence shown in Equation 18. Q is O, S, CH₂ or CHCH₃; R₁ is not SO₂CH₃, Br or NO₂. Equation 18 The compounds are contacted with 1.0 equivalents of n -BuLi at -78°C in a solvent such as THF to give a 3-lithio species via metal-halogen exchange. The lithio species is reacted with sulfur dioxide to give an intermediate sulfinate salt which precipitates and is isolated by filtration. The salt is dissolved in a solvent such as acetic acid and treated with a chlorine source such as N-chlorosuccinimide to give the desired sulfonyl chloride. The bicyclic heterocycles XIII, many of which are reported in the literature, can be prepared by standard methods known to one skilled in the art. The amines of Formula III in Equations 1 and 4 are also important intermediates for the preparation of the compounds of this invention and are described below. The pyrimidines and triazines of Formula (IIIa) to (IIId) below are either known or can be prepared by obvious methods known to one skilled in the art. For a review of the synthesis and reactions of 2-aminopyrimidines (IIIa, Z=CR') see The Chemistry of Heterocyclic Compounds , Vol. 16, John Wiley and Sons, New York (1962). For a review of the synthesis and reactions of 2-amino-s-triazines (IIIa, Z=N) see The Chemistry of Heterocyclic Compounds , Vol. 13, John Wiley, New York (1959), F. C. Schaefer, U.S. Patent 3,154,547 and F. C. Schaefer and K. R. Huffman. J. Org. Chem. , 28 , 1812 (1963). The synthesis of the bicyclic amines IIIb and IIIc is taught in European Patent Application 15,683. The synthesis of bicyclic amines IIId is taught in European Patent Application 46,677. The amines of Formula III where X is OCF₂H or CF₃; or X₁ is OCF₂H and/or Y is WCF₂T wherein W is O or S and T is H, CHClF, CHBrF or CHFCF₃ can be prepared by methods taught in South African Patent Application 82/5045, or by suitable modifications that would be obvious to one skilled in the art. The pyrimidines of Formula IIIa (Z=CH) where Y is -CR₅(OCH₃)₂,-CR₅(OCH₂CH₃)₂, can be prepared according to the methods taught in European Patent Application 84,224 or suitable modifications thereof known to one skilled in the art. The triazine amines of Formula IIIe where X₃ is CH₃ or OCH₃ and R is H or CH₃ can be prepared according to the methods of European Patent Application 94,260. Preparations of 3-amino-1,2,4-triazoles intermediates of Formula (IIIf) are described in European Patent Application 73,562. Many of the aminoheterocyclic intermediates of Formula (III) where R is methyl may be prepared by a two-step procedure as described for IIIg in Equation 19. X, Y and Z are as previously defined. Equation 19 A solution of the amine IIIa in concentrated hydrochloric acid is treated with sodium nitrite solution and the chloro compound X is isolated in the usual manner by filtration of the acidic solution. A representative procedure is described by Bee and Rose in J. Chem. Soc. C , 2031 (1966), for the case in which Z = CH, and X = Y = OCH₃. Displacement of the chlorine of X may be accomplished by heating with an excess of methylamine in water to obtain the methylamino heterocycle (IIIg). Agriculturally suitable salts of compounds of Formula I are also useful herbicides and can be prepared in a number of ways known to the art. For example, metal salts can be made by contacting compounds of Formula I with a solution of an alkali or alkaline earth metal salt having a sufficiently basic anion (e.g., hydroxide, alkoxide, carbonate or hydride). Quaternary amine salts can be made by similar techniques. Salts of compounds of Formula I can also be prepared by exchange of one cation for another. Cationic exchange can be effected by direct contacting of an aqueous solution of a salt of a compound of Formula I (e.g., alkali metal or quaternary amine salt) with a solution containing the cation to be exchanged. This method is most effective when the desired salt containing the exchanged cation is insoluble in water. e.g., a copper salt, and can be separated by filtration. Exchange may also be effected by passing an aqueous solution of a salt of a compound of Formula I (e.g., an alkali metal or quaternary amine salt) through a column packed with a cation exchange resin containing the cation to be exchanged. In this method, the cation of the resin is exchanged for that of the original salt and the desired product is eluted from the column. This method is particularly useful when the desired salt is water-soluble, e.g., a potassium, sodium or calcium salt. Acid addition salts, useful in this invention, can be obtained by reacting a compound of Formula I with a suitable acid, e.g., p -toluenesulfonic acid, trichloroacetic acid or the like. In the following examples, all parts are by weight and temperatures in °C unless otherwise indicated. "Nujol" is a Trade Mark. Example 1 3-Allylthio-4-bromothiophene 48,4 g (0.20 mol) of 3,4-dibromothiophene was added to a -78°C solution of 0.21 mol of n -butyllithium (130 mls of a 1.6 M solution in hexanes, Aldrich) in 200 mls of anhydrous ether under a nitrogen atmosphere at such a rate that the temperature did not rise above -70°C. The mixture was stirred at -78°C for 15 minutes and treated with 6.4 g (0.21 mol) of elemental sulfur causing the temperature to rise to -50°C. The suspension was recooled to -78°C, stirred for 1 hour, treated with 18.2 g (0.21 mol) of allyl bromide and allowed to warm to 20°C. The solution was washed with water and brine, dried over MgSO₄ and concentrated to give 47.5 g of an orange oil. 38 g of this oil was chromatographed on 500 g of SiO₂ eluting with hexane to give 30.2 g of the desired product as a colorless oil. 90 MHz NMR (CDCl₃): δ 7.4-7.1 (AB, 2H, arom); 6.2-5.6 (m, 1H, vinyl); 5.2-4.9 (m, 2H, vinyl); 3.45 (d, 2H, CH₂). IR (neat) 3100, 1630, 1470, 1320, 980, 930 cm⁻¹. Example 2 3-Bromo-6,7-dihydro-5H-thieno[3,2-b]thiopyran A solution of 30.2 g (0.13 mol) of 3-allylthio-4-bromothiophene and 10.3 mls (0.13 mol) of pyridine in 250 mls of toluene was refluxed for 68 hours, cooled, washed with 1 N HCl solution. 1 N NaOH solution, water and brine and dried over MgSO₄ and concentrated to give 27.2 g of an amber oil. The oil was chromatographed on 500 g of SiO₂ eluting with hexane to give 16.2 g of the desired product as a colorless oil (90% purity). 90 MHz NMR (CDCl₃): δ 7.15 (s, 1H, arom); 3.1-2.7 (m, 4H, CH₂'s); 2.3-2.0 (m, 2H, CH₂). IR (neat) 3100, 2920, 1510, 1310, 1110, 960, 900 cm⁻¹. Example 3 6,7-Dihydro-5H-thieno[3,2-b]thiopyran-3-sulfonamide A solution of 11.8 g (0.05 mol) of 3-bromo-6,7-dihydro-5H-thieno[3,2- b ]thiopyran in 50 mls of anhydrous ether was added dropwise to a solution of 0.055 mol of n -butyllithium (1.6 M in hexane) in 100 mls of anhydrous ether such that the temperature remained below -70°C. The solution was stirred for 15 minutes at -78°C, treated with 3.0 mls (0.07 mol) of liquified SO₂ (exotherm to -50°C), allowed to warm to 20°C and stirred for 16 hours. The resulting precipitate was filtered, washed with ether and hexane and dried to give 12.5 g of the sulfinate salt as a cream colored powder, m.p. >300°C. 9.7 g (0.043 mol) of this salt was dissolved in 80 mls of glacial acetic acid and treated with 5.7 g of N-chlorosuccinimide. After 5 minutes, the solution was poured into ice-water and the resulting precipitate was filtered, washed with water and hexane and dried to give 8.15 g of the sulfonyl chloride as a yellow powder, m.p. 80-87°C. The sulfonyl chloride was dissolved in 100 mls of methylene chloride and treated with 2.5 mls of liquified ammonia at -78°C. The mixture was warmed to 20°C, 100 mls of 1 N HCl was added and the methylene chloride phase was separated, washed with brine, dried over MgSO₄ and concentrated to give 6.2 g of the desired sulfonamide as a white powder, m.p. 146-149°C. 200 MHz NMR (CDCl₃): δ 7.9 (s, 1H, arom); 4.95 (b, 2H, NH₂); 3.10 (m, 2H, CH₂); 2.90 (t, 2H, CH₂); 2.30 (m, 2H, CH₂). IR (nujol) 3360, 3260, 3100, 1545, 1320, 1150, 960 cm⁻¹. Example 4 6,7-Dihydro-5H-thieno[3,2-b]thiopyran-3-sulfonamide, 4,4-dioxide A suspension of 9.0 4 (0.038 mol) of 6,7-dihydro-5H-thieno[3,2-b]thiopyran-3-sulfonamide in 200 mls of methylene chloride was treated with 2.0 equivalents of m -chloroperbenzoic acid at -5°C to 0°C. The mixture was stirred for 30 minutes at 0°C, 200 mls of saturated sodium bicarbonate solution was added and the methylene chloride layer and suspended solids were separated. The methylene chloride layer was concentrated and the combined solids were washed with water and ether and dried to give 7.8 g of the desired sulfonamide as a white powder, m.p. 213-215°C. 90 MHz NMR (CDCl₃): δ 8.2 (s, 1H, arom); 7.2 (b, 2H, NH₂); 3.7-2.2 (m, 6H, CH₂'s). IR (nujol) 3390, 3270, 3100, 1345, 1280, 1150, 1115 cm⁻¹. Example 5 N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-6,7-dihydro-5H-thieno[3,2-b]thiopyran-3-sulfonamide, 4,4-dioxide A mixture of 10.5 g (0.039 mol) of 6,7-dihydro-5H-thieno[3,2-b]thiopyran-3-sulfonamide-4,4-dioxide, 6.9 g of potassium carbonate and 5.3 ml of n -butyl isocyanate were refluxed in 300 mls of dry acetonitrile for 16 hours, cooled and filtered. The solid was dissolved in water, acidified to pH 3 with concentrated HCl and the resulting precipitate was filtered, washed with water and ether and dried in vacuo at 70°C to give 10.7 g of the n -butylurea as a cream colored solid, m.p. 193-195°C. A mixture of 10.2 g of the butylurea, 3.1 mls of butyl isocyanate and 0.1 g of DABCO were heated in 200 mls of dry xylenes and treated with 3.0 ml of liquified phosgene at such a rate that the temperature remained above 134°C. The mixture was refluxed for 1.5 hours, excess phosgene and HCl were purged with dry nitrogen and the mixture was cooled to 20°C. The resulting solid was filtered under nitrogen and washed with dry xylenes to give 7.0 g of the sulfonyl isocyanate as a light gray powder, m.p. 216-230°C, IR 2240 cm⁻¹. 1.4 g of the sulfonyl isocyanate was dissolved in 20 mls of dry methylene chloride and filtered to remove some insolubles. The filtrate was treated with 0.31 g of 2-amino-4,6-dimethoxypyrimidine, heated to reflux for 1 minute and allowed to stir at 20°C for 1.5 hours. The resulting precipitate was filtered, washed with dry methylene chloride and air dried to give 0.37 g of the desired sulfonylurea as a white powder, m.p. 228-230°C. 200 MHz NMR (CDCl₃): δ 12.57 (b, 1H, NH); 8.33 (s, 1H, arom); 7.20 (d, 1H, NH); 5.75 (s, 1H, CH); 3.97 (s, 6H, OCH₃'s); 3.40 (m, 2H, CH₂); 3.05 (m, 2H, CH₂); and 2.60 (m, 2H, CH₂). 1R (nujol) 3380, 1720, 1700, 1600, 1445, 1375, 1195, 1155 cm⁻¹. Following the procedures described in Examples 1-5, the following compounds can be prepared. Formulations Useful formulations of the compounds of Formula I can be prepared in conventional ways. They include dusts, granules, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates and the like. Many of these may be applied directly. Sprayable formulations can be extended in suitable media and used at spray volumes of from a few liters to several hundred liters per hectare. High strength compositions are primarily used as intermediates for further formulation. The formulations, broadly, contain for instance about 0.1% to 99% by weight of active ingredient(s) and at least one of (a) about 0.1% to 20% surfactant(s) and (b) about 1% to 99.9% solid or liquid inert diluent(s). More specifically, they will contain these ingredients in the following approximate proportions: Lower or higher levels of active ingredient can, of course, be present depending on the intended use and the physical properties of the compound. Higher ratios of surfactant to active ingredient are sometimes desirable, and are achieved by incorporation into the formulation or by tank mixing. Typical solid diluents are described in Watkins, et al., "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books, Caldwell, New Jersey, but other solids, either mined or manufacture, may be used. The more absorptive diluents are preferred for wettable powders and the denser ones for dusts. Typical liquid diluents and solvents are described in Marsden, "Solvents Guide," 2nd Ed., Interscience, New York, 1950. Solubility under 0.1% is preferred for suspension concentrates; solution concentrates are preferably stable against phase separation at 0°C. "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood, New Jersey, as well as Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foaming, caking, corrosion, microbiological growth, etc. The methods of making such compositions are well known. Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer or fluid energy mill. Suspensions are prepared by wet milling (see, for example, Littler, U.S. Patent 3,060,084). Granules and pellets may be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See J. E. Browning, "Agglomeration", Chemical Engineering , December 4, 1967, pp. 147ff. and "Perry's Chemical Engineer's Handbook", 5th Ed., McGraw-Hill, New York, 1973, pp. 8-57ff. In the following examples, all parts are by weight unless otherwise indicated. Example 6 The ingredients are blended, hammer-milled until all the solids are essentially under 50 microns, reblended, and packaged. Example 7 The ingredients are blended, coarsely hammer-milled and then air-milled to produce particles essentially all below 10 microns in diameter. The product is reblended before packaging. Example 8 A slurry of wettable powder containing 25% solids is sprayed on the surface of attapulgite granules while tumbling in a double-cone blender. The granules are dried and packaged. Example 9 The ingredients are blended, hammer-milled and then moistened with about 12% water. The mixture is extruded as cylinders about 3 mm diameter which are cut to produce pellets about 3 mm long. These may be used directly after drying, or the dried pellets may be crushed to pass a U.S.S. No. 20 sieve (0.84 mm openings). The granules held on a U.S.S. No. 40 sieve (0.42 mm openings) may be packaged for use and the fines recycled. Example 10 The ingredients are ground together in a sand mill until the solid particles have been reduced to under about 5 microns. The resulting thick suspension may be applied directly, but preferably after being extended with oils or emulsified in water. Example 11 The ingredients are thoroughly blended. After grinding in a hammer-mill to produce particles essentially all below 100 microns, the material is reblended and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) and packaged. Example 12 The active ingredient is dissolved in the solvent and the solution is sprayed upon dedusted granules in a double cone blender. After spraying of the solution has been completed, the blender is allowed to run for a short period and then the granules are packaged. Example 13 The ingredients are blended and ground together in a sand mill to produce particles essentially all under 5 microns in size. Example 14 The salt is added directly to the water with stirring to produce the solution, which may then be packaged for use. Example 15 The active ingredient is dissolved in a solvent and the solution is sprayed upon dedusted granules in a double-cone blender. After spraying of the solution has been completed, the material is warmed to evaporate the solvent. The material is allowed to cool and then packaged. Example 16 The ingredients are blended and milled to pass through a 100 mesh screen (149 microns). This material is then added to a fluid bed granulator, the air flow is adjusted to gently fluidize the material, and a fine spray of water is sprayed onto the fluidized material. The fluidization and spraying are continued until granules of the desired size range are made. The spraying is stopped, but fluidization is continued, optionally with heat, until the water content is reduced to the desired level, generally less than 1%. The material is then discharged, screened to the desired size range, generally 14-100 mesh (1410-149 microns), and packaged for use. Example 17 The ingredients are blended and ground in a hammer-mill to produce a material essentially all passing a U.S.S. No. 50 screen (0.3 mm opening). The concentrate may be formulated further if necessary. Example 18 The ingredients are blended and ground in a hammer-mill to produce particles essentially all below 100 microns. The material is sifted through a U.S.S. No. 50 screen (0.3mm opening) and then packaged. Example 19 The ingredients are thoroughly blended, coarsely hammer-milled and then air-milled to produce particles essentially all below 10 microns in size. The material is reblended and then packaged. Example 20 The ingredients are combined and ground together in a sand mill to produce particles essentially all below 5 microns. The product can be used directly, extended with oils, or emulsified in water. Example 21 The active ingredient is blended with attapulgite and then passed through a hammer-mill to produce particles substantially all below 200 microns. The ground concentrate is then blended with powdered pyrophyllite until homogeneous. Utility Test results indicate that the compounds of the present invention are active herbicides. They should have utility for broad-spectrum pre- and/or post-emergence weed control in areas where complete control of all vegetation is desired, such as around fuel storage tanks, ammunition depots, industrial storage areas, parking lots, drive-in theaters, around billboards, highway and railroad structures. Alternatively, many of the subject compounds should be useful for plant growth modification, such as growth retardation. For such use, an effective but substantially non-phytotoxin amount of the compound is applied. The rates of application for the compounds of the invention are determined by a number of factors, including their use as selective or general herbicides, the crop species involved, the types of weeds to be controlled, weather and climate, formulations selected, mode of application, amount of foliage present, etc. In general terms, the subject compounds should be applied at levels of around 50 to 1000 g/ha, the lower rates being suggested for use on lighter soils and/or those having a low organic matter content, for plant growth modification or for situations where only short-term persistence is required. The compounds of the invention may be used in combination with any other commercial herbicide examples of which are those of the triazine, triazole, uracil, urea, amide, diphenylether, carbamate and bipyridylium types. Combinations with mefluidide are useful as well. The herbicidal and plant growth modifying properties of the subject compounds were discovered in the greenhouse. The test procedures and results follow. Test A Seeds of crabgrass (Digitaria sp.), barnyardgrass ( Echinochloa crusgalli ), wild oats ( Avena fatua ), sicklepod ( Cassia obtusifolia ), morningglory ( Ipomoea sp.), cocklebur ( Xanthium pensylvanicum ), sorghum, corn, soybean, cotton, sugar beet, rice, wheat and purple nutsedge ( Cyperus rotundus ) tubers were planted in a growth medium and treated pre-emergence with the chemicals dissolved in a non-phytotoxic solvent. It will be noted in the data that in some instances velvetleaf (Abutilon theophrasti) has been substituted for sicklepod (Cassia obtusifolia) . At the same time, these crop and weed species were treated with a soil/foliage application. At the time of treatment, the plants ranged in height from 2 to 18 cm. Treated plants and controls were maintained in a greenhouse for sixteen days, after which all species were compared to controls and visually rated for response to treatment. The ratings, summarized in Table A, are based on a numerical scale extending from 0 = no injury, to 10 = complete kill. The accompanying descriptive symbols have the following meanings: C = chlorosis or necrosis; E = emergence inhibition; G = growth retardation; H = formative effect; and U = unusual pigmentation. It will be understood that treated plants sometimes exhibited more than one effect, in which case each effect was rated independently. Test B Post-emergence Two round pans (25 cm diameter by 12.5 cm deep) were filled with Woodstown sandy loam soil. One pan was planted with blackgrass ( Alopecurus myosuroides ), sugar beets, nutsedge ( Cyperus rotundus ) tubers, crabgrass ( Digitaria sanguinalis ), sicklepod ( Cassia obtusifolia ), teaweed ( Sida spinosa ), jimsonweed ( Datura stramonium ), velvetleaf ( Abutilon theophrasti ), and giant foxtail ( Setaria faberii ). The other pan was planted with wheat, cotton, rice, corn, soybean, wild oats ( Avena fatua ), cocklebur ( Xanthium pensylvanicum ), morningglory ( Ipomoea hederacea ), johnsongrass ( Sorghum halepense ) and barnyardgrass ( Echinochloa crusgalli ). The plants were grown for approximately fourteen days, then sprayed post-emergence with the chemicals dissolved in a non-phytotoxic solvent. Pre-emergence Two round pans (25 cm diameter by 12.5 cm deep) were filled with Woodstown sandy loam soil. One pan was planted with blackgrass ( Alopecurus myosuroides ), sugar beets, nutsedge, crabgrass, sicklepod, teaweed, jimsonweed, velvetleaf, and giant foxtail. The other pan was planted with wheat, cotton, rice, corn, soybean, wild oats, cocklebur, morningglory johnsongrass and barnyardgrass. The two pans were sprayed pre-emergence with the chemicals dissolved in a non-phytotoxic solvent. Treated plants and controls were maintained in the greenhouse for 28 days, then all treated plants were compared to controls and visually rated for plant response. Response ratings are based on a scale of 0 to 10: where 0 = no effect, and 10 = complete control. The type of response is indicated by letters where G = growth retardation and C = chlorosis and/or necrosis. Response ratings are contained in Table B.

Claims: A compound of the formula: wherein J is E is a bridge of 3 to 4 atoms, containing 0-2 heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen and also containing 1 to 4 atoms of carbon, said bridge together with the two carbon attachment sites forming a non-aromatic 5 to 6 membered carbocyclic ring, an aromatic 5 to 6 membered heterocyclic ring, or a non-aromatic 5 to 6 membered heterocyclic ring, with the proviso that two oxygen atoms must be separated by at least one atom of carbon and that oxygen and sulfur are only linked to each other if the sulfur is in the form of -SO- or -SO₂-; G is O, S or N-R; W is O or S; R is H or CH₃; R'₁ is H, CH₃ or Cl when G is S and is H when G is O or N-R; R₁is H, CH₃, OCH₃, Cl, Br, SCH₃, SO₂CH₃ or NO₂; and A is wherein X is H, C₁-C₄ alkyl, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, C₁-C₄ haloalkyl, C₁-C₄ haloalkylthio, C₁-C₄ alkythio, halogen, C₂-C₅ alkoxyalkoxy, amino, C₁-C₃ alkylamino or di(C₁-C₃ alkyl)amino; Y is H, C₁-C₄ alkyl, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, C₁-C₄ haloalkylthio, C₁-C₄ alkylthio, halogen, C₂-C₅ alkoxyalkyl, C₂-C₅ alkoxyalkoxy, amino, C₁-C₃ alkylamino di(C₁-C₃ alkyl)amino, C₃-C₄ alkenyloxy, C₃-C₄ alkylnyloxy, C₂-C₅ alkylthioalkyl, C₁-C₄ haloalkyl, C₃-C₅ cycloalkyl, C₂-C₄ alkynyl; or N(OCH₃)CH₃ ; W is O or S; m is 2 or 3; R a is H or CH₃; R b is C₁-C₂ alkyl; R c is C₁-C₂ alkyl; Z is CH, N, CCH₃, CC₂H₅, CCl or CBr; Y₁ is O or CH₂; X₁ is CH₃, OCH₃, OC₂H₅ or OCF₂H; X₂ is CH₃, C₂H₅ or CH₂CF₃; Y₂ is OCH₃, OC₂H₅, SCH₃, SC₂H₅, OCF₂H, SCF₂H, CH₃ or CH₂CH₃; X₃ is CH₃ or OCH₃; and Y₃ is H or CH₃; provided that a) when W is S, then R is H, A is A-1, Z is CH or N, and Y is CH₃, OCH₃, OC₂H₅, CH₂OCH₃, C₂H₅, CF₃, SCH₃, OCH₂CH=CH₂, OCH₂C≡CH, OCH₂CH₂OCH₃, CH(OCH₃)₂, OCH₂CF₃ or c) when X is Cl, F or Br, then Z is CH and Y is OCH₃, OC₂H₅, NH₂, NHCH₃ N(CH₃)₂ or OCF₂H; g) when X or Y is OCF₂H, then Z is CH; and their agriculturally suitable salts. A compound of the formula wherein J is R is H or CH₃; R₁' is H, CH₃ or Cl; R₁ is H, CH₃, OCH₃, Cl, Br, SCH₃, SO₂CH₃, or NO₂; R₂ is H, Cl or C₁-C₄ alkyl; R₃ is H, Cl or C₁-C₄ alkyl; R₄ is H or C₁-C₄ alkyl; R₅ is H or CH₃; R₆ is H, R₈, SR₈, SO₂R₈, OR₈, C(O)R₈, CO₂R₈, NR₈R₄, CN or Si(CH₃)₂R₉; R₇ is H, C₁-C₆ alkyl, Cl, Br, CN, NO₂, SR₉, SO₂R₉, CO₂R₉ or C(O)R₉; R₈ is C₁-C₆ alkyl, C₂-C₆ alkenyl, or C₂-C₆ alkynyl, each optionally substituted by one or more halogens and/or R₁₁, C₂-C₆ epoxyalkyl, C₃-C₆ cycloalkyl, C₄-C₇ cycloalkylalkyl, or R₉ is C₁-C₄ alkyl, R₁₀ is H, F, Cl, Br, CH₃, OCH₃, CN, NO₂, SCH₃, SO₂CH₃ or CF₃; R₁₁ is OR₁₂, OC(O)R₁₂, OC(O)NR₉R₁₂, OSO₂R₁₂, OSi(CH₃)₂R₉, Si(CH₃)₂R₉, SR₁₂, SOR₁₂, SO₂R₁₂, SCN, CN, NO₂, C(O)R₁₂, C(O)OR₁₂, C(O)NR₄R₁₂, or L; R₁₂ is H, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₃-C₆ cycloalkyl or n is 0 or 1; Q is O, S, SO, SO₂, CH₂ or CHCH₃: and L is a 5- or 6-membered aromatic heterocycle, a 5-or 6-membered dihydroaromatic heterocycle or a 5- or 6-membered tetrahydroaromatic heterocycle each containing 1-4 heteroatoms selected from the group consisting of 0-1 oxygen atoms, 0-1 sulfur atoms and 0-4 nitrogen atoms, also each optionally substituted with 1-4 CH₃, 1-2 OCH₃, 1 SCH₃, 1 Cl, 1 N(CH₃)₂ or 1 CN or L is a 5- or 6-membered lactone, lactam or cycloalkanone optionally substituted with 1-4 CH₃; G is O, S or NR; W is O or S; R₁, R'₁ and A are as defined in claim 1; said provisos a), c) and gl as defined in claim 1 apply; and provided further that b)the total number of carbon atoms in R₂ and R₃ is less than or equal to 4; d) when J is J₁ or J₂, then R₂ and R₃ are other than Cl; e) the total number of carbons atoms in R₄ and R₅ is less than or equal to 4; f) when J is J₅, J₆, J₇ or J₈ and n = O, then R₄ is H; and their agriculturally suitable salts. A compound of claim 2 wherein J is R is H or CH₃; R₁ is H, CH₃, OCH₃, Cl or Br; R₂ is H, Cl or C₁-C₄ alkyl; R₃ is H, Cl or C₁-C₄ alkyl; R₄ is H or C₁-C₄ alkyl; R₅ is H or CH₃; R₆ is H or C₁-C₄ alkyl; Q is O, S, SO, SO₂, CH₂ or CHCH₃; n is 0 or 1; A is X is CH₃, OCH₃, OCH₂CH₃, Cl, F, Br, CH₂F, OCF₂H or CF₃; Y is H, CH₃, OCH₃, OC₂H₅, CH₂OCH₃, NH₂, NHCH₃, N(CH₃)₂, C₂H₅, CF₃, SCH₃, OCH₂CH=CH₂, OCH₂C≡CH, OCH₂CF₃, CN, N₃, OCH₂CH₂OCH₃, CH₂SCH₃, CR a (WCH₃)₂, CR a (WCH₂CH₃)₂, or WCF₂T wherein W is O or S, R a is H or CH₃ and T is H, CHClF, CHBrF or CHFCF₃; Z is CH, N, CCH₃, CC₂H₅, CCl or CBr; Y₁ is O or CH₂; X₁ is CH₃, OCH₃, OC₂H₅ or OCF₂H; X₂ is CH₃, C₂H₅ or CH₂CF₃; Y₂ is OCH₃, OC₂H₅, SCH₃, SC₂H₅, CH₃ or CH₂CH₃; X₃ is CH₃ or OCH₃; and agriculturally suitable salts thereof. A compound of Claim 3 wherein R is H, W is O, and G is O or S. A compound of Claim 2 wherein R is H, W is is O and G is O or S. A compound of Claim 5 wherein A is A-1, X is CH₃, OCH₃, Cl, Br, OCH₂CF₃ or OCF₂H; Y is C₁-C₃ alkyl, cyclopropyl, C≡CH, OCH₃, OC₂H₅, CH₂OCH₃, NH₂, NHCH₃, N(CH₃)₂, C₂H₅, CF₃, SCH₃, OCH₂CH=CH₂, OCH₂C≡CH, OCH₂CH₂OCH₃, CR a (OCH₃)₂, CH a (OCH₂CH₃)₂ or OCF₂H; and Z is CH or N. A compound of Claim 6 wherein R₁ is H, Cl, Br or CH₃; R₂, R₃ and R₄ are H or C₁-C₃ alkyl; R₆ is H, R₈, C(O)R₈ or CO₂R₈; R₇ is Cl, Br, CO₂CH₃ or CO₂CH₂CH₃; R₈ is C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₃-C₆ cycloalkyl or C₄-C₇ cycloalkylalkyl and R₁₁ is OCH₃, OCH₂CH₃, CN, CO₂(C₁-C₄ alkyl), OH or C(O)CH₃. A compound of Claim 7 wherein G is S, Y is CH₃ or OCH₃ and X is CH₃, OCH₃, Cl, or Br. A compound of Claim 8 where J is J-1. A compound of Claim 8 where J is J-3. A compound of Claim 8 where J is J-5. A compound of Claim 8 where J is J-7. A compound of Claim 8 where J is J-9. A compound of Claim 8 where J is J-11. A compound of Claim 8 where J is J-13. The compound of Claim 1 which is N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-6,7-dihydro-5H-thieno-[3,2-B]thiopyran-3-sulfonamide, 4.4-dioxide. The compound of Claim 1 which is N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-6,7-dihydro-5H-thieno[3,2-B]thiopyran-3-sulfonamide, 4,4-dioxide. The compound of Claim 1 which is N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-5,6-dihydro-5-methylthieno[3,2-B]-thiophene-3-sulfonamide-4,4-dioxide. The compound of Claim 1 which is N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-5,6-dihydro-5-methylthieno[3,2-B]-thiophene-3-sulfonamide-4,4-dioxide. The compound of Claim 1 which is N-[(4-chloro-6-methoxypyrimidin-2-yl)aminocarbonyl]-5,6-dihydro-5-methylthieno[3,2-B]-thiophene-3-sulfonamide-4,4-dioxide. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of any of Claims 1 to 20 and at least one of the following: surfactant, solid or liquid diluent. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of any of Claims 1 to 20. A method for regulating the growth of plants which comprises applying to the locus of such plants an effective but substantially non-phytotoxic amount of a plant growth regulant selected from compounds of any of claims 1 to 20. A method for the preparation of a compound of claim 1 or 2 which comprises: (a) reacting an isocyanate or isothiocyanate of formula with an amine of formula wherein J, A and R are as defined in claim 1 or 2; (b) reacting a sulfonamide of formula with a heterocyclic isothiocyanate of formula wherein J and A are as defined in claim 1 or 2, to obtain a product wherein W is S and R is H; (c) reacting a sulfonamide of formula wherein J is as defined in claim 1 or 2, other than J₅, J₆, J₉ and J₁₀ as defined in claim 2, with a methylcarbamate of formula wherein R and A are as defined in claim 1 or 2; (d) reacting a sulfonylcarbamate of formula wherein J is as defined in claim 1, with said amine of formula III; (e) reacting a sulfonamide of formula wherein J is as defined in claim 1 or 2, with a phenylcarbamate of formula wherein L and A are as defined in claim 1 or 2; or (f) reacting a bicyclic heterocycle of formula with a sulfamoyl chloride of formula wherein J, A and R are as defined in claim 1 or 2. Claims for the following Contracting State : AT A process of the preparation of a compound of the formula: wherein J is E is a bridge of 3 to 4 atoms, containing 0-2 heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen and also containing 1 to 4 atoms of carbon, said bridge together with the two carbon attachment sites forming a non-aromatic 5 to 6 membered carbocyclic ring, an aromatic 5 to 6 membered heterocyclic ring, or a non-aromatic 5 to 6 membered heterocyclic ring, with the proviso that two oxygen atoms must be separated by at least one atom of carbon and that oxygen and sulfur are only linked to each other if the sulfur is in the form of -SO- or -SO₂-; G is O, S or N-R; W is O or S; R is H or CH₃; R'₁ is H, CH₃ or Cl when G is S and is H when G is O or N-R; R₁is H, CH₃, OCH₃, Cl, Br, SCH₃, SO₂CH₃ or NO₂; and A is wherein X is H, C₁-C₄ alkyl, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, C₁-C₄ haloalkyl, C₁-C₄ haloalkylthio, C₁-C₄ alkythio, halogen, C₂-C₅ alkoxyalkoxy, amino, C₁-C₃ alkylamino or di(C₁-C₃ alkyl)amino; Y is H, C₁-C₄ alkyl, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, C₁-C₄ haloalkylthio, C₁-C₄ alkylthio, halogen, C₂-C₅ alkoxyalkyl, C₂-C₅ alkoxyalkoxy, amino, C₁-C₃ alkylamino di(C₁-C₃ alkyl)amino, C₃-C₄ alkenyloxy, C₃-C₄ alkylnyloxy, C₂-C₅ alkylthioalkyl, C₁-C₄ haloalkyl, C₃-C₅ cycloalkyl, C₂-C₄ alkynyl; or N(OCH₃)CH₃ ; W is O or S; m is 2 of 3; R a is H or CH₃; R b is C₁-C₂ alkyl; R c is C₁-C₂ alkyl; Z is CH, N, CCH₃, CC₂H₅, CCl or CBr; Y₁ is O or CH₂; X₁ is CH₃, OCH₃, OC₂H₅ or OCF₂H; X₂ is CH₃, C₂H₅ or CH₂CF₃; Y₂ is OCH₃, OC₂H₅, SCH₃, SC₂H₅, OCF₂H, SCF₂H, CH₃ or CH₂CH₃; X₃ is CH₃ or OCH₃; and Y₃ is H or CH₃; provided that a) when W is S, then R is H, A is A-1, Z is CH or N, and Y is CH₃, OCH₃, OC₂H₅, CH₂OCH₃, C₂H₅, CF₃, SCH₃, OCH₂CH=CH₂, OCH₂C≡CH, OCH₂CH₂OCH₃, CH(OCH₃)₂, OCH₂CF₃ or c) when X is Cl, F or Br, then Z is CH; g) when X or Y is OCF₂H, then Z is CH; or an agriculturally suitable salt thereof; which comprises: (a) reacting an isocyanate or isothiocyanate of formula with an amine of formula wherein J, A and R are as defined above; (b) reacting a sulfonamide of formula with a heterocyclic isothiocyanate of formula wherein J and A are as defined above, to obtain a product wherein W is S and R is H; (c) reacting a sulfonamide of formula wherein J is as defined above, other than J₅ , J₆, J₉ and J₁₀ as defined in claim 2 hereinafter with a methylcarbamate of formula wherein R and A are as defined above; (d) reacting a sulfonylcarbamate of formula wherein J is as defined above, with said amine of formula III; (e) reacting a sulfonamide of formula wherein J is as defined above, with a phenylcarbamate of formula wherein L and A are as defined above; or (f) reacting a bicyclic heterocycle of formula with a sulfamoyl chloride of formula wherein J, A and R are as defined above. A process for the preparation of a compound of the formula: wherein J is R is H or CH₃; R₁' is H, CH₃ or Cl; R₁ is H, CH₃, OCH₃, Cl, Br, SCH₃, SO₂CH₃, or NO₂; R₂ is H, Cl or C₁-C₄ alkyl; R₃ is H, Cl or C₁-C₄ alkyl; R₄ is H or C₁-C₄ alkyl; R₅ is H or CH₃; R₆ is H, R₈, SR₈, SO₂R₈, OR₈, C(O)R₈, CO₂R₈, NR₈R₄, CN or Si(CH₃)₂R₉; R₇ is H, C₁-C₆ alkyl, Cl, Br, CN, NO₂, SR₉, SO₂R₉, CO₂R₉ or C(O)R₉; R₈ is C₁-C₆ alkyl, C₂-C₆ alkenyl, or C₂-C₆ alkynyl, each optionally substituted by one or more halogens and/or R₁₁, C₂-C₆ epoxyalkyl, C₃-C₆ cycloalkyl, C₄-C₇ cycloalkylalkyl, or R₉ is C₁-C₄ alkyl, R₁₀ is H, F, Cl, Br, CH₃, OCH₃, CN, NO₂, SCH₃, SO₂CH₃ or CF₃; R₁₁ is OR₁₂, OC(O)R₁₂, OC(O)NR₉R₁₂, OSO₂R₁₂, OSi(CH₃)₂R₉, Si(CH₃)₂R₉, SR₁₂, SOR₁₂, SO₂R₁₂, SCN, CN, NO₂, C(O)R₁₂, C(O)OR₁₂, C(O)NR₄R₁₂, or L; R₁₂ is H, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₃-C₆ cycloalkyl or n is 0 or 1; Q is O, S, SO, SO₂, CH₂ or CHCH₃: and L is a 5- or 6-membered aromatic heterocycle, a 5-or 6-membered dihydroaromatic heterocycle or a 5- or 6-membered tetrahydroaromatic heterocycle each containing 1-4 heteroatoms selected from the group consisting of 0-1 oxygen atoms, 0-1 sulfur atoms and 0-4 nitrogen atoms, also each optionally substituted with 1-4 CH₃, 1-2 OCH₃, 1 SCH₃, 1 Cl, 1 N(CH₃)₂ or 1 CN or L is a 5- or 6-membered lactone, lactam or cycloalkanone optionally substituted with 1-4 CH₃; G is O, S or NR; W is O or S; R₁, R'₁ and A are as defined in claim 1; said provisos a), c) and g) as defined in claim 1 apply; and provided further that b) the total number of carbon atoms in R₂ and R₃ is less than or equal to 4; d) when J is J₁ or J₂, then R₂ and R₃ are other than Cl; e) the total number of carbons atoms in R₄ and R₅ is less than or equal to 4; f) when J is J₅, J₆, J₇ or J₈ and n = O, then R₄ is H;. or an agriculturally suitable salt thereof; which comprises performing any of processes (a) to (f) as defined in claim 1, wherein J, R and A are as defined above, except that J is not J₅, J₆, J₉ or J₁₀ in process (c). A process of claim 2 wherein J is R is H or CH₃; R₁ is H, CH₃, OCH₃, Cl or Br; R₂ is H, Cl or C₁-C₄ alkyl; R₃ is H, Cl or C₁-C₄ alkyl; R₄ i s H or C₁-C₄ alkyl; R₅ is H or CH₃; R₆ is H or C₁-C₄ alkyl; Q is O, S, SO, SO₂, CH₂ or CHCH₃; n is 0 or 1; A is X is CH₃, OCH₃, OCH₂CH₃, Cl, F, Br, CH₂F, OCF₂H or CF₃; Y is H, CH₃, OCH₃, OC₂H₅, CH₂OCH₃, NH₂, NHCH₃, N(CH₃)₂, C₂H₅, CF₃, SCH₃, OCH₂CH=CH₂, OCH₂C≡CH, OCH₂CF₃, CN, N₃, OCH₂CH₂OCH₃, CH₂SCH₃, CR a (WCH₃)₂, CR a (WCH₂CH₃)₂, or WCF₂T wherein W is O or S, R a is H or CH₃ and T is H, CHClF, CHBrF or CHFCF₃; Z is CH, N, CCH₃, CC₂H₅, CCl or CBr; Y₁ is O or CH₂; X₁ is CH₃, OCH₃, OC₂H₅ or OCF₂H; X₂ is CH₃, C₂H₅ or CH₂CF₃; Y₂ is OCH₃, OC₂H₅, SCH₃, SC₂H₅, CH₃ or CH₂CH₃; X₃ is CH₃ or OCH₃; and agriculturally suitable salts thereof. A process of Claim 3 wherein R is H, W is O, and G is O or S. A process of Claim 2 wherein R is H, W is is O and G is O or S. A process of Claim 5 wherein A is A-1, X is CH₃, OCH₃ Cl, Br, OCH₂CF₃ or OCF₂H; Y is C₁-C₃ alkyl, cyclopropyl, C≡CH, OCH₃, OC₂H₅, CH₂OCH₃, NH₂, NHCH₃, N(CH₃)₂, C₂H₅, CF₃, SCH₃, OCH₂CH=CH₂, OCH₂C≡CH, OCH₂CH₂OCH₃, CR a (OCH₃)₂, CH a (OCH₂CH₃)₂ or OCF₂H; and Z is CH or N. A process of Claim 6 wherein R₁ is H, Cl, Br or CH₃; R₂, R₃ and R₄ are H or C₁-C₃ alkyl; R₆ is H, R₈, C(O)R₈ or CO₂R₈; R₇ is Cl, Br, CO₂CH₃ or CO₂CH₂CH₃; R₈ is C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₃-C₆ cycloalkyl or C₄-C₇ cycloalkylalkyl and R₁₁ is OCH₃, OCH₂CH₃, CN, CO₂(C₁-C₄ alkyl), OH or C(O)CH₃. A process of Claim 7 wherein G is S, Y is CH₃ or OCH₃ and X is CH₃, OCH₃, Cl, or Br. A process of claim 8 where J is selected from J-1, J-3, J-5, J-7, J-9, J-11 and J-13. A process of Claim 1 wherein the product is a compound selected from N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-6,7-dihydro-5H-thieno-[3,2-B]thioyran-3-sulfonamide, 4,4-dioxide; N-[(4,6-dimethoxypyrmidin-2-yl)aminocarbonyl]-6,7-dihydro-5H-thieno[3,2-B]thiopyran-3-sulfonamide, 4,4-dioxide; N-[4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-5,6-dihydro-5-methylthieno[3,2-B]-thiophene-3-sulfonamide-4,4-dioxide; N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-5,6-dihydro-5-methylthieno[3,2-B]-thiophene-3-sulfonamide-4,4-dioxide, and N-[(4-chloro-6-methoxy pyrimidin-2-yl) aminocarbonyl]-5, 6-dihydro-5-methylthieno[3,2-B]-thiophene-3-sulfonamide-4,4-dioxide. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of formula (I) as defined in any of Claims 1 to 10 and at least one of the following: surfactant, solid or liquid diluent. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of formula (I) as defined in any of Claims 1 to 10. A method of Claim 12 wherein a compound defined in Claim 10 is applied, or an agriculturally suitable salt thereof. A method for regulating the growth of plants which comprises applying to the locus of such plants an effective but substantially non-phytotoxic amount of a plant growth regulant selected from compounds of formula (I) as defined in any of Claims 1 to 10.

Inventors: PASTERIS, ROBERT JAMES
Applicants: E.I. DU PONT DE NEMOURS AND COMPANY
Application year: 1984
Main classification: C07D495
IPC codes: C07D333, C07D521, C07D495, A01N47