FORMULATION COMPONENT
The present invention relates to agrochemical compositions comprising certain
benzamide compounds and to the use of those benzamide compounds as adjuvants,
especially in formulations, in particular in agrochemical formulations and in
environmentally friendly formulations. The invention further extends to certain novel
benzamide compounds.
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). Typically, 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 certain benzamide
compounds, in particular those comprising alkyl and/or alkoxylated chains, are
surprisingly effective adjuvants, significantly enhancing the biological activity of active
ingredients, in particular agrochemicals.
EP0044955 describes liquid herbicidal compositions based on a mixture of
pyidazone derivatives and biscarbamates dissolved in an acid amide. These liquid
compositions are said to have improved stability: the acid amide has a low water
solubility thus minimising the tendency for the active ingredient to crystalise out, and
stability of the biscarbamate in the solution is good.
WO201 1/010082 describes the use of certain benzamides as solvents, in
particular for agrochemicals.
WO2006/127399 describes high load concentrate compositions comprising the
active ingredient metaflumizone, an optional bridging agent, a surfactant and a suitable
carrier solvent. N,N-diethyl-m-toluamide is mentioned as a suitable carrier solvent.
None of the above-mentioned prior art describes the use of compounds of
formula (I) as described herein as adjuvants, in particular as bioefficacy adjuvants, for
agrochemicals, i.e. as compounds capable of enhancing the biological efficacy of an
agrochemical.
In a first aspect, the invention provides for the use of a compound of formula (I)
as an ad uvant,
(I), wherein m is an integer of 1, 2 , or 3 ; n is an integer of 0 , 1, 2 ,
or 3 ; R is C(0)NR R4; each R2 is independently C1-15 alkyl, each R3 is independently H,
or C -6 alkyl, each R4 is independently C _8 alkyl, the group the group -[AO] x-R5, wherein
x is an integer of 0 to 20, each A is independently C -4 alkyl, and each R5 is
independently H, C _ alkyl, or NH2.
Certain compounds of formula (I) are novel and as such form further aspects of
the resent invention. Thus the invention also provides a compound of formula (I)
(I), wherein m is an integer of 1, 2 , or 3 ; n is an integer of 0 , 1, 2 ,
or 3 ; R is C(0)NR R4; each R2 is independently Ci. 5 alkyl, each R3 is independently H,
or C -6 alkyl, each R4 is independently C _8 alkyl, the group -[AO] x-R5, wherein x is an
integer of 0 to 20, each A is independently C _ alkyl, and each R5 is independently H,
Ci-4 alkyl, or NH2; provided that when m is 1 and n is 1: (i) when R2 is methyl in the meta
position then R3 is not ethyl when R4 is ethyl, and R3 is not methyl when R4 is methyl; (ii)
when R2 is methyl in the ortho position then: R3 is not methyl when R4 is propyl or tertbutyl,
R3 is not n-propyl when R4 is ethyl, n-propyl, or n-butyl, R3 is not n-butyl when R4
is methyl, ethyl or n-butyl, R3 is not iso-butyl when R4 is iso-butyl, R4 is not methyl when
R3 is H, propyl, tert-butyl, or n-pentyl, R4 is not n-propyl when R3 is ethyl, R4 is not nbutyl
when R3 is ethyl, R4 is not pentyl when R3 is H or methyl, R4 is not 2-ethyl-hexyl
when R3 is H or methyl; and (iii) when R2 is methyl at the para position or ethyl at the
ortho position, R3 and R4 are not both methyl.
In further aspects the invention provides a compound of formula (I) as defined
hereinbefore, wherein at least one R4 is the group -[AO] XR5 , as well as a compound of
formula (I) as defined hereinbefore wherein at least one R2 is at the para position.
In yet further aspects, the invention provides (a) an agrochemical composition
comprising a novel compound of formula (I) as defined hereinbefore in combination with
an agrochemical; (b) a method of making an agrochemical composition comprising
combining a novel compound of formula (I) with said agrochemical; and (c) the use of an
agrochemical composition of the invention in controlling pests.
Alkyl groups and moieties are straight or branched chains, and unless explicitly
stated to the contrary, are unsubstituted. Examples of alkyl groups are methyl, ethyl,
propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl,
tetradecyl and pentadecyl groups.
In particularly preferred embodiments of the invention, the preferred values for m,
n and x , as well as the preferred groups for R , R2 , R3 , R4 , R5 , and A, in any combination
thereof, are as set out below.
As stated above the value of m is stated as 1, 2 , or 3 . Furthermore, the value of
n is also stated as 1, 2 , or 3 . In one set of embodiments, the sum of the values of n and
m will be 3 or greater, i.e. this encompasses compounds of formula (I) wherein m is 1
and n is either 2 or 3 , as well as compounds of formula (I) wherein n is 1 and m is either
2 or 3 .
In some embodiments m is 1 or 2 , more preferably 1. In some embodiments n is
0 , 1 or 2 , more preferably 1. In further embodiments, both n and m are 1. In still further
embodiments n is 0 and m is 1. In embodiments wherein at least one R4 group is
-[AO] XR5 , it is preferred that n is 0 or 1. In embodiments where m is 1 and R4 is not
-[AO] XR5 , it is preferred that n is 1.
R2 is defined above as the group C S alkyl and where n is greater than 1, each
R2 group is independently defined as such.
It is preferred that each R2 group is independently a C 2 alkyl group, and in
particularly preferred embodiments each R2 is independently methyl, or C 6-12 alkyl, more
preferably methyl or a straight chain C 6-12 alkyl group, even more preferably a methyl,
hexyl, octyl, decyl or dodecyl, and most preferably a methyl or dodecyl group.
In further preferred embodiments at least one R2 group will be present at the
para position.
When n is 1, R2 may be as defined above, however, in some embodiments it is
preferred that when R2 is at the ortho or para position it is a C2-12 alkyl group, more
preferably a C6-12 alkyl group, more preferably still a straight chain C6-12 alkyl group, and
most preferably a hexyl, octyl, decyl or dodecyl group.
R is defined herein as the group C(0)NR R4, wherein each R3 is independently
H, or Ci-6 alkyl and each R4 is independently C _8 alkyl, or the group -[AO] xR5, wherein x
is an integer of 0 to 20, each A is independently C _4 alkyl and each R5 is independently
H, C - alkyl, or NH2
Preferably in at least one R group, R3 is selected from the group consisting of H,
methyl, ethyl, propyl or butyl; more preferably H, methyl ethyl, n-propyl, n-butyl or isobutyl,
more preferably still H or ethyl, and most preferably H.
Preferably in at least one R group, R4 is selected from the group consisting of
C2 -8 alkyl and the group -[AO] xR5, wherein A, x and R5 are as defined above. In further
preferred embodiments x is 1 or greater, preferably 2 or greater, more preferably 2 , 4 , 5 ,
6 , 7 , 8 , 9 , 10, 11, 12, 13, 18 or 19.
The skilled man will appreciate that since the value of x can be up to 20, and
since each A may independently be methyl, ethyl, propyl or butyl, the substructure
-[AO] x- may comprise methoxy, ethoxy, propoxy and/or butoxy units in any combination
up to a tridecamer, and also includes polymethoxylate chains, polyethoxylate,
polypropoxylate chains, and polybutoxylate chains up to 20 units in length.
Preferably at least one A group will be ethyl or propyl. In one set of preferred
embodiments x is an integer of 7-18 inclusive, and in a particularly preferred set of
embodiments x is an integer of 7-18 inclusive and each A group is ethyl.
In a further set of preferred embodiments A is ethyl , x is 7 or 8 , and R5 is NH2.
In a further set of preferred embodiments R4 will be the group
NH2
wherein 'a', 'b' and 'c' are integers and the sum of 'a', 'b' and 'c' is equivalent to the
value of x as defined hereinbefore. In particularly preferred embodiments, 'b' has a
value of 9 and the sum of 'a' and 'c' is approximately 3 or 4 .
As stated above, each R5 is independently selected from the group consisting of
H, Ci-4 alkyl, and NH2 Unless stated otherwise herein in respect of specific
embodiments, it is preferred that R5 is selected from the group consisting of H, ethyl,
propyl or NH2, more preferably H or NH2.
Illustrative examples of compounds for use as adjuvants in the present invention
are given in Table 1 below, which also shows selected H NMR (400MHz) data, all
obtained with CDCI3 as the solvent. The following abbreviations are used throughout
this description:
"NMR" = nuclear magnetic resonance spectrum.
s = singlet broad
d = doublet doublet of doublets
t = triplet quartet
m = multiplet parts per million
Table 1: Adjuvants for use in the invention (N/A means, with respect to characterising data, that the data
not obtained)

As stated above, certain compounds of formula (I) are novel. One group of such
novel compounds are those wherein the sum of m and n is three or greater. Also novel
are compounds of formula (I) (I),
wherein m is an integer of 1, 2 , or 3 ; n is an integer of 1, 2 , or 3 ; R is C(0)N R R4; each
R2 is independently C1-15 alkyl, each R3 is independently H, or C _6 alkyl, each R4 is
independently C _8 alkyl , or the group -[AO] x-R5, wherein x is an integer of 0 to 12 , each
A is independently C -4 alkyl, and each R5 is independently C _ alkyl, or NH2; provided
that when m is 1 and n is 1: (i) when R2 is methyl in the meta position then R3 is not ethyl
when R4 is ethyl, and R3 is not methyl when R4 is methyl; (ii) when R2 is methyl in the
ortho position then: R3 is not methyl when R4 is propyl or tert-butyl, R3 is not n-propyl
when R4 is ethyl, n-propyl, or n-butyl, R3 is not n-butyl when R4 is methyl, ethyl or nbutyl,
R3 is not iso-butyl when R4 is iso-butyl, R4 is not methyl when R3 is H, propyl, tertbutyl,
or n-pentyl , R4 is not n-propyl when R3 is ethyl , R4 is not n-butyl when R3 is ethyl,
R4 is not pentyl when R3 is H or methyl, R4 is not 2-ethyl-hexyl when R3 is H or methyl;
and (iii) when R2 is methyl at the para position or ethyl at the ortho position, R3 and R4
are not both methyl.
Also novel are compounds of formula (I)
(I), wherein m is an integer of 1, 2 , or 3 ; n is an integer of 0 , 1, 2 ,
or 3 ; R is C(0)NR R4; each R2 is independently Ci. 5 alkyl, each R3 is independently H,
or C -6 alkyl, each R4 is independently C _8 alkyl, or the group -[AO] x-R5, wherein x is an
integer of 0 to 20, each A is independently C _ alkyl, and each R5 is independently H,
Ci-4 alkyl, or NH2 provided that at least one R4 is the group -[AO] x-R5.
Also novel are compounds of formula (I)
(I), wherein m is an integer of 1, 2 , or 3 ; n is an integer of 0 , 1, 2 ,
or 3 ; R is C(0)NR R4; each R2 is independently C Salkyl, each R3 is independently H ,
or C -6 alkyl, each R4 is independently C _8 alkyl, or the group -[AO] x-R5, wherein x is an
integer of 0 to 20, each A is independently C _4 alkyl, and each R5 is independently H,
Ci-4 alkyl, or NH2 provided that at least one R2 group is in the para-position.
For compounds of the invention, preferences for the integers m, n and x , as well
as for the substituents R , R2, R3, R4, R5 and A are as described hereinbefore.
Compounds of formula (I) as defined hereinbefore may either be obtained
commercially e.g. Compound 1 (N, A/-diethyl-3-methylbenzamide or N, N-diethyl-mtoluamide
may be obtained from Alfa Aesar US or Carbone Scientific UK) or easily
synthesised from readily available starting material using routine techniques known in
the art (with respect to Compound 1, see for example Wang, B. J-S., 1974 J . Chem. Ed.
51(10): 631), or as described hereinafter and in the Examples.
In general compounds of formula (I) may be prepared according to reaction
scheme 1 below:
Reaction scheme 1
(II) (Ml) (I)
Benzoic acid derivatives of formula (II) (wherein R2 and n are as defined herein)
can be converted to acid chlorides of formula (III) using for example thionyl chloride.
The acid chloride can be reacted with a primary or secondary amine (wherein R3 and R4
are as defined herein) to form the aromatic amide of choice. The skilled man will
appreciate that polyethylene, or other polyalkyl- or mixed polyalkyl-, mono- or di-amines
can be used as the amine. Compounds of formula (II) and suitable amines are readily
available or may be synthesised using routine techniques with which the skilled man is
familiar.
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, and a particular feature of the adjuvancy exhibited by the
compounds of formula (I) is their ability to enhance bioefficacy. 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. As shown herein, compounds of formula (I) are particularly efficacious as
adjuvants in herbicidal compositions.
The term adjuvant as used herein refers to a compound which is capable of
enhancing the biological activity of an active ingredient (in particular an agrochemical).
Thus, the biological activity of a composition comprising an adjuvant and an active
ingredient will be greater than the biological activity of the active ingredient in the
absence of the adjuvant. This may be evidenced by directly comparing the biological
activity of a composition comprising an agrochemical and adjuvant according to the
invention with the biological activity of the agrochemical in the absence of said adjuvant.
Alternatively, it may also be evidenced by comparing the biological activity of a
composition comprising an agrochemical and an adjuvant according to the invention
with the biological activity of the agrochemical in combination with a known adjuvant. In
some cases, the observed efficacy of the combination of ingredients according to the
invention can sometimes be significantly higher than that which would be expected from
the individual ingredients used (i.e. synergism may be observed).
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.
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.
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, fenvalerate, imiprothrin, permethrin and halfenprox.
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, and oxabetrinil.
Of course, the various editions of The Pesticide Manual [especially the 14th and
15th editions] and the also disclose details of agrochemicals, any one of which may
suitably be used with the present invention.
The skilled man will appreciate that compositions of the invention may comprise
one or more of the agrochemicals as described above.
Compositions of the invention will typically comprise the agrochemical in an
amount that is recommended in the art. Typically a compound of formula (I) will
comprise from about 0.0005% to about 90% v/v of the total composition.
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% v/v, more preferably 10 to 50% v/v agrochemical.
Ready-to-use compositions of the invention will typically comprise from 0.0001% to 1%
v/v, more preferably from 0.001% to 0.5% v/v, and more preferably still from 0.001% to
0.1% v/v agrochemical.
Typically a compound of formula (I) will comprise from about 0.0005% to about
90% v/v of the total composition. Where the density of the adjuvant is approximately 1
the skilled man will appreciate measurements of v/v approximate measurements of w/v
and typically v/v is a more appropriate measure where the compound of formula (I) is a
liquid. In concentrated form, compositions of the invention typically comprise a
compound of formula (I) from 1% to 80% (v/v orw/v) preferably from 5% to 60% (v/v or
w/v) and more preferably from 10% (w/v or v/v) to 40% (w/v or v/v). Ready to use
compositions of the invention typically comprise a compound of formula (I) from about
0.05% to about 1% w/v (or v/v) of the total composition, more preferably still from about
0.1% to about 0.5% w/v (or v/v) of the total composition. In specific embodiments the
aromatic ester will be included at concentrations of 0.1%, 0.2%, 0.25%, 0.3%, 0.4% or
0.5% w/v (or 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 30281A 1 (see from page 46, line 5 to page
51, 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.
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.
Compounds and/or 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 a microcapsule.
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.
EXAMPLE 1 Synthesis of 4-Dodecyl-N-[2-(2-{2-[2-(2-{2-[2-(2-hydroxy-ethoxy)-
ethoxy]-ethoxy}-ethoxy)-ethoxy]-ethoxy}-ethoxy)-ethyl]-benzamide
(Compound No. 2)
4-Dodecyl-N-(2-{2-[2-(2-{2-[2-(2-ethoxy-ethoxy)-ethoxy]-ethoxy}-ethoxy)-ethoxy]-
ethoxy}-ethoxy)-benzamide (Compound 2 in Table 1 above) was synthesised by
reacting para-dodecylbenzoic acid with octaethylene oxide amine, using N,N'-
dicyclohexylcarbodiimide (DCC) as a coupling agent.
Use of 4-Dodecyl-N-[2-(2-{2-[2-(2-{2-[2-(2-hydroxy-ethoxy)-ethoxy]-
ethoxy}-ethoxy)-ethoxy]-ethoxy}-ethoxy)-ethyl]-benzamide
(compound No. 2) as an adjuvant in nicosulfuron formulations
Compound No. 2 (see Example 1 and Table 1 above) was tested in a
glasshouse against four weed species in combination with the herbicide nicosulfuron.
An agrochemical composition was prepared containing 0.2 % v/v of the adjuvant in a
track sprayer and was applied at a volume of 200 litres per hectare. Nicosulfuron was
applied at either 30 or 60 grams of pesticide per hectare on weeds which had been
grown to the 1.3 or 1.4 leaf stage. The weed species were Chenopodium album
(CHEAL), Abutilon theophrasti (ABUTH), Brassica perenni (BRAPP), and Digitaria
sanguinalis (DIGSA).
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
in Table 2 below are mean averages over the two rates of nicosulfuron, three replicates
and the three assessment timings. The results are compared to those obtained for
nicosulfuron in combination with the commercially available tank mix adjuvant
Turbocharge ® D (Syngenta Crop Protection Canada, Inc.), and it can be seen in each
case superior weed control is observed when Compound 2 is included in the formulation
as an adjuvant.
TABLE 2 Mean percentage kill results for nicosulfuron in the presence of compound no. 2 compared
to nicolsulfuron in the presence of Turbocharge ® D.
Adjuvant CHEAL ABUTH BRAPP DIGSA Mean (g/ha)
Compound No 2 80 47. 1 86.4 83. 1 73.9
Turbocharge 76.7 4 1.7 80.6 64.8 65.9
EXAMPLE 3 Use of compound No. 2 as an adjuvant for fomesafen.
Compound No. 2 was tested in a glasshouse against four weed species in
combination with the herbicide fomesafen. An agrochemical composition was prepared
containing 0.2 % v/v of the adjuvant in a track sprayer and was applied at a volume of
200 litres per hectare. Fomesafen was applied at either 60 or 120 grams of pesticide
per hectare on weeds which had been grown to the 1.3 or 1.4 leaf stage. The weed
species were Chenopodium album (CHEAL), Abutilon theophrasti (ABUTH), Setaria
viridis (SETVI), and Xanthium strumarium (XANST).
Each spray test was replicated six 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 and 14 days following application. The results shown in
Table 3 below are mean averages over the two rates of fomesafen, six replicates and
the two assessment timings, and are compared to the efficacy of fomesafen in the
absence of adjuvant.
Table 3 Mean percentage kill results for fomesafen in the presence and absence of compound 2
Mean across
Adjuvant ABUTH CHEAL SETVI XANST species
Compound 2 90 34. 1 4 1.7 68.8 58.6
None 60.8 43.3 38.2 45.8 47.0
EXAM PLE 4 Use of compound 2 as an adjuvant for mesotrione
Compound No. 2 was tested in a glasshouse against four weed species in
combination with the herbicide mesotrione. An agrochemical composition was prepared
containing 0.2 % v/v of the adjuvant in a track sprayer and was applied at a volume of
200 litres per hectare. Mesotrione was applied at either 60 or 120 grams of pesticide
per hectare on weeds which had been grown to the 1.3 or 1.4 leaf stage. The weed
species were Amaranthus retroflexus (AMARE), Abutilon theophrasti (ABUTH),
Brachiaria platyphylla (BRAPP), and Digitaria sanguinalis (DIGSA).
Each spray test was replicated six 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 6 , 14 and 2 1 days following application. The results shown
in Table 4 below are mean averages over the two rates of mesotrione, six replicates and
the three assessment timings. The results are compared to those obtained for
mesotrione in combination with the commercially available tank mix adjuvant
Turbocharge ® D (Syngenta Crop Protection Canada, Inc.).
TABLE 4 Mean percentage kill results for nicosulfuron in the presence of compound 2 compared to
nicolsulfuron in the presence of Turbocharge ® D.
Mean across
Adjuvant AMARE ABUTH BRAPP DIGSA species
Compound 2 63.5 73.3 68.2 83.4 72. 1
Turbocharge 67.2 73.8 58.2 79.7 69.8
EXAM PLE 5 Use of compound 1 (N, N-diethyl-3-methylbenzamide) as an adjuvant
for fomesafen
Compound 1 (N, A/-diethyl-3-methylbenzamide) was tested in a glasshouse
against four weed species using the herbicide fomesafen. An agrochemical composition
was prepared containing 0.2 % v/v of the adjuvant in a track sprayer and was applied at
a volume of 200 litres per hectare. Fomesafen was applied at either 60 or 120 grams of
pesticide per hectare on each of the weed species. The weed species and their growth
stage at spraying were Chenopodium album (CHEAL; growth stage 13/14), 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
in Table 5 below are mean averages over the two rates of fomesafen, three replicates
and the three assessment timings, and are compared to the efficacy of fomesafen in the
absence of adjuvant.
Table 5 Mean percentage kill results for fomesafen in the presence and absence of compound 1.
Mean across
Adjuvant CHEAL ABUTH SETVI XANST species
Compound 1 80.3 38.9 15.8 35.6 42.6
None 77.5 20 10.6 42.8 37.7
EXAMPLE 6 Use of compound 1 as an adjuvant for mesotrione
Compound 1 was tested in a glasshouse against four weed species using the
herbicide mesotrione. A 20% w/w stock emulsion of compound 1 was prepared
additionally containing 2% w/w Gohsenol®GL03 and 2% w/w Pluronic®PE10500 as
surfactants. Using this, an agrochemical composition was prepared containing 0.2 %
v/v of the adjuvant in a track sprayer and was applied at a volume of 200 litres per
hectare. Mesotrione was applied at either 45 or 90 grams of pesticide per hectare on
each of the weed species. The weed species and their growth stage at spraying were
Amaranthus tuberculatus (AMATE; growth stage 13/14), Brachiaria decumbens (BRADE;
growth stage 13/14), Digitaria sanguinalis (DIGSA; growth stage 14), and Polygonum
convolvulus (POLCO; growth stage 11/1 1.5).
Each 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
in Table 6 below are mean averages over the two rates of mesotrione, three replicates
and the three assessment timings, and are compared to the efficacy of mesotrione in
absence of adjuvant.
Table 6 Mean percentage kill results for mesotrione in the presence and absence of compound 1.
Mean across
Adjuvant AMATE BRADE DIGSA POLCO species
Compound 1 7 1.7 28.9 28.6 87.2 54. 1
None 65.6 26.7 23 73.3 47. 1
EXAMPLE 7 Use of compound 1 as an adjuvant for nicosulfuron
Compound 1 was tested in a glasshouse against four weed species using the
herbicide nicosulfuron. A 20% w/w stock emulsion of compound 1 was prepared
additionally containing 2% w/w Gohsenol®GL03 and 2% w/w Pluronic®PE10500 as
surfactants. Using this, an agrochemical composition was prepared containing 0.2 %
v/v of the adjuvant in a track sprayer and was applied at a volume of 200 litres per
hectare. Nicosulfuron was applied at either 30 or 60 grams of pesticide per hectare on
each of the weed species. The weed species and their growth stage at spraying were
Abutilon theophrasti (ABUTH; growth stage 13), Chenopodium album (CHEAL; growth
stage 14), Digitaria sanguinalis (DIGSA; growth stage 13), and Setaria viridis (SETVI;
growth stage 13).
Each spray test 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 7 below are mean averages over the two rates of nicosulfuron, three replicates
and the two assessment timings, and are compared to the efficacy of nicosulfuron in the
absence of an adjuvant.
Table 7 Mean percentage kill results for nicosulfuron in the presence and absence of compound 1.
Mean across
Adjuvant ABUTH CHEAL DIGSA SETVI species
Compound 1 72.9 63.8 89.4 93.4 8 1.3
None 69.2 50.8 87.9 92 75
EXAMPLE 8 Use of compound 1 as an adjuvant for pinoxaden
The adjuvant shown in example 1 was tested in a glasshouse against four weed
species in combination with the herbicide pinoxaden. A 20% w/w stock emulsion of
compound 1 was prepared additionally containing 2% w/w Gohsenol®GL03 and 2% w/w
Pluronic®PE10500 as surfactants. Using this, an agrochemical composition was
prepared containing 0.2 % v/v of the adjuvant in a track sprayer and was applied at a
volume of 200 litres per hectare. Pinoxaden was applied at either 7.5 or 15 grams of
pesticide 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 8 are mean averages over the two rates of pinoxaden, three replicates and the
two assessment timings, and are compared to the efficacy of pinoxaden in the absence
of adjuvant.
Table 8 Mean percentage kill results for pinoxaden in the presence and absence of compound 1.
Mean across
Adjuvant ALOMY AVEFA LOLPE SETVI species
Novel adjuvant 1 22.5 29.2 20.8 15.8 22. 1
Pinoxaden 2 1.2 20.8 12.5 15 17.4
EXAMPLE 9 Production of ethoxylated aromatic amides (Compounds 3, 4, 5, and
6)
Compounds 3 , 4 , 5 , and 6 from table 1 above were prepared in the following
manner. Four samples of monoamines of polyethylene glycol (A, B, C, & D) were
purchased from St Andrews chemicals, St Andrews University, St Andrews, Scotland.
These were stated as having, 5 , 10, 15, and 20 ethylene oxide moieties respectively, but
following nmp spectroscopic analysis were found to have the average number of
ethylene oxide moieties as shown in Table 9 .
Table 9 Degree of ethoxylation of polyethylene glycol monoamine samples as assessed by nmp
spectroscopy.
Sample Average no of EO units determined
A: Monoethanolamine 4 EO 5
B: Monoethanolamine 9 EO 10.2
C: Monoethanolamine 14 EO 14.5
D: Monoethanolamine 19 EO 19.2
Each of these amines (A, B, C, and D) was used to produce an aromatic amide
using the general methodology described below.
Monoethanolamine polyethylene oxide was added to a reaction flask with
benzoyl chloride and the solvent tetrahydrofuran. The flask was sealed and placed in a
microwave reactor. The sample was heated to 140°C and 7 bar pressure for five
minutes. Table 10 summarises reactant quantities and product yield for the individual
reactions.
TablelO
PEG Benzoyl chloride THF (ml) Amide product Amide yield %
monoethanolamine (g) (with reference
sample (g) to Table 1
above)
A ( 1 .01) 0.687 5 Compound 3 85
B (1) 0.424 5 Compound 4 78
C (1) 0.239 5 Compound 5 93
D (0.96) 0.216 5 Compound 6 76
The resulting amide products were purified by dissolution in acetone followed by
precipitation with hexane. Product structures were checked with nmr spectroscopy and
confirmed as those given in Table 1 above.
EXAMPLE 10 Production of an ethoxylated aromatic amide
Benzoyl chloride was reacted with the diamine of polyethylene oxide with an
average of 8 EO using the methodology described in Example 8 above. This formed an
aromatic amide with the structure of Compound 7 as shown in Table 1 above.
EXAMPLE 11 Production of ethoxy/propoxylated aromatic amide
Benzoyl chloride was reacted with Jeffamine® ED600 (Huntsman Performance
Products, Texas, USA)
The Jeffamine® ED series of polyether amines are polyether diamines based on
a predominantly PEG backbone. They have the following representative structure:
H2N NH,
CH, CH, CH,
For Jeffamine® ED600 the characteristics are as follows: y -9.0, (x + z) -3.6,
molecular weight -600.
The reaction formed a mixed benzoate amide ester of the
polyethylene/polypropylene copolymer carrying a terminal amino group. The degree of
ethoxylation and propoxylation is mixed, with the ester having on average 9EO moieties
and on average 3.6 PO moieties.

CLAIMS
Use of a com ound of formula (I) as an adjuvant
wherein m is an integer of 1, 2 , or 3 ;
n is an integer of 0 , 1, 2 , or 3 ;
R is C(0)NR R4;
each R2 is independently C1- 5 alkyl,
each R3 is independently H, or C _6 alkyl,
each R4 is independently C _8 alkyl, or the group -[AO] x-R5 wherein x is
an integer of 0 to 20, each A is independently C -4 alkyl, and each R5 is
independently H, C _ alkyl, or NH2.
2 . A compound of formula (I) as defined in claim 1, provided that when m is 1 and n
is 1:
(i) when R2 is methyl in the meta position then R3 is not ethyl when R4 is ethyl,
and R3 is not methyl when R4 is methyl;
(ii) when R2 is methyl in the ortho position then: R3 is not methyl when R4 is
propyl or tert-butyl, R3 is not n-propyl when R4 is ethyl, n-propyl, or n-butyl, R3 is
not n-butyl when R4 is methyl, ethyl or n-butyl, R3 is not iso-butyl when R4 is isobutyl,
R4 is not methyl when R3 is H, propyl, tert-butyl, or n-pentyl, R4 is not npropyl
when R3 is ethyl, R4 is not n-butyl when R3 is ethyl, R4 is not pentyl when
R3 is H or methyl, R4 is not 2-ethyl-hexyl when R3 is H or methyl; and,
(iii) when R2 is methyl at the para position or ethyl at the ortho position, R3 and
R4 are not both methyl.
A compound of formula (I) as defined in claim 1 or claim 2 wherein at least one
R4 is the group -[AO] x-R5 wherein A, x , and R5 are as defined in claim 1.
A compound of formula (I) as defined in any one of claims 1 to 3 , wherein at
least one R2 is at the para position.
5 . A compound according to any one of claims 2 to 4 , wherein:
each R2 is independently methyl or C6 -12 alkyl;
and wherein in at least one R , R3 is selected from the group consisting of H,
methyl, ethyl, propyl or butyl;
and R4 is selected from the group consisting of C2-s alkyl and the group -[AO] xR5
wherein A is ethyl or propyl and x is an integer of 7-18.
An compound according to any one of claims 2 to 5 , wherein in at least one R ,
R3 is H and R4 is the group
wherein 'b' has the value of 9
and the sum of 'a' and 'c' is 3 or 4 .
7 . A compound according to any one of claims 2 to 6 , wherein n is 1 and m is 1 or 2 .
8 . A compound according to any one of claims 2 to 7 , wherein n is 1 and m is 1.
9 . A compound according to any one of claims 2 to 7 , wherein n is 0 and m is 1.
10. Use of a compound as defined in any one of claims 2 to 9 as an adjuvant.
11. An agrochemical composition comprising a compound as defined in any one of
claims 2 to 9 , and an agrochemical.
12. An agrochemical composition according to claim 11 wherein the compound of
formula (I) comprises from about 0.0005% to about 90% w/v of the total
composition.
13. An agrochemical composition according to claim 11 or 12 wherein the
agrochemical 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, clodinafoppropargyl,
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,
cloquintocet-mexyl, cyometrinil, dichlormid, fenchlorazole-ethyl, fenclorim,
flurazole, fluxofenim, mefenpyr-diethyl, MG-191, naphthalic anhydride, and
oxabetrinil.
An agrochemical composition according to any one of claims 11 to 13 wherein
the composition is formulated as, or comprised by a microcapsule.
An agrochemical composition according to any one of claims 11 to 14, wherein
the composition is an emulsion concentrate (EC) or dispersion concentrate (DC).
An agrochemical composition according to any one of claims 11 to 15,
comprising at least one additional component selected from the group consisting
of an agrochemical, an adjuvant, a surfactant, an emulsifier, and a solvent.
17. Use of an agrochemical composition as defined in any one of claims 11 to 16 to
control pests.
18. A method of controlling a pest, comprising applying a composition as defined in
any one of claims 11 to 16 to said pest or the locus of said pest.
19. A method of making an agrochemical composition comprising providing:
i . an agrochemical
ii. and a compound of formula (I) as defined in any one of claims 2 to
9 ;
and combining the agrochemical, and compound of formula (I).
20. A method according to claim 19, wherein the agrochemical composition is as
defined in any one of claims 11 to 16.
2 1. A method of increasing the efficacy of an agrochemical comprising combining a
compound of formula (I) as defined in any one of claims 1 to 9 with said
agrochemical.