DE2810031A1 - ALPHA- OR BETA-SUBSTITUTED ISOVALERIAN ACEUREESTER CONTAINING SCHAEDLING INJECTENT - Google Patents

Description

description

The invention relates to new insecticides which have an isovalerxanoic acid ester with a substituent group as the active ingredient contained in the Oi or ß-position, the isovaleric acid ester the general formula

CH ₃

' CH

'. rnnrvi I / γ

COOCH

A O

X X "CH

wherein Z is hydrogen, .. C ₅ V or C CH ₂ ,

x as / _x

X .CH .. X _n ^ ^ ^0Η \ /

ZC CH or ^C , meaning

• ² XY tet,

^χ X

1 '

when S is hydrogen, or .hydrogen- ₍ C - ^

represents if E "'- / V ^ t ₁ ^{/ oäer}

X t-H

X / ^CH _X / ^X

C is CH ₂ -, α then ^: when -2 is / ^C Ss ^ ^, cyano

X X CH

or ethynyl represents or otherwise represents hydrogen, cyano or ethynyl, provided that X and Y are the same or are different and are each chlorine or bromine.

The isovalerxanoic acid ester substituted in the CT or ß-position The general formula (I) includes four types of substituted isovalerxanoic acid esters represented by the following general formulas (I-A), (I-B), (I-C) and (I-D) can be:

809838/0722

/ -irr / "* Ή

C _{H </} CH ₃

X CH

C CH

X CH COOCH- / ⁷ M

(A: -CN or -C =

CH ₀ CH

CH

X JCH, CH

C CH ₀ COOCH-

² i

X A

f \

(A: -H, -CN or -C = CH)

(I-A) (I-B)

CH ₀ CH ₀

X ^ CH C COOCH

f ^CH 2 ^CH 2 A

(A: -H, -CN or -C = CH) (I-C)

CH CH

CH CH ₀ A

i ²

(A: -H, -CN or -C = CH) (I-D)

809838/0722

28 1003]

Since the discovery of BHC and DDT there has been a stormy - development of insecticides that are used as active ingredients Organophosphorus compounds, carbamates, chlorinated organic compounds or other types of compounds and used in agriculture and horticulture. The use of such insecticides has one causes a noticeable increase in the yield of useful plants, so that certain amounts of useful plants in a reproducible manner can be harvested without being influenced by climatic conditions. However, wise such insecticides used for agricultural and horticultural purposes not only have high toxicity towards human Weser, and domestic animals, but also cause high levels of environmental pollution. The chronic toxicity as well as the accumulation of such poisons is a major problem today. Furthermore are in many Areas agricultural pests such as green rice singing chirps, plant hoppers, etc. compared to the conventional Pest control parts that contain organic phosphorus compounds or carbamates have become resistant. Therefore there is a considerable need to create substitute active ingredients for the known active ingredients. Pyrethroid pesticides, such as allethrin, phthalthrin, resmethrin, furamethrin, pyrethrin etc. that have been used to combat have been used by household pests are not only of low toxicity to humans and pets, but also exert excellent pesticidal effectiveness that lasts long against harmful ones Insects out. In addition, they are known that the pests have little resistance to them to develop. As a result of their extremely low stability to light and their low residual activity however, these compounds cannot be used as pesticides in agriculture or in horticulture, replace organophosphorus or carbamate pesticides.

809838/0722

28T003I

Because of these circumstances, pesticides for agriculture and horticulture have been developed, which take advantage of the properties of pyrethroids, the traditional agricultural pesticides are not appropriate.

Of these recently developed pesticides are 3-phenoxybenzyl (Hl ·) ice, trans-2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylate (Permethrin, U.S. Patent 4,024,163) of the formula

and CX-cyano-3-phenoxybenzyl-CX- (4-chlorophenyl) isovalerate (Fenvalerate, U.S. Patent 3,996,244) of the formula

mentioned.

However, due to their high toxicity to fish, the applicability of these compounds is considerable restricted to those places where they would contaminate river water etc. if they were used. It was also reported that 3-phenoxybenzyl-Q (- (2,2-dichlorovinyl) isovalerate the formula

98 38/0722

281003t

Λ * V

CA COOCH ₂ -

and Ql- (allyl- or 3,3-dimethylallyl) -isovaleric acid esters of the following formulas

or

wherein A 'is hydrogen, alkynyl or cyano, a pesticidal activity against pests in the Agriculture, horticulture and household (Japanese Patent Publication No. 125723/1976 and U.S. Patent 4,042,710). However, none of these compounds have fully satisfactory pesticidal activity.

The invention has therefore set itself the task of creating a pesticide that has the characteristic properties of pyrethroids and moreover has a higher residual activity than the pyrethroids. The object is achieved by providing a number of isovalerxanoic acid esters with a substituent in the (X or β-position. It has been found that a class of 0 (~ or β-substituted isovalerxanoic acid esters of the general formula (I) markedly increased one has pesticidal effectiveness compared to the conventionally used allethrin, these compounds having excellent resistance to

809838/0722

over exposure to light as well as excellent hydrolysis resistance and very good residual activity exhibit. In addition, many of the compounds are not very toxic to fish. The Q- or ß-substituted Isovaleric acid esters of the general formula (I) are not only effective against pests in agriculture and in horticulture, which include rice plants, useful plants growing in dry fields, cotton plants, fruit trees, etc. infested, such as green rice hoppers (Nephotettia cincticeps UHLER), Planthoppers (Spgatella furcifera HORVATH, Nilaparvata lugens STÄL, Laodelphax striatellus FALLEN, etc.) Rice stem borer (Chilo suppressalis WALKER),

Cabbage-eating armyworms (Mamestra brassica LINNE), cabbage cockroaches (Plutella maculipennis CURTIS), moths and insects of the genus Catocala, conventional cabbage worms (Pieris rapae crucivora BOISDUVAL), Japanese giant silk spiders (Dictyoploca japonica BUTLER), rural leaf peas Scale insects, mustard beetles (Phaedon cochleariae Fab.), Cotton boll beetles, pink-colored larvae of the owl moth (Pectinophora gossypiella Saund), tobacco beetles, mites etc. are pesticidally effective, but also show excellent pesticidal activity against household pests such as house flies, mosquitoes, cockroaches, etc. ). It should be noted that when the CK- or β-substituted isovaleric acid ester of the general formula (I) is a racemate, excellent effects are also obtained when the racemate is broken down.

Of the Of-substituted isovaleric acid esters of the general Formula (I) have the (X-substituted isovaleric acid esters of the general formula (I-A) and the Of-substituted isovaleric acid ester of the general Formula (I-B) have a particularly pronounced pesticidal activity against the above-mentioned pests. the CX-substituted isovaleric acid esters of the general formula (I-A) and the (X-substituted isovaleric acid esters) of the general formula (I-B) have a more pronounced one

809838/0722

killing effect on pests in agriculture and horticulture, such as green rice leaf hoppers, as the known compound 3-phenoxybenzyl- (K- (2,2-dichlorovinyl) -isovalerate. In particular, the OC- (cyano- or -äthinyl) -3- phenoxybenzyl ester of (X- (2,2-dihalovinyl or -3, 3-dihalogenallyl) isovaleric acid has an excellent killing effect on pests in agriculture and horticulture.

Of the ß-substituted isovaleric esters of the general formula (IC) and the ß-substituted isovaleric esters of the formula (ID), the 3-phenoxybenzyl esters have a pronounced pesticidal activity against household pests such as house flies, while the ^ - (cyano- or -äthinyl) - 3-phenoxybenzyl esters have a pronounced killing effect on pests in agriculture and horticulture, such as green rice leaf hoppers. Most of the Oi- or ß-substituted isovaleric acid esters have an extremely low toxicity to fish and can be used in a promising manner as pesticides in those places where river water pollution and contamination can occur. Despite their varied pesticidal activities, the Λ- or ß-substituted isovaleric acid esters of the general formula (I) have a low toxicity towards humans and animals. Most of these compounds are hardly toxic to fish. They have a high resistance to light and hydrolysis and excellent residual activity.

The (X- or ß-substituted isovaleric acid esters of the general formula (I) are not only insecticides but also have a promising repellant effect against mites and / or produce synergistic effects with other biologically active compounds. Thus, the compounds (I) can be inexpensive as a control agent against insects occurring in agriculture and horticulture, insects that infest forests, insects that have a harmful effect on harvested crops, household insects, mil-

809838/0722

ben or other pests belonging to the following families: Tettigoniidae, Gryllidae, Gryllotalpxdae, Blattidae, Reduviidae, Pyrrhocoridae, Cimicidae, Delphacidae, Aphididae, Diaspididae, Pseudococcidae, Scarabaeidae, Dermestidae, Coccinellidae, Tenebrionidae, Chrysomelidae, Bruchidae, Tineidae, Noctuidae, Lymantriidae, Pyralidae, Culicidae, Tipulidae, Stomoxydae, Trypetidae, Muscidae, Calliphoridae, Pulicidae, Tetranychidae and Dermanyssidae.

Examples of OC- or ß-substituted isovaleric acid esters of the general formula (I) are given below:

Connection no.

(D

(2)

Structural formula

cji · γ " < O s ^ ss ^ - COOCH- \ CN 3

"^ -Cyano-B-phenoxybenzyl- Ci- (2,2-dichlorovinyl) isovalerate

CJl-

COOCH

CECH \

^f f W

CX -ethynyl-3-phenoxybenzyl - C \ - (2,2-dichlorovinyl) isovalerate

809838/0722

Connection no .

Structural forms? "10031

(3) Br

BrV

CN

CX'-cyano-S-phenoxybenzyl-3C- (2,2-dibromovinyl) isovalerate

(4)

cscH ~ \ ₀ . // Vs

(5)

(6) Oc '-Äthinyl-3 -phenoxybenzyl- octyl (2, 2-dibromovinyl) -isovalerat

Cl-

Cl

3-phenoxybenzyl- OC - (3,3-dichloroallyl) isovalerate

Cl

COOCH-CN

^! X-cyano-3-phenoxybenzyl-0c '- (3, 3-dichloroallyl) isovalerate

809838/0722

Connection no .

81003 1;

Structure formula

(7)

(8th)

(9)

(10)

cooch

-f ^

\ V

CJU

CS /

C * ethynyl-3-phenoxybenzyl-Ct- (3, 3-dichloroallyl) isovalerate

Br. • Br

COOCH,

3-phenoxybenzyl- 0 (- (3,3-dibromoallyl) isovalerate

Br

Br

: Y

(X -Cyano-S-phenoxybenzyl-CX- (3, 3-dibromoallyl) isovalerate

Br Br

COOCH

CK -Athynyl-S-phenoxybenzyl-Cx - (3, 3-di bromallyl) isovalerate

(11) O Q

, COOCH,

3-phenoxybenzyl-ß- (3,3-dichloroallyl) isovalerate

809838/0722

Connection no .

Structural formula

(12)

Cl

.COOCH CN

CX-Cano-S-phenoxybenzyl-ß- (3,3-dichloroallyl) isovalerate

(13)

(X- Ethynyl-3-phenoxybenzyl-ß- (3 _r 3-dichloroallyl) -isovalerate

(14) Br

Br

COOCH

3-phenoxybenzyl-ß- (3,3-dibromoallyl) isovalerate

(15) Br Br

CV-Cyano-S-phenoxybenzyl-ß- (3,3-dibromoallyl) -isovalerat

809838/0722

Connection no .

Structural formula

(16)

V>

Br Br

Cl -ethynyl-3-phenoxybenzyl-ß- (3,3-dibromoallyl) isovalerate

(17) APPROX.

Cl

Cl

3-phenoxybenzyl-ß- (1,3,3-trichloroallyl) isovalerate

(18) C91

kX,

I Cl

COOCH CN

(X -Cyano-S-phenoxybenzyl-ß- (1,3,3-trichloroallyl) isovalerate

(19) Cl

Cl '

COOCH

C £

OC -ethynyl-S-phenoxybenzyl-ß- (1,3,3-trichloroallyl) isovalerate

80983S / 0T22

Connection no.

Structural formula

(20)

Y C £

3-phenoxybenzyl-ß- (l-chloro-3,3-dibromoallyl) isovalerate

(21)

(22)

Ct -Cyano-3-phenoxybenzyl-ß- (1-chloro-3, 3-dibromoallyl) isovalerate

CJl

i> "-Ethynyl-3-phenoxybenzyl-β- (1-chloro-3,3-dibromoallyl) isovalerate

(23)

COOCH,

- Br

3-phenoxybenzyl-ß- (1-bromo-3,3-dichloroallyl) isovalerate

809838/0722

Connection no .

Structural formula

(24)

cooch — Λ y

CN "\

Br

\ J / W

(25)

Oc-cyano-3-phenoxybenzyl-ß- (1-bromo-3,3 dichlorallyl) isovalerate

Br

CX -ethynyl-3-phenoxybenzyl-ß- (1-bromo-3,3-dichloroallyl) isovalerate

(26)

c V

COOCH

Br

2 \ _

3-phenoxybenzyl-3- (1,3,3-tribromoallyl) isovalerate

(27)

(X -Cyano-S-phenoxybenzyl-ß- (1,3,3-tribromoallyl) -isovalerat

809838/0722

Compound no. Structural formula

(28)

Ov-ethynyl-3-phenoxybenzyl-ß- (1,3,3-tribromoallyl) isovalerate

Of the C \ - or ß-substituted isovaleric acid esters of general formula (I) are the ft'-substituted isovaleric acid esters of the general formula (I-A), the CX'-substituted isovaleric acid esters of the general formula (I-B) and the ß-substituted isovaleric acid esters of the general formula (I-C) new compounds. You can easily look at the following Prepare methods (i.) To (iii):

809838/0722

CX ₃ Y

X.

- 23 -

Treatment with fine base "" '

COOR

(It)

COOR (HU) X ₃ C

2310031

COOR

COOR

reduction

hydrolysis

COOR

(I'-A)

COOH

_Halogenating agent

(IV)

OY-

tertiary amine

Ester exchange ""

0OCH

(I-A)

Γ / COOR

^X or

COOR
(V)

(VI)

(VH)

Treatment with a base k COOR OOR

(vm)

hydrolysis

COOR COOH

(IX)

X.

COOH COOH

(X)

-CO.

(I'-B)

X
and or

809838/0722

cooii

R ^

Ester interchange

ORiGINiAL INSPECTED

- 24 -

COOCH

281003ί

Ozonolysis

COOR

(XI)

(XH)

(I'-B)

OH

(XIII)

(XIV)

CHX3

catalyst

^X 3 ^C

-HX X

Treatment jitit "

(XV) a base "

COOR

UP- <!
Ä

COOCH-

Ester exchange (iü-1)

_00R Ozono lyse-- OHC ^ / \, COOR

O-

(OT

(XVI)

86-9 «387 0-722

^X - ^ , COOR

X
(I'-C)

where R is lower alkyl, X and Y are the same or different and are each chlorine or bromine and A is hydrogen, cyano or ethynyl.

The CV-substituted isovaleric acid esters of the general formula (IA) are prepared by process (i) described above. First, a compound of the general formula (II) and a tetrahalomethane, for example tetrachloromethane (carbon tetrachloride), tetrabromomethane (carbon tetrabromide) or monobromotrichloromethane, are heated to 80 to 150 ^° C. in the presence of an initiator which generates free radicals, such as benzoyl peroxide (BPO), azobutyronitrile isobutyric , Acetyl peroxide or tert-butyl perbenzoate, heated to obtain a compound of the general formula (III). Then this compound of the general formula (III) with a base, such as 1, 5-diazabicyclo / 3,4,07-nonen-5 (DBN), 1, 5-diazabicyclo / 5,4, 0_7-undecene-5 ( DBU), sodium ethylate, KaÜum tert-butoxide, sodium hydroxide or the like. Treated, and the product obtained is reduced to a compound of the general formula (I'-A). The treatment with a base described above is in zv / eckmäßiger manner in a solvent such as chloroform, carbon tetrachloride, benzene, toluene, methanol, ethanol, tetrahydrofuran, η-hexane or the like., At a temperature of about 0 to about 100 ⁰ C. carried out. The reduction reaction is preferably carried out in an atmosphere of hydrogen gas and in the presence of a reduction catalyst, for example palladium-on-carbon, palladium-on-barium sulfate or palladium black, a solvent such as methanol, ethanol or η-hexane being used. One works at a temperature between room temperature and 100 ^° C.

809838/0722

Then the compound of the general formula (I'-A) is hydrolyzed in a conventional manner to the free carboxylic acid (I "-A), which in turn is treated with a halogenating agent such as thionyl chloride, thionyl bromide, phosphorus trichloride, phosphorus tribromide, phosphorus oxychloride, phosphorus oxybromide or the like., to obtain the corresponding carboxylic acid halide (I " ¹ -A) is treated. This carboxylic acid halide (I " ¹ -A) is further reacted with an alcohol of the general formula (IV) in the presence of a tertiary amine, such as pyridine or triethylamine. The O ( -substituted isovaleric acid ester of the general formula (IA An (X'-substituted isovaleric acid ester of the general formula (IA) can also be prepared from a compound of the general formula (I'-A) or a free carboxylic acid of the formula (I "-A) by various other methods known per se v / ground, for example by the following methods: (a) after a transesterification process, which consists in reacting a compound of the general formula (I'-A) directly with an alcohol of the general formula (IV), (b) after an esterification reaction, which consists in a denydrating condensation, which is carried out in such a way that a free carboxylic acid of the general formula (I "-A) is reacted with an alcohol (IV), ( c) an esterification process, during which a salt of a free carboxylic acid (I "-A) is reacted with an alkali metal, silver or an organic tertiary base with a sulfoxylate or halide of an alcohol (IV) or a quaternary ammonium salt thereof, and (d ) an esterification reaction which consists in making the acid anhydride of the free carboxylic acid (I "-A) react with an alcohol (IV).

The Oi-substituted isovaleric acid esters of the general Formula (I-B) can be prepared by process (ii) described above. First is a lower alkyl ester of isopropylmalonic acid of the general formula (V) with a halogen compound of the general formula (VI) or (VII), such as 1,1-dichloro-3-bromo-i-propene, 1,1-dibromo-3-chloro-1-propene, 1,1,3-trichloro-1-propene, 1,1,3-tribromo-1-propene, 3,3,3-trichloro

809838/0722

propene, 3,3,3-tribromo-i-propene or the like =, reacted in the presence of a basic reagent at a temperature between 0 and 100 ⁰ C to produce a compound of the general formula (VIII). Examples of such basic reagents are sodium methylate, sodium ethylate, sodium tert-butylate, potassium tert-butylate, sodium hydride, sodium amide, butyllithium, sodium hydroxide, potassium hydroxide, sodium carbonate, 1,5-diazobicyclo / 5,4,0_7-undecene-5 ( DBU) and 1, S-diazabicyclo / S, 4, Q7 ~ nonen-5 (DBN). Then the compound of the general formula (VIII) is reacted with potassium hydroxide, sodium hydroxide or the like and then neutralized with an acid. By means of this hydrolysis treatment, which is known per se, the monoester of the general formula (IX) and / or the dicarboxylic acid of the general formula (X) can be obtained. Depending on the hydrolysis conditions, for example depending on the relative amount of potassium hydroxide, sodium hydroxide or the like, based on the compound of the general formula (VIII), as well as depending on the time and the reaction temperature, etc., either a compound of the general formula ( IX) or a compound of the general formula (X) or a mixture of (IX) and (X) can be obtained. The Monoester of the general formula (IX) and / or the dicarboxylic acid of the general formula (X) is a Dacarboxylierungsreaktion subjected by heating to a temperature between 120 and 250 ⁰ C, whereby a compound of general formula (1'-B) and / dder a free carboxylic acid of the general formula (I "-B) is obtained. If the compounds of the general formula (I ¹ -B) and the free carboxylic acid of the general formula (I" -B) are obtained as a mixture, then these compounds can be separated from one another Distillation or the like. Be separated. Optionally, the mixture can also be hydrolyzed to convert the compound of the general formula (I ¹ -B) into the free carboxylic acid (I "-B). The compound of the general formula (I'-B) can also be easily prepared by the method ( ii-1 are prepared). Thus, ozone gas is 7 d unsaturated Carbonsäureesters the general formula (XI) in a solvent such as methanol or η-hexane in a solution of $, bubbled at -20 ⁰ C to -10 ⁰ C, a Aldehyde compound of the general formula (XII)

309838/0722

is obtained. This compound of the general formula (XII) is then subjected to the so-called Wittig reaction, ie reacted with the phospholane which is formed from tripheny! Phosphine and a carbon tetrahalogen oxide (US Pat. No. 4,024,163), a compound of the general formula ( I ¹ -B) is obtained in a simple manner. The above-mentioned carbon tetrahaloxide is preferably carbon tetrachloride or carbon tetrabromide. The Wittig reaction is conveniently carried out in the solvent which has been used to prepare the phospholane, but it can also be carried out in any other solvent that does not affect the Wittig reaction, for example in methylene chloride, benzene or the like CC-substituted isovaleric acid ester of the general formula (IB) can be obtained in such a way that either the compound of the general formula (I ¹ -B) or the free carboxylic acid of the general formula (I "-B) undergoes an ester exchange reaction similar to the method described above (i) is subjected.

The β-substituted isovaleric acid ester of the general formula (IC) can be prepared by process (iii) described above. First, an o-carboxylic acid ester (XIII) is left on 3-methyl-2-butene-1-oil in the presence of an acidic catalyst, such as propionic acid, butyric acid, valeric acid, p-toluenesulfonic acid, phenol or hydroquinone, at a temperature between 120 and 160 ⁰ C. This reaction gives the jft 0 -unsaturated carboxylic acid ester (XIV) (Japanese Patent Publication 65710/1976 and 86410/1976). Then this iT, Q -unsaturated carboxylic acid ester (XIV) is reacted with chloroform in the presence of a catalyst, for example in the presence of a free radical initiator such as azobisisobutyronitrile (AIBN), benzoyl peroxide (BPO), acetyl peroxide, di-tert-butyl peroxide, tert .-butyl peracetate, tert-butyl perbenzoate, tert-butyl perphthalate, tert-butyl-hydroperoxide or the like, ·, and at a temperature between 60 and 150 ⁰ C, the addition compound (XV) is obtained. This addition compound (XV) is then treated with a base such as sodium methylate, sodium ethylate, sodium tert-

80S838 / 0722

butylate, potassium tert-butylate, sodium isoamylate, 1,5-diazabicyclo / 5, 4, 0j7-undecen-5 (DBU), 1,5-diazabicyclo £ 3, 4, 0 / -nonen-5 (DBN), sodium hydroxide, potassium hydroxide, sodium amide, sodium hydride, butyl lithium or the like., treated at a temperature between -70 and + 150 ⁰ C, whereby a compound of general formula (I'-C) is obtained. The compound of the general formula (I'-C) can also be prepared by method (iii-1). This process can be carried out in the same manner as the process (ii-1) except that the compound of the general formula (XVI) is used in place of the compound of the general formula (XI). The ß-substituted isovaleric acid ester of the general formula (IC) can be obtained by an ester exchange reaction of the compound of the general formula (I'-C) in a manner analogous to the above-described process (i).

The ß-substituted isovaleric acid ester of the general formula (I-D) is only used as an intermediate in the synthesis of 2,2-Dimethyl-3- (2,2-dichlorovinyl) -cyclopropanecarboxylic acid known, which is the acid portion of the above-mentioned permethrin (Japanese Patent Publications 98248/1976, 125251/1976 and 125252/1976). The ß-substituted isovaleric acid ester of the general formula (I-D) can be easily prepared, for example according to the following procedure (iv)

- halogenating agents

(XVIE)

tertiary amine - "- X

where X and Y are identical or different and each represent chlorine or bromine, A is hydrogen, cyano or ethynyl is.

First, an .f-lactone of the general formula (XVII) is reacted with a halogenating agent to obtain a carboxylic acid halide of the general formula (I " ¹ -D). If the halogenating agent is thionyl chloride, phosphorus pentachloride or phosphorus oxychloride, a compound is obtained of the general formula (I " ¹ -D) where Y is a chlorine atom, while a compound of the general formula (I '" -D) in which Y stands for bromine is obtained when thionyl bromide or phosphorus pentabromide is used, for example, as halogenating agent (Japanese Patent Publication No. 121 £ 0/1977) The carboxylic acid halide of the general formula (I '"-D) can also be prepared by the method which consists in combining a Y-lactone of the general formula (XVII) with a thionyl halide in the presence of a Lewis acid catalyst, for example zinc chloride, tin tetrachloride or the like. As well as a hydrogen halide. The carboxylic acid halide of the general formula (I '"-D) is then reacted in an inert solvent with an alcohol of the general formula (IV) in the presence of a tertiary amine, such as pyridine or triethylamine, a β-substituted isovaleric acid ester of the general formula ( ID) is easily obtained (Japanese Patent Publication No. 125150/1977).

The Of- or ß-substituted isovaleric acid ester of the general Formula (I) (hereinafter referred to as active ingredient) can be used in the form of conventional formulations, for example in the form of solutions, emulsifiable concentrates, wettable powders, suspensions, dusts, grains, microfine grains, powders, coatings, aerosols, mosquito smoke snakes, Incense, slow-acting incense, electric mosquito smoke mats, capsules or Like. These formulations can be prepared by conventional methods, for example by mixing the active

809838/0722

Substance with a volume-generating agent, such as a liquid, a solid or a liquefied one Gas as a diluent or carrier (optionally with a surfactant such as an emulsifier and / or a dispersant and / or a foaming agent). If water is used as a volume-generating agent, then an organic solvent can be used as a cosolvent.

Suitable liquid diluents are, for example, aromatic ones Hydrocarbons such as xylene, toluene, benzene, alkylnaphthalenes etc., chlorinated aromatic or aliphatic hydrocarbons such as chlorobenzene, chloroethylene, methylene chloride etc., aliphatic or alicyclic hydrocarbons, such as cyclohexane, paraffin (for example mineral oil distillate), alcohols such as butanol, glycol and the ethers and esters of these Compounds, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, Cyclohexanone etc., strongly polar solvents such as dimethylformamide, dimethyl sulfoxide, acetonitrile etc. as well Water.

Under a liquefied gas diluent is a liquid to understand, which is gaseous at normal temperature and pressure. Mention may be made of aerosol propellants, for example dichlorodifluoromethane, Trichlorofluoromethane etc.

Preferred examples of solid diluents or carriers are finely divided naturally occurring minerals such as kaolin, clay, talc, lime, quartz, attapulgite, montmorillonite , diatomaceous earth, etc., as well as finely divided synthetic minerals such as aluminum oxide, silicates, etc.

Preferred examples of emulsifiers and foaming agents are nonionic and anionic emulsifiers, such as polyoxyethylene-aliphatic Carboxylic acid esters, polyoxyethylene-aliphatic Alcohol ethers, such as alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and albumin hydrolyzate. Preferred examples of dispersants are consumable

809838/0722

te lignosulfite liquid and methyl cellulose.

Adhesives such as carboxymethyl cellulose, powdery, granular or high molecular weight latex-like naturally occurring or synthetic compounds such as gum arabic, polyvinyl alcohol, polyvinyl acetate etc., can be used for Production of these formulations are used. Furthermore, colorants such as inorganic pigments, for example Iron oxide, titanium oxide, etc., as well as organic dyes such as alizarin dyes, azo dyes, phthalocyanine dyes etc., are introduced into the formulations.

The pesticidal effectiveness of the active ingredients according to the invention can also be improved by adding synergistic agents, for example N-octylbicycloheptene dicarboximide (trademark MGK-264), a mixture of N-octylbicycloheptene dicarboximide and alkylarylsulfonate (trademark MGK-5026), octachlorodipropyl ether, Piperonyl butylate, etc. The stability of the above-mentioned active ingredients, which are used as active ingredients of the Pest formulations can be present by the addition of an antioxidant of the phenolic, amine or another Type can be increased, for example by adding 2,6-di-tert-butyl-4-methylphenol (BHT), 2,6-di-tert-buty! Phenol etc.

Insecticidal agents or formulations with improved activity can be obtained by using the active ingredient according to the invention in combination with other pesticides. Such pesticides are chlorinated organic pesticides, such as DDT, BHC, methoxychlor etc., carbamates such as 1-naphthyl-N-methylcarbamate, 3,4-dimethylphenyl-N-methylcarbamate, 3,5-dimethylphenyl-N-methylcarbamate, 2-isopropoxyphenyl-N-methylcarbamate etc., organophosphorus compounds such as 0,0-dimethyl-O- (3-methyl-4-nitrophenyl) -phosphorothionate, DDVP / Ö, O-dimethyl-O- (2,2-dichlorovinyl) phosphate /, Diazinon, phenthione, 0,0-dimethyl-O-4-cyanophenylphosphorothionate, OjO-Diitiethyl-S-ZOf (ethoxycarbonyl) -benzylj-phosphorodithioate, 2-methoxy-4H-1,3,2-benzodioxaphosphorine-2-sulfide, O-ethyl-O-4-cyanophenyl-phenylphosphonothionate etc., cyclopropanecarboxylic acid esters, such as pyre-

809838/0722

thrin, allethrin, N- (3,4,5,6-tetrahydrophthalimido) -methylcrysanthemate (Tetrair.ethrin), S-benzyl-S-furylmethylchrysanthemate (resmethrin), S-propargylfurfurylchrysanthemate (furamethrin), 5-propargyl-2-propargyl -3-furylmethylchrysanthemate (proparthrin), 3-phenoxybenzylchrysanthemate (phenothrin), Oi-ethynyl-3-phenoxybenzylchrysanthemate, 3-phenoxybenzyl, 2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylate (permethrin), "-Ethynyl-3-phenoxybenzyl-2, 2-dimethyl-3- (2, 2-diochlorovinyl) -cyclopropanecarboxylate / 0 (-Cyano-3-phenoxybenzyl-2, 2-dimethyl-3- (2,2-dichlorovinyl) -cyclopropanecarboxylate etc. and substituted acetic acid esters, such as (X -Cyano-3 ~ phenoxybenzyl-vX - (4-chlorophenyl) -isovalerate, Oi-ethynyl-3 ~ phenoxybenzyl-Oi - (4-chlorophenyl) -isovalerate etc., mentioned.

In each formulation, the active ingredient is generally present in an amount from 0.01 to 95% by weight, preferably in one Amount from 0.1 to 90% by weight.

The active ingredient can be used in any of the formulations described above or formulated for further administration forms. The content of the active ingredient in each The form of application can vary within a wide range will. The concentration of the active ingredient in such an application form can be between 0.0000001 and 100% by weight and preferably vary in an amount from 0.001 to 10% by weight.

The pesticides that contain one of the active ingredients according to the invention, can be used according to routine methods that are adapted to the respective application.

The following synthesis examples, test examples, formulation examples and action examples illustrate the invention. In the formulation and action examples, all parts of the data relate to weight. The numbers of the compounds correspond to the Oi- or β-substituted isovaleric acid esters (1) to (28) of the general formula (I).

809838/07

Synthesis Example · 1

A mixture of 4.4 g of ethyl · -Oc-isopropyiacrylat and 40 g Honobromtrichiormethan 0.14 g of tert-Butyiperbenzoat added, whereupon the whole mixture is heated to 120 ⁰ C for a period of 12 hours. The reaction mixture is distilled to remove the low-boiling fraction and then subjected to a destination under reduced pressure, whereby 8.5 g of ethyl · --X -bromo-Oi- ( 2,2,2 -tricMoräthyl ·) -isovarate with a bp of 132 to 136 ° C / 0.8 mmHg (yield 81%) can be obtained.

6.0 g of the ethyl &'-bromo-Of'-C 2,2,2-trichioethyl) -isovaierats are suspended in 20 g of Ctaoroform. After adding 3.5 g of 1,5-diazabicyclo- / 5,4,0_7-undecen-5 (DBU), the solution is stirred at room temperature for a period of 2 hours. The reaction mixture is then diluted with dietary ether, washed with water and dilute aqueous hydrochloric acid, and dried over anhydrous magnesium sulfate. The low-boiling fraction is removed by destination, whereby 4.6 g of an oily product are obtained. On the basis of the NMR spectrum and the GC mass spectrum, this product is identified as ethyl-C \ '-isopropyl-β-trichloromethyl-acrylate, which contains a certain amount of ethyl-C \' -bromo-Oi '- (2,2-dichiorvinyl) -isovaierat contains 4.6 g of the eternal product raised above are dissolved in 50 ml of ethanol, followed by the addition of 0.4 g of a 5% panadium 3Uf -KoMe the solution is stirred in a hydrogen gas atmosphere at 55 ° C for a period of 6 hours. Finally, the reaction mixture is filtered to remove the catalyst, whereupon the ethanol is destined. The method described above gives 3.9 g of ethyl - 0 ("- (2,2-dichlorovinyl) isovalate in the form of an oil. 3.9 g of this ethyl - 0 {- Dissolve (2 ^ -dichiorvinyl ·) -isovaierats in 20 ml · ethanol · and add a solution of 2.0 g sodium hydroxide in 10 ml · water of the above-described ethanoi ^ solution The mixture is kept at room temperature for a period of 10 hours stirred. After completion

809838/0722

during this period the ethanol is distilled off. The residue is neutralized with aqueous hydrochloric acid and extracted with diethyl ether. The ethereal solution gives 2.9 g of CK- (2,2-dichlorovinyl) isovaleric acid with the following NMR spectrum (yield: 84%, based on ethyl-Oi'-brom- ζΚ - (2,2,2-trichloroethyl) ) -isovalerate)

CCl
NMR spectrum (60 MHz) <J ⁴

0.97 (d, J = 7Hz), 1 _t 03 (d, J = 7Hz), 6H; 1.83-2.36 (m) 1H; 3.23 (d, J = IOHz), 3.35 (d, J = IOHz) 1H; 6.04 (d, J = IOHz) IH.

1.8 "g of (X- (2, 2-dichlorovinyl) isovaleric acid are dissolved in 15 ml of dry benzene, followed by the addition of 3.5 g of thionyl chloride. The mixture is refluxed for a period of 5 hours. and then distilled to remove the low-boiling fraction .. According to the method described above, Oi- (2,2-dichlorovinyl) isovaleroyl chloride is obtained, This chloride is dissolved in 20 ml of benzene and 2.0 g of Oi-ethynyl-3-phenoxybenzyl alcohol is added Then 2.9 g of pyridine is added. The mixture is stirred at room temperature for a period of 8 hours. The resulting reaction mixture is diluted with diethyl ether, washed with water and dilute aqueous hydrochloric acid, and dried over anhydrous magnesium sulfate The low-boiling fraction is then distilled off, whereupon the residue is chromatographed on a silica gel column (benzene / n-hexane = 1: 1, volume / volume) The method described above gives 2.6 g of (χ'-ethyny 1-3-phenoxybenzyl-0 ('- (2,2-dichlorovinyl) isovalerate (compound (2)) with the following properties (yield: 71%, based on'Ck'- (2, 2-dichlorovinyl) isovaleric acid)

Nuclear Magnetic Resonance Spectrum (60 MHz) O ^ 3:

0.78-1 _f 06_ (m) 6H, 1, 80-2, 47 (m) 1H, 2.61 (d, J = 2Hz) 1H, 3.29 (dd, J = 7Hz + 10.Hz) 1H, 6.00 (d, J = IOHz) 1H, 6.44 (d, J = 2Hz) 1H, 6, & 5-7.55 (m) 9H
Elemental analysis (calculated in brackets) _;

809838/0722

C% 65.65 (65.52)
H% 5.09 (5.00)

Synthesis example 2

2.0 g of C * '- (2,2-dichlorovinyl) isovaleric acid are dissolved in 20 ml of dry benzene, followed by the addition of 6.0 g of thionyl chloride. The mixture is refluxed overnight. It is then distilled to remove the low-boiling fraction, yielding CY- (2,2-dichlorovinyl) isovaleroyl chloride. This (X- (2,2-dichlorovinyl) isovaleroyl chloride is dissolved in 25 ml of dry benzene, followed by the addition of 2.3 g of OC-cyano-3-phenoxybenzyl alcohol, followed by 2.4 g of pyridine. The mixture is stirred at room temperature overnight. The reaction mixture obtained is diluted with diethyl ether, washed with water and dilute aqueous hydrochloric acid, dried over anhydrous magnesium sulfate and distilled to remove the low-boiling fraction. Column chromatography is carried out using the residue, whereby 3, 2 g of iX-cyano-3-phenoxybenzyl- (X- (2, 2-dichlorovinyl) isovalerate (compound (1)) is obtained, which has the following properties (yield: 78%, based on Of- (2.2 -Dichlorovinyl) -isovaleric acid).

run
Nuclear Magnetic Resonance Spectrum (60 MHz) 6 ^ 3:

0.78-1.04 (m) 6H, 1.74-2.40 (m) 1H, 3.31 (dd, J = 7Hz + 10Hz) 1H 5.95 (d, J = 10Hz) 1H, 6.33 (s) 1H, 6.87-7.53 (m) 9H Elemental analysis (calculated in brackets): C% 62.28 (62.39)

H% 4.70 (4.74)

Synthesis example 3

10.5 g of sodium hydride (approx. 50%) are washed with η-hexane and suspended in 430 g of benzene with stirring. 36.8 g of diethyl isopropyl malonate are added to this suspension, whereupon the Mix for a period of about 40 minutes on

809838/0722

281003t

The reaction mixture is allowed to reflux stand for a period of about 20 minutes and cool, whereupon 37.9 g of 1, i-dichloro-3-bromo-i-propene in different portions can be added. The mixture is then stirred under reflux for a period of 1.5 hours. After cooling down the reaction mixture is washed with water and dilute hydrochloric acid over anhydrous magnesium sulfate dried and distilled to remove the low-boiling fraction. The oil obtained is further reduced under Distilled pressure, 52.3 g of diethylisopropyl {3.3 dichloroallyl) malonate, which has the following NMR spectrum possesses (yield: 92%, based on diethyl isopropyl malonate).

NMR spectrum (60 MHz) p

0.94 (d, J = 7Hz) 6H, 1.22 (t, .J = 7Hz) 6H, 2.04-2.44 (m) 1H, 2.64 (d, J = 7Hz) 2H, 4.16 (q, J = 7Hz) 4H, 5.90 (t, J = 7Hz) 1H

8.8 g of the diethylisopropyl (3,3-dichloroallyl) malonate described above are dissolved in 20 g of ethanol. A solution of 6.4 g of potassium hydroxide in 10 g of water is added to the ethanol solution described above. The mixture is refluxed overnight. The reaction mixture is then distilled to remove the ethanol. Sufficient dilute hydrochloric acid is added to acidify the residue. The residue is extracted with diethyl ether. The ethereal layer is dried over anhydrous magnesium sulfate and distilled to remove the low-boiling fraction. This method gives a mixture of isopropyl (3,3-dichloroallyl) malonic acid and monoethyl isopropyl (3,3-dichloroallyl) malonate. This mixture is subjected to a decarboxylation reaction at 180 to 230 ⁰ C under a reduced pressure of 35 to 60 mitiHg, whereupon 6.0 g of a mixture of Oi- (3,3-dichloroallyl) isovaleric acid and ethyl Ci - (3.3 dichlorallyl) isovalerate is obtained. 6.0 g of the decarboxylated mixture described above are dissolved in 20 g of ethanol. A solution of 1.2 g of sodium hydroxide in

809838/0722

10 g of water is added to the solution described above. The mixture is refluxed for 4 hours after which the ethanol is distilled off. The residue is acidified with dilute hydrochloric acid and extracted with diethyl ether. The ether layer is dried over anhydrous magnesium sulfate and distilled to remove the low-boiling fraction. The method described above gives 4.2 g of (X- (3,3-dichloroallyl) isovaleric acid with the NMR spectrum given below (yield: 70%, based on diethyl isopropyl (3,3-dichloroallyl) malonate).

NMR Spectrum (50 MHz) S ^^ Ai

HMo

1.01 (d, J = 7Hz) 6H, 1.67-2.67 (m) 4H, 5.94 (t, J = 7Hz) 1H

2.1 g of 0 (- (3,3-dichloroallyl) isovaleric acid are admixed with 3.0 g of thionyl chloride and 10 g of benzene, and the mixture is refluxed for a period of 5 hours Fraction distilled. This method gives (X- (3,3-dichloroallyl) isovaleroyl chloride. This chloride is dissolved in 30 g of dry benzene, followed by the addition of 2.0 g of 3-phenoxybenzyl alcohol. Then 2.0 g g of pyridine is added dropwise and the mixture is stirred at room temperature overnight. The reaction mixture is then diluted with diethyl ether, washed with dilute hydrochloric acid and water, dried over anhydrous magnesium sulfate and distilled to remove the low-boiling fraction. The viscous oil obtained as a residue is column chromatographed 3.1 g of 3-phenoxybenzyl-Qf "(3,3-dichloroallyl) isovalerate (compound £ 5)) are obtained with the following Properties (yield: 79%, based on OC- (3,3-dichloroallyl) -isovaleric acid.

ο ΓΠΡ1

NMR spectrum (60 MHz) ° TMS ^s

0.94 (d, J = 7Hz) 6H, 1.65-2.66 (m) 4H, 5.14 (s) 2H, 5.87 (t, J = 7Hz) 1H, 6.83-7.60 (m) 9H

809838/0722

Elemental analysis (calculated in brackets): C% 64.20 (64.13)

H% 5.58 (5.64)

Synthesis examples 4 and 5

The procedure described in Synthesis Example 3 is repeated, with the exception that 2.3 g of 3-cyano-3-phenoxybenzyl alcohol or 2.3 g of 3 (-ethynyl-3-phenoxybenzyl alcohol are used instead of 2.0 g of 3-phenoxybenzyl alcohol These methods give the corresponding (X- (3,3-dichloroallyl) isovalerylic acid esters (compound (6) or compound (7)). The yields, NMR spectra and elemental analysis values of these esters are summarized below:

Compound (6): Yield 3.5 g (84%)

NMR spectrum (60 MHz) p

0.78-1.05 (m) 6H, 1.63-2.52 (m) 4H,

5.60-5.94 (m) 1H, 6.38 (s) 1H, 6.85-7.55 (m) 9H

Elemental analysis (calculated in brackets)

C% 63.09 (63.17) H% 4.95 (5.06)

Compound (7): Yield 3.0 g (72%)

NMR spectrum (60 MHz)

fCDCl O _TMS

0.81-1.05 (m) 6H, 1.62-2.55 (m) 4H, 2.63 (d, J = 2Hz) 1H, 5.67-5.98 (m) 1H, 6, 47 (d, J = 2Hz) 1H, 6.87-7.55 (m) 9H elemental analysis (calculated in brackets) C% 66.31 (66.20)
H% 5.38 (5.31)

Synthesis example 6

In 100 g of methanol, 10.0 g of ethyl C \ be -allylisovalerat (general formula (XI), wherein R = -CH ₂ CH ₃₎ were dissolved, with cooling at -20 to -10 ⁰ C and stirring ozone gas into the solution weh-

809838/0722

bubbled in over a period of 8 hours. The reaction mixture is then added to 100 g of dimethyl sulfide at room temperature, whereupon the mixture is stirred at this temperature overnight. The reaction mixture is then distilled under reduced pressure to remove the low boiling fraction. The residue is diluted with 50 g of diethyl ether. Following the addition of 4 g of calcium chloride, hydrogen chloride gas is bubbled into the mixture at room temperature over a period of 10 minutes. Then 5 g of anhydrous potassium carbonate are added and the mixture is stirred thoroughly. The diethyl ether solution is washed with water, dried over anhydrous magnesium sulfate and distilled under reduced pressure to remove the low-boiling fraction. According to the method described above, 9.0 g of ethyl 2-isopropyl-3-formyl propionate (general formula (XII), where R = -CH ₂ CH ₃ ) (yield: 89%, based on ethyl-Oi- allyl isovalerate. The NMR spectrum of the aldehyde is as follows: (60 MHz) 'S ^ g ¹ ^: 9.74)

12.5 g of carbon tetrabromide are dissolved in 240 g of methylene chloride, followed by the addition of 19.8 g of triphenylphosphine connects. The mixture is stirred thoroughly. This mixed solution is 5 g of ethyl 2-isopropyl-3-formyl propionate, which has been prepared in the manner described above is added, whereupon the mixture is left over at room temperature Night is stirred. The low-boiling fraction is then distilled under reduced pressure, whereupon the residue is stirred well with diethyl ether and water. The diethyl ether layer is under reduced pressure to remove the low-boiling Fraction distilled. Petroleum ether is added to the residue. After thorough stirring, the petroleum ether solution becomes further distilled under reduced pressure to remove the low-talking fraction. The oily residue obtained is purified by distillation under reduced pressure. According to the method described above, 4.6 g are obtained Ethyl Oc'- (3,3-dibromoallyl) isovalerate (yield: 48%, based on on ethyl 2-isopropyl-3-formyl propionate)

809838/0722

NMR spectrum (60 MHz)

0.88 (d, J = 6.5Hz) 6H, 1.20 (t, J = 7Hz) 3H, 1.65-2.38 (m) 4H, 4.09 (q, J = 7Hz) 2H, 6.35 (t, J = 7Hz) 1H

1.1 g of sodium hydroxide are dissolved in a mixture of 7 g of water and 20 g of ethanol, whereupon 4.6 g of the ethyl CX- (3,3-dibromaliyl) isovalerate obtained above are added to the solution described above. The mixture is stirred at room temperature overnight and then refluxed for 3 hours. The reaction mixture is then distilled to remove ethanol. The residue is acidified by adding dilute hydrochloric acid and extracted with diethyl ether. The ether layer is dried over anhydrous magnesium sulfate and the low-boiling fraction is distilled off. The method described above gives 3.7 g of (3,3-dibromoallyl) isovaleric acid, the NMR spectrum of which is given below (yield: 88%, based on ethyl- Qi - (3,3-dibromoallyl) - isovalerate).

Nuclear Magnetic Resonance Spectrum (60 MHz) OgJJg 3:

0.92 (d, J = 6.5Hz) 6H, 1.67-2.42 (m) 4H, 6.39 (t, J = 7, Hz) 1H, 10.63 (S) 1H

2.0 g of Ot- (3,3-dibromoallyl) -isovaleric acid are dissolved in 20 g of benzene, followed by the addition of 4.7 g of thionyl chloride and 2 drops of N, N-dimethylformamide. The mixture is refluxed overnight and then distilled to remove the low boiling fraction. Qi (3,3-dibromoallyl) isovaleroyl chloride is obtained as the residue. This Oi '- (3,3-dibromoallyl) isovaleroyl chloride is dissolved in 30 g of dry benzene, whereupon 1.5 g of OC-ethynyl-3-phenoxybenzyl alcohol are added. This is followed by the dropwise addition of 1.6 g of pyridine. The mixture is stirred at room temperature overnight. The reaction mixture is then further ^{stirred at 40 to 50 °} C. for a period of 2 hours, whereupon it is diluted with diethyl ether, washed with dilute hydrochloric acid and water, over

809838/0722

281003)

anhydrous magnesium sulfate is dried and distilled to remove the low-boiling fraction. The viscous oil obtained is purified by column chromatography to give 2.0 g of (γ-ethynyl-3-phenoxybenzyl (X - (3, 3-dibromoallyl) isovalerate (compound (10)), which has the following properties ( Yield: 59%, based on Oi- (3,3-dibromoallyl) isovaleric acid) -

Λ CT) Pl
Nuclear Magnetic Resonance Spectrum (60 MHz) ^{ö TZc 3:}

0.74-1.03 (m) 6H, 1.60-2, 43 (m) 4H ₁ .
2.53-2.63 (Hi) IH, 6.12-6.50 (m) 2H, 6.8-4-7.50 (m) Elemental analysis (calculated in parentheses): C% 54.66 (54 .57)
H% 4.40 (4.38)

Synthesis Examples 7 and 8

The procedure described in Synthesis Example 6 is carried out with the exception that 1.4 g of 3-phenoxybenzyl alcohol or 1.5g OC-cyano-3-phenoxybenzyl alcohol instead the 1.5 g of CK'-Athiny 1-3-phenoxybenzyl alcohol are used These methods give the corresponding (X- (3,3-dibromoallyl) -isovaleric acid ester (compound (8) or compound (9)). The yields, NMR spectra and elemental analysis values of the esters are summarized below:

Compound (8): Yield 2.6 g (81%)

* · PDPl NMR spectrum (60 MHz) f) ^;

0.91 (d, J = 6.5Hz) 6H, 1.65-2.50 (m) 4H,

5.09 (s) 2H, 6.35 (t, J = 7Hz) 1H,

6.87-7.50 (m) 9H

Elemental analysis (calculated in brackets)

C% 52.18 (52.31)

H% 4.55 (4.60)

809838/0722

Compound (9): Yield 2.2 g (65%)

Elementary analysis (calculated in brackets) C% 51.97 (52.10)
H% 4.12 (.4.17)

Synthesis example 9

A pressure-resistant tubular reaction vessel is filled with a mixture of 20.0 g of ethyl 3,3-dimethyl-4-pentenate, 200 g of chloroform and 1.0 g of tert-butyl perbenzoate. After the tube has been closed, the contents are ^{heated to 120 °} C. for a period of 20 hours. Then, the reaction mixture is distilled to remove the low-boiling fraction and then subjected to distillation under reduced pressure. The method described above gives 27.2 g of ethyl β- (3,3,3-trichloropropyl) isovalerate (ethyl 6,6,6-trichloro-3,3-dimethylhexanoate) (yield: 77%) .

Bp. 90 - 92 ° C / 0.6 mmHg
NMR spectrum (60 MHz)

1.07 (s), 1.26 (t, J = 7Hz) 9H; 1.67-2.03 (m) 2H; 2.24 (s) 2H; 2.60-2.95 (m) 2H; 4.17 (q, J = 7Hz) 2H

2.5 g of metallic sodium are dissolved in 50 g of ethanol, whereupon 20.0 g of the ethyl β- (3,3,3-trichloropropyl) isovalerate described above be added to the solution. The mixture is refluxed for a period of 8 hours held. The reaction mixture is neutralized with a solution of hydrogen chloride in dry ethanol and up concentrated about 1/20 of the original volume. To this concentrate 100 g of ice water are added, whereupon the mixture is extracted with diethyl ether. The ethereal layer is dried over anhydrous magnesium sulfate and removed to remove the low-boiling fraction distilled. The method described above gives 13.7 g of ethyl-ß- (3 , 3-dichloroallyl) isovalerate (ethyl 6, 6-dichloro-3, 3-diethyl 5-hexenoate). The NMR spectrum is given below (from

8 0 9838/0722

prey: 79%).

NMR spectrum (60 MHz) <

0.99 (s) 6H, 1.20 (t, J = 7.5Hz) 3H, 2.09-2.35 (m) 4H ₇ 4.07, (q, J = 7.5Hz) 2H, 5 , 94 (t, J = 7.5Hz) 1H

Become a solution of 2.2 g sodium hydroxide in 15 g water 10.0 g of the ethyl β- (3,3-dichloroallyl) isovalerate described above and given 20 g of ethanol. The mixture is refluxed for a period of 4 hours. The reaction mixture is distilled to remove the ethanol, acidified with aqueous hydrochloric acid and extracted with diethyl ether. The ethereal layer is over dried anhydrous magnesium sulfate and distilled to remove the low-boiling fraction. According to the above Method, 8.2 g of β- (3,3-dichloroallyl) isovaleric acid are obtained (6,6-dichloro-3,3-dimethyl-5-hexenoic acid). The NMR spectrum this compound is shown below (yield: 93%).

NMR spectrum (60 MHz)

1.04 (s) 6H, 2.14-2.34 (m) 4H, 5.94 (t, J = 7.5Hz) 1H

3.0 g are added to 2.1 g of β- (3,3-dichloroallyl) isovaleric acid Thionyl chloride and 10g benzene added. The mix will refluxed for a period of 5 hours. The reaction mixture is then used to remove the low boiling point Fraction distilled, with ß- (3,3-Dichlorallyl) -isovaleroylchlorxd is obtained as a residue. This ß- (3,3-Dichlorallyl) -isovaleroylchlorxd is in 30 g dry benzene dissolved, whereupon 2.0 g of 3-phenoxybenzyl alcohol was added to the solution will. This is followed by the dropwise addition of 1.6 g of pyridine, followed by the mixture at room temperature is stirred overnight. The reaction mixture is then diluted with diethyl ether, with aqueous hydrogen chloride Acid and water washed, dried over anhydrous magnesium sulfate and removed to remove the low-boiling

809838/0722

Fraction distilled. The oily residue obtained is purified by column chromatography. 2.8 g are obtained in this way 3-phenoxybenzyl-ß- (3,3-dichloroallyl) isovalerate (compound (11)) with the following properties (yield: 71%, be * attracted to ß- (3,3-dichloroallyl) isovaleric acid).

NMR spectrum (60 MHz) p

0.93 (S) OH, 2.03-2.23 (m) 4H, 4.98 (s) 2H, 5.88 (t, J = 7.5Hz) 1H, 6.76-7.50 (m) 9H

Elemental analysis (calculated in brackets):

C% 64.08 (64.13)

H% 5.60 (5.64)

Synthesis Examples 10 and 11

The procedure described in Synthesis Example 9 is repeated, with the exception that 2.2 g of Oi-cyano-3-phenoxybenzyl alcohol or 2.2 g of Oc-ethynyl-3-phenoxybenzyl alcohol instead the 2.0 g of 3-phenoxybenzyl alcohol are used. After these Methods one obtains the corresponding esters of ß- (3,3-DichlorallyI) -isovaleric acid (Connection (12) or connection (13)). The yields, NMR spectra and elemental analysis values these esters are summarized below:

Compound (12): Yield 3.4 g (81%)

Nuclear Magnetic Resonance Spectrum (60 MHz) O ^ _M g 3:

1.01 (s) 6H; 2.19 (d, J-8Hz), 2.30 (s) 4H; 5.89 (t, J = 8Hz) 1H; 6.38 (s) 1H; 6.90-7.50 (m) 9H Elemental analysis (calculated in brackets) C% 62.98 (63.17) H% 5.06 (5.06)

809838/0722

Connection (13)

Yield 3.3 g (79%) NMR spectrum (60 MHz) S.

281003 i

3:

0 _r 96 (s) 6H, 2.07-2.28 (m) 4H, 2.53 (d, J = 2Hz) 1H, 5.87 (t, J = 8Hz) 1H, 6.44 (d, J = 2Hz) 1H, 6.83-7.50 (m) 9H

Elemental analysis (calculated in brackets) C% 66.05 (66.20) H% 5.19 (5.31)

Synthesis Example 12

62.7 g of 3,3-dimethyl-4- (2,2-dichlorovinyl) -4-butanolide are dissolved in 150 g of benzene dissolved. At room temperature, hydrogen chloride gas is released into the solution for a period of Bubbled in for 1 hour. Then 3.0 g of zinc chloride are added and the mixture is refluxed. Under ongoing Introduction of hydrogen chloride gas, 107.0 g of thionyl chloride are added dropwise over a period of 1 Hour added. The mixture is further heated at this temperature for a period of 4 hours, whereupon Excess thionyl chloride and benzene are distilled off under reduced pressure. The residue is reduced under reduced Distilled pressure, leaving 49.1 g of 3,3-dimethyl-4,6,6-trichloro-5-hexenoyl chloride with the following properties can be obtained (yield: 62%).

4 ^:

Bp 79-81 ° C / 0.65 mmHg
NMR Spectrum 60 (MHz) 0

1.14 (s) 3H, 1.17 (s) 3H, 2.87 (d, J = 17Hz) 1 4.83 (d, J = 10.5Hz) 1H, 6.04 (d, J = IOHz ) 1H

3.22 (d, J = 17Hz) lH,

2.6 g of 4,6,6-trichloro-3,3-dimethyl-5-hexenoyl chloride are added to 30 g of dry benzene dissolved, whereupon 2.0 g of 3-phenoxybenzyl alcohol are added to the solution. Then it closes the dropwise addition of 2.4 g of pyridine. The mixture is stirred at room temperature overnight. The reaction mixture is then diluted with diethyl ether, with dilute

809838/0722

281003

aqueous hydrochloric acid and water washed over dried anhydrous magnesium sulfate and distilled to remove the low-boiling fraction- Das as a residue Accruing viscous oil is purified by column chromatography. According to the method described above, one obtains 3.9 g of 3-phenoxybenzyl-ß- (1,3,3 ~ trichloroallyl) isovalerate (3-phenoxybenzyl-4,6,6-trichloro-3,3-dimethyl-5-hexenoate, Connection (17)). The NMR spectrum and the elemental analysis are given below: (Yield: 91%)

NMR spectrum (60 MHz)

1.03 (S) OH ₇ 2.18 (d, J = 15Hz) 1H, 2.52 (d, J = 15Hz) 1H, 4.87 (d, J = 10, 5Hz) 1H, 5.02 ( s) 2H, 6.02 (d, J = 10.5Hz) 1H, 6.80-7.50 (m) 9H

Elemental analysis (calculated in brackets):

C% 58.85 (58.97)

H% 5.02 (4.97)

Synthesis Examples 13 and 14

The procedure described in Synthesis Example 12 is repeated with the exception that 2.3 g of (X-cyano-3-phenoxybenzyl alcohol or 2.3 g of 0 (-ethynyl-3-phenoxybenzyl alcohol can be used instead of 2.0 g of 3-phenoxybenzyl alcohol. The method described above gives the corresponding esters of β- (1,3,3-trichloroallyl) isovaleric acid (Connection (18) or connection (19)). The yields, NMR spectra and analysis values of these esters are shown below summarized:

Compound (18): Yield 3.8 g (84%)

Nuclear Magnetic Resonance Spectrum (60 MHz) C ^^ ^X 3:

TMS

1.08 (s) 6H; 2.33 (bd, J = 15Hz), 2.66 (bd, J = 15Hz) 2H; 4.80 (d, J = 10.5Hz (1H; 6.02 (d, J = 10.5Hz) 1H; 6.36 (s) iH; 6.92-7.58 (m) 9H

Elemental analysis (calculated in brackets) CS 58.45 (58.36) H% 4.41 (4.45)

S0983S / 0722

281003

Connection (19):

CDCl

3:

Yield 3.6 g (80%)
NMR spectrum (100 MHz)

0.94 (s) 6H; 2.11 (d, J = 15Hz), 2.14 (d, J = 15Hz), 2.38 (d, J = 15Hz), 2.41 (d, J = 15Hz), 2.45 (d, J = 2Hz) 3H; 4.69 "(d, J = -11Hz), 4.72 (d, J = 11Hz) 1H; 5.86 (d, J = 11Hz) 1H; 6.30 (d, J = 2Hz) 1H;

6.70-7.25 (m) 9H

Elemental analysis (calculated in brackets)

C% 61.25 (61.14)

H% 4.60 (4.68)

Test example 1 Test to determine the killing effect on house flies

according to the local application method

Each test compound is carefully weighed and a 1% solution and a 0.1% solution of the sample in acetone are made up. A 1 μΙ portion of one of the solutions described above is placed with a micropipette on the thoracic back of female adult house flies (Musca domestica) that have been anesthetized with ether, after which the flies are placed in a high-walled bowl with food, be introduced. The dish is covered with a metal wire mesh and kept at 25 ° C. After 24 hours, the Test flies examined for fatalities, determining the percentage of mortality. The results come from the Table I below. 30 test flies are used per concentration group.

809838/0722

INSPECTED

28TO031

- 49 Table I.

Test compound no.

Mortality,% "-

μ g / fly

Ρ g / fly

(1) (2) (5) (6). (7) (8) (9) (10) (11) (12) (13) (17) (18) (19) Allethrin 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100

100 100 100 100 90 100 100 100 100

100

50

COOCH

2 X =,

Test example 2 Test to determine the killing effect on green rice

leaf hops by the method of local application

Each test compound is precisely weighed out, followed by 0.1% solutions can be made in acetone. Female adult green rice leafhopper (Nephotettix cincticeps UHLER) are with Carbon dioxide gas anesthetized, whereupon 0.5 μΐ of the above solution described is applied with a micropipette to the thoracic abdominal portion of each leafhopper. The test leafhoppers are then kept at 25 ° C with access to rice plant seedlings. Each group consists from 15 green rice leaf hoppers. After 24 hours, the leafhoppers are examined for deaths, followed by mortality is calculated as a percentage for each connection. The results are shown in Table II.

Table II

Test compound no. ιΤ 8Ω9838 )
/ η Mortality,% ^: 22nd (D not-less than 90% (2) II (6) Il (7) Il (9) II (10) Il (12) Il (13) ti 40%

Test example 3 Test to determine the killing effect on cockroaches

according to the local application method

Each test compound is precisely weighed and 1% solutions in acetone are made. Then 1 μΐ becomes the above described solution with a micropipette on the abdominal part of each female cockroach (Blattella germanica Linne), who is under ether anesthesia. The cockroaches are placed in a high-walled bowl, in which is feed is transferred. After the bowl has been covered with a metal wire mesh, it is kept at 25 ° C held. 15 cockroaches per group are used. After 24 hours, the test cockroaches are examined for deaths, whereupon the percent mortality is calculated for each group. The test results are shown in Table III below emerged.

Table III

Test connection
- No. Mortality,% (1)
(2)
(6)
(7) 100
80
100
80

Test example 4
Light stability test

80 mg of each test compound are dissolved in 2.0 ml of acetone. A 5 μΙ portion of the solution is on a glass plate (Micro Standard Cover Glass, 18m / m Q No. 1, 200 pcs, Matsunami Glass Ind., Ltd.), whereupon the acetone evaporates will. Then a similar glass plate is placed on the plate described above in such a way that the Test solution is sandwiched between the plates.

809838/0722

281003

The sample is exposed to the direct action of sunlight at an atmospheric ^{temperature of 12 °} C. for a predetermined period of time. As a non-irradiated comparison sample, a similar sample is covered with an aluminum foil. The test solution is washed away with 1.0 ml of methanol containing 0.04 % dioctyl phthalate as a standard. High speed liquid chromatography is performed using the washing solutions to determine the residual amount of the test compound. The percentage of residue is shown in Table IV. The percentage of the residue is calculated using the value of the comparison sample covered with the aluminum foil as a standard.

Table IV

O CO CO

fs »fs»

Test connection ITr. ,; Rucks ti
'Bestrah:
. 4 h. .. and,%
Lunar time ■
8 "h ' 1 93 90 2 97 100 5 99 98 6th 92 92 7th 96 96 10 97 97 11 100 96 12th 92 90 13th 100 100 17th 100 100 18th 98 97 19th 97 92 Allethrin 35 17th

2810: 03!

Test example 5 Test to determine the resistance to hydrolysis

In approximately 8 ml of acetone are 100 g of each test compound dissolved, and 1.0 g of water is added to the solution to make a mixed solution. This mixed solution is refluxed for a period of 2 days after which the acetone is distilled off. After a concentration to about half of the original volume and after adding oxoctyl phthalate as a reference substance, the remaining amount the compound by high speed liquid chromatography determined. The percentage of the residue is calculated. The results are shown in Table V.

O
CjO
CO
^ 3

Table V Residue, % more than 90 -Tesb connection Er ... ti (2) fl (6) 11 (7) IT (11) ■ 1 (12) (18)

281003]

Test example 6 Test to determine toxicity to fish

In 5 1 of water, 250 g of Sorpol 3M-200 (registered trademark of Toho Chemical Co., Ltd.) or Tween-20 (commercial product) as an emulsifying agent (surfactant), and 2 _r 5 ml of an acetone solution given that one of the test compounds in a predetermined concentration. The mixture is stirred well to make a test water. Ten female Guppies with an aging of 3 to 4 months are used in the test water, which is maintained at a temperature of 25 ⁰ C. The concentration of the test compound at which 90% or more of the guppies are killed over a period of 48 hours is determined (this concentration is referred to as LC _gQ ). The results are shown in Table VI.

O
CD
GO
CO

Table VI i not I. not ^LC 90! less than 10 parts
per 1 million tie.
ti Test connection No. ir (2)
(5) Il (7) Il (3) Ii! (10) (11) Il ■ (12) \ (13) u! (17) II j (18) more than 0.5 ppm- I.
11 I.
ft ' (19) Allethrin
Permethrin
Fenvalerate

- 55 Formulation example 1

0.2 part of each of compounds (1), (2), (5) to (13) and (17) are prepared, followed by 0.8 parts of each of piperonyl butylate can be added. A sufficient amount of kerosene to adjust 100 parts is then added to this mixture added, followed by stirring. This method gives an oil formulation of each compound.

Formulation example. 2

0.1 part of resmethrin is added to 0.1 part of each of compounds (1) to (17), followed by the addition of a sufficient amount of kerosene to adjust 100 parts. The mixture is stirred. This is a Obtain oil preparation of each compound.

Formulation example 3

To 0.1 part of each of Compounds (1) to (28) is added 0.08 part of permethrin, followed by the addition a sufficient amount of kerosene to adjust 100 parts. The mixture is used to obtain an oil preparation stirred by each compound.

Formulation Example · 4

0.2 part of 2-isopropoxyphenyl-N-methylcarbamate is added to 0.2 part of each of the compounds (1), (2), (5) to (13) and (17) to (19) and 5 parts of xylene are added. The preparation is in a sufficient amount of kerosene to set 100 parts dissolved. In this way an oil preparation is obtained of every connection.

Formulation example 5

For each 30 parts of one of the compounds (1), (2), (5) to (13) and (17) to (1 φη ^^^ / ^ 'ΐΝ- ^{165 x} Y ^{l01 and} 20 parts of Sor-

pol SM-200 (surfactant, trademark of Toho Chemical Co., Ltd.) was added. The mixture is stirred and dissolved well. This produces 30% emulsifiable concentrates obtain.

Formulation example 6

To 20 parts of each of the compounds (1), (2), (5) to (9) and (11) to (13) are added 20 parts of 0,0-dimethyl-O-4-cyanophenylphosphorothioate (Thianox, trademark of Sumitomo Chemical Co., Ltd.), 20 parts of Sorpol SM-200 (a surfactant Agent, trademark of Toho Chemical Co., Ltd.) and 40 parts of xylene. The mixture will dissolve stirred well, an emulsifiable concentrate of each compound being obtained.

Formulation example 7

To 20 parts of each of the compounds (1), (2), (5) to (13), (17) to (19) and (21) are 5 parts of Sorpol SM-200 (surfactant, trademark of Toho Chemical Co., Ltd.), followed by thorough mixing connects. With the addition of 75 parts of a talc with a particle size of 0.05 mm, the mixture becomes thorough stirred in a grinder. A wettable powder is obtained by the method described above of every connection.

Formulation example 8

To 15 parts of each of the compounds (1), (2) and (5) to (13) are 15 parts of 1-naphthyl-N-methylcarbamate and 5 Parts of Sorpol SM-200 (surfactant, trademark of Toho Chemical Co., Ltd.) are given, followed by a thorough mixing follows. With the addition of 65 parts of a talc with a particle size of 0.05 mm the mixture thoroughly in a comminuting device to obtain a wettable powder of each compound

809838/0722

dung stirred.
Formulation example 9

5 parts of piperonyl butoxide are added to 1 part of each of the compounds (1), (2), (5) to (13) and (17) to (20), whereupon the mixture is dissolved in 20 parts of acetone. With the addition of 94 parts of a one particle size diatomaceous earth of 0.05 mm, the mixture is stirred well and mixed in a grinder, with the acetone is evaporated. The method described above gives powders which contain the respective compounds.

Formulation Example 10

Become 0.4 parts of each of the compounds (1) to (19) 0.1 part resmethrin, 1.5 parts octachlorodipropyl ether and 28 parts of a refined kerosene. The solutions obtained in this way are placed in aerosol containers bottled. After the valve has been attached, each container is filled with 70 parts of a propellant (liquefied Petroleum gas). This method results in an aerosol formulation of each compound.

Formulation Example 11

To 0.3 part of each of the compounds (1), (2) and (5) to (13) is added 0.3 part of DDVP, followed by the mixture is dissolved in a mixture of xylene and refined kerosene. A total of 15 parts are produced. Each solution is filled into an aerosol container. After the valve has been put on, each container is filled with 85 Parts of a propellant (liquefied petroleum gas) filled through the filling valve. According to the method described above an aerosol preparation of each compound is obtained.

809838/0722

Formulation Example 1 2

0.5 parts of BHT and 99.0 parts of a mosquito fumigation material are added to 0.5 parts of each of the compounds (1) to (13). which contains pyrethrum residue, sawdust, starch etc. The mixture is mixed evenly and processed into a mosquito snake in a conventional manner.

Formulation Example 13

To 0.05 g of each of the compounds (1), (2), (5), (8), (10) and (11) are added 0.02 g of furamethrin, 0.15 g of piperonyl butoxide and 0.1 g BHT given. The mixture is dissolved in an appropriate amount of chloroform. This solution will evenly adsorbed on the surface of an asbestos mat with a size of 2.5 χ 1.5 cm and a thickness of 0.3 mm. An asbestos mat of the same size and thickness is placed on the treated surface. After this method gets a fibrous fumigation mat that can be heated on a hot plate.

Effect example 1

Using the compounds (1), (2), (6), (7), (9), (10), (12) and (13) prepared according to Formulation Example 5 Emulsifiable concentrates are each diluted 300 times with water. Then each of the dilutions sprayed on rice seedlings 25 days after sowing in an amount of 10 ml / pot. The pot comes with a wire mesh covered, whereupon 15 green rice leaf hoppers released under the net v / earth. After 24 hours, the leaf hoppers are examined for death. The mortality (%) is in the case of one any of the compounds (1), (2), (6), (7), (9), (10), (12) and (13) not below 90%.

809838 ^ 0722

- 59 Effect example 2

A test to determine the killing effect on house flies (Musca domestica) is carried out using the mist deposition method. carried out, whereby the oil preparations are used, which have been obtained according to the formulation example 1 from the compounds (1), (2), (5) to (11) and (17). To The flies are examined for deaths for 24 hours. The mortality (%) is for each of the compounds (1), (2),

(5) to (11) and (17) not less than 90%.

Effect example 3

According to the mist deposition method, a test is carried out to determine the killing effect on house flies, wherein the oil preparations are used, which using formulation example 2 from the compounds (1), (2), (5) to (11) and (17) have been produced. After 24 hours, the flies are examined for fatalities. the Mortality (%) is not less than 90% in the case of any of the compounds (1), (2), (5) to (11) and (17).

Effect example 4

According to the mist deposition method, a test is carried out to determine the killing effect on house flies, wherein the oil preparations are used, which according to the formulation example 3 from the compounds (1), (2), (5) to (11) and (17) have been obtained. After 24 hours, the flies are examined for fatalities. The percentage the mortality is not less than 90% in the case of each of the compounds (1), (2), (5) to (11) and (17).

809838/0722

Claims (7)

MÜLLER-BORE · T) EUIEL · SCHÖN EERTEL Γ AT EN TA N "VVl. LT E 2 April 7, 1978 DR. WOLFGANG MÜLLER-BORE (PATENT ADVOCATE FROM 1927-1375) DR. PAUL DEUFSL. DIPL.-CHEM. DR. ALFRED SCHÖN. DIPL.-CHEM. WERNER HERTEL. DIPL.-PHYS. S / K 1.9-78 KURARAY CO., LTD. Sakazu, Kurashiki-City, Japan pesticides containing α- or ß-substituted isovaleric acid esters Patent claims 1. ^N pesticides, characterized in that ..- ■ it is an α- or ß-substituted isovaleric acid ester of the general formula as active ingredient 809838/072? H MiTJiCFIKJT 88-YOU Il EUTSTR. 1 · 1 · Ο.ΗΓ1 · ΑΟΙΙ SG07S0 · K-VIl E L: MITEIiOPAT-TEL. (OSW) 174003 ■ TELEX S-31ÜS3 ORIGINAL INSPECTED 2810Ü3J 1v - ^ J where Z is hydrogen / ^C ^ / or ^{c CH} 2, X CH χ Z ² V CH ₀ _ ■ "C-" CH. -, , 2 or t ι if Z? 7asser- X XY is fabric, or represents hydrogen, '< , C ₅ V /,. ^^ ^ CH ₉ if ZX CH " ¹ ^ ' A. • χ A is cyano or ethynyl when ZC '/ ^is ' ^ ^{617 ansonsi} _χ / ^ CH is hydrogen, cyano or ethynyl, and X and Y are the same or different and are each chlorine or bromine contains. 2. Pesticide according to claim 1, characterized in that that the active ingredient is an Oi-substituted isovaleric acid ester the general formula CfL C. CH H ^X COOCH- ^^ .-Λ where A is cyano or ethynyl and X is chlorine or bromine. 3. Pesticide according to claim 2, characterized in that that the active ingredient from «(-Cyano-3-phenoxybenzyl- (2,2-dichlorovinyl) isovalerate the formula ^consists 4. Pesticide according to claim 2, characterized in that that the active ingredient from CV-ethynyl-3-phenoxybenzyl-CX - (2,2-dichlorovinyl) isovalerate of the formula C2 ^^^ C00CH - / _ \> . C = CHX _0- ^ / ^ consists. 5. Pesticides according to claim 1, characterized that the active ingredient consists of a Cf-substituted isovaleric acid ester of the general formula consists in which A is hydrogen, cyano or ethynyl and X is chlorine or bromine. 6. Pesticides according to claim 5, characterized in that the active ingredient from -. ^ - Ethynyl-3-phenoxybenzyl- ^; 7i - (3, 3-dibromoallyl) isovalerate of the formula Br Br COOCH-V ^ y consists. SO 9838/0722 7. Pesticide according to claim 5, characterized in that that the active ingredient from 3f-cyano-3 ~ -phenoxybenzyl-C \ '- (3 , 3-dichlorallyl) isovalerate of the formula Cl O- consists. Pest control agent according to Claim 1, characterized that the active ingredient consists of a ß-substituted isovaleric acid ester of the general formula consists in which A is hydrogen, cyano or ethynyl and X is chlorine or bromine. 9. Pesticide according to claim 1, characterized in that that the active ingredient from a ß-substituted isovaleric acid ester of the general formula CH consists in which A is hydrogen, cyano and ethynyl and X and Y are identical or different and are each chlorine or bromine. 809838/0722 10. vV'-substituted isovaleric acid ester of the general formula CH- CH_
\ ^3/3 CH CH
"CH COOCH ' where A is cyano or ethynyl and X is chlorine or bromine. . «^ -Substituted isovaleric acid ester according to claim 1 0, characterized in that it is made from Of-cyano-3-phenoxybenzyl (X - (2,2-dichlorovinyl) isovalerate of the formula consists. 12. (X-substituted isovaleric acid ester according to claim 10, characterized in that it is made from Qf-ethynyl-3-phenoxybenzyl-CY- (2,2-dichlorovinyl) isovalerate the formula C2. CS- consists. 13. ^ -substituted isovaleric acid ester of the formula 809838/072 C ι CH CH ν / CH COOCH wherein A is hydrogen, cyano or ethynyl and X Means chlorine or bromine. 14. 0 ( -substituted isovaleric acid ester according to claim 13, characterized in that it consists of Ct-ethynyl-3-phenoxy benzyl-CX- (3,3-dibromoallyl) isovalerate of the formula Br COOCH · Br C = CH consists. 15. Of-substituted isovaleric acid ester according to claim 13, characterized in that it consists of (X -Cyano-3-phenoxybenzyl-OC - (3,3-dichloroallyl) isovalerate of the formula Cl Cl COOCH
ι
CN consists. 16. ß-substituted isovaleric acid ester of the general formula 8Q983S / G722 -Ι ΟΙ, CH Nf Nf / CH; c .COOOi- ν VS C CH CH CH ₂ CH ₂ wherein A is hydrogen, cyano or ethynyl and X is chlorine or bromine. 809838/0722