DE3230775A1 - Aryl fatty acid propargyl esters, their preparation and use as insecticides - Google Patents

Abstract

The invention relates to aryl fatty acid propargyl esters of the general formula <IMAGE> where m is 0 or 1, R1 stands for hydrogen and, if m = 0, for cyano, thiocyanato, halogen, alkoxy having 1 to 4 carbon atoms and also for alkylthio groups having 1 to 4 carbon atoms, R2 denotes hydrogen and halogen, R denotes hydrogen, halogen, alkyl having 1 to 6 carbon atoms and methoxy and n is 0 or an integer from 1 to 5. The compounds according to the invention have insecticidal activity.

Description

Consortium for Electrochemical Munich, July 26th, 1982

_T,. ", _" LC-PAT / Dr.Ra / hu

Industry GmbH

Co 8202

Propargylic aryl fatty acid, their preparation and use as insecticides.

The invention relates to new propargylic aryl fatty acid esters, processes for their manufacture and their use as insecticidal agents.

Insecticidal agents which have an ethynyl group, an ester function and aryl groups as structural elements already known. For this, reference is made to E-PS 0 006 630, for example. These are mostly complex ones Molecules that are only accessible via correspondingly complex manufacturing processes.

A selection of aryl fatty acid propargyl ester has now been found, which, due to their relatively simple chemical structure, are more easily accessible and nonetheless survive characterized by high insecticidal potency.

The invention relates to compounds of the general formula

R R

II ²

CH (CH) -

^ 0-CH- C ^ CH

R *

- 2

where m is 0 or 1,

R. for hydrogen and, if m = 0, for cyano, thiocyanato, Halogen, alkyloxy with 1 to 4 carbon atoms as well as for Alkylthio groups with 1 to 4 carbon atoms, R_ means hydrogen and halogen,

R is hydrogen, halogen, alkyl having 1 to 6 carbon atoms and methoxy means and

η is O or an integer from 1 to 5.

R. preferably denotes hydrogen and halogen. Again, among the halogens are chloride, bromide and iodide, in particular Chloride preferred.

Examples of alkyloxy groups with 1 to 4 carbon atoms, those for R, are; .the methoxy-, the ethoxy-, the n-propyloxy-, the iso-propyloxy, the n-butyloxy, the isobutyloxy group ·, Especially the methoxy group.

Examples of alkylthio groups having 1 to 4 carbon atoms are the thio groups corresponding to the abovementioned Alkoj: y groups, in particular the methylthio group.

R "preferably represents hydrogen and chlorine. Further examples of R ₂ are bromide and iodide.

m = preferably 0.

R preferably denotes hydrogen, chlorine, bromine, iodine, methoxy, and also alkyl groups having 1 to 3 carbon atoms, namely Methyl, ethyl, n-propyl and iso-propyl. From the group of Halogens, chlorine is particularly preferred.

Further examples of R are alkyl groups such as η-butyl, ι isobutyl, tert-butyl, n-pentyl, isopentyl and n-hexyl.

η is preferably an integer from 0 to 4, in particular.

others 0 to 3 and particularly preferably 0, 1 or 2.)

For η = 1 the substituent is in ortho-, meta- or _; ·

para position, especially in para position to the fatty acid -

ester residue. If η = 2, the ortho / para and meta / para positions are \ |

If η = 3, the ο, ο ¹ , ρ 'substitution type is preferred. \\

If η = 4, a meta position is preferably unsubstituted. yy

Examples of compounds according to the invention are: Propargyl phenylacetate

Propargy of 4-methy 1-phenylacetic acid! . Propargyl 2,4-dimethyl-phenylacetate

Propargylic acid 4-chloro-phenylacetate Propargyl 2,4-dichloro-phenylacetate

Propargylic acid 3-chloro-phenylacetate \ ·

3 »4_Dichlorophenylacetic acid propargyl ester .1

Propargylic acid 4-bromo-phenylacetate. . ■]

Propargylic acid 3,4-dibromo-phenylacetate I ^

Propargylic acid 4-methoxy-phenylacetate \\

Propargyl 4-ethyl-phenylacetate H '

Propargylic acid 4-n-propyl-phenylacetate ;;

Propargylic 2.4.6-trichloro-phenylacetate h

Propargyl 4-methyl-phenyl-oC -bromoacetate 1

2 .4-Dimethyl-phenyl-Ci6 -bromo 'ssigsäurepropargylester ij

Propargyl propargylic acid 4-chloro-phenyl-O6 -bromoacetate i 2.4-dichloro-phenyl-c ^. -propargyl bromoacetate

Propargyl 4-methoxy-phenyl-oi-bromoacetate ■; ',

-A-

- 4 -

! Propargylic acid propargylic acid 4-Bromo-phenyl-oi- -bromoacetate

Propargyl propargylic acid 4-methyl-phenyl-O6 chloroacetate 2.4-Dimethyl-phenyl-oi-chloroacetic acid vopargyl ester ί 4-chloro-phenyl-ok-chloroacetic acid pro-argyl ester

; Propargyl propargylic acid 2.4-dichloro-phenyl-ol-chloroacetate

ί Propargyl propargylic acid 4-methoxy-phenyl-o6-chloroacetate

; Propargyl propargylic acid 4-methyl-phenyl-oC -cyanoacetate

, 4-chloro-phenyl- oL -cyanoacetic acid propargyl ester

2 .4-Dimethyl-phenyl-Ci6-propargylic acid ester 2.4-dichlorophenyl-oC-propargylic acid propargyl ester ψ. Propargyl propargylic acid 4-methoxy-phenyl-oC -cyanoacetate

I: 4-Ethyl-Phenyl- oC -cyanoacetic acid prepargyl ester

Propargyl propargylic acid 3.5-dichloro-phenyl-ol-cyanoacetate.

4-methyl-phenyl-oi. ^ propargyl methoxyacetate ^; Propargylic acid 4-chloro-phenyl-O6-methoxy-acetic acid

i ·; Propargylic acid 4-bromo-phenyl-oC-methoxy-acetic acid

[i 2.4-dichloro-phenyl-ca ^ -methoxy-acetic acid prepargyl ester

Propargylic acid 4-methoxy-phenyl-csi-methoxy-acetic acid

ί, ί, 4-chloro-phenyl-C3C -raethylthio-acetic acid propargyl ester

il 4-methyl-phenyl-oC -methylthio-acetic acid propargyl ester

) \ 4-Methoxy-phenyl- oL -methylthio-acetic acid propargyl ester

■ '4-chloro-phenyl-α-thiocyanato-acetic acid ^ propargyl ^ st ^ r

I '''. Propargylic acid 4-methyl-phenyl-w-thiocyanato-acetic acid

|! 4-methoxy-phenyl-a-thiocy? Nto-acetic acid prooargyl ester

i ". 2 ^ -Dichlorophenyl-o-thiocyanato-essJgssurspropargylester

'4-chloro-phenyl-a-ethoxy-2ssigs2urepropargylestsr

Propargylic acid 4-ethyl-phenyl-a-ethoxy-acetic acid 4-ethoxy-phenyl-a-ethoxy-acetic acid prronargylestr Propargylic acid 4-methoxy-phenyl-η-ethoxy-acetic acid

ß- (chlorophenyl) propionic acid propargyl ester ß- (4-bromophenyl) propionic acid propargyl ester ß- (4-Methoxyphenyl) propionic acid propargyl ester ß- (2,4-Dimethylphenyl) propionic acid propargyl ester ß-iChlorphenyD-a-chloropropionic acid propargyl ester Propargyl ß- (chlorophenyl) -a-bromopropionate Propargyl 2-chlorophenylacetate Propargyl 2-methoxyphenylacetate Propargyl 3-methoxyphenylacetate Propargylic acid 3,4-dimethoxyphenylacetate Propargylic acid 2-methylphenylacetate Propargylic acid 3-methylphenylacetate Propargylic acid 2-chloro-4-methylphenylacetate Propargylic acid 4-tert-butylphenylacetate Propargylic propargylic acid 2.4.6-trimethylphenylacetate Propargyl 4-isopropylphenylacetate Propargyl e-dichloro-S-methylphenylacetate Propargylic acid 4-fluorophenylacetate Propargyl phenyl-a-bromoacetate Propargyl pheny1-a-chloroacetate

The compounds according to the invention are prepared according to known esterification methods of propargyl alcohol nj.it the corresponding aryl fatty acids or their Derivatives.

A preferred process for making compounds of the formula

R ₁ R- O

I ¹ J ² , Il

.CH iCH) _m C.

where m is 0 or 1,

R. for hydrogen and, when m = 0 for cyano, thiocyanato, halogen, alkyloxy with 1 to 4 carbon atoms and for alkylthio groups with 1 to 4 carbon atoms, R ₉ denotes hydrogen and halogen, R denotes hydrogen, halogen, alkyl with 1 to 6 carbon atoms and methoxy means and
η 0 or an integer before »1 to 5 is characterized in that compounds of the formula

^R n

where R,, R ₂ , R, η and m have the meaning given above.

A for chloride, bromide, iodide, alkoxycarbonyloxy and acyloxy stands

with propargyl alcohol, optionally in the presence of an acid binder, implemented.

Among the alkoxycarbonyloxy groups are the methoxycarbonyloxy and the ethoxy group is preferred. Examples of acyloxy groups are the ßenzoyloxy and 2,2-dimethylpropionyloxy groups.

Tertiary amines such as triethylamine, pyridine, dimethylcyclohexylamine and others are particularly suitable as acid binders. used.

The reactions are mostly carried out in inert solvents such as benzene, toluene, xylenes, petroleum ether, cyclohexane and the like. I

executed. ¹ p

The reaction temperatures are in the range from -10 ⁰ C to 100 ⁰ C ¥ b,

The employed as starting substances Arylfettspuren or fe their derivatives are, if they are not already presentation on the market f \ lent, accessible by known methods: * j

Such aryl fatty acids for which m = 0 are, for example on the implementation of the corresponding benzyl halides, in particular of the corresponding benzyl chlorides with cyanide and subsequent saponification of the benzyl cyanide to give the corresponding Aryl acetic acid available. Mostly acidic saponification is used. In the case; that acid-labile aryl residues are present,

however, the basic hydrolysis of the cyanide is recommended. The cyanides mentioned are particularly advantageous as a result of the phase transfer-catalyzed reaction of the non-polar reaction Benzyl chlorides dissolved in organic solvents are accessible with an aqueous alkali metal cyanide solution. As a phase transfer

Mj ■ ι

% Catalysts can be quaternary ammonium or phosphonium · \ ϊ | use salts and crown ether.

above to produce the corresponding benzyl halides, in particular the 'H sondere the Benzylchlcride, a variety of synthesis \ l be followed because:

y The chlorination of, if appropriate, may be mentioned as an example

ti on the benzene nucleus containing further substituents toluene

i | compounds at the bensyl position, chloromethylation,

pi optionally substituted benzenes according to Blanc with chlorine

;,; hydrogen and formaldehyde in the presence of zinc chloride

^: j or in the case of less reactive benzene derivatives with oL -,

s oi ¹ - dichlorodimethyl ether in the presence of concentrated

'; Sulfuric acid.

To produce such compounds according to the invention for the m = 1, the corresponding ß-Arylpropionäuren are used as starting compounds, which in turn "by catalytic Hydrogenation with elemental hydrogen from the corresponding cinnamic acids are accessible. Suitable catalysts are i.a. Raney nickel, palladium on activated carbon and others

Those according to the invention substituted in the CC position to the ester function .Connections where m = 0 are available via the

* ti 1

• · ■ ·

speaking o6-halogenated arylacetic acids accessible, the optionally be subjected to a further nucleophilic exchange reaction. The o6 - halogenated aryl fatty acids are again available, for example, from Hell-Volhardt-Zelinski, wherein the fatty acid is halogenated with a mixture of chlorine and / or bromine and red phosphorus in the oö-position.

The compounds substituted in the o6 position to the ester function, for which m = 1 means sirxc · over the corresponding oC-halogen-ß-aryl-propionic acids accessible. The named Propionic acids can, for example, according to British Patent 1,077,194 by adding an aryldiazium halide, in particular of the chloride, of methyl acrylate and subsequent transesterification with formic acid.

The compounds according to the invention have insecticidal activity on. They are suitable for combating insects, especially beetles, butterflies and mites. Examples of beetles to be controlled according to the invention are those from the family of the Dermestidae, the Cucujidae, the Chrysomelidae, the Bruchidae, the Curculionidae and the Tenebrionidae.

Specific examples of beetle species to be controlled according to the invention are Sitophilus granarius, Sitophilus oriyzae, Oryzaephilus surinamensis, Dermestes maculatus, Tribolium castaneum Tribolium convusum, Acanthoscelides obtectus, Tenebrio molitor, Epilachna varivestis, and others.

Examples of the effects of mites are in particular the Tetranychus and Panonychus families. Special examples of effects

- 10 -

·· if ■ ■

- io -

are Tetranychus urticae and Panonychus ulmi.

In the order of the butterflies, the family of the peride in particular is combated. A special 'example is Pieris brassicae.

The insecticidal compositions according to the invention are particularly suitable for storage protection, e.g. B. to combat pests in food and grain stores.

To combat the pests, the agents are applied in effective amounts directly to the pests or their habitat. In the case of surface application, the application rates are generally 0.005-0.01 g of active ingredient per m ² .

The active compounds according to the invention can be applied alone or in a mixture with other pesticides, in particular insecticidal agents will.

In general, they are used as mixtures with solid or liquid diluents or as solutions in solid or liquid solvents are used, with active ingredient contents of 0.01 to 95 wt.

The mixtures or solutions are generally used as emulsion concentrates, Suspension concentrates, pastes, wettable powders, dusts, granulates or microcapsules are produced.

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Emulsion concentrates and pastes generally contain ' 10 to 60% by weight, preferably 15 to 40% by weight of active ingredient,

2 to 25% by weight of dispersing auxiliaries and organic solvents

solvent and / or water. ►

Wettable powders usually contain 10 to 80% by weight, preferably 15 to 70% by weight of active ingredient, 1 to 10 % by weight of dispersing agent.

excipients and 10 to 89% by weight of inert ingredients. <|

Granules and dusts contain inert ingredients as well as ΐ parts, binders and / or coating materials 1 to 10 fs

% By weight, preferably 5 to 10% by weight , of active ingredient. Ü

Applied according to the invention: \\

As dispersing aids z. B. alkyl and aryl sulfonates, Methyl cellulose, polymeric sulfonic acids and their salts, polyalcohols, fatty acid esters, fatty alcohol ethers, fatty amines;

as an organic solvent e.g. B. alcohols such as ethanol, butanols, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, Aromatics such as toluenes and xylenes;

as inert components e.g. B. kaolin, china clay, talc, Calcium carbonate, highly dispersed silica, silica gels, kieselguhr, diatones, gypsum, corn, meal, thickeners, such as starch, carboxymethyl cellulose;

as a binder z. B. Magnesium sulfate, plaster of paris, gum arabic; for example, the insecticides according to the invention are such as

- 12 -

t *: ι «··. t ■ ι

- 12 -

j is formulated as follows:

1. Emulsion concentrate: 50 % by weight of active ingredient _: 42 % by weight of N-methyl-pyrrolidone

8% by weight nonylphenol polyglycol ether

^; 2. Wettable powder: 50% by weight of active ingredient

41.5% by weight of silica (trade name

^:: "Silitin")

2 wt. 56 sodium lignosulfonate 5% by weight of alkyl polyglycol ether, ·,;. 1.5 wt% polypropylene glycol

'3. suspension concentrate .:
50 % by volume of active ingredient

5 wt% ethylene glycol

'1.5 wt -.% Highly dispersed silicic acid

; i ("HDK")

ί; 0.5% by weight of dust

* 5% by weight octylphenol polyglycol ether

38 wt -.% Water

The active ingredients according to the invention can be applied in any take place in a suitable form, which may be mentioned by way of example: pouring, spraying, atomizing, dusting, brushing, pickling.

The invention will now be explained in more detail using examples:

example 1

Vf Preparation of propargylic acid 2,4-dimethylphenylacetate

<! | a) in a mixture of 106 g of m-xylene, 531 g of concentrated

; - 13 -

Hydrochloric acid and 39 g of paraformaldehyde was introduced for 5 hours hydrogen chloride at 70 "C The organic phase was separated and distilled together with the toluene extracts of the aqueous phase have been in the boiling range of 96 -.. 100 ⁰ C at 12 Torr 105 g corresponding to 65% the theory obtained 2,4-dimethylbenzyl chloride.

b) 10 g of tetrabutylammonium bromide were added to 103 g of 2,4-dimethylbenzyl chloride (according to a) and 86 g of potassium cyanide in 50 ml of water. The exothermic reaction heated the reaction mixture to 60 "C. After the reaction had subsided, the organic phase was separated off and distilled. 89 g, corresponding to 94 % of theory, of 2,4-dimethylbenzyl cyanide were obtained. Boiling range 86 to 91" C at 0.05 Torr.

c) 85 g of 2,4-dimethylbenzyl cyanide (according to b) were stirred in 50% strength sulfuric acid ^{at 150 ° C. for 5 hours.} The mixture was then poured onto ice and made alkaline with 2η NAOH and finally the organic phase was extracted with ether.

The remaining aqueous phase was acidified with 2 η hydrochloric acid and the carboxylic acid obtained as a precipitate was taken up in ether. 96 g, corresponding to 84 % of theory, of 2,4-dimethylphenylacetic acid were obtained.

d) A solution of 16.4 g of 2,4-dimethylphenylacetic acid (according to c)) and 11 ml of thionyl chloride in 50 ml of cyclohexane was kept at 80 ^° C. until the evolution of gas ceased. Excess thionyl chloride was then distilled off together with cyclohexane. The remaining acid chloride was dissolved in 20 ml of toluene and added dropwise to a mixture of 6.2 g of propargyl alcohol and 15 g of triethylamine in 100 ml of toluene.

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- 14 -

The reaction temperature was 50 ^° C. The reaction mixture was finally taken up in 100 ml of ether, then extracted with 1 η hydrochloric acid and then with saturated sodium hydrogen carbonate solution. The organic phase was then dried with sodium sulfate and concentrated. The subsequent distillation produced 18.2 g of propargylic 2,4-dimethylphenylacetate, corresponding to 90 % of theory. Boiling range 91 - 93 ⁰ C at 0.05 Torr.

Example 2

The preparation of propargylic acid 4-chlorophenyl-oO-bromoacetate.

a) 16 g of elemental bromine were added dropwise at 90-100 ° C. to 18.9 g of 4-chlorophenylacetic acid chloride. After 21/2 hours, the excess bromine was stripped off. The crude product was finally ^{distilled at 90 to 96 °} C. and 0.05 torr 22.9 g, corresponding to 85 % of theory, of 4-chlorophenyl- ° ί- -bromoacetic acid chloride were obtained.

b) To a solution of 1.68 g of propynol and 5 g of pyridine in 20 ml of absolute toluene, a solution of 8.04 g of 4-chlorophenyl-cs-bromoacetic acid chloride (according to a)) in 20 ml of absolute toluene was added dropwise with stirring. The reaction mixture was then taken up in ether / water and the organic phase was separated off. This organic phase was finally extracted with 1 η hydrochloric acid and then with saturated sodium hydrogen carbonate solution, dried with sodium sulfate and concentrated. Distillation at 120 ° C. and 0.2 torr gave 5.2 g, corresponding to 60 % of theory, of propargyl 4-chlorophenyl-oL-bromoacetate.

- 15 -

- 15-

Example 3

Insecticidal activity of compounds according to the invention against Beetle. .

In each case 10 test animals were lined with filter paper Petri dishes with a diameter of 9.5 cm are counted and in a thermostatically controlled environment at 23 to 24 "C and for 6 hours Exposure (700 lux) retained. .

The active ingredients according to the invention were each applied by impregnating the filter paper with 1 ml of an aqueous solution formulated as a spray liquor and having the following concentration j J before the animals were placed in the Petri dish. \ l

The Kop.taktffektur.g was finally rated in% mortality. The following table shows the effective doses in the form of the active ingredient content in ppm, at which 50 %

of the treated animals were killed. \

- 16 -

Ki ι Ii go Ii M f I

J ^,. ,. O I I I t

I. - 16 -

Table 1

V>, active ingredient

Phenylacetic acid propargy lester

It 4-chloro-phenylacetic acid propargyl

fi ester

'> ϊ 4-Bromo-phenylacetic acid propargyl-

.i ;. ' ester

t; \ 2-chloro-4-methyl-phenylacetic acid

p propargyl ester

| S | 2.4-dichloro-phenylacetic acid propargyl

0 ester

fi 4-methoxy-phenylacetic acid propargyl

| "" i ester

l '< 2-methyl -. "» henylacetic acid propargyl-

■;] ester

: | Propargyl 4-methyl-phenylacetic acid

'.; ester

f; 2,4-dimethyl-phenylacetic acid propar- ',; gylester

Propargylic acid 4-ethyl-phenylacetate

^; 4-tert-butyl-phenylacetic acid

propargyl ester

Propargylic acid 4-chlorophenyl-cvC-chloro-acetic acid

^LD 50 in ppm at Sitophilus
grananus Sitophilos
oryzea 125 125 30th 125 60 60 60 30th 30th 60 125 125 15th 125 15th 15th 60 60 60 60 30th 125 60 125

- 17 -

Example 4

Insecticidal effectiveness of propargylic acid 4-chlorophenylacetate against various harmful organisms.

The procedure of Example 3 was repeated, whereby the insecticidal effectiveness of propargylic 4-chlorophenylacetate was tested against a selection of beetles. The effectiveness was rated in% mortality at the active ingredient concentrations given in the table below.

Table 2

Insecticidal effectiveness of propargylic acid 4-chlorophenylacetate.

Beetle

Oryzaephilus surinamensis Acanthoscelides obtectus Tribolium castaneu.n Tribolium confusum

% Mortality Active ingredient
concentra
options 80 125 90 125 100. 62 100 125

Example 5

Effectiveness of propargyl 4-chlorophenylacetate against Epilachna varivestis.

In each case 10 larvae or beetles of Epilachna varivestis were obtained

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V - 18 -

deposited in a beaker with a diameter of 9 cm and a height of 4.5 cm, which contained French bean leaves for food. The leaves and the test animals were each with 2 ml of a sprayed as a spray liquor formulated active ingredient solution of the concentration given below.

Results:

After 48 hours at an active ingredient concentration of 500 ppm for the larvae is 100% mortality, and for the beetles at an active ingredient concentration of 250 ppm one 80 56ige mortality determined.

Example 6

Effectiveness of propargylic 3,4-dichlorophenyl acetic acid against spider mites (Tetranychus urticae).

French beans grown in plastic pots under greenhouse conditions were infected with spider mites. The temperature in the greenhouse was 24 ° C. and the air humidity was 40-60 %. The exposure time at 800 lux was 8 hours.

3 days after infection, the tops and bottoms of the leaves of the French beans were sprayed with the active ingredient content 250 ppm, sprayed dripping wet.

5 days after application,% mortality was found to be infestation rated.

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r · · · · «tit

It ·· · ·

t t ·· ι »· ■:

- 19 -

Result; _:

i; Mortality in the larvae 96 % ;),

Mortality in d- ^ n adults 92 %. ^

H example 7 jl

Effectiveness of ß- (4-chlorophenyl) -propionic acid propargyl ester i | against Pieris brassicae.

In beakers (diameter 9 cm, height 4.5 cm) containing cabbage leaves as food, 10 larvae of the large cabbage white butterfly (Pieris brassicas) were counted. Ever been beaker! 2 ml of a spray liquor containing ß- (4-chlorophenyl) propionpropargyl; ester in a concentration of 500 ppm, ₍ sprayed .

After 2 days, the larvae were rated for destruction.

Result;

The mortality was 80 %.

Claims (3)

Patent claims: Ii compounds of the general formula O CH ₀ C ^ = - CH J t "n ² il where m is 0 or 1, R, for hydrogen and, if m ^ 0 for cyano, thiocyanato, halogen, alkyloxy with 1 to 4 carbon atoms and for alkylthio groups with 1 _: up to 4 carbon atoms, R means hydrogen and halogen R is hydrogen, halogen, alkyl having 1 to 6 carbon atoms and methoxy means and η is 0 or an integer from 1 to 5. 2. A method for producing compounds according to claim 1, characterized in that compounds the formula R ₁ ^ ι I. JQ-CH- ( ^R n ■ III · · ο · 1 I t where R ,, R-, R, η and m have the meaning given according to claim 1 own, and A represents chloride, bromide, iodide, alkoxycarbonyloxy and acyloxy with propargyl alcohol, optionally in the presence of an acid binder implemented. 3. Insecticidally active compositions which contain at least one compound according to claim 1.