AROMATIC PHOSPHATE ESTERS AS AGROCHEMICAL
FORMULATION COMPONENT
This invention relates to the use of aromatic phosphate esters as adjuvants in
compositions, particularly for agrochemical use, as well to compositions comprising such
an aromatic phosphate ester, in combination with at least one agrochemical and
optionally at least one surfactant. The invention further extends to methods of making
and using such compositions. In particular the present invention relates to such
compositions when formulated as, or comprised by, an emulsion concentrate (EC).
The efficacy of the active ingredients (Als) in an agrochemical composition can
often be improved by the addition of further ingredients. The observed efficacy of the
combination of ingredients can sometimes be significantly higher than that which would
be expected from the individual ingredients used (synergism). An adjuvant is a
substance which can increase the biological activity of an Al but is itself not significantly
biologically active. The adjuvant is often a surfactant, and can be included in the
formulation or added separately, e.g. by being built into emulsion concentrate
formulations, or as tank mix additives.
In addition to the effect on biological activity, the physical properties of an
adjuvant are of key importance and must be selected with a view to compatibility with
the formulation concerned. For instance, it is generally simpler to incorporate a solid
adjuvant into a solid formulation such as a water-soluble or water-dispersible granule. In
general adjuvants rely on surfactant properties for biological activity enhancement and
one typical class of adjuvants involves an alkyl or aryl group to provide a lipophilic
moiety and a (poly)ethoxy chain to provide a hydrophilic moiety. Much has been
published on the selection of adjuvants for various purposes, such as Hess, F.D. and
Foy, C.L., Weed technology 2000, 14, 807-813.
The present invention is based on the discovery that aromatic phosphate esters
of formula (I)
O
1 3 R— O-P-O— R3
IO
R (I)
wherein
R is optionally substituted phenyl, R2 is optionally substituted phenyl and R3 is
C7-C20 alkyl, are surprisingly effective adjuvants, significantly enhancing the biological
activity of agrochemical active ingredients. Such aryl phosphate esters have in the past
typically found utility as flame retardant plasticizers, as well as anti-wear or extremepressure
additives in lubricants.
US2927014 discloses phosphonate and phospinate compounds for use as
herbicides. WO 93/04585 discloses alkyl phosphonate esters and alkyl phosphinates
esters for use as adjuvants in herbicidal compositions. WO 03/0999012 also discloses
specific alkyl phosphonates as well as aryl phosphonate esters generically for use as
adjuvants in insecticidal compositions. WO 98/00021 discloses the use of 2-ethylhexyl
phenyl tetradecylphosphinate and 2-ethylhexyl phenyl octadecyl phosphinate as
adjuvants for the fungicide fluquinconazole.
EP1 0 18299 and EP0579052 both describe the use of alkyl phosphate esters as
"accelerator adjuvants" for herbicidal compositions. WO 00/56146 describes the use of
organic esters of orthosphosphoric acid as surfactants/solvents suitable for stabilisation
and controlling crystallisation in liquid formulations of herbicides. WO 03/105588
discloses the use of inter alia organic, more specifically alkyl, phosphate esters as
adjuvants for metal chelates of mesotrione. US201 1/0098178 describes a liquid
herbicidal composition containing pinoxaden and an adjuvant, where the adjuvant is a
built-in adjuvant consisting of a triester of phosphoric acid with aliphatic or aromatic
alcohols and/or a bis-ester of alkyl phosphonic acids with aliphatic or aromatic alcohols.
US6,627,595 discloses the use as solvents in agrochemical formulations, of triesters of
phosphoric acid with various alcohols.
However, none of the above prior art specifically discloses the use of aryl
phosphate esters as dislosed herein as adjuvants, or more specifically as a bioefficacy
adjuvant, in agrochemical compositions.
Thus in a first aspect the present invention provides agrochemical composition
wherein the composition is an emulsion concentrate (EC), an emulsion in water (EW), a
microcapsule formulation (CS), dispersion concentrate (DC), suspension of particles in
an emulsion (SE), or a suspension of particles in oil (OD) comprising:
i . an agrochemical active ingredient;
ii. a surfactant;
iii. an aromatic phosphate ester of formula (I)
O
1 3 R— O-P-O— R3
IO
R (I)
wherein
R is optionally substituted phenyl, R2 is optionally substituted phenyl and R3 is
C7-C20 alkyl.
In a second aspect the invention provides a liquid agrochemical composition
comprising:
an agrochemical active ingredient;
a surfactant;
from about 0.05% to about 5% v/v of an aromatic phosphate ester
of formula (I)
O
1 3 R— O-P-O— R3
IO
R (I)
wherein R is optionally substituted phenyl, R2 is optionally substituted phenyl
and R3 is C7-C20 alkyl.
In a third aspect the invention provides for the use of an agrochemical
composition as described herein to control pests.
In a further aspect there is provided a method of controlling a pest, comprising
applying a composition of the invention to said pest or to the locus of said pest.
In yet a further aspect there is provided the use of an aromatic phosphate ester
of formula (I), as an adjuvant in an agrochemical composition comprising an
agrochemically active ingredient, for increasing the biological activity of said
agrochemically active ingredient.
In yet a further aspect there is provided a method of making an agrochemical
composition as described herein, comprising combining an active ingredient, a
surfactant and an aromatic ester of formula (I).
In yet a further aspect there is provided a method of treatment or prevention of a
fungal infection in a plant comprising applying a composition comprising
i . an fungicidal active ingredient;
a surfactant;
an aromatic phosphate ester of formula (I).
The term aromatic phosphate ester as used herein with reference to compounds
of formula (I) includes reference to individual isomers of specific compounds, isomeric
mixtures of specific compounds, and mixtures of more than one specific compound of
formula (I). Accordingly, compositions of the invention may comprise one or more
compound of formula (I) as defined herein.
Alkyl groups and moieties are straight or branched chains, and unless explicitly
stated to the contrary, are unsubstituted. Examples of suitable alkyl groups for use in
the invention include straight and branched-chain heptyl, octyl, nonyl, decyl, undecyl,
dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl
and eicosyl groups.
The term optionally substituted phenyl, preferably refers to a phenyl that
substituted with one, two or three groups, which may be the same or different.
Preferably each substitution is independently a Ci-C4 branched- or straight-chain alkyl
group. Preferences for individual substituents are stated below and may be combined
as desired unless otherwise stated.
R is optionally substituted phenyl, R2 is optionally substituted phenyl and R3 is
C7-C20 alkyl. In preferred embodiments R and/or R2 is phenyl and R3 is C8-Ci 0 alkyl and
more preferably R3 is 2-ethylhexyl or isodecyl.
The skilled person will appreciate that compounds of formula (I) may exist in
different isomeric forms and it is contemplated that the use of individual isomers as well
as mixtures thereof fall within the scope of the invention.
Preferred examples of specific compounds of formula (I), which may be used in
the invention include isodecyl diphenyl phosphate (CAS registry No. 29761-21-5,
available from Supresta, European Regional Sales Office, Hoefseweg 1, PO box 2501 ,
3800 GB Amersfoort, Netherlands, under the tradename Phosflex®390), 2-
ethylhexyldiphenyl phosphate (CAS registry No. 1241-94-7; available from Supresta,
supra, under the tradename Phosflex®362).
As stated previously, the present invention is based on the unexpected finding
that compounds of formula (I) are particularly good adjuvants, in particular in
agrochemical formulations. Accordingly, such adjuvants may be combined with an
active ingredient, which is an agrochemical, in order to form an agrochemical
composition. The present invention extends to such agrochemical compositions as well
as to a method of making such an agrochemical composition, wherein said method
comprises combining a compound of formula (I) with an agrochemical. The noun
"agrochemical" as used herein incorporates herbicides, insecticides, nematicides,
molluscicides, funcgicides, plant growth regulators, and safeners.
Suitable herbicides include bicyclopyrone, mesotrione, fomesafen, tralkoxydim,
napropamide, amitraz, propanil, pyrimethanil, dicloran, tecnazene, toclofos methyl,
flamprop M, 2,4-D, MCPA, mecoprop, clodinafop-propargyl, cyhalofop-butyl, diclofop
methyl, haloxyfop, quizalofop-P, indol-3-ylacetic acid, 1-naphthylacetic acid, isoxaben,
tebutam, chlorthal dimethyl, benomyl, benfuresate, dicamba, dichlobenil, benazolin,
triazoxide, fluazuron, teflubenzuron, phenmedipham, acetochlor, alachlor, metolachlor,
pretilachlor, thenylchlor, alloxydim, butroxydim, clethodim, cyclodim, sethoxydim,
tepraloxydim, pendimethalin, dinoterb, bifenox, oxyfluorfen, acifluorfen, fluoroglycofenethyl,
bromoxynil, ioxynil, imazamethabenz-methyl, imazapyr, imazaquin, imazethapyr,
imazapic, imazamox, flumioxazin, flumiclorac-pentyl, picloram, amodosulfuron,
chlorsulfuron, nicosulfuron, rimsulfuron, triasulfuron, triallate, pebulate, prosulfocarb,
molinate, atrazine, simazine, cyanazine, ametryn, prometryn, terbuthylazine, terbutryn,
sulcotrione, isoproturon, linuron, fenuron, chlorotoluron and metoxuron. The invention is
particularly suitable for application in combination with the herbicides employed in the
Examples described herein. Particularly preferred classes of herbicide are sulfonylurea
herbicides (especially nicosulfuron), nitrophenyl ether herbicides (especially fomesafen),
benzoylcyclohexanedione herbicides (especially mesotrione), and phenylpyrazole
herbicides (especially pinoxaden).
Suitable fungicides include isopyrazam, mandipropamid, azoxystrobin,
trifloxystrobin, kresoxim methyl, famoxadone, metominostrobin and picoxystrobin,
cyprodanil, carbendazim, thiabendazole, dimethomorph, vinclozolin, iprodione,
dithiocarbamate, imazalil, prochloraz, fluquinconazole, epoxiconazole, flutriafol,
azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, hexaconazole,
paclobutrazole, propiconazole, tebuconazole, triadimefon, trtiticonazole, fenpropimorph,
tridemorph, fenpropidin, mancozeb, metiram, chlorothalonil, thiram, ziram, captafol,
captan, folpet, fluazinam, flutolanil, carboxin, metalaxyl, bupirimate, ethirimol,
dimoxystrobin, fluoxastrobin, orysastrobin, metominostrobin and prothioconazole.
Particularly preferred classes of fungicides are pyrazole fungicides (especially
isopyrazam) and conazole fungicides (especially cyproconazole).
Suitable insecticides include thiamethoxam, imidacloprid, acetamiprid,
clothianidin, dinotefuran, nitenpyram, fipronil, abamectin, emamectin, bendiocarb,
carbaryl, fenoxycarb, isoprocarb, pirimicarb, propoxur, xylylcarb, asulam, chlorpropham,
endosulfan, heptachlor, tebufenozide, bensultap, diethofencarb, pirimiphos methyl,
aldicarb, methomyl, cyprmethrin, bioallethrin, deltamethrin, lambda cyhalothrin,
cyhalothrin, cyfluthrin, cyantraniliprole, fenvalerate, imiprothrin, permethrin and
halfenprox. The avermectin class of insecticides is particularly preferred. The invention
is particularly suitable for application in combination with the following insecticides:
abamectin, cyantraniliprole, and thiomethoxam, 2-ethylhexyldiphenyl phosphate is a
particularly effective adjuvant for these three insecticides.
Suitable plant growth regulators include paclobutrazole and 1-
methylcyclopropene.
Suitable safeners include benoxacor, cloquintocet-mexyl, cyometrinil, dichlormid,
fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, mefenpyr-diethyl, MG-191 ,
naphthalic anhydride, oxabetrinil and N-(2-methoxybenzoyl)-4-[(methylaminocarbonyl)
amino]benzenesulfonamide.
Of course, the various editions of The Pesticide Manual [especially the 14th and
15th editions] also disclose details of agrochemicals, any one of which may suitably be
used with the present invention.
The skilled person will appreciate that compositions of the invention may
comprise one or more of the agrochemicals as described above.
The skilled person will appreciate that compositions of the invention may be in
the form of a ready-to-use formulation (e.g. as a water-based formulation suitable for
spray application) or in concentrate form suitable for further dilution by the end user, and
the concentration of agrochemical and compound of formula (I) will be adjusted
accordingly. Compounds of formula (I) may be manufactured and/or formulated
separately, and in order to be used as an adjuvant these may be added to a separate
agrochemical formulation at a subsequent stage, typically immediately prior to use.
Compositions of the invention will typically comprise the agrochemical in an
amount that is recommended in the art. Generally the agrochemical will be present at a
concentration of about 0.001% to 90% w/v. The skilled man will appreciate that
compositions of the invention may be in the form of a ready-to-use formulation or in
concentrate form suitable for further dilution by the end user, and the concentration of
agrochemical and compound of formula (I) will be adjusted accordingly. In concentrated
form, compositions of the invention typically comprise agrochemical at 5 to 75% w/v,
more preferably 10 to 50% w/v agrochemical. Ready-to-use compositions of the
invention will typically comprise from 0.0001% to 1% w/v, more preferably from 0.001%
to 0.5% w/v, and more preferably still from 0.001% to 0.1% w/v agrochemical.
Typically a compound of formula (I) will comprise from about 0.0005% to about
90% v/v of the total composition. When in concentrated form, compositions of the
invention typically comprise a compound of formula (I) from 1% to 80% v/v, preferably
from 5% to 60% v/v and more preferably from 10% v/v to 40% v/v. Ready to use
compositions of the invention typically comprise a compound of formula (I) from about
0.05% to about 5% v/v of the total composition, preferably from about 0.05% to 2% v/v
of the total composition, more preferably from about 0.1% to about 1% v/v of the total
composition, and more preferably still from about 0.1% to about 0.5% v/v of the total
composition. In specific embodiments the aromatic ester will be included at
concentrations of 0.05%, 0.1%, 0.2%, 0.25%, 0.3%, 0.4% or 0.5% v/v of the total
composition. Compounds of formula (I) may be manufactured and/or formulated
separately, and in order to be used as an adjuvant these may be added to a separate
agrochemical formulation at a subsequent stage, typically immediately prior to use.
Compositions of the invention may be formulated in any suitable manner known
to the man skilled in the art. As mentioned above, in one form a composition of the
invention is a formulation concentrate which may be diluted or dispersed (typically in
water) by an end-user (typically a farmer) in a spray tank prior to application.
Additional formulation components may be incorporated alongside compounds of
formula (I) or compositions of the invention in such formulations. Such additional
components include, for example, adjuvants, surfactants, emulsifiers, and solvents, and
are well known to the man skilled in the art: standard formulation publications disclose
such formulation components suitable for use with the present invention (for example,
Chemistry and Technology of Agrochemical Formulations, Ed. Alan Knowles, published
by Kluwer Academic Publishers, The Netherlands in 1998; and Adjuvants and Additives:
2006 Edition by Alan Knowles, Agrow Report DS256, published by Informa UK Ltd,
December 2006). Further standard formulation components suitable for use with the
present invention are disclosed in WO2009/1 30281 A 1 (see from page 46, line 5 to page
5 1, line 40).
Thus, compositions of the present invention may also comprise one or more
surfactants or dispersing agents to assist the emulsification of the agrochemical on
dispersion or dilution in an aqueous medium (dispersant system). The emulsification
system is present primarily to assist in maintaining the emulsified agrochemical in water.
Many individual emulsifiers, surfactants and mixtures thereof suitable for forming an
emulsion system for an agrochemical are known to those skilled in the art and a very
wide range of choices is available. Typical surfactants that may be used to form an
emulsifier system include those containing ethylene oxide, propylene oxide or ethylene
oxide and propylene oxide; aryl or alkylaryl sulphonates and combinations of these with
either ethylene oxide or propylene oxide or both; carboxylates and combinations of
these with either ethylene oxide or propylene oxide or both. Polymers and copolymers
are also commonly used. Preferred surfactants are polyvinyl alcohols and ethylene
glycol-propylene glycol block copolymers, and combinations thereof.
Compositions of the present invention may also include solvents, which may
have a range of water solubilitites. Oils with very low water solubilities may be added to
the solvent of the present invention for assorted reasons such as the provision of scent,
safening, cost reduction, improvement of the emulsification properties and alteration of
the solubilising power. Solvents with higher water solubility may also be added for
various reasons, for instance to alter the ease with which the formulation emulsifies in
water, to improve the solubility of the pesticide or of the other optional additives in the
formulation, to change the viscosity of the formulation or to add a commercial benefit.
Other optional ingredients which may be added to the formulation include for
example, colourants, scents, and other materials which benefit a typical agrochemical
formulation.
Compositions of the invention may formulated for example, as emulsion or
dispersion concentrates, emulsions in water or oil, as microencapsulated formulations,
aerosol sprays or fogging formulations; and these may be further formulated into
granular materials or powders, for example for dry application or as water-dispersible
formulations. Preferably compositions of the invention will be formulated as, or
comprised by an emulsion concentrate (EC), an emulsion in water (EW), a microcapsule
formulation (CS), a suspension of particles with an emulsion of (suspoemulsion; SE), a
dispersion concentrate (DC) or an oil suspension (OD).
Compositions of the invention may be used to control pests. The term "pest" as
used herein includes insects, fungi, molluscs, nematodes, and unwanted plants. Thus,
in order to control a pest a composition of the invention may be applied directly to the
pest, or to the locus of a pest.
Compositions of the invention also have utility in the seed treatment arena, and
thus may be applied as appropriate to seeds.
The skilled man will appreciate that the preferences described above with
respect to various aspects and embodiments of the invention may be combined in
whatever way is deemed appropriate.
Various aspects and embodiments of the present invention will now be illustrated
in more detail by way of example. It will be appreciated that modification of detail may
be made without departing from the scope of the invention.
EXAMPLES
Unless otherwise stated within a specific Example, all aromatic phosphate esters
employed were initially formulated as 20% w'w emulsions containing 2% w/w
Gohsenol®GL03 (a polyvinyl alcohol, Nippon Gohsei, Hull, UK) and 2% Pluronic®
PE10500 (an ethylene glycol-propylene glycol block copolymer BASF Aktiengesellschaft,
Ludwighsafen, Germany) as surfactants.
Example 1 Use of aromatic phosphate esters as adjuvants in agrochemical
compositions of isopyrazam
The efficacy of the following aromatic phosphate esters, tricresyl phosphate and
Phosflex®362 (2-ethylhexyl diphenyl phosphate) as adjuvants in compositions
comprising isopyrazam was tested and compared to the standard formulations (both EC
and SC) of the fungicide, which lack this type of adjuvant, as well as to the efficacy of
tris-(2-ethylhexyl)phosphate as an adjuvant.
Wheat plants were inoculated with the fungus Septoria tritici. Five days after
inoculation the plants were sprayed with a diluted emulsion concentrate or suspension
concentrate formulation of the fungicide isopyrazam at rates of 3, 10, 30 and 100 mg of
the fungicide per litre of spray solution, using a laboratory track sprayer which delivered
the spray at a rate of 200 litres per hectare. Spray tests were also carried out with
diluted suspension concentrate additionally comprising each of the adjuvants described
above. These adjuvants were added to the spray solution at a rate of 0.2 % v/v, based
on the quantity of spray liquor. The leaves of the plants were assessed visually 14 days
after the spray application and the damage was expressed as the percentage of the leaf
area infected. Each spray test was replicated three times across the four application
rates and the modelled means of these results are shown in Table 1 below.
Table 1 Mean % infection of wheat plants with S. tritici treated with isopyrazam in the presence and absence
of phosphate ester adjuvants. A standard Tukey HSD test was carried out to assess whether each result
was statistically different from the other results and this is expressed as a letter: tests with the same letter
are not statistically different (p<0.05).
Treatment Mean % Infection
Blank 22.2 A
Standard Isopyrazam SC 10.8 B
Standard Isopyrazam SC + Tricresyl phosphate 11.3 B
Standard Isopyrazam SC + Tris-(2ethyl-hexyl)phsophate 11.1 B
Standard Isopyrazam SC + Phosflex®362 4.8 C
Standard Isopyrazam EC 8.6 B
As can be seen from Table 1 the aromatic phosphate ester adjuvants were as
efficacious as the standard suspension concentrate and emulsion concentrate
formulations of izopyrazam. Furthermore, Phosflex® 362 was more efficacious as an
adjuvant than any of the other compounds tested.
Example 2 Use of aromatic phosphate esters as adjuvants in agrochemical
compositions of cyproconazole
The efficacy of tricresyl phosphate and Phosflex®362 (2-ethylhexyl diphenyl
phosphate) as adjuvants in compositions comprising cyproconazole was tested and
compared to the standard SC formulation of the fungicide, which lacks this type of
adjuvant, as well as to the efficacy of tris-(2-ethylhexyl)phosphate as an adjuvant.
As in Example 1, wheat plants were inoculated with the fungus Septoria tritici.
Five days after inoculation the plants were sprayed with a diluted suspension
concentrate formulation of the fungicide cyproconazole at rates of 3, 10, 30 and 100 mg
of the fungicide per litre of spray solution, using a laboratory track sprayer which
delivered the spray at a rate of 200 litres per hectare. Spray tests were also carried out
with diluted suspension concentrate additionally comprising each of the phosphate ester
adjuvants described above. These adjuvants were added to the spray solution at a rate
of 0.2 % v/v, based on the quantity of spray liquor. The leaves of the plants were
assessed visually 14 days after the spray application and the damage was expressed as
the percentage of the leaf area infected. Each spray test was replicated three times
across the four application rates and the modelled means of these results are shown in
Table 2 below.
Table2 Mean % infection of wheat plants with S. tritici treated with cyproconazole in the presence and
absence of phosphate ester adjuvants. A standard Tukey HSD test was carried out to assess whether
each result was statistically different from the other results and this is expressed as a letter: tests with the
same letter are not statistically different (p<0.05).
Treatment Mean % Infection
Blank 23. 1 A
Standard cyproconazole SC 9 .1 B
Standard cyproconazole SC + Tricresylphosphate 7.4 B
Standard cyproconazole SC + Tris(2-ethylhexyl)phosphate 3.8 C
Standard cyproconazole SC + Phosflex®362
As can be seen from Table 2 the aromatic phosphate ester adjuvants were as
efficacious as the standard suspension concentrate formulation of cyproconazole, and
again, Phosflex®362 performed best as an adjuvant out of the compounds tested.
Example 3 Use of aromatic phosphate esters as adjuvants in agrochemical
compositions of nicosulfuron
The efficacy of the aromatic phosphate esters tricresyl phosphate, Phosflex®362
(2-ethylhexyl diphenyl phosphate) and triphenyl phosphate were tested in a glasshouse
against four weed species using the herbicide nicosulfuron. An agrochemical
composition was prepared containing 0.5 % v/v of the adjuvant Atplus® 4 11F in a track
sprayer, and was applied at a volume of 200 litres per hectare. The other adjuvants
were tested at a arte of 0.2 % v/v. Nicosulfuron was applied at a rate of either 30 or 60
grams of pesticide per hectare to weeds which had been grown to the 1.3 or 1.4 leaf
stage. The weed species were Chenopodium album (CH EAL), Abutilon theophrasti
(ABUTH), Setaria viridis (SETVI ) and Digitaria sanguinalis (DI GSA).
Each spray test was replicated three times. The efficacy of the herbicide was
assessed visually and expressed as a percentage of the leaf area killed. Samples were
assessed at time periods of 14 and 2 1 days following application . The results shown in
Table 3 below are mean averages over the two rates of nicosulfuron, three replicates,
four weed species and the two assessment timings, and are compared to the efficacy of
nicosulfuron in the absence of adjuvant and nicosulfuron in the presence of the known
tank mix adjuvant Atplus®4 11F.
The results show all three aromatic phosphate esters were efficacious as
adjuvants, with tricresylphosphate and 2-ethylhexyl diphenyl phosphate (Phosflex®362)
performing particularly well.
Table 3 Mean percentage kill results for nicosulfuron in the presence and absence of tricresyl phosphate,
Phosflex®362, triphenylphosphate, or Atplus®41 1F. A standard Tukey HSD test was carried out to
assess whether each result was statistically different from the other results and this is expressed as a letter:
tests with the same letter are not statistically different (p<0.05).
Treatment Mean across species
Nicosulfuron +Atplus®41 1F 66.6 A
Nicosulfuron + tricresylphosphate 63.2 AB
Nicosulfuron +Phosfiex®362 63.0 AB
Nicosulfuron + triphenylphosphate 59. 1 B
Nicosulfuron 42.5 C
Example 4 Use of aromatic phosphate esters as adjuvants in agrochemical
compositions of pinoxaden
The efficacy of the aromatic phosphate esters tricresyl phosphate, Phosflex®362
(2-ethylhexyl diphenyl phosphate) and triphenyl phosphate were tested in a glasshouse
against four weed species using the herbicide pinoxaden . An agrochemical composition
was prepared containing 0.5 % v/v of the adjuvant TEH P in a track sprayer and was
applied at a volume of 200 litres per hectare. The other adjuvants were tested at a rate
of 0.2 % v/v. Pinoxaden was applied at either 7.5 or 15 grams per hectare on each of
the weed species. The weed species and their growth stage at spraying were
Alopecurus myosuroides (ALOMY; growth stage 13), Avena fatua (AVEFA; growth stage
12); Lolium perenne (LOLPE; growth stage 13), Setaria viridis (SETVI ; growth stage 14).
Each spray test was replicated three times. The efficacy of the herbicide was
assessed visually and expressed as a percentage of the leaf area killed. Samples were
assessed at time periods of 14 and 2 1 days following application . The results shown in
Table 4 below are mean averages over the two rates of pinoxaden, three replicates, four
weeds and the two assessment timings. The results were compared to the efficacy of
pinoxaden in the absence of an adjuvant and pinoxaden in the presence of either TEHP
(tris-2-ethylhexyl phosphate) or acetyl tributyl citrate.
Table 4 Mean percentage kill results for pinoxaden in the presence and absence of tricresyl phosphate,
Phosflex®362, triphenyl phosphate, TEHP, or acetyl tributyl citrate. A standard Tukey HSD test was
carried out to assess whether each result was statistically different from the other results and this is
expressed as a letter: tests with the same letter are not statistically different (p<0.05).
Treatment Mean across species
Pinoxaden + TEHP 69.8 A
Pinoxaden + Phosflex®362 68.8 A
Pinoxaden + tricresylphosphate 49.9 B
Pinoxaden + acetyl tributyl citrate 43.5 B
Pinoxaden + triphenyl phosphate 40.3 B
Pinoxaden 16.0 C
The results show that all aromatic phosphate esters are efficacious as adjuvants
for pinoxaden.
Example 5 Use of aromatic phosphate esters as adjuvants in agrochemical
compositions of mesotrione
The efficacy of the aromatic phosphate esters tricresyl phosphate, Phosflex®362
(2-ethylhexyl diphenyl phosphate) and triphenyl phosphate as adjuvants were tested in a
glasshouse against four weed species using the herbicide mesotrione. An agrochemical
composition was prepared containing 0.5 % v/v of the adjuvant Turbocharge ® with the
test comopund in a track sprayer and was applied at a volume of 200 litres per hectare.
The other adjuvants were tested at a rate of 0.2 % v/v. Mesotrione was applied at either
60 or 120 grams per hectare on weeds which had been grown to the 1.3 or 1.4 leaf
stage. The weed species and their growth stage at spraying were Polygonum
convolvulus (POLCO; growth stage 13), Brachiaria platyphylla (BRAPL; growth stage
13), Digitaria sanguinalis (DIGSA; growth stage 13) and Amaranthus tuberculatus
(AMATU; growth stage 13).
Each spray test was replicated three times. The efficacy of the herbicide was
assessed visually and expressed as a percentage of the leaf area killed. Samples were
assessed at time periods of 7, 14 and 2 1 days following application. The results shown
below in Table 5 are mean averagesover the two rates of mesotrione, three replicates,
four weeds and the three assessment timings. The results were compared to the
efficacy of mesotrione in the absence of an adjuvant as well as in the presence of the
commercial tank-mix adjuvant Turbocharge® , tested at 0.5 % v/v and the adjuvant
tributyl citrate applied at 0.2% v/v.
Table 5 Mean percentage kill results for mesotrione in the presence and absence of tricresyl
phosphate, Phosflex®362, triphenylphosphate, Turbocharge® or tributyl citrate. A standard
Tukey HSD test was carried out to assess whether each result was statistically different from the other
results and this is expressed as a letter: tests with the same letter are not statistically different (p<0.05).
Treatment Mean across species
Mesotrione + Turbocharge® 50.8 A
Mesotrione + Phosflex®362 50.8 A
Mesotrione + tricresylphosphate 49.2 A
Mesotrione + triphenylphosphate 48.4 A
Mesotrione + acetyl tributyl citrate 48.0 A
Mesotrione 34.0 A
The results show all aromatic phosphate esters are effective as adjuvants for
mesotrione.
Example 6 Use of aromatic phosphate esters as adjuvants in agrochemical
compositions of fomesafen
The efficacy of the aromatic phosphate esters tricresyl phosphate, Phosflex®362
(2-ethylhexyl diphenyl phosphate) and triphenyl phosphate as adjuvants were tested in a
glasshouse against four weed species using the herbicide fomesafen. An agrochemical
composition was prepared containing 0.5 % v/v of the adjuvant Turbocharge ® in a track
sprayer and was applied at a volume of 200 litres per hectare. The other adjuvants
were tested at a rate of 0.2 % v/v. Fomesafen was applied at a rate of either 60 or 120
grams per hectare on weeds which had been grown to the 1.3 or 1.4 leaf stage. The
weed species and their growth stage at spraying were Chenopodium album
(CHEAL;growth stage 14), Abutilon theophrasti (ABUTH; growth stage 12), Setaria
viridis (SETVI; growth stage 13), and Xanthium strumarium (XANST; growth stage 12).
Each spray test was replicated three times. The efficacy of the herbicide was
assessed visually and expressed as a percentage of the leaf area killed. Samples were
assessed at time periods of 7, 14 and 2 1 days following application. The results shown
below in Table 6 are mean averages over the two rates of fomesafen, three replicates,
four weeds and the three assessment timings. The results were compared to the
efficacy of fomesafen in the absence of an adjuvant as well as in the presence of the
commercial tank-mix adjuvant Turbocharge® and the adjuvant tributyl citrate.
Table 6 Mean percentage kill results for fomesagen in the presence and absence of Turbocharge®,
Phosflex®362, acetyl tributyl citrate, tricresylphosphate, or triphenyl phosphate. A standard Tukey
HSD test was carried out to assess whether each result was statistically different from the other results and
this is expressed as a letter: tests with the same letter are not statistically different (p<0.05).
Treatment Mean across species
Fomesafen + Turbocharge® 35.2 A
Fomesafen + Phosflex®362 33.0 AB
Fomesafen + acetyl tributyl citrate 3 1.7 AB
Fomesafen + tricresylphosphate 29.9 AB
Fomesafen + triphenylphosphate 29.0 B
Fomesafen 14.3 C
The results show all aromatic phosphate esters were effective as adjuvants for
Use of an aromatic phosphate ester adjuvant in an agrochemical
composition containing abamectin
The efficacy of the aromatic phosphate ester Phosflex® 362 (2-ethylhexyl diphenyl
phosphate) as an adjuvant in a composition containing abamectin was tested and
compared to the efficacy of an abamectin composition without the Phosflex® 362
present, and to the efficacy of an abamectin composition containing triethyl phosphate.
The Phosflex® 362 and the triethyl phosphate were present at 0.14 % v/v in the
abamectin compositions. The surfactants tristyrylphenol ethoxylate phosphate ester,
sodium salt and tristyrylphenol ethoxylate were present in all the abamectin
compositions tested.
Two week old French bean (Phaseolus vulgaris) plants were infested with a mixed
population of two spotted spider mite Tetranychus urticae. One day after infestation the
plants were treated with the test compositions, with a track sprayer from the top with a
rate of 200 litres per hectare. Plants were incubated in the greenhouse for 10 days and
the evaluation was done on mortality against Larva and Adults, just on the lower side
(untreated) of the leaves. Each experiment was replicated twice and the results were
averaged. The mortality against Larva and Adults was then averaged.
In the control experiment the beans were sprayed with water and no mortality was
observed. The beans were sprayed with phosphate ester compositions without
abamectin present, containing 0.14 % v/v Phosflex® 362 or 0.14 % v/v triethyl
phosphate and no mortality was observed in each case.
Table 7 % Mortality of Tetranychus urticae treated with abamectin
presence and absence of an aromatic phosphate ester adjuvant.
As can be seen from Table 7 the inclusion of the aromatic phosphate ester Phosflex®
362 as an adjuvant for abamectin provided more effective control of Tetranychus urticae
than the treatment containing abamectin with no adjuvant present. It can also be seen
that Phosflex® 362 was considerably more effective than the alkyl phosphate ester
triethyl phosphate.
CLAIMS
1. An agrochemical composition wherein the composition is an emulsion
concentrate (EC), an emulsion in water (EW), a microcapsule formulation (CS),
dispersion concentrate (DC), suspension of particles in an emulsion (SE), or a
suspension of particles in oil (OD) comprising:
an agrochemical active ingredient;
a surfactant;
an aromatic phosphate ester of formula (I)
O
1 3
R— O-P-O— R3
IO
R (I)
wherein
R is optionally substituted phenyl, R2 is optionally substituted phenyl and
R3 is C 7-C20 alkyl.
2. A liquid agrochemical composition comprising:
an agrochemical active ingredient;
a surfactant;
from about 0.05% to about 5% v/v of an aromatic phosphate ester
of formula (I)
O
1 3
R— O-P-O— R3
IO
R (I)
wherein R is optionally substituted phenyl, R2 is optionally substituted phenyl
and R3 is C7-C20 alkyl.
3. An agrochemical composition according to claim 1 or 2 wherein R and R2 are
phenyl and R3 is C8-Ci 0 alkyl.
4. An agrochemical composition according to any one of claims 1 to 3, wherein the
aromatic phosphate ester is selected from the group consisting of: 2-
ethylhexyldiphenyl phosphate and isodecyl diphenyl phosphate.
An agrochemical composition according to any one of the preceding claims
wherein the active ingredient is present at a concentration in the range from
about 0.001% to about 90% w/v.
An agrochemical composition according to anyone of the preceding claims
wherein the active ingredient is selected from the group consisting of:
bicyclopyrone, mesotrione, fomesafen, tralkoxydim, napropamide, amitraz,
propanil, pyrimethanil, dicloran, tecnazene, toclofos methyl, flamprop M, 2,4-D,
MCPA, mecoprop, clodinafop-propargyl, cyhalofop-butyl, diclofop methyl,
haloxyfop, quizalofop-P, indol-3-ylacetic acid, 1-naphthylacetic acid, isoxaben,
tebutam, chlorthal dimethyl, benomyl, benfuresate, dicamba, dichlobenil,
benazolin, triazoxide, fluazuron, teflubenzuron, phenmedipham, acetochlor,
alachlor, metolachlor, pretilachlor, thenylchlor, alloxydim, butroxydim, clethodim,
cyclodim, sethoxydim, tepraloxydim, pendimethalin, dinoterb, bifenox, oxyfluorfen,
acifluorfen, fluoroglycofen-ethyl, bromoxynil, ioxynil, imazamethabenz-methyl,
imazapyr, imazaquin, imazethapyr, imazapic, imazamox, flumioxazin,
flumiclorac-pentyl, picloram, amodosulfuron, chlorsulfuron, nicosulfuron,
rimsulfuron, triasulfuron, triallate, pebulate, prosulfocarb, molinate, atrazine,
simazine, cyanazine, ametryn, prometryn, terbuthylazine, terbutryn, sulcotrione,
isoproturon, linuron, fenuron, chlorotoluron, metoxuron, isopyrazam,
mandipropamid, azoxystrobin, trifloxystrobin, kresoxim methyl, famoxadone,
metominostrobin and picoxystrobin, cyprodanil, carbendazim, thiabendazole,
dimethomorph, vinclozolin, iprodione, dithiocarbamate, imazalil, prochloraz,
fluquinconazole, epoxiconazole, flutriafol, azaconazole, bitertanol,
bromuconazole, cyproconazole, difenoconazole, hexaconazole, paclobutrazole,
propiconazole, tebuconazole, triadimefon, trtiticonazole, fenpropimorph,
tridemorph, fenpropidin, mancozeb, metiram, chlorothalonil, thiram, ziram,
captafol, captan, folpet, fluazinam, flutolanil, carboxin, metalaxyl, bupirimate,
ethirimol, dimoxystrobin, fluoxastrobin, orysastrobin, metominostrobin,
prothioconazole, thiamethoxam, imidacloprid, acetamiprid, clothianidin,
dinotefuran, nitenpyram, fipronil, abamectin, emamectin, bendiocarb, carbaryl,
fenoxycarb, isoprocarb, pirimicarb, propoxur, xylylcarb, asulam, chlorpropham,
endosulfan, heptachlor, tebufenozide, bensultap, diethofencarb, pirimiphos
methyl, aldicarb, methomyl, cyprmethrin, bioallethrin, deltamethrin, lambda
cyhalothrin, cyhalothrin, cyfluthrin, fenvalerate, imiprothrin, permethrin,
halfenprox, paclobutrazole, 1-methylcyclopropene, benoxacor, cloquintocetmexyl,
cyometrinil, dichlormid, fenchlorazole-ethyl, fenclorim, flurazole,
fluxofenim, mefenpyr-diethyl, MG-191 , naphthalic anhydride, and oxabetrinil
7. An agrochemical composition according to anyone of the preceding claims
wherein the composition is formulated as, or comprised by a microcapsule.
8. An agrochemical composition according to any one of the preceding claims,
comprising at least one additional component selected from the group consisting
of an agrochemical, an adjuvant, a surfactant, an emulsifier, and a solvent.
9. An agrochemical composition according to any one of the preceding claims
which is a ready-to-use composition suitable for application to a crop, a pest or
the locus of said pest.
10. Use of an agrochemical composition as defined in any one of claims 1 to 9 to
control pests.
11. Use of an aromatic phosphate ester as defined in any one of claims 1 to 4 as an
adjuvant in an agrochemical composition comprising an agrochemically active
ingredient, for increasing the biological activity of said agrochemically active
ingredient.
12. A method of controlling a pest, comprising applying a composition as defined in
any one of claims 1 to 9 to said pest or the locus of said pest.
13. A method of treatment or prevention of a fungal infection in a plant comprising
applying a composition comprising
i . an fungicidal active ingredient;
ii. a surfactant;
iii. an aromatic phosphate ester of formula (I)
O
1 3 R— O-P-O— R3
IO
R (I)
wherein
R is optionally substituted phenyl, R2 is optionally substituted phenyl and R3 is
C7-C20 alkyl.
14. A method of making an agrochemical composition comprising providing:
i . an agrochemically active ingredient;
ii. a surfactant;
iii. and an aromatic ester of formula (I) as defined in any one of
claims 1 to 4;
and combining the agrochemically active ingredient, surfactant, and aromatic
ester of i , ii and iii.
15. A method according to claim 14, wherein the agrochemical composition is as
defined in claims 1 to 9.