Compositions containing phosphoric esters associated with one stabilizing.

PATENT AS AFRICAN AND MALAGASY

INDUSTRIAL PROPERTY

P. 887

In Yaounde (Cameroon) International Patent Classification: 01 - c 07 no. 03856 has

Oo.imvi.

10 September 1971 to 16 hr 30 demand of Mn

the O.A.M.P.I. (G.P. no. 54,360) called by the business:

FBCN - g-Ciba Geigy residing in Swiss.

DELIVERED THE

Publishes at n° of official ballot

Priority: Patent application filed in France under

the no. 70, 33 013 11 September 1970 on behalf of the company said: I.E.-Ciba Geigy sec. has.

Compositions of phosphoric esters associated

to a stabilizer.

The present invention relates to a method for stabilizing phosphoric esters pesticides and, as new industrial products, to HAse found compositions of phosphoric esters thus stabilized.

The phosphoric esters are now widespread in

the purpose pesticides and, in particular, as insecticides; their interest is due primarily to their speed of action and the lack of a build-up of these compounds in the living tissue as a result of their rapid in situ hydrolysis.

The latter feature giving them a clear advantage over the pesticides called "chlorinated" constitutes, however, a major drawback; the sensitivity of some phosphoric esters to moisture, even simply than the atmosphere, is such that their decomposition takes place before they could act on the pests: esters are responsive are more particularly those containing a weight such as or alkyl radicals, for example, the radicals methyl, ethyl, propyl or isopropyl, attached to 1' anion of phosphoric; it occurs, contact with water molecules, decomposition, at least partial, of these esters by protonation, it is to say by moving a light alkyl remains in favor of a hydrogen atom.

Among esters are sensitive, must be mentioned especially phosphates 0 - (dichloro 2.2 vinylej and 0.0-dimethyl, known as the common DICKLORVOS and the abbreviation DDYP whose use in the insecticidal devices from the permanent "evaporators" found a huge development in recent years.

Various stabilizing means have already been recommended to limit the decomposition of such esters but they feel generally toxic as phenols, amines and nitrogen-containing heterocyclic lightweight; another interesting class of stabilizers comprises azo compounds and hydrazonic groups but these have high dye so that they cannot always be employed. It was also recommended the use of anhydrides or epoxides, but it is known that these compounds act by fixing, water molecule, free acid molecule; see that this process is limited stoichiometrically and that stabilization ceases once the entire stabilizer is input in response; this leads to use large proportions of these stabilizers, which is uneconomical.

the present invention aims to achieve stabilization of phosphoric esters pesticides by implementing more effective substances and which overcomes the disadvantages above exposed.

Certain derivatives of the phenylalkyl have been recommended as synergists of insecticide, it is to say, as boosters the action insecticides in contact with insects and this, to the highest levels of the order of 200 to 500 i°, calculated on the total weight of the insecticidal compounds; it has never been found prior to the present invention been found that the derivatives of the phenylalkyl particularly, to low levels ', to preserve the phosphoric esters against the protonation.

the invention therefore concerns the pesticidal compositions

comprising

(Has) at least one phosphoric ester pesticide containing molecule has at least one alkyl radical containing one to three carbon atoms,

(D) a stabilizing agent said ester to decomposition by protonation and used in a proportion of between 0.2 and 10 i° and preferably, between 0.5 and 6 $, calculated on the weight of the phosphoric ester, said composition being characterized in that the stabilizer is selected from the compounds of the chemical class of benzodioxoles and 1.5 ·

Such a composition may contain, optionally, a solvent of the phosphoric ester, solid or liquid with or without pressure; it may also, optionally, contain one or inert additives mineral or organic.

. the invention also relates to a method for stabilizing a phosphoric ester pesticidal, having in the molecule at least one alkyl radical containing one to three carbon atoms, optionally in admixture with a solvent of the phosphoric ester, solvent that is solid or liquid at room temperature with or without pressure and/or optionally in admixture with one or admixtures therefor with the phosphoric ester, said method being characterized in that the phosphoric ester is added to, or to the mixture that contains the, 0.2 to 10/>calculated on the weight of the phosphoric ester, an agent capable of stabilizing said phosphoric ester against the protonation and being constituted by at least one chemical compound selected from the class of benzodioxoles and 1.3.

In a preferred embodiment, the invention is also directed to the pesticidal compositions comprising the components (has) and (d) above-defined and in addition, as component (d), at least one second stabilizing agent said phosphoric ester pesticide against decomposition by protonation, the second agent being selected from the elemental sulfur, sulfur compounds are bivalent as defined in Patent № deposited the same day as the present application, and the diazenes as defined in Patent № deposited 11 March 1970.

This second stabilizing agent, used in an amount between 0.1 and 5 f° about, calculated on the weight of the estest.er phosphoric pesticidal, increases the stabilizing effect of the main agent to demonstrate a sustained action synergistic stabilizing.

According to a preferred embodiment, the total amount of stabilizing agent is between 0.5 and 6 $calculated on the weight of the phosphoric ester. Proportion suggested by the invention, the phenylalkyl having no affect as synergist toxicity on the insecticidal phosphoric ester.

the benzodioxoles preferred for the implementation of the invention are defined by the general formula I:

wherein m 1 or 2 may represent; and

X represents an alkylene bridge a to 7 carbon atoms, alkenylene of 2 to bridge 7 carbon atoms or 4 to 7 alkadienylene bridge of carbon atoms;

R¹ represents the following components:

(has) hydrogen,

(d) alkyl of one to 6 carbon atoms, unsubstituted or substituted by phenyl or nitro,

(d) alkenyl of 2 to 6 carbon atoms, unsubstituted or substituted by phenyl or nitro,

(d.) nitro group,

(i) halogen with an atomic number not exceeding 35

(f.) alal.coxy light; and

(HAS) m represents only 1,

R represents one of the following constituents of the formula I:

(has) hydrogen,

(d) light alkyl,

(d) alkenyl lightweight,

(d.) halogen with an atomic number not exceeding 17,

(i) nitro group,

(f.) the grouping - HM=hïï

wherein each of R ^, Rj and the R ' j is independently of the others represents the same or various constituents' among the following:

hydrogen, light alkyl, alkoxy lightweight, hydroxyl, one nitro, chlorine, bromine and alkylthio lightweight;

the moiety - (grams) THIS VBE1)

THE W - 2^DEGREES

b.

the £wherein R represents a hydrogen atom or alkyl

lightweight;

the moiety - (hr)

>°v

wherein each Z and Z ', independently of the other, represents one of the following constituents:

a direct bond (activated c-c) or an oxygen atom (- 0 -) wherein R " represents a hydrogen atom or an alkyl or lightweight

a lightweight aa.lcoxy;

(i to) the grouping

wherein R represents an alkyl ^ of one to 6 carbon atoms or an oxa-alkyl of at most 15 carbon atoms and from one to two oxygen atoms as ring members;

R represents one of the following constituents of the formula I:

(i in) a cyano;

THE R .,

(ii) the grouping

THE N -

wherein R ^ represents a hydrogen atom, an alkyl or alkanoyl lightweight lightweight, and

_ R represents a hydrogen atom or an alkyl lightweight, 5

or:

The R ^ and R, _ together with the nitrogen to which

•they are bound, represent a group unsubstituted or substituted with alkyl lightweight, chosen from the groups of pyrrolidino, piperidino, morpholino and azepino; '

(iii) the group - c0 rg, wherein

RG is a of the following constituents:

(has) hydrogen;

(d) the group - 0m, wherein m represents a hydrogen atom or a metal ion equivalent;

(d) light alkyl;

(d.) alcalc.oxy lightweight;

(i) 2 to have oxidized coxy of 7 carbon atoms;

(f.) alkyloxy-alkoxy-alk AI oxy 4 to 10 carbon atoms;

(gm) phenyl unsubstituted or substituted by one or more of the following substituents: light alkyl, alkoxy which is lightweight, chloro and bromo;

(hr) the grouping - n-

wherein each of R and R ^ ^, independently of the other nts is selected from H, alkyl or phenyl lightweight;

(iv) the group - S-alkyl

T-

0

wherein "alkyl" represents alkyl of one to 8 carbon atoms;

(volts) the grouping - 0 rg

wherein RG is a light alkyl or oxa-alkyl of at most 15 carbon atoms and from one to three oxygen atoms as ring members'

(vi) the group - 0 c-F.;

O

, R.,

■^R 9

wherein each RG and R ^, independently of the other,

represents a hydrogen atom or a light alkyl, or R_{the n} and R ' y taken together with the nitrogen atom to which they are bonded,

represent groups of pyrrolidino, piperidino, morpholino and azepino;

or

(D) m is 1,

R and R ' taken together represent a divalent groups of the following:

(oc) the grouping

?10

T-⁰ ^

10

THE HC-R.

^{THE RC} -^Rïo

wherein each of R_{] 0} , Of Rj_Q , R."₀ , independently of the others, is hydrogen, alkyl lightweight, alk-oxycarbonyl. 2 to 5 carbon atoms, or the group - C00M wherein m is as defined above;

(iF ) the array 12

^ / 6 - C. J R11

H

wherein R ^ ^ represents one of the following constituents:

hydrogen, alkyl lightweight, iEA lightweight alkyloxy, lightweight alcancyle or benzoyl, and

The R^2 represents one of the following constituents:

hydrogen, light alkyl, alkoxy which is lightweight

or the grouping•^R an IR^{the R}

wherein n represents 1 or 2

The R ^ represents an alkylene bridge of 2 to 4 carbon atoms, and

each of R and R! ^ j is, independently of the other_> represents a hydrogen atom or an alkyl lightweight,

or R ^ ^ I-and R taken together with the nitrogen atom to which they are bound•, represent groups of pyrrolidino, piperidino, morpholino and azepino.

The organic constituents above under formula I and qualified above and in the description that follows and in the claims as "lightweight" have up to six, and preferably, one or two to four carbon atoms.

Also included among the benzodioxoles of formula I salts more or less volatile■adduct formed between the benzodioxoles having a basic function and suitable inorganic or organic acids. The term "metal ion" used in defining "the m" above comprises ammonium ion3

RH I R-R in which R, R-. R and R_{the O} each represent the W X Y ^ 'to X' W-Y-Z-* independently of one another a hydrogen atom or an organic residue, especially a light alkyl.

the term "phenylalkyl" used in the examples that follow still means the phenylalkyl-to-1.3 ·

benzodioxoles of particularly preferred between those defined by formula I are chosen from the following classes 1) simple benzodioxoles defined by formula 1'

(I-^F. )

wherein R_& is selected from the following components:

hydrogen, fluorine, chlorine, bromine, alkyl of one to.. six carbon atoms, unsubstituted or substituted by nitro or phenyl, alkenyl of 2 to 4 carbon atoms, nitro alkenyl of 2 to 4 carbon atoms, styryl and nitro;

Wherein R ' is selected from the following components:

iC *

hydrogen, fluorine, chlorine, bromine, alkyl of one to six carbon atoms ";

Such compounds are, for example, the following:

a) phenylalkyl

b) nitro 5 phenylalkyl

c) phenylalkyl fluoroorganic 5

d) phenylalkyl platinic 5

e) bromo 5 phenylalkyl

f) dichloride 5.6 phenylalkyl

g) dibromo 5.6 phenylalkyl

h) methyl-5 phenylalkyl

i) propyl 5 phenylalkyl

j) isobutyl 5 phenylalkyl

k) phenylalkyl-butyl-5

l) hexyl 5 phenylalkyl

m) methyl-5 propyl 6 phenylalkyl

n) dimethyl-5.6 phenylalkyl

o) (nitro 2-propyl) phenylalkyl -5

ρ) phenylalkyl vinyl 5

q) allyl 5 phenylalkyl

r) (propen-L-yl-) phenylalkyl -5

s) phenylalkyl methallyl 5

t) allyl 5 methyl-6 phenylalkyl

u) allyl 5 butyl 6 phenylalkyl

ν) styryl-quinolinium 5 phenylalkyl

w) (vinyl-nitro 2) phenylalkyl -5

χ) (nitro 2 propen-L-yl-) phenylalkyl -5

y) benzyl 5 phenylalkyl;

2) benzodioxoles carbonylated defined by the formula II

III)

wherein X is a direct bond or an alkylene or alkenylene group, each group containing up to seven carbon atoms in straight or branched chain;

represents a hydrogen atom or an alkyl radical having one to 4 carbon atoms or phenyl optionally substituted by one or two radicals weight alkyl residue or a carbamoyl optionally substituted by one or two radicals weight alkyl or phenyl; and represents a hydrogen atom, an alkyl radical lightweight, chlorine, bromine or fluorine or nitro. Such compounds are, for example the following:

a) formyl 5 phenylalkyl

b) chloro 5 formyl 6 phenylalkyl

c) formyl 5 nitro 6 phenylalkyl

d) (formyl 2 vinylaromatic) phenylalkyl -5

e) acetyl-5 phenylalkyl

f) acetyl-5 methyl-6 phenylalkyl

g) propionyl 5 phenylalkyl

h) benzoyl 5 phenylalkyl

i) butyryl 5 phenylalkyl

j) (carbamoyl 2 ethyl) phenylalkyl -5

k) (the n-methylcarbamoyl-2 ethyl) phenylalkyl -5

l) (n métbylcarbamoyl-to-3-propyl) phenylalkyl -5

m) (hr-methylcarbamoyl-1 propyl 2) phenylalkyl -5 η) (the n-butylcarbamoyl-to-2 Chloroethyl) phenylalkyl -5 ο) (the n, n-dimethylcarbamoyl-2 Chloroethyl) phenylalkyl -5 ρ) (hence he-phenylcarbamoylmethylene 2 Chloroethyl) -5 Q-phenylalkyl) (the n, n diphénylcarbamoyl-to-2 Chloroethyl) phenylalkyl -5 R.) (oxo 2-propyl) phenylalkyl -5

s) (butyl-oxo 3) phenylalkyl -5

t) (butyl-oxo 2) phenylalkyl -5

u) (oxo 2 pentyl ether) -5 benzodioxole_

ν) Umethyl-to-4-benzoyl) -2 vinylj -5 phenylalkyl of W) (oxo 2 ethylhexyl) phenylalkyl -5

χ) phenylalkyl benzoylmethyl-to-5

y) (oxo 3 buten-to-1-yl) phenylalkyl -5

ζ) (methyl-4-benzoyl) methyl 5 phenylalkyl ') (oxo 3 methyl 2 butene polymers and 1-yl) -5 phenylalkyl b.') (dimethyl 2.4-benzoyl) methyl 5 phenylalkyl i.) (oxo 3 methyl 2 pentene 1-yl) phenylalkyl of -5) (ethyl-4-benzoyl) methyl 5 ℮· phenylalkyl) (oxo 3 pentyl 2 butene polymers and 1-yl) phenylalkyl F. -5 ') (oxo 3 ethyl 2 butene-1-yl) -5 phenylalkyl grams *) (ethyl-benzoyl 2) phenylalkyl -5

hr ') (benzoyl 3-propyl) phenylalkyl -5

the I ') (oxo 3 isopropyl 2 butene-1-yl) phenylalkyl -5 j) (vinyl-benzoyl 2) phenylalkyl -5

k1⁾ (acetyl 3 Diethylhydroxylamine and N 2.2-propyl) phenylalkyl -5 1') (ethyl-formyl 2) phenylalkyl -5

the m¹ )* n--5 phenylalkyl) enzodioxole of O ') (acetyl 7 hepyl) phenylalkyl -5

3) carboxylated benzodioxoles defined by formula III

(Iii) wherein X and are such that they have been defined in 2), R._C. representing a hydrogen atom or an alkyl radical containing■one to four carbon atoms or an alkenyl radical or an lightweight oxa-alkyl containing from three to seven carbon atoms or a radical dioxabicyclo alkyl containing five to ten carbon atoms or a phenyl radical; such compounds are, for example, the following:

a) carboxy 5 phenylalkyl

b) phenylalkyl raéthoxycarbonyl and 5

c) phenylalkyl ethoxycarbonyl-5

d) phenylalkyl-butoxycarbonyl-5

e) (ethoxy-2 ethoxy) carbonyl 5 phenylalkyl

f) (dioxabicyclo 3.6 decyl) phenylalkyl-oxycarbonyl-to-5

g) (carboxy 2 vinylaromatic) phenylalkyl -5

h) (carboxy 2 ethyl) phenylalkyl -5

i) (carboxy 2 heptene and 1-yl) phenylalkyl -5

k) (methoxycarbonyl-2 vinylaromatic) phenylalkyl -5

l) (vinyl-butoxycarbonyl 2) phenylalkyl -5

m) (carboxy 2 vinylaromatic) phenylalkyl -5 nitro 6

n) carboxy 5 nitro 6 phenylalkyl

o) ethoxycarbonyl-5 nitro 6 phenylalkyl

p) (carboxymethyl) phenylalkyl -5

q) (carboxy 4 butadiene-1.3-yl) phenylalkyl -5

r) carboxy 5 chloro 6 phenylalkyl

s) ethoxycarbonyl-5 methyl-6 phenylalkyl

t) phenoxycarbonyl-to-5 phenylalkyl

u) (phenoxycarbonyl-methyl) phenylalkyl -5

v) phenylalkyl allyloxycarbonyl-to-5

4) nitrile benzodioxoles defined by formula IV

(IV)

wherein X and are such that they have been defined in 2); such compounds are, for example, the following:

a) cyano 5 phenylalkyl

b) cyano 5 nitro 6 phenylalkyl

c) phenylalkyl cyanomethyl-5

d) (cyano 2 Chloroethyl) phenylalkyl -5

℮) (cyano 2 vinylaromatic) phenylalkyl -5

f) (cyano 2 vinylaromatic) phenylalkyl -5 nitro 5

g) (cyano 2 Hepten L-yl) phenylalkyl -5

h) (cyano 5 pentyl ether) phenylalkyl -5

i) (cyano 2 hepyl) phenylalkyl -5

j) cyano 5 chloro 6 phenylalkyl

k) cyanomethyl compounds and 5 methyl 6 phenylalkyl

5) benzodioxoles hydroxylated defined by the formula Y

wherein Y is a direct bond or an alkylene containing from one to four carbon atoms in a straight chain or branched alkenylene or lightweight; the R ^ represents a hydrogen atom ^ μη methyl group, a chlorine atom or a bromine atom; such compounds are, for example, the following:

a) hydroxy 5 phenylalkyl

b) hydroxymethyl-5 phenylalkyl

c) (hydroxy 2 ethyl) phenylalkyl -5

d) (hydroxy 1 ethyl) phenylalkyl -5

e) (hydroxy 5-propyl) phenylalkyl -5

f) (hydroxy 1-propyl) phenylalkyl -5

g) (butyl-hydroxy 1) phenylalkyl -5

h) chloroacetamide 6 hydroxymethyl-5 phenylalkyl

i) hydroxy 5 methyl-6 phenylalkyl

j) hydroxymethyl-5 methyl-6 phenylalkyl

k) hydroxy 5 bromo 6 phenylalkyl

l) (hydroxy 3 yl-butene-1) phenylalkyl -5

6) benzodioxoles amine defined by the formula VI

wherein JE and I are such that they have been defined respectively in 2) and 5); and, the same or different, each representing a hydrogen atom or an alkyl radical of one to four carbon atoms, one of which may be further an alkanoyl residue containing from one to four carbon atoms and R ^ ^ and R can also, together, and with the nitrogen atom to which they are bonded, form a residues of pyrrolidino, piperidino, morpholino and azepino; such compounds are, for example, the following:

a) (n-, N-dimethylamino) phenylalkyl -5

b) (the n, the R-dimethylaminomethyl) phenylalkyl -5 '.

c) (amino 2-propyl) phenylalkyl -5

d) (the R-formyl-R methyl aminomethyl) phenylalkyl -5

e) (R acetylamino) phenylalkyl -5

f) (R butyrylamino-to-2-propyl) phenylalkyl -5

g) (ïT-methylamino-2 ethyl) phenylalkyl -5

h) (the n, n diethylamino-2 polybutyl) phenylalkyl -5

i) (wherein R, R dibutylamino-to-2 ethyl) phenylalkyl -5

j) piperidinomethyl-to-5 phenylalkyl

k) (azépinyl-to-1) methyl-5 phenylalkyl

l) (morpholino 2 ethyl) phenylalkyl -5

m) (methyl-4 piperidino) methyl-5 phenylalkyl

n) (pyrrolidino 2 ethyl) phenylalkyl -5

o) aminomethyl-5 nitro 6 phenylalkyl

p) (amino 2-propyl) phenylalkyl -5 nitro 6

q) (d, 1H-dimethylaminomethyl) phenylalkyl -5 nitro 6

r) piperidino-5 phenylalkyl

s) (n-, N-dimethylamino-3 yl-butene-1) phenylalkyl -5

t) (N-methylamino-2 ethyl) isopropyl 6 henzodioxole -5

u) (amino 2-propyl) methyl 6 henzodioxole -5

ν) (amino 2-propyl) chloroacetamide 6 henzodioxole -5

7) henzodioxoles having a function sulfoxide defined by the formula VII

(VII)

wherein Y is as it has been defined in 5) but preferably an alkylene bridge, I_Q. representing an alkyl radical containing one to eight carbon atoms and representing a hydrogen atom or an alkyl radical containing from one to four carbon atoms; such compounds are, for example, the following:

a) (butyl-methylsulfinyl-to-2) -5 henzodioxole

b) (butylsulfinyl and 2 ethyl) -5 henzodioxole

c) (butylsulfinyl and 2-propyl) -5 henzodioxole

d) (octylsulfinyl and 2-propyl) -5 henzodioxole

e) (octylsulfinyl and 2 ethyl) -5 henzodioxole

f) (octylsuifinyl-to-5-propyl) -5 henzodioxole

g) methyl-6 (octylsulfinyl and 2-propyl) -5 henzodioxole

h) propyl 6 (octylsulfinyl and 2. -propyl) -5 henzodioxole

i) butyl 6 (octylsulfinyl and 2-propyl) -5 henzodioxole

the j) (octylsulfinyl and 2 ethyl) chloroacetamide 6 henzodioxole -5

8) having at least one function henzodioxoles ether oxide defined by formula VIII

(Viii) wherein Y and R ' are such that they have been defined respectively in 5) and 7), R._F. representing an alkyl radical containing from one to four carbon atoms or alkoxy radical-alkyl

2 to 7 carbon atoms, or alkoxy radical-alkoxy-alkyl of 4 to 10 carbon atoms, or alkoxy radical-alk: an oxy-alkoxy-alkyl of 5 to 15 carbon atoms, or a radical phénylejde such compounds are, for example, the following:

a) methoxy-5 phenylalkyl

b) phenylalkyl-butoxy-5

c) (ethoxy-2 ethoxy) phenylalkyl -5

d) (ethoxy-2 methyl) phenylalkyl -5

e) (methoxy-2-propyl) phenylalkyl -5

f) (a butyl-butoxy 2) phenylalkyl -5

g) (trioxa-a 2, 5, 8 dodecyl) phenylalkyl -5

h) methyl-5 (trioxa-a 2, 5, 8 dodecyl) phenylalkyl -6

i) propyl 5 (trioxa-a 2, 5, 8 dodecyl) phenylalkyl -6

j) butyl 5 (trioxa-a 2, 5, 8 dodecyl) phenylalkyl -6

k) chloroacetamide 6 phenylalkyl ethoxymethyl-5

l) (methoxy-3 yl-butene-1) phenylalkyl -5

m) phenoxymethyl-to-5 phenylalkyl

n) ethoxy-5 nitro 6 phenylalkyl

o) (trioxa-a 3, 6, 9 undecyl-to-2) oxy 5 phenylalkyl

p) ethyl-5 (trioxa-a 5, 6, 9 undecyl-to-2) oxy 5 phenylalkyl

9) benzodioxoles having acetal function defined by formula IX

(IX)

wherein R_grams represents an alkyl radical containing from one to four carbon atoms or an alkoxyalkyl of 2 remains to 7 carbon atoms or alkoxy-alkoxy-alkyl of 4 to 10 carbon atoms, and

The R ' represents a hydrogen atom, a chlorine atom, bromine-O

or fluorine, a nitro group or a light alkyl; such compounds are, for example, the following:

a) (dimethoxy) methyl-5 phenylalkyl

b) (diisobutoxy) methyl-5 phenylalkyl

c) a bis (ethoxy-2 ethoxy) methyl-5 phenylalkyl

d) the bis (ethoxy-butoxy 2) methyl-5 phenylalkyl

e) the bis (oxypropylene-butoxy 2) methyl-5 phenylalkyl

f) a bis (dioxabicyclo 3.6 decyloxy) methyl-5 phenylalkyl

g) of bis (methyl-5 dioxabicyclo 4.7 dodecyloxy) methyl-5 phenylalkyl hr) (dipropyloxy) methyl-5 phenylalkyl

i) (dipropyloxy) methyl-5 chloro 6 phenylalkyl

j) (dipropyloxy) methyl-5 nitro 6 phenylalkyl

k) (dipropyloxy) methyl-5 methyl-6 phenylalkyl

10) carbamic benzodioxoles having a function defined by formula X

wherein Y is as defined in 5 was), and, the same or different, each representing a hydrogen atom or an alkyl radical of one to four carbon atoms and possibly, also, together form, with the nitrogen atom, piperidino, morpholino or pyrrolidino; such compounds are, for example, the following:

a) carbamoyloxy group-a 5 phenylalkyl

b) (N-methylcarbamoyloxy) phenylalkyl -5

c) (hence he-to-butylcarbamoyloxy) phenylalkyl -5

d) (yen, n dipropylcarbamoyloxy) phenylalkyl -5

e) (d, f pentamethylene carbamoyloxy group) phenylalkyl -5

f) phenylalkyl Carbamoyloxymethyl and 5

g) (the n, n diméthylcarbamoyloxyméthyl) phenylalkyl -5

h) (Lfs, n diéthylcarbamoyloxy and 2 ethyl) phenylalkyl -5

i) (n butylcarbamoyloxy and 2 a butyl) phenylalkyl -5

j) (the n, n-tetramethylene-propyl-carbamoyloxy group and 2) phenylalkyl -5

k) (N-methylcarbamoyloxy-to-3 yl-butene-1) phenylalkyl -5

l) phenylalkyl morpholinocarbamoyloxyméthyl and 5

m) of n-isopropylcarbamoyloxy-to-5 methyl 6 phenylalkyl

η) of n-propylcarbamoyloxy-to-5 nitro 6 phenylalkyl

ο) n éthylearbamoyloxy-to-5 chloro 6 phenylalkyl

ρ) phenylalkyl pipéridinocarbonyloxy and 5

11) benzodicxoles dioxane ring-bearing defined by the formula XI

(XI)

wherein R ^ is just as they were defined in 7), ^ the R representing a hydrogen atom, a methyl radical or ethyl; such compounds are, for example, the following :.

a) (dioxane-1.3 yl 4) phenylalkyl -5

b) (dioxane-1.3 yl 4) phenylalkyl -5 methyl-6

c) (dioxane-1.3 yl 4) phenylalkyl -5 propyl 6

d) (methyl-5 dioxane-1.3 yl 4) phenylalkyl -5

e) (methyl-5 dioxane-1.3 yl 4) phenylalkyl -5 propyl 6

f) (ethyl-5 dioxane-1.3 yl 4) phenylalkyl -5

12) benzodioxoles of tetralin derivatives defined by the formula XII

the same or different, each representing a hydrogen atom, a methyl group, a carboxy group or an alkoxy group containing carbonyl, in total, two to five carbon atoms; such compounds are, for example, the following:

a) tetrahydro-5, 6, 7, 8 naphtho (2.3 d) a dioxole-to-1.3

b) trimethyl-5, 6, 7 tetrahydro-5, 6, 7, 8 naphtho (2.3 d) a dioxole-to-1.3

c) dimethyl-6.7 tetrahydro-5, 6, 7, 8 naphtho (2, 3 - β) a dioxole-to-1.3

d) the dicarboxy-to-5.6 tetrahydro-5, 6, 7, 8 naphtho (2.3 d) a dioxole-to-1.3

e) the dicarboxy-to-5.6 methyl-7 tetrahydro-5, 6, 7, 8 naphtho (2.3 d.) a dioxole-to-1.3

f) a bis (ethoxy-carbonyl) -5.6 methyl-7 tetrahydro-5, 6, 7, 8 naphtho (2.3 d) a dioxole-to-1.3

g) of bis (propoxocarbonyl) -5.6 methyl-7 tetrahydro-5, 6, 7, 8 naphtho (2.3 d) a dioxole-to-1.3

h) of bis (butoxycarbony1) -5.6 ethyl-7 tetrahydro-5, 6, 7, 8 naphtho (2.3 d) a dioxole-to-1.3

13) the dioxabicyclooctanebenzodioxoles derivatives defined by the formula XIII

in which Z and 'Z-' alike or different, represent, each a direct bond or an oxygen atom; and R 00, same or different, is chosen from hydrogen, the methyl and methoxy; such compounds are, for example, the following:

a) a bis (phenylalkyl-to-1.3 yl 5) -2.6 dioxabicyclo 3.7 (3, 3, 0) octane number bibi.cyclo andb) of bis (phenylalkyl-to-1.3 yl 5 alkyloxy) -2.6 dioxabicyclo 3.7 bicyclo-octane number (3, 3, 0)

c) (phenylalkyl-to-1.3 yl 5) -2 (phenylalkyl-to-1.3 yl 5 alkyloxy) -6 dioxabicyclo (3, 5, 0) bicyclo-octane to 3.7

d) (phenylalkyl-to-1.3 yl 5) -2 (methoxy-6 phenylalkyl-to-1.3 yl 5) -6 dioxabicyclo 3.7 bicyclo-octane number (3, 3, 0)

e) (phenylalkyl-to-1.3 yl 5) -2 (methyl-6 phenylalkyl-to-1.3 yl 5) -6 dioxabicyclo 3.7 bicyclo-octane number (3, 3, 0)

f) a bis (methoxy-6 phenylalkyl-to-1.3 y1 and 5) 2.6 dioxabicyclo 3.7 bicyclo-octane number (3, 3, 0)

g) of bis (methyl-6 phenylalkyl-to-1.3 y1 and 5) -2.6 dioxabicyclo 3.7 bicyclo-octane number (3, 3, 0)

14) benzodioxoles drifts 1' indole derivatives defined by the

wherein R_fIT represents a hydrogen atom or an alkyl radical having one to 4 carbon atoms or alkoxy radical having from one to 4 carbon atom, each of these radicals may faculca -

THE R,

/¹¹

anstruther carry a group - the n'as defined

in 10), the R ' representing a hydrogen atom or an alkyl radical with m

of one to 4 carbon atoms or a radical of one to have an oxy 4 carbon atoms or a radical of 2 to 4 alkanoyl group or benzoyl radical. Such compounds are, for example, the SUI provides VBE1'd has) (1.3 dioxolo) 4.5 ' f the j ^ "} indole derivatives

b) methyl 3 (1.3 dioxolo) [j4, 5 indole derivatives

c) ethyl-3 (1.3 dioxolo) ^ 4, 5 - ^ ΐ indole derivatives

d) butyl 3 (1.3 dioxolo) [4.5 F.] indole derivatives

e) dimethyl-2.3 (1.3 dioxolo) {^, 5 a-YF indole derivatives

f) methoxy-3 (1.3 dioxolo) ^ 4.5 to-YF indole derivatives

g) isobutoxyethyl and 3 (1.3 dioxolo) [4.5 f] indole derivatives

h) dimethoxy-2.3 (1.3 dioxolo) ^ 4, 5 - ΐ] indole derivatives

i) ethyl-2-methoxy-3 (1.3 dioxolo)[has, the indole 3/5 a-f) (wherein R, N-dimethylamino-2 ethyl) -3 (1.3 dioxolo)/^, 5 a-f7indole K.) (the n-methylaminomethyl 3-propyl) -3 (1.3 dioxolo)/4.5 to-f7^inàole

l) (amino 2 éthoxyl) -3 (1.3 dioxolo)/4.5 to-f7indole

m) (the n, n diethylamino-2 éthoxyl) -3 (1.3 dioxolo)/4, where n ÿindole) (pyrrolidino 2 ethoxy) -3 (1.3 dioxolo)/4.5 to-f7indole

0) (piperidino-2 ethoxy) -3 (1.3 dioxolo)/4.5 to-f7indole

p) acetyl 2 (pyrrolidino 2 ethoxy) -3 (1.3 dioxolo/4.5 to-f7indole Q-) butyryl 2 (pyrrolidino 2 ethoxy) -3 (1.3 dioxo-. 10)/4.5 to-f7indole r) benzoyl 2 (pyrrolidino 2 ethoxy acetic acid) -3 (1>3 dioxolo)/15/iiihole 4.5 a-f) benzodioxoles carrying an imine function defined by

the formula XV

wherein R represents an optional substituent selected from three alkyl radicals of one to 4 carbon atoms, alkoxy radicals of one to 4 carbon atoms, chlorine, bromine, nitro, hydroxy, methylthio and; such compounds are, for example, anilines following the R-substituted by the group piperonylidene:

a) aniline in

b) methyl-4 of aniline

c) aniline-butyl 4

d) aniline-dimethyl 2.4

g) aniline-trimethoxy-2, 4, 6

h) of aniline-butoxy 4

i) aniline-nitro 3

j) chloroacetamide 5 aniline-dimethoxy-2.4

k) aniline-platinic 2

l) aniline-dichloride 2.3

m) chloro 4 methyl-2 aniline-..

n) aniline-methylthio-4

o) bromo 2 nitro 4 of aniline

p) aniline-hydroxy 2

q) chloroacetamide 5 methyl 2 aniline derivatives

r) aniline-bromo 4

s) aniline-dichloride 2.5

t) aniline-trichloro 2, 3, 5

u) aniline-trimethyl-2, 4, 6

v) T-butyl 4 of aniline

and the following anilines:

x) the n - (chlorophenyl 3' piperonylidene) - aniline derivatives

y) the n - (methyl-3' piperonylidene) - (methyl-4 of aniline)

z) the n - (nitro 3' piperonylidene) - (nitro 3 aniline derivatives);

16) salts of benzodioxoles having an acid function or phenolic defined in 3), 5) and 12), said salts containing cationic part as a metal such as, for example, sodium, potassium, calcium, zinc, cadmium, copper, nickel, cobalt, iron, manganese, silver, lead, barium, strontium and aluminum or ammonium ion derivative. ammonia, an amine derivative containing from one to three alkyl radicals of one to four carbon atom, as, for example, methylamine, dimethylamine, trimethylamine, diethylamine, triethylamine, butylamine, dibutylamine and tributylamine, or derived from a nitrogen-containing heterocycle, such as pyridine, morpholine, n-methyl morpholine, the piperidine derivatives and the pipecolins.

Such salts are, for example, the following:

- the sodium salt of compound 111 (has), Ill-(grams), (d) the III, III-V-(R.) (has), XII as (D.) and XII (I);

- the ammonium salt of the compound-Ill(has), 111 (hr), lll (meters), lil (w) V. (I-) and XII (D.);

- the neutral salt zinc compound 111 (has), a V (has) and (I) Xll embodying such salts is particularly interesting when the phosphoric ester implemented has already undergone a protonation, the salt introduced then acts as stabilizer, initially as a neutralizer of the acidic phosphoric ester by exchanging therewith its cation against a proton;

this neutralization is favorable for the stabilization, because it has been observed by the applicant that the holding of the phosphoric esters was better when they contained no acidic byproducts; the phenylalkyl stripped of its cation stabilizing retains its properties and thereby acts in a second time.

17) Salts of benzodioxoles having a function basic defined in 6) and 14), said salts being formed with an inorganic acid such as hydrochloric, sulfuric, carbonic, boric, hydrobromic, phosphoric or TiN dicarboxylated mono or organic acid such as acetic, propionic, benzoic, succinic, adipic, phthalic, maleic or phenylacetic acid. The such salts are, for example, the following:

a) to O) chloride, sulphate, calcium carbonate, a borate, bromide, hydrogen phosphate, dihydrogeno phosphate, acetate, proprionate, a benzoate, succinate ester, ethyl butyrate, phthalate, maleate and phenylacetate (ii, n-dimethylamino) phenylalkyl -5 (FV (has)).

p) to Z) and¹ ) to) the salts of acidic in same has) to O), of the (1.3 dioxolo) 4.5 f indole derivatives (aogtao Parks (has)).

The solvents of the phosphoric ester can be advantageously hydrocarbons series aliphatic, alicyclic and aromatic which are solid or liquid at room temperature with or without pressure. The such solvents are used singly or in admixture. Their solvency for the phosphoric ester and/or benzodioxole can optionally be reinforced by the addition of cosolvents which can be selected from the groups of aliphatic ketones, hydroxyl compounds, ethers-oxides, esters, amides, nitriles and halogenated hydrocarbons containing at most 12 carbon atoms. The other solvents which can be used in the compositions according to the present invention are halogenated hydrocarbons containing at most 12 carbon atoms, ethers-oxides and esters formed 'by the aliphatic alcohols, cycloaliphatic or aralcoylic or phenols and aliphatic acids or diacids such as phthalic acid, sebacic acid and adipic acid or, alternatively, the phosphoric esters phosphoric triesters as non-pesticidal methyl, ethyl, butyl, oo.ctyle, decyl, dodecyl, phenyl, cresyl, diphenyl, tertiobutylphényle, andc.... solvents useful in the compositions of the present invention may also be solid compounds as, ' for example, synthetic organic resins such as homopolymers and copolymers derived from vinyl (acetate, propionates is,

the butyrate VBE1, oxides, formed, acetal, butyral resin, chloride, and c...

and/or derivatives and/or vinylidene alkenes (ethylene, propylene oxide, butylene, andc...) and/or styrene and/or and/or vinylpyrolidones cellulose derivatives (méthyloxyde, éthyloxyde, benzyloxyde, acetate, cellulose propionate, methyl butyrate, phthalate, nitrates, andc...) and/or isoprene and/or butadiene and/or acrylic or methacrylic acid esters and/or allyl esters (phthalate, isophthalate, am ' léate, triallyl cyanurate, andc...)* such resins organic synthesis may also come from the interaction of compounds with reactive functions, as in the case of resins called "epoxy", resulting from the.

condensation of an epoxy on a polyphenol, resins "polyester", resulting from the action of a polyacid on a polyol, polyurethanes, resulting from the condensation of a polyisocyanate with a polyol, or resins of the coumarone-indene.

A solid compound useful as a solvent may also be a natural resin as, for example, rosin, shellac or tall oil resin or waxy.

Adjuvants include inert minerals that may be introduced into the compositions according to the present invention, it may be cited, for example, brick, pumice, vermiculite, kaolin, dried clay, calcium carbonate, the pyrophyllite, dolomite, glass fiber, gypsum, talc, natural silica, fossil or not, artificial silica and metal oxides. Adjuvants include inert organic insertable into the compositions according to the invention, it may be cited, for example, wood flour, cellulose fiber, starch, starch, sugars and/or diluents such as paraffin solvents little, that may have its qualities-modified synthetic organic resins and/or salts formed by the alkoylamino amines and aliphatic acids and/or amino derivatives of montmorillonite such as bentones.

Additional stabilizers are advantageously selected from sulfur, sulfur compounds are bivalent, the

- oxiranes and the metalliferous azo compounds or derivatives thereof. A composition according to the present invention may also contain one or more natural or artificial flavoring materials, an active material such as a complement acaricidal agent, an insect repelling agent, a bird repellent agent, an antifungal agent, an agent plant growth regulator, a herbicide or a bactericidal agent.

Thus formulated, the composition according to the present invention may therefore be solid or liquid. It may be disposed on a porous or fibrous solid support. The carrier may be formed, for example, by a paper, a felt wool, cotton and/or synthetic fiber, a cellulose compressed as the wood fibers, cereal, wax and cotton, a nonwoven, a carton of paperboard-or a glass fiber.

Such a composition is advantageously used as a pesticide. the presence of a phenylalkyl phosphoric stabilizer provides increased resistance to the destructive effect of the water contained in the composition and ambient humidity as will the following experiments show the data which are included as examples.

The OH - has EXPERIMENTAT!

Was used squares of 10 x 10 centimeters cut in a carton cellulose manufactured by French

FIORONI S. A. under the reference 200; at the time of use, this

2

cardboard weighed 870 g at the m, it is to say, 8.7 g per square. the squares of cardboard were sorted into three series of three units numbered a-0 to-2; the squares-0 have been impregnated with 12.5 g of DDVP and other squares have been impregnated with 12.5 g of a solution of DDVP in one of the following compounds 1 to the content of <OF:

-1: (octylsulfinyl and 2-propyl) phenylalkyl-to-1.3 -5

-2: propyl 5 (trioxa-a 2, 5, 8 dodecyl) phenylalkyl-to-1.5 -6 thus impregnated with the squares were suspended in a room in which the temperature was maintained at 22 + 2 °c and whose relative humidity was close to 40.

At the end of 15 days, the amount of of DDVP destroyed by hydrolysis was measured potentiometrically (it has been determined, further, that the hydrolysis of DDVP in the above conditions exposed leads to an acidic phosphate ester and that the metering potentiometric acidity single or of the first acidity of this ester would establish vulnerable group of of DDVP hydrolyzed).

II has been taken into account in the acidity present in DDVP and it was deduced from the results obtained.

the amounts of $broken down by hydrolysis of DDVP which was recorded together in the table below:

(assigned values in the sign + scattering results in each series):

)

)

)

)

)

>

)

, -;

Apparatus by using a square of cardboard, as in the expérimen cloth has, but size 5 x 10 cm and joined by two, back to back, with staples; at the time of use, this carton weighed 895 g/m; these cartons double were distributed in four numbered series of b 0 to b-a 2; the squares B 0 were impregnated with, each, with 12.5 g of DDVP and the other cartons were impregnated with double, each, with 12.5 g of a solution at 1.5 i° in DDVP of one of the following compounds:

- Β-1: ailyl-to-5 phenylalkyl-to-1.3

- Β-2: formyl 5 phenylalkyl-to-1.3

the squares thus impregnated were suspended in a room in which the temperature was maintained at 22 + 2 °c and whose■hygrometry was close to 70.

the I

At " the end of 15 days, the amount of of DDVP destroyed by hydrolysis was measured as experimentation has; the amounts with fo

' of of DDVP decomposed thus recorded are indicated in the table below:

EXPERIMENTATIOU C.

Was used cartons as described in double B-experimentation, but whose weight was 885 g/m. Such cartons double were distributed in four sets called c 0 to c-3; the cartons double c 0 were impregnated with each, with 12.5 g of DDVP, * the other cartons were impregnated with double, each, with 12.5 g of a solution at 2 the I " in DDVP of one of the following compounds:

C - 1: (trioxa-a 3, 6, 9 undecyl-to-2 alkyloxy) -5 benzodioxo3e-to-1.3

C 2: the bis (propoxycarbonyl) -5.6 methyl-7 tetrahydro-5, 6, 7, 8 naphtho (2.3 d) a dioxole-to-1.3

C 3: equimolar mixture of bis (phenylalkyl-to-1.3 yl 5) -2.6 dioxabicyclo 3.7 the bicyclo (3, 3, 0) octane and (phenylalkyl-to-1.3 yl 5)~2 (phenylalkyl-to-1.3 y1-to-5 alkyloxy) -6 dioxabicyclo 3.7 bicyclo-octane number (3, 3, 0).

the cartons thus impregnated were suspended in a room in which the temperature was maintained at 22 + 2 °c * 1 and whose ' relative humidity was close to 65•

At the end of 15 days, the amounts of $of DDVP have destroyed

been measured as it is said in 1' experimentation has and recorded as follows:

EXPERIMENT D.

Was used cartons as described in double B-experimentation, but whose weight was 890 g/m. Such cartons double were divided into nine sets called d 0 to d-8; the cartons were impregnated with d 0, each, with 12.5 g of DDVP; the other cartons were impregnated with double, each, with 12.5 g of a - 3 solution to i° in DDVP of one of the following compounds:

D 1: hydroxy 5 phenylalkyl-to-1.3

D 2: bales and 5 phenylalkyl-to-1.3

D 3: (propene-1-yl) phenylalkyl-to-1.3 -5

D 4: acetonyl 5 phenylalkyl-to-1.3

D 5: (oxo 3 purpose ene-1-yl) phenylalkyl-to-1.3 -5

D 6: cyanomethyl-5 phenylalkyl-to-1.3

D 7: (amino 2-propyl) phenylalkyl-to-1.3 -5

D 8: (methyl-5 dioxane-1.3 yl 4) phenylalkyl-to-1.3 -5 thus impregnated with the cartons were suspended in a room in which the temperature was maintained at 22 + 2 °c and whose relative humidity was between 70 and 75.

' At the end of 12 days, the quantities % of of DDVP destroyed were measured as it is called in the experiment a and recorded as follows:

(D 0 D 1 D 2 D 3 D 4 D 5 D 6 D 7 D 8

(

(

(41.3 [+ tu - 0 + 0.02 0.3 - 0 + 1.0 9.2 + 0.07 0.8 + 0.2 3.4 0 + 0.2 2.1

<

EXPERIMENT I

Was used cartons as described in double B-experimentation, but whose weight was 910 g/m. Such cartons have been distributed into six series called e 0 E-5; the cartons double e 0 were impregnated with, each, with 12.5 g of DDVP. The other cartons were impregnated with double, each, with 12.5 g of a solution in the DDYP of one of the following compounds makers hereinafter:

E 1:2 lo of benzoylméthyl-to-5 phenylalkyl-to-1.3

BOTH E 2:2 lo benzodioxole and 1.3

BOTH E 3:2 $ bromo-5 phenylalkyl-to-1.3

BOTH E 4:2 lo nitro-5 phenylalkyl-to-1.3

BOTH E 5:5 i° of cyano-5 phenylalkyl-to-1.3

The cartons thus impregnated were suspended in a room in which the temperature was maintained at 22 +■2 °c and whose relative humidity was close to 74•

At the end of 15 days, the quantities % of DDYP destroyed were measured as it is called in the experiment a and recorded as follows:

Was used cartons as described in double B-experimentation, but whose weight was 835 g/m. Such cartons have been sorted into eight series called f 0 to f-7.

The cartons double e 0 have been^- prepregs, each, with 12.5 g of DDVP. The other cartons were impregnated with double, each.

with 12, 5g a solution, to 3 i° in the DDYP of one of the following compounds:

P 1: (n Phenylcarbamoyl-2-ethyl) -5 phenylalkyl-a 1, 5 f 2: (methyl-4-benzoyl) -2 vinylaromatic -5 phenylalkyl-to-1.5

. F 3: propyl 5 phenylalkyl-to-1.5

F 4: (vinyl-nitro 2) -5 bonzodioxole above 1.5

F 5: n piperonylidene~(aniline-mm.éthyl and 4)

F 6. : N piperonylidene - (chlorophenyl 5 aniline-dimethoxy-2.4) f 7: methoxy-5 phenylalkyl

The cartons thus impregnated were suspended in a room in which the temperature was maintained at 21 + 1 °c and whose relative humidity was close to 65.

At the end of 15 days, the quantities the I= of of DDVP destroyed were measured as it is called in the experiment a and recorded as follows:

0 EXPERIMENT

Was used cartons double as those described in

w experimentation B but whose weight was 910 g/m. Such cartons have been distributed into six; series called g-a 0 to g 5.

The cartons double g 0 were impregnated with, each, with 12.5 g of DDVP. The other cartons were impregnated with double, ' each, with 12.5 g of a solution at 4 DEGREES/DEGREES in DDVP of one of the following compounds:

G 1: methyl-7 tetrahydro-5, 6, 7, 8 naphtho (2.5 d)' dixole-a 1, the dicarboxylate and 556 sodium

G 2: the j/benzodioxcle-a 1, 5) - 5 _l -5 zinc acrylate

G 5: VBE1 (phenylalkyl-to-1.5) piperidin -5 ^ -5 acrylate g 4: the j/benzoclioxole-to-1, .5) - 5j -5 lead acrylate

G 5 • (phenylalkyl-to-1.5) piperidine-carboxylate~5 thus impregnated with the cartons were suspended in a room in which the temperature was maintained at 22 + 2 °c and whose relative humidity was close to 75 *

After 10 days, the quantities the I of of DDVP destroyed were measured as it is called in the experiment a and recorded as follows:

Was used cartons double as those described in

2 experimentation B but whose weight was 910 g/m. Such cartons have been sorted into three series called H 0, ïï - 1 and H-a-2 the cartons double H 0 have been impregnated, each, with 12.5 g of DDVP. the other cartons were impregnated with double, each, with 12.5 g of a solution in DDVP hydrochloride benzoyl 2 (pyrrolidino 2 ethoxy) -3 (1.3 dioxolo) indole derivatives||4.5 f the next concentrations:^J

H 1: 0.2 lo

H 2: 0.5 5^

the cartons thus impregnated were suspended in-a room in which the temperature was maintained at 22 + 2 °c and whose relative humidity was close to 80.

At the end of 15 days, the quantities the I of of DDVP destroyed were measured as it is called in the experiment a and recorded as follows:

The results of experiments a, 3,c, d, e, p, g, h clearly show how DDVP is sensitive to moisture when the packet is not protected; they also show that the hydrolysis can be reduced in large proportions when a bensodioxole is added to the phosphoric ester.

EXPERIMENT^-I

Was used cartons double as those described in

2 b-experimentation, but whose weight was 905 g/m. Double such cartons have been distributed into six 1 - 0 to 1 - 5 series called; the cartons were impregnated with 1 - 0, each, with 12.5 g of DDVP; the other cartons were impregnated with double, each, with 12.5 g of a solution in DDVP as follows:

1 - 1: 1.7 $of (methyl-4 nitro 2 phenylazo) ethoxycarbonyl -1 3 dimethyl-4.4 dioxo 2.6 cyclohexan

1 - 2; 1.7% of ally1-to-5 phenylalkyl-to-1.3

1 - 3:1 $of allyl-to-5 phenylalkyl-to-1.3 + 0.7 1° of (methyl-4 nitro 2 pheny^{the R} rECITAL) -1 ethoxycarbonyl-3 dimethyl-4.4 dioxo 2.6 cyclohexan

1 - 4 ' of 1.7 $(oxo 3 yl-butene-1) -5 phenylalkyl-to-1.3 1 - 5:1 lo of (oxo 3 yl-butene-1) -5 phenylalkyl-to-1.3 + 0.7 £of (methyl-4 nitro 2 phenylazo) -! éthoxycarbonyéthoxycarbony.l and 3 dimethyl-4.4 dioxo 2.6 cyclohexane derivatives.

The cartons thus impregnated were suspended in a room in which the temperature was maintained at 22 + 2 °c and whose relative humidity was close to 77.

At the end of 21 days, the amounts of $of DDVP destroyed were measured as it is called in the experiment a and recorded as follows:

1 - 0 1 - 1 1 - 2 1 - 3 1 - 4 1 - 5

45.1 16.2 1.2 0.7 7.1 0.9

0.7 + 1.9 + 0.3 + 0.1 + 1.3 + 0.1

the results of this experiment demonstrate the interests the stabilizer mixtures according to the invention with the stabilizers belonging to the family of azo compounds; noted, indeed, in the results of the precedent, a synergistic effect of these two types of stabilizers.

Was used cartons double as those described in

p-b-experimentation, but whose weight was 905 g/m '. Such cartons have been sorted into eight double series called a j-0

to j-7, ' the cartons were impregnated with a j-0, each, with 12.5 grams of. Of DDVP; the other cartons were impregnated with double, each, with 12.5 g of a solution in DDVP, as follows

A J-1: 0.2 lo elemental sulfur

A j-2: 1.7 an allyl 5~phenylalkyl-to-1.3

A j-3: 1.5 5^of allyl-to-5 phenylalkyl-to-1.3 + 0.2 elemental sulfur

a j-4: 1.7 ' oF of (oxo 3 yl-butene-1) phenylalkyl-to-1.3~5

A j-5: 1.5 $of (oxo 3 yl-butene-1) phenylalkyl-to-1.3 + 0.2 -5 the I elemental sulfur

A J-6: 1.7 the I of (propene-1-yl) phenylalkyl-to-1.3 -5

A J-7: 1.5 i° of (propene-1-yl) phenylalkyl-to-1.3 + 0.2 -5 %

elemental sulfur.

the cartons thus impregnated were suspended in a

room whose temperature has been mairienue to 22 + 2 °c and whose relative humidity was close to 77.

At the end of 21 days■, the amounts the I of of DDVP destroyed were measured as it is called in the experiment a and recorded as follows:

J.-R.

the results of this experiment demonstrate the interests the stabilizer mixtures according to the invention with a stabilizer such as sulfur complementary; noted, indeed, in the results of the precedent, a synergistic effect of these two types of stabilizers.

Was used cartons as described in double B-experimentation, but dimensions 7 x 10 cm.

Such cartons have been sorted into two series called K 0 and K-1.

the cartons double K 0 were impregnated with, each, with 16.6 g of a composition containing 50 the I dDVP and 50 wt. the I by weight of a mixture containing three parts by weight of vaseline oil and one part by weight of stearone.

The cartons double K 1 were impregnated with, each, with 16.6 g of the same composition in which had replaced 2.1 lo the mixture vaseline oil + stearone, relative to the weight of the composition, by 2 the I of allyl-to-5 benzodioxole and

0.1 the I of (methyl-4 nitro 2 phenylazo) -1 ethoxycarbonyl-5 dimethyl-4.4 dioxo 2.6 cyclohexane derivatives.

The cartons double thus impregnated have been placed, each, in a pouch made of polyethylene/aluminum complex, the face polyethylene being within, and the bags have been sealed by solder. After storage for eight months at 40 °c, the bags were opened and their contents were subjected to analysis under the conditions described in the experiment has; the amounts has been recorded foo of DDVP of decomposed as follows:

EXPERIMENT I

We prepared four series of compositions containing 50 the I weight of DDVP; the series have been designated 1 - 0 to 1 - 5; the compositions contained 50 L 0 the I by weight of xylene; the compositions K 1 to K-3 contained the following stabilizers, the complement to 100^being ensured by the xylene:

1 - 1:2 lo of allyl-to-5 phenylalkyl-to-1.3

1 - 2:1 ^ elemental sulfur

1 - 3:2 the I of allyl-a 5 + 1 phenylalkyl-to-1.3 the I elemental sulfur.

These compositions are confined, each, in a closed vial placed at a temperature of 60 °C; after 36 days, the vials have been opened and their content was analyzed under the conditions described in the experiment has; the amounts has been recorded the I of of DDVP destroyed as follows:

the results of experiments K and 1 show interests stabilizers according to the invention for the preservation or storage of phosphoric esters and compositions containing them; they confirm, further, the interest associations between the stabilizers according to the invention and the other stabilizers.

EXPERIMENT OF M

•was used cartons of 5 x 10 cm as those described in the experiment of b, but left in a single thickness.

Such cartons have been sorted into four series called m 0 m-3. the cartons were impregnated with m 0, each, with 6 g of phosphate 0 - (dibromo 2.2 vinyl) and 0 ,O-dimethyl.

the other cartons were impregnated with, each, with 6 g of a solution of one of the following compounds has an I 2 in the phosphate 0 - (bromo~2, 2 vinyl) and 0 ,O-dimethyl.

M 1. : (oxo 3 yl-butene-1) phenylalkyl-to-1.3 -5

M 2: (amino 2-propyl) -5 benzcdioxole-to-1.3

M 3: (trioxa-a 3, 6, 9 undecyl-to-2 alkyloxy) -5 bensodioxole-to-1.3 thus impregnated with the cartons were suspended in a room in which the temperature was maintained at 22 + 2 °c and whose relative humidity was close to 60.

After 16 days, the quantities lo ester destroyed were measured potentiometrically. it has been taken into account in the acidity originally present in the phosphoric ester (equivalent to 7j4 the I ester) and it was deduced from the results obtained.

N-EXPERIMENT

Was used cartons of 5^{the X} 10 cm horn those described experimentation b., but left in a single thickness.

Such cartons have been distributed in c of InQ series called it-a-0 to II 4.

The cartons were impregnated with n 0, each, with 6 g of phosphate 0 - (vinyl-dichloro 2.2) and 0 ,O-diethyl.

The other cartons were impregnated with, each, with 6 g of a solution of one of the following compounds 2 to the I in the phosphate 0 - (vinyl dichloride 2.2) and 0 ,O-diethyl.

N 1: (oxo 3 purpose ene-1 ÿl) phenylalkyl-to-1.3 -5

N 2: (amino 2-propyl) phenylalkyl-to-1.3 -5

N 3: (trioxa-a 3, 6, 9 undecyl-to-2 alkyloxy) phenylalkyl-to-1.3 -5 LT 4: allyl 5 phenylalkyl-a 1, 3

The cartons thus impregnated were suspended in a room in which the temperature was maintained at 22 + 2 °c and whose relative humidity was close to 60.

After 43 days, the quantities the I ester destroyed were measured as it is called in the experiment a and recorded as follows (acidity initially derived and corresponding to 2.5 i° ester):

Some formulations are described below in order to illustrate the invention and without any limitation.

The benzodioxoles used are called as follows to facilitate drafting.

Phenylalkyl: allyl 5 phenylalkyl-to-1.3

Phenylalkyl of b: (propene-1-yl) phenylalkyl-to-1.3 -5 phenylalkyl C.: hydroxy 5 phenylalkyl-to-1.3

Phenylalkyl'd: (trioxa-a 3, 6, 9 undecyl-to-2 alkyloxy) phenylalkyl-to-1.3 -5 phenylalkyl I: (oxo 3 yl-butene-1) phenylalkyl-to-1.3 -5

The sulfur compounds are used as stabilizers complementary are named as follows:

Sulfur compound has: mercapto 2 benzothiazole derivatives

B-sulfur compound: zinc salt of the benzthiazole mercaptoimidazole 2 sulfur compound C.: sulfide bis (ir, ît methoxybenzoate) sulfur compound D.: bis (n-, n diméthylthiocarbamoyls) sulfur compound I: thioacetamide

P-sulfur compound: 17.17-to-dimethyldithiocarbamate zinc sulfur compound gm -: disulfide benzothiazolyl-a 2

The azo compounds used as stabilizers complementary are called as follows, with the exception of the azobenzene by name:

Diazene has: (phenylazo 4 phenylazo) naphthalene -1 methylaminomethyl 2 b-diazene: (methyl-4 nitro 2 phenylazo) -1 ethoxycarbonyl-3 dimethyl-4.4 dioxo 2.6 cyclohexane derivatives.

C-diazene: phenylazo 1 naphthol 2

D-diazene: phenylazo 4 ii, ït-diethylaniline

I diazene: (1, 2) chromium complex, in admixture, azo compounds of the following:

(hydroxy 2 nitro 5 phenylazo) -1 naphthol 2, the sodium salt (0.4 moles) ά℮ (hydroxy 2 nitro 4 phenylazo) -1 naphthol 2, sodium salt (0.3 moles) (hydroxy 2 nitro 3 terttert.amyl-to-5 phenylazo) -1 naphthol 2, salt

5 (0.3 moles) of sodium.

EXAMPLES 1 HAS 10

Insecticidal compositions comprising DDVP as phosphoric ester and at least one henzodioxole as stabilizer

^ main of this ester, which may also include a solvent of the ester and/or a complementary stabilizer selected from sulfur, sulfur compounds, and azo compounds of oxiranes (value expressed in percentages by weight).

the Vx ER ER

VJ1. The O vjivji ο

EXAMPLES 11 HAS 20

Insecticidal compositions comprising DDVP as phosphoric ester, at least one main phenylalkyl as stabilizer of this ester, a mineral oil or a paraffin oil as a solvent, an Al canonelourde as cosolvent and, in many cases, additional stabilizer selected from sulfur, sulfur compounds, and azo compounds of oxiranes.

(Values expressed in percentages by weight).

Semi refined oil, having a density equal to 0.86? ' has 15 °c

and a freezing point adjacent -42 °c.

Semi refined oil having a density equal to Ο, 87 θ has 15 °c

and a viscosity of 1 to 50 °c °7 Engler on .,

Examples 21 to 30

Insecticidal compositions comprising DDVP as phosphoric ester, at least one main phenylalkyl as stabilizer of this ester, an adjuvant solid or semi-solid selected from paraffin, petrolatum and petrolatum, a solvent chosen from alkanones heavy and, in many cases, additional stabilizer selected from sulfur, sulfur compounds, and azo compounds of oxiranes.

(Values expressed in percentages by weight).

MV VMS

THE VH-O

l \ α 5

U1

IV)

O

ν π

σ

VJl

technical product yellow color with dropping point at over 4' 7 °c.

brown color product having a point drop of around 72 °c.

Examples? 1 to 40

Insecticidal compositions usable in an evaporator wick consisting of a reservoir and a wick dipped in the composition and having a portion in the open air. The compositions comprise DDVP as phosphoric ester, a solvent for the ester chosen from IEA donkeys, a cosolvent selected from chloro-1 decane, the trioxa-a 5, 6, 9 undecane and pentadecane triexa and 5, 8, 11, at least one bensodioxole as stabilizer main of the phosphoric ester and, in many cases, additional stabilizer selected from sulfur, sulfur compounds, and the compounds of oxiranes azoîques.

(Value expressed in poucentages by weight).

v->! V ->>VBE1 - j-I-ER "■■ν π * -

iU ο ο vji ο

(d) boosting solvent known as diglycol-diethyl-ether sold under the trade mark "Diéthylcarbitol" by the American Society the union carbide-chimiques Co of York.

(c.¹ ) Boosting solvent known as diglycol dibutyl ether.. marketed under the trademark "Dibutylcarbitol" by the house advantage for the union carbide-coextruded cited above.

(c. ") distillation cut between 189° 205 °c and branched aliphatic hydrocarbons synthesized, containing a mixture of decane, undecane and dodecane, from the company Esso's standards.

Examples 41 to 50

Insecticidal compositions comprising DDVP as phosphoric ester, at least one main phenylalkyl as stabilizer of this ester, an odorant selected from linalool, ionone, menthone, linalyl acetate, terpenes orange and lemon terpenes and, in many cases, additional stabilizer selected from sulfur, sulfur compounds, and the compounds of oxiranes azoïaues.

(Values expressed in percentages by weight).

U1 u1 UI of Ru ->•

o O O a

Examples 51 to Gq

Insecticidal compositions comprising DDVP as phosphoric ester, at least one main benzodiorole as stabilizer, a thermoplastic synthetic resin as solid solvent, an ester solvent used as heavy complementary together, in some cases, as a plasticizer for the resin and, in many cases, additional stabilizer selected from sulfur, sulfur compounds,, of oxiranes and azo compounds.

(Values expressed in percentages by weight).

v-RO " O-O-ER vji ER o1 table VI

5C

(d.) copolymers of ethylene and / £67 33 / ° of vinyl acetate having inherent viscosity of 0.78 to fortify 0.25 g in 100 ml of toluene to 30 °c.

EXAMPLES 6170 &

Insecticidal compositions comprising DDVP as phosphoric ester, at least one main phenylalkyl as stabilizer of this ester, a paraffin, as solid builder, a silica mineral fossil as adjuvant, and, in many cases, additional stabilizer selected from sulfur, sulfur compounds, and azo compounds of oxiranes, a copolymer of ethylene and vinyl acetate as an agent for improving the mechanical properties of the paraffin, a pigment and/or a modified montmorillonite as dispersing agent to maintain the homogeneity of the composition prior to cooling.

(Values expressed in percentages by weight).

γ ο γ ο - vjj "•

iU ο vji ο vjivji ο

(℮) irgalithe Bay condo/yellow

(i ') product from the reaction, in a molar ratio 2:1, oleic acid and the diamine mixture according to:

(10 $) Amino HexadécylaminopropylcneOctadécylaminopropylene octadecylaminopropylene amino amino (5 $) (85 $)

(i ") mixture of dimethyl dihexadécylammonium montmorillonite clay (70 $) and dimethyl dioctadécylammonium montmorillonite clay.

It is obvious that the invention is not limited to formulations of freshly exposed, which was especially illustrative of the multiple applicability of 1' disclosure. In particular, DDVP can be changed in the formulations, by ester phospnoric selected from the following:

(1) Phosphate of dichloro-2.2 and dimethyl vinyl;

(2) Phosphate of dichloro-2.2 vinyl diethyl;

(3) Phosphate of dichloro-2.2 vinyl and dipropyl;

(4) Phosphate of dichloro-2.2 vinyl and dibutyl;

(5) The phosphate dibromo 2.2 and dimethyl vinyl;

(6) Phosphate dibromo 2.2 vinyl diethyl;

(7) The phosphate dibromo 2.2 vinyl and dipropyl;

(8) Phosphate bromo-2 chloro 2 vinyl dimethyl;

(9) The phosphate bromo-2 chloro 2 vinyl diethyl;

(10) Phosphate of dichloro-2.2 vinyl, ethyl and methyl;

(11) The phosphate dibromo 1.2 dichloroallyloxy 2.2 and dimethyl ethyl;

(12) Phosphate dibromo 1.2 dichloroallyloxy 2.2 ethyl and diethyl;

(13) Phosphate bromo-1 dichloroethylene 2, 2, 2 dimethyl ethyl and;

(14) The phosphate bromo-1 dichloroethylene 2, 2, 2 ethyl and diethyl;

(15) The phosphate tetrabromo 1, 2, 2, 2 dimethyl ethyl and;

(16) phosphate

diethyl;

(17) phosphate

dimethyl;

(18) phosphate

diethyl;

(19) a phosphate he and

dimethyl;

(20) Phosphate

diethyl;

of tétrahromo-a 1, 2, 2, 2 ethyl and

of dihromo-a 1.2 dichloroallyloxy 2.2 propyl and dihromo-a 1.2 dichloroallyloxy 2.2 propyl and of dichloro-2.2 methyl-1 vinyl and

of dichloro-2.2 methyl-1 vinyl and

the thionophosphates corresponding, for example:

(21) The thiono phosphate of dichbro and 2.2 and dimethyl vinyl.