Title of Invention

"AN INSECTICIDAL COMPOSITION COMPRISING AN INSECTICIDE AND A PHOSPHONATE OR AN ALKOXYLATED DERIVATIVE"

Abstract An insecticidal composition comprising an insecticide and a phosphonate or an alkoxylated derivative or dimer thereof having the formula (I) wherein the ratio by weight of insecticide to the compound of formula (I) is from 50:1 to 1:400 and wherein R1 and R2 are independently an alkoxy group containing from 4 to 20 carbon atoms or a group -[OCH2CHR4]n-OR5 wherein R4 is hydrogen, methyl or ethyl, n is from 0 to 50 and R5 is hydrogen or an alkyl group containing from 1 to 20 carbon atoms; and R3 is (i) an alkyl or alkenyl group containing from 4 to 20 carbon atoms (ii) optionally substituted phenyl or (iii) a group of formula (II) and wherein R6 is an alkoxy group containing from 4 to 20 carbon atoms or a group -[OCH2CHR4]n -OR5 as herein defined and R7 an alkoxy group containing from 4 to 20 carbon atoms or a group -[OCH2CHR4]-OR5 as defined for R1 and R2.
Full Text PHOSPHONATES AND DERIVATIVES THEREOF AS ENHANCERS OF THE ACTIVITY OF INSECTICIDES
The present invention relates to a composition and in particular to an insecticidal composition, more particularly an insecticidal composition containing an organic phosphonate adjuvant.
USP 2927014 discloses the use of a range of organic phosphonate and phosphinate compounds as herbicides. WO 9304585 discloses the use of certain organic phosphinate and phosphonate compounds as adjuvants to enhance the activity of certain herbicides. WO 9418837 teaches the use of a specific phosphonate, bis (2-ethyl hexyl) 2-ethyIhexyl phosphonate, as adjuvant to improve the bioperformance of specified herbicides. In WO9800021 there is disclosed that certain phosphonate or phosphinate compounds provide improved fungicidal activity in combination with certain fungicides such as fluquinconazole and azoxystrobin.
The applicants have now found that insecticide activity can be surprisingly enhanced by the use of an organic phosphonate adjuvant.
According to the present invention there is provided an insecticidal composition comprising an insecticide and a phosphonate or an alkoxylated derivative or dimer thereof having the formula (I)
(Formula Removed)
wherein R1 and R2 are mdependently an alkoxy group containing from 4 to 20 carbon atoms or a group -[OCH2CHR4]n-OR5 wherein R4 is hydrogen, methyl or ethyl, n is from 0 to 50 and R5 is hydrogen or an alkyl group containing from 1 to 20 carbon atoms; and R3 is (i) an alkyl or alkenyl group containing from 4 to 20 carbon atoms (ii) optionally substituted phenyl or (iii) a group of formula (D)
(Formula Removed)
These compounds work by disrupting the action of gamma-aminobutyric acid (GAB A), the major inhibitory neurotransmitter in the CNS. GAB A is released from the presynaptic membrane and crosses the synapse where it binds to the GAB A receptor. This receptor is coupled to a chloride ion channel that is opened in the presence of GAB A. This opening allows the net influx of chloride ions into the polarised nerve cell hence reducing the potential across the nerve membrane (since at rest the inside of the nerve membrane is more positive than the outside). This means that when the nerve fires, the change in potential is smaller than in the absence of GAB A and hence the nerve impulse is effectively dampened.
GABA agonists include the avermectins that are macrocyclic natural products that can disrupt a variety of chloride ion channels. They actually mimic the action of GABA resulting in permanent opening of the chloride ion channels resulting in insect paralysis. Abamectin, emamectin (usually as a salt form) and milbemectin are examples of this chemistry. Examples of GABA antagonists include the fiprils exemplified by fipronil and the older compounds such as the "cyclodiene" organochlorine compounds such as endosulfan. d) Sodium Channel Disrupters
Sodium channels are vital for nerve transmission. At rest a nerve membrane will have a potential difference of approximately 60 mV across it by virtue of the fact that there are more sodium ions on the outside than on the inside. When a nerve impulse travels along the cell, sodium ion channels open in the membrane allowing sodium ions to flood into the cell inducing a positive peak of potential to flow along the nerve cell. Normally these channels close very quickly and sodium ions are pumped out of the cell to restore the resting potential. Sodium channel disrupters hold these channels open for longer periods preventing re-polarisation. Type-1 pyrethroids (and veratrum alkaloids) prevent re-polarisation for 0.01-0.1 seconds, which results in multiple-spike firing of neurons leading to convulsions, whereas type-II pyrethroids can prevent re-polarisation for minutes or longer leading to lack of coordination. Pyrethroid chemistries are examples of this mode of action. Pyrethroids are synthetic analogues of natural products from Chrysanthemum flowers of which pyrethrin-I is typical. They can be classed into two types according to the alcohol portion. Type-I pyrethroids are the first generation and tend to be rather photochemically unstable. Type-II pyrethroids are derived from gamma-cyano-3-phenoxybenzyl alcohol and are about 10x more potent. Some type-II pyrethroids can have an altered acid portion too, incorporating a phenyl
ring. This chemistry includes tefluthrin, permethrin, bifenthrin, a- cypermethrin, deltamethrin, P-cyfluthrin, lambda-cyhalothrin, gamma-cyhalothrin, esfenvalerate and tau-fluvalinate. Other Na channel disruptors include Indoxacarb;
(e) Respiration Inhibitors
These include chemical classes such as (i) Site-1 inhibitors for example fenpyroximate, fenazaquin, tebufenpyrad, tolfenpyrad and pyrimidifen and uncouplers. Uncouplers have the effect of uncoupling respiration from ATP production. The proteins in the respiratory electron transport chain use the energy produced from respiration to pump protons across the inner mitochondrial membrane. ATP synthase then uses this pH gradient to drive the synthesis of ATP. Uncouplers are lipophilic weak acids that are able to diffuse through membranes in both neutral and anionic forms and hence can ferry protons across the inner mitochondrial membrane. This destroys the pH gradient and hence removes the driving force for ATP synthesis. Chlorfenapyr is an example of an insecticide of this type;
(f) Octopamine Agonists
Octopamine is another neurotransmitter in the insect CNS (not present in vertebrates). It regulates behavioural arousal in the insect. Octopamine binding to the receptor leads to the increased production of c-AMP, which initiates neuronal excitation. Amidines cause over stimulation of these processes resulting in behaviour such as convulsions and continuous flight. An example of an octopamine agonist is Amitraz;
(g) Insect growth regulators - IGR's
Benzoyl ureas are examples of this mode of action. These compounds inhibit the biosynthesis of chitin, the polysaccharide that is the major structural component (~ 50%) of insect exoskeleta. When the insect comes to moult, in the presence of these compounds there is insufficient chitin to complete the construction of the new exoskeleton and hence the insect will die during or immediately after moult. These compounds are not actually "growth regulators" in a hormonal sense, but the term was coined due to the misshapen bodies of the dead insects treated with these compounds. These compounds work best on insects that moult often (e.g. lepidoptera), but their use has been limited because they are only taken up by ingestion and activity is growth stage dependent hence they tend to be slow acting. However this also leads to a very clean environmental toxicity profile and hence these
compounds are often used in IPM programs. Examples of insecticides of this class include diflubenzuron, flufenoxuron, chlorfluazuron, hexaflumuron, lufenuron, and novaluron. Others insect growth regulator chemistries (with different effects to the benzoyl ureas) include buprofezin, pyriproxyfen, cyromazine, tebufenoside, methoxyfenoside and etoxazole; (h) Other modes of action
In this sector there are a number of significant insecticide chemistries which have new modes of action (or ill-defined modes of action). These include diafenthiuron, pymetrozine and propargite.
Preferred insecticides include chlorpyrifos, profenofos, pirimicarb, imidacloprid, acetamiprid, nitenpyram, clothianidin, thiacloprid, thiamethoxam, MTI-446 (from Mitsui), spinosad, abamectin, emamectin benzoate, fipronil, -cyhalothrin, x-cyhalothrin, indoxacarb, fenpyroximate, tebufenpyrad, chlorfenapyr, lufenuron, cyromazine, diafenthiuron, and pymetrozine. Compositions of the present invention are particularly suitable for the insecticides thiamethoxam, spinosad, abamectin, emamectin, benzoate, fipronil, lambda-cyhalothrin,, gamma-cyhalothrin indoxacarb, fenpyroximate, tebufenpyrad, chlorfenapyr, lufenuron, cyromazine, diafenthiuron, and pymetrozine.
The compositions of the invention may contain an active ingredient that is capable of systemic movement in the plant or a contact insecticide, particularly if the pest targets are cryptic feeders (such as leaf miner).
The compositions are particularly useful in combating certain insect classes such as chewing pests for example Lepidoptora, and sucking pests such as aphid spp.
Surprisingly it has been found that the compositions of the invention have no undue phtototoxic effects on host plants at acceptable rates of use.
Both mixtures of compounds of formula (I) and mixtures of insecticides may be used in the composition of the present invention. Compositions of the present invention may contain further additives conventionally incorporated in insecticidal compositions including further adjuvant(s) such as surfactants and insecticide synergists or other components such as anti-freeze agents, polymers, stickers, photoprotectants, mineral oils, plant oils and derivatives. A number of insecticide synergysts are known to those skilled in the art and a specific example is piperonyl butoxide.
The compound of formula (I) may be added to an insecticidal composition at the tank mix stage and compositions of the invention include such tank-mix compositions
dilute and ready for application. Alternatively the compound of formula (I) may be incorporated into a concentrated composition that is designed to be diluted prior to application. The nature of the compound of formula (I) may vary depending on the nature of the substituents from a liquid to a solid and from slightly water soluble to highly water insoluble. One skilled in the art will be able to use conventional techniques to provide compositions of the invention which are for example solids or liquids carried on a suitable solid support, including for example wettable powders (WP or SP-soluble powder), wettable granules (WG-water dispersible granule or SG-soluble granule), dispersions of solids or liquids in liquids such as suspension concentrates, oil based suspension concentrates, oil flowables, such as SC (suspension concentrate) or OF (oil miscible fiowable), emulsions and mixtures such as EW (emulsion in water), EO (emulsion in oil), SE (supension-emulsion), solutions such as EC (emulsifiable concentrate), DC (dispersible concentrate), UL (ultra-low volume liquid), SL (soluble liquid) and special formulations such as microencapsulated compositions. Preferred compounds of formula (I) are generally oily liquids with limited water solubility. These can therefore be easily incorporated into solutions in oils by typical mixing, optionally in combination with one or more emulsifiers or absorbed onto solid carriers such as clays or silicas for incorporation into dry products. Similarly, compounds of formula (I) which are oily liquids may be used to prepare dispersions of an insecticide in the compound of formula (I) or to prepare solutions containing the compound of formula (I) and an insecticide or to prepare mixed dispersion systems where for example the insecticide is present as a suspension concentrate and the compound of formula (I) is present as an oil-in-water emulsion. Other combinations will occur to those skilled in the art.
Adjuvants are normally applied as a percentage of the spray volume applied per hectare. Water volume per hectare is normally about 2001/ha but can vary from 50 to greater than 3000 for special applications in top fruit. Adjuvants are nominally applied at volumes of from 0.05% to 1.0% of the spray volume per hectare. Taking 2001/ha as an average, typical rates of adjuvant will therefore be in the region of 100g (0.05%) to 2000g (1.0%) per hectare. Typical insecticide rates range from 10g/ha to 5kg. Therefore one skilled in the art will expect ratios which cover these typical use rates for both active and adjuvant. These relate directly to ratio (by weight) of insecticide to the compound of formula (I) from 50:1 to 1:400. It is preferred that ratio by weight of the insecticide to the compound of formula (I) is from 25:1 and 1:25 and especially 10:1 and 1:10.
Although it is contemplated that these compositions will generally be applied diluted in water for application to a target crop, the scope of the present invention includes the use of formulations of the invention in ultra-low-volume form, for example in arid areas. The compositions of the invention may also be used for example in bark penetration formulations where there is a desire to enable rapid penetration of an insecticide through tree bark. In addition the compositions of the invention may be used for the treatment and protection of plant seeds using formulations known to the skilled person.
The present invention is illustrated by the following Examples.
EXAMPLE 1
The activity of a range of insecticides combined with 0.5% bis (2-ethylhexyl)-2-ethylhexyl phosphonate (BEEP) was compared with a corresponding formulation containing no bis (2-ethylhexyl)-2-ethylhexyl phosphonate in a test of curative control of L1/L2 Liriomyza huidobriensis, leaf miner. The results are set out in Table 1 and show % control of this leaf miner within bean leaves.
Table 1
(Table Removed)
EXAMPLE 2
The activity of lambda-cyhalothrin, profenofos and indoxacarb combined with 0.5 %
bis (2-ethylhexyl)-2-ethylhexyl phosphonate (BEEP) was compared with a corresponding
formulation containing no bis (2-ethylhexyl)-2-ethylhexyl phosphonate in a feeding/contact
test against Plutella xylostella. The results are set out in Table 2 and show % control.
Table 2
(Table Removed)
EXAMPLE 3 The activity of lambda-cyhalothrin, as Karate 10CS with 0.5% bis (2-ethylhexyl)-2-
ethylhexyl phosphonate (BEEP) was compared with a Karate 10CS containing no bis (2-
ethylhexyl)-2-ethylhexyl phosphonate in a translaminar test (3 day assessment time) against-
R2 Myzus persicae. The results are set out in Table 3 and show % control.
Table 3
(Table Removed)
EXAMPLE 4
The activity of thiamethoxam as Actara 25 WG with bis(2-ethylhexyl) octyl
phosphonate (BEOP) at 0.5% was compared with Actara containing no bis(2-ethylhexyl)
octyl phosphonate in a translaminar test (3 day assessment time) against Aphis gossypii. The
results are set out in Table 4 and show % control.
Table 4
(Table Removed)











WE CLAIM:
1. An insecticidal composition comprising an insecticide and a phosphonate or an alkoxylated derivative or dimer thereof having the formula (I)
(Formula Rempved)
wherein the ratio by weight of insecticide to the compound of formula (I) is from 50:1 to 1:400
and wherein R1 and R2 are independently an alkoxy group containing from 4 to 20 carbon atoms or a group -[OCH2CHR4]n-OR5 wherein R4 is hydrogen, methyl or ethyl, n is from 0 to 50 and R5 is hydrogen or an alkyl group containing from 1 to 20 carbon atoms; and
R3 is (i) an alkyl or alkenyl group containing from 4 to 20 carbon atoms (ii) optionally substituted phenyl or (iii) a group of formula (II)
(Formula Rempved)
and wherein R6 is an alkoxy group containing from 4 to 20 carbon atoms or a group
-[OCH2CHR4]n -OR5 as herein defined and R7 an alkoxy group containing from 4 to 20 carbon atoms or a group -[OCH2CHR4]-OR5 as defined for R1 and R2.
2.An insecticidal composition as claimed in claim 1, wherein R1 and R2 are alkoxy groups containing from 4 to 10 carbon atoms and R3 is an alkyl group containing from 4 to 10 carbon atoms.
3. An insecticidal composition as claimed in claim 2, wherein R1 , R2 and R3 contain from 4 to 8 carbon atoms.
4. An insecticidal composition as claimed in claim 3 wherein the phosphonate is bis-(2-ethylhexy-2-ethylhexylphosphonate, bis-(2-ethylhexyl)-octylphosphonate or bis(butyl)-butylphosphonate.
5. An insecticidal composition as claimed in claim 4 wherein the phosphonate is bis-(2-ethylhexyl)-2-ethylhexylphosphonate.
6. An insecticidal composition as claimed in any preceding claim wherein the insecticide is selected from chlorpyrifos, profenofos, pirimicarb, imidacloprid, acetamiprid, nitenpyram, clothianidin, thiacloprid, thiamethoxam, MTI-446, spinosad, abamectin, emamectin benzoate, fipronil, lambda-cyhalothrin, gamma-cyhalothrin, indoxacarb, fenpyroximate, tebufenpyrad, chlorfenapyr, lufenuron, cyromazine, diafenthiuron, and pymetrozine.

Documents:

3203-DELNP-2004-Abstract-(09-03-2011).pdf

3203-delnp-2004-abstract.pdf

3203-DELNP-2004-Claims-(09-03-2011).pdf

3203-delnp-2004-claims.pdf

3203-DELNP-2004-Correspondence Others-(08-08-2011).pdf

3203-DELNP-2004-Correspondence-Others-(09-03-2011).pdf

3203-delnp-2004-correspondence-others.pdf

3203-delnp-2004-description (complete).pdf

3203-DELNP-2004-Form-1-(09-03-2011).pdf

3203-delnp-2004-form-1.pdf

3203-delnp-2004-form-18.pdf

3203-DELNP-2004-Form-2-(09-03-2011).pdf

3203-delnp-2004-form-2.pdf

3203-DELNP-2004-Form-3-(08-08-2011).pdf

3203-DELNP-2004-Form-3-(09-03-2011).pdf

3203-delnp-2004-form-3.pdf

3203-delnp-2004-form-5.pdf

3203-DELNP-2004-GPA-(09-03-2011).pdf

3203-delnp-2004-gpa.pdf

3203-delnp-2004-pct-101.pdf

3203-delnp-2004-pct-210.pdf

3203-delnp-2004-pct-304.pdf

3203-delnp-2004-pct-409.pdf

3203-delnp-2004-pct-416.pdf

3203-DELNP-2004-Petition 137-(09-03-2011).pdf


Patent Number 248623
Indian Patent Application Number 3203/DELNP/2004
PG Journal Number 30/2011
Publication Date 29-Jul-2011
Grant Date 28-Jul-2011
Date of Filing 18-Oct-2004
Name of Patentee SYNGENTA LIMITED
Applicant Address EUROPEAN REGIONAL CENTRE, PRIESTLEY ROAD, SURREY RESEARCH PARK, GUILDFORD, SURREY GU2 7YH, ENGLAND
Inventors:
# Inventor's Name Inventor's Address
1 DAVID STOCK , CATHERINE JULIA PIPER SYNGENTA LIMITED, JEALOTT'S HILL INTERNATIONAL RESEARCH STATION, BRACKNELL, BERKSHIRE RG42 6EY, ENGLAND
2 JULIE LYNNE RAMSAY SYNGENTA LIMITED, JEALOTT'S HILL INTERNATIONAL RESEARCH STATION, BRACKNELL, BERKSHIRE RG42 6EY, ENGLAND
3 MARK STEVEN BIRCHMORE SYNGENTA CROP PROTECTION AG, SCHWARZWALDALLEE 215, CH-4058 BASEL, SWITZERLAND
4 PATRICK JOSEPH MULQUEEN SYNGENTA LIMITED, JEALOTT'S HILL INTERNATIONAL RESEARCH STATION, BRACKNELL, BERKSHIRE RG42 6EY, ENGLAND
5 RICHARD BRIAN PERRY SYNGENTA LIMITED, JEALOTT'S HILL INTERNATIONAL RESEARCH STATION, BRACKNELL, BERKSHIRE RG42 6EY, ENGLAND
PCT International Classification Number A01N 57/20
PCT International Application Number PCT/GB2003/02210
PCT International Filing date 2003-05-22
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 0211924.6 2002-05-23 U.K.