CA1076476A - Process for increasing the power of insecticidal phosphoric esters and new insecticidal compositions - Google Patents

Abstract

Abstract of the Disclosure A liquid insecticidal composition is described which consists of a homogeneous solution comprising:
(A) an amount of insecticidal material, consisting of at least one organo-phosphorus compound which is solid at 20°C, sufficient to achieve the insecticidal effect and not exceeding the amount which can be dissolved completely in the remainder of the composition;
(B) from 0.2 to 10 parts by weight, per one part by weight of insecticidal material A, of at least one carbon compound which is liquid at 25°C, has a low volatility, is a poor solvent for the insecticidal material A and has a vapour pressure at 25°C
which does not exceed 0.01 mm Hg; and (C) at least one carbon compound which is liquid at 25°C, is volatile, is a good solvent for the active material and for the liquid B, has a vapour pressure at 25°C at least equal to 5 mm Hg and is present insufficient amount to form a complete and homogeneous solution with the amounts of the components A
and B which are present.

Description

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The present invention relates to a process ~or increasing the power of solid insecticidal materials belonging to the category of the phosphoric or thiophosphoric esters and to compositions prepared in accordance with the said process.
The said compositions are either in the ~orm of homogeneous liquid solutions, which contain, in addition to the said insec-ticidal material, at least one llquid o~ low volatility which is a poor solvent for the said material, and at least one vola-tile liquid which is a good solvent for the said materials,orthey are in the form of solld compositions prepared from these solutions.
me use of solid phosphoric or thiophosphoric esters as insecticidal materials has been known for a number of years and various types of compositions containing these active ;;~
materials have been proposed and/or marketed such as, for example, powders, baits and liquids.
The liquids are very widely accepted because they are very adaptable in use; they can be used in all kinds of appa-ratus; for example they can be applied by means as diverse as spraying devices, brushes and aerosol containers which con-tain a compressed or liquefied gas; they make it possible to produce any desired dilutions with perfect distribution of the active material.
Two ~nown liquid forms can be produced ~rom solid phos-phoric or thiophosphoric esters, namely suspensions and solutions.
The suspension.s present problems which are well-known . .

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For these reasons, solutions are generally preferred.
However, these also exhibit disadvantages; in particular, the presence of the liquids used as solvents favours the pene-tration of the active material into the porous materials to which the solution is applied, such as, for example, walls and ceilings; as a result, the efficacy of the composition at the surface of the treated materials ~ecreases rapidly, which is particularly objectionable if it is desired to achieve pro-tection against harmful insects such as flies, mosquitoes, cockroaches, ants, wasps and the like; -the tendency is there-fore frequently to renew the application, which is rather uneconomical and ~urthermore results in the treated surfaces having a messy appearance due -to the accumulation of -the liquid products.
On the other hand, when using only very volatile solvents, the active material will crystallise on the surface o~ the treated material and can no longer be absorbed by the latter; however, the Applicant has found that7 ,, "

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in that case, the efficacy of the active material was greatly reduced.
AnotheT possibility of avoiding, at least partly, the above disad-vantages consists in employing solutions in solvents of low volatility, con-taining a high concentration of active material; however, this entails a real danger because of the considerable toxicity of the insecticidal materials in question.
The present invention proposes a remedy for all these disadvantages, based on the observation made by the applicant that, when a solid phosphoric or thiophosphoric ester precipitates from a liquid which is a poor solvent therefor, then as a result of the evaporation of a volatile co-solvent which, ~ :
together with the ester and the poor solvent, formed a homogeneous solution before evaporation, the said ester has a very high efficacy and exhibits this : :
for a long period of time even if the solution is applied to an absorbent material. The invention thus proposes a liquid insecticidal composition con-` sisting of a homogeneous solution comprising: ~A) as active ingredient, at least one insecticidal organo phosphate compound which is chosen from 0,0- ;
dimethyl S-~4-aza-6-chloro-2-oxo-benzoxazol-3-y~ -methyl thiophosphate, 0,0-diethyl 0-(3,5,6-trichloro-pyrid-2-yl) thiophosphate, 0,0-dimethyl 0-~2,5-dichloro-4-iodo-phenyl) thiophosphate, 0,0-dimethyl 0-(2,4,5-trichloro-phenyl) thiophosphate, 0,0-dimethyl S-(6-chloro-2-oxo-benzoxazol-3-yl)-methyl dithio- -~:
phosphate, 0,0-dimethyl(2,2,2-trichloro-1-hydroxy)-ethyl-phosphonate and 0,0- ;~
diethyl-S-(2-oxo-4-aza-benzoxazol-3-yl)-methyl dithio-phosphate, ~B) 0.2 to 10 parts by weight, per part by weight of component A, of at least one carbon com-pound which is liquid at 25C, is chemically inert towards the insecticidal material A, has a solvent power (or dissolving capacity) for component A which at 20C is less or equal to 5 parts by weight of A per 100 parts by weight of :
B and has a vapour pressure at 25C ranging from 0 to 0.1 mm Hg, and (C) at least one carbon compound which is liquid at 25C, is chemically inert towards the insecticidal material A, has a solvent power ( or dissolving capacity) for :
component A which at 20C is ; ~2 ~ 4 ~ ;.
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at least equal to 5 parts by weight of A per 100 parts by weight of C, has a vapour pressure at 25~C ranging from 5 to 600 mm Hg, component C beîng present in amount sufficient to form a homogeneous solution with the amounts of the components A and B present.
The insecticidal composition according to the invention can further-more comprise: .
D) optionally, a supplementary insecticidal material chosen fromamongst the ortho-substituted phenyl N-methyl-carbamates; and E) optionally, an adjuvant which is soluble, is inert towards A ~ B
I C and is chosen from amongst E') liquids which are poor solvents or non-solvents for the active material and have a vapour pressure at 25C equal to or greater than 0.01 mm Hg;
E") non-volatile solid diluents;
E"') liquefied gases which can be used as propellants;
E"") supplementary insecticidal acti~e materials, different from A and from D and ;~
E""') dyestuffs, perfumes and stabilisers. `-~
The preferred compositions according to the invention are those in ; :
which the insecticidal phosphoric ester is chosen ~ ~ 5 ' ', ~ ~' . ' .

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1(3~7~;4~6 from amongst at least one of the following compounds:
(1) O,O-dimethyl S-(4-aza-6-chloro-2-oxo-benzoxazol-3-yl)-methyl thiophosphate (otherwise referred to as AZAMETHIPHOS);

(2) O,O-diethyl 0-(3,5,6-trichloro-pyrid-2-yl) thio-phosphate (otherwise referred to as CHLORPYRIPHOS);

(3) O,O-dimethyl 0-(2,5-dichloro-4-iodophenyl) thio-phosphate (otherwise referred to as IODOFENPHOS);

(4) O,O-dimethyl 0-(2,4,5-trichlorophenyl) thio-phosphate (otherwise referred to as TRICHLORMETAP~IOS);
- (5) O,O-dimethyl S-(6-chlora-2-oxo-benzoxazol-3-yl)-methyl dithiophosphate (otherwise referred -to as PHOSALON~);
and (6) O,O-dimethyl 2,2,2-trichloro-1-hydroxyethyl phos-phonate (otherwise referred to as TRICHLORPHON).
Preferably, the amount of insecticidal material A does not exceed 10% of the total weight of the liquid composition and represents at least 0. 2% of the total weight of the com-ponents A + B + C.
The liquid of low volatility, B, is used in a pro-portion of between 0.2 and 10 parts by weight per partbyweight of insecticidal material; it has in fact been observed that below 0,2 part the effect provided by the liquid of low volatility becomes too slight to be useful; above 10 parts, the effect indeed persists, bu-t after application the composition remainS
` - excessively liquid and accordingly the disadvantages, mentioned -. . earlier, which are inherent in compositlons which remain in the : O:f _ .~ _ , . ~

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5 parts by weight of the liquid of low volatility per part of insecticidal material A.
The liquid of low volatility, B, preferably has a vapour pressure at 25C which is less than 0.005 mm Hg. Its dissolv-~ing capaci-ty for the insecticidal material, A, at 20C, is at most 5 parts of A per 100 parts of B, by weight; preferably, this proportion is at most 3 parts of A. The liquid B is thus a diluent for the active material A. ~t must be chemically inert -towards this active material A, towards the liquid C and towards the other components which may be present in the com-position according to the invention. ~:
It will be seen that the partial amount of insecticidalmaterial A which remains dissolved in the liquid B after evaporation of the liquid C, will not exceed 50% of the total weight of A present in the composition, and in the case of the pre~er~ed limits this amount is at most 15% of the weigth of Ao This is an important feature of the invention.
The liquid of low volatility, B, can be virtually non-volatile and can have a vapour pressure at 25C which is less than 10 6 mm Hg.
The liquid of low volatility, B, is preferably chosen from amongst aliphatic hydrocarbons, halogenated aliphatic hydro-carbons, halogenated aromatic hydrocarbons, esters of aliphatic acids, esters of aromatic acids, heterocyclic compounds, pre-ferably heterocyclic compounds of which the hetero atom is g-- ::
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Oxygen, high-molecular alcohols, polyols, ether-alcohpls and amino-alcohols, aliphatic mercaptans, high-molecular ketones and natural oils.
Amongst these, aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, es-ters of aliphatic acids, esters of aromatic acids, oxygen-containing heterocyclic compounds, alco-hols, polyols and ketones are generally preferred.
In particular, the liquid of low volatility, B, can for example be chosen from amongst one or more of the following solvents, provided, however, that the dissolving capacity of the resulting liquid for the insecticidal material A li~es, at 20C, ~ -.
between the limits indicated above: a vaseline oil, a paraffin oil, hexadecane, l-bromo-tetradecane, l-chloro-hexadecane, tetrachlorodiphenyl, isopropylmyristate, dioctyl adipate, dibutyl phthalate, dioctyl phthalate, didecyl phthalate, bis-; (tridecyl) phthalate, 5-(3,~,9-t~oxa-2-hydroxy-undecyl)-1,3-ben2o-dioxole, l-dodecanol, l-tridecanol, glycerol, dibutyl ether of diethylene glycol (dibutyl carbitol), 2-amino-2- ;
ethyl-propane-1,3-diol,tertiary dodecanethiol and oleone (9726-pentadiatriacontadien-18-one), oc-tanoic acid, oleic acid, 2-dodecylsuccinic anhydride, olive oil and linseed oil.
The liquid of low volatility, B, is preferably chosen from amongst the ~ollowing solvents: vas.eline oil, paraffin oil, hexadecane, l-chloro-hexadecane, isopropyl myristate, dioctyl adipate, dioctyl sebaceate, dibutyl phthalate, dioctyl phthalate, didecyl phthalate, bis-(tridecyl) phthalate, 5-(~,6,9-trioxa-und~cyloxy-2)-1,3-benzodioxole, 1 tridecanol, glycerol and oleone. ~ :
;: ~ All these diluents B have a vapour pressure, at 25C, ,,, ,~ .. ,.. . . . ..... .... ~., .~ .

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of less than 0.01 mm Hg, and dissolving capacities for the active materials, at 20C, ranging from 0 to 5 parts by weight of A per 100 parts by weight o~ B
The volatile liquid C preferably has a vapour pressure, at 25C, greater than 80 mm Hg; preferably, it is miscible in all proportions with the liquid B; its dissolving capacity for the insecticidal material A, at 20C, is at least five parts by weight of A per 100 parts of C and preferably greater than ten parts per 100. The amount of liquid C required in the .
composition depends on its solvent power for the insecticidal ~:
material A and the liquid B and on the amount of each of these components; the amount of liquid C to be used must always be sufficient to afford a complete and homogeneous solution.
Accordingly, the liquid C is a solvent for the active material A.
It is chemically inert towards this active material, towards the liquid B and towards the other ingredients which may be present in the composition according to the invention The volatile liquid C is preferably chosen from amongst.
halogenated aliphatic hydrocarbons, aromatic hydrocarbons, aliphatic esters, heterocyclic compounds, prefera~ly oxygen-containing heterocyclic compounds, and aliphatic alcohols, ethers and ketones.
In particular, the volatile liquid C can be, for example, one of the followi.ng solvents, or a mixture of two or more of these solvents, provided however that the dissolving capacity, at 20C, of this liquid for the insecticidal material A lies within the limi-ts indicated above: methylene chloride, 7 ~:
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chloroform, benzene, methyl acetate, ethyl acetate, isopropyl :
acetate, propyl acetate, isobutyl acetate and/or butyl acetate, :-methyl propionate and/or ethyl propionate, me-thyl butyrate and/or ethyl butyrate, 2-methoxyethyl acetate, tetrahydrofurane, dioxane, e-thoxyethane, methanol, ethanol, isopropanol, methoxy-ethanol, acetone, methyl e-thyl ketone and butan-2-one In general, it is preferableto choose the volatile liquid C from amongst halogenated aliphatic hydrocarbons, aromatic hydrocarbons, aliphatic esters, oxygen-containing heterocyclic compounds, aliphatic alcohols, aliphatic ethers and aliphatic ketones.
Thus, the liquids C which are more particularly preferred because their vapour pressures at 25C are between about 80 and about 500 mm Hg and their solvent powers towards the active materials proposed by the invention vary between a value of 10 parts by weight of A per 100 parts by weight of C and ~; miscibility in all proportions Preferably, the liquids B and C are miscible in all proportions.
: The supplementary insecticidal material D can, for example, be chosen from amongst the following ortho-substituted phenyl N-methylcarbamates: orthocresyl N-methylcarbamate, 2-: ethyl-phenyl N-methylcarbamate, 2-isopropyl-phenyl N-methyl-carbamate, 2-tertiary butyl-phenyl N-methylcarbamate, 2-sec.-butyl-phenyl N-methylcarbamate, 2-tertiary amyl-phenyl N-methylcarbarnate, 2-methoxy-phenyl N-methylcarbamate, 2-ethoxy-phenyl N-methylcarbamate, 2-isopropoxy-phenyl N-methylcarbamate rr- O
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(otherwise referred to as ARPROCARB), 2-isobu-toxy-phenyl N~
methylcarbamate, 2-tertiary butoxy-phenyl N-methylcarbamate, 2-sec.-butoxy-phenyl N-methylcarbamate, 2-propargyloxy-phenyl N-methylcarbamate, 2-dimethoxymethyl-phenyl N-methylcarbamate, 2-diethoxymethyl-phenyl N-methylcarbamate, 2-(1,~-dioxolan-2-yl)-phenyl N-methylcarbamate (otherwise referred to as DIOXACARB) 9 2-(4-methyl-1,3-dioxolan-2-yl)-phenyl N-methyl-carbamate, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)-phenyl N-methyl-carbamate, 2-(1,3-dioxan-2-yl)-phenyl N-methylcarbamate, 2-(4-methyl-1,3-dioxan-2-yl)-phenyl N-methylcarbamate and 2,2-dimethyl-1,3-benzodioxol-4-yl N-me-thylcarbamate (otherwise re-ferred to as BENDIOCARB).
The liquids E' are chosen from amongst the liquids having a vapour pressure, at 25C, of between 0 01 and 10 mm Hg.
Their dissolving capacity for the insecticidal material A at 20C is at most 5 parts by weight of A per 100 parts by weight of E'. These liquids E' are thus more volatile diluents than the diluents B; they make it possible to reduce the required proportion of liquid B and, by evaporating substantially more rapidly than the latter, they impart, after a certain time, a drier appearance to the composition after application and evaporation of the liquid C.
The liquids E' are preferably chosen from amongst the :
liquids having a vapour pressure, at 25C, grea-ter than 10 mm Hg ~ :;
and even greater than 40 mm Hg, and a dissolving capacity for :
the insecticidal material A, at 20C, equal to or pre~erably less than 5 parts by weight of A per 100 parts by weight o~ E'.
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They thus make it possible to dilute the liquid C if the latter has a very high solven-t power.
The liquids E' are chosen, for example, from amongst aliphatic hydrocarbons, aromatic hydrocarbons, halogenated aliphatic hydrocarbons, alkoxyalkanes, saturated aliphatic alcohols of more than two carbon atoms, and heavy ketones.
The liquids E' which, at 25C, have a vapour pressure of less than 10 mm Hg are, for example, mixtures o~ saturated aliphatic hydrocarbons, or aliphatic alcohols having at least five carbon atoms, such as amyl alcohol or l-octanol, and heavy ketones such as laurone (tricosan-12-one) and/or stearone (pentatriacontan-18-one).
The liquids E' which,.at 25C, have a vapour pressure greater than 10 mm ~g are, for example, mixtures o~ saturated aliphatic hydrocarbons, pentane, hexane, heptane, butyl chlor-ide, l,l,l-trichioroethane, trichloroethylene, benzene and ;~
isopropanol.
Amongst these, hexane, isopropanol, octanol, mixtures of saturated hydrocarbons such as "Isopar L" and laurone are very particularly preferred The compositions according to the invention can also contain non-volatile solid diluents E" chosen from amongst natural or synthetic waxes, natural or synthetic resins and _ solid hydrocarbons; they are used, preferably, in a low pro-portion whicn does not exceed 10% by weigh-t of the composition The waxes are, ~or example, c'nosen from amongst beeswax, candelilla wax, carnauba wax, Japan wax, montan wax, synthetic ...
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waxes obtained from chlorinated naphthalene, glycol stearates and solid fatty ketones.
The resins are chosen, for example, from amongst colophony, gum lac and synthetic organic resins such as homo-polymers and copolymers based on vinyl derivatives (vinyl acetate, vinyl propionate, vinyl butyrate, vinyl ethers or vinylformal), on alkenes (ethylene, propylene, butylene and the like) and/or on styrene and/or vinylpyrrolidones and/or cellu-losic derivatives (the methyl, ethyl or benzyl ethers of cellulose, cellulose acetate, propionate, butyrate, phthalate, nitrate and the like) and/or on isoprene and/or on butadiene and/or on acrylic or methacrylic esters and/or on allyl esters (allyl phthalate, isophthalate, maleate, cyanurate and the like); such organic synthetic resins can also arise from the interaction of compounds with reactive groups, as in the case of the so-called "epoxy" resins, resulting from the condensation-of an epoxide with a polyphenol, in the case of "polyester"
resins, resulting from the action of a polyacid on a polyol, in the case of the polyurethanes, resulting from the condensation of a polyisocyanate with a polyol, and in the case of resins of the coumarone-indene type. - ;
The solid hydrocarbons are chosen, for example, from amongst the micro-crystalline and macro-crystalline alkanes having at least 2~ carbon atoms, and their mixtures, known under the names of microwax, tank bottomwax, ozokerite, cereslne, paraffin and isoparaffin.
The liquefied gases E"' which can be used as propellants .J /,3 ' ' , .. .,._ .. , . . .... ". ... .,.. ,, .... _,,. _._.. ,. ,.. ,.. :.. ,. . . , .~ .. . . .
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are, for example, chosen from amongst bu-tane, isobutane, pro-pane, methoxymethane, trichlorofluorome-thane, dichlorofluoro-methane, 1,2-dichloro-1,1,2,2-tetrafluoroethane, tetrafluoro-methane and octafluorocyclobutane.
The supplementary insecticidal active materials E"l' are preferably non-solvents or poor solvents for the insecticidal material A. They are chosen, for example, from amongst liquid organophosphorus compounds, natural pyrethrins, rotenone, synthetic pyrethrinoids, N,N'-dibutyl--para-chlorobenzene-sulphonamide, 1,4,4a,5 9 6,7,8,8-octahydro-3a,4,7,7a-tetrahydro-4,7-methano-indane, hexachlorocyclohexane, 1,2,3,4,10,10-endo-exohexachloro-6,7-epoxy-1,4,4a,5,6,7,8,8a-octahydro-1,4-5,8-dimethano~aphthalene and the various carbamate esters of D such as~ for example, l-dimethylcarbamyl-5-methyl-pyrazol-3-yl dimethylcarbamate, 3-methyl-1-phenyl-pyrazol-5-yl dimethylcar-bamate and 4-methyl-2-propyl-pyrimid-6-yl dimethylcarbamate.
In general terms, the introduction, into the composition, of liquids which have both a very low volatility and are good solvents for the insecticidal material A will be avoided.
Preferably, the presence of water, beyond the amount which corresponds to the normal contents of commercial technical products, will also be avoided.
The compositions according to the invention are intended to be applied to any surface frequented by the insects to be destroyed; they can also serve for the preparation of solid products which contain the active material A in a superactiva-ted form; these solid products are prepared from carriers such as, t.l~ .
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for example, cardboard made from cellulose, asbestos or waste paper, wool and/or cotton fel-ts, mineral or organic granules and powders such as talc, kaolin, dried clay, fossil silicas, synthetic silicas, non-fossil natural silicas, vermiculite, magnesium silicate, aluminium silicate, calcium phosphate, calcium carbonate, wood flour, soya flour and nutshell flour The invention thus also provides a process for the preparation of a solid insecticidal composition containing the elements A
and B, and, optionally, D and E, already defined, and a solid carrier chosen from amongst cardboards, felts, and mineral or organic granules and powders, the process being characterised in that the said carrieris impregnated with a composition accord- ~ -ing to the invention which comprises the elements A, B and C
and, optionally, D, and in that thereafter the liquid C is caused to evaporate. The value of the compositions-according to the invention is demonstrated in the experiments related below.
EXPERIMENT A
The following nine compositions A-O to A-8 were pre-pared in an aerosol container (values expressed in percentages by weight): :

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~07~;~76 (a) 0,O~Dimethyl S-(6-chloro-2-oxo-4-aza-benzoxazol-3-yl~-methyl thiophosphate or 0,0-dimethyl S-[6-chloro-oxazolo(4,5-b)-2(3H)-pyridin-3-one]-me-thyl thiophosphate.
(a') A liquid which has a vapour pressure, at 25C, of less than 0.0001 mm Hg and a dissolving capacity of 1.6 parts o~
Azamethiphos in lO0 parts at 20C.
(a") A liquid which has a vapour pressure, at 25C, of about O.001 mm Hg and a dissolving capacity o~ 0.7 part of Azame-th-iphos in lO0 parts at 20C.
(a"') A li~uid which has a vapour pressure, at 25C, of less than 0.0001 mm Hg and a dissolving capacity of 4.3 parts of Azamethiphos in 100 parts at 20C.
(a"") Abbreviation for 5-(3,6,9-trioxa-undecyloxy-2)-1,3-benzodioxole; a liquid which has a vapour pressure, at 25C, -~;
of less than 0.005 mm Hg and a dissolving capacity of 4.6 parts of Azamethiphos in lO0 parts at 20C.
(b) Semi-refined oil having a density of 0.870 at 15C, a viscosity of 1.7 Engler at 50C, a vapour pressure, at 25C, -~
of less than 0.001 mm Hg and virtually zero dissolving capacity for Azamethiphos at 20C.
(b') A liquid which has a vapour pressure, at 25C, of about 0.005 mm Hg and a dissolving capacity o~ 0.5 part of Azameth-iphos in lO0 parts at 20C.
~b") A liquid which has a vapour pressure, at 25C, of less than 0.000001 mm Hg and a dissolving capacity o~ about 2.2 parts o~ Azamethiphos in 100 parts at 20C.
(b"') A liquid which has a vapour pressure, at 25C, of about . , . . " . :. . , , ., . . ~ . ~

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0.0001 mrn Hg and a dissolving capacity of 4.5 parts of Aza-methiphos in 100 parts at 20C
(c) A liquid which has a vapour pressure, at 25C, of 176 mm Hg and a dissolving capacity o~ 94 parts of Azamethiphos in 100 parts at 20C.
(c') A liquid which has a vapour pressure, at 25C, of 420 mm Hg and a dissolving capacity of 144 parts of Azamethiphos in 100 parts at 20C.
The contents of each of these containers was distribu-ted by spraying over one of the faces of glass plates of size 20 x 10 cm, at the rate of 800 mg per pla-te; 5 plates were thus prepared for each composition. Two days after this preparation, insecticidal efficacy tests were carried out on insects of the species Blatta germanica which were placed on the treated face of the pla-tes for one minute and were then placed under observation in aerated wide-mouthed bottles;
thereafter, the cumulative proportion of dead insects or of insects in a state of dorsal decubitus (KD%) was noted every 15 minutes; 10 insects were placed on each plate, representing ~-a total of 50 (+ 5) insects per composition.
The table below indicates the results recorded.

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Time ln minutes A-0 ¦A-1 A-2 A-~ A-4 A-5 A-6 A-7 A-8 17 98 g8 96100 62 Z6 62 100 36 100 98 96 _ 66 40 77 _ 42 _ 98 96 _ 68 L~4 84 _ 44 _ 99 97 _ 72 52 88 _ 105 48 _ 99 97 _ 76 54 88 _ 120 49 _ 100 97 _ 76 60 89 _ :
135 49 _ _ 97 _ 77 68 90 _ ;~
150 53 _ _ 98 _ 77 74 90 _ 165 53 _ _ 98 ~ 78 7L~ 91 _ 180 55 _ _ ~ ~ 78 7~ 93 _ -EXPERIMENT B
The procedure of Experiment A was employed, using ~.
compos1tions A-0, A-l, A-2, A-4, A-7 and A-8 and employing insects of the species Periplaneta americana.
The table below indicates the results recorded (KD%). :

.

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. _ Time in minu-tes A-0 A-1 A-2 A-4 A-7 A-8 _ . _. ~ _ O L~ L~ 6 2 10 ~5 0 25 18 34 8 55 4 61 2L~ 72 3o 79 16 73 ~g 96 54 98 105 20 77 45 96 66 100 :`
120 26 79 51 97 72 _ 135. 36 85 53 98 82 _ 180 46 89 ~ 100 88 _ - EXPERIMENT C
.
The f~owing two compositions C-0 and C~l were prepared in an aerosol container (values expressed in percentages by weight):

~:~ = Composition - _r :_ A Azamethiphos 1 ¦ 1 _ _ _ .
B Didecyl phthalate (a') . 2 , . ~
C Methylene chloride (c') 19 17 . . ___ _ . _ E" Trichlorofluoromethane 40 40 __ Dichlorodifluoromethane 40 40 These compositions were each tes-ted on one hundred lnsects of the species Musca domestica, 5 to 7 days old and flying freely in a room of size 28 m3, For each test, a weight of 4 grams of composition was vapourised into the atmos-phere of the room, and every three minu-tes the number of insects knocked down was noted. The operation was repeated ~o . .
. . . . : . .
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.
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:

1(~i7~;4 76 five times for each composition, making a to-tai of 500 ~ 50 insects tested per composition.
The cumulatlve proportions of insects knocked down (KD%) are indicated in the table below:

Time in minutes C - 0 C - 1 _ .. ,'' ' .
18 . 20 54 24 . 32 69 EXPERIMENT D
_ The procedure of Experiment C was employed, but using the following compositions D-0 and D~ alues expressed in percentage by weight)~
, _ _ _ . . ~ ~ ~ .
Composition D - 0 D - 1 _ _ _ _ . _ A Azamethiphos ' 0.5 0.5 . ~ , B Didecyl phthalate (a') ` _ 2 . , . _ _, . ___ -C Methylene chloride (c') 19 17 i:
. _ _ _. _ _ . D Dioxacarb 0.5 0.5 _ _. r E"' Trichlorofluoromethane 40 40 . Dichlorodifluoromethane 40 40 :

- :

~: l j, , : ; 1 The cumula-tive proportions of insects knocked down (KD%) are indicated in the table below:

Time in minutes D - O

17 30 : :

: 24 39 59 . 30 _ 55 67 , EXPERIMENT E
The procedure of Experi.ment A was employed, using the following compositions E-O to E-I in experiments on inse¢ts of the species Biatta germanica (values expressed in percent-- ages by weight): :
,, . ~ _ , -~ .
Composition E - O E - I . ~ ~
_ _ _ , : A Azamethiphos 1 1 _ . B Dioctyl phthalate (d) _ 4 :~ , _ , . .
: Methylene chloride (c') 26 26 C Tetrahydrofurane (c) 2 2 . . _ . D Dioxacarb 1 1 _ .~E" Trichloro~luoromethane 35 33 ~_ Dichlorodi~luoromethane 35 33 . __, :~ (d) A liquid which has a vapour pressure, at 25C, of less :

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~ '6 than 0.0001 mm Hg and a dissolving capacity of 2.4 parts of Azamethiphos in 100 parts at 20C, The table below indicates the results recorded (KD%):
_ Time in minutes E - 0 E - I
_ .

loO
105 45 _ 120 45 : -EXPERIMENT F
The procedure of Experiment A was employed, using the .
following compositions F-O to F-I in experiments on insects of the species Blatta germanica (values expressed in percentages , by weight): ~:
_ _ _ _ _ _ _ I
Composition . F - O F - I
_ , . . ~ --A Azamethipnos _ _ _ _ B Dioctyl phthalate (d) _ 4 :
_ _ ~
C Methy~ene chloride (c') 26 26 Tetrahydrofurane (c) . 2 2 -_ _ . .
D Arprocarb 1 1 _ _ _ . . _ E"' Trichlorofluoromethane 35 33 _ Dichlorodifluoromethane 35 33 :-' ~3 ~ ~ , .

:

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. ~ !
: . ' . ' ' ': ' ' ' : : ' ~7~;~76 The table below indica-tes -the results recorded (KD%):

_ _ . I
Tlme in minutes F - F - .-. _ , ~0 16 95 lg lOo 52 _ 59 _ :
64 _ :
105 66 _ 120 69 _ EXPERIMENT G
_ . The procedure of Experiment A was employed, using the following compositions G-0 to G-I in experiments on insects of the species Blatta germanica (values expressed in percentages by weight):
_ _ 1 Composition G - 0 G - I
. . , _ . , , ~
A Azamethiphos . 1 I
B Dioctyl phthalate (d) _ 4 _ . . _ C Methylene chloride (c') 26 26 Tetrahydrofurane (c) 2 2 _. . _ _. _ D Bendiocarb 1 1 _ _ _ .
;: Trishlorofluoromethane 35 33 En Dichlorodi~luoromethane 35 33 The table below indicates -the resul-ts recorded (KD%):

_ ~_ ...... .. . . . .
. , . , : , , . , :

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. . . . .

, ~
Time in minutes G - 0 G - I
___, _ ___ Z~ _ 29 _ `
42 _ 105 49 _ 51 _ _ EXPERIMENT H
A solution H-l having the following constitution (values expressed in percentages by weight) was prepared: :
Azamethiphos: 8 Dioctyl phthalate (d): 16 Acetone (c"): 76 (c") A liquid having a vapour pressure~at 25C, of 225 mm Hg and a dissolving capacity, at 20C, of 44 parts of Azamethiphos in 100 parts, This solution was poured into a malaxator containing very fine talc powder (less than 0.5% retained on a 50 microns screen); after malaxating so as to achieve good distribution of the solution on the powder, the acetone is evaporated by means of a stream of hot air (50C). The proportions of talc and of solution were chosen so as to give a final powder H-l having the following composition (values expressed as percentages by weight):

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;. .: . . ~ , . , 1~76~'7ti Azamethiphos: 2.5 Dioctyl phthalate: 5.0 Talc: 92.5 In addition, a conventional formulation Hl-0 was pre-pared as follows by intimately mixing the constituents (values expressed as percentages Dy weight):
Azamethiphos: 2.5 Talc: 97.5 -This mixture was passed through a pin mill so as to give a powder of which less than 0.05% is retained on a 50 microns screen. ~ ;
Insecticidal efficacy tests were carried out on insects of the species Aphis fabae, which were placed in Petri dishes at the rate of twenty insects ~+ 10/~ per dish. Eight dishes were used, of which four had been treated with powder H'-0 at the dosa of 0.5 milligram per square centimetre, and four others had been treated with powder H'-l at the same dose.
Every three minutes, the percentage of insects which appeared dead was noted.
The table below indicates the cumulative percentages noted each time:
. _ __ _ ................................. :
Time in minutes H'-0 H'-l . _ _ 21 4 lL~
2L~ 6 20 ;~ _ 23 51 Z~
~

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,XPERIMENT I
The following two liquid compositions I-0 and I-1 were prepared (values expressed in percentages by weight):
. __ Composition I - 0 I - 1 ~ .
A Chlorpyrifos 7 7 . ._ B Glycerol (d') _ 7 _ _ _ _ _ C Acetone (e) 46.5 43 _ Methanol (e') 46.5 _ _ _ (d') A liquid which has a vapour pressure, at 25C, of less than 0.0001 mm Hg and a dissolving capacity, at 20C, of 0.3 part of Chlorpyrifos in 100 parts.
(e) A liquid which has a vapour pressure, at 25C, o~ 225 mm Hg and a dissolving capacity, at 20C, of 650 parts of .
Chlorpyrifos in 100 parts.
(e') A liquid which has a vapour pressure, at 25C, of 127 .
mm Hg and a dissolving capacity, at 20C, of 43 parts of :~
Chlorpyrifos in 100 parts.
These solutions were each deposi-ted on one of the faces of glassplatesofsize 10 x 20cm at the rate o~ 0.8 millilitre per plate. After evaporation of the solvent mixture, the plates .were placed within contact of insects of the species Blattella germanica under the conditions described in Experiment A.
The results (KD%) are summarised in the table below:

.
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Time in minutes I - 0 I - 1 ~ 45 6 _ EXPERIMENT_J
The following two liquid compositions J-0 and J-l were prepared (values expressed in percentages by weight):
. _ _ _ . _ Composition J - 0 J - 1 __ __ A Iodofenphos 2 2 _ ~_ B Hexadecane (s') _ 4 , __ , , _ .
C Acetone (v) 49 47 Benzene (x) 49 47 __ _ .
(s') A liquid having a vapour pressure, at 25C, of about 0,003 mm Hg and a dissolving capacity, at 20C, of 2,8 parts of Iodofenphos in 100 parts;
(v) A liquid having a vapour pressure, at 25C, of 225 mm Hg and a dissolving capacity, a-t 20C, of 48 parts of Iodofenphos in 100 parts;
(x) A liquid having a vapour pressure, at 25C, of 95 mm Hg and a dissolving capacity, at 20C, of 61 parts of Iodofenphos in 100 par-ts.
These solutions were each deposited on the bottom of a Z.~

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~7~76 Petri dish of 16 centimetres diameter at the rate of 2 milli-litres per dish. After evaporation of the solvent mi~ture, insects of the species Attagenus piceus were deposited at the rate of 10 insects per disc; 5 repeats were run, representing a to-tal of 50 insects per composi-tion. Every fifteen min-utes, the number of dead insects or insects in a state of dorsal decubitus (KD%) was noted.
The table below indicates the mean values (KD%) of the results recorded.
. _ _ Time in minutes J - 0 J - 1 .. _ . ::

135 2 20 .

225 2 58 ;, zq ~ .
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EXPERIMENT K
The following two liquid compositions K-0 and K-l were prepared (values expressed in percentages by weight):
_ _._ _ Composition K - 0 K - 1 _ . .
ATrichlormetafos 4 4 _ _ __ _ .. . , __ BHexadecane (s') _ 4 _, _ ~
C Methylene chloride (f) 96 92 , ~ ., (f) A liquid having a vapour pressure of 420 mm Hg at 25C
and a dissolving capacity, at 20C, of 670 parts of Trichlor-metaphos in 100 parts.
These solutions were each deposited on one of the faces of glass plates of size 20 x 20 cm, carrying one gram of sugar powder distributed over their surface, at the rate of 2.4 milli-litres per plate. After evaporation of the methylene chlor-ide, each of these plates was placed in a one metre cube cage, each containing one hundred insects of the species Musca domestica. Every 3 minutes, the percentage of dead insects or insects in a state of dorsal decubitus was noted (KD%).
The results are summarised in the table below:

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- . . ... . .

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. . .
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._ . _ _ .
Time in minutes K - 0 K - 1 I'' 11 i 60_ _ 16 67 ;

EXPERIMENT_L ;~- :
: The following two liquid compositions L-0 and L-l were prepared (values expressed in percentages by weight):
_ ___ . Composition L - 0 L - 1 _ _ , _ k Phosalone 0.5 0.5 ~ __~
B Paraffin oil (g) _ 2.5 _ _ . _ . _ C Methylene chloride (w) 99.5 97 ~:

(g) A liquid which can be frozen at -27C, and has a den- ~-sity of 0.851 at 15C, a vapour pressure, at 25C, of less than ;:; :
0,001 mm Hg and a dissolving capacity, at 20C, of 2,4 parts o~ Phosalone in 100 parts;
(w) A liquid having a vapour pressure, at 25C, of 420 mm Hg and a dissolving capacity, at 20C, o~ ~0.4 parts of Phosalone in 100 parts.
., .
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1076~76 These solutions were sprayed onto young bean plants infes-ted with insects of the species Aphis fabae at the rate .
of 2 millilitres per plant. 6 plants were used for each of the solutions and after two hours the percentage of insects which were dead or appeared dead was recorded for each plant, The results are summarised in the table below, Mean values: 29.7 68 ~:
EXPERIMENT M . .
The following two liquid compositions M-0 and M-l were :
prepared (values expressed in percentages by weight):
_ ' . ~ . __ _ :
Composition M - 0 M - 1 . ,. _ . _ . ~ , : A Trichlorfon 1 1 ~ _ _ _ _ ._ _ r B Dioctyl adipate (r') _ 3 ~ .
_ _ _ _ _ ~
Chloro~orm (u) 66 64 1:
I C Benzene (x) 33 32 ~ .
(u) A liquid having a vapour pressure, at 25C, of 194 mm Hg ti and a dissolving capacity, at 20C, of 750 parts of Trichlorfon , in 100 par-ts, .: , . :, 3~ .
':
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... . . , , , .. . , :
.,, : " . ` , ~7~476 (r1) A liquid having a vapour pressure, at 25C, of about o,oo6 mm Hg and a dissolving capacity, at 20C, of 2,1 parts .
o~ Trichlorfon in 100 parts;

These solutions were each deposited on the bottom of a Petri dish and insects of the species Attagenus piceus were introduced as in Experiment J.
The table below indicates the mean values (KD%) of the results recorded, ,::

. _ _ _ _ _. 6 16 . 120 6 2~

1~0 6 45 300 lZ 100 ::;

The preceding experimen-ts show the value of the com-positions according to the invention; in all the cases, the efficacy of the insecticidal material proved to be markedly ;.~ improved when the solution which contained the material also , ~ .
contained, in accordance with -the invention, a non-volatile liquid which is a poor solvent for the said material and a :. J,~ :
~:. 33 , .

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volatile material which is a good solvent for the said material.
EXPE~IMENT N
The following five aerosol compositioins N-O to N-4 were prepared (values expressed in percentages by weight):

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(h) Abbreviation for 0,0-diethyl S-(2-oxo-4-aza-benzoxazol-3-yl)-me~hyl dithiophosphate;
(i) A liquid having a vapour pressure, at 25C, of about 0.001 mm Hg a~d a dissolving capacity of 3.6 parts of D.B.D.P.
in 100 parts at 20C;
(i') A liquid having a vapour pressure, at 25C, of about 0.001 mm Hg and a dissolving capacity of 1.15 par-ts of D.B.D.P.
in 100 parts at 20C;
(i") Semi-refined oil described in (b) and having virtually zero dissolving capacity for D.B.D.P. at 20C;
(i"') Abbreviation of 5-(3,6,9-trioxa-undecyloxy-2)~
benzodioxole, a liquid having a vapour pressure, at 25C, of less than 0.005 mm Hg and a dissolving capacity of 5 parts of D.B D.P. in 100 parts at 20C;
(j) A liquid having a vapour pressure, at 25C, of 121 mm Hg and a dissolving capacity of 18.6 parts of D.B.D.P. in 100 ~ ~-parts at 20C;
(j') A distlllation cut, between 189 and 205C, of branched`
aliphatic hydrocarbons obtained synthetically, which is marke-ted by Messrs. ESS0 STANDARD, contains a mixture of decanes, undecanes and dodecanes, have vapour pressures,at 25C, of between 0.2 and 2 mm Hg and a dissolving capacity, at 20C, of about 0.15 par-t of D.B.D.P. in 100 parts.
The content of each of the containers was sprayed onto one of the faces of a fabric composed of wool fibres and syn-thetic fibres, at the rate of 400 mg per dm2. Discs of .~ .
, 70 mm diameter were cut from this fabric and each face, treated -, :
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t;4~76 face upwards,are placed in the bot-tom-of a Petri dish of the same internal diameter. One hour later, insects of the species Sitophilus granarius were in-troduced into the dishes at the rate of 10 insects per dish.
For each aerosol, ten dishes were used. Every six minutes, the cumulative proportion of dead or paralysed insects (KD%) was noted.
The table below indicates the results recorded.

Time in minutes N-O N-l ~-2 N-4 _ ___ ___ I '.. ':

24 1 40 ~3 24 35 : ~-~ 56 56 47 44 . 36 10 75 77 ~5 58 ; 42 15 87 90 75 68 -47 99 loo 98 83 _ _ _ N.B The addition of this experiment makes it possible to eliminate, page 26, the sitophili from amongst the coleoptera.
These experiments were concerned with certain orthoptera, diptera, hemiptera and coleoptera; of course, the compositions according to the invention are equally applicable to the des-truction of other species of orthoptera such as, for example, crickets, grasshoppers and mole-crickets, diptera, such as, for example, stable flies, house mosquitoes and yellow-fever `

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mosquitoes, hemiptera such asJ for example, bugs and triatomids, and cole-optera such as, for example, varieties of Oryznophilus, Dermestes, Trogodoram, Tribolium, Guathocerus, Tenebrio, Sltophilus and Leptinotarsa, as well as other orders of insects such as, for example, hymenoptera ~ants), lepidoptera ~Sitotroga and Plodia), isoptera ~termites) and heteroptera ~house bugs).
The compositions below are given as supplementary examples of the invention or in some cases as reference examples ~values expressed in parts b~ weight).

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(p) A liquid having a vapour pressure, at 25C, of about 0.001 mm Hg and a dissolving capaci-ty, at 20C, of 2.9 parts of Dimethoate or 1.5 parts of Trichlorphon in 100 parts;
(p') A liquid having a vapour pressure, at 25C, of less than 0 0001 n~l Hg and a dissolving capacity, at 20C, of 1 7 parts o~ Trichlorphon in 100 par-ts;
(q) A liquid which can be frozen a-t -27C and having a density of 0.851 at 15C, a vapour pressure, a-t 25C, of less than 0 001 mm Hg and a dissolving capacity, at 20C, of about 5 parts of Iodofenphos in 100 parts; :
(q') A liquid having a vapour pressure, at 25C, of less than 0 0001 m~ Hg and a dissolving capacity, at 20C, of 0.5 part of Fospirate or 0.2 part of Iodo~enphos in 100 parts 3 ;
(r) A liquid having a vapour pressure, at 25C, of less than 0.00001 mm Hg and a dissolving capacity, at 20C, of : 4 parts of Dimethoate or 1 2 parts of Azamethiphos in 100 parts; :~
(s) A liquid having a vapour pressure~ at 25C, of less :
than 0 0001 Lm Hg and a dissolving capacity, at 20C, of~ ~ :
2.8 parts of Trichlorphon in 100 parts;
(s') A liquid having a vapour pressure, a-t 25C, of abou-t 0.003 mm Hg and a dissolving capacity, at 20C, of 4 2 parts of Trichlormethaphos, or of 2 ~ parts of Iodofenphos or of at least 0 1 part of Trichlorphon in 100 parts;
(u') A liquid having a vapour pressure, a-t 25C, of 90 mm Hg and a dissolving capacity, at 20C, of 46 parts of Azamethiphos in 100 parts; `
(v) A liquid having a vapour pressure, at 25C, of 225 mm Hg , :. , , , . ... , .

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, 9~6 and a dissolving capacity, at 20C, of 13.6 parts of Dimethoate or 48 parts ~f Iodofenphos in 100 par-ts; - -(v') A liquid having a vapour pressure, at 25C, of 216 mrn Hg and in which Trichlormetaphos is miscible in all propor-tions at 20C;
(w) A li~uid having a vapour pressure, at 25C, of 420 mm Hg and a dissolving capacity, at 20C, of 86 parts of Iodofenphos or 30.4 parts of Phosalone in 100 parts;
(w') A liquid having a vapour pressure, at 25C, of 530 rnm Hg and a dissolving capacity, at 20C, of 24 parts of Trichlorphon in 100 parts;
(x) A liquid having a vapour pressure, at 25C, of 95 mm Hg and a dissolving capacity, at 20C, of 61 parts of Iodofenphos or 1~.2 parts of Trichlorphon in 100 parts;
(x') A liquid having a vapour pressure, at 25C, of 59 mm Hg and a dissolving capacity, at 20C, of 63 parts of Chlorpyri~os .
or 20 parts of Fospirate in 100 parts; -(y) A liquid having a vapour pressure, at 25C, of 0.07 mm H~
and a dissolving capacity, at 20C, of 5 6 parts of Fospirate in 100 parts;
(y') A distillation cut, between 189 and 205C, of branched aliphatic hydrocarbons obtained synthetically, which is marketed `;~
by Messrs. ESS0 Standard, contains a mixture o~ decanes, undecanes and dodecanes, have vapour pressures,at 25C, of ~.
between 0 2 and 2 rnm Hg and has a dissolving capacity, a-t 20C, .; ;
of about 0 2 part o~ Azamethlphos in 100 parts; ~:
(z) A liquid having a vapour pressure, at 25C, o~ 1.51 mm Hg ~L ~ .
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and a dissolving capacity, at 20C, o.f 3.3 par-ts of Iodofenphos in 100 parts;
(z'). A liquid having a vapour pressure~ at 25C, of 44 mm Hg and a dissolving capacity, at 20C, of 2,3 parts of Iodofen-phos in 100 parts.

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Claims (19)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A liquid insecticidal composition consisting of a homogeneous solu-tion comprising: (A) as active ingredient, at least one insecticidal organo-phosphate compound which is chosen from 0,0-dimethyl S-[4-aza-6-chloro-2-oxo-benzoxazol-3-yl]-methyl thiophosphate, 0,0-diethyl 0-(3,5,6-trichloro-pyrid-2-yl) thiophosphate, 0,0-dimethyl 0-(2,5-dichloro-4-iodo-phenyl) thiophosphate, 0,0-dimethyl 0-(2,4,5-trichloro-phenyl) thiophosphate, 0,0-dimethyl S-(6-chloro-2 oxo-benzoxazol-3-yl)-methyl dithiophosphate, 0,0-dimethyl (2,2,2-trichloro-l-hydroxy)-ethyl-phosphonate and 0,0-diethyl-S-(2-oxo-4-aza-benzoxazol-3-yl)-methyl dithio-phosphate, (B) 0.2 to 10 parts by weight, per part by weight of component A, of at least one carbon compound which is liquid at 25°C, is chemi-cally inert towards the insecticidal material A, has a solvent power (or dis-solving capacity) for component A which at 20°C is less or equal to 5 parts by weight of A per 100 parts by weight of B and has a vapour pressure at 25 C
ranging from 0 to 0.1 mm Hg, and (C) at least one carbon compound which is li-quid at 25°C, is chemically inert towards the insecticidal material A, has a solvent power (or dissolving capacity) for component A which at 20°C is at least equal to 5 parts by weight of A per 100 parts by weight of C, has a vapour pressure at 25°C ranging from 5 to 600 mm Hg, component C being present in amount sufflcient to form a homogeneous solution with the amounts of the com-ponents A and B present.

2 A composition according to claim 1, comprising: (A) from 0.01 to 10%, calculated relative to the total weight of the composition, of at least one of the indicated insecticidal organo-phosphorus compounds which is solid at 20°C;
(B) from 0.01 to 10%, calculated relative to the total weight of the composi-tion, of an organic diluent which is liquid at 25°C and (C) from 15 to 99.8%, calculated relative to the total weight of the composition, or an organic sol-vent which is liquid at 25°C and is chemically inert towards the components A
and B.

3. A composition according to claim 1 or 2, in which the liquid B has a vapour pressure at 25°C of 0 to about 0.005 mm Hg.

4. A composition according to claim 1 or 2, in which the liquid B has a dissolving capacity for the insecticidal material A at 20°C, ranging from 0 to about 3 parts by weight of A per 100 parts by weight of B.

5. A composition according to claim 1 or 2, in which the liquid C has a vapour pressure at 25°C ranging from 80 to about 550 mm Hg.

6. A composition according to claim 1 or 2, in which the liquid C has a dissolving capacity for the insecticidal material, at 20°C, greater than 10 parts by weight of A per 100 parts by weight of C.

7. A composition according to claim 1, in which the liquid of low vola-tility, B, is chosen from amongst aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, halogenated aromatic hydrocarbons, esters of aliphatic acids, es-ters of aromatic acids, heterocyclic compounds, alcohols, polyols, ether-al-cohols, amino-alcohols, aliphatic mercaptans, ketones, aliphatic acids, their anhydrides and natural oils.

8. A composition according to claim 7, in which the liquid of low vola-tility, B, is chosen from amongst the following diluents: vaseline oil, para-ffin oil, hexadecane, l-bromo-tetradecane, l-chloro-hexadecane, tetrachlorodi-phenyl, isopropyl myristate, dioctyl adipate, di-(2-ethylhexyl) adipate, dioc-tyl sebacate, dibutyl phthalate, dioctyl phthalate, didecyl phthalate, bis-(tridecyl) phthalate, 5-(3,6,9-trioxa-undecyloxy-2)-1,3-benzodioxole, l-dode-canol, l-tridecanol, glycerol, the dibutyl ether of diethylene glycol, 2-amino-2-ethyl-propane-1,3-diol, tertiary dodecanethiol, oleone, octanoic acid, oleic acid, 2-dodecylsuccinic anhydride, olive oil and linseed oil.

9. A composition according to claim 7, in which the liquid of low vola-tility, B, is chosen from amongst aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, esters of aliphatic acids, esters of aromatic acids, oxygen-con-taining heterocyclic compounds, alcohols, polyols and ketones.

10. A composition according to claim 9, in which the liquid of low vola-tility, B, is chosen from amongst: vaseline oil, paraffin oil, hexadecane, 1-chloro-hexadecane, isopropyl myristate, dioctyl sebacate, dioctyl adipate, di-butyl phthalate, dioctyl phthalate, didecyl phthalate, 5-(3,6,9-trioxa-undecyl-oxy-2)-1,3-benzodioxole, 1-tridecanol, glycerol and oleone.

11. A composition according to claim 1, in which the volatile liquid C
is chosen from amongst aliphatic hydrocarbons, halogenated aliphatic hydrocar-bons, aromatic hydrocarbons, aliphatic esters, heterocyclic compounds, alipha-tic alcohols, aliphatic ethers, aliphatic ketones, nitro-alkanes and nitrilo-alkanes.

12. A composition according to claim 11, in which the volatile liquid C
hs chosen from amongst methylene chloride, trichloromethane, chloroform, ben-zene, methyl acetate, ethyl acetate, isopropyl acetate, propyl acetate, iso-butyl acetate and/or butyl acetate, methyl propionate and/or ethyl propionate, methyl butyrate and/or ethyl butyrate, 2-methoxy-ethyl acetate, tetrahydro-furane, dioxane, ethoxyethane, methanol, ethanol, isopropanol, methoxyethanol, acetone, methyl ethyl ketone, butan-2-one, nitromethane and acetonitrile.

13. A composition according to claim 11, in which the volatile liquid C
is chosen from amongst halogenated aliphatic hydrocarbons, aromatic hydrocarbons, aliphatic esters, oxygen-containing heterocyclic compounds aliphatic alcohols, aliphatic ethers and aliphatic ketones.

14. A composition according to claim 1, and comprising (D) from 0.01 to 10%, relative to the weight of the composition, of a supplementary insecticidal material chosen from amongst the ortho-substituted N-methyl-carbamates of the general formula:

(I) wherein R represents an aIkyl radical containing 1 to 5 carbon atoms, an alk-oxy radical containing 1 to 4 carbon atoms, a propargyloxy radical, a diethoxy-methyl radical, a dimethoxymethyl radical, a 1,3-dioxan-2-yl radical, a 1,3-lioxolan-2-yl radical or one of these two latter radicals carrying one or two methyl groups.

15. A composition according to claim 14, in which R represents the iso-propoxy radical, the 1,3-dioxolan-2-yl radical or the 2,2-dimethyl-1,3-benzodio-xol-4-yl radical.

16. A composition according to claim 1, 2 or 14, and comprising an adju-vant E chosen from amongst: (E') liquids which are poor solvents or non-sol-vents for the active material and having a vapour pressure at 25°C equal to or greater than 0.01 mm Hg; (E") non-volatile solid diluents or carriers; (E"?) liquefied gases which can be used as propellants; (E"") supplementary insecti-cidal active materials different from A and D; and (E"") dyestuffs, perfumes and stabillsers.

17. A composition according to claim 1, whlch furthermore comprises a diluent E' which is liquid at 25°C, is a poor solvent or non-solvent for the active material A, is chemically inert towards the other components of the com-position, is soluble in the mixture of A+B+C, has a vapour pressure at 25° C

ranging from 0.2 to 100 mm Hg and has a dissolving capacity for the active ma-terial ranging from 0.005 to 5 parts by weight of A per 100 parts by weight of E'.

18 A composition according to claim 17, in which the liquid E' is chosen from amongst hexane, isopropanol, octanol, laurone and a mixture of aliphatic hydrocarbons.

19. A process for the preparation of a solid insecticidal composition in which a composition according to claim 1, 2 or 14, is applied to the surface of a pulverulent or non-pulverulent solid carrier, and in which the liquid C
is then allowed to evaporate.