DE1642266A1 - Pest repellants - Google Patents

Description

FARBWERKE HOECHST AG von-ialt * Heister-Lucius & Br-üning File number: P 16 42 266.5 '- Hoe 67 / F 169

Date: January 7th, 1970
Dr. Km / dm

Pesticides. ■

The invention relates to pesticides, those by a content of phosphoric acid esters of the general Formula I.

(ι)

RR
^K 2 · ^R 3

where R is alkyl groups with 1, 2 or 3 carbon atoms and R ^, Rp and R, hydrogen or halogen atoms, preferably chlorine or bromine, are *

The active ingredients are prepared by using a trialkylphosph.lt of the general formula II.

(RO) ₃ P (II)

wherein R has the meaning given above, with a halogenated Butenone of the general formula III

R ₁ Cl

0 = a »C Cl

C = C - Cl

I f

& 2 R3

wherein R ₁ , R ₂ and R _{v have} the meaning given above, is reacted.

It is useful to carry out this reaction in the presence of inert organic Solvents, e.g. of hydrocarbons, such as

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Carry out petroleum ether, gasoline or benzene.

The halogenated butenones, which are used as starting materials for the production of the active ingredients, can by Halogenation of the corresponding butanones and subsequent elimination of hydrochloric acid or chlorine can be produced.

The new phosphoric acid esters used as active ingredients according to the invention have good biocidal properties, especially insecticidal and acaricidal effects. You can therefore especially against animal pests, such as biting and sucking insects and mites can be used. The active ingredients according to the invention stand out against each other known phosphoric acid esters due to their superior effectiveness and their lower toxicity to warm blooded animals. Your loading. A particular advantage is that it is surprising after a rapid and thorough initial effect on the plant are quickly degraded and can no longer be detected after a short time. This property is e.g. in fruit, Vegetable and fodder cultivation is valuable for pest control shortly before harvest. The new active ingredients are therefore suitable destroy pests that appear shortly before harvest, especially on plant-based products which are to be put for consumption as soon as possible due to perishability or deterioration in quality.

The new phosphoric acid esters show up as pesticides superior effects over known compounds of similar constitution. They excel in their effect, for example the diethyl 1-phenyl-2-chlorovinyl phasphate known from US Pat. No. 2,956,073, Example 12. In addition, they are compared to the after in terms of their short residence time on the plant of DAS 1 060 659, Table 1, Example I, known 0,0-diinethyl-NT-methylcarbamoylmethyldithiophosphate and the one recommended as a spray before harvest, according to US Patent 2,685,552, Example 1, superior to known dimethyl (i-carbomethoxy-i-propen-2-yl) phosphate (see E, Heller, Cooperative Plant Protection Council

1098 17/19 A4 BATHROOM ORIGINAL

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TB ⁷ TZuF "

geber, Frankfurt 1965, page 152, and O.R. Klimmer, demolition a toxicology and therapy of poisoning, Bonn, 1963, Page 42J

The phosphoric esters according to the invention can be used in the customary mixtures with solid or liquid inert carriers, adhesives, wetting agents, dispersants and grinding aids as Wettable powders, emulsions, suspensions, dusts or. Granules are used. They can be treated with other insecticides, Fungicides or nematocides !! Mix.

Mineral substances such as aluminum silicates, clays, kaolin, chalks, silica chalk, can be used as carrier substances. Talc, kieselguhr or hydrated silica or preparations of these mineral substances with special additives, e.g. chalk greased with sodium stearate. As a carrier for liquid preparations can contain all common and suitable organic solvents, for example toluene, xylene, Diacetone alcohol, cyclohexanone, isophorone, benzines, paraffin oils, Dioxane, dimethylformamide, dimethyl sulfoxide, ethyl acetate, Butyl acetate, tetrahydrofuran, chlorobenzene and others can be used.

Glue-like cellulose products or polyvinyl alcohols can be used as adhesives be used.

All suitable emulsifiers such as oxyethylated can be used as wetting agents Alkylphenols, salts of aryl- or alkylarylsulfonic acid c-n, Salts of methyl taurine, salts of methyl kogasine sulfonic acids or soaps can be used.

Cell pitch (salts of lignin sulfonic acid), Salts of kaphthalenesulfonic acid as well as under certain circumstances hydrated silicas or diatomaceous earth are used.

Suitable inorganic or organic salts such as sodium sulfate, ammonium sulfate, sodium carbonate, Hatrius-

109817/1944

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bicarbonate, sodium thiosulfate, or sodium stearate. Sodium acetate be used.

Examples

In the tables below are the effects of the active compounds according to the invention against a large number of pests listed.

The active ingredients according to the invention are designated as follows:

Dimethyl-i-trichlorovinyl-2-chlorovinyl phosphate as V / 1; Diethyl 1-trichlorovinyl-2'-chlorovinyl phosphate as W 2;

The comparison substances are designated as follows:

Diethyl i-phenyl-2-chlorovinyl phosphate

(known from US Pat. No. 2,956,073) as Comp. Ij

Dimethyl (1-carboromethoxy-1-propen-2-yl) phosphate (known from US Pat. No. 2,685,552) "as Comp. II;

Ο, Ο-dimethyl-N-methylcarbamoylmethyldithiophosphate (known from DAS 1060 659) as cf. III;

The symbol 0 in the tables means that the substance in question had no effect in the concentration tested «

To the insecticidal and acaricidal effectiveness of the new To determine phosphoric acid esters, various application methods were used.

109817/1944

BATH ORIGINAL

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Example 1 ^v '■

Citrus trees kept in pots, which are similar to those in citrus plantations As a pest frequently occurring scale insect Pseudococcus citri were infected, - with aqueous dilutions a pesticide that consists of the following ingredients:

15 % active ingredient

20 % highly dispersed silica (Silcasil S) 54 % magnesium aluminum silicate (^ 'SiIitin Z) 10 % cell pitch (salt of lignin sulfonic acid) 1% oleyl methyl tauride sodium (^ Hostapon T)

Example 2

Known in cotton and alfalfa as a pest bugs Oncopeltus fasciatus were sprayed a Schädlingsfcekämpfungsmijttels in a spray apparatus with aqueous dilutions and shortly thereafter exposed to untreated plants, resulting in cylindrical Gazekäfigen were _e The pesticide each consisted

30 % active ingredient

50 % cyclohexane

20 % Nony! Phenol with 10 ethylene oxide units

Example 5

The specified active ingredients were in different Concentrations dissolved in acetone and this solution evenly distributed on r-iindes filter paper, so that of the solutions with the specified concentrations in each case

0.15 ml came to 1 cm. After the acetone had evaporated, the filter papers were placed on the bottom of glass vessels and on the one hand chicken mites and on the other hand ticks were placed on the filter papers «,

9 811/19

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Example 4

For the systemic examination, stalks were kept in pots Field beans populated with Doralis fabae aphids, wrapped 1 cm above the ground with equal amounts of cotton wool and surround it with plastic wrap. In this bandage were each 2 cm of emulsions or by means of an injection syringe Introduced suspensions of the same active ingredient content.

Table 1 below shows the percentage mortality of the specified pests under the specified test conditions shown at different drug concentrations.

BAD ORIGJNAL 109817 / 19U

Table 1 Concentration of active ingredient in % / mortality in %

OO CO

Active ingredient Example 1 Example 2 Example 3 Chicken mites
Demn. gal-
linae Ticks
Ornitodo-
Γμ $ ffiou-
uci. ia Example 4 I.
■ <] Scale insect
Pseudococcus bug
Oncopeltus
fasciatus Scrape
Periplaneta
americana 0.005 % ■
100 % dead 0.025%
100 % to1 systemic
effect I. W 1 0.006 %
99 % dead 0.025 %
after 1 day
100 % dead 0.0005 %
100% dead 0.005 %
100? 6 dead 0.05%
.100 % dead 2rng
; 100% dead V 2 0.006 %
100 % dead 0.025 %
after 2 days
100 % dead 0.0005 '%
100 % dead
i 0.01 %
, 80% dead 0.1%
• 0 1mg
9596-dead See I. 0.05%
0 0.05%
0 0.005 %
60 Jo dead 0

ro

m cn

KO

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Example 5

Emulsion concentrates consisting of

30 % active ingredient

50% cyclohexanone

20 % Nony! Phenol with 10 ethylene oxide units

were emulsified with water to give spray mixtures of various active ingredient concentrations. Field beans (Vicia fabae) populated with bean aphids (Doralis fabae) were treated with equal amounts of these spray mixtures of the active ingredients to be compared. For comparison, series of pest-free field beans were treated simultaneously in the same way and were populated with aphids at certain time intervals after the treatment. Table 2 below shows the immediately effective limit concentrations of the substances to be compared at 100% mortality and the effect of different concentrations after a different number of days after application of the agent to the plant. In addition, Table 2 shows the toxicity of the compounds to be compared to warm-blooded animals as LD-Q.

Dimethyl-1-trichlorovinyl-2,2-dichlorovinylphosphate show an activity similar to that of the phosphoric acid esters according to the invention listed above and dimethyl 1- (1,2-dichlorovinyl) -2 ~ chlorovinyl phosphate.

ORIGINAL BATHROOM 109817/19 A4

Table 2

Active ingredient Concentration/
% Mortality Concentration/
after days /
% Mortality Warmblood toxicity
^IB 50 • w ι 0.00075 56/100 0.05 96/1 day
0 16 mg / kg rat ¥ 2 0.003? O / 100 0.05 96/3 days / 90
0.05 96/6 days / 50 6 mg / kg rat See II 0.00075 # / 100 0.025 96/6 days / 80
0.05 96/6 days / 100
0.05 96/8 days / 95
0.05 96/10 days / 65 4-7 mg / kg rat See Ill 0.00075 96/100
* 0.05 96/3 weeks / 100

Claims (5)

16Λ2266 claims ■ 1) Pesticides, characterized by a content of phosphoric acid esters of the formula RO -0-C ». > _c _ _c _ _C1 it ^R 3 wherein R is alkyl groups with 1, 2 or 3 carbon atoms and R ^, R ₂ and RZ are hydrogen or halogen atoms, preferably chlorine or bromine. 2) Pesticides, characterized by a content of dimethyl-i-trichlorovinyl-2-chlorovinyl phosphate. 3) Pesticides, characterized by a content of diethyl i-trichlorovinyl-2-chlorovinyl phosphate. 4) Pesticides, characterized by a Dimethyl 1-trichlorovinyl-2,2-dichlorovinyl phosphate content. 5) Pesticides, characterized by a content of dimethyl-.1- (1,2-dichlorovinyl) -2-chloro-vinylphosphate. e Unteriaaen 109817/1944