DE1161079B - Preparations for the control of insects and ticks - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

Boarding school Class: A Ol η

GERMAN

PATENT OFFICE

EDITORIAL

German KL: 451-9 / 20

Number:
File number:
Registration date:
Display day:

G 32059IV a / 451
April 13, 1961
January 9, 1964

The invention relates to a new agent for controlling insects and ticks.

There are already various, substituted or unsubstituted O-aryl carbamates with free or in the aryl radical with mono- or dialkyl-substituted amino group as herbicides, fungicides, acaricides, insecticides and as Wormers have been described.

In particular, it has N-methyl-1-naphthyl carbamate gained importance as an insecticide. Among those substituted by a lower alkyl radical in the benzene nucleus N-methyl-O-phenylcarbamates are the o-, m- and p-Isopropylphenyl-N-monomethylcarbamate and the three isomeric o-, p- and m-tert-butylphenyl-N-monomethylcarbamates has been described as having an insecticidal effect (Agricult. and Food Chemistry, Vol. 2 [1954], P. 864, and French patent 1 209 385).

It has now surprisingly been found that O-m-sec.butylphenylcarbamate or N-methyl-O-msec.butylphenylcarbamate according to the formula

Preparations for the control of insects and ticks

Applicant:

J. R. Geigy A.G., Basel (Switzerland)

Representative:

Dr. F. Zumstein, Dipl.-Chem. Dr. rer. nat. E. Assmann and Dipl.-Chem. Dr. R. Koenigsberger,
Patent Attorneys, Munich 2, Bräuhausstr. 4th

Named as inventor:

Dr. Jürg Rumpf, Binningen, Basel,

Dr. Enrico Knüsli, Riehen, Basel (Switzerland)

Claimed priority:

Switzerland of April 14, 1960 (No. 4274)

.0 —CO —NH-R

CH

CH ₂ CH ₃

CH _S

in which R denotes a hydrogen atom or the methyl radical, and mixtures thereof with the corresponding o- and p-isomers, the previously known aryl carbamates in the insecticidal effect and in the Effect against ticks are superior. The N-methyl-O-m-sec-butylphenylcarbamate and its mixture with its corresponding o- and p-isomers is the compound not methylated on the nitrogen or their isomer mixture somewhat superior in terms of effectiveness.

The two m-substituted new active ingredients defined above can be obtained either by reaction of m-sec.Butylphenol or its mixture with o- and p-sec.Butylphenol, with a carbamyl halide the general formula

Shark - CO - NH - R

II

where "Hai" means chlorine or bromine and R has the above meaning, or by reacting one reactive carbonic acid derivative of an m-sec-butylphenol of the general formula

O —CO —X

CH ₃

or a mixture of the o-, m- and p-isomers, in which X is a halogen atom or an alkoxy group means with ammonia or methylamine.

The N-methyl-O-m-sec-butylphenylcarbamate or its isomer mixture can also by reacting the corresponding sec-butylphenols with Methyl isocyanate can be obtained.

Instead of the pure m-sec-butylphenol, the easily accessible isomer mixture of the three sec-butylphenols is usually used as the starting material. This mixture of isomers can easily be obtained in a known manner by reacting phenol with sec.Butanol in the presence of a condensing agent, such as. B. zinc chloride, aluminum chloride, sulfuric acid, etc. ZnCl _{2 is} preferably used at 160 to 200 ° C. with a molar ratio of phenol to butanol to ZnCl ₂ = 1: 1.2: 2.2. This creates an isomer mixture of sec-butylphenols in which all three isomers are present in approximately the same amount.

309 778/363

No protection is claimed for the processes for preparing the active compounds. That by reacting the mixture of the three isomeric sec.Butylphenols with a carbamyl halide of The liquid carbamate isomer mixture resulting from general formula II surprisingly has approximately the same strong effect on the pests mentioned as the corresponding pure m-sec.Butylphenylcarbamate itself, nevertheless the pure o- and

condensation products of ethylene oxide into consideration. As a solvent for the production of Emulsion concentrates are suitable, for. B. cyclic hydrocarbons such as benzene. Toluene or in particular Xylene and ketones such as acetone. Butanone, cyclohexanone or methylcyclohexanone.

Suspensions can be obtained by suspending wettable powders in water, which in turn by combining solid active ingredients with

p-isomers less effective or almost ineffective io surface-active substances or of solid or liquidind. In the case of the isomer mixture, it is either a solid active ingredient with a solid powdery carrier and surfactants.

Furthermore, the active ingredients can also be used in organic

identical carbamate mixtures are formed.

The active ingredients are N-methyl-O-m-sec.butylphenylcarbamate, M.p. 57 to 59 ° C (from petroleum ether),

to assume a synergistic effect, or the absorption-improving properties of the mixture play a role a role.

The content of the mixtures of m-substituted Phe-15 solvents, e.g. B. in chlorinated hydrocarbons or carbamates can be z. B. by bromine substances such as trichlorethylene. or in medium petrol determine the secondary butylphenols or by means of leum fractions, if necessary with the addition of auxiliary substances Infrared spectra of secondary butylphenol mixtures and solvents, such as acetone or higher ketones, determine the carbamates obtained from it. It can be solved. Finally, the active ingredients can too from the IR spectra it can be seen that at Ver 20 in the form of aerosol, smoke or steam in the air Turn of normal and secondary butanols are used, especially in

Pantries or greenhouses. If desired, the biological effect

broaden the new resources by adding others

the isomer mixture of N-methyl-Oo-, -m- and 25 insecticidal active ingredients, such as. B. hexachlorocyclohexane -p-sek.butylphenylcarbamat, Kp. _{0 01} 106 to Hl ⁰ C, hexane, Dichlordiphenyltrichloräthan, toxaphene, CAI, and the isomeric mixture of o-, m- and p-sek.Butyl- ciumarseniat, (p -nitrophenyl) -diäthyl-thiophosphate, phenylcarbamate, Kp. _{0, 0008} 115 to 125 ° C, to mention. (3-chloro-4-nitrophenyl) dimethyl thiophosphate, [2-iso-The new active ingredients and their isomer mixtures propyl-4-methylpyrimidyl- (6)] diethyl thiophosphate, depending on the intended application method, 30 (/? , /? - dichlorovinyl) dimethyl phosphate. (: \ - Hydroxy in the usual way with suitable carriers and / ^, ^, / 3-trichloroethyl) -phosphonic acid dimethyl ester or or distribution agents to dusts, suspensions SO ^ -DicarbäthoxyäthyO-OO-dimethyl-dithiophosions, emulsions or solutions are combined, phat, of acaricidal or fungicidal substances, such as. B. which a fine distribution of the active ingredients on the S - ^ - chlorophenylmercaptomethylj-O ^ -diethyl-dithio before infestation by insects and / or ticks to 35 phosphate, S - (2,5 - dichloro - phenylmercaptomethyl) -protective plants , Animals and substrates guarantee 0,0-diethyl-dithiophosphate or N-trichloromethane strips.

For the application of the active compounds suitable dusts can, for. B. by mixing
solid or liquid active ingredients or by common 40
same mixing of solid active ingredients with a solid one
Carrier are produced. As such, come in
Question: Talc, diatomaceous earth, kaolin, bentonite,
Calcium carbonate, boric acid or tricalcium phosphate.
On the other hand, the substances can also be distributed evenly in 98 to 95 parts by means of butylphenyl carbamate (melting point 57 to 59 ° C in petroleum, a volatile solvent on the carrier substances)

sulfenyl-tetrahydrophthalimide. Methanesulfon - N - trichloromethanesulfenyl-p-chloro-anilide or sulfur, or from herbicidal substances.

Some typical application forms are given in the following examples.

example 1 2 to 5 parts of active ingredient, e.g. B. N-methyl-O-m-sec.

be raised.

For the preparation of emulsions, the active compounds can be used as such or after dissolution in organic solvents, such as. B. xylene, be emulsified in water, which has a surface-active Contains substance. For use in practice, however, it is usually more advantageous to go through first Combination of liquid active ingredients with surface

TaIk, e.g. B. by mixing the active ingredient with part of the talc and the concentrate obtained finely ground with the remaining talc.

This dust is suitable for. B. to combat of potato aphids.

Example 2

By mixing and then grinding active ingredients or solid or liquid active ingredients 55 10 parts of active ingredient, e.g. B. the mixture of N-Memit inert organic solvents and ober- thyl-Oo-, -m- and -p-sec.butylphenylcarbamate (Kp. ₀ , ₀₁ surface-active substances to produce concentrates, wel- 106 to Hl ⁰ C), with 82 parts of kaolin or chalk and before their turn single-phase systems, ie solutions, mixing with 8 parts of wetting and dispersing agents, or multiphase systems and with water z. B. processed with ethylene oxide condensation products to ready-to-use emulsions 60 alkyl phenols or higher alcohols can be obtained. Both a concentrate, which is cationic with 50 to 200 parts of water, such as. B. quaternary ammonium salts,
anion-active, such as. B. Soap, soft soap, salts of
aliphatic long-chain sulfuric acid monoesters,
long-chain alkoxyacetic acids and aliphatic-aro- 65
matic sulfonic acids, and as nonionic surfactants such. B. polyethylene glycol ether of
Fatty alcohols or of dialkylphenoien and poly-

a z. B. to combat fruit growing and viticulture pests, such as codling moth, excellently suitable Spray results.

Example 3

20 parts of active ingredient, e.g. B. The mixture of N-methyl-OO, -m- and -p-sek.butylphenylcarbamat (Kp. _{0, 01}

106 to lirC), 50 parts of xylene and 30 parts of ethylene oxide condensation product of alkylphenols are mixed to give an emulsion concentrate which, after dilution with 50 to 400 parts Water to combat ectoparasites, e.g. B. from ticks, excellently suited.

Example 4

1 to 2 parts of active ingredient, e.g. B. The mixture of ο-, ρ- ίο and m-sek.Butylphenylcarbamat (Kp. _{0, 0008} 115 to 125 ⁰ Q, are dissolved in 10 parts of xylene and 89 to 88 parts of petroleum of boiling range 180 to 22O ⁰ C and produce a spray which is particularly suitable, for example, for combating household and stored pests.

The superiority of the sec.Butylphenylcarbamates according to the invention over the best known analogous compounds of the O-arylcarbdamate series with regard to insecticidal action is evident from the following comparative tests: The best known compounds were compared with N-methyl-1-naphthylcarbamate (I) and N-methyl-Om-tert-butylphenylcarbamate (II) with the compounds according to the invention N-methyl-Om-sec. butylphenylcarbamate (III),
Mixture of the 0-, m- and p-isomers of N-methyl-O-sec-butylphenylcarbamate (IV) and mixture of the o-, m- and p-isomers of sec-butylphenylcarbamate (V).

The following comparison methods were used:

a) 10 mg of active ingredient were brought from acetone solution into Petri dishes and this after Chasing away the solvent with twenty houseflies each; the time it takes everyone to lie on their backs Flying passed was determined (contact test).

b) As a) but with a hundred grain beetles.

c) Aphids (Aphis fabae) on Vicia faba plants were mixed for 10 seconds from a distance of 50 cm O, 17oigen emulsions of the active ingredients sprayed, the The number of fallen animals was determined after certain periods of time (spray test).

d) DDT-resistant potato beetle larvae were placed on potato plants which had been previously sprayed with a 0.27 ₀ aqueous emulsion of the active ingredients. After certain periods of time, the dead and unable to walk are counted.

The results are compiled in the following table:

Ver (a) (b) try (d) am Parlors grain (c) Colorado beetle manure to fly Beetle sheet larvae _ 5 ^Ä lice 2 ^Λ : 1007ο I. - 2 ^A 24 ^A : 80% 30 ': 1007 ₀ II 40 ' 18 ' 24 *: 33% 15 ': 100% III 19 ' 1 ^Ä : 100% 30 ': 1007 ₀ IV - ■ 1 ^Ä 1 ": 100% 30 ': 1007ο V 5 ^A : 1007o

h = hours; '= Minutes; - = no effect.

The percentages in columns (c) and (d) indicate dead, fallen or unfit animals the specified time periods.

The new compounds, in particular the N-methyl-Om-sec.butylphenylcarbamate (III) or its mixture with the corresponding o- and p-isomers (IV) are thus the known compounds (I) and (II) in their activity against houseflies , Grain weevils and bean aphids and also to some extent against Colorado beetle larvae. The N-methyl-Om-sec.butylphenylcarbamate and its mixture with the corresponding o- and p-isomers is similar to the well-known N-methyl-1-naphthylcarbamate in the effect against meal moths, mealybugs, oleander scale insects and against ticks (argasines) , in particular leather ticks (ornithodorus moubata), and against mosquitoes (adult animals and larvae) of the genera Aedes, Culex and Anopheles and against other ectoparasites, e.g. B. bed bugs, clearly superior and surpasses it in the long-term effect against grain beetles quite considerably. The toxicity DL _{60 of} the mixture of the three isomeric N-methyl-O-sec.butylphenylcarbamates against mice and rats is 44 mm7kg per os.

Claims (1)

Claim: Means for combating insects and ticks, characterized by a Content of O-m-sec-butylphenylcarbamate or N - methyl - O - m - sec.butylphenylcarbamate, optionally mixed with the corresponding 0 and p isomers. 309 778/363 12.63 © Bundesdruckerei Berlin