Symbol of the Government of Canada


Patent Document Number: 2637695

(54) English Title: NOVEL COMPLEX FOR USE IN STABILIZING HERBICIDAL COMPOSITIONS AND METHODS FOR SYNTHESIZING AND USING THE SAME

(54) French Title: NOUVEAU COMPLEXE A UTILISER POUR STABILISER DES COMPOSITIONS HERBICIDES ET METHODES DE SYNTHESE ET D'UTILISATION DE CELUI-CI


Claims:

Note: Claims are shown in the official language in which they were submitted.



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WHAT IS CLAIMED IS:


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.



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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(0)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.



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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(in) N-tallow-1,3-
diamineopropane, ethoxylated(n) N-tallow-1,3- diaminopropane,
ethoxylated(n) N-tallow-1,3-diaminopropane,
C. N,N-bis[.alpha.-ethyl-.omega.-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-((o-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-(.omega.-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,



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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



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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:



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Image
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.



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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:

Image
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:


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a. a herbicidal compound capable of transesterification and subject to
relatively rapid hyrolysis 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:

Image
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


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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:

Image
whereupon said triethanolamine prevents an undesirable acid catalyzed
hydrolysis of fenoxaprop ethyl, fenoxaprop p-ethyl and said complex prevents
an
undesirable transesterification of said pyrasulfotole.

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:

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


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Image
comprising the steps of
a. combining pyrasulfotole, triethanolamine and
dodecylbenzenesulfontate calcium in a suitable stoichiometric
amount with an excess of triethanolamine to ensure close to neutral
or the slight basicity of the mixture;
b heating the combination to reflux or in a pressure bottle or reactor
the temperature from -20░C to 250 degree C in a solvent selected
from the group consisting of a non-proton donating or weak
proton-donating solvent such as but not limited to aromatic solvent
such as benzene, toluene, xylene, Aromatic 100, Aromatic 150, or
Aromatic 200 or mixtures there of; and other non-aromatic solvent
and non-proton-donating solvent such as an ether such as
tetrahydrofuran or a carbonate such as propylene carbonate and the
mixture solvents of above,
c. isolating by precipitation, crystallization and filtration a complex of
the formula:


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Image

d. washing said complex with a solvent; and
e. collecting the complex.

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]n M(+ 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.


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

48. A calcium-containing complex of the following x-ray structure
Image
wherein said complex has the intensity and breadth of herbicidal activity of
pyrasulfotole but exhibits better grass control compared with that of
pyrasulfotole
in control of grass such as yellow foxtail (Setaria glauca) and large
crabgrass
(Digitaria sanguinalis).

49. A complex of the following X-ray structure
Image
wherein said complex controllably delivers pyrasulfotole to a site of action.

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.


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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.


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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;


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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.


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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.

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.