DE1198605B - Insecticidal agent - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

Number:
File number:
Registration date:
Display day:

AOIn

German class: 451-9 / 36

1198 605
S 89201 IV a / 45 1
January 23, 1964
August 12, 1965

The invention relates to an insecticidal composition which is characterized in that it is effective Component at least one Ο, Ο-dimethyl-O- [2-chloro-1 - (dihalophenyl) vinyl] phosphate of the general formula

\ ° ^CHC1

> —O —C —R

Insecticidal agent

CH ₃ O ^x
contains where R is a group

Cl or

The new effective phosphates are therefore, 0.0 - dimethyl - O - [2 - chloro -1 - (2,4 - dichlorophenyl) viftyl] phosphate, hereinafter referred to as compound A; 0,0-dimethyl-O- [2-chloro-1 - (4-chloro-2-bromophenyl) vinyl] phosphate, hereinafter referred to as compound B and O, O-dimethyl-O- [2-chloro-1 - (2,5-dichlorophenyl) vinyl] phosphate, hereinafter referred to as compound C.

The compounds A, B and C are made by reacting trimethyl phosphite with 2,2,2 ', 4'-tetrachloroacetophenone, 2,2,4'-trichloro-2'-bromoacetophenone or with 2,2,2 ^/ , 5' -Tetrachloroacetophenone produced. The reaction is preferably carried out by slow addition of the stoichiometric amount of trimethylphosphite to the corresponding Tetrahalogenacetophenon at a temperature of about 40 to about 60 ° C and then heating the mixture to a temperature of about 90 to 110 ⁰ C. crystallized by cooling, in general the desired Product from the reaction mixture. It can be washed out with a suitable solvent, e.g. B. pentane, or by crystallization from a suitable solvent or solvent mixture, e.g. ether-ligroin or ether-pentane.

The compounds used as starting substances 2,2,2 ', 4-tetrachloroacetophenone, 2,2,4'-trichloro - 2 '- bromoacetophenone or 2,2,2', 5 '- tetrachloroacetophenone are known per se Way by reacting dichloroacetyl chloride with m-dichlorobenzene, l-bromo-3-chlorobenzene or p-dichlorobenzene produced in the presence of aluminum chloride.

Applicant:

Shell Internationale Research Maatschappij

N.V., The Hague

Representative:

Dr.-Ing. F. Wuesthoff, Dipl.-Ing. G. Pulse and
Dipl.-Chem. Dr. rer. nat. E. Frhr. v. Bad luck man,
Patent Attorneys, Munich 9, Schweigerstr. 2

Named as inventor:
Loyal Francis Ward, Jr., Modesto, Calif .;
Donald David Phillips, Metuchen, NJ
(V. St. A.)

Claimed priority:

V. St. v. America January 25, 1963
(253 980, 254 005),
dated October 23, 1963
(318 152)

In this production method of 2,2,4'-trichloro-2'-bromoacetophenone however, it was found that the bromine atom and possibly the chlorine atom can migrate in the ring. So could by gas-liquid chromatography be shown that the crude product is a mixture of isomers, with various positions of the bromine and possibly the chlorine atoms in the phenyl ring, the main product being 2,2,4'-trichloro-2'-bromoacetophenone is present. As an insecticide, however, there is no need for pure O, O-dimethyl-O- [2-chloro-1 - (4-chloro-2-bromophenyl) vinyl] phosphate use as the mixture of isomers made from the crude 2,2,4'-trichloro-2'-bromoacetophenone is also effective. Hence can to react the isomer mixture of the bromotrichloroacetophenones with trimethyl phosphite and that use the mixture of isomers obtained here as an insecticide.

The agents according to the invention were found to be effective insecticides against a number of insects, which are typical of different species of insects, including flies, moths, mites, bed bugs,

509 630/390

Mosquitoes, worms. Caterpillars, grain beetles and beetles. The compounds are against two-winged insects (Flies), beetle-like insects (beetles), caterpillars and worms are particularly effective.

The agents according to the invention are effective against both immature and adult plants infesting insect forms effective. In this way, the compounds kill "worms," not including the actual ones Worms are to be understood, but those generally known under the designation "worms" immature insect forms such as larvae including e.g. B. the larvae of the western spotted cucumber beetle (Diabrotica undecimpunctata undecimpunctata), the earwigs (Heliothis zea), the cabbage worms (Pieris rapae), and wireworms (Limonius canus) of the Pacific coast.

Compound A has a moderately long duration of action and is therefore of particular value as Insecticide, if the plants for a certain period of time, for example during the Growth and / or flowering period to be protected against insects, the presence of the However, insecticide z. B. is undesirable during harvest time and / or a later season. Compound B has a long-term effect on surfaces and is therefore particularly suitable for combating from flies and mosquitoes. Compound B has a moderately long duration of action in soil and is therefore of particular use for the during a certain period, e.g. B. during the growth and / or flowering period, protection of plants against those living in the soil Insects, while the presence of the insecticide, for example during harvest and / or a later season is undesirable. Compound C exerts despite its high insecticidal effectiveness only has a very low toxic effect on mammals and is therefore still applicable, when many otherwise effective insecticides cannot be used. Such uses are e.g .:

1. The fight against parasites which attack warm-blooded animals;

2. The control of tree-infesting insects by applying the insecticide and / or in the trees;

3. The fight against insects kept in granaries and warehouses Products infested;

4. Use as a fumigant or for insect control by spraying public places, such as restaurants, airplanes. Buses, offices and markets;

5. Use for insect control in and around the home.

The active compounds can be used for insecticidal purposes according to known methods will. You can z. B. spray or otherwise in the form of a solution or dispersion use. They can also be attached to an inert, finely divided solid carrier such as talc, bentonite, Gypsum or pyrophyllite, absorb and apply as dust. For spraying. Brush on or dip suitable solutions can be found using those well known in horticulture as carriers inert substances are produced as solvents, including neutral hydrocarbons, such as kerosene and other light petroleum distillates of medium viscosity and volatility. Auxiliaries, such as distributing agents or wetting agents, can also be added to the solution, e.g. B. fatty acid soaps, . Rosin salts, saponins. Gelatine, casein, fatty alcohols with at least 10 carbon atoms, Alkylarylsulfonates, alkylsulfonates with at least 10 carbon atoms, phenol-ethylene oxide condensation products and C12 to car amines and ammonium salts. These solutions can be used as used or preferably in the form of an aqueous dispersion or emulsion as a spray be used. The active compounds can also be processed into wettable powders be that an active compound, mixed with a dispersant and optionally one finely divided solid carrier included. The insecticides according to the invention can also be used as an aerosol, e.g. B. by spraying into the atmosphere with the aid of a compressed gas.

The insecticidal compositions of the invention can also be in the form of a for storage or storage Have transport suitable concentrate, with z. B. 10 to 95 percent by weight of the active ingredient according to the invention or a more dilute preparation, with e.g. B. 0.00001 to 10 weight percent, preferably 0.01 to 0.5 percent by weight of active ingredient, based on the total weight of the agent.

The active compounds can be used together with other insecticidal active ingredients, for example the naturally occurring insecticides such as pyrethrum, Rotenone and Sabadilla, the various synthetic insecticides including dichlorodiphenyltrichloroethane, benzene hexachloride, thiodiphenylamine, the cyanide, tetraethyl pyrophosphate, 0,0-diethyl-O-p-nitrophenylthionopnospnat, azobenzene, 0.0 - dimethyl - O - 2.2 - dichlorovinyl phosphate. Dimethyl 1,2-dibromo-2,2-dichloroethyl phosphate or Arsenic, lead and / or fluorine compounds are used.

In the examples below, "parts" are parts by weight, unless otherwise stated:

example 1

Using a neutral petroleum distillate with the boiling range of kerosene or Solutions of compound A were prepared from acetone as a solvent. Under use of the common house fly (Musca domestica) as a test insect, experiments were carried out, wherein that of Y. P. Sun, Journal of Economic Entomology. Vol. 43, pp. 45 ff. (1950). procedure described was applied.

Parallel tests were carried out with the known under the trade name "Dieldrin" and against House flies highly effective 1,2.3.4,10,10-hexachloro-6,7-epoxy-l , 4,4a, 5,6,7,8,8a-octahydro-1,4,5.8-dimethanonaphthalene. In the following Table shows the ratio of the amount as a measure of the relative toxicities of the two compounds listed on compound A for the amount of dieldrin required to kill the test insects by 50% were required. This ratio is expressed here as the toxicity index, with dieldrin being arbitrary the toxicity was assigned 100. A compound with a toxicity index of 50 has therefore half the effectiveness of dieldrin

and one with a toxicity index of 200 has twice the potency of dieldrin.

Similarly, the toxicity of the compound A against the phylloxera (Drosophila melanogaster) determined, using as a standard insecticide the O, O - dimethyl S - (1,2-dicarbethoxyethyl) phosphorodithioate known under the trade name "Malathion" was used. binding applied in the solution. The results are shown in Table 2:

Table 2

Mean Lethal Concentration (LC50) (g / 100 ml solvent)

Table 1 ¹⁰ tested
link Tetranychus
telarius Heliothis
zea Sitophilus
oryzae i Pieris
rapae Tested connection Toxic
Musca domestica itsindex
Ver
mSoiier "^ dungA 0.15 0.0085 0.003 0.001 A. 212 1000 at game 1

Accordingly, compound A is twice as toxic to the house fly as dieldrin and to phylloxera Ten times as toxic as malathion.

Example 2

Using acetone as the solvent, solutions of Compound A were prepared and diluted with water containing an emulsifier. The solutions were examined for their toxicity to the double-spotted spider moth (Tetranychus telarius), for which purpose groups of plants infested by the insects were sprayed under controlled conditions. In various experiments, only the concentration of the toxic agent was changed while the same volume of spray agent was always used. Table 2 shows the concentration of the toxic agent in the sprayed solution that is required to kill the test insects by 50%, ie the LC 50 concentration. specified. The effectiveness of compound A against corn earworm (Heliothis zea) was determined by enclosing corn earworm larvae in cages on cut broad bean plants immersed in water after preparations made by mixing acetone solutions of the compounds to be tested with water had been sprayed onto the plants. For each test, two parallel tests were carried out and different tests were carried out with different concentrations of the compound to be tested in the liquid preparations. The LC50 values are compiled in Table 2. In a similar manner, experiments were carried out with caterpillars of the imported cabbage worm (Pieris rapae), the results of which (LC50) are shown in Table 2. The effectiveness of compound A against the rice beetle (Sitophilus oryzae) was by pouring adult rice weevil with a measured amount of the solution of f. compound to be tested in a container with a perforated bottom, wherein excess solution proceeded immediately, ₀ determined. 10 seconds after pour the beetle, these were dried with blotting paper, in containers The number of beetles killed, including the moribund beetles, was counted. Various parallel tests were carried out and various concentrations of the substances to be tested were carried out (Oncopeltus fasciatus) and the German kitchen sc (Blatella germanica), solutions of the compound to be tested in acetone were placed on Petri dishes by means of a pipette and the acetone was allowed to evaporate. The number of milligrams of the compound to be tested per Petri dish resulted from the amount of pipetted solution and its concentration. The dishes were stored at 26.7 ° C and 50% relative humidity. Adult large milkweed tails and German cockroaches were kept on the treated dishes for 24 hours and the kill was then determined. The results are expressed below as the concentration in milligrams of test substance per dish which were required to kill 50% of the insects, ie as the LC 50 concentration.

Table 3

Tested connection

Connection A

LC ₆₀

Oncopeltus

fasciatus

0.0042

Example 4

Blatella

germanica

1.0

To determine the toxicity of Compound A against larvae of mosquitoes (Anopheles albimanus) became the amount of 1% acetone solution required to achieve the desired concentration of compound A dissolved in 100 ml of water. In two parallel experiments, ten larvae each were found of the fourth stage of development of Anopheles albimanus. The solution was left for 24 hours act on the larvae and then counted the kill. For determining the LC 50 concentration various concentrations of the tested compound expressed in parts by weight of tested compound per million parts by weight Solution, applied. The results are shown in Table 4.

'Table 4

Tested connection

LC »(ppm)

0.02

Example 5 Example 6

The residual effect of compound A was determined by adding acetone solutions of the compound A sprayed on plywood panels and test insects in cages on the treated panels held, with a series of tests immediately after application of the test substance and others Test series were carried out at intervals of one week each. The test insects were fully grown House flies (Musca domestica) and Anophelesalbimanus mosquitoes. At a dosage of 911 mg Tested connection per square meter of wood surface resulted in connection A a 67% kill of house flies and 100% killing of mosquitoes after 4 weeks.

'5 Following the procedure of Example 1, the activity of Compound B over the common Determined house fly (Musca domestica). In Table 5 is the concentration of the toxic Mean in percent by weight of the toxic agent per volume of solvent as LC 50 concentration specified. Following the procedure described in Example 2 for Heliothis zea, the effectiveness of compound B against Heliothis zea, against larvae (caterpillars) of Plutella maculipennis and against Caterpillars determined by Pieris rapae. The efficacy of Compound B against Sitophilus oryzae was determined determined by the method described in Example 5.

Tabel

Checked
link Musca
domestica Heliothis
zea Sitophilus
oryzae Plutella
maculipennis Pieris
rapae B. 0.0045 0.0065 0.0035 0.00034 0.00188

Example 7

Following the procedure described in Example 3 for Oncopeltus fasciatus and Blatella germanica was the effectiveness of compound B against phylloxera (Drosophila melanogaster) and the large milkweed bug (Oncopeltus fasciatus) examined. The following are the LC 50 concentrations listed as milligrams of tested compound per bowl.

Table 6 _χ

Checked connection

Connection B

LC ₅₀ (mg / dish)

Drosophila
melanogaster

0.000058
Example 8

Oncopeltus
fasciatus

0.0026

Following the procedure of Example 4, the activity of compound B against mosquito (anopheles albimanus) larvae. The results are shown in Table 7.

Tabel 7th LC ₅₀ (ppm) Tested connection 0.107 B.

Example 9

The residual activity of Compound B was determined according to the procedure of Example 5. It 100% killing of house flies and 100% killing of mosquitoes according to Go 8 weeks found.

Example 10

Compound B solutions were sprayed onto coarse-haired mats to mimic animal skins and biting flies immediately afterwards and at certain intervals after the treatment (Stomoxys calcitrans) applied to the treated area for 10 minutes, with the following Results:

Apply immediately after

Treatment 95% kill,

Apply 3 days after the

Treatment 100% kill,

Apply 7 days after the

Treatment 94% kill.

Example 11

The effectiveness and essential duration of action of compound B in soil has been demonstrated using the following experiments:
An acetone solution of the compound to be tested was sprayed onto earth while it was being circulated in a mixer so that the compound was evenly distributed in the earth and a concentration of 3.3 parts by weight of test substance per million parts by weight of earth was achieved. The earth was then dried to remove the acetone, moistened with water and divided into jugs. The jars were tightly closed and kept at a temperature of 26.7 ° C. One day after the earth was poured into the jars, certain jars were opened and larvae of the western spotted cucumber beetle (Diabrotica undecimpunctata undecimpunctata) in the third stage of development were introduced into the earth. The jugs were sealed, left to stand for 24 hours and the death rate was then determined. This procedure was repeated 15 days after the treated soil was placed in the jugs. The following results were obtained:

Table 8

Checked
link

° / o destruction on the specified day after

Introducing the connection to be tested

into the earth

after ITag

100

after 15 days

75

ίο

Example 12

Using a neutral petroleum distillate with a boiling range corresponding to kerosene or of acetone as a solvent, solutions of the compound C were prepared and experiments on the Pea louse (Macrosiphum pisi) carried out by removing groups of plants contaminated with the insects sprayed under controlled conditions. Different attempts only differed here in terms of the concentration of the toxic agent. The total volumes were the same in all experiments Spray used.

Furthermore, the effectiveness of compound C against the house fly (Musca domestica), the corn earworm (Heliothis zea), caterpillars of the diamond-backed moth (Plutella maculipennis), the imported ones Cabbage worm (Pieris rapae) and the rice beetle (Sitophilus oryzae) in the previous examples described way checked. In addition, experiments were carried out with larvae of the elm aphid (Galerucella luteola) carried out according to the method described in Example 5 for Heliothis zea. Table 9 shows the LC 50 concentrations of compound C for the insects mentioned listed.

Table 9
Mean Lethal Concentration (LC50) (g / 100 ml solvent)

Checked
link Macrosiphum
pisi Musca
domestica Heliothis
zea Sitophilus
oryzae Plutella
maculipennis Pieris
rapae Galerucella
luteola C. 0.0004 0.037 0.008 0.0073 0.00076 0.0024 0.0049

At the concentrations used in these experiments no phytotoxicity of the insecticidal agent was observed.

Example 1 * 3

The acute oral toxicity of compound C for mammals (LD50 in milligrams per kilogram Body weight, in male mice and rats) was found to be very low and was over 2000. 1- (dihalophenyl) vinyl] phosphate of the general formula

CHCl

Claims (1)

Claim: Insecticidal agent characterized by having an active ingredient content at least one O, O-dimethyl-O- [2-chloro- 35 wherein R is a group 509 630/390 8.65 © Bundesdruckerei Berlin