NL7908503A - M- (P-BROMOMENOXY) -ALPHA-CYANBENZYL TRANS- OR TRANS- -RICH-2,2-DIMETHYL-3- (2,2DICHLOROVINYL) CYCLOPROPANIC CARBOXYLATE, METHODS FOR PREPARING THIS COMPOUND, AND / OR ANYTHING ACARICIDE PREPARATIONS OF LOW TOXICITY FOR MAMMALS AND / OR FISH CONTAINING THE COMPOUND - Google Patents

Description

4 49 392 / Bos / AS 1 * m- (p-Bromophenoxy) - tt-cyanobenzyl trans- or trans-rich- 2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropane carboxylate, methods of preparing this compound as well as insecticidal and / or acaricidal compositions of low toxicity to mammals and / or fish containing the compound.

The present invention relates to m- (p-bromophenoxy) - «- cyanobenzyl trans- or trans-rich 2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylate of the formula 1, on the preparation of this compound, on an insecticide and / or acaricide containing the compound as an active ingredient, on an insecticide and / or acaricidal composition of low fish toxicity and / or low mammalian toxicity characterized in that it compound of the formula I and contains at least one organophosphorus ester of the formula 2 of the formula sheet, wherein R 1 and each an alkyl group having 1-4 carbon atoms, X 1, X 2 and X 2 each an oxygen or sulfur atom, Y 2 and Y2, which may be the same or different, each represent an alkyl group of 1-3 carbon atoms, methyl mercapto, cyano or nitro group or a halogen atom (chlorine, bromine) and Z represent a carbon or nitrogen atom and n is 0 or 1, and / or a carbamic acid ester of the formula 3 of the formula sheet, wherein R is a gross ep is of the formula 4 or 5 of the formula sheet, wherein X represents an alkyl or alkoxy-25 group having 1-4 carbon atoms and η is 1 or 2, in a ratio of 1-100 parts by weight of the compound containing the formula 1 to the ester of formula 2 and / or 3, and to an insecticide and / or acaricide obtained by mixing this preparation with a carrier or diluent and, if necessary, an additive.

The term "trans-rich" means that the trans / cis ratio is not less than 75/25.

An insecticide is one of the indispensable products for maintaining agricultural production at a high level through the eradication of a wide variety of insect pests that damage agricultural crops. Furthermore, an insecticide provides a very effective means of achieving the object of the 790 85 03 * 2 i

> I

prevent infectious diseases from spreading through the eradication of those insects that transmit most such diseases. Thus, the role the insecticide plays in maintaining an expected higher standard of living for humanity is of great importance. Numerous excellent insecticides have so far been invented and successfully brought to real application in various fields. On the other hand, however, organochlorine insecticides such as BHC (benzenehexa-10 chloride) and DDT (1,1,1-trichloro-2,2-bis (p-chlorophenyl) -ethane) have become significantly limited in their applications due to the emergence of insect pests that are resistant to these compounds, as well as the problems of environmental pollution and their toxicity to 15 different organisms that are not the target of the control. The problem of resistant insects has become increasingly urgent with other insecticides, such as those of the organic phosphate ester type and the carbamate type, which were expected to replace the organochlorine insecticides. Under these conditions, the arrival of new and improved insecticides with suspense is expected.

Among the properties characteristic of an improved insecticide are today considered to be particularly required, apart from a high insecticidal activity, low toxicity to organisms which are not the target of control, including humans and animals, and essentially non-persistence in order to minimize environmental pollution. Natural pyrethrin possesses some of the characteristics listed above that are required for an improved insecticide, as it has low toxicity to humans and animals and is easily decomposable under outdoor environmental conditions. However, the natural pyrethrin, in comparison to organic phosphate esters and carbamate compounds, is inferior in insecticidal activity, worse in residual activity because of too rapid decomposition and more expensive. For these reasons, the use of natural 790 85 03 Λ 3 ƒ pyrethrin is limited to such areas as insect control in the household and the like (EMMrak, "Advantages and Disadvantages of Pyrethrum", in "PYRETHRUM" (JECasida), Academy Press, New York and 5 London (1973) pp. 307-311).

A large number of studies were undertaken to make up for the defects of natural pyrethrin and as a result, several superior synthetic pyrethroid insecticides were generated.

Of these, in particular, those described in Nature, 248, 710 (1974) by M. Elliott et al., British Patent No. 1,413,491 and U.S. Patent 3,996,244, are characterized by (1) exceptionally high insecticidal activity and rapid attack, (2) sufficient residual activity without persistence for the environment as long as that of an organochlorine insecticide, (3) comparatively low toxicity to humans and animals, and (4) exceptional insecticidal activity against pests of insects that are resistant to relative to organic phosphate esters and / or carbamates. As a result, studies are now being undertaken on a global scale to bring these synthetic pyretroids into practical application; in some districts where the spread of resistant pests is becoming more significant, the real application has already begun.

However, as demonstrated by J. Miyamoto in "Environmental Health Perspectives", 14, 15 (1976), pyretroid insecticides, including natural pyrethrin, generally exhibit high toxicity to fish. Insecticides are used to a great extent for controlling insect pests in paddy fields, for controlling aquatic insect pests, such as mosquito and mosquito larvae, and for applying them over the air in an area where there are lakes, ponds or rivers. Scattered. It is predictable that application of the superior synthetic pyretroid insecticides to the above areas will be limited 7S0 8 5 03 κ 4 due to their toxicity to fish. For this reason, reducing the toxicity of pyretroids to fish is an urgent problem.

Based on the idea that insecticides will make a big step forward when compounds can be successfully developed that combine the aforementioned strengths of the pyretroid insecticides with low toxicity to fish, cbor applicant was extensively investigated and as a result 10 found that of the geometric isomers based on the steric configuration of the carboxyl group of the compound of formula 1, the trans isomer and preparations obtained by mixing the compound of formula 1 with at least one organophosphorus ester with the formula 2 and / or carbamic acid ester of the formula 3 have the characteristics which meet the aforementioned objectives. In this way, the present invention was accomplished.

In particular, when the preparations according to the invention contain the compound of the formula 1 and the organophosphorus ester of the formula 2 and / or carbamic acid ester of the formula 3 in a weight ratio of 1 to 100, they exhibit a synergistically increased control effect against harmful organisms, but their toxicity does not exceed the sum of the toxicity of each component. Therefore, the compositions of the invention are of great importance in bringing about the eradication of the aforementioned aquatic insects.

Although part of the compounds according to the invention has been broadly described in German Offenlegungsschrift 2,615,435.8, no specific description is found therein with regard to structural formula, physical constants, insecticidal activity, fish toxicity and mammalian toxicity. the compounds of the invention.

While having exceptional insecticidal and acaricidal activity, the compounds of the invention are low in fish toxicity (eg carp, "killifish", rainbow trout and blue gill "). They are therefore suitable for controlling aquatic insect pests, such as those found, for example, in paddy fields, lakes and marshes, ponds and pools, rivers, or forest areas in which they are spread. Since they also exhibit low toxicity to warm-blooded mammals (eg, mice and rats) and low phytotoxicity to crops, their fields of application are very wide.

Because of their high insecticidal activity and high residual activity, they are useful for controlling the following wide variety of insect pests, in particular for controlling Nephotettix cincticeps which is resistant to conventional insecticides and needs a new insecticide for its control .

In rice fields: 20 Hemiptera;

Delphacidae (plant cicadas) (e.g. Sogatella furcifera, Nilaparvata lugens, Laodelphax striatellus)

Deltocephalidae (leaf cicadas) 25 (e.g. Nephotettix cincticeps, Tettigela viridis,

Inazuma dorsalis)

Aphididae (aphids) (e.g. Rhopalosiphum padi)

Pentaomidae (scabies, scale insects) 30 (e.g. Nezara antennata, Aeschynteles maculatus,

Leptocorixa corbetti, Eysarcoris ventralis)

Lepidoptera (moths and butterflies) (e.g. Chilo suppressalis, Tryporyza incertulas, Choristoneura fumiferana, Dendrolimus spectabilis, 35 Susumia exiqua, Cnaphalocrocis medinalis, Sesamia interens)

Coleoptera (beetles) (e.g. Oulema oryzae, Echinocnemus squameus) 790 35 03 r 6

Diptera; (e.g. Agromyza oryzae, Chlorops oryzae,

Hylemya platura, Aedes aegypti, Anopheles stephansi,

Culex pipiens pa-liens) 5 Aearina (mites) (e.g. Tetranychus cinnabarinus, T. urticae, Oiigonychus hondoensis)

The ester according to the invention / represented by the formula 1 consists in the form of optical isomers, consequently of the asymmetric carbon atoms in both the carboxylic acid and the alcohol component. An ester prepared by conventional methods is a mixture of such isomers. All isomers are within the scope of the invention.

A main object of the invention is to provide a new cyanobenzyl carboxylate of the formula 1 which is useful as an insecticide and acaricide.

Another object of the invention is to provide a process for preparing the cyanobenzyl carboxylate of the formula 1.

A further object of the invention is to provide an insecticidal or acaricidal composition containing this cyanobenzyl carboxylate of the formula 1.

These and other objects and advantages of the invention will become apparent from the foregoing and the following descriptions.

The cyanobenzyl carboxylate of the formula 1 of the invention can be prepared by various methods, typical examples of which will be described below.

Preparation Method A, by reaction between an alcohol and a carboxylic acid halide.

An alcohol of the formula VI of the formula sheet 35 and a trans-acid halide, preferably trans- or trans-rich acid chloride, of the formula 7 of the formula sheet, wherein X represents a halogen atom (bromine, chlorine, iodine), react in the presence of a 790 85 03 t * 7 organic tertiary base (e.g. triethylamine or pyridine) in an inert solvent (e.g. benzene, toluene, ether or hexane) at -30 ° to 100 ° C for 30 min to 10 hours to obtain the intended ester.

Preparation method B, by reaction between an alcohol and a carboxylic anhydride.

A mixture of an alcohol of formula 6 and a trans- or trans-rich carboxylic anhydride of formula 8 of the formula sheet is reacted in an inert solvent (eg benzene, toluene, hexane or acetone) at -20 ° 100 ° C for 1 to 10 hours to obtain the intended ester.

Preparation method C, by reaction between an alcohol 15 and a carboxylic acid.

A mixture of an alcohol of the formula 6 and a trans- or trans-rich carboxylic acid of the formula 9 of the formula sheet is reacted in an inert solvent (eg benzene, toluene or xylene) in the presence of a dehydrating condensing agent (e.g. dicyclohexylcarbodiimide) at 0 ° to 150 ° C for 30 min to 10 hours to obtain the intended ester.

Preparation Method D, by reaction between a halide 25 and an organic tertiary base salt of a carboxylic acid.

A mixture of a halide of formula 10 of the formula sheet, wherein Y represents a halogen atom (bromine, chlorine, iodine) and a trans- or trans-rich carboxylic acid of the formula 9 is reacted with an organic tertiary base (eg triethylamine or trimethyl amine) in an inert solvent (e.g., acetone, benzene or dioxane) to convert the carboxylic acid into its salt and the whole mixture is reacted at 0 ° to 150 ° C for 30 min to 10 hours to obtain the intended ester.

Preparation Method E, by reaction between a halide and an alkali metal salt of a carboxylic acid.

790 85 03 '8'

A mixture of a halide of formula 10 (wherein Y has the above meaning) and an alkali metal salt of a trans or trans-rich carboxylic acid of formula 11 of the formula sheet, wherein M is an alkali metal (e.g. sodium or potassium ) is reacted in a two-phase system of water and an inert solvent (eg toluene, heptane or benzene) in the presence of a phase transfer catalyst (eg tetra-n-butylammonium bromide or benzyltriethylammonium chloride) at 0 ° to 150 ° C

for 30 minutes to 10 hours to obtain the intended ester.

Preparation Method F, by reaction between an aldehyde, an alkali metal cyanide and an acid halide.

15 F-1. A mixture of an aldehyde of the formula 12 of the formula sheet with an alkali metal cyanide and a trans or high sulfur halide formula 7 (wherein X is as defined above) is reacted in an inert solvent (e.g. benzene or toluene) in the presence of a phase transfer catalyst (e.g., dibenzo-18-crown-6 or dicyclo-hexyl-18-crown-6) at 0 ° to 150 ° C for 30 minutes to 20 hours to obtain the intended ester.

F-2. A mixture of an aldehyde of the formula 12, an alkali metal cyanide and a trans- or trans-rich acid halide of the formula 7 (wherein X has the above meaning) is reacted in a two-phase system of water and an inert solvent (eg benzene, hexane or toluene) in the presence of a phase transfer catalyst (eg tetra-n-butylammonium bromide or benzyltriethylammonium chloride) at 0 ° to 100 ° C for 30 min to 10 hours, to obtain the intended ester .

The cyanobenzyl carboxylate obtained by any of the above-mentioned methods can, if necessary, be purified by, for example, chromatography or distillation.

OC cyanobenzyl alcohol, one of the starting materials 790 85 03 9 materials, is readily obtained from a corresponding aldehyde by the method described by C. Hilgetag et al. In "Preparative Organic Chemistry", biz. 875. The halide can be obtained in good yield from the above alcohol by using a halogenating agent such as phosphorus halide, according to the method described in "Organic Synthesis" / Coll. Vol. III / biz. 793. trans and trans-rich 2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylic acid 10 can be obtained by the method described in Nature 246/169 (1973) by M. Elliott et al. , Pestic. Sci. 5,791 (1974) by M. Elliott et al. And published Japanese Patent Application 95045 (1976). The carboxylic acid chloride and the carboxylic anhydride can be obtained in good yields from the carboxylic acid according to the method described by R.B. Wagner et al. In "Synthetic Organic Chemistry" / biz. 546 and biz. 558.

Practical and presently preferred embodiments of the preparation of the cyanobenzyl carboxylate of the formula 1 are illustrated in the following embodiments.

Example I (Preparation Method A).

0.95 g (12.0 mmol) of pyridine was added to a solution of 1/82 g (6/0 mmol) of m- (p-bromophenoxy) oucyanobenzyl alcohol in 10 ml of anhydrous benzene.

To the resulting mixture, while stirring and maintaining the temperature below 5 ° C in an ice bath, a solution of 1.37 g (6.0 mmol) of dl-trans-2/2-dimethyl-3- (2 was added dropwise). 2-dichlorovinyl) -30 cyclopropanecarbonyl chloride in 5 ml anhydrous benzene. After the addition was complete, the reaction mixture was allowed to react at room temperature and stirred overnight. After dissolving the precipitated pyridine hydrochloride by adding water to the reaction mixture, the aqueous layer was separated. The organic layer was washed with 5% hydrochloric acid, saturated aqueous sodium hydrogen carbonate solution and then saturated aqueous sodium chloride solution.

790 85 03 10

After drying over anhydrous sodium sulfate, the aqueous layer was evaporated under reduced pressure. The residue was chromatographed on silica gel to give 2.76 g of m- (p-bromophenoxy) -1-cyanobenzyl dl-trans-2,2-dimethyl-5- 3- (2,2-dichlorovinyl) cyclopropanecarboxylate as a pale yellow liquid (93% yield).

Example II (Preparation Method B).

To a solution of 1.82 g (6.0 mmol) m- (p-bromophenoxy) -ct-cyanobenzyl alcohol in 10 ml toluene 10 2.40 g (6.0 mmol) dl-trans-rich (cis / trans = 20/80) - 2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylic anhydride. The resulting mixture was stirred at room temperature for 3 hours and then heated at reflux for 1 hour. After cooling, the reaction mixture was washed with a 5% aqueous sodium hydroxide solution to remove the carboxylic acid. The organic layer was washed with saturated aqueous sodium chloride solution and dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure to obtain 2.85 g of m- (p-bromophenoxy) -Λ-cyanobenzyl dl-trans-rich (cis / trans = 20 / 8Q) -2,2-dimethyl-3- (2,2-dichlorovinyl) -cyclopropanecarboxylate was obtained as an orange liquid (96% yield).

Example III (Preparation method Cj.

To a solution of 1.52 g (5.0 mmol) m- (p-bromophenoxy) -Ct-cyanobenzyl alcohol and 1.05 g (5.0 mmol) dl-trans-2,2-dimethyl-3- (2 2-dichlorovinyl) cyclopropanecarboxylic acid in 10 ml anhydrous benzene, 2.06 g 30 (10 mmol) dicyclohexylcarbodiimide was added. The mixture was stirred overnight. The precipitated dicyclohexylurea was removed by filtration and the filtrate was evaporated. The residue was chromatographed on silica gel to give 2.28 g of m- (p-bromo-35-phenoxy) -1-cyanobenzyl dl-trans-2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylate pale yellow liquid (92% yield).

Example IV (Preparation Method D).

790 8 5 03 11

To a solution of 2.2 g (6.0 mmol) m- (p-bromophenoxy) -1-cyanobenzyl bromide and 1.50 g (7.2 mmol) dl-trans-2,2-dimethyl-3- (2 2-dichlorovinyl) cyclopropanecarboxylic acid in 20 ml of acetone was added dropwise, with stirring at 15 ° 5 to 20 ° C, a solution of 0.81 g (8.0 mmol) of triethylamine in 5 ml of acetone. The mixture was then allowed to reflux for 2 hours and then cooled to room temperature. The reaction mixture was filtered to remove the precipitated triethylamine hydrobromide and the filtrate was evaporated under reduced pressure. The residue was chromatographed on silica gel to yield 2.58 g of m- (p-bromophenoxy) -1-cyanobenzyl dl-trans-2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropane-15 carboxylate. pale yellow liquid (87% yield).

Example V (Preparation Method E).

A solution of 2.20 g (6.0 mmol) m- (p-bromo-phenoxy) -d-cyano-benzyl bromide in 10 ml of toluene and a solution of 1.66 g (7.2 mmol) of sodium dl-trans- rich (cis / trans = 20/80) -2,2-dimethyl-1-3- (2,2-dichlorovinyl) -cyclopropane carboxylate in 7 ml of water were mixed.

After adding 0.081 g (0.25 mmol) of tetra-n-butyl ammonium bromide, the mixture was stirred at 70 ° to 80 ° C for 4 hours. The reaction mixture was washed with saturated aqueous sodium chloride solution and dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure to yield 2.88 g of m- (p-bromophenoxy) - t-cyano-benzyl dl-30 trans-rich (cis / trans = 20/80) -2,2-dimethyl-3- ( 2,2-dichlorovinyl) cyclopropanecarboxylate was obtained as an orange liquid (yield 97%).

Example VI (Preparation Method F-1).

To a suspension of 0.44 g (9.0 mmol) of sodium 35 cyanide and 0.10 g of dibenzo-18-crown-6 in 10 ml of anhydrous benzene was added dropwise with stirring at room temperature. 1.66 g (6.0 mmol) m- (p-bromophenoxy) benzaldehyde and 1.43 g 730 8 5 03 f 12 (6.30 mmol) dl-trans-2,2-dimethyl-3- (2, 2-dichlorovinyl) -cyclopropanecarbonyl chloride in 10 ml anhydrous benzene. The mixture was then further stirred overnight. The reaction mixture was washed with saturated aqueous sodium chloride solution and the solvent was evaporated. The residue was chromatographed on silica gel, yielding 2.82 g (m- (p-bromophenoxy) -'-cyanobenzyl dl-trans-2,2-dimethyl-3- (2,2-dichloro-vinyl) cyclopropanecarboxylate obtained as a pale yellow liquid (yield 95%).

Example '' VII (Preparation method F-2).

To a solution of 0.37 g (7.5 mmol) sodium cyanide and 0.012 g (0.037 mmol) m-phenoxybenzyltriethyl ammonium chloride in 5 ml water was added dropwise, with stirring at room temperature, a solution of 1.39 g (5 .0 mmol) m- (p-bromophenoxy) benzaldehyde and 1.19 g (5.25 mmol) dl-trans-2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarbonyl chloride in 10 ml toluene. The resulting mixture was stirred at room temperature for 20 hours and then washed with saturated aqueous sodium chloride solution. The organic layer was dried over anhydrous sodium sulfate and the solvent was evaporated, yielding 2.42 g of m- (p-bromophenoxy) -1-cyanobenzyl dl-trans-2,2-dimethyl-25- (2,2- dichlorovinyl) cyclopropanecarboxylate was obtained as an orange liquid (98% yield).

The compound of formula I obtained has the following characteristics: 790 0 5 03 13

.¾ .. dP dP dP ·· dP dP cP. · DP dP dP

irt C CO CN <sO ^ kO VO CO fiOOO H

5 ο ο h m <Ti ccovoco 0) cm t "o <3>, ti co cn cm ^ cintM £ Γ2 ^ ^ | h om (Dm Om 0 Rj> ^ yyy ......

H§ OÖKI2 möa »OOM1Z

m cj <n o ^ 1 r- m m <n * · tj \ - ”d r-l 5 x o

Ai (D * φ «Ö in U fi cn Q 00 ° ¢ 0 -H S c

M

8

5 H

i-l Ο H. *

£? 1 .S

N 'ö 2 c · τί r * I -p Cl O ^ CD oj (ti <D ® ^

Λ * · (Ö -3 ^ S

S m r-l S S 5 (ti> 1 £ ™ (Ö i w (ti II, c> i «8 Ü 1 Λ 3 £ £ 5 1 r-l 5-4 I ti V ti

*> 1 (ti ϊί Η Λ iL

0 rj ο V + J cm> 1

1 4-1 fi 1 ^ ** N

.— ^ ω ns?> ®N 2 g (ti> ι · Η Λ

x ”ft ο I U

O-ti 0 O w <n (ti

d I 54 fii I O

a) cm a to T-itH ö

44-0 ö ·, Η S

β (ΜΗ S M £; (ti OIO 0 I 4Jft 0 m> i p 2 g p m c o £ £ § ft b (d ^ (ti -rl a 1 5_j, —i I M (ti 0 0.43>, ft + * '7 *

- I d w I (Μ O

I i — 1 -Η I '“j * ·

g (ti> g Ό CM O

til fi -H Ό fl • rl Λ μ · - »rr Ο O r-l 01> z w" "7908503 14

As examples of the organophosphorus esters of the formula II the following compounds can be mentioned: 0.0-dimethyl 0- (3-methyl-4-nitrophenyl) phosphoacthioate 5 (Sumithion) 0,0-dimethyl 0- (3-methyl-4 - (methylthio) phenyl) thiophosphate (Baycid) 0,0-diethyl 0- (2-isopropyl-4-methyl-6-pyrimidinyl) -phosphorothioate (Diaginon) 10 0,0-dimethyl 0-4-cyanophenylphosphonium kioioate (Cyanox ) 0,0-di-n-propyl p-methylthiophenyl phosphate (Kayaphos) 0,0-diisopropyl S-benzylphosphone ± hiolate (IBP)

As examples of the carbamic acid esters of the formula 3 the following compounds can be mentioned: 1-naphthyl N-methyl carbamate (NAC) 3,4-xylyl N-methyl carbamate (MPMC) 3-methylphenyl N-methyl carbamate (MTMC) 2 sec .butylphenyl N-methyl carbamate ('BPMC) 20 2-isopropoxyphenyl N-methyl carbamate (PHC) 2-isopropylphenyl N-methyl carbamate (MIPC)

When applying the compound of the invention as an insecticide and / or acaricide, it can be used as such without mixing with other ingredients, but generally it is used in the form of a pesticidal composition by mixing with a carrier for improving its handling as a pesticide; and such a preparation can be further diluted before use if necessary.

In the preparation of pesticidal preparations, the compound of the invention may be formulated in a manner similar to that used in conventional pesticides using techniques 790 8 5 03 15 known to those skilled in the art and not other special precautions required.

The compound according to the invention can be used for the intended use in any of the forms such as emulsifiable concentrate, wettable powder, dusting powder, granules, fine granules, oil preparations, aerosol, heating smoke developing agent (mosquito coil, electrically heated mosquito mat), smoke-developing preparation such as a mist former, non-heated smoke de-10 coiling agent, poisoned bait, etc.

The compounds of the invention can be used in combinations of two or more members to enhance insecticidal and acaricidal activity. The activity may also be enhanced by incorporation with pyretroid synergists such as <X- (2- (2-butoxyethoxy) ethoxy) -4,5-methylenedioxy-2-propyltoluene (referred to as "piperonyl butoxide"), 1, 2-methylenedioxy-4- (2- (2-octylsulfinyl) propyl) benzene, 4- (3,4-methylenedioxyphenyl) -5-methyl-1,3-dioxane, N- (2-ethylhexyl) - Bicyclo [2,2,3,3] hepta-5-en-2,3-dicarboxyimide, octachlorodipropyl ether, isobornyl thiocyan acetate and others. synergists effective for pyretrins.

Although highly resistant to sunlight, heat and oxidation, the compound of the invention can be further stabilized against severe oxidative conditions by incorporation of an appropriate amount of stabilizers. Suitable stabilizers are antioxidants and ultraviolet absorbers, including phenol derivatives and bisphenol derivatives such as BHT (2,6-di-30 tert-butyl-4-methylphenol) and ΒΗΆ (2-tert-butyl-4-methoxyphenol) ); arylamines such as phenyl-naphthylamine, phenyl-i-naphthylamine and phenetidine-acetone condensate; and benzo-phenone compounds.

The insecticidal and / or acaricidal compositions according to the invention contain 0.001 to 80.0%, preferably 0.01 to 50% by weight, of an active ingredient.

Practical embodiments of the insecticidal or acaricidal compositions of the invention are illustrated with 7SO 85 03 16 in the following examples, wherein all parts and percentages are parts by weight and percentages by weight.

Sample preparation '1.

10 parts of the compounds (1) or (2) were mixed with 15 parts of "Sorpol 3005X" (a mixture of a non-ionic surfactant - polyoxyethylene phenylphenol derivative - and an anionic surfactant - alkylarylsulfonate -) and 75 parts of xylene. The mixture was carefully stirred, mixed and dissolved to give a 10% emulsifiable concentrate.

Preparation example 2.

0.2 part of the compounds (1) or (2) were dissolved in 20 parts of acton, mixed with 99.8 parts of clay with a particle size of 48 µm, carefully stirred and freed from the acetone by evaporation, to obtain a 0.2% dusting powder formulation of the compound.

Preparation example 3.

The compound (1) or its isomer with an acid portion in the dl-cis form was mixed with organophosphorus insecticides and / or carbamate insecticides, dissolved in acetone, mixed with PAP (isopropyl acid phosphate) and clay with a particle size of 48 µm and "white 25 carbon" if necessary, mixed by careful stirring and freed from the acetone by evaporation, to obtain dusts for dusting. The compositions of the different preparations are listed in Table A.

Table A.

730 8 5 03 17 0 g 1 1 1 «· = = ', 1 1 1 1 1« ‘] § CM 04

III

„Ë ë« Λ ^ ^ .....>: «^ ^ CO £ 1 <y \ <J \ ^

rH

g <10 = =. ..........

ffi CM

w

O

I I I

ui i ..... «.

r | j m <n

- *! §§ y 1 H 8 1 H

J I 55 µgSfflHSÖS

(¾ I u rt ff) I r.

e! | I

3 * 5 m «H m ö d d <8 ê B d m I I I I '1 o .9 UI Ή Ή Q ioi Q rj (-; a.s 5 a $ s i ||

Ij 'S IsIIè 11 ii J J S ï ί 0 ® “83 Λ 0? 1-1 Q HO) S'0 8 “1 ~ - H Cno ________ E U - * * * .........

η dm s ss § 3if sr p es ___ ’dS1 · - .OMCsin-M;

_μ ρ O i — 1 cM (v1'M, LnC0t ~ -CÖ (r> <H'-l'-l, -lrH

approx. ~ - - - - - - - - - - - 790 3 5 03 18

I I

a) <y -d = = = = 111111 ^ =

CN CN

III

J J J

'Ö Ό Ό ^ --- ^ Μ σ> er \ σι

I — I

a) j Ό 0

I I

0) = = = = = 0) =

fd tJ

n cm 1 till

& I

I I I s * 1 -aJ u 1¾ = = = = Ό = ro n rH1 g a g δ .2 8 8,,. . . , 3 .2 § 3 3 § ή ϋ ύ j> · Η ο N (ΰ -d-d i & <g fei & Mi

3 (Ö rl (Ö Q]? P

CO CQ P K H, CO CO

J

«Η · Η (D O

= = = .........

| SR * 3 .¾1 °

-Mil N H

ιΗ · Η ** d o ii o in S'f'SoS ^ oiHCMtn ^ LnG’f ^ 'γη dciclcliiCiCitiSCiüïï 790 8 5 03 19 β 01 pH _ _ _ _ _______ Ό

CM

β I.

-¾ 3 (1) 13 10 Β = = = = s s s in s ~ ιη <ν ^ «? ιη σ 'θ' Η

Ό_ _ _ _ --SESSS

CM

ο ο § § 5 β) 0) Φ J φ φ • I, Ό Ό Ό, ιιιι • d'O'Ü “Μ1 m ιη, in»

Ij | η | ri | p | h Ö Ö <r 3 _ _ _ _ 0) m s s s = Öi Ό Ό

g CM CM

i> I I I S 8 8 III

ë 3 5 i • H O N fd (¾ S ïS1 5 ï * 1 & h w S Q K fi 01 § * 5} Λ JLiJ «0) pH <D \ m -μ 01 in

I — i ® pH -HO

8So 1.0 "" §.§ ~ "" ~ "· B. BÜ £ N ö n * -cn

- 3 - 01 CM

pH £ 4 r-i -r)

3 -P Ό O II

óo σ \ o ΐ-! "cm η« 31 m m oo σ \ om om co ro ro co co n co co rg 780 3 5 03 '20 fl 1 == = = Μ Ό

CM

I I

M J

d ό in Ln

CM = s CM S

«. *

CO

σ> σι Η ω «s Β

CM

8 i 8 8 8 8 8

• rH rH rH rH rH

<MJ ® J <8 Ό Ό Ό Ό Ό Ξ in in in in m S O '· - u' n - u "S 2 H OH Hi H Sh 2 h B g SB aa 3 ces U <8 g ,,, I.

J> W H i 1 8 ójÜ'0 -P "^ in H tn o m H ** Φ U o 'S'm = = = = &> g - y ^

N + C0 '-' tfl CM

d 'Ö II

N / -N »·" - * O iH CN 00 ^ <3 * 790 8 5 03 21

Preparation example 4.

50 parts of compounds (1) or (2) were mixed well with 5 parts of "Sorpol 5029-0" (a special anionic surfactant), mixed with 45 parts of diatomaceous earth having a particle size of 48 µm and carefully mixed in a mill to obtain a 50% wettable powder of each compound.

Preparation example 5.

The compound (1) or its isomer with an acid portion in the dl-cis form was mixed with organophosphorus insecticides and / or carbamate insecticides, carefully mixed with "Sorpol 5029-0" or "Sorpol 2495G" (mixture of special nonionic and anionic surfactants), mixed with diatomaceous earth having a particle size of 48 pra and "white carbon", carefully mixed in a mill, to obtain a wettable powder preparation. The compositions of the different preparations are listed in Table B.

Table B

790 S 5 03 22 = ö d c φ Φ

¢) 0 Η H

Ü Ί $ = = 1 11 $ = =

Ju O 3

1 | I II

Q Φ (!) CD Φ 0) P T3 Φ = srQS = rO> a = • S § 00 Ή V0 00

Q (0 LD Γ "<^ 5 LD

l f ...... ..

0 o o o

CQ O I ÜJ I -O I

m σι tn cn m g \

<y \ (N CT CN c = = (T1 CM

«S * o" M · O o CM LD CM LO CM in d + j 3 s § i “3 ... 3 i i • l yes 8 y ιλ y y y o

g I u-H ü i η B

9 1

EH I

8 8 8 SS III

m3 do ω ω S ω S Φ α) ου 0¾¾¾ ο ό ο na ^ ^ + 1 ίκι Όΐη ID So 2¾ rq Ln §8 | Ν -ÖN Ν I ιι 3 "3" ff 9 I S ’S S 1 iS ·

O-HCnfflH CQCOPQ

§ d 1 λ § oj

m1 d ifl I

"7 P 0 d + J \ · rj, H H <D H w 8> 8 2 11.

1 ^ «f§ ~.

ί 0f ..... lit 5 N d Ν -Γ0 Ή ^ fo - · cn cm ¢ 1 rl Μ H -rj

> Ό -P Ό 0 II

You.

ίο Φ · &. Hiê + J fcj +4 ί Q d 13®2 __, -s § o S in cm co C? In Co oo cn fl) £ L | Q- | «W * · ^ ^> ^ · v- * ·’ w • 'w' ffl 790 8 5 03 23

<D

* 0 = I 1 1 o = r ** i

I I

= * 0 = = = Ό

^ VO

Γ-. VO

g s σ> cn ^ o _ cn in = = --- §5 S S S § Yy

i — 1 iH r-! r-i rH fH

0) 0) 0 0) 0) Θ • I Π3 φ * 3 d * Ό d 0 I I in in m m o p

J I (N CN CN CN Ή i — I

II I I I I I I

Φ tn I — Ϊ

Sc * ü d u ® Ά Ά o 3rd S'0

ιΛ Ήθ Ή O

cQ £ - <1 1 1 1 i i 0 cn cn 1 = = = = = Ό

CN

or? cn cn st * before Ή r-l r-I .-) rH ^ 790 35 03 24

The exceptional insecticidal and acaricidal activity and surprisingly low toxicity to the compounds of the invention for mammals and fish are illustrated hereinafter by means of 5 test examples. In the test examples, comparative preparations were prepared in a similar manner as the test preparations, under using known compounds listed in Table C.

t

Table C

7308503 25 νο m σ>

r-I

4J W

I p I! h m «η col g1 -y ral & 1 Ό. Ü tfl - q) to 01: β ο 1 ° 8 § δo flira

H 51 lo -9 rH il r-i y I

do co U (Π Offl O 9 I o ^. »<· iö» 5Ü3 52 43Ώ2 | JJ * H ^ ¢ 0¾ * Π H * Li · Lj · · * J (5 CM ffl -! CQ - * 1¾1 ^ + JI +} 3 § 3

I I I

II τ '3 | il fl J n * 0 (Ö 5-1 p - u I r h +> y • OlQi r-i CM> -i - & n -ria> 1 -s “9

u UiH Xi CM Q Η H

j io 5 ι23 oo I i I 31 «

1 4 si * S

Yy N1 -H - ill & g · Η 3 d> CM +> -rto S r *

B I m S Rg, IS

3 15 8¾ 33 II

S §, -8 Is hS, §.§ CQ υ · Η -Λ> 1 5 Virt '7 .2¾ Sg J7 JLci Λ1! · § i «

& T fl $, Is & T

Ocn Η P rfiQ ö o

S 4l E? Hi 1 H <»H

Ιί1 P * 6 X% s si && a ·? si s §-, Λ-Η 8 - Q CM H-l -3 y -H -d ii? §> i o cm ^ 7 o 5 p

~ CM «W s’ M-l Y YCM H -d> P

^ cm "h T> k Λ £ ™ £« y • HO '£ 5 5¾ (!) -> - l &> Λ _ ^ _ aj aj * 0? S' o '2. ^ jy. 5? >> ww 790 85 03 26 i 0 £ g 8 5 a $ r, r, na to η η η n ns 3 feiftosggyg 3333335335 700 85 03 27

Trial example 1.

The compound (1) was tested for fish toxicity (fish toxicity) and insecticidal activity.

5 Experimental method.

(1) Fish toxicity test.

A group of 10 members of Oryzias latipes (0.2-0.3 g / fish) was released into a 10 L glass vessel containing 10 L of a test preparation. The test preparation was prepared by dissolving or suspending the test compound in "Tween 80" and diluting successively with dechlorinated tap water. After 48 hours, the dead and live animals were counted to determine the mean tolerance limit (48 hours) value (TG / g in ppm).

(2) Insecticidal efficacy test.

Test emulsion preparations were prepared in the same manner as in Preparation Example 1.

Efficacy against Nephotettix cincticeps.

The test insect was resistant to carbamates (hereinafter referred to as R type). The active ingredient content of the test preparation was varied in four levels within the range of 500 to 1 ppm. The test preparation was sprayed on 180 ml plastic cups in which rice plants were grown one month old from seeding and placed on a turntable, the application amount being 15 ml per 2 cups.

After air drying, the plant was covered with a mesh cage. A group of 15 adult females of R-type 30 Nephotettix cincticeps were released into each cage and kept at 26 ° C in an artificial climate condition. After 24 hours, the dead and living animals were observed. The mean lethal concentration (LC ^ q in ppm) was calculated from the mortality determined by 3-fold repeated experiments.

Results.

The fish toxicity and insecticidal activity of the compounds of the invention were shown as Table 790 35 03 28 in Table D. To clarify fish toxicity and the high activity against certain insects characteristic of the compounds of the invention, a safety coefficient for fish was calculated from the test results of fish toxicity and insecticidal activity by the following comparison:

Safety- Gift.igh.eid for fish (TG (ppm)) coefficient - -—- 10 for fish Insecticide, T „,, Λλ efficacy (LC50 (ppm)>

These results are also shown in Table D.

In the case of cincticeps, the calculation was based on a concentration of the test compound in water obtained by assuming that a test preparation with an active ingredient content corresponding to LC5Q (ppm) was sprayed over an underwater rice field, with a water depth of 5 cm, in an amount of 100 l per 10 ares 20 and the total active ingredient was absorbed by the water.

For example, in the case of Compound (1), the amount of water per 10 acres of the underwater paddy field, at a water depth of 5 cm, is 50 tons. When a preparation having the active ingredient content equivalent to LC ^ g (ppm) of the compound (1) is sprayed in an amount of 100 l per 10 ares, the concentration of the compound (1) in the water is 0.007 ppm . The fish toxicity (TG ^ g) of the compound. (1) is 6.0 ppm. The safety coefficient for fish (857.1) is obtained by dividing 6.0 by 0.007.

Table D.

790 8 5 03 29 id 1: ¾ r-imco ^ roo 3 0 ^ 'ω Ο Γ ^ νοοΜΟΓ' Φ m G £ m 1-1 £ as 8 (D Cfi Λ fa .§ 3 ya HQ m fi> g $ P * ^ φ Ό n ai

G

^ YY & |

S h ë H

S “„ s ω] Φ G ° S 'Q) -d Γ' «3 U3 <2 £ $

u jj ö ft o - <m> -ι i-i J5 S

• I -H g -H ο ο ο ο ο r- cr \ · a Its Sï “Ο o o o o o fl I? Ö i -S ss a g ~ § 8 i * m f | §

G1 G -H

U 3 I

® TiB

§ If

o £ inooooo cqg-P

nS rocoratOLno l> g 1-1 co G gi.

g -η ω

+3 A! -H

§ 13 “rfl Η φ 1 5 ft *>„ 1 || HE I>!> G 2- CN S ο <D ·· οσιοοοσ »> -

ft-ι V K ^ K * »* 1 fQ

• H M> Ο Ο Ο Ο Ή S .'- 'J8 H 5.

S 'CO I 3 3Βε I' (5 ^ I 3 iji "5 Ξ 3 Ή • H,»

, Q O

oj 6, 0:> g www - - - a 790 85 03 30

Trial example 2.

The connections. (1) and (2) were mixed in a predetermined ratio, formulated into an emulsifiable concentrate according to preparation example 1 5 and diluted with water so that the amount of active ingredient was 10 ppm. The test preparation was sprayed over early stage rice plants, planted in a 1/10000 are Wagner pot, in an amount of 15 ml per pot. After air drying, the plant 10 was covered with a mesh cage in which 15 adult females R-type Nephotettix cincticeps were released. The pot was kept at 26 ° C in an artificial climate condition. After 24 hours, the dead and living animals were observed and mortality was obtained from the 3-fold repeated experiments; the results were as reported in Table E.

TABLE E.

Compound Percentage of the mixture of dl-trans and dl-cis 20 Compound (1) 99 80 50

Compound (2) 1 20 50

Mortality (%) 100 100 70

Test example 3.

The compound (1.) and its isomer with an acid portion in the dl-cis form were mixed in a predetermined ratio and "Tween 80" was added thereto. After stirring, the mixture was diluted with dechlorinated tap water so that the amount of active ingredient was 1 ppm. 10 l of the test solution were placed in a 10 l glass vessel and 10 "killi-fishes" (Oryzias latipes) were released therein.

After 48 hours, survival rate was determined by triplicate tests; the results were as reported in Table F.

790 8 5 03 31 TABLE F.

Compound Percentage of the mixture of dl-trans and dl-cis

Compound (1) 99 80 50 5 Compound (2) 1 20 50

Average survival rate 100 100 41

Test example 4.

The emulsion preparation containing the compound (1) described in Preparation Example 1 was diluted with water. The active ingredient content of the test preparation was varied in four levels within the range of 150 to 10 ppm. The test preparation was sprayed on 180 ml plastic cups in which rice plants were grown and placed on a turntable, the amount applied being 15 ml per 2 cups. After air drying, the plants were covered with a wire mesh cage. A group of 15 adult Laodelphax striatellus females were released into each cage and maintained at 26 ° C in an artificial climate condition. After 24 hours, the dead and living animals were observed. The mean lethal concentration (LC ^ in ppm) was calculated from the mortality as determined from a 3-fold repeated experiment; the results were as reported in Table G.

TABLE G.

Connection LC50

Compound (1) 70.0 790 8503 f 32

Taste example 5-.

The wettable powder containing the compound (1) described in preparation examples 4 and 5 was diluted with water to an active ingredient content of 500 ppm and used as the test preparation.

A group of 5 rice seedlings on the 10th day after sowing was dipped into the test preparation and dried in air. The treated seedlings were placed in a plastic cup of 5.5 cm diameter and 3.5 cm height, together with 10 larvae of Chilo suppressalis in the third stage. After 10 days, the dead and live animals were observed and the mortality was determined? the results were as reported in Table H.

TABLE H.

15

Wettable powder preparation Mortality (%) no.

(1) 100 (2) 100 20 (3) 100 (7) 100 (8) 100 (9) 100 (15) 100 25 (16) 100

Compound (1) 100

Test example 6.

The emulsifiable concentrate containing the compound (1) described in Preparation Example 1 was diluted with distilled water to an active ingredient content of 0.1 ppm. A group of 30 fully grown Aedes aegypti larvae was released 790 85 03 33 in each 180 ml plastic cup containing 100 ml of the test preparation. After 24 hours, 100% killing of the larvae was observed.

Test example 7.

The emulsifiable concentrate with the compound (1), described in preparation example 1, was diluted with water to an active ingredient content of 100 ppm. 500 ml of the emulsion was sprayed over runner beans, planted in a 9 cm pot and parasitized with Tetranychus cinnabarinus at each stage of growth. After 5 days, the number of adult females on the plant was counted and rated according to the following criteria: ++: 0-9 adult females are parasitic on one plant +: 10-30 adult females are parasitic on one plant -: 31 or more adult females are parasitic on one plant.

The results were as reported in Table J.

TABLE. J.

Connection Rating

Compound (1) ++

Comparative compound (b) + 25 Blank

Test example 8.

The dusting powder composition containing the compound (1) or its isomer with an acid portion in the dl-cis form, described in Preparation Examples 2 and 3, 30, was applied to ripening rice plants grown in a 1/10000 are Wagner pot, in an amount of 3 kg per 10 ares. The treated plants were then covered with a wire cage and 15 adult females R-type N. cincticeps were released in each cage and maintained at 27 ° C in an artificial climate condition. After 24 hours, the dead and live animals were observed and mortality was determined by 3-fold experiments; the results were as reported in Table K.

TABLE K.

Connection Mortality (%)

Dusting powder (32) 100 10 "(33) 100 (34) 100" (35) 100 (36) 100 (37) 100 15 "(38). 100" (39) 100 "(40) 100" (41) 100 "(42) 100 20" (43) 100 "(44) 100

Compound (1) (dl (acid portion) -cis, trans (cis / trans = 23/77)) 85 0.05% pigeon powder 25 Comparative compound (f) 2% dust 10 (g) "10 (i)" 43 (j ) "30 30 (k)" 60 790 85 03 continued TABLE K.

35 (1) "0 (m)" 25 (n) "40 5 (o)" 25 (p) "20 (q)" 30 (r) "30

Blank 0 10 Sample example 9.

The emulsifiable concentrate from preparation example 1 containing the compound (1) or its isomer with an acid portion in the dl-cis form was diluted with water to an active ingredient content of 400 ppm to obtain a test preparation . Rice plants grown in a Wagner pot were sprayed with 200 ml of the test preparation, dried in air and covered with a mesh cage, in which 15 adult females R-type Nephotettix cincticeps were released. After 24 hours, the dead and live animals were observed to determine the mortality. To determine the residual activity, the pot treated as above was left for 7 days and then the test insect was released into the cage in the same manner as described above. Mortality was assessed after 24 hours. All the above tests were performed in a greenhouse? the results were as reported in Table L.

Table L.

790 3ö 03 TABLE L.

36

Mortality (%)

Link ----- -

Immediately after 7 days after treatment 5 Compound (1) dl-trans 100 100 dl-cis, trans (23/77) 100 100

Comparative compound (e) 100 0 10 (F) 80 0

Blank 0 0

Test example 10.

The wettable powder containing the compound (1) or its isomer with an acid portion in the cis form, described in Preparation Examples 4 and 5, was diluted with water to an active ingredient content of 100 ppm. Rice plants, grown to a height of about 50 cm, were transplanted, 50 cm apart, in soil filled to a depth of 50 cm in a 5 mx 5 mx 2 m plastic container. Water was added to the container so that the water depth was 5 cm and 20 Oryzias latipes were released therein. The test preparation was sprayed over the tray in an amount of 200 L per 10 acres so that it fell on both the plants and the water surface. After 1 hour from treatment, 100 adult females of Nephotettix cincticeps were released into the tray and immediately afterwards the tray was covered with a plastic sheet. After 48 hours, the 30 dead and living animals were observed and the mortality was determined; the results were as reported in Table M.

7S0 8 5 03 TABLE Μ.

37

Compound Mortality (%) N. cincticeps O.latipes

Compound (1) 5 dl-trans 100 0

Compound (1) dl-cis, trans (23/77) 100 O

Wettable powder preparation (1) 100 0 10 "(2) 100 0" (3) 100 0 "(7) 100 0" (8) 100 Ö "(9) 100 0 15" (10) 100 0 "(15 ) 100.0

Blank 0 0

Test example 11.

A 1: 1 mixture of the compound (1) or its isomer with an acid portion in the dl-cis form and Sumithion or NAC was dissolved or suspended in corn oil and the resulting test solution was administered orally to a male mouse in an amount of 0 , 1 ml / 10 g body weight. After 24 hours, mortality was examined to determine the mean lethal concentration (LC5Q in mg / kg); the results were as reported in Table N.

Table N

790 85 03 n TABLE N.

38

Compound LC ^ q (mg / kg)

Compound of formula 1 5 (dl (acid part) -trans isomer) + NAC> 500

Compound of formula 1 (dl (acid part) -trans isomer) + Sumithione> 1000

Compound of formula 1 (dl (acid portion) -cis, trans isomer 10 (cis / trans = 23/77)) + NAC> 500

Compound of formula 1 (dl (acid portion) -cis, trans isomer (cis / trans = 23/77)) + Sumithion> 1000

Compound of formula 1 (dl (acid portion) trans-isomer)> 2000

Compound of formula 1 (dl (acid part) -cis, trans isomer (cis / trans = 23/77))> -2000 NAC 300.20 Sumithion> 1000

Comparative compound (b) 650 "(c) 112" (d) 300 "(e) 370

Conclusions.

790 8 5 03

Claims (23)

2. Process for preparing the compound according to claim 1, characterized in that (A) an alcohol of the formula 6 of the formula sheet is reacted with a trans- or trans-rich acid halide of the formula 7 of the formula sheet, wherein X is a halogen atom, in the presence of an organic tertiary base in an inert solvent; or (B) an alcohol of the formula 6 reacts with a trans- or trans-rich carboxylic anhydride of the formula 8 of the formula sheet in an inert solvent; or (C) an alcohol of the formula 6 reacts with a trans- or trans-rich carboxylic acid of the formula 9 of the formula sheet in the presence of a dehydrating condensing agent in an inert solvent; or (D) a halide of formula 10 of the formula sheet, wherein Y represents a halogen atom, reacts with a trans or trans-rich carboxylic acid of formula 9 in the presence of an organic tertiary base in an inert solvent; or (E) a halide of the formula 10, wherein Y represents a halogen atom, reacts with an alkali metal salt of a trans or trans-rich carboxylic acid of the formula 11, wherein M represents an alkali metal, in a two phase system of water and an inert solvent in the presence of a phase transfer catalyst; or (F) an aldehyde of formula 12 of the formula reacts with an alkali metal cyanide and a 790 3 5 03 trans or trans-rich acid halide of formula 7, wherein X represents a halogen atom, in the presence of a phase transfer catalyst in an inert solvent; or 5 (G) an aldehyde of the formula 12 reacts with an alkali metal cyanide and a trans- or trans-rich acid halide of the formula 7, wherein X represents a halogen atom, in a two-phase system of water and an inert solvent in the presence of a phase 10 transfer catalyst. Insecticidal and / or acaricidal composition of low toxicity to mammals and / or fish, characterized in that it contains, as active ingredient, an insecticidally effective amount of the compound according to claim 1 and an inert carrier. Insecticidal and / or acaricidal composition according to claim 3, characterized in that the amount of the active ingredient is 0.001 to 80.0% by weight. Method for controlling an insect and / or acaride, characterized in that an insecticidally and / or acaricidally effective amount of the compound according to claim 1 is applied to the insect and / or acaride. 6. A method according to claim 5, characterized in that the insect is an insect living in an aquatic place. 7. Insecticidal and / or acaricidal composition, characterized in that it contains an inert carrier and, as active ingredient, an insecticidally and / or acaricidally effective amount of a mixture consisting of m- (p-bromophenoxy) -i Cyanobenzyl trans- or trans-rich 2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylate of the formula 1, an organophosphate of the formula 2 of the formula sheet, wherein and R2 each 790 8 An alkyl group with 1-3 carbon atoms, X2 and X ^ each an oxygen or sulfur atom, Y ^ and Y2 an equal or different alkyl group with 1-3 carbon atoms, methyl mercapto, cyano or nitro group or a halogen-5 atom and Z represent a carbon or nitrogen atom and n is 0 or 1, and / or a carbamate of the formula 3 of the formula sheet, wherein R represents a group of the formula 4 of the formula sheet, wherein X represents an alkyl or alkoxy group having 1-4 represents carbon atoms and n 10 is 1 or 2, or R represents a group of the formula V of the formula sheet. Insecticidal and / or acaricidal composition according to claim 7, characterized in that the amount of active ingredient is 0.001 to 80.0% by weight. Insecticide and / or acaricidal composition according to claim 7 or 8, characterized in that the weight mixing ratio of the compound of the formula 1 to the compound of the formula 2 and / or compound of the formula 3 is within the range of ll to 1: 100. Insecticide and / or acaricidal composition according to any one of claims 7-9, characterized in that the compound of the formula II is 0,0-dimethyl 25- (3-methyl-4-nitrophenyl) phosphorothioate. Insecticidal and / or acaricidal composition according to any one of claims 7-9, characterized in that the compound of the formula II is 0,0-dimethyl 4-methylthio-m-tolylphosphorothionate. Insecticidal and / or acaricidal composition according to any one of claims 7-9, characterized in that the compound of the formula II is 0,0-diethyl 2-isopropyl-6-methyl-4-pyrimidinylphosphorothionate. Insecticide and / or acaricidal composition according to any one of claims 7-9, characterized in that the compound of the formula II is 0,0-dimethyl 0-4-cyanophenylphosphorothionate. Insecticidal and / or acaricidal composition according to any one of claims 7-9, characterized in that the compound of the formula II is 0,0-dipropyl p-methylthiophenyl phosphate. Insecticidal and / or acaricidal composition according to any one of claims 7-9, characterized in that the compound of the formula II is 0,0-diisolopropyl S-benzylphosphorothiolate. Insecticidal and / or acaricidal composition according to any one of claims 7-15, characterized in that the compound of the formula 3 is 1-naphthyl-N-methyl carbamate, Insecticidal and / or acaricidal composition according to any one of claims 7-15, characterized in that the compound of the formula 3 is 3,4-xylyl-methyl carbamate. Insecticidal and / or acaricidal composition according to any one of claims 7-15, characterized in that the compound of the formula 3 is 3-methyl-phenylmethyl-carbamate. Insecticide and / or acaricidal composition according to any one of claims 7-15, characterized in that the compound of the formula 3 is 2-sec-butylphenylmethylcarbamate. 20. Insecticidal and / or acaricidal composition according to any one of claims 7-15, characterized in that the compound of the formula 3 is 2-isopropylphenylmethylcarbamate. Insecticidal and / or acaricidal composition according to any one of claims 7-15, characterized in that the compound of the formula 3 is 2-isopropyl-phenyl N-methyl carbamate, 7S0 f 3 03 λ 22. Insecticidal and / or acaricidal composition according to claim 10-1 / 9, characterized in that the compound of the formula II contains 0,0-dimethyl-4-nitro-m-tolylphosphorothionate and the compound of the formula III 2-sec.butylphenylmethylcarbamate. Insecticidal and / or acaricidal composition according to Claims 10 and 17, characterized in that the compound of the formula 2 contains 0,0-dimethyl 10 4-nitro-m-tolylphosphorothionate and the compound of the formula 3 3,4-xylylmethyl carbamate is. 24. Method for controlling an insect and / or acaride, characterized in that an insecticidally and / or acaricidally effective amount of a preparation according to any one of claims 7-23 is applied to the insect and / or acaride. 790 3 5 03 * BrO ° <) I / Cl \ cH-0-C-CH-CH-CH = cr I \ / Xcl CN ^ CH3 CH3 Ri "° \ il2,} ί (1> V (CH2) nQ R2_-Xl y2 R - OCNHCHo II * 3 0 Xn - <y i- * 790 8 5 03 Sumitomo Chemical Company, Limited II 4 Br - ^ CHOH 6 CN. / CH = C \ ci XC-CH - CH II \ / 7 0 c / \ CH3 ch3 l C \ H ^ Cl / Xc - / 0 * / V Xc- \ Λ "/ \ CH3 CH3 ° / 2 f / C1 / CH = </ XC1 9 HO-C-CH - CH I! \ / Oc / \ '? J CH3 CH3 Sumitomo Chemical Company, Limited 790 85 03 A »III Br - ^ VQ— ^ CH-Y I 10 CN / C1 CH = C / XC1 MO-C-CH - CH II \ / 'noc 11 / \ CH3 CH3 Br ^ - ° -Q 12. XCHO 1- 790 85 03 Sumitomo Chemical Company, Limited