CS208462B2 - Insecticide,acaricide and fungicide means and method of making the active substance - Google Patents

Description

(54) An insecticidal, acaricidal and fungicidal composition and a process for the manufacture of an active ingredient

The present invention relates to an insecticidal, acaricidal and fungicidal composition comprising as active ingredient at least one novel cyclopropanecarboxylic acid ester. The invention further relates to a process for the preparation of these cyclopropanecarboxylic acid esters.

The novel cyclopropanecarboxylic acid esters correspond to the general formula I in which

X Br

III-C-CH-CH

AND

Br

-CH-C-O-CH

AND

CH, (I)

R1 is hydrogen, methyl, cyano or ethynyl, X is chloro or bromo and

Y is halogen, methyl or trifluoromethyl.

Halogen means fluorine, chlorine, bromine or iodine, in particular fluorine or chlorine.

The compounds of formula I are prepared in a manner known per se, for example as follows:

X Br

1) XC.-CH-CH-CH-COOH + Z-CH-f-VOX I / c ^from Br .. / X.

acid binding agent (I) (II)

X Br

I |

2) XC-CH-CH-CH-CO 2 + HO-CH ^{1 with} r ^{z 1}

Br / x R / X C

acid binding agent (I)

X Br ii

3) XC-CH-CH-CH-COOH + HO-CH ^1x c ^z

Br / h ₃ c ch ₃ (II) water binding agent (i)

X Br (v)

4) X - C - C - CH - CH - COOR + HO - CHO - X

Br

V / \ _ h ₃ c ch ₃ (VI)

V M (V)

-ROH (I)

X

5) C = CH-CH — CH-COOCH / VI ^{x R1} bromo (I)

In formulas III, V and VII the symbols Η, β Ϊ have the meanings given for formula I

In formulas III and IV, Z represents a halogen atom, in particular chlorine or bromine, and in formula VI, R represents a C1-C4 alkyl group, in particular a methyl or ethyl group.

Suitable acid-binding agents for processes 1 and 2 are, in particular, tertiary amines such as trialkylamine and pyridine, furthermore hydroxides, oxides, carbonates and acid carbonates of alkali and alkaline-earth metals and alkali metal alkoxides such as potassium tert-butoxide and sodium methoxide.

For example, dicyclohexylcarbodiimide can be used as the water-binding agent for process 3.

Processes 1 to 5 are carried out at a reaction temperature of between -10 and 120 ° C, mostly between 20 and 80 ° C at normal or elevated pressure, preferably in an inert solvent or diluent. Suitable solvents or diluents are, for example, ethers and ether compounds such as diethyl ether, dipropyl ether, dioxane, dimethoxyethane and tetrahydrofuran; amides such as N, N-dialkylated carboxylic acid amides; aliphatic, aromatic and halogenated hydrocarbons, in particular benzene, toluene, xylenes, chloroform and chlorobenzene, nitriles such as acetonitrile, dimethylsulfoxide and ketones such as acetone and methyl ethyl keto.

The starting materials of formulas II to VII are known or can be prepared analogously to known methods.

✓

The compounds of formula I occur as a mixture of different optically active isomers, unless uniform optically active starting materials are used in the preparation. Various mixtures of isomers may be separated into the individual isomers according to known methods. A compound of formula I is to be understood as meaning both the individual isomers and mixtures thereof.

The compounds of formula I are suitable for controlling various animal and plant pests.

In particular, the compounds of the formula I are suitable for combating insects, phytopathogenic mites and germs, for example of the order of the butterflies (lepidoptera), beetles (Coleoptera), homoptera (Heteroptera), diptera (Diptera), acarina, Thysanoptera, Orthoptera, Anoplura, Siphonaptera, Mallophaga, Thysa ara, Isoptera, Psocoptera and Hymenoptera.

In particular, the compounds of the formula I are suitable for combating insect pests, in particular voracious insect pests, in ornamental and crop plants, in particular in cotton crops (for example against Spodoptera littoralis and Heliothis virescens) and in vegetable crops (for example Colorado potato beetle [ Leptinotarsa decemlineata] and peach aphid [Myzus persicae]).

The active compounds of the formula I also show a very favorable action against flies, such as the house fly (Musea domestica) and mosquito larvae.

The acaricidal or insecticidal effect can be substantially extended and adapted to the given conditions by the addition of further insecticides and / or acaricides. Suitable additives are, for example, organic phosphorus compounds, nitrophenols and their derivatives, formamidines, ureas, other pyrethrin-type compounds as well as carbamates and chlorinated hydrocarbons.

With particular preference, the compounds of the formula I are also combined with substances which have a synergistic or potentiating effect on the pyrethroids. Examples of such compounds are, but are not limited to, piperonyl butoxide, propynyl ether, propynyl oximes, propynyl carbamates and propynyl phosphates, 2- [3,4,4-methylenedioxyphenoxy) -3,6,9-trioxaundecane (Sesamex and Sesoxane, respectively), 2-methylenedioxy-4- (2- (octylsulfonyl) propyl) benzene.

The compounds of formula I may be used alone or together with suitable carriers and / or other additives. Suitable additives may be solid or liquid and corresponding to those customary in the preparation of such compositions, such as natural or regenerated substances, solvents, dispersants, wetting agents, adhesives, thickeners, binders and / or fertilizers.

The compositions according to the invention are prepared in a manner known per se by thoroughly mixing and / or grinding the active compounds of the formula I with suitable carriers, optionally with the addition of dispersants or solvents inert to the active compounds.

Active substances may be present and used in the following forms of processing:

solid processing forms: dusting, spreading, granulate (coated granulate), impregnated granulate and homogeneous granulate;

liquid processing forms: (a) water-dispersible concentrates of the active substance: wettable powders, pastes, emulsions;

(b) solutions.

The active substance content of the above-described compositions is between 0.1 and 95%, provided that concentrations of up to 99.5% or even pure active substance can be used when applied from aircraft or other suitable application devices. The active compounds of the formula I can be used in the formulations, for example, as follows (parts are parts by weight):

Popi'aš:

The following substances are used for the preparation of (a) 5% and (b) 2% dusts:

(a) 5 parts active substance 95 parts talc;

(b) 2 parts active substance part highly dispersed silicic acid 97 parts talc.

The active ingredient is mixed with the carriers and the mixture is ground.

Granulate:

The following substances are used to prepare the 5% granulate:

parts of the active substance

0.25 parts of epichlorohydrin

0.25 parts of cetyl polyglycol ether

3.50 parts of polyethylene glycol parts of kaolin (grain size 0.3-0.8 mm).

The active ingredient is mixed with epichlorohydrin and the mixture is dissolved in 6 parts of acetone, after which polyethylene glycol and cetyl polyglycol ether are added. The solution thus obtained is sprayed on to the solution and then the acetone is evaporated off under vacuum.

Wettable powder:

For the preparation of a) 40%, b) and c) 25%, d), 0% wettable powder, the following substances are used:

(a) 40 parts of active substance parts of lignin sulphonic acid sodium salt 1 part of dibutylnaphthalenesulphonic acid sodium salt. 54 parts silicic acid;

(b) 25 parts of active substance

4.5 parts of lignin sulphonic acid calcium salt

1.9 parts of a mixture of chalk (provenance Champagne) and hydroxyethylcellulose (1: 1),

1.5 parts by weight of dibutylnaphthalenesulfonic acid sodium

19.5 parts of silicic acid

19.5 pieces of chalk (Prov. Champagne)

28.1 parts of kaolin;

(c) 25 parts of active substance

2.5 parts isooctylphenoxypolyethylenethanol

1.7 parts of chalk (prov. Champagne) and hydroxyethylcellulose (1: 1)

8.3 parts of sodium aluminum silicate

16.5 parts of diatomaceous earth 46 parts of kaolin;

d) 10 parts of active substance parts of the mixture of sodium salts of saturated sulphated fatty alcohols parts of the condensation product of naphthalenesulphonic acid and formaldehyde

8 / parts of kaolin.

The active ingredient is thoroughly mixed with the additive in suitable mixers and ground in appropriate mills and rollers. A wettable powder is obtained which is suitable for dilution with water to prepare suspensions of the desired concentrations.

Emulsifiable concentrates:

For the preparation of a) 10%, b) 25% and o) 50% emulsifiable concentrate, the following substances are used:

(a) 10 parts of active substance

3.4 parts of epoxidized vegetable oil

3.4. Part of a combined emulsifier consisting of a glycol ether of a fatty alcohol and a calcium salt of an alkylarylsulphonic acid, parts of a dimethylformamide

43.2 parts of xylene;

(b) 25 parts of active substance

2.5 parts of epoxidized vegetable oil parts of a mixture of alkylarylsulphonate and fatty alcohol polyglycol ether parts of dimethylformamide

57.5 parts xylene;

(c) 50 parts of active substance;

4.2 parts of polyglycol ether of tributylphenol

5.8 parts dodecylbenzenesulfonic acid calcium salt parts cyclohexanone 20 parts xylene.

Emulsions of any desired concentration can be prepared from such concentrates by dilution with water.

Spraying agent:

The following ingredients are used to prepare a) 5% and b) 95% of the spray composition:

(a) 5 parts by weight of epichlorohydrin (parts by weight of gasoline (boiling range 160 to 190 ° C));

(b) 95 parts active ingredient parts epichlorohydrin.

Example 1

Preparation of 3- (2 ', 2'-Dichloro-1', 2'-dibromethyl) -2,2-dimethylcyclopropanecarboxylic acid alpha-cyano-N- (3-trifluoromethylphenoxy) benzyl ester

14.5 g of alpha-cyano-m- (3-trifluoromethylphenoxy) benzyl 3- (2 ', ^2' -dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate acid are dissolved in 100 ml of carbon tetrachloride. Bromine (4.77 g) was added dropwise at 20-30 ° C. The reaction mixture was stirred for two hours.

After distilling off the carbon tetrachloride, a compound of the formula is obtained

Cl O CN

I II I

CI-C-CH-CH-CH-CO-CH ¹¹ XT

Br Br% h ₃ c ch ₃

CF, with elsewhere (mixture of isomers) having a refractive index of n = 1 and 1.5823

The following compounds can be prepared in an analogous manner:

Cl Br o

I I V

CI-C-CH-CH-CH-C-O-CH

Br

In / ch ₃ ch ₃

n °: 1.5688 mixture of isomers

Cl Br O ¹¹ II

CI-C-CH-CH-CH-C-O-CH-O-O

AND

Br

X ch ₃ ch ₃

n °: 1.5689

Cl Br

O

II

CI-C-CH-CH-CH-CO-CH 2 ^{x 1} L

Br _Z C CN ch _3> ch ₃ i trans np ° 1 1.5439

Cl Br O

II II,

CI-C-CH-CH-CH-CO-CH11 ^;

Br / ^C \ CN

CH, CH,

° C: 1.5799 ΐ trans

Cl-C

AND

Br

Cl Br

AND

- <1 H-CH-CH-C-O-CH

X

CH, CH,

, 40

1.5695 - cis

Cl Br

I I

CI-C-CH-CH-CH-CO, CH ¹ V

Br / \

CH, CH,

n °: 1.5809

Cl Br

CI-C-CH-CH-CH-CO, CH, -

Br ₃ ch ₃

Cl Br

CI-C-CH-CH-CH-CO ₂ CH ₂ -Z \

P \ ... ° -Q- _f η £ ^υ : 1.5810

Cl Br i

CI-C-CH-CH-CH-CO (CH3) II \ / ^Z | - W) = \ ^CN ° ~ O

X ch ₃ n ₃ nj? ⁹ : 1, 5641

Cl Br! í.

Cl-O-CH-CH-CH-CO ₂ CHBr

X.

Ί

CN

F ° X to ⁹ _: 1.5656

Cl Br

Cl-C-CH-CH-CH-CO ₂ CH-G>

'' y v

Br ₃ ch ₃

CN nn ⁹ : 1.5658

Cl B i ci-c-ch-ch-ch-co ₂ ch ₂

I c

Br ./ \

Cl CH ₃ CH ₃ n ^ ° of 1.5854

Br Br ^{1 1} / = \ f

Br-C-CH-CH-CH-CO ₂ CH _{2 -} 4 A f ₃ 'ch ₃ ^0- d /

Br n °; 1,5900

Br Br I I

Br-C-CH-CH-CH-CO ₂ CH, F

LV ^x

Br zK ch ₃ ch ₃ ° -O

4 °; 1,5832

Br Br

Br-C-CH-CH-CH-CO ₂ CH ₂

Br from ^C \ ch ₃ ck ₃

Cl ° x: 1.6025

Br Br

I I

Br-C-CH-CH-CH-CO, CH

I \ ι

Br CN

CH

I ₃ = CH ₃ F \ ° Á_Z ^"F

Πρ °: 1.5855

Example 2

Insecticidal fire effect

Cotton plants are sprayed with a 0.05% aqueous emulsion of the active ingredient (obtained from a 10% emulsifiable concentrate).

After the spray layer has dried, the cotton plants are always occupied by larvae of the species Spodoptera littoralis and Heliothis virescens in the third larval stage. The experiment was carried out at 24 ° C and 60% relative humidity.

The compounds of Example 1 exhibit good insecticidal ingestion activity against Spcdoptoro larvae in the above test. littoralis and Heliothis virescens.

The test results are shown in the table below.

Example 3

Acaricidal effect

Bean plants (Phassolus vulgaris) are contaminated 12 hours prior to the acaricidal effect test by applying an infested piece of leaf with a spider mite (Tetranychus urticae). Overlaps of the moving stages are sprayed with a chromatographic sprayer with emulsifiable test preparations so as not to lose the spray suspension.

After 2 and 7 days, the larvae, adults and eggs were scored for both live and dead individuals and expressed as a%. For the duration of the experiment, the treated plants were kept in greenhouse cabins at 25 ° C.

The compounds of Example 1 are active in the above test against adults, larvae and eggs of the spider mite (Tetranychus urticae).

The test results are shown in the table below:

Table . '

Minimum concentration in ppm to achieve 100% mortality

Spodoptera littoralis larvae

Heliothis virescens larvae

Tetranychus urticae larvae

About CN

Br

II

-F

400

Cl

O

II

100 ALIGN!

100 ALIGN!

400 continued table

Spodoptera littoralis larvae

Heliothis virescens larvae

Tetranychus urticae larvae

CH ₃ *? C = CH - CH - CH - COO - CH, γη ^X \ /

CH, ~>200> 200 ch ₃ ch ₃ (known substance from Dutch patent specification 7 409 256)

Cl

O

II

CN

CI-C-CH-CH-CH-CO-CH 2 In ^Br _3- h ₃

CF,

400

Cl

AND

CN

CI-C-CH-CH-CH-CH-O-CH-O-O- [2-]

200

Br Br from ^C \ ch ₃ ch ₃

Cl

Cl O CN

I II I

CI-C-CH-CH-CH-CO-CH II ^x c ^from Br BrCH ₃ CH ₃

400

Cl

CN

AND

CI-C-CH-CH-CH-C-O-CH-m-O-CH

For CI <CH X ύΠβ in 3

100 ALIGN!

Claims (6)

OBJECT OF THE INVENTION Insecticidal, acaricidal and fungicidal composition, characterized in that it contains at least one cyclopropanecarboxylic acid ester of the general formula I as an active ingredient. X Br, O 11 'II C-CH-CH-CH-C-O-CH I, Y Br z \ CH, (I) X 208462 in which R 1 is hydrogen, methyl, cyano or ethynyl, X is chloro or bromo and Y represents halogen, methyl or trifluoromethyl, together with carriers and / or other additives. 2. The composition according to item 1, characterized in that it contains a compound of the formula as active ingredient Cl About CN Cl --C - CH - CH - CH - C - O - CH - Br Br Z \ H ₃ C ch ₃ 3. A composition according to claim 1, wherein the active ingredient is a compound of formula Cl About CN CI-C-CH-CH-CH-C-Oi i Br Br / \ H ₃ c CH ₃ ° - ^CH CTíX 4. A composition according to claim 1, characterized in that: The composition of claim 1 wherein the active ingredient is a compound of formula Cl About CN CI-C-CH-CH-CH-CO-CH ^{1 X} c ^/ Br.Br h ₃ c ch ₃ 5. A composition according to claim 1, wherein the active ingredient is a compound of formula Cl o CN • ^X C ^Z Br Br / \ Cl-C-CH-CH - CH-C-O-CH - ^^ j ^ PO ^ jj H ₃ C CH ₃ ^F 6. A process according to claim 1, wherein the compound of formula (I) is brominated Xy ^x C = CH-CH = CH-COO-i-ii-O-rr ^ x ^of X and Lil iz \ ^H 1 H ₃ C CH ₃ in which R 1, X and Y are as defined in point 1.