U.S. patent application number 13/981571 was filed with the patent office on 2014-02-20 for formulation component.
This patent application is currently assigned to SYNGENTA LIMITED. The applicant listed for this patent is Ian Perry. Invention is credited to Gordon Bell, Richard Brian Perry, Julia Ramsay, David Stock, Philip Taylor.
Application Number | 20140051580 13/981571 |
Document ID | / |
Family ID | 43769540 |
Filed Date | 2014-02-20 |
United States Patent
Application |
20140051580 |
Kind Code |
A1 |
Bell; Gordon ; et
al. |
February 20, 2014 |
FORMULATION COMPONENT
Abstract
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 and a process to prepare such novel
compounds.
Inventors: |
Bell; Gordon; (Bracknell,
GB) ; Perry; Richard Brian; (Bracknell, GB) ;
Ramsay; Julia; (Bracknell, GB) ; Stock; David;
(Bracknell, GB) ; Taylor; Philip; (Bracknell,
GB) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Perry; Ian |
|
|
US |
|
|
Assignee: |
SYNGENTA LIMITED
Guildford, Surrey
GB
|
Family ID: |
43769540 |
Appl. No.: |
13/981571 |
Filed: |
November 29, 2011 |
PCT Filed: |
November 29, 2011 |
PCT NO: |
PCT/EP11/71251 |
371 Date: |
October 9, 2013 |
Current U.S.
Class: |
504/215 ;
504/219; 504/333; 504/348; 504/358; 564/161 |
Current CPC
Class: |
A01N 37/18 20130101;
A01N 47/36 20130101; A01N 37/20 20130101; A01N 37/18 20130101; A01N
41/10 20130101; A01N 41/10 20130101; A01N 25/00 20130101; C07C
233/69 20130101; A01N 2300/00 20130101; A01N 41/06 20130101; A01N
43/90 20130101; A01N 41/10 20130101; A01N 41/06 20130101; A01N
47/36 20130101; A01N 2300/00 20130101; A01N 41/06 20130101; C07C
233/65 20130101; A01N 37/20 20130101; A01N 47/36 20130101; A01N
43/54 20130101; A01N 43/90 20130101 |
Class at
Publication: |
504/215 ;
564/161; 504/358; 504/333; 504/348; 504/219 |
International
Class: |
A01N 25/00 20060101
A01N025/00; A01N 43/90 20060101 A01N043/90; A01N 47/36 20060101
A01N047/36; A01N 41/06 20060101 A01N041/06; A01N 41/10 20060101
A01N041/10 |
Foreign Application Data
Date |
Code |
Application Number |
Jan 24, 2011 |
GB |
1101209.3 |
Claims
1-17. (canceled)
18. A compound of formula (I) for use as an adjuvant in an
agrochemical composition comprising an agrochemical active
ingredient ##STR00027## wherein m is 1; n is an integer of 0, 1, 2,
or 3; R.sup.1 is C(O)NR.sup.3R.sup.4; each R.sup.2 is independently
C.sub.1-15 alkyl, each R.sup.3 is independently H, or C.sub.1-6
alkyl, each R.sup.4 is independently C.sub.1-8 alkyl, or the
group-[AO].sub.x--R.sup.5 wherein x is an integer of 0 to 20, each
A is independently C.sub.1-4 alkyl, and each R.sup.5 is
independently H, C.sub.1-4 alkyl, or NH.sub.2.
19. A compound of formula (I) as defined in claim 1 wherein R.sup.4
is the group-[AO]x-R.sup.5 wherein A and R.sup.5 are as defined in
claim 1 and x is an integer of 1 to 19.
20. A compound according to claim 19, wherein at least one R.sup.2
is at the para position.
21. A compound according to claim 19, wherein: each R.sup.2 is
independently methyl or C.sub.6-12 alkyl; and wherein in at least
one R.sup.1 and R.sup.3 is selected from the group consisting of H,
methyl, ethyl, propyl or butyl; and R.sup.4 is the
group-[AO].sub.xR.sup.5 wherein A is ethyl or propyl and x is an
integer of 7-18.
22. An compound according to claim 19, wherein in at least one
R.sup.1, R.sup.3 is H and R.sup.4 is the group ##STR00028## wherein
`b` has the value of 9 and the sum of `a` and `c` is 3 or 4.
23. A compound according to claim 19, wherein n is 1.
24. A compound according to claim 19, wherein n is 0.
25. An agrochemical composition comprising a compound as defined in
claim 19, and an agrochemical active ingredient.
26. An agrochemical composition according to claim 25, wherein the
compound of formula (I) comprises from about 0.0005% to about 90%
w/v of the total composition.
27. An agrochemical composition according to claim 25, 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, 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, cloquintocet-mexyl, cyometrinil,
dichlormid, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim,
mefenpyr-diethyl, MG-191, naphthalic anhydride, and
oxabetrinil.
28. An agrochemical composition according to claim 25, wherein the
composition is formulated as, or comprised by a microcapsule.
29. An agrochemical composition according to claim 25, wherein the
composition is an emulsion concentrate (EC) or dispersion
concentrate (DC).
30. An agrochemical composition according to claim 25, comprising
at least one additional component selected from the group
consisting of an agrochemical, an adjuvant, a surfactant, an
emulsifier, and a solvent.
31. A method of controlling a pest, comprising applying a
composition as defined in claim 25 to said pest or the locus of
said pest.
32. A method of making an agrochemical composition comprising
providing: i. an agrochemical ii. and a compound of formula (I) as
defined in claim 19; and combining the agrochemical, and compound
of formula (I).
33. A method according to claim 32, wherein the agrochemical is as
defined in claim 27.
34. A method of increasing the efficacy of an agrochemical
comprising combining a compound of formula (I) as defined in claim
18 with said agrochemical.
Description
[0001] 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.
[0002] The efficacy of the active ingredients (AIs) 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.
[0003] 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.
[0004] 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.
[0005] 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.
[0006] WO2011/010082 describes the use of certain benzamides as
solvents, in particular for agrochemicals.
[0007] 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.
[0008] 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.
[0009] In a first aspect, the invention provides for the use of a
compound of formula (I) as an adjuvant,
##STR00001##
wherein m is an integer of 1, 2, or 3; n is an integer of 0, 1, 2,
or 3; R.sup.1 is C(O)NR.sup.3R.sup.4; each R.sup.2 is independently
C.sub.1-15 alkyl, each R.sup.3 is independently H, or C.sub.1-6
alkyl, each R.sup.4 is independently C.sub.1-8 alkyl, the group the
group-[AO].sub.x--R.sup.5, wherein x is an integer of 0 to 20, each
A is independently C.sub.1-4 alkyl, and each R.sup.5 is
independently H, C.sub.1-4 alkyl, or NH.sub.2.
[0010] Certain compounds of formula (I) are novel and as such form
further aspects of the present invention. Thus the invention also
provides a compound of formula (I)
##STR00002##
wherein m is an integer of 1, 2, or 3; n is an integer of 0, 1, 2,
or 3; R.sup.1 is C(O)NR.sup.3R.sup.4; each R.sup.2 is independently
C.sub.1-15 alkyl, each R.sup.3 is independently H, or C.sub.1-6
alkyl, each R.sup.4 is independently C.sub.1-8 alkyl, the
group-[AO].sub.x--R.sup.5, wherein x is an integer of 0 to 20, each
A is independently C.sub.1-4 alkyl, and each R.sup.5 is
independently H, C.sub.1-4 alkyl, or NH.sub.2; provided that when m
is 1 and n is 1: (i) when R.sup.2 is methyl in the meta position
then R.sup.3 is not ethyl when R.sup.4 is ethyl, and R.sup.3 is not
methyl when R.sup.4 is methyl; (ii) when R.sup.2 is methyl in the
ortho position then: R.sup.3 is not methyl when R.sup.4 is propyl
or tert-butyl, R.sup.3 is not n-propyl when R.sup.4 is ethyl,
n-propyl, or n-butyl, R.sup.3 is not n-butyl when R.sup.4 is
methyl, ethyl or n-butyl, R.sup.3 is not iso-butyl when R.sup.4 is
iso-butyl, R.sup.4 is not methyl when R.sup.3 is H, propyl,
tert-butyl, or n-pentyl, R.sup.4 is not n-propyl when R.sup.3 is
ethyl, R.sup.4 is not n-butyl when R.sup.3 is ethyl, R.sup.4 is not
pentyl when R.sup.3 is H or methyl, R.sup.4 is not 2-ethyl-hexyl
when R.sup.3 is H or methyl; and (iii) when R.sup.2 is methyl at
the para position or ethyl at the ortho position, R.sup.3 and
R.sup.4 are not both methyl.
[0011] In further aspects the invention provides a compound of
formula (I) as defined hereinbefore, wherein at least one R.sup.4
is the group-[AO].sub.x--R.sup.5, as well as a compound of formula
(I) as defined hereinbefore wherein at least one R.sup.2 is at the
para position.
[0012] 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.
[0013] 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.
[0014] In particularly preferred embodiments of the invention, the
preferred values for m, n and x, as well as the preferred groups
for R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, and A, in any
combination thereof, are as set out below.
[0015] 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.
[0016] 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 R.sup.4 group is
-[AO].sub.xR.sup.5, it is preferred that n is 0 or 1. In
embodiments where m is 1 and R.sup.4 is not -[AO].sub.xR.sup.5, it
is preferred that n is 1.
[0017] R.sup.2 is defined above as the group C.sub.1-15 alkyl and
where n is greater than 1, each R.sup.2 group is independently
defined as such.
[0018] It is preferred that each R.sup.2 group is independently a
C.sub.1-12 alkyl group, and in particularly preferred embodiments
each R.sup.2 is independently methyl, or C.sub.6-12 alkyl, more
preferably methyl or a straight chain C.sub.6-12 alkyl group, even
more preferably a methyl, hexyl, octyl, decyl or dodecyl, and most
preferably a methyl or dodecyl group.
[0019] In further preferred embodiments at least one R.sup.2 group
will be present at the para position.
[0020] When n is 1, R.sup.2 may be as defined above, however, in
some embodiments it is preferred that when R.sup.2 is at the ortho
or para position it is a C.sub.2-12 alkyl group, more preferably a
C.sub.6-12 alkyl group, more preferably still a straight chain
C.sub.6-12 alkyl group, and most preferably a hexyl, octyl, decyl
or dodecyl group.
[0021] R.sup.1 is defined herein as the group C(O)NR.sup.3R.sup.4,
wherein each R.sup.3 is independently H, or C.sub.1-6 alkyl and
each R.sup.4 is independently C.sub.1-8 alkyl, or the
group-[AO].sub.xR.sup.5, wherein x is an integer of 0 to 20, each A
is independently C.sub.1-4 alkyl and each R.sup.5 is independently
H, C.sub.1-4 alkyl, or NH.sub.2
[0022] Preferably in at least one R.sup.1 group, R.sup.3 is
selected from the group consisting of H, methyl, ethyl, propyl or
butyl; more preferably H, methyl ethyl, n-propyl, n-butyl or
iso-butyl, more preferably still H or ethyl, and most preferably
H.
[0023] Preferably in at least one R.sup.1 group, R.sup.4 is
selected from the group consisting of C.sub.2-8 alkyl and the
group-[AO].sub.xR.sup.5, wherein A, x and R.sup.5 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.
[0024] 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].sub.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.
[0025] 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.
[0026] In a further set of preferred embodiments A is ethyl, x is 7
or 8, and R.sup.5 is NH.sub.2. In a further set of preferred
embodiments R.sup.4 will be the group
##STR00003##
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.
[0027] As stated above, each R.sup.5 is independently selected from
the group consisting of H, C.sub.1-4 alkyl, and NH.sub.2 Unless
stated otherwise herein in respect of specific embodiments, it is
preferred that R.sup.5 is selected from the group consisting of H,
ethyl, propyl or NH.sub.2, more preferably H or NH.sub.2.
[0028] Illustrative examples of compounds for use as adjuvants in
the present invention are given in Table 1 below, which also shows
selected .sup.1H NMR (400 MHz) data, all obtained with CDCl.sub.3
as the solvent. The following abbreviations are used throughout
this description:
[0029] "NMR"=nuclear magnetic resonance spectrum.
TABLE-US-00001 s = singlet br = broad d = doublet dd = doublet of
doublets t = triplet q = quartet m = multiplet ppm = parts per
million
TABLE-US-00002 TABLE 1 Adjuvants for use in the invention (N/A
means, with respect to characterising data, that the data was not
obtained) Com- .sup.1H-NMR data: pound (ppm/number of No. Structure
Hs/multiplicity) 1 ##STR00004## N/A 2 ##STR00005## N/A 3
##STR00006## N/A 4 ##STR00007## N/A 5 ##STR00008## N/A 6
##STR00009## N/A 7 ##STR00010## N/A 8 ##STR00011## 7.35-7.15 (4H,
m); 5.70 (1H, br); 3.40 (2H, m); 2.45 (3H, s); 1.55 (1H, m); 1.40
(2H, m); 1.35-1.25 (6H, m); 1.00-0.90 (6H, m). 9 ##STR00012##
7.35-7.25 (2H, m); 7.20-7.15 (2H, m); 5.80 (1H, br); 3.40 (2H, m);
2.45 (3H, s); 1.60 (2H, m); 1.35 (4H, m); 0.95 (3H, t). 10
##STR00013## (complex due to restricted rotation) 7.30-7.10 (4H,
m); 5.05 & 3.75 (1H, 2m); 3.00 & 2.65 (3H, 2 s); 2.30 (3H,
2s); 1.15 & 1.10 (6H, d and m). 11 ##STR00014## 7.30-7.15 (4H,
m); 3.60-3.20 (2H, br); 3.10-2.85 (2H, br); 2.30 (3H, s); 2.15 (1H,
m); 1.85 (1H, m) 1.00 (6H, d); 0.75 (6H, d). 12 ##STR00015##
(complex due to restricted rotation) 7.30-7.10 (4H, m); 3.55 and
3.05 (2H, br and t); 3.10 and 2.80 (3H, 2s); 2.30 (3H, 2s); 1.70
and 1.50 (2H, 2m); 1.00 and 0.75 (3H, 2t). 13 ##STR00016##
7.25-7.10 (4H, m); 2.75 (3H, s); 2.30 (3H, s); 1.55 (9H, s). 14
##STR00017## (complex due to restricted rotation) 7.30-7.15 (4H,
m); 3.80-3.20 (2H, br); 3.15 and 3.05 (2H, 2m); 2.30 (3H, 2s);
1.70, 1.45 and 1.10 (4H, 3m); 1.25, 1.05, 1.00 and 0.75 (6H, 4t).
15 ##STR00018## (complex due to restricted rotation) 7.30-7.10 (4H,
m); 3.80-3.10 (2H, br); 3.05 (2H, m); 2.30 (3H, s); 1.70, 1.45 and
1.10 (6H, 3m); 1.00 (3H, m); 0.75 (3H, m). 16 ##STR00019## (complex
due to restricted rotation) 7.30-7.15 (4H, m); 3.55 and 3.10 (2H,
br and t); 3.10 and 2.80 (3H, 2s); 2.30 (3H, s); 1.70, 1.50,
1.40-1.35, 1.20 and 1.10 (6H, 5m); 0.95 and 0.80 (3H, 2t). 17
##STR00020## 7.30-7.15 (4H, m); 3.80-3.20 (2H, br); 3.00 (2H, br);
2.30 (3H, s); 1.70 (2H, m); 1.50 (2H, m); 1.00 (3H, t); 0.75 (3H,
t). 18 ##STR00021## (complex due to restricted rotation) 7.30-7.10
(4H, m); 3.55 and 3.10 (2H, br and t); 3.10 and 2.80 (3H, 2s); 2.30
(3H, s); 1.65, 1.50-1.40 and 1.15 (4H, 3m); 1.00 and 0.80 (3H,
2t).
[0030] 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)
##STR00022##
wherein m is an integer of 1, 2, or 3; n is an integer of 1, 2, or
3; R.sup.1 is C(O)NR.sup.3R.sup.4; each R.sup.2 is independently
C.sub.1-15 alkyl, each R.sup.3 is independently H, or C.sub.1-6
alkyl, each R.sup.4 is independently C.sub.1-8 alkyl, or the
group-[AO].sub.x--R.sup.5, wherein x is an integer of 0 to 12, each
A is independently C.sub.1-4 alkyl, and each R.sup.5 is
independently C.sub.1-4 alkyl, or NH.sub.2; provided that when m is
1 and n is 1: (i) when R.sup.2 is methyl in the meta position then
R.sup.3 is not ethyl when R.sup.4 is ethyl, and R.sup.3 is not
methyl when R.sup.4 is methyl; (ii) when R.sup.2 is methyl in the
ortho position then: R.sup.3 is not methyl when R.sup.4 is propyl
or tert-butyl, R.sup.3 is not n-propyl when R.sup.4 is ethyl,
n-propyl, or n-butyl, R.sup.3 is not n-butyl when R.sup.4 is
methyl, ethyl or n-butyl, R.sup.3 is not iso-butyl when R.sup.4 is
iso-butyl, R.sup.4 is not methyl when R.sup.3 is H, propyl,
tert-butyl, or n-pentyl, R.sup.4 is not n-propyl when R.sup.3 is
ethyl, R.sup.4 is not n-butyl when R.sup.3 is ethyl, R.sup.4 is not
pentyl when R.sup.3 is H or methyl, R.sup.4 is not 2-ethyl-hexyl
when R.sup.3 is H or methyl; and (iii) when R.sup.2 is methyl at
the para position or ethyl at the ortho position, R.sup.3 and
R.sup.4 are not both methyl.
[0031] Also novel are compounds of formula (I)
##STR00023##
wherein m is an integer of 1, 2, or 3; n is an integer of 0, 1, 2,
or 3; R.sup.1 is C(O)NR.sup.3R.sup.4; each R.sup.2 is independently
C.sub.1-15 alkyl, each R.sup.3 is independently H, or C.sub.1-6
alkyl, each R.sup.4 is independently C.sub.1-8 alkyl, or the
group-[AO].sub.x--R.sup.5, wherein x is an integer of 0 to 20, each
A is independently C.sub.1-4 alkyl, and each R.sup.5 is
independently H, C.sub.1-4 alkyl, or NH.sub.2 provided that at
least one R.sup.4 is the group-[AO].sub.x--R.sup.5.
[0032] Also novel are compounds of formula (I)
##STR00024##
wherein m is an integer of 1, 2, or 3; n is an integer of 0, 1, 2,
or 3; R.sup.1 is C(O)NR.sup.3R.sup.4; each R.sup.2 is independently
C.sub.1-15 alkyl, each R.sup.3 is independently H, or C.sub.1-6
alkyl, each R.sup.4 is independently C.sub.1-8 alkyl, or the
group-[AO].sub.x--R.sup.5, wherein x is an integer of 0 to 20, each
A is independently C.sub.1-4 alkyl, and each R.sup.5 is
independently H, C.sub.1-4 alkyl, or NH.sub.2 provided that at
least one R.sup.2 group is in the para-position.
[0033] For compounds of the invention, preferences for the integers
m, n and x, as well as for the substituents R.sup.1, R.sup.2,
R.sup.3, R.sup.4, R.sup.5 and A are as described hereinbefore.
[0034] Compounds of formula (I) as defined hereinbefore may either
be obtained commercially e.g. Compound 1
(N,N-diethyl-3-methylbenzamide or N,N-diethyl-m-toluamide 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.
[0035] In general compounds of formula (I) may be prepared
according to reaction scheme 1 below:
##STR00025##
[0036] Benzoic acid derivatives of formula (II) (wherein R.sup.2
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 R.sup.3
and R.sup.4 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.
[0037] 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.
[0038] 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).
[0039] 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, 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 and metoxuron.
[0040] 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.
[0041] 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.
[0042] Suitable plant growth regulators include paclobutrazole and
1-methylcyclopropene.
[0043] Suitable safeners include benoxacor, cloquintocet-mexyl,
cyometrinil, dichlormid, fenchlorazole-ethyl, fenclorim, flurazole,
fluxofenim, mefenpyr-diethyl, MG-191, naphthalic anhydride, and
oxabetrinil.
[0044] Of course, the various editions of The Pesticide Manual
[especially the 14.sup.th and 15.sup.th editions] and the also
disclose details of agrochemicals, any one of which may suitably be
used with the present invention.
[0045] The skilled man will appreciate that compositions of the
invention may comprise one or more of the agrochemicals as
described above.
[0046] 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.
[0047] 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.
[0048] 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 or w/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.
[0049] 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.
[0050] 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.
[0051] 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 WO2009/130281A1 (see from page 46, line 5 to page
51, line 40).
[0052] 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.
[0053] 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.
[0054] Other optional ingredients which may be added to the
formulation include for example, colourants, scents, and other
materials which benefit a typical agrochemical formulation.
[0055] 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.
[0056] 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.
[0057] Compositions of the invention also have utility in the seed
treatment arena, and thus may be applied as appropriate to
seeds.
[0058] 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.
[0059] 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}-ethox-
y)-ethoxy]-ethoxy}-ethoxy)-ethyl]-benzamide (Compound No. 2)
[0060]
4-Dodecyl-N-(2-{2-[2-(2-{2-[2-(2-ethoxy-ethoxy)-ethoxy]-ethoxy}-eth-
oxy)-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.
EXAMPLE 2
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
[0061] 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).
[0062] 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 21 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.RTM. 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-US-00003 TABLE 2 Mean percentage kill results for
nicosulfuron in the presence of compound no. 2 compared to
nicolsulfuron in the presence of Turbocharge .RTM. D. Adjuvant
CHEAL ABUTH BRAPP DIGSA Mean (g/ha) Compound No 2 80 47.1 86.4 83.1
73.9 Turbocharge 76.7 41.7 80.6 64.8 65.9
EXAMPLE 3
Use of Compound No. 2 as an Adjuvant for Fomesafen
[0063] 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).
[0064] 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-US-00004 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 41.7 68.8 58.6
None 60.8 43.3 38.2 45.8 47.0
EXAMPLE 4
Use of Compound 2 as an Adjuvant for Mesotrione
[0065] 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).
[0066] 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 21 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.RTM. D
(Syngenta Crop Protection Canada, Inc.).
TABLE-US-00005 TABLE 4 Mean percentage kill results for
nicosulfuron in the presence of compound 2 compared to
nicolsulfuron in the presence of Turbocharge .RTM. 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
EXAMPLE 5
Use of Compound 1 (N,N-diethyl-3-methylbenzamide) as an Adjuvant
for Fomesafen
[0067] Compound 1 (N,N-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).
[0068] 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 21 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-US-00006 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
[0069] 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.RTM.GLO3 and 2% w/w Pluronic.RTM.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 11/11.5).
[0070] 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 21 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-US-00007 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 71.7 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
[0071] 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.RTM.GLO3 and 2% w/w Pluronic.RTM.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).
[0072] 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 21 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-US-00008 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 81.3 None 69.2 50.8 87.9 92 75
EXAMPLE 8
Use of Compound 1 as an Adjuvant for Pinoxaden
[0073] 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.RTM.GLO3 and 2% w/w
Pluronic.RTM.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).
[0074] 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 21 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-US-00009 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 21.2 20.8 12.5 15 17.4
EXAMPLE 9
Production of Ethoxylated Aromatic Amides (Compounds 3, 4, 5, and
6)
[0075] 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-US-00010 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
[0076] Each of these amines (A, B, C, and D) was used to produce an
aromatic amide using the general methodology described below.
[0077] 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.degree. C. and 7 bar pressure for five minutes. Table
10 summarises reactant quantities and product yield for the
individual reactions.
TABLE-US-00011 TABLE 10 Amide product PEG Benzoyl (with reference
monoethanolamine chloride to Table 1 Amide sample (g) (g) THF (ml)
above) yield % 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
[0078] 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
[0079] 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
[0080] Benzoyl chloride was reacted with Jeffamine.RTM. ED600
(Huntsman Performance Products, Texas, USA)
[0081] The Jeffamine.RTM. ED series of polyether amines are
polyether diamines based on a predominantly PEG backbone. They have
the following representative structure:
##STR00026##
[0082] For Jeffamine.RTM. ED600 the characteristics are as follows:
y .about.9.0, (x+z) .about.3.6, molecular weight .about.600.
[0083] 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.
* * * * *