DE2029375A1 - - Google Patents

Description

PATENT LAWYERS

dr. w. Schalk · DiPL-iNG. peter WiRTH 2029375

DIPL.-ING.G. E. M. DANNENBERG · DR. V. SCHMIED-KOWARZIK.

6 FRANKFURT AM MAIN,

SK / Eh

OR ESCHENHEIMER STR. 39

Case No.

Air Products and Chemicals, Inc. 1339 Chestnut Street Philadelphia, Pa., USA

Δ · "* -!, 2 Λ-triazolines _{im (} j pesticides containing them

The present invention relates to the synthesis of new prepa »

rate of phosphate derivatives of certain 3-substituted Δ -1 ₉ 2.4 · * triasoline compounds. It relates in particular to the phosphate derivatives

of 3-fluoroalkyl-Δ -1,2,4-triazoline-5-thiones and 3-chlorodifluoromethyl-Δ -1 ^^ - triazoline - ^ - thions, the good insecticides and acaricides are. It also relates to the use of these compounds for agricultural purposes.

00.9852 / 2280

A similar compound is already described in "J.Sci.Fd.Acrric", Volume 19, Pages ^ S- ¹ M (1968), for example, B _o i-üiäthoxyph'osphinthioylthiomethyl-3, ^ - dimethyl- ² -l , 2, ^ - triazolin-5-thione, which has both insecticidal and acaricidal properties. However, this compound is available only in the broadest sense with the erfindunrspemätien compounds m context.

The present invention relates to phosphate derivatives of Δ 1,2,4-triazoline-5-thione compounds _? through the-? the following general structural formula can be represented «

H ₂ -NCH ₂ XP

R ₁

In this formula, R ₁ stands for a fluoroalkyl radical with 1 to 7 carbon atoms or a chlorodifluoromethyl radical, R ₂ for lower alkyl groups with 1 to 7 carbon atoms, R, and R each for an alkyl, alkoxy or alkylamino radical with 1 to 7 Carbon atoms or for phenyl radicals and Y and X each for oxygen or sulfur.

The compounds of formula I are very effective broad spectrum insecticides and acaricides <,

112/1210

BAD ORSGfNAL

The present invention also includes those obtained as intermediates Tria ^ oleic compounds from which the compounds of formula I can be produced. These compounds can be in tautomeric form exist and have the following structural formula

In this formula, R ₁ stands for fluoroalkyl radicals with 1 to 7 carbon atoms or for a chlorodifluoromethyl radical and R "for lower alkyl radicals with 1 to 7 carbon atoms.

The present invention also relates to triazoline intermediates the general formula

(in)

in the R. for a fluorine alkyl contains 1 to 7 carbon atoms or a chlorodifluoroisethyl radical and R ″ for a lower alkyl radical with 1 to 7 carbon atoms.

009852/2280

Finally, the present invention also includes triazoline intermediates of the following general structural form

NCELZ

in which R _{1 stands} for a fluoroalkyl radical having 1 to 7 carbon atoms or a chlorodifluoromethyl radical, R _? represents a lower alkyl radical with 1 to 7 carbon atoms and S represents halogen * such as, for example, chlorine, bromine or iodine.

In the description and claims, R., R «, R, and R. always the same meanings.

The compounds of structural formulas II, III and IV are used for the preparation of compounds of structural formula I, the insecticides and acaricides with broadband effect.

The compounds according to the invention are preferably through a multi-stage process produced. In the first stage of the procedure a ^ -1,2,4-triazolin-5 ~ thione of the formula II according to one of the produced the following equations:

009852/2280

BATH ORIGINAL

_ ₅ _

Reflux in

(1) R, COOU + H ₀ NNHCNHR ₉ ^v '1 2 "2 azeotrope

(2) (R ₁ CO) ₂ O + H ₂ NNIICNHR ₂

^0H - ^IJ

Depending on the particular substituents R ₁ and R _p , the above processes lead to different yields. The choice of the preferred method is therefore an empirical decision based on experience with the respective substituents. For example, R can stand for trifluoromethyl, difluoromethyl, pentafluoroethyl, 2-trifluoromethylpropyl, chlorodifluoromethyl radicals or the like, while the substituent R_ can be a methyl, ethyl, butyl, hexyl, heptyl radical or the like. The most suitable method can easily be determined by one skilled in the art from the description herein.

The carboxylic acids used in the above processes are commercially available or can be prepared by known processes. The thiosemicarbazides are also known and commercially available, or they can be obtained by conventional methods, for example by reacting hydrazine hydrate (ΝρΗ, .Η ^
produce"

with a suitable isothiocyanate (R NCS),

The compounds of structural formula II can with aldehydes, such as ζ "Β", Formaldehyde, acetaldehyde, propionaldehyde or the like. To compounds

009852/2280

£, ■ -: “ORiGiNAL

of structural formula III, e.g. to "l-hydroxymethyl-4-

methjjrl-5-trifluoromethyl-Λ -1,2,4-triazoline-5-thione.

The hydroxymethyl derivatives can e.g. with thionyl chloride, phosphoropentachloride, Phosphorotribroinid or the like. Reacted, whereby compounds of structural formula IV are obtained, for example 1-chloromethyl-4-methyl-3-trifluoromethyl-Λ -1 »2,4-triazoline-5-thione. The above reaction generally takes place at temperatures less than 70 in an inert organic solvent such as benzene, chloroform or the like, and under an inert atmosphere such as nitrogen.

The end products of structural formula I can, for example, from 1-hydroxymethyl

4-methyl-3-haloalkyl- ^ -1,2,4-triazoline-5- "thione (structural formula III) or the corresponding 1-halomethyl compounds (structural formula IV) can be produced by known methods. Below some of these procedures are summarized ι

NCH ₂ Cl

H_ NCH ₂ SP (R ₃ ) (R)

S + HSP (R ₃ ) (R ₄ )

Here R, and R ^ each represent an alkyl ₉ alkylamino,

Alkoxy or phenyl »

S2 / 12

2nd N.

-S- + HSP

^C 6 ^H 5

N NCH ₂ SP;

N.

A stands for acid-binding agents, such as, for example, Ha CO _7. , Triethylamine, pyridine, etc. In place of the free acids, salts of the acids, for example ammonium, sodium, potassium salts, etc., can also be used.

NCU ₂ OH.

• r

S + ClP (R ₃ ) (R ₄ )

N NCK ₂ OP (R ₃ ) (R ₄ )

Here R, and R. stand for alkyl, alkylanino, alkoxy or phenyl radicals.

4th N.

NCH _n OH

S + Cl ₃ PR ₃

MCH-OPR-Cl

R here represents an alkyl, alkylamino, alkoxy or phenyl radical, R. for an alkyl radical.

009852/2280

R,

V ^H s

NCH_OP (R,) (ORJ

NCH OPR Cl

R "" represents an alkyl, alkylamino, alkoxy or phenyl group

and R. for an alkyl radical.
4th

N NCH ₂ OH

H_ HCH ₂ OP (R ₃ ) (R ₄ )

ti

S + ClP (R ₃ ) (R ₄ )

H .

Here R and R. stand for alkoxy radicals.

The reactions listed above can take place between about room temperature and about 80 in water or organic solvents such as benzene, methanol, ethanol, acetone, butanone, ethyl acetate and the like. be performed.

It has been found that the compounds according to the invention of Formula I especially by the presence of a fluoroalkyl or chlorodifluoromethyl group in the 3 "position of the phosphate derivatives

^ -1,2,4-triazoline compounds are marked. This connection

009852/2280

BATH ORIGINAL

fertilizers have excellent insecticidal and acaricidal properties. Some of these compounds also show very good ovicidal properties Properties, while the previously known similar compounds do not have this effectiveness. Certain compounds according to the invention of formula I have relatively high LD-Q values and show nevertheless excellent insecticidal and acaricidal properties.

The compounds of the formula I according to the invention can be used in various Wise and in different concentrations to be processed to insecticides and / or acaricidal preparations. It is known, that the biological effectiveness of a preparation for a specific purpose is determined by the type and concentration of the active ingredient, as can also be determined by the method of application of the active ingredient.

The compounds according to the invention can be used as simple solutions Active ingredient in a suitable solvent in which the active ingredient is completely soluble in the desired concentration will. Such solvent systems are e.g. water, alcohols, acetone or other organic solvents. These simple solutions can be modified by giving them various surface-active agents, emulsifiers or dispersants, coloring agents, odorants, anti-foaming agents, other pesticides or so-called "dormant" oils "(see" Concise Chemical and Technical Diet. ", 1947t P.J542)»

0098.52 / 2280

which supplement the effectiveness of the pesticides according to the invention or improve, or add other aids to bring about a biological response desired for the intended use.

The compounds according to the invention are also suitable for production other preparations known in agriculture and industry that the active ingredient e.g. in the form of granules with a relatively large Particle size, as dusty3 powder, wettable powder, emulsifiable Concentrate, aerosol spray mixture or the like. Contain. These Preparations can contain all auxiliaries and carrier materials, normally used in agriculture and industry, to facilitate the dispersion of the active ingredient in pesticidal chemicals. The supplements can only go up to about 0.25 wt 95 wt .- $ or more of the active ingredient.

Powdered preparations are made by mixing the active ingredient with finely divided solids which act as dispersants and carriers for the compound. Examples of such solids are talc, Kieäelgu-hr, finely divided clay, Fuller's earth or other known organic or inorganic solids. The solids used to produce the powdered preparations generally have a particle size of 50 LL or less. The concentration of the active ingredient in these powders is generally about 0.25 wt% up to 30 wt% or more. Granular preparations r / erdsn er «= ■ hold by the active ingredient in i?

- 11 -

an inert solid such as sand, attapulgite clay, gypsum, corn kernels or anciere inorganic or organic solids, adsorbed or impregnated these particles with the active ingredient. With such grainy ones In preparations, the active ingredient is generally used in an amount of 1.0% by weight up to 20% by weight or more, based on the total weight of the preparation.

Wettable powders are solid preparations in which the active ingredient is in or absorbed on a sorbent carrier, such as finely divided clay, talc, gypsum, lime, wood flour, Fuller's earth, kieselguhr or the like or is adsorbed. These preparations preferably contain 50% by weight up to 80% by weight of active ingredient. The wettable powders also contain usually a small amount of a wetting, emulsifying or diapering agent, as the dispersion of the powder in water or a other liquid carrier chosen for the particular application is facilitated.

Emulsifiable concentrate preparations are homogeneous liquids or Pastes containing the active ingredient which can be dispersed in water or other liquid carrier for ease of use. Such egg-emulsifiable concentrates can either only consist of the active ingredient and a liquid or solid emulsifier, or they can also be other, relatively less volatile organic Solvents contain such as isophorone, dioxane, heavy aromatic naphthas, xylene or dinethylformasside. The active ingredient is here usually present in an amount of 10 wt. 5 & up to 70 wt. f4.

009852/2280

In aerosol spray preparations, the active ingredient is converted into a substance by evaporation low-boiling, dispersing solvent carrier, such as Freon, dispersed in finely divided form.

The compounds of the formula I according to the invention can be used with others Pesticides, bactericides, fungicides and the like are given together, to achieve a certain biological effect.

The following examples serve to illustrate the present Invention.

I. Establishing the intermediate connections example 1

(a) A solution of 4 S 4-methyl-i-trifluoroacetylthiosemicarbazide and 30 ecm of a 10% aqueous sodium carbonate solution was refluxed for about 2 hours. The mixture was cooled to about 10 and acidified with hydrochloric acid to give a crude solid product. This crude product was recrystallized from ethylene chloride petroleum ether and gave 4-methyl-5-trifluoromethyl-A ² -1,2,4-triazoline-5-thione as the end product; F »119-120 °.

Analysis CHK, SF, ϊ Ber. Found * ■ 4 4 5 3— ——

C 26.25 $ 25.90 H 2.20 io 2.16 N 22.96 io 22.92

0098S2 / 2280 _BÄD

(b) 10.5 S 4-Mathylthiosemicarbazid were added to a solution of 100 ecm xylene and 10.6 g of difluoroacetic acid, whereupon the

under ■

30 obtained suspension / a Dean-Stark trap as long as Reflux was heated until no more water was obtained. The reaction mixture was cooled to about 12 and filtered, yielding 13.5 g of 3-difluoromethyl-4-methyl-Δ 1,2,4-triazoline-5-thione5 as product F «171-174 °.

Analysis 0.H ₁ -N _x SF ₀ : - Calc. Found —— 4 5 j £ ~ "

C 29.09 fo 29.46 % H 3.05 $ 3.11 "/ ο N 25.44 # '25.73 f> r

According to the procedure described above, the following were summarized Compounds of structural formula II produced «

Compound R _1- R ^

CF, C ₂ H ₅

CClF ₀ CH ₃

CF 2 CHF 5 C ₂ F ^ CHCH CH ₃ CF ₃ CClF ₂

009852/2280

Example 2

(a) 20 g of the compound according to Example i (a) and 21 g of a 37% aqueous solution of formaldehyde were heated to 60 for 1 hour, so that a complete solution was achieved. The reaction mixture was concentrated in vacuo and the residue was dissolved in 100 ecm of ethyl acetate. The ethyl acetate solution was dried over anhydrous sodium sulfate and concentrated in vacuo; an oil was obtained that 3. solidified to a wax on standing. The product obtained was 21 g of 1-Hydroxy ™ methyl-4-methyl-3-trifluoromethyl-Δ -1 ₉ 2,4-triazoline-5-thione.

According to the procedure described above, the following compounds were made the structural formula III producedι

Compound R ₄ R.

CHP ₂ , CH,

CHF ₂ C ₄ H

■ C ₂ F ₅ CH ₅

CHCH-- CH _Z

CF

CClF ₂ GH,

^{Β / Φ}

- 15 -

(a) 21 g P'a de3 product of Example 2 in a round bottom flask nut a mixture of 55 cc of benzene and 2 ^l j _t 6 cc of thionyl chloride meshed, which had been previously cooled in an ice bath to about. 5 The mixture was kept under a nitrogen atmosphere. Then nitrogen was bubbled through the mixture until the hydrogen chloride gun no longer formed. Then the Reqktionsmischun ^ under

(from l κ)

a vacuum-focused. The product ^ became uncrystalline from petroleum ether

lized; no vami ^ -.iac 1-chlorosethyl-4-aethyl-3-trifluoromethyl-A -

Found

1,?, 4-trifi2olin-S-thione obtained; F - 4O-43 ^0th ·

Analysis C, H.CIF, N, S; Ber.

C 25.88 ic 26.01 ° jo

H 2.17 1 * ' 2.33 io

K 16.11 <fv 18.16? Ö

According to deji. The method described above v <urden other compounds the structural formula IV produced, however, the products 1 to of Example 2 was used in place of "the product of Example 2 (a) became.

Connect u η _? τ R. R

¹ " ^CP 3. ^C 2 ^H 5

CHF ₂ CHCH ₂ - CH ₅ CHF ₂ 52/2280 ^C 4 ^H C ₂ F ₅ CH ₅ CH, CH ₅ CCIF2
0098 CH ₅

II. Preparation of compounds of structural formula I from the intermediate compounds

Example 4

(i) 4 g of the product from Example 3 (a) and 3.5 g ammonium diethyldithiophosphate were refluxed for about 3 hours in 200 ecm acetone. The reaction mixture was cooled to about 10, filtered and the filtrate concentrated under a vacuum ; an oil was obtained which solidified on cooling to room temperature. The product was recrystallized from aqueous methanol and yielded 5 g of 1-diethoxyphosphinothioylthiomethyl-4-methyl-3-trifluoromethyl-II, 1,2,4-triazoline-5 / 4H7-thione, at a temperature of 88-90 °.
Analysis CXJ F, O "SP; Her. Gef. J

C $ 28.37> 28.58 % J.

H 3.97 $ 3.90 ic j

i N 11.03 i » 11.00 ic

Further compounds of structural formula I were prepared at

™ where X and Y stood for sulfur and R ₁ , R,., R, and H. those below

ι * ■ 3 4

have listed meanings »

009852/2280

BATH

link ^R 1 2 CP. 3 CF 4th CP, 5 C F 6th C F 7th CHF ₂ θ CHF "

10

CH

CF

CClF

- ^ ₂ - OC ₂ H ₅ R.
4th C ₂ H ₅ OCH, OC ₂ H ₅ CH ₅ Isopropoxy OCH ₅ CH, OCH, Isopropoxy CH ₃ OC ₂ H ₅ . OCH, CH ₅ OC ₂ H ⁵ OC ₂ H ₅ OC ₂ H ₅

CHCm- CH,

CH,

OC ₂ H ₅

OC ₂ H ₅

Example 5

A mixture of 10.0 g of the product from Example 3 (a), 11.0 g of diphenylphosphinodithioic acid (CgH ₁ -) ₂ PSSH and 4.4 g of triethylamine in benzene Y / is heated to reflux for > hours. The solids were filtered off from the cooled reaction mixture and the benzene filtrate was concentrated in vacuo to an oil. The oil was crystallized from a benzene-light petroleum mixture and gave the product 1-diphenylphosphinothioylthio-methyl-4-ethyl-3-trifluoromethyl-Δ 1,2,4-triazoline-5 / 4H7-thione} F = 123-126 ° .

009852/2280

Example 6

A mixture of 8.0 g of the product from Example 2 (a), 6.6 g of ethyl phosphorochloridate (C "ELO) POCl and 5.2 ecm of triethylamine in benzene was refluxed for 3 hours and then stirred overnight at room temperature. The solids were filtered off and the filtrate was concentrated to an oil. The oil was washed with a 2 figs of aqueous sodium carbonate solution and the residue was extracted with diethyl ether. The ether extract was dried over anhydrous sodium sulfate and concentrated to an oily residue which was identified as irDia oxyphosphinomethyl-4-diethyl-3-trifluoromethyl-Δ -1, 2,4.

Example 7

A mixture of 8.0 g of the product from Example 2 (a), 4 »2 g of ethyl phosphorochloridothioate (CpHJ-O) PPSCl and 5» 4 ccffl of triethylamine was refluxed in benzene for 3 hours and then stirred overnight at room temperature. The insolubles were filtered off and the filtrate was concentrated to an oil. The oil was washed with two aqueous sodium carbonate solutions and the insoluble substances were extracted with diethyl ether. The ether extract was dried over anhydrous sodium sulfate and concentrated to an oily residue which was identified as 1-diethoxyphosphinothioylmethyl-4-methyl ~ 3-trifluoromethyl-Λ -1, 2,4-triazolin-5 _< / 4H7-thione *,

/ 7 <O5 "^ S (G) ftl

H && E P

BATH

- 19 -

ffe-isriel H

A Kir: cLun; <from 6.0 g of the product of Example 2 (a), 4 »6 g Äthylphcsphordichloridothioit C _? H, .PSC1 and 4 ecm triethylamine in 100 ecm rhzcl was stirred overnight at room temperature. The insolubles were filtered off, and the filtrate was concentrated to an oily residue, which was washed with a 2% aqueous sodium carbonate solution. The residue was extracted with ether and the ether extract dried over anhydrous sodium sulfate and concentrated to an oily residue.

A mixture which contained 5 »2 g of the above-described reaction product, 0.7 g of absolute ethanol and 1, -jg triethylaciin, was refluxed in 50 ecm of benzene for 3 hours. The cooled reaction mixture was filtered and the filtrate concentrated to an oily residue, which was washed with a 2 J aqueous sodium carbonate solution. Then the residue was extracted with diethyl ether, the diethyl ether extract was dried over anhydrous sodium sulfate and concentrated to a 1) 1 , which as 1-ethoxyethyl

phosphinyithioyJmethyl-4-ethyl-3-trifluorine-ethyl- ^ -1,2,4-triazoline identified became.

0 0 9 8 5 2/2280 BAD

III. Insecticidal and acaricidal effectiveness

Various compounds of structural formula I from Example 4 and other examples were tested for their biological effectiveness in the Control of insects and acarids studied the sur control The methods used for certain pests are described below and the tables summarize the results obtained together.

A. Experiments with the Mexican beetle The compounds were dissolved in acetone and diluted to the desired concentration with deionized water containing a suitable wetting and emulsifying agent Active ingredient-containing solutions dipped, air-dried and placed on racks that were provided with an underground water source. 3 plants were used for each dilution.

As soon as the plants were dry, TO larvae (third-instar) of the Mexican bean beetle (Epilachna varivestis) placed on the plants who were surrounded with a cage; the larvae stayed for 48 hours on the plants, after this time it was determined how high the annihilation rate of the insects was. The results are shown in Table I.

009852/2280

BADORiGiNAL

- .21 -

Tabel I. 100 100 -59. ι - concentration in tpm 10 · —5_. '■ link
from example Destruction rate in $ 100 100 100 -25. 100 100 500 100 100 100 100 13th --- 4-1 100 100 100 100 40 100 73 4-2 100 100 100 100 100 80 27 4-3 100 100 100 87 100 20th -. 4-4 100 100 100 80 80 27 4-5 100 100 100 •volume 1Π Π • 4-6 100 87 100 100 I UU
100 I UU
100 4-7
4-10 20th 7th 100 mm mm mm mm mm ^ 7th 100 100

Β »Try the Heorworm

The procedure of Experiment A was repeated to ensure effectiveness of the compounds in combating the. To determine army worms. The results are summarized in Table II.

Table II.

link
from example Annihilation <? Squote in 500 250 ⁰ L - ν
/ O · "Λ onzen iooo 100 100 200 100
mm-mmma. 4-1 100 90 50 4-2 87 93 27 4-3 100 7th 0 - 0 4-4 20th 27 13th 0 4-5 40 93 27 0 4-6 100 ...... 0 4-7 100 38

009852/2280

C. Experiments with the pea aphid

Chemical solutions were made in the manner described in Book A

sheet

manufactured. Pea mice (Macrosiphum pisi), that is, fully grown were, about 5 Sprayed for seconds and then onto untreated Windsor bean plants set. In each experiment 10 lice per plant and 3 plants each were used. The results are shown in Table III.

Table III _m IZl in fo - Consentration in tpm JK) -i_ link
from example Destruction rate 100 100 Yes. Ji 10 500 100 100 57 97 23 4-1 100 96 96 100 40 88 90 4-2 100 87 87 93 96 100 43 4-3 96 100 93 90 84 13th 4-4 100 93
* 83 93 93 - - 4-5 100 33 Θ0 4-6 100 95 13th 4-7 80 80 4-10 50 90

D. Experiments with acarids

Chemical solutions were prepared according to the procedure of Experiment A. Cranberry bean plants spinning from two-spotted droppings (Tetranychus telarius)

009852/2280

at different ages were affected in these solutions get-iucht. The plants were air dried and placed on Given racks that provide an underground water source was. 3 plants were used in each experiment. The destruction rate was determined after 48 hours. The results are in the table IV summarized.

Table IV

link

from Bei ;; pie 1 Vernichtun ^ aquote in j> - Concentration in TpM

500 250 125 50 "25 £ 10

4-1 100 100 100 100 100 91 68

4-2 100 100 100 100 89 50

4-3 100 100 100 100 95 97 96

4-4 100 100 100 100 93 83 81

4-5 100 100 100 100 54 50 50 4-6 TOO 100 100 fOO 77 36 11 4-7 - - 100 96

4-10 100 it) o 100 100 - 100 74

5. 79 43 36 -

6 55 53 19 - -

7 100 100 71 48 15

8 37 23 20 - -

009852/2280

• Et study of residual toxicity

Using some compounds of structural formula I, which according to the method of Example 4 had been prepared. Was investigated how much the remaining toxicity of the deposited active ingredients J

on the leaves of the treated plants. «According to the procedure of Experiment A, solutions were prepared from the compounds and applied to the plants. As a test insect was again the Mexican bean beetles used. The destruction rate was determined after the larvae of this beetle 72 hours ^ of a Enclosed in a cage on the treated plants, Table V shows the effectiveness of the compounds against these Larvae at different times after treating the leaves "

Table V

link

from example TgM Vernichtun ^ g uote in fo (72 hours) - old pressure '.

O days, 4 days, days. Vy days 22 Tape 27 Doors 4-1 2 '100 100 - - ---

4 - 1 · 10 100 - 100 100 5 0 4 - 7 2 100 100 - - 4-7 10 100-100-100

Ft Systeiniache insecticidal effectiveness
Young cranberry bean plants with the first leaves falling into one; Soils with low moisture content were grown with 20 ecm! treated with an aqueous solution of a compound of structural formula I by using the solution to irrigate the soil. All loading

009852/2280

actions were carried out 3 times. 24 hours after treatment, the plants were continuously watered underground for 72 hours. 48 hours after the solution was applied to the floor

". ■ · sheet -

adult peas / lice are placed on the leaves of the plants and kept on the plants for 48 hours with the help of a cage. the The extermination rate was determined after the insects had 72 hours had spent on the plants. The results are from Table VI to see.

Table VI

link

from the example of the destruction rate in Yes (72 hours) - concentration in TPM

-25. ■ -JO 5

4-1 100 40 ο

4-7 '- 100 ■ .-—'.

G. Ovicidal Efficacy ''

Some of the compounds according to the invention also gave very good results when used as ovicides. Liquid, on the above Preparations prepared in the manner described below were used in those listed below Concentrations brought into contact with plant leaves to which the eggs of various insects were attached. Under "Ovicides Effectiveness "indicates the percentage of eggs that did not mature. Under" Effectiveness remaining "it is stated what percentage on hatched larvae in contact with the treated ones Scroll died. The results were obtained after exposing the eggs and hatched larvae to the test compounds for 6 days was.

0 098 5 2/2280

Quotation of annihilation in jo

link
from example TpM Ovicidal effectiveness Remaining effectiveness 95 4-1 25th 100 - _> —— 4-7 . 25th 50 4-10 125 100

The results summarized in the tables clearly show that the compounds of structural formula I according to the invention are excellent have insecticidal and acaricidal properties.

009852/2280

Claims (1)

Claims ι in which R _{1 is} a fluoroalkyl radical having 1 to 7 carbon atoms or oil is chlorodifluoromethyl radical, R "represents a lower one Alkyl radical with 1 to 7 carbon atoms and Q for H, -CH-OH, or - - P , with 2 for chlorine, bromine or iodine X and Y each represent oxygen or sulfur and R, and R. independently of one another for alkyl, alkoxy or alkylamino radicals 4th with 1 to 7 "carbon atoms or stand for phenyl radicals. 2. Compound according to claim 1, characterized in that the3 Q stands for -CH ₇ XPY (R,) (R.), Where R- and R. are lower alkoxy, lower alkyl or phenyl radicals. 009852/2280 3 · Compound according to claim 2, characterized in that R. stands for a trifluoromethyl radical, R _? for a methyl radical, R, and R. for an ethoxyrefit and X and Y for sulfur. 4 · Compound according to claim 2, characterized in that R ₁ for one for trifluoromethyl radical, R "for an ethyl radical, R_ and R / an ethoxy radical and X and Y are sulfur. ^^ 5 · Compound according to claim 2, characterized in that R ₁ for one Trifluoromethyl radical, R "for a methyl radical, R, and R. for an ilethoxy radical and X and Y stand for sulfur, 6 · Connection according to claim 2, characterized in that R. for a Trifluoromethyl radical, R «for a methyl radical, SL and JL for an isopropoxyreet and X and Y stand for sulfur, 7 «A compound according to claim 2 _t wherein R ₁ is a Pentafluoräthylreet, R_ is a methyl group, R. H and for a Methoxyresb and Y and X is sulfur. 8. A compound according to claim 2, characterized in that R _{1 is} for one Pentafluoroethyl radical, R "for a methyl radical, R, and R. for an ethoxy radical and X and Y are sulfur. 9 «connection according to claim 2, characterized in that R. for one Difluoromethyl radical, R "for a methyl radical, R, and R. for an ethoxy radical and X and Y are sulfur. 10.Verbconnection according to claim 2, characterized in that R ₁ for a difluoromethyl radical, R ^ for a butyl radical, R, and R. for an ethoxy radical and X vxiS. Ύ stand for sulfur. 009852/2280 -.29 - 11, compound according to claim 2, characterized in that R 'stands for a 2-Trifluormethylpropylrest, R »for a methyl radical, H, and R. for an ethoxy radical and X and Y stand for sulfur " 12. A compound according to claim 2, characterized in that R _{1 is} a chlorodifluoromethyl _{radical, R p is} a methyl radical, R, and R. are an Äthüxyrest and X and Y are sulfur, 13 »Connection according to claim 2, characterized in that Rv for one Trifluoromethyl radical, R "for a methyl radical, R, and R. for a phenyl radical and X and Y are sulfur. 14. A compound according to claim 2, characterized in that R _{1 is} a trifluoromethyl radical, R _? for a methyl radical, R, and R, for an ethoxy radical, X and Y for oxygen. 15. A compound according to claim 2, characterized in that R. for one Trifluoromethylrest, R "for a Hethylrest, R, and R- for one Ethoxy radical, X for oxygen and Y for sulfur. ; 16. A compound according to claim 2, characterized in that R _{1 is} for one Trifluoromethyl radical, R ₂ for a methyl radical, R for an ethoxy radical, R. for an ethyl radical, X for oxygen and Y for sulfur. 17 · Pesticidal preparation, characterized in that it is used as a pesticidal Active ingredient contains a compound of claims 1 to 16 wherein Q is for -CH ₂ X - P ^R 4
stands »The patent attorney 009852/2280 BATH ORIGINAL