Stable herbicidal compositions containing metal chelates of herbicidal dione compounds

• US 5,912,207 A
• Filed: 01/31/1997
• Issued: 06/15/1999
• Est. Priority Date: 01/31/1997
• Status: Expired due to Term

• Current Assignee: Syngenta Limited (China National Chemical Corporation)
• Original Assignee: Zeneca Incorporated (Astrazeneca PLC)
• Inventors: Chen, Jinling, Scher, Herbert B.
• Primary Examiner(s): CLARDY, S
• Application Number:
  US08/792,340
• Time in Patent Office: 865 Days
• Field of Search: 504/116, 504/190, 504/348, 544/64, 544/225, 546/2, 546/11, 548/402
• US Class Current: 504/190
• CPC Class Codes: A01N 2300/00 Combinations or mixtures of active ingredients covered by classes A01N27/00 - A01N65/48 with other active or formulation relevant ingredients, e.g. specific carrier materials or surfactants, covered by classes A01N25/00 - A01N65/48
• CPC Class Codes: A01N 35/06 containing keto or thioketo groups as part of a ring, e.g. cyclohexanone, quinone; Derivatives thereof, e.g. ketals
• CPC Class Codes: A01N 37/26 containing the group; Thio analogues thereof
• CPC Class Codes: A01N 41/10 Sulfones; Sulfoxides
• CPC Class Codes: A01N 59/16 Heavy metals; Compounds thereof
• CPC Class Codes: A01N 59/20 Copper
• CPC Class Codes: C07C 2601/14 The ring being saturated
• CPC Class Codes: C07C 311/21 having the nitrogen atom of at least one of the sulfonamide groups bound to a carbon atom of a six-membered aromatic ring

Abstract

Metal chelates of herbicidal dione compounds of the formula ##STR1## are chemically stable for long periods of time under normal as well as extreme temperature conditions. Chemically stable liquid herbicidal formulations containing metal chelates of the herbicidal compounds of formula (I) and water, an organic solvent or a liquid co-herbicide and processes for producing chemically stable herbicidal compositions containing such metal chelates are also described.

Claims

1. A chemically stable herbicidal composition comprising, in a liquid medium, a di- or trivalent transition metal chelate of an herbicidal dione of the formula (I):

##STR6## wherein R¹ represents a straight- or branched-chain alkyl, alkenyl or alkynyl group containing up to six carbon atoms which is optionally substituted by one or more halogen atoms;

a cycloalkyl group containing from three to six carbon atoms optionally substituted by one or more R³ groups or one or more groups selected from halogen, --CO₂ R⁴ ;

--SR⁵ and --OR⁵ ;

a cycloalkenyl group containing five or six carbon atoms optionally substituted by one or more R³ groups or one or more halogen atoms or a group --CO₂ R⁴ or a group of the formula --(CH₂)_p -phenyl-(R⁶)_q ;

R² represents cyano;

--COR⁷ ;

--CO₂ R⁷ ;

or --S(O)_m R⁸ ;

or

R¹ and R² together with the carbon atoms to which they are attached form a five- or six-membered 1,3-cycloalkanedione group, which 1,3-cycloalkanedione group is optionally substituted with from one to six substituents independently selected from halogen, (C₁ -C₆)alkyl, (C₁ -C₆)alkoxy, (C₁ -C₆)haloalkyl, (C₃ -C₆)cycloalkyl, cyano, nitro, (C₁ -C₆) haloalkoxy, --CO₂ R⁹, --S(O)_m R¹⁰, --NR¹¹ R¹², --C(O)R¹³, --SO₂ NR¹¹ R¹², phenyl and phenyl substituted with one or more halo or C₁ -C₄ alkyl groups, wherein two substituents on the same carbon atom of the 1,3-cycloalkanedione group taken together can form an alkylene group having 2 to 6 carbon atoms;

R³ represents a straight-or branched chain alkyl, alkenyl or alkynyl group containing up to six carbon atoms optionally substituted by one or more halogen atoms;

or a cycloalkyl group containing from three to six carbon atoms;

R⁴ represents a straight- or branched-chain alkyl group containing up to six carbon atoms optionally substituted by one or more halogen atoms;

or a cycloalkyl group containing from three to six carbon atoms;

R⁵ represents a straight- or branched-chain alkyl group containing up to three carbon atoms;

R⁶ represents a halogen atom or a group selected from --R⁴, nitro, cyano, --CO₂ R⁴, --NR⁶¹ R⁶² and --OR⁴ ;

R⁶¹ represents hydrogen, a straight- or branched-chain alkyl group containing up to six carbon atoms optionally substituted by one or more halogen atoms, or a cycloalkyl group containing from three to six carbon atoms;

R⁶² represents a straight- or branched-chain alkyl group containing up to six carbon atoms optionally substituted by one or more halogen atoms, a cycloalkyl group containing from three to six carbon atoms, or a group selected from --COR⁴, --CO₂ R⁴ and --CONR⁴ R⁶¹ ;

wherein R⁴ and R⁶¹ are part of a group --CONR⁴ R⁶¹ they may, together with the nitrogen to which they are attached, form a five- or six-membered ring optionally having one additional heteroatom in the ring which is oxygen or nitrogen, wherein the ring is optionally substituted by one or more alkyl groups containing up to three carbon atoms; and

when R⁶¹ and R⁶² are part of a group --NR⁶¹ R⁶² they may, together with the nitrogen to which they are attached, form a five- or six-membered ring optionally having one additional heteroatom in the ring which is oxygen or nitrogen, wherein the ring is optionally substituted by one or more alkyl groups containing up to three carbon atoms;

R⁷ represents hydrogen or straight- or branched-chain alkyl group containing up to six carbon atoms;

R⁸ represents (C₁ -C₆)alkyl, (C₁ -C₆)haloalkyl, (C₁ -C₆)cyanoalkyl (C₃ -C₈)cycloalkyl optionally substituted with halogen, cyano or (C₁ -C₄)alkyl;

or phenyl optionally substituted with one to three of the same or different halogen, nitro, cyano, (C₁ -C₄)haloalkyl, (C₁ -C₄ alkyl, (C₁ -C₄)alkoxy or --S(O)_m R⁸ ;

R⁹ represents (C₁ -C₄)alkyl;

R¹⁰ represents (C₁ -C₄)alkyl, (C₁ -C₄)alkyl substituted with halogen or cyano, phenyl or benzyl;

R¹¹ and R¹² independently represents hydrogen or (C₁ -C₄)alkoxy;

R¹³ represents (C₁ -C₄)alkyl or (C₁ -C₄)alkoxy;

X represents a halogen atom;

a straight- or branched-chain alkyl or alkoxy group containing up to six carbon atoms which is optionally substituted by one or more groups --OR¹⁵ or one or more halogen atoms;

or a group selected from nitro, cyano, --CO₂ R¹⁶, --S(O)_m R¹⁵, --O(CH₂)_r OR¹⁵, --COR¹⁶, --OSO₂ R¹⁸, --NR¹⁶ R¹⁷, --SO₂ NR¹⁶ R¹⁷, --CONR¹⁶ R¹⁷ and --CSNR¹⁶ R¹⁷ ;

R¹⁵ represents a straight- or branched-chain alkyl group containing up to six carbon atoms which is optionally substituted by one or more halogen atoms;

R¹⁶ and R¹⁷ each independently represents a hydrogen atom;

or a straight- or branched-chain alkyl group containing up to six carbon atoms which is optionally substituted by one or more halogen atoms;

R¹⁸ represents a straight- or branched-chain alkyl, alkenyl or alkynyl group containing up to six carbon atoms optionally substituted by one or more halogen atoms;

or a cycloalkyl group containing from three to six carbon atoms;

each Z independently represents halo, nitro, cyano, S(O)_m R², OS(O)_m R², (C₁ -C₆)alkyl, (C₁ -C₆)alkoxy, (C₁ -C₆)haloalkyl, (C₁ -C₆)haloalkoxy, carboxy, (C₁ -C₆)alkylcarbonyloxy, (C₁ -C₆)alkoxycarbonyl, (C₁ -C₆)alkylcarbonyl, amino, (C₁ -C₆)alkylamino, (C₁ -C₆)dialkylamino having independently the stated number of carbon atoms in each alkyl group, (C₁ -C₆)alkylcarbonylamino, (C₁ -C₆)alkoxycarbonylamino, (C₁ -C₆)alkylaminocarbonylamino, (C₁ -C₆)dialkylaminocarbonylamino having independently the stated number of carbon atoms in each alkyl group, (C₁ -C₆)alkoxycarbonyloxy, (C₁ -C₆)alkylaminocarbonyloxy, (C₁ -C₆)dialkylaminocarbonyloxy, phenylcarbonyl, substituted phenylcarbonyl, phenylcarbonyloxy, substituted phenylcarbonyloxy, phenylcarbonylamino, substituted phenylcarbonylamino, phenoxy or substituted phenoxy;

m is zero, one or two;

n is zero or an integer from one to four;

p is zero or one;

q is zero or an integer from one to five; and

r is one, two or three.

2. A chemically stable herbicidal composition according to claim 1, wherein said liquid medium is a member selected from the group consisting of water, organic solvents and liquid herbicides.

3. A chemically stable herbicidal composition according to claim 1, wherein the transition metal is selected from the group consisting of Cu⁺², Co⁺², Zn⁺² and Ni⁺².

4. A chemically stable herbicidal composition according to claim 1 having a pH of between about 2 and about 7.

5. A chemically stable herbicidal composition according to claim 1, wherein the molar ratio of the compound of formula (I) to the transition metal is between about 2:

1 and 2;

5.

6. A chemically stable herbicidal composition according to claim 1, further comprising at least one co-herbicide.

7. A chemically stable herbicidal composition according to claim 6, wherein said co-herbicide is selected from the group consisting of acetanilides, tralkoxydim, bromoxynil and its esters, thiafluamide, MCPA and its esters, 2,4-D and its esters, and fluroxypyr meptyl.

8. A chemically stable herbicidal composition according to claim 6, wherein said liquid medium is a co-herbicide.

9. A chemically stable herbicidal composition according to claim 6, wherein said liquid medium is water.

10. A chemically stable herbicidal composition according to claim 6, wherein said liquid medium comprises a microencapsulated co-herbicide dispersed in water.

11. A chemically stable herbicidal composition according to claim 1, wherein the herbicidal dione is of the formula:

##STR7## wherein X, Z and n have the same meanings as in claim 1;

each Q independently represents C₁ -C₄ alkyl or --CO₂ R^a wherein R^a is C₁ -C₄ alkyl; and

z is 0 or an integer from 1 to 6.

12. A chemically stable herbicidal composition according to claim 11, wherein z is zero;

X is chloro, bromo, nitro, cyano, C₁ -C₄ alkyl, --CF₃, --S(O)_m R¹⁵ or --OR¹⁵ ; and

n is one or two; and

each Z is independently chloro, bromo, nitro, cyano, C₁ -C₄ alkyl, --CF₃, --OR¹⁵, --OS(O)_m R² or --S(O)_m R².

13. A chemically stable herbicidal composition according to claim 11, wherein the herbicidal dione is a member selected from the group consisting of 2-(2'"'"'-nitro-4'"'"'-methylsulfonylbenzoyl)-1,3-cyclohexanedione, 2-(2'"'"'-nitro-4'"'"'-methylsulfonyloxybenzoyl)-1,3-cyclohexanedione and 2-(2'"'"'-chloro-4'"'"'-methylsulfonylbenzoyl)-1,3-cyclohexanedione.

14. A chemically stable herbicidal composition according to claim 1, wherein the herbicidal dione is of the formula:

##STR8## wherein;

R⁵⁰ is a straight- or branched-chain alkyl group containing up to six carbon atoms which is optionally substituted by one or more halogen atoms which may be the same or different;

or a cycloalkyl group containing from three to six carbon atoms which is optionally substituted by one or more groups selected from R⁵⁵ and one or more halogen atoms which may be the same or different;

one of R⁵¹ and R⁵³ is --S(O)_t R⁵⁶ and the other of R⁵¹ and R⁵³ is a halogen atom;

a straight- or branched-chain alkyl group containing up to six carbon atoms which is substituted by --OR⁵⁵ ;

--R⁵⁵ ;

nitro;

cyano;

--SR⁵⁵ ;

--OR⁵⁵ ;

--O(CH₂)_s OR⁵⁵ ;

or --CO₂ R⁵⁵ ; and

when R⁵¹ is --S(O)_t R⁵⁶, R⁵³ may be hydrogen;

R⁵² and R⁵⁴, which may be the same or different, each is a halogen atom;

a hydrogen atom;

a straight- or branched-chain alkyl group containing up to six carbon atoms which is substituted by --OR⁵⁵ ;

--R⁵⁵ ;

nitro;

cyano;

--OR⁵⁵ ;

--O(CH₂)_s OR⁵⁵ ;

or --CO₂ R⁵⁵ ;

R⁵⁵ and R⁵⁶, which may be the same or different, each is a straight- or branched-chain alkyl group containing up to six carbon atoms which is optionally substituted by one or more halogen atoms which may be the same or different;

s is an integer from 1 to 3; and

t is zero, 1 or 2.

15. A chemically stable herbicidal composition according to claim 14, wherein R⁵⁰ is a cycloalkyl group.

16. A chemically stable herbicidal composition according to claim 14, wherein the herbicidal dione is a member selected from the group consisting of 2-cyano-1- 2-chloro-3-ethoxy-4-(ethylsulfonyl)phenyl!-3-cyclopropylpropan-1,3-dione;

2-cyano-1- 4-chloro-2-(methylsulfonyl)phenyl!-3-cyclopropylpropan-1,3-dione;

2-cyano-1- 2-methylsulfonyl-4-(trifluoromethyl)phenyl!-3-cyclopropylpropan-1,3-dione; and

2-cyano-1- 4-bromo-2-(methylsulfonyl)phenyl!-3-cyclopropylpropan-1,3-dione

20. A process for producing a chemically stable composition of claim 1, comprising the steps of:

adding an herbicidal dione of formula (I) to a liquid medium to produce a first mixture;

adding an aqueous solution of a di- or trivalent transition metal salt to said first mixture, said metal salt solution being added in an amount sufficient to provide a stoichiometric excess of said metal relative to said herbicidal dione;

allowing said metal salt and said herbicidal dione to react for a period of time sufficient to convert all of said herbicidal dione to its corresponding metal chelate; and

then

adjusting the pH of the resulting composition to between about 2 and 7.

21. A process according to claim 20, wherein said liquid medium is water.

22. A process according to claim 21, wherein said liquid medium comprises a microencapsulated herbicide dispersed in water.

23. A process according to claim 20, wherein said herbicidal dione is solid and said process comprises the steps of:

milling said herbicidal dione;

adding an herbicidal dione of formula (I) to a liquid medium to produce a first mixture;

adding an aqueous solution of a di- or trivalent transition metal salt to said first mixture, said metal salt solution being added in an amount sufficient to provide a stoichiometric excess of said metal relative to said herbicidal dione;

allowing said metal salt and said herbicidal dione to react for a period of time sufficient to convert all of said herbicidal dione to its corresponding metal chelate; and

then

adjusting the pH of the resulting composition to between about 2 and 7.

24. A process according to claim 20, wherein said process comprises the steps of:

adding an herbicidal dione of formula (I) to a liquid medium to produce a first mixture;

adjusting the pH of said first mixture to about 10; and

then

adding an aqueous solution of a di- or trivalent transition metal salt to said first mixture, said metal salt solution being added in an amount sufficient to provide a stoichiometric excess of said metal relative to said herbicidal dione;

allowing said metal salt and said herbicidal dione to react for a period of time sufficient to convert all of said herbicidal dione to its corresponding metal chelate; and

then

adjusting the pH of the resulting composition to between about 2 and 7.

17. A dry, chemically stable herbicidal composition comprising a di- or trivalent transition metal chelate of an herbicidal dione of the formula (I):

##STR9## wherein R¹ represents a straight- or branched-chain alkyl, alkenyl or alkynyl group containing up to six carbon atoms which is optionally substituted by one or more halogen atoms;

a cycloalkyl group containing from three to six carbon atoms optionally substituted by one or more R³ groups or one or more groups selected from halogen, --CO₂ R⁴ ;

--SR⁵ and --OR⁵ ;

a cycloalkenyl group containing five or six carbon atoms optionally substituted by one or more R³ groups or one or more halogen atoms or a group --CO₂ R⁴ or a group of the formula --(CH₂)_p -phenyl-(R⁶)_q ;

R² represents cyano;

--COR⁷ ;

--CO₂ R⁷ ;

or --S(O)_m R⁸ ;

or

R¹ and R² together with the carbon atoms to which they are attached form a five- or six-membered 1,3-cycloalkanedione group, which 1,3-cycloalkanedione group is optionally substituted with from one to six substituents independently selected from halogen, (C₁ -C₆)alkyl, (C₁ -C₆)alkoxy, (C₁ -C₆)haloalkyl, (C₃ -C₆)cycloalkyl, cyano, nitro, (C₁ -C₆)haloalkoxy, --CO₂ R⁹, --S(O)_m R¹⁰, --NR¹¹ R¹², --C(O)R¹³, --SO₂ NR¹¹ R¹², phenyl and phenyl substituted with one or more halo or C₁ -C₄ alkyl groups, wherein two substituents on the same carbon atom of the 1,3-cycloalkanedione group taken together can form an alkylene group having 2 to 6 carbon atoms;

R³ represents a straight-or branched chain alkyl, alkenyl or alkynyl group containing up to six carbon atoms optionally substituted by one or more halogen atoms;

or a cycloalkyl group containing from three to six carbon atoms;

R⁴ represents a straight- or branched-chain alkyl group containing up to six carbon atoms optionally substituted by one or more halogen atoms;

or a cycloalkyl group containing from three to six carbon atoms;

R⁵ represents a straight- or branched-chain alkyl group containing up to three carbon atoms;

R⁶ represents a halogen atom or a group selected from --R⁴, nitro, cyano, --CO₂ R⁴, --NR⁶¹ R⁶² and --OR⁴ ;

R⁶¹ represents hydrogen, a straight- or branched-chain alkyl group containing up to six carbon atoms optionally substituted by one or more halogen atoms, or a cycloalkyl group containing from three to six carbon atoms;

R⁶² represents a straight- or branched-chain alkyl group containing up to six carbon atoms optionally substituted by one or more halogen atoms, a cycloalkyl group containing from three to six carbon atoms, or a group selected from --COR⁴, --CO₂ R⁴ and --CONR⁴ R⁶¹ ;

wherein R⁴ and R⁶¹ are part of a group --CONR⁴ R⁶¹ they may, together with the nitrogen to which they are attached, form a five- or six-membered ring optionally having one additional heteroatom in the ring which is oxygen or nitrogen, wherein the ring is optionally substituted by one or more alkyl groups containing up to three carbon atoms; and

when R⁶¹ and R⁶² are part of a group --NR⁶¹ R⁶² they may, together with the nitrogen to which they are attached, form a five- or six-membered ring optionally having one additional heteroatom in the ring which is oxygen or nitrogen, wherein the ring is optionally substituted by one or more alkyl groups containing up to three carbon atoms;

R⁷ represents hydrogen or straight- or branched-chain alkyl group containing up to six carbon atoms;

R⁸ represents (C₁ -C₆)alkyl, (C₁ -C₆)haloalkyl, (C₁ -C₆)cyanoalkyl (C₃ -C₈)cycloalkyl optionally substituted with halogen, cyano or (C₁ -C₄)alkyl;

or phenyl optionally substituted with one to three of the same or different halogen, nitro, cyano, (C₁ -C₄)haloalkyl, (C₁ -C₄ alkyl, (C₁ -C₄)alkoxy or --S(O)_m R⁸ ;

R⁹ represents (C₁ -C₄)alkyl;

R¹⁰ represents (C₁ -C₄)alkyl, (C₁ -C₄)alkyl substituted with halogen or cyano, phenyl or benzyl;

R¹¹ and R¹² independently represents hydrogen or (C₁ -C₄)alkoxy;

R¹³ represents (C₁ -C₄)alkyl or (C₁ -C₄)alkoxy;

X represents a halogen atom;

a straight- or branched-chain alkyl or alkoxy group containing up to six carbon atoms which is optionally substituted by one or more groups --OR¹⁵ or one or more halogen atoms;

or a group selected from nitro, cyano, --CO₂ R¹⁶, --S(O)_m R¹⁵, --O(CH₂)_r OR¹⁵, --COR¹⁶, --OSO₂ R¹⁸, --NR¹⁶ R¹⁷, --SO₂ NR¹⁶ R¹⁷, --CONR¹⁶ R¹⁷ and --CSNR¹⁶ R¹⁷ ;

R¹⁵ represents a straight- or branched-chain alkyl group containing up to six carbon atoms which is optionally substituted by one or more halogen atoms;

R¹⁶ and R¹⁷ each independently represents a hydrogen atom;

or a straight- or branched-chain alkyl group containing up to six carbon atoms which is optionally substituted by one or more halogen atoms;

R¹⁸ represents a straight- or branched-chain alkyl, alkenyl or alkynyl group containing up to six carbon atoms optionally substituted by one or more halogen atoms;

or a cycloalkyl group containing from three to six carbon atoms;

each Z independently represents halo, nitro, cyano, S(O)_m R², OS(O)_m R², (C₁ -C₆)alkyl, (C₁ -C₆)alkoxy, (C₁ -C₆)haloalkyl, (C₁ -C₆)haloalkoxy, carboxy, (C₁ -C₆)alkylcarbonyloxy, (C₁ -C₆)alkoxycarbonyl, (C₁ -C₆)alkylcarbonyl, amino, (C₁ -C₆)alkylamino, (C₁ -C₆)dialkylamino having independently the stated number of carbon atoms in each alkyl group, (C₁ -C₆)alkylcarbonylamino, (C₁ -C₆)alkoxycarbonylamino, (C₁ -C₆)alkylaminocarbonylamino, (C₁ -C₆)dialkylaminocarbonylamino having independently the stated number of carbon atoms in each alkyl group, (C₁ -C₆)alkoxycarbonyloxy, (C₁ -C₆)alkylaminocarbonyloxy, (C₁ -C₆)dialkylaminocarbonyloxy, phenylcarbonyl, substituted phenylcarbonyl, phenylcarbonyloxy, substituted phenylcarbonyloxy, phenylcarbonylamino, substituted phenylcarbonylamino, phenoxy or substituted phenoxy;

m is zero, one or two;

n is zero or an integer from one to four;

p is zero or one;

q is zero or an integer from one to five; and

r is one, two or three.

18. A dry, chemically stable herbicidal composition according to claim 17, further comprising at least one co-herbicide.

19. A dry, chemically stable herbicidal composition according to claim 18, wherein said co-herbicide is selected from the group consisting of acetanilides, tralkoxydim, bromoxynil and its esters, thiafluamide, MCPA and its esters, 2,4-D and its esters, and fluroxypyr meptyl.