FR2474818A1 - INSECTICIDAL GRANULAR FORMULATIONS BASED ON CHEMICALLY STABLE PHOSPHORIC DERIVATIVES AND METHOD FOR CONTROLLING INSECTS - Google Patents

Abstract

Insecticidal, nematocidal or acaricidal, chemically stable formulations in the form of granules or powders which contain, as active ingredient, phosphoric, thiophosphoric or dithiophosphoric esters, and, as a carrier, a solid material composed of absorbant particles or powder, are characterised in that an adduct or an adduct mixture from the class of the optionally polyethoxylated amines is used as stabiliser, the formulation being composed of: A) active ingredient 1 to 50% by weight B) stabiliser 1 to 4% by weight C) solid carrier to 100% by weight.

Description

 NEW INSECTICIDE FORMULATIONS.

 The present invention relates to novel insecticidal, nematocidal and acaricidal granular formulations and, more particularly, to chemically stable granular formulations containing as the active ingredient phosphoric, thiophosphoric and dithiophosphoric aesthers as stabilizers of addition or mixtures of adducts belonging to the family of polyoxyethyl amines and as carriers for solid substances.

Phosphoric, thiophosphoric and dithiophosphoric esters are well known, and their use in agriculture as insecticides, acaricides and nematocides is also known. Among these esters, the following may be mentioned: "Dimethoate" [0,0-dimethyl-S- (N-methylcarbamoylmethyl) phosphorodithioate];
"Malathion" [0,0-dimethyl-S - {(1,2-diethoxycarbonyl) ethyl} phosphoro-dithioate]
"Diazinon" [0,0-Diethyl-O- (2-isopropyl-6-methyl-pyrimidin-4-yl) phosphorothioa
"Terbufos" [C, O-diethyl-S-tert-butylthiomethyl phosphorodithioate];
"Disulphoton" [0,0-diethyl- {S-2- (ethylthio) ethyl} phophorodithioate];
"Phentoate" [0,0-dimethyl-S- (alpha-ethoxycarbonyl benzyl) phosphorodithioate].

 The granular formulations containing said active ingredients supported on absorbent mineral substances have the disadvantage of having a low chemical stability with time, quite insufficient to guarantee a biological activity of the active ingredient.

 In order to overcome these disadvantages, several solutions have been suggested.

Among others, the use of additives capable of inhibiting the action of the component of a mineral substance; for example, the use of glycols, acids, polyglycols, alcohols, ketones and other analogous compounds has been suggested (J. Agric., Food Chem., vol 10, 1962, p. 248).

 It has been found, and this is the object of the present invention, that compounds or mixtures of compounds belonging to the family of polyoxyethyl amines inhibit over time the degradation of the active ingredients fixed on mineral support, which makes it possible to maintain unchanged the insecticidal, acaricidal and nematocidal activity of the active ingredients themselves.

 The subject of the present invention is therefore chemically stable insecticidal, acaricidal and nematocidal formulations in granular or pulverulent form, the active principle of which consists of phosphoric, thiophosphoric and dithiophosphoric esters on a solid support consisting of absorbent granules or powders used as carriers, characterized in that adducts or mixtures of the adducts belonging to the family of polyoxyethyl amines are used as stabilizers.

Said formulations have the following composition:
A - active ingredient - i at 50% eh
B - stabilizer - 1 to 4% in
C - solid support - qs 100%.

The main constituent forming the active principle of the formulation according to the present invention may be: # Dimethoate - 0,0-dimethyl-S- (N-methylcarbamoylmethyl) -phosphorodithioate;
Phenatoate - O-dimethyl-S- (alpha-ethoxycarbonylbenzyl) phosphorodithioate;
Nalatiin-O-dimethyl-S- [1,2-di (ethoxycarbonyl) ethyl] phosphorodithioate; Diazinon-O-diethyl-O- (2-isopropyl-6-methyl-phenidin-4-yl) phosphoro thloate;
Terbufos-O, O-diethyl-S- (t-butyl-tniomethyl) -phosphorodithioate; # disulfoton - 0,0-diethyl-S- [2-ethylthio) ethyl] phosphorodithioate;
Phorate-O-diethyl-S - [(ethylthio) methyl] phophorodithioate;
Idinfos-0,0-diethyl-O- [1-methyl-3- (2,2-dichlorovinyl) -1,2,4-triazol-5-yl] thiophosphate.

dans laquelle:
R représente un groupe alkyle saturé ou insaturé comportant 8 à 18 atomes
de carbone, et x + y est compris entre 0 et 40.The compounds which constitute the addition products or mixtures of the adducts belonging to the family of polyoxyethyl amines are tertiary amines comprising two polyoxyethylene groups attached to the nitrogen atom and corresponding to the general formula:

in which:
R represents a saturated or unsaturated alkyl group having 8 to 18 atoms
of carbon, and x + y is from 0 to 40.

 Polyoxyethylated amines are compounds which are already well known but only for their dispersant, humidifying and adsorbing properties in polarography.

 The main compounds constituting the solid support on which the active ingredient is adsorbed are granular and fibrous absorbent substances, such as, for example, bentonite, attapulgite, pumice, sepiolite, talc, kaolin, diatomaceous earth, colloidal silica and the like.

 With the formulations thus formed, the chemical stability of the antiparasitic agents constituted by the phosphoric, thiophosphoric and dithiophosphoric esters increases considerably thanks to the action of the added polyoxyethyl amine.

 In order to prepare the formulations of the present invention, the procedure is carried out according to the well-known principles of the formulation methods.

 Other objects and advantages of the present invention will appear more clearly on reading the following examples, given by way of illustration and not limitation.

EXAMPLE 1 Degradation of Terbufos on various granular supports
2.1 parts by weight of technical Terbufos (having a titre of 95.7) are distributed over 97.9 parts by weight of granular bentonite.

The granular product finished, dried, fluidifies, after 7 days of storage at 540C has a content of active ingredient (abbreviated "pa" in the remainder of this description) of 0.6, which corresponds to a loss of 70, 6% evaluated by gas chromatography.

With the same p.a. and following the same procedure as above, there is a loss of p.a. on sepiolite, pumice and sintered diatomite.

The results obtained were recorded in Table I, below (where the results observed with the bentonite) were also noted. TABLE I

Content <SEP> in <SEP> Terbufos <SEP> - <SEP>% <SEP> in <SEP> weight
<tb> Loss
<tb> Support <SEP> in
<tb><SEP>%
<tb> Initiale <SEP> After <SEP> u <SEP> days <SEP> to <SEP> 54 C
<tb>#<SEP> BENTONITE <SEP> 2.04 <SEP> 0.60 <SEP> 70.6
<tb>#<SEP> SEPIOLITE <SEP> 2.03 <SEP> 0.19 <SEP> 90.6
<tb>#<SEP> PUMICE <SEP> 2.08 <SEP> 0.91 <SEP> 56.2
<tb>#<SEP> DIATOMITE <SEP> Sintered <SEP> 2.01 <SEP> 0.12 <SEP> 94
<tb> TABLE II

constitué d'un mélange renfermant 5% de C14+ 30% de C16 + 20% de C18 saturé + 45% de C18 insaturé (ce mélange sera désigné par R1 dans la suite de la présente description) et x + y = 2, 5, 15; ou bien constitué d'un mélange renfermant 8% de Ce + 7% de Cio + 50% de C12 + 16% de C14 + 9% de C16 + 5% de Cie saturé + 5% de Cis insaturé (on designera ce mélange par R2), avec x + y = 2, 5, 15
Pour calculer la degradation du p.a. on tient compte de la quantité de
Terbufos au départ, à la température ambiante, et après 7 jours à 54 C.Products <SEP> Concentration <SEP> in
<tb> addition <SEP> stabilizers <SEP> Terbufos
<tb> Principle <SEP> Loss
<tb> active <SEP> Initial,
<tb> 7 <SEP> days
<tb> over <SEP> R1 <SEP> R2 <SEP> X + Y <SEP>% <SEP> into <SEP> weight <SEP>% <SEP> into <SEP> weight <SEP> into
<tb> to <SEP> 54 C,
<tb> to <SEP> Temperatures <SEP>% <SEP> to <SEP> Weight <SEP>%
<tb> ture
<tb> ambient
<tb> * <SEP> Terbufos
<tb> * <SEP> Bentonite <SEP> R1 <SEP> 2 <SEP> 2 <SEP> 2.06 <SEP> 1.76 <SEP> 14.5
<tb> * <SEP> Bentonite <SEP> R1 <SEP> 5 <SEP> 2 <SEP> 1.91 <SEP> 1.62 <SEP> 15.2
<tb> * <SEP> Bentonite <SEP> R1 <SEP> 15 <SEP> 2 <SEP> 1.83 <SEP> 1.55 <SEP> 15.3
<tb> * <SEP> Bentonite <SEP> R2 <SEP> 2 <SEP> 2 <SEP> 1.94 <SEP> 1.73 <SEP> 10.8
<tb> * <SEP> Bentonite <SEP> R2 <SEP> 5 <SEP> 2 <SEP> 2.08 <SEP> 1.87 <SEP> 10.1
<tb> * <SEP> Bentonite <SEP> R2 <SEP> 15 <SEP> 2 <SEP> 1.92 <SEP> 1.70 <SEP> 11.4
<tb> * <SEP> Bentonite <SEP> Monoethylene Glycol <SEP> - <SEP> 2 <SEP> 2,12 <SEP> 0.66 <SEP> 68.8
<tb> * <SEP> Bentonite <SEP> - <SEP> Diethylene <SEP> 2 <SEP> 2.26 <SEP> 0.96 <SEP> 57.5
<tb> glycol
<Tb>
EXAMPLE 2 Influence of Stabilizing Addition Products on Granular Formulations
consisting of Terbufos on Bentonite
The procedure is as in Example 1, and with the same formula: 2% by weight of an addition product belonging to the family of polyoxyethyl amines of general formula is added to the latter:

consisting of a mixture containing 5% C14 + 30% C16 + 20% saturated C18 + 45% unsaturated C18 (this mixture will be designated by R1 in the following description) and x + y = 2, 5, 15; or consisting of a mixture containing 8% Ce + 7% Cio + 50% C12 + 16% C14 + 9% C16 + 5% saturated Cie + 5% unsaturated Cis (this mixture will be R2), with x + y = 2, 5, 15
To calculate the degradation of the pa one takes into account the quantity of
Terbufos initially, at room temperature, and after 7 days at 54 C.

 The results obtained were recorded in Table II, above.

Working under the same conditions, comparative tests were carried out with samples to which monoethylene glycol and diethyleneglocyol were added instead of the polyoxyethylated amines.

 The results of these tests were also recorded in Table II.

EXAMPLE 3 Influence of Stabilizing Addition Products on Granular Formulations
of Terbufos on pumice stone
The process is carried out according to the method already described in Example 1, to prepare a formulation based on the same pa but placed on a granular pumice support and using as a stabilizer the mixture of adducts R1 with x + y = 5.

 The finished product has an initial Terbufos titer of 1.95%.

After 7 days of storage at 54 ° C., the p.a. content amounts to 1.90%, ie a loss of 2.5%.

 A comparison test is carried out on a sample having an initial Terbufos content of 2.08%, but to which the stabilizer has not been added. After 7 days of storage at 54 C, the p.a. content is only 0.91%, which corresponds to a loss of 56.2%.

EXAMPLE 4 Influence of stabilizing adducts on a 2% formulation
of Turbufos on sepiolite-
By operating as in Example 2, a formulation having the same active principle is prepared, but on a granular sepiolite support and using as stabilizer 4% of the mixture of adducts R2 with x + y = 5.

The finished product has an initial Terbufos titre of 2%; after 7 days of storage at 54 ° C., the p.a. content is 1.68%, ie a loss of 16%.

EXAMPLE 5 Qualitative Evaluation of Terbufos Degradation at 2% on Bentonite
depending on the amount of stabilizing addition product
The stability tests are subjected to 1 g of granular bentonite formulation containing 2% by weight of Terbufos and various amounts of R1 and
R2 and various x + y, for 7 days and at 54 C.

 After this test period, the formulation is treated with CH 2 Cl 2 to extract the pI, and a fraction of this solution is subjected to thin layer chromatography (TLC) in order to quantitatively evaluate the rate of degradation of pI. at. depending on the amount of stabilizing adduct.

 10 μl of the solution of p.a. is then deposited on a "Bakerflex" -silicone gel chromatography plate IB2 0.2 mm thick.

As a reference, an equal amount of non-formulated Terbufos is deposited.

The elution mixture consisted of 97% n-hexane and 3% ethyl acetate (by volume), and as a developer, a hydroalcoholic solution of PdCl 2 was sprayed.

 In Table III, below, qualitative results relating to Terbufos formulations containing different amounts of stabilizing adduct were recorded.

TABLE III - Qualitative Evaluation (Thin Layer Chromatography)
2% Terbufos degradation on granular bentonite,
depending on the amount and type of addition product
stabilizing.

<Tb>

<SEP> Product <SEP> Appearance <SEP> qualitative
<tb><SEP> of addition <SEP> stabilizer <SEP> in <SEP> chromatography
<tb><SEP> in <SEP> thin <SEP> layer <SEP> *
<tb> After <SEP> 7 <SEP> days
<tb><SEP> R1 <SEP> R2 <SEP> x <SEP> + <SEP> y <SEP>% <SEP> in <SEP> pds <SEP> Initial
<tb> to <SEP> 54 C
<tb><SEP> R2 <SEP> R2 <SEP> O <SEP> 2 <SEP> 7 <SEP> 1 <SEP>
<tb><SEP> R1 <SEP> - <SEP> 2 <SEP> 1 <SEP> 1 <SEP> 2
<tb><SEP> R1 <SEP> - <SEP> 2 <SEP> 2 <SEP> 1 <SEP> 1
<tb><SEP> R1 <SEP> - <SEP> 2 <SEP> 3 <SEP> 1 <SEP> 1
<tb><SEP> R1 <SEP> - <SEP> 5 <SEP> 1 <SEP> 1 <SEP> 2
<tb><SEP> R1 <SEP> - <SEP> 5 <SEP> 2 <SEP> 1 <SEP> 1
<tb><SEP> R1 <SEP> - <SEP> 5 <SEP> 3 <SEP> 1 <SEP> 1
<tb><SEP> R1 <SEP> - <SEP> 15 <SEP> 1 <SEP> 1 <SEP> 2
<tb><SEP> R1 <SEP> ~ <SEP> 15 <SEP> 2 <SEP> 1 <SEP> 1 <SEP>
<tb><SEP> R1 <SEP> - <SEP> 15 <SEP> 3 <SEP> 1 <SEP> 1
<tb><SEP> R1 <SEP> - <SEP> 40 <SEP> 2 <SEP> 1 <SEP> 1
<tb><SEP> ~ <SEP> R2 <SEP> 2 <SEP> 1 <SEP> 1 <SEP> 2
<tb><SEP> R2 <SEP> 2 <SEP> 2 <SEP> 1 <SEP> 1
<tb><SEP> R2 <SEP> 2 <SEP> 3 <SEP> 1 <SEP> 1
<tb><SEP> R2 <SEP> 5 <SEP><SEP> i <SEP> 5 <SEP> 2
<tb><SEP> - <SEP> R2 <SEP> 5 <SEP> 2 <SEP> 1 <SEP> 1
<tb><SEP> ~ <SEP> R2 <SEP> 5 <SEP> 3 <SEP> 1 <SEP> I <SEP>
<tb><SEP> ~ <SEP> R2 <SEP> 15 <SEP> 1 <SEP> 1 <SEP> 2
<tb><SEP> - <SEP> R2 <SEP> 15 <SEP> 2 <SEP> 1 <SEP> 1
<tb><SEP> - <SEP> R2 <SEP> 15 <SEP> 3 <SEP> 1 <SEP> 1
<Tb>
NOTE from Table III: - The number I indicates a gradation of between 0 and 15%.

- The number 2 indicates a degradation between 16 and 50%.

- The number ? induces a degradation between 51 and 1008. TABLE IV

Qualitative <SEP> aspect
<tb> Product
<tb> in <SEP> chromotagraphy
<tb> addition <SEP> stabilizer
<tb> Support <SEP> in <SEP> layer <SEP> thin <SEP> *
<tb> Principle <SEP> active
<tb> granular
<tb> R2 <SEP> X + Y <SEP>% <SEP> in <SEP> weight <SEP> initial <SEP> 7 <SEP> days
<tb> è <SEP> 54 C
<tb>#<SEP> Terbufos <SEP> Earth <SEP> sintered <SEP> from <SEP> - <SEP> - <SEP> - <SEP> 1 <SEP> 3
<tb> diatoms
<tb>#<SEP> Terbufos <SEP> Earth <SEP> sintered <SEP> from <SEP> R2 <SEP> 5 <SEP> 2 <SEP> 1 <SEP> 1
<tb> diatoms
<tb>#<SEP> Terbufos <SEP> Earth <SEP> sintered <SEP> from <SEP> R2 <SEP> 5 <SEP> 4 <SEP> 1 <SEP> 1
<tb> diatoms
<tb> Note from Table IV: * 1 indicates a degradation between 0 and 15%.

2 indicates a degradation of between 16 and 50%.

3 indicates a degradation between 51 and 100%.

EXAMPLE 6 Qualitative Evaluation of the 2% Terbufos Decay on Land of
sintered diatom as a function of the amount of additive product
The procedure is the same as in Example 5 and a formulation is prepared based on the same active ingredient, but placed on a sintered diatomaceous earth support, using different amounts of R2.

 The formulations are subjected to stability tests. For this purpose, leave 7 days at 54 C.

 After this time, the formulations were subjected to TLC analysis for qualitative evaluation of the degradation of the p.a. following the procedure of Example 5.

The experimental results thus obtained are indicated in the
Table IV, above.

EXAMPLE 7 Influence of stabilizing adducts on granular formulations
of Disulfoton on various supports
5.25 parts by weight of technical Disulfoton (95.7%) are mixed with 4 parts by weight of the mixture of adducts R2 with stabilizing X + y = and are distributed over 90.75% of the product. Granular sepiolitis.

The granular finished product, dried and fluid at an initial
Disulfoton of 5.02.

 After storage for 7 days at 54 ° C., the content of active principle is equal to 5% according to the analysis by gas chromatography.

 A similar sample prepared for comparison without addition of stabilizer has an initial active ingredient content of 4.80 by weight; after 7 days of storage at 540, the active ingredient content is 4.11%, which corresponds to a loss of 14.3%.

 Similar results are obtained when bentonite is used as a carrier instead of as a sepiolite.

All these results have been reported in Table 5 below (where the results obtained with Sépiolite have also been recorded). TABLE V

Product
<tb> of addition <SEP> stabilizer <SEP> Content <SEP> in <SEP> disulfoton
<tb> Principle <SEP> Support <SEP> Loss
<tb> active <SEP> in
<tb> Initial, <SEP> 7 <SEP> days <SEP> to
<tb> (pa) <SEP> R2 <SEP> X + Y <SEP>% <SEP> in <SEP> pds <SEP>%
<tb>% <SEP> in <SEP> weight <SEP> 54 C.
<Tb>

% <SEP> in <SEP> weight
<tb>#<SEP> DISULFOTON <SEP> SEPIOLITE <SEP> - <SEP> - <SEP> - <SEP> 4.80 <SEP> 4,11 <SEP> 14,3
<tb>#<SEP> DISULFOTON <SEP> SEPIOLITE <SEP> R2 <SEP> 5 <SEP> 4 <SEP> 5.02 <SEP> 5.00 <SEP> 0
<tb>#<SEP> DISULFOTON <SEP> BENTONITE <SEP> - <SEP> - <SEP> - <SEP> 4.47 <SEP> 3.66 <SEP> 18.1
<tb>#<SEP> DISULFOTON <SEP> BENTONITE <SEP> R2 <SEP> 5 <SEP> 2 <SEP> 4.24 <SEP> 4.24 <SEP> 0
<tb> TABLE VI

Principle <SEP> active <SEP> Product <SEP> Aspect <SEP> positive
<tb> addition <SEP> stabilizer <SEP> in <SEP> chromatography
<tb> Support <SEP> granular <SEP> in <SEP> layer <SEP> thin <SEP> *
<tb> Type <SEP>% <SEP> in <SEP> wt <SEP> R2 <SEP> X + Y <SEP>% <SEP> in <SEP> wt <SEP> Initial <SEP> 7 <SEP> days
<tb> to <SEP> 54 C
<tb>#<SEP> TERBUFOS <SEP> 10 <SEP> Stone <SEP> Pumice <SEP> - <SEP> - <SEP> - <SEP> 1 <SEP> 3
<tb>#<SEP> TERBUFOS <SEP> 10 <SEP> Stone <SEP> Pumice <SEP> R2 <SEP> 5 <SEP> 2 <SEP> 1 <SEP> 1
<tb>#<SEP> TERBUFOS <SEP> 15 <SEP> Sepiolite <SEP> - <SEP> - <SEP> - <SEP> 1 <SEP> 3
<tb>#<SEP> TERBUFOS <SEP> 15 <SEP> Sepiolite <SEP> R2 <SEP> 5 <SEP> 4 <SEP> 1 <SEP> 1
<tb>#<SEP> TERBUFOS <SEP> 15 <SEP> Earth <SEP> Sintered <SEP> from <SEP> - <SEP> - <SEP> - <SEP> 1 <SEP> 3
<tb> diatoms
<tb>#<SEP> TERBUFOS <SEP> 15 <SEP> Earth <SEP> sintered <SEP> from <SEP> R2 <SEP> 5 <SEP> 2 <SEP> 1 <SEP> 1
<tb> diatoms
<tb>#<SEP> DISULFOTON <SEP> 15 <SEP> Sepiolite <SEP> - <SEP> - <SEP> - <SEP> 1 <SEP> 3
<tb>#<SEP> DISULFOTON <SEP> 15 <SEP> Sepiolite <SEP> R2 <SEP> 5 <SEP> 4 <SEP> 1 <SEP> 1
<tb> Note of Table VI :: * The number 1 indicates a degradation between 0 and 15%
The number 2 indicates a deterioration between 16 and 50%
The number 3 indicates a degradation between 51 and 100%.

EXAMPLE 8 Qualitative Evaluation of the Degradation of Terbufos and Disulfoton on
various supports depending on the amount of stabilizer
The procedure is as in Example 5, and formulations are prepared at 10% and 15% Terbufos on pumice, Sepiolite and sintered diatomaceous earth, and 15% Disulfoton formulations.
Sepiolite, using various amounts of R2.

 These formulations are subjected to stability tests for 7 days, at 54 ° C.

 After this period, the formulations are subjected to analysis by thin layer chromatography, in order to qualitatively evaluate the degradation undergone by the active principle, as in Example 5.

The experimental results are recorded in Table VI, above. t
EXAMPLE 9
The procedure is carried out according to the same procedure as in Example 1, and a formulation is prepared from 5.25 parts by weight of technical Phentoate and 2 parts by weight of stabilizer R1, x + y being equal to 5, on support. granular bentonite.

 The initial content of p.a. is 4.88, and after 7 days of storage at 54 ° C., the p.a. content is 3.95% (according to gas-liquid chromatography), a loss of 19%. An analogous sample, prepared for comparison without the addition of stabilizer, takes an initial p.a.

of 4.81%. After 7 days of storage at 54 C, the p.a. content is 3.62%, a loss of 24.7%.

EXAMPLE 10 Qualitative Evaluation of the Diazinon and Idinfos Degradation at 5%
concentration on granular Bentonite and on Sepiolite as a function of
the amount of stabilizing adduct.

0.4 g of formulation containing 5% by weight of technical Diazinon are subjected to
R2 being used as adduct, on bentonite and on granular sepiolite at stability tests at 54 C respectively, for 7 days.

 After this period, the formulation is treated with 3 g of CH 2 Cl 2 in order to extract the active ingredient.

TABLE VII

Product <SEP> Appearance <SEP> qualitative <SEP> in
<tb> addition <SEP> stabilizer <SEP> chromatography <SEP> in <SEP> layer <SEP> thin *
<tb> Principle <SEP> active <SEP> Support <SEP> Granular
<tb> R2 <SEP> X + Y <SEP>% <SEP> in <SEP> weight <SEP> Initial <SEP> 7 <SEP> days, <SEP> to <SEP> 54 C
<tb>#<SEP> DIAZINON <SEP> BENTONITE <SEP> - <SEP> - <SEP> - <SEP> 1 <SEP> 3
####
<tb>#<SEP> DIAZINON <SEP> SEPIOLITE <SEP> - <SEP> - <SEP> - <SEP> 1 <SEP> 3
<tb>#<SEP> DIAZINON <SEP> SEPIOLITE <SEP> R2 <SEP> 5 <SEP> 4 <SEP> 1 <SEP> 1
<tb>#<SEP> IDINFOS <SEP> ** <SEP> BENTONITE <SEP> - <SEP> - <SEP> - <SEP> 1 <SEP> 3
<tb>#<SEP> IDINFOS <SEP> BENTONITE <SEP> R2 <SEP> 5 <SEP> 2 <SEP> 1 <SEP> 1
<tb>#<SEP> IDINFOS <SEP> SEPIOLITE <SEP> - <SEP> - <SEP> - <SEP> 1 <SEP> 3
<tb>#<SEP> IDINFOS <SEP> SEPIOLITE <SEP> R2 <SEP> 5 <SEP> 4 <SEP> 1 <SEP> 1
<tb> Notes from Table 7: * The number 1 indicates a degradation between 0 and 15%.

The number 3 indicates a degradation between 51 and 100%.

** Registered trademark of MONTEDISON Company.

 Similarly, 0.49 of formulation containing 5% technical Idinfos plus R2 is treated as a stabilizer, supported respectively on bentonite and on granular sepiolite.

 Both formulations were subjected to TLC analysis to qualitatively evaluate the degradation of the active ingredient by following the procedure of Example 5.

 The eluent mixtures used for the two active ingredients consist of a solution of 85% n-hexane and 15% acetone (by volume); as a developer, an alcoholic solution of Pic12 is sprayed.

The experimental results are shown in Table VII, above.
EXAMPLE 11
Influence of stabilizing adducts on granular formulations
different phorate on different supports
4.9 parts by weight of technical phosphorate (92.5% strength) are mixed with 2 parts by weight of a mixture of adducts R2 with x + y = 5 as stabilizer and are sprayed. on 93.1 parts by weight of granular bentonite.

 The finished, dry and fluid granular product has an initial phorate content of 4.39%.

 After storage for 7 days at 54 ° C, the p.a. content is 4.26S, a loss of 3% based on chromatography.

 An analogous sample is prepared for comparative purposes without addition of stabilizer. it has an initial content of active ingredient of 4.00%.

After 7 days of storage at 540C, the active ingredient content is 2.45%, a loss of 38.7%.

 Similar results are obtained by using sintered diatomaceous earth or sepiolite instead of bentonite as support.

 The experimental results have been compiled in Table VIII below (where the results obtained with bentonite have also been recorded).

TABLE VIII

Product
<tb> Content <SEP> in <SEP> Phorate
<tb> addition <SEP> stabilizer
<tb> Principle <SEP> Support <SEP> Loss
<tb> in
<tb> active <SEP> Initial. <SEP> 7 <SEP> days
<tb> R2 <SEP> x + y <SEP>% <SEP> in <SEP> wt
<tb>% <SEP> in <SEP> wt <SEP> to <SEP> 54 C <SEP>%
<tb>% <SEP> in <SEP> wt
<tb>#<SEP> PHORATE <SEP> BENTONITE <SEP> - <SEP> - <SEP> - <SEP> 4.00 <SEP> 2.45 <SEP> 38.7
<tb>#<SEP> PHORATE <SEP> BENTONITE <SEP> R2 <SEP> 5 <SEP> 2 <SEP> 4.39 <SEP> 4.26 <SEP> 3
<tb>#<SEP> PHORATE <SEP> SEPIOLITE <SEP> - <SEP> - <SEP> - <SEP> 3.68 <SEP> 2.19 <SEP> 40.5
<tb>#<SEP> PHORATE <SEP> SEPIOLITE <SEP> R2 <SEP> 5 <SEP> 4 <SEP> 4.58 <SEP> 4.05 <SEP> 11.6
<tb>#<SEP> PHORATE <SEP> EARTH <SEP> SIN <SEP> FROM <SEP> - <SEP> - <SEP> - <SEP> 4.27 <SEP> 2.54 <SEP> 40.5
<tb> DIATOMES
<tb>#<SEP> PHORATE <SEP> EARTH <SEP> SIN <SEP> FROM <SEP> R2 <SEP> 5 <SEP> 2 <SEP> 4.55 <SEP> 4.48 <SE> 1.5
<tb> DIATOMES
<tb> TABLE IX
Residual contact activity on Agrotis upsilon, expressed as a mortality rate with the indicated doses and times.

<SEP> rate of SEP activity after
<tb> Dose,
<tb> Products
<tb> kg / ha <SEP> as
<Tb>

0 <SEP> 4 <SEP> 6 <SEP> 8 <SEP> 12 <SEP> 19
<tb> day <SEP> days <SEP> days <SEP> days <SEP> days <SEP> days
<tb>#<SEP> Terbufos <SEP><SEP> 10 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 86 <SEP> 53 <SEP> 8
<tb>#<SEP> Composition <SEP> containing
<tb> 2.54% <SEP> of <SEP> Terbufos <SEP> on <SEP> 10 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 86 <SEP> 62
<tb> stone <SEP> pumice <SEP> stabilized.
<Tb>

# <SEP> Composition <SEP> containing
<tb> 2.41% <SEP> of <SEP> Terbufos <SEP> on <SEP> 10 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 93 <SEP> 68 <SEP> 36
<tb> stabilized bentonite <SEP>.
<Tb>

PAINTINGS

Product
<tb> Content <SEP> in <SEP> Disulfoton
<tb> addition <SEP> stabilizer
<tb> Principle <SEP> active <SEP> Support <SEP> Loss
<tb> (pa) <SEP> After <SEP> 7 <SEP> in
<tb> Initial,
<tb> R2 <SEP> x <SEP> + <SEP> y <SEP>% <SEP> in <SEP> wt <SEP> days <SEP> to <SEP> 54 C.
<Tb>

% <SEP> in <SEP> wt <SEP>%
<tb>% <SEP> in <SEP> wt
<tb>#<SEP> DISULFOTON <SEP> Clay <SEP> calcined <SEP> - <SEP> - <SEP> - <SEP> 2.60 <SEP> 2.37 <SEP> 8.8
<tb>#<SEP> DISULFOTON <SEP> Clay <SEP> calcined <SEP> R2 <SEP> 5 <SEP> 1 <SEP> 2.56 <SEP> 2.46 <SEP> 3.9
<tb>#<SEP> DISULFOTON <SEP> Clay <SEP> calcined <SEP> - <SEP> - <SEP> - <SEP> 4.99 <SEP> 4.60 <SEP> 7.8
<tb>#<SEP> DISULFOTON <SEP> Clay <SEP> calcined <SEP> R2 <SEP> 5 <SEP> 2 <SEP> 5,13 <SEP> 5,14 <SEP>
EXAMPLE 12 I Biological Activity on Agroti ypoilon
We take an earth of medium composition, we divide it into packages of
10 kilos and put them in plastic boxes (38 x 29 cm x 19 cm); this soil is treated by uniformly distributing on its surface granular formulations based on terbufos on pumice and on bentonite and is harrowed so as to evenly distribute the compounds to be studied, at the rate of 10 kg / ha of active substance, then they are sprinkles.

 At successive time intervals, the soil is infested with Agrotis ypailon larvae of the last age (5th age) and fed with maize seeds.

 By way of comparison, untreated soil is infested under the same conditions as larvae of the same age. Six days after infection, the percent mortality of the larvae is compared to the mortality rate of the control larvae (larvae distributed in the untreated soil).

The results of these tests are shown in Table IX, above.
EXAMPLE 13 Influence of stabilizing adducts on the formulations of
Disulfoton on calcined clay
Samples are prepared according to the method described in Example 7 and using calcined clay as the support.

The results obtained have been reported in Table X, also above. t
Of course, the present invention is not limited to the examples and embodiments mentioned above; it is capable of many variants accessible to those skilled in the art, depending on the intended applications and without departing from the spirit of the invention.

Claims (13)

 1.- Insecticidal, nematocidal, acaricidal formulations in granular or powder form, chemically stable and containing as active ingredient phosphoric, thiophosphoric, dithiophosphoric esters and as a carrier a solid substance consisting of granules or absorbent powders, characterized in that the compounds of the family of polyoxyethyl amines, as stabilizers, are used as adducts or additive mixtures, said formulations having the following composition:  A - active ingredient - 50% by weight  B - stabilizer - 4% by weight  C - solid support - q .. p. 100%.  2. Formulations according to claim 1, characterized in that the active ingredient is preferably used in a proportion of 2 to 15% by weight.  3. Formulations according to claim 1, characterized in that the active ingredient is O, O-dimethyl-S- (N-methyl-carbamoylbenzyl) -phosphorodithioate.  4. Formulations according to claim 1, characterized in that the active ingredient is O, O-dimethyl-S- (alpha-ethoxycarbonylbenzyl) -phosphorodithioate.  5. Formulations according to claim 1, characterized in that the active ingredient is O, O-dimethyl-S- [1,2-di (ethoxycarbonyl) ethyl] phosphodithioate.  6. Formulations according to claim 1, characterized in that the active ingredient is O, O-diethyl-O- (2-isopropyl-6-methyl-pyrimidin-4-yl) phosphorothioate.  7. Formulations according to claim 1, characterized in that the active ingredient is 0,0-diethyl-S- (t-butyl-thiomethyl) -phosphorodithioate.  8. Formulations according to claim 1, characterized in that the active ingredient is O, O-diethyl-S-E2-ethylthio) ethyl] phosphorodithioate.  9. Formulations according to claim 1, characterized in that the active ingredient is 0,0-diethyl-S - [(ethylthio) methyl] phosphorodithioate.  10. Formulations according to claim 1, characterized in that the active ingredient is 0,0-diethyl-O- [1-methyl-3 (2,2-dichlorovinyl) -1,2,4-triazol-5). -ylthiophosphate.  11. Formulations according to claim 1, characterized in that the addition products or additive mixtures constituting the stabilizer have the general formula:

 in which:  R is a saturated or unsaturated alkyl group having 8 to 18 carbon atoms  carbon, and x + y is between 0 and 40.  12. Formulations according to claim 1, characterized in that the solid support is bentonite, sepiolite, pumice, talc, kaolin, diatomaceous earth or clay.  13.- method for controlling insect infestations, characterized in that one uses a formulation according to any one of claims 1 to 12, which is distributed on the ground to be protected.