EC FORMULATIONS COMPRISING ORGANOPHOSPHATE INSECTICIDES

Abstract

Solvent formulations under EC form comprising (% by weight): 10-40% of one or more compounds having an insecticidal activity selected among those of the organophosphate class, comprising the following group (formula (I)):

##STR00001## wherein: L.sub.1 is selected between oxygen and sulphur, L.sub.2 and L.sub.3, equal to or different from each other, are selected from oxygen, sulphur or a NH group, with the proviso that at least one from L.sub.1, L.sub.2 and L.sub.3 is sulphur and at least one from L.sub.1, L.sub.2 and L.sub.3 is oxygen, M is selected from oxygen, sulphur or NH; 1-20% of an additive formed of methyl or ethyl esters of fatty acids having a C.sub.10-C.sub.20 chain, saturated or unsaturated, or mixtures thereof, the fatty acids deriving from vegetal oils; 3-15% of one or more surfactants selected from non ionic and anionic surfactants, or thereof mixtures;
the complement to 100% being one or more organic solvents having the following characteristics: capable to solubilize the active principle, expressed as % by weight, at room temperature (20-25 C.) for at least 5%; preferably 10%, more preferably at least 20%, substantial immiscible with water.

Claims

1. EC formulations comprising (% by weight): 10-40% of one or more actives selected among the organophosphates, comprising in the molecule the following structure (formula (I)): ##STR00004## wherein: L.sub.1 is selected between oxygen and sulphur, L.sub.2 and L.sub.3, equal to or different from each other, are selected from oxygen, sulphur or a NH group, with the proviso that at least one from L.sub.1, L.sub.2 and L.sub.3 is sulphur and at least one from L.sub.1, L.sub.2 and L.sub.3 is oxygen, M is selected from oxygen, sulphur or NH; 1-20% of an additive methyl or ethyl esters of fatty acids having a C.sub.10-C.sub.20 chain, saturated or unsaturated, and mixtures thereof; 3-15% of one or more surfactants selected from non ionic and anionic surfactants, or mixtures thereof; the complement to 100% being one or more organic solvents having the following characteristics: capable to solubilize the active principle, expressed as % by weight, at room temperature (20-25 C.) for at least 5%; immiscible with water;

2. Formulations according to claim 1, wherein the organophosphate compounds have the following formula (II): ##STR00005## wherein: L.sub.1, L.sub.2, L.sub.3 and M are as defined above, A is selected from one of the following groups: a linear or when possible branched alkyl C.sub.1-C.sub.10, the aliphatic chain optionally containing one or more heteroatoms, preferably one or two, selected from 0, S, and/or a group selected between CO and SO; wherein the hydrogen atoms of the chain are optionally substituted with one or more of the following groups: halogen; CH(COOR.sub.3); a radical of an ester of succinic acid of formula CH(COOR.sub.3)CH.sub.2(COOR.sub.3), R.sub.3 being C.sub.1-C.sub.4 alkyl; when the alkyl chain C.sub.1-C.sub.10 is linear the chain end carbon atom is optionally substituted with one or more halogen atoms; when A alkyl is C.sub.1, it is monosubstituted or bisubstituted; when A alkyl C.sub.1 is monosubstituted one hydrogen atom of the alkyl is substituted with one of the following groups: (CO)NH(CH.sub.3); 1,3,4-thiadiazol-2(3H)-one-yl, wherein the hydrogen atom of the carbon atom at position 5 of the ring is substituted with a group R.sub.3O alcoxy; phthalimido; 3,4-dihydro-4-oxobenzo[d]-[1,2,3]-triazinyl; 2,3-di-hydro-2-oxo-1,3-benzoxazolyl wherein the hydrogen atom of the carbon atom at position 6 of the ring is substituted with one halogen atom; 2-oxo[1,3]-oxazol[4,5-b]pyridin-(2H)-yl wherein the hydrogen atom of the carbon atom at position 6 of the pyridinyl ring is substituted with halogen; when A alkyl is C.sub.1 bisubstituted, the substituents are respectively an ethoxycarbonyl group and a phenyl group; an aromatic ring of 6 carbon atoms having one or two substituents selected from the following group: halogen; CN; NO.sub.2; SCH.sub.3; R.sub.3 and COORS, wherein R.sub.3 is as defined above; a substituent selected from the following: pyridinyl substituted with one or more halogen atoms; (CO)CH.sub.3; 2-oxo-2H-chromenyl wherein two hydrogen atoms, each linked to a different carbon atom of the ring, are substituted respectively with an halogen group and a R.sub.3 group as defined above; pyrimidinyl wherein an hydrogen atom of one or two carbon atoms of the ring is substituted with a group selected from halogen, R.sub.3 as defined above, diethylamino; 1,2-oxazolyl wherein the hydrogen atom of a carbon atom of the ring is substituted with a phenyl group; pyrazolyl substituted with one phenyl group, said phenyl being optionally substituted with an halogen atom; 1,6-dihydro-6-oxo-pyridazinyl wherein a hydrogen atom of a carbon atom of the ring is substituted with a phenyl group; R1 and R2, equal to or different from each other, have the following meanings: hydrogen, linear or when possible branched C.sub.1-C.sub.10alkyl, for example CH.sub.3, C.sub.2H.sub.5, C.sub.4H.sub.9; optionally when the alkyl chain of R.sub.1 and R.sub.2 is linear one or two COORS groups are linked to the aliphatic chain end carbon atom.

3. Formulations according to claim 1 wherein the organophosphate compounds are selected from the following: Acephate, azamethiphos, azinphos-ethyl, azinphos-methyl, cadusafos, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlofenthion, dichlorvos, dicrotophos, dimethoate, dimethylvinphos, disulfoton, ethoprophos, famphur, fenamiphos, fenitrothion, fenthion, heptenophos, isofenphos-methyl, isopropyl-0-(methoxyamino thiophosphoryl) salicylate, isoxathion, malathion, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion, parathion-methyl, phenthoate, phorate, phosalone, phosmet, phosphamidon, pirimiphos-methyl, profenofos, prothiofos, pyraclofos, pyridaphenthion, quinalphos, tebupirimfos, temephos, terbufos, thiometon, triazophos, trichlorfon, vamidothion.

4. Formulations according to claim 3 wherein the organophosphate compounds are selected from chlorpyrifos, chlorpyrifos methyl, dimethoate and phosmet.

5. Formulations according to claim 1 wherein the methyl and/or ethyl esters of fatty acids C.sub.10-C.sub.20 additive A) are obtained by transesterification of vegetal oils selected from rape oil, soya oil, sunflower seed oil and canola oil with methyl or ethyl alcohol; the chain of said C.sub.10-C.sub.20 acids optionally contains one or more unsaturations of the ethylene type, in a number not higher than 3 and in alternated positions along the chain.

6. Formulations according to claim 5 wherein the methyl and/or ethyl esters of the carboxylic C.sub.10-C.sub.20 acids and mixtures thereof are characterized by the following analytical parameters: TABLE-US-00003 Acid value (mg KOH/g) 1 Iodine value (g I.sub.2/100 g) 105-120 Residual water (% by weight) 0.2 Density at 25 C. (g/ml) 0.875-0.877

7. Formulations according claim 1 wherein the organic solvents are selected from the following group: alkylbenzenes having a number of carbon atoms from 7 to 20 and mixtures thereof, the alkyl being linear or branched; linear or branched C.sub.7-C.sub.9 alkyl esters of acetic acid.

8. Formulations according to claim 1 wherein the non ionic surfactants are selected from the following: linear or branched polyethoxylated C.sub.10-C.sub.18 fatty alcohols, wherein the ethoxyl number (EO) ranges from 5 to 10; polyethoxylated castor oil wherein the ethoxyl number ranges from 15 to 40; polyethoxylated distyrylphenols having an ethoxyl number comprised between 12-25; polyethoxylated tristyrylphenols having an ethoxyl number 15-40; C.sub.12-C.sub.18 mono-di and tri-esters of polyethoxylated sorbitan wherein the ethoxyl number ranges from 4 to 20; C.sub.10-C.sub.16 mixtures of alkyl polyglycosides optionally polyethoxylated or polypropoxylated wherein said alkylpolyglycosides have a different ethoxyl or propoxyl number, comprised between 10 and 25; polyethoxylated-polypropoxylated C.sub.8-C.sub.14 aliphatic alcohols; polyaryl phenolethoxylated wherein the ethoxyl/propoxyl number is comprised between 15 and 40.

9. Formulations according to claim 1 wherein the anionic surfactants are selected from the following group: alkaline or alkaline-earth salts of C.sub.9-C.sub.16 alkylbenzensulphonates; alkaline or earth-alkaline salts of C.sub.10-C.sub.14 alkylsulphates.

10. Formulations according to claim 1 wherein mixtures of non ionic and anionic surfactants are used.

11. Formulations according to claim 10, wherein the percentage of non ionic surfactants is in the range from 40 to 80% referred to the total percent weight of the surfactants of the EC formulation.

12. Formulations according to claim 1 comprising as optional components pesticides of classes different than organophosphates, said optional pesticides being soluble in the organic solvent of the solvent formulation under EC form at the used concentrations, the solvent percentage being decreased by an amount equal to that of the optional pesticides added.

13. A process for preparing the EC formulations of claim 1 comprising the following steps: a) solubilization of the active and of the optional pesticides in the organic solvent used for the EC preparation, b) addition of one or more surfactants selected from non ionic and anionic surfactants or thereof mixtures, c) addition of the additive formed of methyl and/or ethyl esters of fatty acids, as defined above.

14. Use of an additive formed of ethyl and/or methyl esters of fatty acids, or mixtures thereof, of claim 1, to reduce the odor deriving from the field distribution of the solvent formulations under the EC form, diluted with water at the application dose and comprising as active one or more organophosphates.

Description

EXAMPLES

Characterization

Acid Value

[0069] The determination is carried out according to AOCS cd 3d-63.

Iodine Value

[0070] The determination is carried out according to Oleon OA-020.

Residual Water

[0071] The determination is carried out according to AOCS Ca 2e-84.

Density

[0072] The determination is carried out according to ISO 3675.

Odour Evaluation

[0073] A field application in an orchard has been simulated by using an atomizer. 300 ml of the formulated product have been diluted in 100 l (liters) of water. About 1500 l/ha have been used.
A group of 9 persons was trained for odour evaluation according to the following score numerical scale:

TABLE-US-00002 0 No odour 1 The operator perceives an unusual odour, but he cannot be sure if it can be attributed to the insecticidal treatment. 2 The operator perceives an unusual, but not unpleasant, odour, that he attributes to the insecticidal treatment 3 The operator perceives an unusual odour, slightly unpleasant, that he attributes to the insecticidal treatment 4 The operator perceives an unpleasant odour and he feels unconfortable to stay near the treated area 5 The operator perceives a very unpleasant odour and he feels as air is almost unbreathable to the point that he cannot stay in that place for a long time. 6 The odour perceived is extremely unpleasant to the extent that for him it is impossible to remain in that place.
Three evaluation meeting assessments respectively at 2, 6 and 24 hours from the application in field have been overall carried out. The numerical values of the scores processed by statistical computing by using an ARM software. The statistical analysis has been based on Bartlett's test and Student-Newman-Keuls (S-N-K) multiple comparison test.

Example 1

Preparation of EC Containing chlorpyriphos-methyl

[0074] 22.1 g of technical chlorpyriphos-methyl having 97% purity are mixed with 52.9 g of Solvesso 150 ND under stirring. 5.0 g of Geronol FF6E (mixture of calcium dodecyl-benzenesulphonate and ethoxylated polyarylphenol wherein dodecylbenzene sulphonate <15% by weight and polyarylphenol ethoxylated is comprised between about 25% and about 65% by weight, the difference to 100 being a mixture of solvents and 5.0 g of Geronol FF4E (mixture of calcium dodecylbenzenesulphonate and polyarylphenol ethoxylated wherein dodecylbenzene sulphonate is comprised between 25% and about 50% and polyarylphenol ethyoxylated <25%, are added, the difference to 100 being a mixture of solvents. Then 15.0 of biodiesel additive, formed of methyl esters of C.sub.10-C.sub.20 vegetable oils are added under stirring by heating at 40 C.

Example 2

[0075] The formulation of Example 1 was used but comprising a lower amount of biodiesel, equal to 10% on the total composition (initially 15% by weight), and by adding a corresponding amount (5% by weight) of solvent.

Example 3

[0076] The formulation of Example 1 was used but comprising an amount of biodiesel equal to 20% and decreasing the solvent amount of 5% by weight.

Example 4 Comparative

[0077] The preparation of Example 1 was repeated but omitting the addition of biodiesel and increasing of an equal amount (15.0 g) the solvent used.

Example 5

Evaluation of the Odour of the Formulation of Example 1 and of Example 4 Comparative

[0078] The method described in the characterization was used by employing the composition of Example 1 and the composition of Example 4 comparative.

[0079] By using the composition of Example 1 after two hours from the application in field no significant odour due to chlorpyriphos-methyl was felt.

[0080] By using the composition of Example 4 comparative after the same period of time the odour had an intensity comparable with the initial one.