Protoporphyrinogen oxidase inhibitors

A method of preparing a compound of formula (III)

• or a salt thereof, wherein:
• X is CH or N;
• R1b is CH2C(O)C1-4alkyl or N(R1e)R1f;
• R1c is H, C1-4alkyl, C1-4alkenyl, C1-4alkynyl, C(O)C1-2alkyl, or OC1-4alkyl;
• R1f is H, C1-6alkyl, C(O)C(O)C1-4alkyl, C(O)R1g, or S(O)2R1g, or R1e and R1f together with the intervening nitrogen atom form a 5-6 membered ring, optionally containing up to two C(O) ring members;
• R19 is C1-4alkyl, C1-4alkenyl, phenyl, Het, N(Rh)2, OC1-4alkyl, C3-6cycloalkyl, or CH2(OCH2CH2)4CH3, wherein each alkyl group is optionally substituted with up to 3 F atoms, phenyl, C3-6cycloalkyl, OH, or OC1-4alkyl, wherein each cycloalkyl group is optionally substituted with OH or OC1-4alkyl, wherein each phenyl is optionally substituted with up to 3 Cl or F atoms, and wherein Het is a 5-6 membered heterocyclic ring containing up to two ring members selected from O, N, S, or S(O)2 and optionally substituted with OH or OC1-4alkyl;
• each Rh is, independently H, C1-4alkyl, benzyl, or phenyl;
• each of R2 and R3 is Cl or F;
• and
• each of R4, R5, and R6 is F or H, wherein Ring A comprises at least 4 F atoms, the method comprising:
• reacting a compound of Formula (a) with a compound of Formula (b), in the presence of a palladium catalyst, to produce a compound of Formula (c), wherein the compounds of Formula (a), Formula (b), and Formula (c) have the following structures:
• wherein R is an alkyl group and Hal is Br or I;
• reacting a compound of Formula (c) with sulfurochloridic acid to produce a compound of Formula (d) having the following structure:
• treating a compound of Formula (d) with ammonium hydroxide to produce a compound of Formula (g) having the following structure:
• and
• reacting a compound of Formula (g) with an alkylating, sulfonating, or acylating agent of Formula (h):
• R1b-L2 (h),
• wherein L2 is a halogen or an active ester leaving group;
• to produce a compound of formula (III).

A method of preparing a compound of formula (III)

• or a salt thereof, wherein:
• X is CH or N;
• R1b is CH2C(O)C1-4alkyl or N(R1e)R1f;
• R1e is H, C1-4alkyl, C1-4alkenyl, C1-4alkynyl, C(O)C1-2alkyl, or OC1-4alkyl;
• R1f is H, C1-6alkyl, C(O)C(O)C1-4alkyl, C(O)R11, or S(O)2R1g, or R1e and R1f together with the intervening nitrogen atom form a 5-6 membered ring, optionally containing up to two C(O) ring members;
• R11 is C1-4alkyl, C1-4alkenyl, phenyl, Het, N(Rh)2, OC1-4alkyl, C3-6cycloalkyl, or CH2(OCH2CH2)4CH3, wherein each alkyl group is optionally substituted with up to 3 F atoms, phenyl, C3-6cycloalkyl, OH, or OC1-4alkyl, wherein each cycloalkyl group is optionally substituted with OH or OC1-4alkyl, wherein each phenyl is optionally substituted with up to 3 Cl or F atoms, and wherein Het is a 5-6 membered heterocyclic ring containing up to two ring members selected from O, N, S, or S(O)2 and optionally substituted with OH or OC1-4alkyl;
• each Rh is, independently H, C1-4alkyl, benzyl, or phenyl;
• each of R2 and R3 is Cl or F;
• and
• each of R4, R5, and R6 is F or H, wherein Ring A comprises at least 4 F atoms, the method comprising:
• reacting a compound of Formula (i) with a compound of Formula (k), in the presence of a Cu(I) catalyst, to produce a compound of Formula (c), wherein the compounds of Formula (i), Formula (k), and Formula (c) have the following structures:
• wherein Hal is Br or I and M is sodium or potassium;
• reacting a compound of Formula (c) with sulfurochloridic acid to produce a compound of Formula (d) having the following structure:
• treating a compound of Formula (d) with ammonium hydroxide to produce a compound of Formula (g) having the following structure:
• and
• reacting a compound of Formula (g) with an alkylating, sulfonating, or acylating agent of formula (h):
• R1b-L2 (h),
• wherein L2 is a halogen or an active ester leaving group;
• to produce a compound of formula (III).

An herbicidal composition comprising:

• (i) a compound of formula (I)
• or a salt thereof, wherein
• X is CH or N;
• R1 is —SR1a or —S(O)2R1b;
• R1a is C1-4alkyl optionally substituted with phenyl, C(O)OR1c, or C(O)N(R1c);
• each R1c is, independently, H, CH2CH2OC(O)R1d, or optionally substituted C1-4alkyl, wherein the optional substituents are C3-6cycloalkyl, C(O)OC1-4alkyl, or up to 3 F atoms, or two R1c with an intervening nitrogen atom form a 5-6 membered ring optionally substituted with C(O)OH or C(O)OC1-4alkyl;
• R1d is C1-4alkyl or C1-4alkenyl;
• R1b is CH2C(O)C1-4alkyl or N(R1e)R1f;
• R1e is H, C1-4alkyl, C1-4alkenyl, C1-4alkynyl, C(O)C1-2alkyl, or OC1-4alkyl;
• R1f is H, C1-6alkyl, C(O)C(O)C1-4alkyl, C(O)R19, or S(O)2R1g, or R1e and R1f together with the intervening nitrogen atom form a 5-6 membered ring, optionally containing up to two C(O) ring members;
• R1g is C1-4alkyl, C1-4alkenyl, phenyl, Het, N(Rh)2, OC1-4alkyl, C3-6cycloalkyl, or CH2(OCH2CH2)4CH3, wherein each alkyl group is optionally substituted with up to 3 F atoms, phenyl, C3-6cycloalkyl, OH, or OC1-4alkyl, wherein each cycloalkyl group is optionally substituted with OH or OC1-4alkyl, wherein each phenyl is optionally substituted with up to 3 Cl or F atoms, and wherein Het is a 5-6 membered heterocyclic ring containing up to two ring members selected from O, N, S, or S(O)2 and optionally substituted with OH or OC1-4alkyl;
• each Rh is, independently H, C1-4alkyl, benzyl, or phenyl;
• each of R2 and R3 is Cl or F;
• and
• each of R4, R5, and R6 is F or H, wherein Ring A comprises at least 4 F atoms;
• and
• (ii) at least one compound selected from the group consisting of an herbicide compound of group B and a safener of group C;
• wherein,
• a weight ratio of the compound of formula (I) to the at least one compound selected from the group consisting of the herbicide compound of group B and the safener of group C is 1:0.1 to 1:50;
• wherein,
• the herbicide compound of group B is selected from the group consisting of acetolactate synthase inhibitors, acetyl-CoA carboxylase inhibitors, protoporphyrinogen IX oxidase inhibitors, 4-hydrophenylpyruvate dioxygenase inhibitors, phytoene desaturase inhibitors, photosystem II inhibitors, very long chain fatty acid synthesis inhibitors, microtubule formation inhibitors, auxin herbicides, enolpyruvylshikimate 3-phosphate synthase inhibitors, and glutamine synthase inhibitors, or an agriculturally acceptable salt or derivative of any of the foregoing;
• and
• the safener of group C is selected from the group consisting of benoxacor, cloquintocet, cyometrinil, cyprosulfamide, dichlormid, dicyclonone, dietholate, fenchlorazole, fenclorim, flurazole, fluxofenim, furilazole, isoxadifen, mefenpyr, mephenate, naphthalic anhydride, oxabetrinil, 4-(dichloroacetyl)-1-oxa-4-azaspiro[4.5]decane, 2,2,5-trimethyl-3-(dichloroacetyl)-1,3-oxazolidine, and N-(2-methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfon-amide.

A method for controlling weeds, the method comprising:

• applying a compound of formula (I) and at least one compound selected from the group consisting of an herbicide compound of group B and a safener of group C, simultaneously or sequentially, to a place where weeds are growing or will grow;
• wherein:
• the compound of formula (I) is of the following structure:
• or a salt thereof, wherein
• X is CH or N;
• R1 is —SR1a or —S(O)2R1b;
• R1a is C1-4alkyl optionally substituted with phenyl, C(O)OR1c, or C(O)N(R1c)2;
• each R1c is, independently, H, CH2CH2OC(O)R1d, or optionally substituted C1-4alkyl, wherein the optional substituents are C3-6cycloalkyl, C(O)OC1-4alkyl, or up to 3 F atoms, or two R1c with an intervening nitrogen atom form a 5-6 membered ring optionally substituted with C(O)OH or C(O)OC1-4alkyl;
• R1d is C1-4alkyl or C1-4alkenyl;
• R1b is CH2C(O)C1-4alkyl or N(R1e)R1f;
• R1e is H, C1-4alkyl, C1-4alkenyl, C1-4alkynyl, C(O)C1-2alkyl, or OC1-4alkyl;
• R1f is H, C1-6alkyl, C(O)C(O)C1-4alkyl, C(O)R1g, or S(O)2R1g, or R1e and R1f together with the intervening nitrogen atom form a 5-6 membered ring, optionally containing up to two C(O) ring members;
• R1g is C1-4alkyl, C1-4alkenyl, phenyl, Het, N(Rh)2, OC1-4alkyl, C3-6cycloalkyl, or CH2(OCH2CH2)4CH3, wherein each alkyl group is optionally substituted with up to 3 F atoms, phenyl, C3-6cycloalkyl, OH, or OC1-4alkyl, wherein each cycloalkyl group is optionally substituted with OH or OC1-4alkyl, wherein each phenyl is optionally substituted with up to 3 Cl or F atoms, and wherein Het is a 5-6 membered heterocyclic ring containing up to two ring members selected from O, N, S, or S(O)2 and optionally substituted with OH or OC1-4alkyl;
• each Rh is, independently H, C1-4alkyl, benzyl, or phenyl;
• each of R2 and R3 is Cl or F;
• and
• each of R4, R5, and R6 is F or H, wherein Ring A comprises at least 4 F atoms;
• the herbicide compound of group B is selected from the group consisting of acetolactate synthase inhibitors, acetyl-CoA carboxylase inhibitors, protoporphyrinogen IX oxidase inhibitors, 4-hydrophenylpyruvate dioxygenase inhibitors, phytoene desaturase inhibitors, photosystem II inhibitors, very long chain fatty acid synthesis inhibitors, microtubule formation inhibitors, auxin herbicides, enolpyruvylshikimate 3-phosphate synthase inhibitors, and glutamine synthase inhibitors, or an agriculturally acceptable salt or derivative of any of the foregoing;
• and
• the safener of group C is selected from the group consisting of benoxacor, cloquintocet, cyometrinil, cyprosulfamide, dichlormid, dicyclonone, dietholate, fenchlorazole, fenclorim, flurazole, fluxofenim, furilazole, isoxadifen, mefenpyr, mephenate, naphthalic anhydride, oxabetrinil, 4-(dichloroacetyl)-1-oxa-4-azaspiro[4.5]decane, 2,2,5-trimethyl-3-(dichloroacetyl)-1,3-oxazolidine, and N-(2-methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfon-amide.