DE2707154A1 - PROCESS FOR POTENTIFICATION OF INSECTICIDAL PHOSPHORIC ACID ESTERS AND NEW INSECTICIDE COMPOSITIONS - Google Patents

Description

PROCESS FOR POTENTIFICATION OF INSECTICIDAL PHOSPHORIC ACID ESTERS AND NEW INSECTICIDE COMPOSITIONS.

The present invention is a method for potentiating solid, to the class of phosphoric acid or Thiophosphoric acid esters belonging to insecticidal substances as well as compositions produced by said process, those in the form of liquid homogeneous solutions, which are characterized in that they are in addition to said insecticidal substance at least one difficult, the former bad dissolving liquid as well as at least one volatile, said substances contain good dissolving liquid, or in the form of

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solid compositions prepared from these solutions are present.

The use of solid phosphoric or thiophosphoric acid esters as insecticidal substances has been known for several years, and various ones containing these active substances Composition types such as powders, baits, and liquids are suggested and / or are commercially available has been brought.

The liquids are very widely used because they are very adaptable in use; you can use in apparatus of all kinds; for example, by means as diverse as spray devices, Brushes and an aerosol container containing compressed or liquefied gas are used; she allow any desired dilution under "absolutely perfect Make distribution of the active ingredient.

Solid phosphoric or thiophosphoric acid esters can be used to produce two well-known liquid forms:

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Suspensions and solutions.

The suspensions lead to problems well known in the art: their stability is always short-lived, so that they can practically only be prepared at the time of application, which requires additional work for the user and for the Manufacturers all of the difficulties that manufacture brings with it always accompanied by wettable powders, such as the need for a very high degree of fineness and for one that is present in the powder A pair of surfactants adapted to the active ingredient and the fillers.

For these reasons, solutions are generally preferred. However, these also have disadvantages: in particular the presence of the liquids used favors penetration of the active ingredient into the porous materials such as for example, walls and ceilings to which the solution is applied; consequently, the effectiveness of the composition decreases on the treated material surface quickly, which is particularly uncomfortable when you are against annoying insects like Wants to protect flies, mosquitoes, cockroaches, ants, wasps, etc.; the application will therefore be repeated many times, and this is quite uneconomical and continues to do because of the accumulation liquid products, the treated surfaces are dissimilar.

It is possible to use only very volatile solvents, so that the active ingredient crystallizes on the treated material surface and can no longer be absorbed by this; on the other hand has the Applicant found that in this case the benefit of the

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Active ingredient is greatly reduced.

Another way to at least partially avoid the above disadvantages is that you can Active ingredient highly concentrated solutions in volatile solvents begins; however, this brings a real danger because of the non-negligible toxicity of the relevant insecticidal substances.

In relation to all these disadvantages, the present invention provides a remedy, which is based on observations by the applicants in that a solid phosphoric or thiophosphoric acid ester has a very high efficiency and even this When the solution is applied to absorbent material, it lasts for a long time if the said ester is in a poorly dissolving one Liquid due to evaporation of a volatile auxiliary solvent, which formed a homogeneous solution with the former before evaporation, precipitates. Accordingly the invention proposes a liquid insecticide composition which is a homogeneous liquid solution containing:

A) an amount of at least one ^{insecticidal substance which is solid at 20 °} C. and which is solid at 20 ° C. is sufficient to achieve the insecticidal effect and does not exceed that amount which can be completely dissolved in the rest of the composition;

B) at least has a liquid at 25 ° C, schwerfltichtige carbon compound which is a poor solvent for the insecticide substance A, at 25 ⁰ C a vapor pressure of not more than 0.01 Torr and the used proportion between

70983 "5? (Π92

0.2 and 10 parts by weight per part of insecticidal material; and

At 25 ⁰ C comprises C) at least one liquid at 25 ⁰ C, volatile carbon compound which is a good solvent for the active substance and the fluid B have a vapor pressure of at least 5 Torr and is present in sufficient quantity with the quantities present of the components A and B form a complete and homogeneous solution.

The insecticide composition according to the invention can also included:

D) optionally a complementary insecticidal substance selected among ortho-substituted phenyl-N-methylcarbamates; and

E) optionally a soluble auxiliary substance which is inert towards A + B + C, selected from

E ^f / liquids that dissolve the active ingredient poorly or not at all and ^{have a vapor pressure at 25 °} C. which is the same

Is 0.01 Torr or higher;

E "/ non-volatile solid extenders;

E ¹¹¹ / liquefied oases that can be used as propellants; E "" / from A and D different complementary Ineektieidffekt-

fabrics; and

Emu / dyes, perfumes and stabilizers.

The solid insecticidal substances A can be selected, for example, from the following:

0, O-dimethyl-0- (1,2-dibromo-2,2-dichloräthyl) phosphate (or NALED), Melting point: 25 ⁰ C; OjO.OO-tetramethyl-OjO-

(4,4 * -phenyl-thiophenyl) -bis-thiophosphate, melting point: 30 ⁰ C; 0,0-Diinethyl-0- (2,4,5-trichlorophenyl) -thiophosphate (or TRICHLORMETAFOS), melting point: 41 ° C; 0,0-diethyl-O- (3,5,6-trichloropyrid-2-yl) -thiophosphate (or CHLOROPYRIFOS), melting point: 43 ° C; 0, O-dimethyl-S- (2-methoxy-äthylcarbamoylmethyl) dithiophosphate (or AMIDITHION), melting point: 46 ⁰ C; 0, O-dimethyl-0- (3,5,6-trichloropyrid-2-yl) thiophosphate (or METHYL-CHLOROPYRIFOS), melting point: 47 ° C; 0, O-dimethyl-S- (6-chloro-2-oxo-benzoxazol-3-yl) -methyl-dithiophosphate (or PHOSALON), melting point: 48 ° C; 0,0-dimethyl-S-2- (2-methylcarbamoylethyl) thioethyl thiophosphate (or VAMIDOTHION), melting point: 48 ° C; 0,0-dimethyl-S- (methylcarbamoylmethyl) -dithiophosphate (or DIMETHOAT), melting point: 52 ° C; 0, O-dimethyl-0- (2-chloro-4-nitrophenyl) thiophosphate (or DICAPTHON), melting point: 52 ° C; 0, O-dimethyl-0- (1-methylcarbamoyl-prop-1-en-2-yl) phosphate (or MONOCROTOPHOS), melting point: 54 ° C; 0, O-dimethyl-0- (4-bromo-2,5-dichloro-phenyl) -thiophoßphat (or bromophos), melting point: 54 ⁰ C; 0-methyl-0- (2-chloro-4-tertiary-butyl-phenyl) -N-methyl-phosphoramidate (or crufomate), Melting point: 6O ⁰ C; 0, O-dimethyl-S- (morpholinocarbonylmethyl) -di thiophosphate (or MORPHOTHION), melting point: 64 ⁰ C; 0,0-dimethyl-S- (äthylcarbamoylmethyl) dithiophosphate (or METHYLÄTHOAT), melting point: 68 ⁰ C; 0,0-dimethyl-S-phthalimidomethyl dithiophosphate (or PHTALOPHOS), melting point: 72 ⁰ C; 0,0-dimethyl- (4-oxo-l, 2,3-benzotriazine-3-yl) methyl dithiophosphate (or azinphos-METHYL), melting point: 74 ⁰ C; 0.0-

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Dimethyl-O- (2,5-dichloro-4-iodophenyl) -thiophosphate (or JODOFENPHOS), melting point: 76 ⁰ C; 0,0-dimethyl- (2,2,2-trichloro-1-hydroxy-ethyl) -phosphonate (or TRICHLORPHONE), melting point: 48 ° C; 0,0-Dimethyl-S- (6-chlor-2-oxo-4-azabenzoxazol-3-yl) -methyl-thiophosphate (or AZAMETHIPHOS), melting point: 89 ⁰ C; 0,0-diethyl-0- (3,4-butano-coumarin-7-yl) thiophosphate (or CUMITHOAT), melting point: 89 ° C; 0,0-dimethyl-0- (3,5,6-trichloro-pyrid-2-yl) phosphate (or FOSPIRAT), melting point: 92 ⁰ C; 0,0-dimethyl-S- (5-methoxy-4-oxo-pyran-2-yl) -thiophophate (or ENDOTHION), melting point: 95 ° C; 0, O-diethyl-0- (3-chloro-4-methyl-coumarin-7-yl) thiophosphate (or CUMAPHOS), melting point: 95 ⁰ C; 0,0-dimethyl-0- [2-chloro-1- (2,4,5-trichlorophenyl) -vinyl] phosphate (tetrachlorvinphos respectively), melting point: 97 ⁰ C; O, O-diethyl-S- (2-oxo-4-aza-benzoxazol-3-yl) methyl dithiophosphate, melting point: 99 ⁰ C; and 0,0-dimethyl-S- (4,6-diamino-l, 3,5-triazin-2-yl) methyl dithiophosphate (or menazon), Melting point: 162 ⁰ C.

According to the invention, those compositions are preferred in which the insecticidal phosphoric acid ester is below at least one of the following connections is selected:

(1) 0,0-Dimethyl-S- (4-aza-6-chloro-2-oxo-benzoxazol-3-yl) -methyl-thiophosphate (or AZAMETHIPHOS);

(2) 0,0-diflthyl-0- (3,5,6-trichloro-pyrid-2-yl) -thiophosphate (or CHLORPYRIPHOS);

(3) 0,0-dimethyl-0- (2,5-dichloro-4-iodophenyl) thiophosphate (or IODOFENPHOS);

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(4) 0,0-Dimethyl-0- (2,4,5-trichlorophenyl) -thiophosphate (resp. TRICHLORINE METAPHOS);

(5) 0,0-Dimethyl-S- (6-chloro-2-oxo-benzoxazol-3-yl) -methyldithiophosphate (or PHOSALON); and

(6) 0, O-dimethyl-2,2,2-trichloro-1-hydroxyethyl-phosphonate

(or TRICHLORPHONE).

The amount of insecticidal substance A is preferably not more than 1096 of the total weight of the liquid composition and represents at least 0.2% of the total weight of the ingredients A + B + C.

The non-volatile liquid B is in an insecticidal substance A between 0.2 and 10 parts by weight per part lying proportion used; in fact, it was observed that it was caused by the non-volatile liquid Effect below 0.2 parts becomes too weak to serve the purpose; the effect persists above 10 parts although still, but the composition remains too liquid after use, and the disadvantages mentioned above, the the compositions remaining in the homogeneous liquid state after use then occur again. The proportion of non-volatile liquid is preferably between 1 and 5 parts by weight per part of insecticidal substance A.

The hardly volatile liquid B preferably has a vapor pressure of less than 0.005 Torr at 25 ⁰ C. Its solubility for insecticide substance A at 20 ° C amounts to at most 5 parts of A to 100 parts by weight of B; this proportion is preferably at most 3 parts A. The

Liquid B is therefore a diluent for the active ingredient A. It is compared to this active ingredient A, the liquid C and further constituents which may be present in the composition according to the invention chemically inert.

It can be seen that the total amount of insecticidal substance A present in the composition and after evaporation the liquid C is dissolved in the liquid B can exceed 50% by weight A n: \ cht, and in the case of the preferred Limit values, this amount is a maximum of 15 wt. -96 A. This special feature is an important characteristic of the invention.

The schwerfltichtige liquid B can be handy nichtfltichtig and at 25 ⁰ C have a vapor pressure of less than 10 "Torr.

The non-volatile liquid B is preferably selected from aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, halogenated aromatic hydrocarbons, esters of aliphatic acids, esters of aromatic acids, heterocyclic compounds, preferably heterocyclic oxygen compounds, higher alcohols, polyols, ether alcohols and amino alcohols, aliphatic mercaptans and natural, higher ketones Oil.

Among these, preference is generally given to aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, Esters of aliphatic acids, esters of aromatic acids

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Acids, heterocyclic oxygen compounds, alcohols, polyols and ketones.

In particular, you can, for example, the low volatility liquid B under one or more of the following Select solvent, provided that the resulting liquid has the ability to dissolve the insecticide substance A at 20 C is within the limits given above: a petroleum jelly, a paraffin oil, hexadecane, 1-bromo-tetradecane, 1-chloro-hexadecane, tetrachlorodiphenyl, Isopropyl myristate, dioctyl adipate, dibutyl phthalate, Dioctyl phthalate, didecyl phthalate, bis (tridecyl) phthalate, 5- (3,6,9-Trioxa-undecyloxy-2) -1, 3-benzodioxole, 1-dodecanol, 1-tridecanol, glycerine, diethylene glycol dibutyl ether (dibutyl carbitol), 2-Amino-2-ethyl-1,3-propanediol, tertiary dodecanethiol and oleon (9,26-pentatriakontadien-18-one), octanoic acid, oleic acid, 2-dodecylsuccinic anhydride, olive oil and Linseed oil.

The low-volatility liquid B is preferably selected from the following solvents: Vaseline oil, Paraffin oil, hexadecane, 1-chloro-hexadecane, isopropyl myristate, Dioctyl adipate, dioctyl sebazinate, dibutyl phthalate, dioctyl phthalate, didecyl phthalate, bis (tridecyl) phthalate, 5- (3,6,9-trioxa-undecyloxy-2) -l, 3-benzodioxole, 1-tridecanol, glycerine and oleon.

All of these diluents B have ^{a vapor pressure below 0.01 Torr at 25 °} C., and their ability to dissolve the active ingredients is in the range from 0 to ^{20 ° C.}

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• A

5 parts by weight of A to 100 parts by weight of B.

The volatile liquid C preferably has a vapor pressure above 80 Torr ^{at 25 ° C .;} it is preferably miscible with liquid B in all proportions; their dissolving capacity for the insecticidal substance A is at ^{least five parts by weight of A per 100 parts of C and preferably more than ten parts per 100 at 20 °} C. The amount of liquid C required in the composition depends on its dissolving capacity for the insecticidal substance A and the liquid B and the Amount of each of these components, and the amount of liquid C to be used must always be sufficient to achieve a complete and homogeneous solution. The liquid C thus represents a solvent for the active substance A. It is chemically inert towards this active substance, the liquid B and the other constituents which may be present in the composition according to the invention.

The volatile liquid C is preferably selected from aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, aromatic hydrocarbons, aliphatic esters, heterocyclic compounds, preferably heterocyclic oxygen compounds, among aliphatic alcohols, ethers and ketones.

In particular, the volatile liquid C can, for example, be one of the following solvents or a mixture of two or more of these solvents, provided that the dissolving power of these

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Liquid for insecticide A at 20 ° C is within the limit values given above: dichlorine than, tricloromethane, Chloroform, benzene, methyl, ethyl, isopropyl, propyl, isobutyl and / or butyl acetate, methyl and / or Ethyl propionate, methyl and / or ethyl butyrate, 2-methoxyethyl acetate, Tetrahydrofuran, dioxane, ethoxyethane, methanol, ethanol, isopropanol, methoxyethanol, acetone, methyl ethyl ketone and butan-2-one.

It is generally preferred to classify the volatile liquid C among halogenated aliphatic hydrocarbons, aromatic hydrocarbons, aliphatic esters, heterocyclic oxygen compounds, aliphatic Alcohols, aliphatic ethers and aliphatic ketones.

Preferred liquids C are those

whose vapor pressures at 25 ° C are between approximately 80 and approximately 500 Torr and their dissolving power for the invention proposed active ingredients between 10 parts by weight of A to 100 parts by weight of C and infinite * miscibility vary.

Liquids B and C are preferably infinitely miscible.

The complementary insecticide D can be used, for example, from the following ortho-substituted phenyl-N-methylcarbamates select: ortho-cresyl-N-methylcarbamate, 2-ethyl-phenyl-N-methylcarbamate, 2-isopropylphenyl-N-methyl-carbamate, 2-tert-butyl-phenyl-N-methyl-

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carbamate, 2-sec-butyl-phenyl-N-methylcarbamate, 2-tertiary-amyl-phenyl-N-methylcarbamate, 2-methoxyphenyl-N-methylcarbamate, 2-ethoxyphenyl-N-methylcarbamate, 2-isopropoxyphenyl-N-ynethylcarbamate (or ARPROCARB), 2-isobutoxyphenyl-N-methylcarbamate, 2-tert-butoxy-phenyl-N-methylcarbamate, 2-sec-butoxyphenyl-N-methylcarbamate, 2-propargyloxyphenyl-N-methylcarbamate, 2-dimethoxymethyl-phenyl-N-methylcarbamate, 2-diethoxymethyl-phenyl-N-methylcarbamate, 2- (1,3-dioxolan-2-yl) -phenyl-N-methylcarbamate (or DIOXACARB), 2- (4-methyl-1,3-dioxolan-2-yl) -phenyl-N-methylcarbamate, 2- (4,5-dimethyl-1,3-dioxolan-2-yl) -phenyl-N-methylcarbamate, 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-methylcarbamate (or BENDIOCARB).

The liquids Ε · are selected from those with a vapor pressure between 0.01 and 10 Torr at 25 ° C. The ability to dissolve insecticidal substance A at 20 ^° C. is at most 5 parts by weight of A per 100 parts by weight of E ¹ . These liquids E ¹ are thus more volatile diluents than diluents B; they make it possible to reduce the required proportion of liquid B and, since they evaporate considerably faster than the latter, they give the composition a drier appearance after the application and evaporation of the liquid C.

The liquids E ¹ are preferably selected from liquids with a vapor pressure exceeding 10 Torr and even 40 Torr at 25.degree. C. and having a dissolving power

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for the insecticide substance A, which at 20 ^° C. is equal to or preferably lower than 5 parts by weight of A per 100 parts by weight of E ¹ . They thus enable the liquid C to be diluted if the latter has a very high dissolving power.

For example, the liquids E ^{1 are selected} from aliphatic hydrocarbons, aromatic hydrocarbons, halogenated aliphatic hydrocarbons, alkoxyalkanes, saturated aliphatic alcohols with more than two carbon atoms and higher ketones.

Examples of liquids E ¹ with a ^{vapor pressure below 10 Torr at 25 °} C. are mixtures of saturated aliphatic hydrocarbons, aliphatic alcohols with at least five carbon atoms such as amyl alcohol or 1-octanol and higher ketones such as lauron (tricosan-12-one) and / or stearon (Pentatriakontan-18-one).

Examples of liquids E 'with a ^{vapor pressure exceeding 10 Torr at 25 °} C. are mixtures of saturated aliphatic hydrocarbons, pentane, hexane, heptane, butyl chloride, 1,1,1-trichloroethane, trichlorethylene, benzene and isopropanol.

. · .— Among these, preference is given to hexane, isopropanol, Octanol, mixtures of saturated hydrocarbons such as "Isopar L" and Lauron.

The compositions according to the invention can also contain non-volatile solid extenders E ″, the are selected from natural or synthetic waxes, natural or synthetic resins and solid hydrocarbons.

709835 ^ 0792

chooses; they are preferably used in a small proportion which does not exceed 10% by weight of the composition. The waxes are, for example, under beeswax, candelilla wax, Carnauba wax, Japan wax, montan wax, synthetic Waxes selected from chlorinated naphthalene, glycol stearates and solid fatty ketones.

The resins are selected, for example, from rosin, rubber lacquer and synthetic organic resins such as homopolymers and copolymers from vinyl derivatives (acetate, propionate, butyrate, ether or formal), alkenes (ethylene, Propylene, butylene, etc.) and / or styrene and / or vinyl pyrrolidones and / or cellulose derivatives (methyl, ethyl or benzyl ether, acetate, propionate, butyrate, phthalate, Nitrate etc.) and / or isoprene and / or butadiene and / or acrylic or methacrylic esters and / or allyl esters, (phthalate, Isophthalate, maleate, cyanurate, etc.); Such synthetic organic resins can also be obtained from the reaction between compounds with reactive functional groups, such as by condensation of an epoxide with a polyphenol so-called "epoxy" resins formed by the action of a polyacid on a polyol "polyester" "resins, polyurethanes formed by condensation of a polyisocyanate with a polyol, and resins from Coumarone / indigenous type.

Solid hydrocarbons are chosen, for example, from microcrystalline and macrocrystalline alkanes with at least 24 carbon atoms and theirs under the name microwax

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known mixtures, tank bottom wax, ozokerite, ceresin, Paraffin and isoparaffin.

The liquefied gases E " ^{1 which} can be used as propellants are selected, for example, from butane, isobutane, propane, methoxymethane, trichlorofluoromethane, dichlorofluoromethane, 1,2-dichloro-l, 1,2,2-tetrafluoroethane, carbon tetrafluoride and octafluorocyclobutane.

- The complementary insecticidal active ingredients E "" are preferably those which do not dissolve the insecticidal substance A at all or only poorly. They are selected, for example, from liquid organophosphorus compounds, natural pyrethrins, Rotenone, synthetic pyrethrinoids, NN ¹ -dibutyl-para-chlorobenzene-sulfonamide, 1,4,4a, 5,6,7,8,8-octahydro-3a, 4,7 , 7a-tetrahydro-4,7-methano-indane, hexachlorocyclohexane, 1,2,3,4,10, 10-endo-exohexachlor-6,7-epoxy-l, 4,4a, 5,6, -7, 8,8a-octahydro-1,45,8-dimethano-naphthalene and carbamic acid esters different from D such as 1-dimethylcarbamyl-5-methyl-pyrazol-3-yl-dimethylcarbamate, 3-methyl-1-phenyl-pyrazole-5- yl dimethyl carbamate and 4-methyl-2-propylpyrimid-6-yl dimethyl carbamate.

In general, one should avoid introducing liquids into the composition, which at the same time are very low volatility and are good solvents for the insecticidal substance A. Also, one should preferably the presence of water in large quantities s, corresponds to a normal level in technical commercial products to avoid.

The compounds according to the invention are for use

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on any surface where insects need to be killed often found, determined; they can also be used to manufacture solid products that superactivate active ingredient A Form included; these solid products are made from carriers such as cellulose cardboard, asbestos, Waste paper, full and / or cotton felts, inorganic or organic granulates or powders such as talc, kaolin, dried Clay, fossil silicas, synthetic silicas, natural non-fossil silicas, Vermiculite, magnesium silicate, aluminum silicate, calcium phosphate, calcium carbonate, wood flour, soy flour and nut shell flour here. The invention thus also relates to a process for the production of a solid insecticidal compound, which contains the elements A and B already defined and optionally D and E on a solid support, de.n under Cardboard, felts and inorganic or organic granules and powders, where the process is characterized is that said carrier with an inventive Impregnated composition that contains the elements A, B and C and optionally D and that one then lets the liquid C evaporate. The importance of the compositions of the present invention is illustrated below reported experiments.

TRIAL A

The following nine compositions A-O to A-8 are prepared in aerosol containers (values expressed as weight #) :

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A. Composition ■ A-O A-I A-2 A-3 A-4 A-5 A-6 A-7 A-8 Azamethiphos (a) 2 2 2 2 2 2 2 2 2 Didecyl phthalate (a «) - 4th - - - - - - - Isopropyl myristate (a ") - - 4th - - - - - - 1-chlorohexadecane (a ^nt ) - - ■ - 4th - - - - - T.U.O.B. (a "") - - - - 4th - - - - -J
O B. Petroleum jelly (b) - - - - - · 4th - - - CD Tridecanol (b ¹ ) - - - - - - 4th - - Oleon (b ") - - - - - - - 4th - Dibutyl phthalate (b ^nt ) - - - - - - - - 4th Tetrahydrofuran (c) 2 2 2 2 2 2 2 2 2 κ » C. Dichloromethane (c ¹ ) 26th 26th 26th 26th 26th 26th 26th 26th 26th Trichlorofluoromethane 35 33 33 33 33 33 33 33 33 E ^nl Dichlorodifluoromethane 35 33 33 33 33 33 33 33 33

(a) O, O-dimethyl-S- (6-chloro-2-oxo-4-aza-benzoxazol-3-yl) methyl thiophosphate or OjO
b) -2 (3H) -pyridin-3-one] methyl thiophosphate.

(a ¹ ) Liquid with a vapor pressure of less than 0.0001 Torr at 25 ^° C. and a resolving power of 1.6 parts

Azamethiphos in 100 parts at 20 ⁰ C.

(a ") Liquid with a vapor pressure of about 0.001 Torr 25 ° C and a dissolving power of 0.7 parts of azamethiphos

in 100 parts at 20 ⁰ C.

(a ^IM ) Liquid with a vapor pressure of less than 0.0001 torr at 25 ° C and a resolving power of 4.3 parts

Azamethiphos in 100 parts at 20 ⁰ C.

(a ¹¹¹¹ ) Abbreviation for 5- (3,6,9-trioxa-undecyloxy-2) -1, 3-benzodioxole; Liquid with a vapor pressure of less than 0.005 Torr at 25 ^° C. and a dissolving power of 4.6

Share Azamethiphos in 100 parts at 20 ⁰ C.

(b) semi refined oil having a density of 0.870 at 15 ⁰ C, a viscosity of 17 ° Engler at 50 ⁰ C, a vapor pressure of less than 0.001 Torr at 25 ⁰ C and virtually no resolution capability for Azamethiphos at 20 ⁰ C.

(b ¹ ) Liquid with a vapor pressure of about 0.005 Torr at 25 ^° C. and a dissolving power of 0.5 part of azamethiphos

in 100 parts at 20 ⁰ C.

(b ") liquid with a vapor pressure less than 0.000001 Torr at 25 ° C and a resolving power of about

2.2 parts of azamethiphos in 100 parts at 20 ^° C.

(b ¹ ") liquid with a vapor pressure of about 0.0001 torr

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at 25 ⁰ C and a resolution of 4.5 parts aza-

methiphos in 100 parts at 20 ⁰ C.

(c) Liquid with a vapor pressure of 176 torr at 25 ° C and a dissolving power of 94 parts of azamethiphos

in 100 parts at 20 ⁰ C.

(c ¹ ) Liquid with a vapor pressure of 420 Torr at 25 ⁰ C and a dissolving power of 144 parts Azamethiphos in

100 parts at 20 ⁰ C.

The contents of each of these containers are distributed by spraying on one side of 20 × 10 cm glass plates in an amount of 800 mg per plate; 5 plates per composition are produced in this way: two days after this production, tests are carried out on insecticidal activity on insects of the species Blatta germanica, which are placed on the treated side of the plates for one minute and then kept under observation in ventilated bulbous glasses; then the cumulative proportion of dead insects or insects in the state of dorsal decubitus is noted every 15 minutes (KD %) ; 10 insects are placed on each plate, ie 50 (ί 5) insects in total per composition.

The table below gives the results recorded.

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Time in minutes A-O A-I A-2 A-3 A-4 A-5 A-6 A-7 A-8 15th 0 65 86 58 70 11 0 6th 50 30th 0 96 96 90 94 43 8th 40 91 45 17th 98 98 96 100 62 26th 62 100 60 36 100 98 96 - 66 40 77 - 75 42 - 98 96 - 68 44 84 - 90 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 74 91 - 180 55 - - 98 - 78 74 93 -

TRIAL B

The procedure is as in Experiment A using the compositions A-O, A-I, A-2, A-4, A-7 and A-8 * as well as under Use of insects of the species Periplaneta amerlcana.

The following table shows the recorded results (KD %).

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· * ■

Time in minutes A-O A-I A-2 A-4 A-7 A-8 15th 0 0 0 2 2 2 30th 0 4th 4th 6th 2 10 45 0 25th 18th 34 8th 55 60 4th 61 24 72 30th 79 75 8th 73 33 86 46 96 90 16 73 39 96 54 98 105 20th 77 45 96 66 100 120 26th 79 51 97 72 - 135 36 85 53 98 82 - '180 46 89 63 100 88 -

TRIAL C

The following two compositions C-O and C-I are prepared in aerosol cans (values expressed as weight #):

composition C-O C-I A. Azamethiphos 1 1 B. Didecyl phthalate (a ¹ ) - 2 C. Dichloromethane (c ¹ ) 19th 17th E "» Trichiorfluoromethane
Dichlorodifluoromethane 40
40 40
40

These compositions are tested each on a hundred 5 to 7 day old insects of the species Musca domestica, which are flying around freely in a 28- nr room. A weight of 4 grams of the composition is evaporated per test

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in the atmosphere of the room and notes the number of fallen insects every three minutes. Pro composition the procedure is repeated five times, i.e. a total of 500 i 50 insects per composition are tested.

The cumulative proportions of fallen insects (KD %) are given in the following table:

Time in minutes C-O C-I 12th 11 25th 15th 15th 41 18th 20th 54 21 26th 62 24 32 69 27 37 73 30th 42 76

TRIAL D

The procedure is as in experiment C, but using the following compositions D-O and D-I (values as Weight-96 expressed):

composition DO 19th D-I A. Azamethiphos 0.5 0.5 0.5 B. Didecyl phthalate (a ¹ ) - 40
40 2 C. Dichloromethane (c ¹ ) 17th D. Dioxacarb 0.5 E "» Tri chi or fluorine than
Dichlorodifluoromethane 40
40

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ΊΟ-

The cumulative proportions of fallen insects (KD 56) are given in the following table:

Time in minutes DO D-I 12th 11 16 15th 17th 30th 18th 2A 42 21 31 52 24 39 59 27 47 64 30th 55 67

TRY

The procedure is as in experiment A using the following compositions E-O and E-I with which experiments are carried out on insects of the species Blatta germanica (values expressed as weight-96):

composition E-O EGG A. Azamethiphos 1 1 B. Dioctyl phthalate (d) - 4th C. Dichloromethane (c ¹ )
Tetrahydrofuran (c) 26th
2 26th
2 D. Dioxacarb 1 1 E "t Trichlorofluoromethane
Dichlorodifluoromethane 35
35 33
33

(d) liquid having a vapor pressure of less than 0.0001 Torr at 25 ⁰ C and a resolution capability of 2.4 parts Azamethiphos in 100 parts at 20 ° C.

709835/0792

- 24 -

The following table shows the recorded results (KD %):

Time in minutes E-O EGG 15th 2 66 30th 5 95 45 7th 98 60 30th 98 75 40 98 90 45 100 105 45 - 120 45 -

TRY F

The procedure is as in experiment A using the following compositions FO and FI, with which experiments are carried out on insects of the species Blatta germanica (values expressed as dev.-% ):

composition F-O F-I A. Azamethiphos 1 1 B. Dioctyl phthalate. (d) - 4th C. Dichloromethane (c ¹ )
Tetrahydrofuran (c) 26th
2 26th
2 D. Arprocarb 1 1 E " ¹ Trichlorofluoromethane
Dichlorodifluoromethane 35
35 VM VM
VM VM

The following table shows the recorded results (KD %):

709835/07 9 2 - 25 -

Time in minutes F-O F-I 15th 2 88 30th 16 95 45 19th 100 60 52 - 75 59 - 90 64 - 105 66 - 120 69 -

TRIAL G

The procedure is as in experiment A using the following compositions G-O and G-I with which one experiments works on insects of the species Blatta germanica (values expressed as weight tf):

composition G-O G-I A. Azamethiphos 1 1 B. Dioctyl phthalate (d) - 4th C. Dichloromethane (c ¹ )
Tetrahydrofuran (c) 26th
2 26th
2 D. Bendiocarb 1 1 E " Trichlorofluoromethane
Dichlorodifluoromethane 35
35 33
33

. The following table shows the recorded results (KD.? 6):

709835/0792

- 26 -

Time in minutes G-O G-I 15th 0 54 30th 10 88 45 12th 100 60 24 - 75 29 - 90 42 - 105 49 - 120 51 -

TRY H

Make a reading H-I of the following composition her (values expressed as% by weight):

Azamethiphos: 8

Dioctyl phthalate (d): 16 acetone (c ^{! T} ): 76

(c ⁿ⁾ liquid having a vapor pressure of 225 Torr at 25 ° C and a resolution capability of 44 parts in 100 parts of azamethiphos at 20 ⁰ C.

This solution is poured into a malaxator containing talc powder of very high fineness (less than 0.596 retained on a 50 micron sieve); After the malaxation, in order to obtain a good distribution of the solution on the powder, the acetone is allowed to ^{evaporate in a warm (50 °} C.) air stream. The proportions of talc and solution are chosen so that a finished powder HI is obtained with the following composition (values expressed as% by weight):

Azamethiphos: 2.5

Dioctyl phthalate: 5.0

709835/0792
- 27 -

IH-

270715A

Talk: 92.5

Additionally, a conventional formulation H'-O is prepared by intimately mixing the ingredients as follows (Values expressed as 96% by weight):

Azamethiphos: 2.5 Talc 97.5

This mixture is passed through a pin mill to obtain a powder of which less than 0.05% with a 50 micron screen.

Tests for the effectiveness of insecticides are carried out on insects of the species Aphis fabae, which are placed in Petri dishes, in an amount of twenty insects (i 10%) per dish. Eight dishes are used, four of which have been treated with the powder H * -0 at a dose of 0.5 milligrams per square centimeter and the other four with the powder H ^f -1 at the same dose. The percentage of apparently dead insects is recorded every three minutes.

The following table shows the cumulative percentages noted in each case:

Time in minutes H'-O H '- 1 18th 4th 10 21 4th 14th 24 6th 20th 27 13th 30th 30th 23 51

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- 28 -

TRIAL I.

The following two liquid compositions 1-0 and 1-1 are prepared (values expressed as % by weight ):

composition I - O I - 1 A. Chlorpyrifos 7th 7th B. Glycerine (d ¹ ) - 7th C. Acetone (s)
Methanol (e ») 46.5
46.5 43
43

(d ¹ ) Liquid with a vapor pressure of less than 0.0001 Torr at 25 ^° C. and a dissolving power of 0.3 parts

Chlorpyrifos in 100 parts at 20 ⁰ C.

(e) Liquid with a vapor pressure of 225 torr at 25 ^° C. and a dissolving power of 650 parts of chlorpyrifos

in 100 parts at 20 ⁰ C.

(e ¹⁾ liquid having a vapor pressure of 127 Torr at 25 ⁰ C and a AuflOsungefähigkeit of 43 parts of chlorpyrifos in

100 parts at 20 ^° C. ^r

These solutions are deposited on one side of 10 × 20 cm glass plates in an amount of 0.8 milliliters per plate. After the solvent mixture has evaporated, the plates are brought into contact with insects of the species Blattella germanica under the conditions described in Experiment A.

The results (KD %) are summarized in the following table:

709835/0792 - 29 -

Time in minutes I - 0 I - 1 45 6th 9 60 18th 33 75 42 59 90 60 85 105 70 92 120 75 95

TRY J

The following two liquid compositions J-O and J-I are prepared (values expressed as% by weight):

composition J-O J-I A. Iodofenphos 2 2 B. Hexadecane (s ¹ ) - 4th C. Acetone (v)
Benzene (x) 49
49 47
47

(s ¹ ) Liquid with a vapor pressure of about 0.003 Torr at 25 ^° C. and a dissolving power of 2.8 parts

Jodofenphos in 100 parts at 20 ° C;

(v) Liquid with a vapor pressure of 225 torr at 25 ⁰ C and a dissolving power of 48 parts iodofenphos in

100 parts at 20 ⁰ C;

(x) liquid with a vapor pressure of 95 Torr at 25 ⁰ C and a dissolving power of 61 parts iodofenphos in

100 parts at 20 ⁰ C.

These solutions are each on the bottom of a Petri dish 16 centimeters in diameter deposited in an amount of 2 milliliters per dish. After evaporation

709835 / ^ 792

insects of the species Attagenus piceus are deposited in the solvent mixture in an amount of 10 insects per disc;
5 repetitions are made for a total of 50 insects per composition. The number of killed or dorsal decubitus insects is recorded every fifteen minutes (KD %). .

The table below gives the mean values (KD %) of the results recorded.

Time in minutes J-O J-I 90 2 6th 105 2 12th 120 2 14th 135 2 20th 150 2 22nd 165 2 25th 180 2 2§ 195 2 34 210 2 40 225 2 58 240 4th 70 255 18th 90 270 20th 98 285 20th 98 300 22nd 100

TRY K

It provides the following two liquid compositions KO and KI ago (values as percent - expressed.%):

709835/0792 - 31 -

composition K-O K-I A. Trichlorometafos 4th 4th B. Hexadecane (s') - 4th C. Dichloromethane (noun) 96 92

(f) Liquid with a vapor pressure of 420 Torr at 25 ^° C. and a dissolving power of 670 parts of Trichlormetafos in 100 parts at 20 ^° C.

These solutions are deposited in a quantity of 2.4 milliliters per plate on each side of 20 × 20 cm glass plates which, spread over their surface, carry one gram of powdered sugar. After the dichloromethane has evaporated, these plates are each placed in cages with a volume of one cubic meter each containing one hundred insects of the Musca domestica species. The percentage of insects killed or in the state of dorsal decubitus is recorded every 3 minutes (KD %) .

The results are summarized in the table below .

Time in minutes K-O K-I 18th 0 3 21 0 6th 24 0 9 27 0 12th 30th 0 21 36 6th 36 42 12th 48 48 13th 54 54 15th 61 60 16 67

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- 32 -

TRY L

270715A

The following two liquid compositions L-O and L-I are prepared (values expressed as # weight):

composition L-O L-I A. Phosalone 0.5 0.5 B. Paraffin oil (g) - 2.5 C. Dichloromethane (w) 99.5 97

(g) at -27 ⁰ C solidifying liquid having a density of 0.851 at 15 ⁰ C, a vapor pressure of less than 0.001 Torr at 25 ⁰ C and a resolution capability of 2.4 parts in 100 parts of phosalone at 20 ° C;

(w) liquid having a vapor pressure of 420 Torr at 25 ° C and a Auflösungsfflhigkeit of 30.4 parts phosalone in 100 parts at 20 ⁰ C.

These solutions are sprayed onto young bean plants infested by insects of the Aphis fabae species Quantity of 2 milliliters per plant. Use 6 plants for each of the solutions and record after two Hours shows the percentage of dead or apparently dead insects for each plant.

The results are summarized in the table below.

709835/0792 - 33 -

L-O L-I 22nd 79 22nd 65 42 76 31 71 26th 58 35 59

Mean values:

29.7
TRY M

The following two liquid compositions M-O and M-I are prepared (values expressed as 96% by weight):

Composition M-O M-I A. Trichlorophone 1 1 B. Dioctyl adipate (r ¹ ) - 3 C. Chloroform (u)
benzene 66
33 64
32

(u) liquid having a vapor pressure of 194 Torr at 25 ⁰ C and a Auflösungsfflhigkeit of 750 parts trichlorphon in 100 parts at 20 ° C;

(r ¹ ) Liquid with a vapor pressure of about 0.006 Torr at 25 ^° C. and a dissolving power of 2.1 parts of trichlorophone in 100 parts at 20 ^° C.

You separate these solutions on the floor one at a time Remove the Petri dish and introduce insects of the species Attagenus piceus as in experiment J.

The following table shows the mean values (KD %) of the recorded results.

709835/0792

-34-

Time in minutes M-O M-I 90 6th 16 120 6th 28 150 6th 38 180 6th 45 210 6th 64 2AO 10 72 270 12th 96 300 12th 100

The foregoing experiments demonstrate the importance of the compositions of the invention; In all cases, the effectiveness of the insecticidal substance is clearly improved if the solution containing it is, according to the invention, a heavy, said substance poorly dissolving liquid and a volatile, the latter good dissolving liquid
includes.

TRY N

The following five aerosol compositions NO to N-4 are prepared (values expressed as 96% by weight):

709835/0792

- 35 -

composition N-O N-I N-2 N-3 N-4 A. D.B.D.P. (H) 0.5 0.5 0.5 0.5 0.5 B. Dibutyl phthalate (i)
Isopropyl myristate (i ¹ )
Petroleum jelly (i ")
TUOB (i " ¹ ) 0.5 0.5 0.5 0.5 C. 1,1,1-trichloroethane (j) 27.8 27.8 27.8 27.8 27.8 E '
E «! Isopar "L" (J ·)
Trichlorofluoromethane
Dichlorodifluoromethane 21.7
20th
30th 21.2
20th
30th 21.2
20th
30th 21.2
20th
30th 21.2
20th
30th

(h) Abbreviation for 0,0-diethyl-S- (2-oxo-4-aza-benzoxazol-3-yl) -methyl-dithiophosphate;

(i) Liquid with a vapor pressure of about 0.001 torr 25 ° C and a dissolving power of 3.6 parts D.B.D.P. in 100 parts at 20 ° C;

(i ¹⁾ liquid having a vapor pressure of about 0.001 Torr at 25 ⁰ C and a resolution capability of 1.15 parts DBDP in 100 parts at 20 ⁰ C;

(i ") Semi-refined oil described under (b) with practically no dissolving power for DBDP at 20 ⁰ Cj (i ¹¹¹ ) Abbreviation for 5- (3.6 _ll 9-trioxa-undecyloxy-2) -1, 3-benzodioxole, a liquid having a vapor pressure of less than 0.005 Torr at 25 ⁰ C and a resolution capability of 5 parts in 100 parts DBDP at 20 ⁰ C;

(3) liquid having a vapor pressure of 121 Torr, at 25 ⁰ C and a resolution capability of 18.6 parts DBDP in 100 parts at 20 ⁰ C;

(j ¹ ) synthetically obtained distillation cut sold by ESSO STANDARD between 189 and 205 ° C from branched aliphatic hydrocarbons, which contains a mixture of decanes, undecanes and dodecanes with between 0.2 and 2 Torr vapor pressures at 25 ⁰ C and has a dissolving power of about 0.15 parts DBDP in 100 parts at 20 ° C.

The contents of this container are each on one side

one made of wool fibers and synthetic fibers

applied fabric sprayed in an amount of 400 mg per dm.

7098 ^^ 0.792

Round pieces with a diameter of 70 mm are cut from this fabric and place them with the treated side facing up on the bottom of a Petri dish of the same internal diameter. An hour later insects of the species Sitophilus granarius are introduced into the shells in a number of 10 insects per bowl.

You work with ten bowls per aerosol. The cumulative percentage of dead or paralyzed insects is recorded every six minutes (KD %) .

The following table shows the recorded results.

Time in minutes N-O N-I N-2 N-3 N-4 12th 0 5 9 8th 9 18th 0 27 26th 12th 16 24 1 40 43 24 » 35. 30th 4th 56 56 47 44 36 10 75 77 65 58 42 15th 87 90 75 68 48 19th 94 96 84 74 54 33 99 99 92 80 60 47 99 100 98 83

These attempts involved some orthoptera, diptera, hemipteran, and coleopteran; it goes without saying that one the compositions according to the invention also for the destruction of other types of orthoptera such as, for example Crickets, grasshoppers and mole crickets, dipteras

70983570792

such as stable flies, common mosquitoes and swine ticks, Hemipteras such as bed bugs and triatoraids as well as coleopteras such as Oryznophilus, Dermestes, Trogodoram, Tribolium, Guathocerus, Tenebrio, Sitophilus and Leptinotarsa and also other insect orders such as Hymenoptera (ants), Lepidoptera (Sitotroga and Plodia), isopters (termites) and heteropterans (house bugs).

The following compositions are given as supplementary examples for the invention (values expressed as % by weight ).

709835/0792

- 39 -

Examples 1 to 12 Liquid formulations under increased or normal pressure »

composition 1 . 2. 3. 4th VJI 6th 7th 8th. 9 · 10 11 12th A. Trichlorometaphos
Chlorpyrifos
Azamethiphos
Dimethoate
Fospirate
Iodofenphos
Trichlorophone
Phosalone I I I I I I H I 2 5 3 ¹ ■ "» ■ ■ '' vj, 6th ι ι ι ι ι ι ι
VJl 1 4th 10 6th B. 1-chloro-hexadecane (s)
Isopropyl myristate (a ") (p)
Paraffin oil (q)
Dioctyl sebazinate (p ')
Hexadecane (s ¹ )
Glycerine (d ') (q »)
Petroleum jelly (b) Il I I I I I
VJI 0.6 20th I I I I I I I ι ι ι ι ι ** ι j 5 CM I
I I I I H I I j 8th
2 1 20th I I I I H I I I I I I CM I II

Examples 1 to 12 (continued)

C. composition 1 2 3 4th 5 6th 7th 8th 9 10 11 12th Acetone (e) (ν) - 33 - - - - - - - 76 - - Methyl acetate (v ¹ ) - - - - - 79 - - - - - - Dichloromethane (c *) (w) - - 52 - - - 40 - 16 - 75 - Ethoxyethane (w ¹ ) - - - - - - - 34 - - - - D. Methanol (e ») - 10 - - - - - - - - - - -a Chloroform (u) - - - - - - - 50 - - - 40 (O Butan-2-one (u ^f ) - - - 91 - - - - - - - - ¹ co Benzene (x) - - - - - - 12th - - - - 30th -P · (Ji E » Ethanol (x ^f ) 84 - - - 76 - - - - - - - I O Arprocarb (D
IO Hexane (z) - - - 2 - - - - - - - Isopropanol (z ¹ ) - - - - - - 10 - - - - - Octanol (y) - - - - - - 17th - - - mm - "Isopar L" (y ¹ ) - - - - 10 r - - - - - - Carnauba wax - - 20th - - - - - - - - - Vinyl acetate ' - - - 3 - - - - - - - - Paraffin 60/62 ⁰ C - - - - - 10 - - - - - - - - - - - - - - - - 5 -

Examples 1 bl3 12 (continued)

E "ι composition 1 2 • - 3 4th VJl 6th 7, 8th 9 10 11 12th Ε «· ι butane
propane
Dichlorodifluoromethane - 40
10 - - - - - - 80 - - - -J
O Diazinon
Dichlorvos
Lindane - - - - - 2 - - - - - 983 Green dye
Yellow dye
Spruce needle oil
lemon oil
Epoxidized soybean oil
Epichlorohydrin - 0.4 - - - - - - - - - 5/0792
42 - 0.5
0.5 0.5 0.7 1 0.6
0.2 0.7 - - η ¹ ^ - 0.3 - - - - - - -

Examples 15 to 21 Solid formulations from liquid compositions.

14th 15th Talk 70 60 - 70 (
i Chlorpyrifos 10 8th - 10 - 16 ' 17th 18th 5 - - - 19th 20th - 100 - 1 - - 21 13th USED CARRIER kaolin - - - USED LIQUIDS Azamethiphos - - - - - - - - - - 4th Dried clay - 30th - I. Trichlorophone - - - - 60 100 - 10 - - - - 70 Aluminum silicate - - - Iodofenphos - - 40 - 10 - - 6th 20th Soy flour - 10 - Dimethoate - - - - - - - - - - - Calcium carbonate 30th - - - - - - - _ Pulp board - - 100 40 - - - - 10 sugar - - - - - - 100 - - Parts by weight of carrier 96.5 98.25 - - - 76 92.5 - 60 - - - 98.9 96 94 98.4 COMPOSITION - - - - - 3

Examples 15 to 21 (continued)

I. -J Didecyl phthalate (a) 13th I. 2 14th 15th 16 17th 18th 19th 20th 21 LC
OC Glycerine (d) (q «) - - - 3 - - - - - B "bis (tridecyl) phthalate (r) Hexadecane (s ¹ ) - - 28 - - - - - - _ Dioctyl adipate (r ^f) 2 4th - - - 10 - - - Isopropyl myristate (p) - - - - - - 20th C acetone (c ") (ν) - - - - - - 10 - - Chloroform (u) - - - - 10 - - - 5 Dichloromethane (c ») (v) - - - 89 - 80 - - 92 Ethoxyflthane (w ¹ ) - - - - 80 - - - - Ethanol (x ¹ ) - - 40 - - - - 70 - Methanol (e ^f ) - - - - - 88 - - D arprocarb 86 - - - - - - - - Dioxacarb - 86 - - - - - - - - 2 - - - - - - - - - 10 - - - - - - - - 7th - - - - - - E ¹ lauron - - 2 - - - - - E "dimetilane - - - - - - - Dieldrin

Examples 15 to 21 (continued)

CD CD CJ

Red dye
Orange dye
Epoxidized soybean oil 13th 14th 15th 16 17th 18th 19th 20th 21 I slipped Parts by weight of liquid - - 1
4th 1 - - 0.5
0.5 - - % A after evaporation 25th 12.5 60 10 20th 30th 20th 25th 20th 2.5 1 6th 0.5 2 3 2 2.5 0.6

(ρ) Liquid with a vapor pressure of about 0.001 Torr at 25 ⁰ C and a dissolving power of 2.9 parts of dimethoate

or 1.5 parts of egg trichlorophone in 100 parts at 20 ° C;

(p ¹ ) Liquid with a vapor pressure of less than 0.0001 Torr at 25 ° C and a resolving power of 1.7

Parts of trichlorophone in 100 parts at 20 ° C;

(q) solidifying liquid at -27 ° C with a density of 0.851 at 15 ⁰ C, a vapor pressure of less than 0.001 Torr at 25 ° C and a Auflösungsfittiigkeit of about 5 parts

Jodofenphos in 100 parts at 20 ⁰ C;

(q ¹⁾ liquid having a vapor pressure of less than 0.0001 Torr at 25 ⁰ C and a resolution capability of 0.5 parts or 0.2 parts Fospirat Jodofenphos in 100 parts at 20 ° C;

(r) Liquid with a vapor pressure of less than 0.00001 Torr at 25 ^° C. and a dissolving power of 4 parts of dimethoate or 1.2 parts of azamethiphos in 100 parts

at 20 ° C;

(s) Liquid with a steam pressure less than 0.0001 Torr at 25 ° C and a resolution of 2.8 parts

Trichlorophone in 100 parts at 20 ⁰ C;

(s ¹⁾ liquid having a vapor pressure of about 0.003 Torr at 25 ⁰ C and a resolution capability of 4.2 parts or 2.8 parts Trichlormetaphos Jodofenphos or at least 0.1

Parts of trichlorophone in 100 parts at 20 ° C;

(u ¹ ) Liquid with a vapor pressure of 90 Torr at 25 ° C and a dissolving power of 46 parts of azamethiphos in

100 parts at 20 ⁰ C;

- 46 -709835/0792

* Ό *

(ν) liquid having a vapor pressure of 225 Torr at 25 ° C and a Auflflsungsfähigkeit of 13 "6 parts of dimethoate or 48 parts in 100 parts Jodofenphos at 20 ⁰ C; (v ¹ ) liquid with a vapor pressure of 216 Torr at 25 ⁰ C, with which Trichlormetaphos is infinitely miscible at 20 ° C; (w) liquid having a vapor pressure of 420 Torr at 25 ° C and a resolution capability of 86 parts or 30.4 parts Jodofenphos phosalone in 100 parts at 20 ⁰ C; (w ¹⁾ liquid having a vapor pressure of 530 Torr at 25 ⁰ C and a resolution capability of 24 parts trichlorphon in 100 parts at 20 ° C;

(x) liquid with a vapor pressure of 95 torr at 25 ° C and a dissolving power of 61 parts of iodofenphos or 17.2 parts of trichlorophone in 100 parts at 20 ° C; (x ¹ ) liquid with a vapor pressure of 59 torr at 25 ° C and a dissolving power of 63 parts of chlorpyrifos or 20 parts of fospirate in 100 parts at 20 ° C;

(y) liquid having a vapor pressure of 0.07 Torr at 25 ⁰ C and a resolution capability of 5.6 parts in 100 parts Fospirat at 20 ⁰ C;

(y ¹⁾ synthetically derived, marketed by the company Esso Standard distillation cut 189-205 ° C aue branched aliphatic hydrocarbons, which contains a mixture of Decanen, undecanes and Dodecanen with between 0.2 and 2 Torr lying vapor pressures at 25 ° C and at 20 ° C has a dissolving capacity of about 0.2 parts of azamethiphos in 100 parts;

- 47 709835/0792

(z) liquid having a vapor pressure of 151 Torr at 25 ⁰ C and a resolution capability of 3 »Jodofenphos 3 parts in 100 parts at 20 ⁰ C;

(z ¹⁾ liquid having a vapor pressure of 44 Torr at 25 ⁰ C and a resolution capability of 2.3 parts Jodofenphos in 100 parts at 20 ° C.

"70983570792

Claims (20)

PATENT CLAIMS Liquid insecticide composition that has a
represents homogeneous liquid solution containing: (A) such an amount of at least one solid ^{at 20 ° C}
Organophosphorus compound insecticidal substance that it is sufficient to achieve the insecticidal effect and that
Amount does not exceed that in the rest of the composition
can be completely resolved; (B) 0.2 to 10 per part by weight of insecticidal substance A
Parts by weight of at least one non-volatile carbon compound which is liquid ^{at 25 0} C ^{1 and which is a poor solvent} for the insecticide A is and at 25 ° C has a vapor pressure of at most 0.01 Torr, and (C) at least one order of at 25 ° C is liquid at 25 ⁰ C, volatile carbon compound which is a good solvent for the active substance and the liquid B, a vapor pressure of at least 5 Torr comprises and is present in sufficient quantity,
existing amounts of ingredients A and B to form a complete and homogeneous solution. 2. Composition according to claim 1, containing: (A) 0.01 to 109%, calculated on the total weight of the composition, at least one insecticidal organophosphorus compound solid at 20 ° C; (B) 0.01 to 10- / o, calculated on the total weight of the composition, of an organic diluent which is liquid at 25 ° C. and which is chemically inert to the insecticidal substance A k in the range of 709835/0792 25 ° C a vapor pressure in the range of 0 to 0.01 Torr to v / ei st - 49 -ORIGINAL INSPECTED and at 20 ^° C. has a dissolving power (or dissolving power) with respect to the insecticidal substance A of less than or at most equal to 5 parts by weight of A per 100 parts by weight of B; and (C) 15 to 99 »8 $, calculated on the total weight of the composition, of an organic solvent which is liquid at 25 ° C and which is chemically inert to ingredients A and B, at 25 ° C a vapor pressure in the range of 5 to 600 torr and at 20 ⁰ C has a dissolving power (or a dissolving power) of at least 5 parts by weight of A per 100 parts by weight of C with respect to the insecticidal substance A. 3 · Composition according to one of claims 1 and 2, characterized in that the insecticidal substance A is included 0,0-dimethyl-5- [4-aza-6-chloro-2-oxo-benzoxazol-3-yl] -methyl-thiophosphate, 0,0-diethyl-O- (3 »5,6-trichloropyrid-2-yl) thiophosphate, 0, O-dimethyl-0- (2,5-dichloro-4-iodo-phenyl) -thiophosphate, 0, O-dimethyl-0- (2,4,5-trichlorophenyl) thiophosphate, 0,0-Dimethyl-S- (6-chlor-2-oxo-benzoxazol-3-yl) -methyl-dithic- phosphate, 0,0-dimethyl- (2,2,2-trichloro-1-hydroxy) ethyl phosphonate and 0,0-diethyl S- (2-oxo-4-aza-benzoxazol-3-yl) methyldithiophosphate selects. 4. Composition according to one of claims 1 to 3 » characterized in that the liquid B has a vapor pressure of 0 to about 0.005 torr at 25 ° C. 5. Composition according to one of Claims 1 to 4, characterized in that the liquid B at 20 ° C has a dissolving capacity for the insecticidal substance A in the range of 709835/0792 - 50 - 0 to about 3 parts by weight of A per 100 parts by weight of B. 6. Composition according to one of claims 1 to 5, characterized in that the liquid C at 25 ⁰ C has a vapor pressure in the range from 80 to about 550 Torr. 7. Composition according to one of claims 1 to 6, characterized in that the liquid C has a dissolving capacity for the insecticidal substance of more than 10 parts by weight of A per 100 parts by weight of ^{C at 2O 0 C.} 8. Composition according to any one of claims 1 to 7, characterized in that one is the difficult-to-volatilize liquid B among aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, halogenated aromatic Hydrocarbons, esters of aliphatic acids, esters of aromatic acids, heterocyclic compounds, alcohols, Polyols, ether alcohols, amino alcohols, aliphatic Mercaptans, ketones, aliphatic acids, their anhydrides and natural oils. 9 «Composition according to claim 8, characterized in that the non-volatile liquid B is selected from the following diluents: vaseline oil, paraffin oil, hexadecane, 1-bromo-tetradecane, 1-chloro-hexadecane, tetrachlorodiphenyl, isopropyl myristate, dioctyl adipate, Di- (2-ethylhexyl) adipate, dioctyl sebazinate, dibutyl phthalate, dioctyl phthalate, didecyl phthalate, bis (trideoyl) phthalate _t 5- (3 »6,9-trioxa-undecyloxy-2) - 1,3-benzodioxole, 1-dodecanol, 1-tridecanol, glycerine, diethylene glycol dibutyl ether, 2-amino-2-ethyl-propane-1,3-diol, tertiary dodecanethiol, oleon, octane 709835/0792 - 51 - acid, oleic acid, 2-dodecylsuccinic anhydride, olive oil and linseed oil. 10. Composition according to claim 8, characterized in that that one of the low-volatility liquid B among aliphatic hydrocarbons, halogenated aliphatic Hydrocarbons, esters of aliphatic acids, esters of aromatic acids, heterocyclic oxygen compounds, Selects alcohols, polyols and ketones. 11. The composition according to claim 10, characterized in that the low-volatility liquid B under Vaseline oil, paraffin oil, hexadecane, 1-chloro-hexadecane, isopropyl myristate, Dioctyl sebazinate, dioctyl adipate, dibutyl phthalate, Dioctyl phthalate, didecyl phthalate, S-C ^ e ^ -trioxa-undecyloxy-2) -l, 3-benzodioxole, 1-tridecanol, glycerine and oleon. 12. Composition according to any one of claims 1 to 11, characterized in that the volatile liquid C is selected from aliphatic hydrocarbons, halogenated aliphatic Hydrocarbons, aromatic hydrocarbons, aliphatic esters, heterocyclic compounds, aliphatic Alcohols, aliphatic ethers, aliphatic ketones, Nltroalkanen and Nitriloalkanen selects. 13 * Composition according to claim 12, characterized in that that the volatile liquid C under dichloromethane, trichloromethane, chloroform, benzene, methyl, ethyl, Isopropyl, propyl, isobutyl and / or butyl acetate, methyl and / or ethyl propionate, methyl and / or ethyl butyrate, 2-methoxyethyl acetate, tetrahydrofuran, dioxane, ethoxyfithane, 709838/0792 - 52 - Methanol, ethanol, isopropanol, methoxyethanol, acetone, methyl ethyl ketone, Butan-2-one, nitromethane and acetonitrile. 14. Composition according to claim 12, characterized in that that the volatile liquid C among halogenated aliphatic hydrocarbons, aromatic Hydrocarbons, aliphatic esters, heterocyclic oxygen compounds, aliphatic alcohols, aliphatic Selects ethers and aliphatic ketones. 15. Composition according to one of claims 1 to 14, characterized in that it is 0.01 to 10%, based on is the weight of the composition containing a complementary insecticidal substance, one of the ortho-substituted N-methyl carbamates the general formula: CH ₃ -NH-CO-O _ where R is an alkyl radical with 1 to 5 carbon atoms, an alkoxy group with 1 to 4 carbon atoms, a propargyloxy group, a diethoxymethyl radical, a dimethoxymethyl radical, a 1,3-dioxan-2-yl radical, a 1,3-dioxolan-2-yl radical or one of these two latter radicals with one or two methyl groups is selected. 16. The composition according to claim 15, characterized in that R represents the isopropoxy radical, the 1,3-dioxolan-2-yl radical or the 2,2-dimethyl-1,3-benzodioxol-4-yl radical. 17. Composition according to one of claims 1 to 16, characterized in that it contains an excipient E, 709835/0792 - 53 - selected from: * · ' (E ¹ ) liquids which dissolve the active ingredient poorly or not at all and have a vapor pressure at 25 ° C. which is equal to or greater than 0.01 torr; (E ") non-volatile solid extenders or carriers; (E" *) liquefied gases which can be used as propellants; (E ¹ " ¹ ) complementary insecticidal active ingredients different from A and D; and
(E ^nMf ) dyes, perfumes and stabilizers. 18. Composition according to one of claims 1 to 17, characterized in that it also contains a diluent E ¹ which is liquid at 25 ° C and which dissolves the active ingredient A poorly or not at all and is chemically inert to the other components of the composition, in the mixture A + B + C is soluble, has a vapor pressure in the range from 0.2 to 100 Torr at 25 ° C. and has a dissolving capacity for the active ingredient in the range from 0.005 to 5 parts by weight of A per 100 parts by weight of E ¹ . 19 * Composition according to claim 18, characterized in that the liquid E ^{1 is selected} from hexane, isopropanol, octanol, lauron and a mixture of aliphatic hydrocarbons. 20. Process for the preparation of solid insecticide compositions, characterized in that there is a composition according to one of the preceding claims to the surface of a solid, powdery or non-powdery Applies carrier and then 3asst the liquid Cvardunsten. - 54 -709835/0792