Novel complex for use in stabilizing herbicidal compositions and merthods for synthesizing and using the same

• US 20120108424A1
• Filed: 07/11/2008
• Published: 05/03/2012
• Est. Priority Date: 12/06/2005
• Status: Active Grant

• Current Assignee: Bayer Cropscience AG (Bayer AG)
• Original Assignee: Bayer Cropscience LP (Bayer AG)
• Inventors: Wu, Tai-Teh, Eagles, Karen L., Edenfield, Michael W.
• Granted Patent: US 8,642,508 B2
• Time in Patent Office: Days
• US Class Current: 504/103
• 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 25/22 containing ingredients stabilising the active ingredients
• CPC Class Codes: A01N 33/12 Quaternary ammonium compounds
• CPC Class Codes: A01N 43/56 1,2-Diazoles; Hydrogenated 1,2-diazoles

Abstract

The present invention is directed to the discovery, isolation, identification and methods of synthesis of a novel chemical complex that can be used to stabilize mixtures of different chemical compounds, and in particular mixtures of different herbicidal compounds.

Claims

1. A novel complex comprising:

a. at least one conjugate base anion of a herbicidal compound; and

b. at least one amine-containing compound having at least one moiety capable of complexing; and

c. and, optionally, at least one cation;

wherein said anion, said amine-containing compound and said optional cation form a complex.

2. The complex of claim 1 wherein said anion is an anion of a pyrazole.

3. The complex of claim 2 wherein said pyrazole is pyrasulfotole.

4. The complex of claim 1 wherein said moiety capable of complexing includes hydrogen bonding between said amine-containing compound and said anion.

5. The complex of claim 1 wherein said amine-containing compound is one or more of the compounds selected from the group consisting of tertiary alkyl amines, secondary alkyl amines, and primary alkyl amines.

6. The complex of claim 5 wherein one or more of the alkyl moieties of the amine has from 1 to 50 carbons.

7. The complex of claim 5 wherein one or more of the alkyl moieties of the amine has from 1 to 10 carbons.

8. The complex of claim 5 wherein one or more of the alkyl moieties of the amine has from 2 to 6 carbons.

9. The complex of claim 5 wherein one or more of the alkyl moieties of the amine is selected from straight chained, branched, or cyclic alkyl moieties.

10. The complex of claim 5 wherein one or more of the alkyl moieties of the amine is, independent of one another, optionally substituted by one or more groups capable of complexing selected from the group consisting of ether groups, including alkoxy, hydroxyl groups, thiol groups, alkylthio, sulfenyl, alkylsulfenyl, sulfinyl, alkylsulfinyl, hydroxysulfonyl, hydroxysulfinyl hydroxysulfenyl, aminosulfonyl, aminosulfinyl aminosulfenyl, hydroxyamino, amido, alkylamido, hydroxycarbonyl, amino, alkylamino, dialkylamino, or combinations of these functional groups that include a carbon to carbon double bond (alkene) or carbon to carbon triple bond (alkyne).

11. The complex of claim 5 wherein one or more alkyl moieties of the alkyl amine may be hydroxylated, ethoxylated, diethoxylated, triethoxylated, or substituted with hydroxyethoxy or hydroxypropoxy groups wherein the number of ethoxy and propoxy groups may be from 1 to 60, provided they are capable of complexing.

12. The complex of claim 5 wherein the alkyl amine is of the formula:

N—

(R—

X)₃

where

R is an alkylene having from 1 to 50, preferably 1 to 10 and still more preferably 2 to 6 carbon atoms, and

X is —

OH, —

OR, —

NH₂, —

NHR, —

NR₂, —

SOR, or —

SO₂R, C(O)NH2, C═

OH, C═

NNH2 C(O)NHR, C(O)OH, C(O)OR with the proviso that at least one of X is —

OH, —

NH₂, NHR, S(O)2OH, S(O)2NH2. S(O)2NHR, NHNH2, NHOH, C(O)NH2, C(O)NHR, C(O)OH, C(O)OR, NROH, C═

NOH or C═

NNH2.

13. The complex of claim 1 wherein the amine-containing compound can be in the form of monoamine or diamine or polyamine.

14. The complex of claim 1 wherein said amine-containing compound is selected from the group consisting of:

a. tertiary amines such as triethanolamine, triisopropanolamine;

b. trialkylamines such as ethyldiethanolamine, N,N,N″

,N″

-tetrakis-(2-hydroxypropyl)ethylene diamine, hydroxylated or alkoxylated tallowalkyl-dimethylamine,

c. ethoxylated alkylamines such as ethoxylated(n) cocoalkylamine, ethoxylated (n) tallowalkylamine, ethoxylated (n) soyaalkylamine, ethoxylated cottonseed amine, oleyl amine ethoxylate, ethoxylated(n) octadecylamine, (ethoxy group numbers n may be from 1 to

     60),

d. ethoxylated diamines, such as ethoxylated(n) N-tallow-1,3-diamineopropane, ethoxylated(n) N-tallow-1,3-diaminopropane, ethoxylated(n) N-tallow-1,3-diaminopropane,

e. N,N-bis[α

-ethyl-ω

-hydroxypoly(oxyethylene)alkylamine;

where the poly(oxyethylene) content is average 3 moles;

the alkyl groups (C14-C18) are derived from tallow, or from soybean or cottonseed oil acids, or other crop or vegetable seeds oil acids;

f. N,N-bis(2-hydroxyethyl)alkylamine, where the alkyl groups (C8-C18) are derived from coconut, cottonseed, soya, or tallow acids or other crops or vegetable seed acids;

g. N,N-Bis 2-(ω

-hydroxypolyoxyethylene)ethyl)alkylamine;

h. the reaction product of 1 mole N,N-bis(2-hydroxyethyl)alkylamine and 3-60 moles of ethylene oxide, where the alkylgroup (C8-C18) is derived from coconut, cottonseed, soya, or tallow acids or other crop or vegetable seed acids;

i. N,N-Bis-2-(ω

-hydroxypolyoxyethylene/polyoxypropylene)ethyl alkylamine;

j. the reaction product of 1 mole of N,N-bis(2-hydroxyethyl alkylamine) and 3-60 moles of ethylene oxide and propylene oxide, where the alkyl group (C8-C18) is derived from coconut, cottonseed, soya, or tallow acids or other crop seeds or vegetable seeds acids;

k. N,N′

-Bis,(2-hydroxyethyl)-C12-C18 alkylamine, N,N′

-bis(polyoxyethylene)cetylamine, N,N′

-is(polyoxyethylene)oleylamine, N,N′

-bis(polyoxyethylene)stearylamine, N,N′

-dinitropentamethyl-enetetramine, ethoxylated abietylamine;

l. secondary amine such as ethylethanolamine;

m. primary amine such as ethanolamine, isopropanolamine,

n. polyoxyethylated primary amine (C14-C18);

the fatty amine is derived from an animal source and contains 3% water, the poly(oxyethylene) content average 20 moles,

o. amines, C14-C15 alkyl, ethoxylated, amines,

p. C16-C18 and C18 unsaturated, alkyl, ethoxylated amines, tallowalkyl, ethoxylated with polyethylene, triethylene tetramine, ethylendiamine, diethyleneamine, diethylenetriamine, N-oleyl-1,3-propanediamine, tetramethylene pentamine, polypropylene glycol bis(2-aminopropyl)ether, 2-[(2-aminoethyl)amino]ethanol, 2-amino-2-methyl-1-propanol; and

q. imines such as N,N′

-disalicylidene-1,2-diaminopropane and hydroxyl substituted.

15. The complex of claim 1 wherein said cation is a metal cation selected from the group consisting of a calcium cation, a magnesium cation, a copper cation, a manganese cation, a sodium cation, a potassium cation, a lithium cation, a iron cation (+2 or +3), a titanium cation, a zinc cation, an aluminum cation, a cobalt cation, a barium cation, a beryllium cation, a boron cation, a chromium cation, a silver cation and combinations thereof.

16. The complex of claim 1 wherein said cation is a non-metal cation selected from the group consisting of protonated amines such as protonated tertiary amines, protonated secondary amines, protonated primary amines, protonated hydroxyalkylamines such as protonated triethanolamine, and protonated triisopropanolamine.

17. The complex of claim 1 wherein said anion is a pyrasulfotole anion, SAID amine-containing compound is triethanolamine and said cation is a calcium cation.

18. The complex of claim 1 wherein said complex comprises two pyrasulfotole anions, a triethanolamine and a calcium cation.

19. The complex of claim 1 wherein said complex comprises two pyrasulfotole, a triethanolamine and two protonated triethanolamine.

20. The complex of claim 1 wherein said anion is capable of transesterification in the presence of an unstable ester in the absence of a weak acid buffer system.

21. The complex of claim 20 wherein said anion is a pyrasulfotole anion.

22. The complex of claim 1 wherein the complex is unsymmetrical.

23. The complex of claim 1 wherein the complex is optically active.

24. The complex of claim 1 wherein the complex is a racemic mixture.

25. A novel complex having the crystal structure of the formula:

26. A herbicidal composition comprising either by addition or by being formed in situ, a complex, said complex comprising at least one conjugate base anion of a herbicidal compound, at least one amine-containing compound having at least one moiety capable of complexing;

and optionally, at least one cation.

27. The herbicidal composition of claim 26 wherein said anion is a pyrazole anion, said amine-containing compound is an alkyl amine of the formula:

N—

(R—

X)₃

where

R is an alkylene having from 1 to 50, preferably 1 to 10 and still more preferably 2 to 6 carbon atoms, and

X is —

OH, —

OR, —

NH₂, —

NHR, —

NR₂, —

SOR, or —

SO₂R, S(O)2OH, S(O)2NH2, NHOH, NROH, C(O)NH2, C(O)OH, C(O)OR, S(O)OH with the proviso that at least one of X is —

OH, —

NH₂, or NHR,

and said cation is selected from the group consisting of a metal cation and a non-metal cation.

28. The herbicidal composition of claim 27 wherein said anion is a pyrasulfotole anion, said amine-containing compound is triethanolamine and said cation is a calcium cation.

29. The herbicidal composition of claim 27 wherein said complex comprises two pyrasulfotole anions, a triethanolamine and a calcium cation.

30. The herbicidal composition of claim 29 wherein said complex has the x-ray structure of formula:

31. The herbicidal composition of claim 26 further comprising fenoxaprop ethyl, fenoxaprop p-ethyl, bromoxynil, or bromoxynil esters, bromoxynil mixed esters such as bromoxynil mixed esters of heptanoate and octanoate and optionally, a safener.

32. The herbicidal composition of claim 31 wherein said safener is selected from the group consisting of mefenpyr, mefenpyr diethyl, isoxadifen, fenchlorazole, or cloquintocet.

33. The herbicidal composition of claim 31 further comprising fenoxaprop p-ethyl, bromoxynil bromoxynil esters, bromoxynil mixed esters such as bromoxynil mixed esters of heptanoate and octanoate and optionally, a safener.

34. The herbicidal composition of claim 33 wherein said safener is selected from the group consisting of mefenpyr, mefenpyr diethyl isoxadifen, fenchlorazole, cloquintocet and combinations thereof.

35. A novel complexing agent for use in stabilizing a herbicidal composition wherein said complexing agent is a reaction product of:

a. a herbicidal compound capable of transesterification and subject to relatively rapid hydrolysis of the esters in the absence of a weak acid buffer system; and

b. a weak acid buffer system.

36. The complexing agent of claim 35 wherein the herbicidal compound is pyrasulfotole and the weak acid buffer system comprises triethanolamine.

37. The complexing agent of claim 36 further comprising a cation.

38. The complexing agent of claim 37 wherein the cation is calcium cation.

39. The complexing agent of claim 38 having the crystal structure of the formula:

40. A method for preventing an undesirable acid catalyzed hydrolysis of fenoxaprop ethyl and/or fenoxaprop p-ethyl and an undesirable transesterification of pyrasulfotole in a herbicidal composition which includes fenoxaprop p-ethyl, pyrasulfotole, bromoxynil, bromoxynil esters, bromoxynil mixed esters such as bromoxynil mixed esters of heptanoate and octanoate and optionally mefenpyr or mefenpyr diethyl comprising:

a. providing a herbicidal composition comprising fenoxaprop p-ethyl, pyrasulfotole, bromoxynil, bromoxynil esters, bromoxynil mixed esters such as bromoxynil mixed esters of heptanoate and octanoate and optionally mefenpyr;

b. adding triethanolamine to said herbicidal composition;

c. forming a complex in said composition having the x-ray structure of the formula;

41. A stable herbicidal composition comprising fenoxaprop p-ethyl, pyrasulfotole, bromoxynil, bromoxynil esters, bromoxynil mixed esters such as bromoxynil mixed esters of heptanoate and octanoate and optionally mefenpyr diethyl and a complex having the x-ray structure of the formula:

42. A method of synthesizing a complex having the x-ray structure of the formula

43. The method of claim 42 wherein the washing solvent is selected from the group consisting of a ketone such as acetone and halogenated solvent such as methylene chloride or the mixture of them.

44. The method of claim 43 comprising the step of employing dodecylbenzensulfonate calcium as a calcium cation delivery agent and as a reaction facilitating agent that renders the reaction mixture homogeneous in the synthesis of the calcium containing complex.

45. A metal complex comprising:

a. an oil or non-oil soluble sulfonate cation of the formula

[R—

S(O)2O]nM(+n), where

M is metal cation such as Ca+2

R is alkyl, aryl which can be substituted with 1 or more alkyl groups at different positions of the aryl ring and the alkyl chain can be linear or branched and the alkyl chain length can be 1 to 30, preferably 8 to 24

n is 1 to 5.

46. The complex of claim 45 where n is 2.

47. The complex of claim 45 wherein said sulfonate cation is dodecylbenzene sulfonate calcium.

69. The complex of claim 45 wherein said sulfonate cation is selected from the group consisting of the calcium salt of Dodecylbenzene sulfonic acid, Undecylbenzene sulfonic acid, Tridecylbenzene sulfonic acid, Tetradecylbenzene sulfonic acid, Pentadecylbenzene sulfonic acid, Hexadecylbenzene sulfonic acid, Heptadecylbenzene sulfonic acid and combinations thereof.

48. A calcium-containing complex of the following x-ray structure

49. A complex of the following X-ray structure

50. The complex of claim 49 wherein said complex is stable in oil-based formulations such as an emulsifiable concentrate formulation and controllably releases said pyrasulfotole upon addition of water to said formulation.

51. A novel herbicidal composition comprising:

a. an acid-sensitive herbicide;

b. a weak acid herbicide;

c. an ester herbicide;

d. an optional safener, and

e. an optional cation donating agent;

wherein said herbicidal composition includes a complex, which complex prevents an acid catalyzed hydrolysis of said acid sensitive herbicide and prevents a transesterification of said weak acid herbicide.

52. The herbicidal composition of claim 51 wherein said cation donating agent is selected from the group consisting of a substituted aryl sulfonate, an alkyl sulfonate cation, a metal hydride, an inorganic salt, a moiety that functions in the manner of a cation donating agent and combinations thereof.

53. The composition of claim 52 wherein said substituted aryl sulfonate cation is dodecylbenzenesulfonate calcium, said metal hydride is calcium hydride, said inorganic salt is selected from the group consisting of NaCl, MgCl₂, CaCl₂, and CaSO₄, and said moiety that functions in the manner of a cation donating agent is selected from the group consisting of a protonated primary, secondary, tertiary amine or a quaternary amine.

54. The composition of claim 51 wherein said acid-sensitive herbicide is fenoxaprop p-ethyl, said weak acid herbicide is selected from the group consisting of a diketone, a triketone and a triketonyl oxime herbicide or keto enol conjugates thereof and combinations thereof, said ester herbicide includes a bromoxynil ester, said optional safener is mefenpyr diethyl, and said optional cation donating agent is dodecylbenzenesulfonate calcium.

55. The composition of claim 54 wherein said weak acid herbicide is selected from the group consisting of pyrasulfotole, isoxaflutole, clethodim and sethoxydim, conjugates thereof and combinations thereof.

56. The composition of claim 51 further comprising an acidic herbicidally active ingredient.

57. The composition of claim 56 wherein said acidic herbicidally active ingredient is selected from the group consisting of 4-chloro-2-methylphenoxy)-acetic acid (also known as mecaphar or MCPA), 2-(4-chloro-2-methylphenoxy)-propanoic acid (also known as mecoprop or MCPP), 4-(4-chloro-2-methylphenoxy)-butanoic acid (also known as MCPB), 2,4-D, dicamba and combinations thereof.

58. The composition of claim 51 wherein said composition is in a formulation selected from the group consisting of a suspension concentrate (SC), a suspoemulsion (SE), an emulsifiable concentrate (EC) and an oil dispersible (OD) formulation.

59. The composition of claim 51 wherein said composition is mixed with one or more compounds selected from the group consisting of fertilizers, fungicides, insecticides including miticides and nematicides, plant growth regulators, insect growth regulators and combinations thereof.

60. A method of controlling plants, including weeds, with a herbicidal composition comprising the step of applying the composition of claim 51 to a plant, to seeds or other propagation material of a plant, to a locus of said plant, to a locus where there is no plant but where prevention of the growth of said plant is desired, and combinations thereof.

61. A novel herbicidal composition comprising:

a. an acid-sensitive herbicide;

b. a weak acid herbicide;

c. an ester herbicide;

d. a buffer;

e. an optional safener, and

f. an optional cation donating agent;

wherein said herbicidal composition includes a complex, which complex prevents an acid catalyzed hydrolysis of said acid sensitive herbicide and prevents a transesterification of said weak acid herbicide.

62. The novel herbicidal composition of claim 61 wherein:

a. said acid sensitive herbicide is present in said composition in a range of about 1 wt % to about 15 wt %;

b. said weak acid herbicide is present in said composition in a range of about 0.5 wt. % to 8 wt. %;

c. said ester herbicide is present in said composition in a range of about 1 wt. % to 30 wt. %;

d. said buffer is present in said composition in a range of about 0.1 wt. % to 10 wt. %;

e. said optional safener is present in said composition in a range of about 0.5 wt. % to 10 wt. %; and

f. said optional cation donating agent is present in said composition in a range of about 0.1 wt % to about 20 wt %.

63. The composition of claim 61 or 62 wherein:

a. said acid-sensitive herbicide is fenoxaprop p-ethyl;

b. said weak acid herbicide is pyrasulfotole;

c. said ester herbicide includes one or more of bromoxynil and bromoxynil mixed esters;

d. said buffer includes triethanolamine;

e. said optional safener is mefenpyr diethyl;

f. said optional cation donating agent is dodecylbenzenesulfonate calcium.

64. The composition of claim 61 further comprising:

g. an acidic herbicidally active ingredient.

65. The composition of claim 64 wherein said acidic herbicidally active ingredient is selected from the group consisting of (4-chloro-2-methylphenoxy)-acetic acid (also known as mecaphar or MCPA), 2-(4-chloro-2-methylphenoxy)-propanoic acid (also known as mecoprop or MCPP), 4-(4-chloro-2-methylphenoxy)-butanoic acid (also, known as MCPB), 2,4-D, dicamba and combinations thereof.

66. The composition of claim 61 wherein said composition is in a formulation selected from the group consisting of a suspension concentrate (SC), a suspoemulsion (SE), an emulsifiable concentrate (EC) and an oil dispersible (OD) formulation.

67. The composition of claim 61 wherein said composition is mixed with one or more compounds selected from the group consisting of fertilizers, fungicides, insecticides including miticides and nematicides, plant growth regulators, insect growth regulators and combinations thereof.

68. A method of controlling plants, including weeds, with a herbicidal composition comprising the step of applying the composition of claim 61 to a plant, to seeds or other propagation material of a plant, to a locus of said plant, to a locus where there is no plant but where prevention of the growth of said plant is desired, and combinations thereof.