DE1143052B - Pest repellent with insecticidal and acaricidal effects - Google Patents

Description

The invention relates to pesticides which have insecticidal and acaricidal properties.

Various organic phosphoric acid esters are already for use as pesticides in agriculture and horticulture, particularly known as aphicides and acaricides.

There have now been new compounds with an advantageous ratio of insecticidal activity found to mammalian toxicity and thus a reduced risk of poisoning.

The compounds according to the invention correspond to the general formula

RO

R ₁ O

PS-CH ₂ -CONR ₁ -COOR ₂ I.

in which R and R ₁ , which can be identical or different, denote alkyl radicals each having 1 to 4 carbon atoms.

R ₂ denotes an aliphatic radical which can be substituted by one or more of the following substituents: halogen atoms, amino radicals, substituted amino radicals, nitro groups, alkoxy radicals, alkylthio radicals, sulfoxy radicals and sulfonyl radicals, the aliphatic group not containing more than 12 carbon atoms. R ₂ can also mean an araliphatic radical, a substituted araliphatic radical or an optionally substituted naphthyl radical. R ₃ represents an alkyl radical with 1 to 4 carbon atoms or an alkenyl radical with 3 carbon atoms.

The radicals R ₂ and R ₃ can be identical to or different from one another.

Preferred new compounds according to the invention are those in whose general formula R _{2 is} an alkyl radical with 1 to 12 carbon atoms, an alkenyl radical with 3 to 12 carbon atoms or a benzyl, p-nitrobenzyl, naphthyl, / S-chloroethyl, means a / S-fluoroethyl, a / 3-ethoxyethyl, a / 3-ethylthioethyl, a dimethylaminoethyl or a diethylaminoethyl radical.

Very particularly preferred compounds are those in whose general formula R _{2 represents} an alkyl radical having 1 to 4 carbon atoms, since these compounds are generally oils at ordinary temperatures, which considerably simplifies their preparation for use.

Thus, R and R _{1 can be} methyl, ethyl, n-propyl, isopropyl or butyl.

Pesticides
with insecticidal and acaricidal effects

Applicant:

The Murphy Chemical Company Limited, St. Albans, Hertfordshire (Great Britain)

Representative: Dr. F. Zumstein,

Dipl.-Chem. Dr. rer. nat. E. Assmann

and Dipl.-Chem. Dr. R. Koenigsberger,

Patent Attorneys, Munich 2, Bräuhausstr. 4th

Claimed priority:

Great Britain May 21 and November 8, 1957

and V. St. v. America December 20, 1957

(No. 16 151, No. 34 910 and No. 704 002)

Max Pianka and Donald John Polton,

St. Albans, Hertfordshire (UK),

have been named as inventors

R ₂ can be methyl, ethyl, n-propyl, isopropyl, η-butyl, tert-butyl, n-hexyl, cyclohexyl, n-nonyl, dodecyl, allyl, isopropenyl, chloroethyl, fluoroethyl, benzyl, nitrobenzyl, naphthyl, / J Ethoxyethyl, ethylthioethyl, dimethylaminoethyl, diethylaminoethyl and R ₃ denote methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or allyl.

If the compounds of the invention contain basic groups in the radical R ₂ , it will be apparent that acid addition salts of such compounds can be prepared, and it will be understood that such salts fall within the scope of the present invention, e.g. B. the hydrochlorides and other salts of inorganic acids and salts of organic acids such as the acidic oxalates. These salts are often of value for the systemic treatment of plants.

The compounds according to the invention generally have a pronouncedly strong insecticidal and / or acaricidal effect. In particular, they have a similar structure compared to many compounds particularly favorable ratio of insecticidal

309 507/318

or acaricidal activity on mammalian toxicity. Some of the new compounds also have how mentions the advantage of being oils at ordinary temperatures, while many similar compounds Are solids. This advantage is particularly valuable for the preparation.

Compounds according to the invention which are of particular interest with regard to their high acaricidal and insecticidal properties Have effectiveness are:

ated phosphoric acid, with chloroacetyl carbaminates implemented.

The compounds of the invention can be formulated for use in any desired manner will. In general, such preparations will contain the insecticidal compound together with a suitable carrier or diluent. Such carriers can and should be liquid or solid by dispersing the toxic substance, its

a) O.O-diethyl-S-iN-acetyl-N-methyl-äthylcarbami- io ease of use.

nat) dithiophosphate (this compound has a liquid formulations thus include solutions

d d

particularly favorable ratio of acaricidal and insecticidal effectiveness to mammalian toxicity),

b) ©, O-diethyl-S-iN-acetyl-N-ethyl-ethyl carbaminate) -dithiophosphate,

c) ©, O-diethyl-S-iN-acetyl-N-isopropyl-ethyl carbaminate) dithiophosphate.

Other valuable compounds are: O-methyl-O-ethyl-S- (N-acetyl-N-methyl-ethylcarbaminate) -dithiophosphate, ©, O-diethyl-S-iN-acetyl-N-methyl-ethylsulfoxyethyl-carbaminate) dithiophosphate and O, O-diethyl-S- (N-acetyl-N-methyl-ethylsulfonylethyl-carbaminate) -dithiophosphate.

or emulsions that can be used as such or that can be made up with water or other diluents to form sprays and the like. In such cases the carrier is a solvent or emulsion base that is not phytotoxic under the conditions of use. In general, such preparations contain a wetting agent, dispersant or emulsifier.

Other liquid preparations include aerosols, in which the toxic substance together with a liquid carrier or propellant is present.

Solid preparations include dusts and wettable powders. Granules and pills and semi-solids

The compounds according to the invention can be used in preparations such as pastes. Such preparations can be made in any desired manner. One can be inert solids or liquid diluents Manufacturing process consists in containing a medium, such as clays, which

may themselves have wetting properties, and / or wetting agents, dispersants or emulsifiers.

Salt of the appropriate phosphorodithioic acid (or the free acid in the presence of an acid-binding agent)

with an N-chloroacetyl, N-bromoacetyl or N-iodine binder and / or adhesive, acetyl-carbamic acid esters can also be used preferably to be included in a fire. Solid preparations medium medium to implement. Another method of making the compounds of the above

given general formula I consists in a Compound of the general formula

RO,

S-X

II

R ₁ O

also include mixtures for thermal smoking devices in which the toxic substance is combined with a solid pyrotechnic component is present. The compounds according to the invention can, if desired in a mixture with compatible, non-basic insecticides and / or non-basic fungicides be used.

in which R and R _{1 have} the meanings given above and X is hydrogen, an alkali metal or ammonium, with a compound of the general formula

Y-CH ₂ CO NR ₃ -COOR,

III

example

0.0 - diethyl - S- (acetyl - N - methyl-methylcarbaminate) dithiophosphate (colorless oil with a refractive index n% ° - 1.5307)

20 parts of active ingredient were mixed with 30 parts of a polyethyleneglycol ether (Lissapol NX) and vei made up to 100 parts by volume with methanol. This solution was diluted with water and yielded a concentration of 0.0025% active ingredient

in which R ₂ and R ₃ have the meanings indicated above 50 99 ° / _o kill of aphids strength and a 85 ° / "represents strength and Y have chlorine, bromine or iodine, umzu- killing greenhouse red spider during immersion.

Further compounds of the general formula I were used under the same conditions. the biological results are shown in the table below.

The experiments listed in the table in the column labeled "Culture" were carried out in such a way that that broad-bean plants associated with Aphis fabae

ethyl ketone, methyl isobutyl ketone and dioxane, Aiko- ⁶ ° were infected, put into a standard culture solution, for. B. methanol, ethanol and isopropanol, were ether, z. B. diethyl ether and diisopropyl ether had been added to 0.05% of the active ingredient in hydrocarbon solvents, e.g. B. petroleum ether, to yield the culture. After 48 hours was a zol and toluene, halogenated hydrocarbons, e.g. B. to observe complete death of aphids, chloroform, carbon tetrachloride, methylene dichloride 65 from which it can be seen that the active ingredient is systemic and chlorobenzene called. Has properties because it is from a culture solution in

Preferably alkali salts, e.g. B. Sodium- taken up the roots of the bean plants and or potassium salts or ammonium salts of the substitute is transported to the leaves. As a result

set, optionally in the presence of a solvent, the process in the presence of an acid-binding agent Is carried out by means if X is hydrogen.

Suitable acid-binding agents are, for example, sodium or potassium carbonate and tertiary bases, z. B. pyridine and triethylamine. Suitable solvents are water, ketones, ζ. Β. Acetone, methyl

are made by the active ingredient after spreading through the system of the plant which is on the leaves or stems of the plant killed aphids.

R ₁ R ₁ R * R ₃ F.
( ⁰ C) 1.5091 Red S
Eintai
Conc
tration
(7o) run down
jchen
Mortification
(<7o) Einta
Conc
tration
(° / o) Leaf
jchen
Mortification
(° / o) lice
Ku
Conc
tration
(° / o) ltur
Mortification
(· /.) C ₂ H, C ₂ H, CH ₃ 1.5060 0.001 100 0.0025 100 0.05 100 C ₈ H ₅ nC ₄ H ₈ CH ₃ 0.005 98 0.005 100 C ₂ H ₅ 3-naphthyl CH ₃ 88 to 89 1.5071 0.005 81 C ₂ H ₅ C ₂ H ₅ C ₂ H, 1.4980 0.001 100 0.0025 100 0.05 100 C ₂ H ₅ C ₂ H, ISO-C ₃ H ₇ 1.5122 0.0025 100 0.005 100 0.05 100 C ₂ H ₅ C ₂ H, Allyl 1.4949 0.001 100 C ₂ H ₅ C ₂ H, nC ₄ H ₉ 0.0025 96 0.005 93

Claims (3)

PATENT CLAIMS:
1. Pesticides with insecticidal and acaricidal action, containing a compound of the general formula RO R ₁ O P _{-S-CH 9} CO-NRo-COOR ₂ I. in which R and R ₁ , which can be the same or different from one another, are alkyl radicals each having 1 to 4 carbon atoms, R _{2 is} an aliphatic radical which is replaced by one or more halogen atoms, amino radicals, substituted amino radicals, nitro groups, alkoxy radicals, alkylthio radicals, sulfoxy radicals and sulfonyl radicals may be substituted, the aliphatic radical containing no more than 12 carbon atoms, or an alkenyl radical with 3 to 12 carbon atoms, or an optionally substituted araliphatic, or an optionally substituted naphthyl _{radical and R 3} an alkyl radical with 1 to 4 carbon atoms or an alkenyl radical with 3 Mean carbon atoms, or an acid addition salt of a basic compound of this formula together with a carrier or diluent. 2. Pesticide according to claim 1, containing a compound in the general formula of which R _{2 is} an alkyl radical having 1 to 4 carbon atoms. 3. Pesticides according to claims 1 to 2 in the form of a solution, a Emulsion, an aerosol, a dusting agent, a wettable powder, a granulate, a pill, a paste or mixture for a thermal smoking device. Considered publications:
German patent specification No. 963 872. © 309 507 / Ϊ18 1.6?