DE2551257A1 - PHOSPHONIC ACID ESTERS AND INSECTICIDAL AGENTS - Google Patents

Description

"Phosphoric acid esters and insecticides" Priority: November 15, 1974, V.St.A., No. 524 376

The most widely used insecticides today include the pyrethrins, the ingredients of some Chrysanthemum species, such as Chrysanthemum cinerariaefolium, which have high insecticidal activity and low warm-blooded toxicity. The relative high costs and uncertainties regarding the supply of pyrethrins have intensified efforts to make synthetic To manufacture insecticides with the valuable properties of pyrethrins, it has long been known that synthetic compounds with a basic structure similar to pyrethrins, e.g. esters of certain substituted cyclopropanecarboxylic acids, especially the 2,2-dimethyl-3- (2-methylpropenyl) -cyclopropanecarboxylic acid, known as chrysanthemum acid, have remarkable insecticidal activity.

The widespread use of pyrethrins and similar synthetic insecticides is based primarily on the discovery that certain Additives increase the activity of these insecticides. This _j

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Additives called synergists are compounds which do not have to have any insecticidal activity themselves. In combination with pyrethrins or similar compounds result however, they have insecticidal agents with significantly greater effectiveness than both components individually. One together with Pyrethrins a very effective and frequently used synergist is piperonyl butoxide; see U.S. Patent 2,550,737, however, many are in combination Effective synergists excellent with pyrethrins are far less effective in combination with allethrin or others synthetic cyclopropanecarboxylic acids.

The invention is based on the object of new compounds for To make available, in combination with 2,2-dimethyl-3- (2,2-dichlorovinyl) -cyclopropanecarboxylic acid 3 ~ phenoxybenzyl ester synergistically enhance their insecticidal and acaricidal effects. This object is achieved by the invention.

The invention thus relates to that characterized in the claims Object.

Specific examples of the radical Ar are the phenyl, pyridyl, Thienyl, pyrryl, furanyl, and isothiazyl groups and the corresponding Benzo derivatives. If η has the value 2 or 3, the radicals R can be identical to or different from one another. Has m the Value 2, the radicals Y can be identical to one another or different.

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The compounds of general formula I ¹ and I are preferred

CH ₂

in which R _{1 is} an alkyl or alkenyl radical having 1 to 6 carbon atoms and Rp is an alkylene radical having 1 to 4 carbon atoms. The radicals Rj and Rg preferably contain 3 or 4 carbon atoms.

O-2-propynyl-O-isobutylphenylphosphonic acid esters are particularly preferred and O-2-propynyl-O-propylphenylphosphonic acid esters.

The one used as a synergist in the agents according to the invention 2,2-Dimethyl-3- (2,2-dichlorovinyl) -cyclopropanecarboxylic acid 3-phenoxybenzyl ester is known; see Nature, Vol. 244 (1973), p. 456 and Nature, Vol. 246 (1973), p. 169, as well as BE-PS 800 006.

The examples illustrate the invention.

example 1

Preparation of O-3-butynyl-O-butylphenylphosphonic acid ester The starting compound, O-butylphenylphosphonic acid chloride, is prepared from dichlorophenylphosphine as follows: A cooled solution of 30.0 g of butanol and 41.4 g of triethylamine in about 300 ml of diethyl ether is added dropwise and with stirring - mixed with a solution of 34.6 g of dichlorophenylphosphine in about 200 ml of diethyl ether. The temperature should not ^{be 0 0 C.}

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exceed. The mixture is then warmed to room temperature, stirred for about 18 hours, filtered and the filtrate evaporated under reduced pressure. The oily residue is distilled under reduced pressure. Yield 39.5 g phenyl * dibutyl phosphonate, bp. 120 ° to 131 ° C / approx. 1.0 Torr =

Chlorine gas is passed into 38.5 g of dibutyl phenylphosphonate for about 3 hours. The resulting butyl chloride is at 50 C distilled off from the mixture under reduced pressure. The remaining colorless oil is dissolved in 100 ml of benzene, washed with 1% sodium hydroxide solution and with water, over Mag dried nesium sulfate and filtered. The filtrate is under evaporated under reduced pressure. Yield 30.6 g of light yellow O-butylphenylphosphonic acid chloride.

A solution of 15.6 g of O-butylphenylphosphonic acid chloride in 15 ml of benzene is added dropwise with stirring to a cooled solution of 5.2 g of 3-butyn-1-ol and 7.5 g of triethylamine in 45 ml of benzene, without increasing the temperature Exceeds 10 ⁰ C. Then the mixture is slowly warmed to about 5O ⁰ C and stirred for 1 hour. The mixture is then left to stand at room temperature for about 18 hours. The mixture is filtered and the filtrate is washed with dilute hydrochloric acid, dilute sodium hydroxide solution and water. Then the washed filtrate is over. Magnesium sulfate dried and concentrated under reduced pressure. The residue is distilled under reduced pressure. Yield 10.1 g of colorless title compound. The temperature of the distillation device and the bath temperature is 91 ° bis

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_r 255125?

106 ⁰ C or 130 to 141 ⁰ C at a pressure of 0.002 Torr.

^C 14 ^H 19 ° 3 ^{P; CH}

calc .: 61.41 7.53

found: 61.61 7.55

Example 2

Preparation of O ^ -propynyl-p-propylphenolphosphonic acid ester 127 g of propanol are added within 30 minutes with stirring and cooling with 126.1 g of phenylphosphonous acid dichloride. The mixture is then warmed to room temperature and stirred for 2 hours ⁰ C and stirred for an additional hour, the excess propanol was removed under reduced pressure on a hot Tiasserbad and distilling the residual oil under reduced pressure as the main fraction Phenylphosphinsäurepropylester is obtained as a clear, colorless oil g in a yield of 88;.. Kp 103rd ° C at 3 Torr; njp 1.5140.

A cooled solution of 3.7 g of 2-propyn-1-ol, 12.8 g of bromotrichloromethane and 7.1 g of triethylamine in 100 ml of benzene is admixed dropwise and with stirring with 10.8 g of propyl phenylphosphinate in 50 ml of benzene. The temperature should not exceed ^{35 0 C.} The mixture is then stirred at room temperature for a further 15 hours. The precipitated triethylammonium bromide is filtered off. The filtrate is washed successively with dilute hydrochloric acid, dilute sodium hydroxide solution and water, dried over magnesium sulfate and filtered. The filtrate is evaporated under reduced pressure. 13.1 g remain

. of a light yellow oil. This oil is at a bath temperature _j

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■ - 6 -

of 109 Ms 118 ⁰ C and distilled at a pressure of 0.001 Torr (diffusion). Yield 10.4 g of the title compound as a clear, colorless oil.
C ₁₂ H ₁₅ O ₃ P; CHP

calc .: 60.50 6.35, 13.00; found: 60.52 6.53 13.15.

Example 3

Preparation of O-2-propynyl-O-sec-butylphenylphosphonic acid ester

The intermediate product phenylphosphinic acid sec-butyl ester is manufactured as follows:

32.2 g of sec-butanol are added over 20 minutes at 5 to 10 ⁰ C under stirring and under nitrogen as protective gas with 25.9 g Phenylphosphonigsäuredichlorid. The mixture is then warmed to room temperature and stirred for about 18 hours. The excess sec-eutanol is distilled off under reduced pressure. Yield 27.8 g of sec-butyl phenylphosphinate, which is identified by IR analysis.

A solution of 3.4 g of 2-propyn-i-olj 9.4 g of carbon tetrachloride and 6.2 g of triethylamine in 100 ml of benzene at 15 to 20 ⁰ C and treated dropwise with stirring with 10 g of phenylphosphinic acid sec-butyl ester in 20 ml of benzene are added. The mixture is then warmed to room temperature and stirred for about 18 hours. The precipitated triethylanimonium chloride is filtered off. The filtrate is successively twice with 1% hydrochloric acid, once with 0.5% sodium hydroxide solution and twice

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. ₇ "

washed with water, dried over magnesium sulfate and filtered. The filtrate is evaporated under reduced pressure. The product is then further concentrated for 6 hours under greatly reduced pressure and with vigorous stirring. Yield 8.0 g of the title compound as an oil. According to the gas chromatographic analysis, the product is 98 percent pure.
C ₁₃ H ₁₇ O ₃ P; CHP

ber .; 61.89 6.79 12.28
found: 62.10 6.77 12.31.

• Example 4

Preparation of O-2-propynyl-O-isobutylphenylphosphonsäureester According to Example 3, 25 are reacted with 9 g Phenylphosphonigsäuredichlorid 32.3 g isobutanol. 28.7 g of isobutyl phenylphosphinate are obtained. 10.0 g Phenylphosphinsäureisobutylester are reacted with 3.4 g of 2-propyn-1-ol, 9, h g of carbon tetrachloride and 6.2 g of triethylamine. According to the gas chromatographic analysis, the product is 98 percent pure. By short path distillation (diffusion pump, a bath temperature of 108 ° to 121 ⁰ C) fractions obtained with a content of 97.8% to 99.5% of the title compound. Yield 8.0 g, identification by IR analysis.
C ₁₃ H ₁₇ O ₃ P; CHP

calc .: 61.89. 6.79 12.28 found: 61.68 6.71 12.05.

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255125?

Example 5

Preparation of 0-4 ~ pentynyl-0-ethylphenylphosphonic acid ester According to Example 1, 5.85 g of 4-pentyn-1-ol are reacted with 11.3 g of O-ethylphenylphosphonic acid chloride. The title compound is at a bath temperature of 120 ° to 130 ⁰ C and a pressure of 0.01 Torr distilled (diffusion system). C ₁₃ H ₁₇ O ₃ P; C HP

ber .: 61 , 90 6, 79 12, 28 found: 61 , 65 7, 04 12, 17th

Example 6

Production of 0-3-Butynvl-0 ~ n-Butvl-2-thienylphosphonic acid ester

According to Example 2, 4.0 g of 3-butyn-1-ol are mixed with 10.3 g of 2-thienylphosphinic acid n-butyl ester implemented. The title compound is by short-path distillation at a bath temperature of 128 ° to

ο 25

140 C and a pressure of 0.005 Torr; n ^ ^ 1.5069.

C ₁₂ H ₁₇ O ₃ PS; CHP

Calculated: 52.93 6.29 11.37

Found: 53.22 6.46 11.48.

Example 7

Preparation of O - ^ - butynyl-O-n-octadecylphenylphosphonic acid ester

According to Example 2, 12.6 g of 3-butynyl phenylphosphinate are obtained reacted with 17.4 g of n-octadecanol. The title compound is recrystallized from hexane. It is a waxy solid that is partially melted at room temperature.

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2551.25? ι

_aim \ j ^ _-

0-zP; 72 C. H P. 69 ber .: 72 , 69 10.24 6, 58 found: , 74 10.33 6,

B e i s ρ i el 8

Production of 0-2-propynyl-0-propyl benr. ylphosphonic acid ester The intermediate product, 0-2-propynylbenzylphosphonic acid chloride, is prepared from benzylphosphinic acid diethyl ester in a multi-stage reaction as follows:

1000 g of diethyl benzylphosphonate and 3.8 liters of 12 η hydrochloric acid are placed in a flask equipped with a heating jacket, stirrer and reflux condenser. The mixture is stirred, ^{heated to 65 °} C., and enough dioxane (200 to 210 ml) is added until a clear solution is obtained. The solution is then refluxed and stirred for 64 hours. The solution is then cooled to 45 to 50 ⁰ C. A solid precipitates out. This is dried in a vacuum drying cabinet at 70 to 74 ° C. for 15 hours. Yield 703 g of benzylphosphonic acid, mp 171-173 ° C.

In one with a stirrer, reflux condenser, ■ Dry sleeve solids funnel and scrubber equipped flask, a slurry of 111.5 g benzylphosphonic acid in 1 liter of hexane is stirred and heated to 35 to 40 ⁰ C. As soon as the first 50 g of a total of 259 g of phosphorus pentachloride are added to the mixture, the reaction begins immediately with evolution of hydrogen chloride. The mixture is then cooled to room temperature

L ^J

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and the remaining phosphorus pentachloride added in 50 g portions within 2 hours. The temperature rises to 60 ^° C. The mixture is then cooled to room temperature and sulfur dioxide is passed in for 15 minutes in order to displace the hydrogen chloride. The solvent is distilled off under reduced pressure, and the product is subjected to brief distillation (pressure 0.01 Torr, bottom temperature 85 to 125 ° C.) under reduced pressure. Yield 123.7 g of benzylphosphonic acid dichloride.

A solution of 39.3 g of n-propanol and 65.9 g of triethylamine in . 400 ml of benzene is added dropwise with stirring with 62 g of benzylphosphonic acid dichloride added in 200 ml of benzene. The mixture is stirred for about 18 hours. Then the resulting Triethylammonium chloride filtered off. The filter residue is washed with benzene, and the washing solutions are trodden with the filter united. The clear Benzollösuxig is four times with each 100 ml 1% hydrochloric acid, twice with 100 ml 1% each Sodium hydroxide solution and finally washed with 100 ml of water. The solution is then dried over magnesium sulfate and filtered. The filtrate is evaporated under reduced pressure and the product is subjected to short-path distillation (pressure 0.06 Torr, bath temperature 115 ° to 128 ° C.) under reduced pressure. Yield 47 g of dipropyl benzylphosphonate,

25th
n _D 1.4883. The identification is carried out by IR analysis. C ₁₃ H ₂₁ O ₃ P; CHP

calc .: 60.93 · 8.26 12.09
Found: 60.97 8.18 12.27

L -J

6 0 9 8 21/10 3 3

■ ^ 5 1

A mixture of 45 g of dipropyl benzylphosphonate, 39 g Sodium hydroxide and 350 ml of distilled water are refluxed and stirred for 20 hours. This will be the original cloudy mixture clear. The pH is then adjusted to about 1 by adding about 125 ml of hydrochloric acid dropwise. A solid precipitates out in the process. Since the solid liquefies on filtration, the product is dissolved by mixing the mixture extracted three times with 200 ml of chloroform each time. The combined chloroform extracts are dried over magnesium sulfate, filtered and evaporated under reduced pressure. A viscous, cloudy liquid is obtained. The product will further concentrated under reduced pressure. Yield 37.5 g of propyl benzylphosphonate as a white, sticky solid.

In one with agitator, gas inlet pipe, cooler and gas scrubber Equipped flask is a mixture of 37.5 g of propyl benzylphosphonate and 94 g of thionyl chloride for 4 1/2 hours stirred at 40 to 50 ° C under nitrogen as a protective gas. To facilitate evaporation of volatile by-products twice 100 ml of benzene was added at room temperature and then distilled off under reduced pressure. The mixture is further evaporated under reduced pressure. yield 40.4 g of O-propyl-benzylphosphonic acid chloride as an amber color Liquid. It is identified by IR spectroscopy.

In one with agitator, condenser with drying sleeve and dropping funnel Equipped flask is a solution of 5.5 g of 2-propyne-1 ~ oil and 9.8 g of triethylamine in 100 ml of benzene dropwise under

L ' ^J

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r 255125? π

Stirring mixed with 20.5 g of O-propylbenzylphosphonic acid chloride in 50 ml of benzene within 30 minutes. The solution is stirred for 15 hours at room temperature. The precipitated triethylammonium chloride is then filtered off and the solution is washed twice with 50 ml of 1% sodium hydroxide solution and once each time with 50 ml of 1% hydrochloric acid and 50 ml of water. The solution is dried over magnesium sulphate, filtered and evaporated under reduced pressure. An amber-colored oil is obtained. The crude product is distilled (0.0001 to 0.00015 torr, bath temperature 120 ⁰ C pressure) in a Molekulardestillötionsvorrichtung. Yield 14.5 g of the title compound as lemon .. yellow oil; n * p 1.5074.

^C 1 3H ₁₇ O ₃ P; 61 C. H P. ber .: 61 , 90 6.79 12.28 found: , 81 6.80 12.16

Example 9

Preparation of O-3- butyn-1-O-propylbenzylphosphonic acid ester According to Example 8, 19.9 g of O-propylbenzylphosphonic acid chloride are reacted with 6.6 g of 3-butyn-1-ol and 9.5 g of triethylamine. Yield 15.6 g of propyl-3-butynyl benzylphosphate. Identification by IR spectroscopy; njp 1.5052. C ₁₄ H ₁₉ O ₃ P; CHP

calc .: 63.15 7.19 11.63. Found: 63.04 7.46 11.63

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Example 10 Preparation of O-2-propynyl-O-ethylbenzylphosphonic acid ester . Identifi-

25 decoration by IR spectroscopy; n ^ 1.5124.

CH η ρ · ph P

ber .: 60, 50 6, 35 13, 00 found: 60, 56 6, 45 12, 73

Example 11

Production of 0 »2-propynyl-0-ethyl-4-chlorobenzylphosphonic acid ester

The reaction is carried out according to Example S, but first the alkynol is reacted with the phosphonic acid ester and then the product is reacted with the alcohol. 4-chlorobenzylphosphonic acid di-2-propynyl ester is thus initially formed from 4-chlorobenzylphosphonic acid dichloride. In the last reaction stage, 2-propynyl 4-chlorobenzylchlorophosphonate is reacted with ethanol to give the title compound. Identification by IR spectroscopy; n ^ ⁵ 1.5218. C ₁₂ H ₁₄ ClO ₃ P; CHN calc .: 52.86 5.18 11.36 found: 53.14 5.36 11.15

example

Preparation of 0-2-propynyl-0-propyl-4-chlorobenzylphosphonic acid ester

According to Example 11, 0-2-propynyl-4-chlorobenzylphosphonic acid chloride is used reacted with n-propanol. You get the title connection

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25 manure. Identification by IR spectroscopy; n _Q 1.5174.

C ₁₃ H _{1 6} C10 ₃ P; 54 C. H 63 10 P. ber .: 53 , 46 5, 81 11 , 80 found: , 72 5, , 14

Example 13

Production of O ^ -propynyl-O-propyl ^^ - dichlorobenzylphosphonic acid ester . . _. ■

The reaction is carried out according to Example 8, but is the 3,4-dichlorobenzylphosphonic acid dichloride by reaction of 505 g of phosphorus pentachloride with 304 g of 3,4-dichlorobenzylphosphonic acid diethyl ester manufactured. The title compound is obtained.

25 identification by IR spectroscopy; n _Q 1.5305-C ₁₃ H ₁₅ Cl ₂ O ₃ P; C H- P

calc .: 48.62 4.71 9.64
Found: 48.34 4.50 9.54

The synergistic effect of the phosphonic acid esters according to the invention with 2,2-dimethyl-3- (2,2-dichlorovinyl) -cyclopropanecarboxylic acid 3-phenoxybenzyl ester is explained below.

Example "14 ..

About 1 microliter of a solution with the equivalent of the specified amount of the compounds to be examined in 100 ml of acetone is applied locally to 12 to 20 3 to 4 day old houseflies. Each concentration is used for 4 to 5 experiments. After 24 hours, the number of living and dead will be Flies determined and mortality calculated. The results are summarized in Table I. _j

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Example 15

According to Example 14, there are synergistic mixtures with change the weight ratios of 2,2-dimethyl-3- (2,2-dichlorovinyl) -cyclopropanecarboxylic acid 3-phenoxybenzyl ester to phenylphosphonic acid isobutyl-2-propinyl ester investigated. the Results are summarized in Table II.

Other special phosphoric acid esters that act as synergists, are:

Ö-i-ethylbutyl-O ^ -hexynyl ^ -chlorobenzylphosphonic acid ester, O-4-pentynyl-O-methylphenylthiophosphonic acid ester, O ^ -Ethoxyethyl-O-T-octinylbenzylphosphonic acid ester, 0-propyl-0-1-methyl ~ 2 ~ propynylbenzylthiophosphonic acid ester, O-methyl-O-1 -methyl-3-butynyl ^ -chlorobenzylphosphonic acid ester, O-isopropyl-O ^ -butynyl ^ -brombenzylphosphonic acid ester, 0-2-pentenyl-0-1, i-dimethyl-3-butynylbenzylphosphonic acid ester, 0-2,4-Dimethylpentyl-0-3-butynyl-1-phenylpropylphosphonic acid ester,

0-2-propenyl-0-2-ethyl-3-butynyl-2-phenylpropylphosphonic acid ester,

O ^ -Methylbutyl-O ^ -butynyl ^ -iodobenzylphosphonic acid ester, 0-methyl-0-3-πιethyl-4-pentinyl-2,3-dichlorobenzylphosphonic acid ester,

0-2-propenyl-0-1-methyl-3-butynyl-2-pyridylmethylphosphonic acid ester,

0-2-methoxypropyl-0-1-ethyl-2-propynylphenylphosphonic acid ester, O-methyl-O-1-ethyl-3-butynylbenzylthiophosphonic acid ester, O-n-propyl-0- (2-methyl-3-butynyl) -3-fluorobenzylphosphonic acid ester, . _

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O-Isoamyl-O-J-butynyl-Z-pyridylphosphonic acid ester, 0-2-methoxyethyl-0-2-propynylphenylthiophosphonic acid ester and O-n-hexyl-O-i-ethyl-Z-propynyl-A-chlorobenzylphosphonic acid ester.

The synergists according to the invention excel in their effectiveness similar connections by far. The type and position of the unsaturated bond has a strong effect in these compounds Influence on the synergistic effectiveness of the compounds. For example, the hydrogenation of the acetylenic to an olefinic bond to a reduction in the synergistic effect. Likewise leads the shift of the acetylenic Binding from the terminal position to decreased activity.

The insecticidal compositions according to the invention can be used against a large number of plant and household pests will. These agents are generally not packaged alone, but together with auxiliary and carrier materials. Specific examples of such agents are sprays and aerosol preparations, dusts, wettable powders, emulsifiable powders Concentrates, solutions, granules and baits.

The concentrates usually contain about 5 to 80 % of the active ingredients, the remainder consists of dispersants, emulsifiers and wetting agents. For practical use, the concentrates are usually mixed with water or other liquids, liquid propellants or solid additives. Baits are made by mixing the concentrates with insect food, for example

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Cornmeal and sugar and possibly insect attractant ^ !, produced. The concentration of the active ingredients in the diluted preparations used for insect control is usually 0.0001 % to 5% by weight.

The use of the insecticidal compositions according to the invention is facilitated the control of plant and household pests. These include insects and mites that interact with cyclopropanecarboxylic acid esters, however, at higher concentrations, can be combated. Examples are flying and crawling Pests of the class Coleoptera (beetles), Hemiptera (true bugs), Homoptera (lice), Diptera (flies), Orthoptera (Cockroaches), acarina (mites and ticks) and Lepidoptera (butterflies and moths and their larvae). Because of the low Warm-blooded toxicity of the agents, they are preferred for combating pests, e.g. flies, mosquitoes, ants, Cockroaches, moths and ticks. They are also used in packaging, for the protection of food and grain, in the Garden, used by pets and livestock.

Synergists and the 2,2-dimethyl-3- (2,2-dichlorovinyl) -cyclopropanecarboxylic acid-3-phenoxybenzyl ester can be used in a relatively wide proportion. In the In practice, the synergist is preferably used in larger amounts, for example in an amount of 2 to 50 parts each Part of cyclopropanecarboxylic acid ester.

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^Γ - 18 -

The inventive insecticidal agents can be used in the following Amounts to be used effectively:

For the control of insects in agriculture: 0.003 to 0.40 kg / ha.

To combat houseflies as a room spray: 75 to 1f) 00 mg of the active ingredient mixture per m.

For use on cattle as a 0.02 to 0.0025 percent solution of the active ingredient mixture.

Outdoor sprays generally ground in one concentration from 5 to 150 liters / ha used. For local protection when applied to surfaces or as room sprays aqueous solutions with 0.1 to 5 percent active ingredient mixture are used will.

Test results are summarized in Tables I and II.

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Table I.

C.yclopropane, mortality from

carboxylic acid synergist (B), mg housefly, (1) ester (A), mg %

If3 ⁶ f ⁵

1.8 9 _f 0

2 _t 5 12.5

3,5 '17 _r 5

50

8th, 5% 11 16%. 26, 27% 53 57% 6% 16% 40% 54% 0, 4%

(A) 2,2-Dimethyl-3- (2,2-dichlorovinyl) -cyclopropanecarboxylic acid 3-phenoxybenzyl ester

(B) O-2-propynyl-O-isobutylphenylphosphonic acid ester

(1) For zv / ei numbers there are 2 tests with 4 to each 5 attempts for each concentration above.

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Table II

Cyclopropanecarboxylic acid ester (A), mg

4 _f 0

7 _r 2

9 _r 6

_r 0

4.0 5.4 7.2

4 _r 5

5.4

7.0

1O ₁ O

4.0 5.2

Synergist (B), mg

3.0 3.2 4.0

2 _r 2

l _r 00 1.50

none

none none none none none

2.0 2 _r 7 3.6

5.63

6.75

8.75

12.50

8.75 10.0 13.0 13.5

15.0 16.0 20 _r 0

15.0 22.0

20.0 30.0

50

amounts
behaves
nis A: B ¹ mortality
of parlors
to fly 22% - 33% - 43% - 71% - 82% 1: 0.5 37% 1: 0.5 53% 1: 0.5 59% 1: 1.25 78% 1: 1.25 73% 1: 1.25 89% l: l _f 25 99% 1: 2.5 64% 1: 2.5 83% 1: 2.5 86% 1: 2.5 91% 1: 5 84% 1: 5 75% 1: 5 92% 1:10 24% 1:10 63% 1:20 17% 1:20 68%

0.4%

(A) 2,2-Dimethyl-3- (2,2-dichlorovinyl) -cyclopropanecarboxylic acid 3-phenoxybenzyl ester

(B) O-2-propynyl-O-isobutylphenylphosphonic acid ester

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Claims (8)

Claims 1. / Phosphonic acid esters of the general formula I. T η (Y) -Ar- (CH) P ^{m n} in which R ^ is a branched or unbranched alkyl, alkenyl or alkoxyalkyl radical with 1 to 20 carbon atoms, R ^ one branched or unbranched alkylene radical with 1 to 6 carbon atoms, X is an oxygen or sulfur atom and R is a hydrogen atom or a methyl group, Ar is an aromatic group Radical and Y represents a halogen atom, η has the value 0, 1, 2 or 3 and m has the value 0, 1 or 2. 2. Compounds according to claim 1 of general formula 1, in which Ar is phenyl, pyridyl, thienyl, pyrryl, furanyl or isothiazyl group or the corresponding benzo derivative . 3. Compounds according to claim 1 of the general formula I-a in which R _{1 is} an alkyl or alkenyl radical having 1 to 6 carbon atoms and R £ is an alkylene radical having 1 to 4 carbon atoms, and η is 0 or 1. 609821/1033 4. Compounds according to claim 3 of the general formula I-a, in which R ^ and IL contain 3 or 4 carbon atoms. 5. 0 ~ 2-propynyl-0-isobutylphenylphosphonic acid ester. 6. O-2-propynyl-O-propylphenylphosphonic acid ester. 7. Process for the preparation of the compounds according to claim 1, characterized in that a compound of the general Formula II R X I Il / O-Ri _(TJ) (Y) _1n -Ar- (CH) _n P <"VLL; in which Z represents a hydrogen, chlorine or bromine atom and R, R ₁ , X, Y, Ar, η and m have the meaning given in claim 1, with an alkynol of the general formula III HCHC-R ₂ -OH in the Rp, an unbranched or branched alkylene radical having 1 to 6 carbon atoms, wherein the reaction is carried out in the presence of a strong base if Z represents a chlorine or bromine atom, or its salt, at temperatures from -10 reacting to 40 ⁰ C, or the reaction is carried out in the presence of trichloromethyl bromide or carbon tetrachloride and a strong base if Z represents a hydrogen atom. 609821/1 033 8. Insecticidal agents, characterized by a content of (A) a phosphoric acid ester according to claims 1 to 6 and (b) 2,2-Dimethyl-3- (2,2-dichlorovinyl) -cyclopropanecarboxylic acid 3-phenoxybenzyl ester in a quantity ratio of a: b of 0.5: 1 Ms 20: 1. 609821/1033