DE1814872A1 - Process for the preparation of epoxy compounds - Google Patents

Description

5 '-ί, Ο ^ Ψ--'

vr '■

-S. DEC. 1968

6101 / 18-02

F. Hoffmann-La Roche & Co. Aktiengesellschaft, Bascl / Schwcfe

Process for the production of epoxy compounds

The present invention relates to a process for the preparation of epoxy compounds of the general formula

GH ₂ OOH ₃

in the A with B and C with D an oxygen bridge each, or A with B a carbon-carbon bond and C with D an oxygen bridge, or A with B. denotes an oxygen bridge and 0 with D denotes a carbon-carbon bond, in each case the largest residues on carbon atoms 2 and 3

cis / trans-, cis- or trans- and on the coals -90982 77 1624

18U872

Substance atoms 6 and 7 are cis-configured,

The method according to the invention is characterized in that that you can get a compound of the formula

II

by exposure to methanol in the presence of an allyl rearrangement acid subjects and converts the ether thus obtained into an epoxide or that a compound of the formula II with allyl rearrangement converted into a primary halide and this either reacts with an alkali metal methoxide and the obtained Product converted into an epoxy, or with an alkali metal alkanoate converts and the product obtained is converted into an epoxy in any order and hydrolyzed and the product obtained primary alcohol reacts with a methyl halide, and that one ...

fc a obtained mixture of 6,7- and 10,11-epoxy compounds desired ™ 15 if necessary.

The starting compound of formula II can, for example, thereby

be prepared that one cis-geranylacetone in the presence of Sodium amide in liquid ammonia reacts with acetylene and the resulting tri-unsaturated compound with the help of a partially inactivated catalyst, e.g. with the aid of a lead / palladium catalyst3 deactivated with quinoline hydrogenated

90982 77 1624

18U872

Leaving methanol in the presence of the cis-nerolidol obtained act on an acid, the desired methyl ether is obtained with allyl rearrangement, the. by treating with a peracid or with a mixture of N-bromosuccinimide and water via the resulting bromohydrin can be converted into an epoxide.

It is expedient to work in the cold, in particular in a temperature range ^{between 0 and 20 ° C.} Suitable acids are, for example, "sulfuric acid or p-toluenesulfonic acid". The presence of a solvent that is immiscible with the reaction mixture, such as hexane or petroleum ether, can be advantageous.

In addition to N-bromosuccinimide / water, organic oxidants are used Peracids such as peracetic acid, perbenzoic acid, m-chloroperbenzoic acid or perphthalic acid are suitable.

It is also the cis-Nerolidol halogenate obtained by allylic rearrangement, implement the halide obtained with a Alkalimetallmethanolat ater and converted into an epoxy, by treatment with one of the above-mentioned organic peracid or with a mixture • won N-bromosuccinimide and V / "

A phosphorus halide, in particular phosphorus tribromide, is preferably used as the halogenating agent. It allows the halogenating agent in the cold, ie primarily acting in a temperature range between -10 ° and + 5 ⁰ C to the cis-nerolidol.

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18U872

However, the halide obtained above may also be with an alkali metal alkanoate, especially with an alkali salt of a lower alkane carboxylic acid having 1-6 carbon atoms such as sodium acetate, be converted to an ester either by treatment with a peracid or with a mixture of N-bromosuccinimide and water converted into a Bpoxide and hydrolyzed to the corresponding alcohol or first hydrolyzed and then epoxidized by treatment with a peracid. The alcohol obtained in both cases is then methylated to give the desired epoxy compound of the formula I.

The methylation is conveniently carried out at room temperature in The presence of a base in an inert solvent, mainly carried out in the presence of sodium hydride in dioxane. Of the methyl halides suitable as methylating agents are methyl iodide preferred.

The epoxidation is expediently carried out in such a way that the compound in question is in an inert solvent, especially in a halogenated hydrocarbon, such as methylene chloride or chloroform dissolves and in an between

^, 0 and the room temperature lying temperature range with a ο

co of the above-mentioned peracids treated or that the oo

^ compound in question suspended in water and treated with a sol- -j. Chen amount of an inert solvent, for example with dioxane, tetra- ¹ ^ hydrofuran or 1,2-dimethoxyethane added that a homogeneous, concentrated solution is formed and in this solution in between

18U872

0 ° and the temperature range lying around room temperature in portions N-bromosuccinimide enters. The resulting bromohydrin can 'converted smoothly into the epoxy by the action of alkalis, in particular by the action of sodium methylate in methanol will.

The particular advantage of the N-bromosuccinimide method lies in the fact that only the terminal double bond is oxidized, while in the case of epoxidation with organic peracids, provided 1 mol of peracid is used, a mixture of 6,7- and 10,11-epoxides is always obtained. Leaves-one on 2 moles of peracid Acting moles of the compound in question gives 6.7; 1Q, II-diepoxides.

909827/1 624

18U872

The products of the process of the formula I are suitable for combating pests. ·.

In contrast to most of the previously known pest control agents which, as contact or feeding poisons, kill, paralyze or drive away the animals, the compounds of the formula I which can be prepared according to the invention intervene in the hormonal system of the animal organism. In the case of insects, for example, the transformation to the imago is disturbed. The generation sequence is interrupted and the animals are killed indirectly. The process products are practically non-toxic for vertebrates. The toxicity of the compounds of the formula I in vertebrates is over 1000 mg / kg body weight. The new connections are also easily broken down. The risk of accumulation is therefore excluded. · The products of the process can therefore be used safely for combating pests in animals, plants, foodstuffs and textiles. - ■ * - - ;.

The products of the process are particularly suitable for controlling invertebrates. As detailed below an active ingredient concentration of 0.01 to 0.1 # is generally sufficient to ensure the desired effect.

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18U872

The active ingredients can e.g. in the form of emulsions, suspensions, Dusts, solutions or aerosols are used. In special cases, the objects to be protected, e.g. food, seeds, textiles and the like directly with the active ingredient concerned or with a solution of the active ingredient are impregnated. The active ingredient can also be used in a form that only occurs through the action of external agents Influences, e.g. in contact with moisture or only releases the active ingredient in the animal body itself. It is also possible, the products of the process mixed with other known pesticides to use.

In the following test reports, some exemplary embodiments are described in detail.

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ο 18U872

example 1

öis-geranylacetone is used in a manner known per se Sodium acetylide condenses in liquid ammonia. The emerging cis-dehydro-nerolidol is then partially to hydrogenated cis-nerolidol.

300 g of 3,7, ll-trimethyl-dodeca-l, 6-cis, 10-trien-3-ol [cis-nerolidol] are mixed with 810 ml of petroleum ether [boiling range 40 ° -45 ° C.] and 31.5 ml of pyridine and at -5 to O ⁰ O dropwise 'over 2 hours with 159 g of phosphorus tribromide in 180 ml of petroleum ether [boiling range 40-45 ⁰ C]. The reaction mixture is for 30 minutes at -5 ° to 0 C _f further stirred then poured onto ice and, after further 3O minutes I5OO ml ether. The Petroläther- / ether phase is separated, washed successively with water and with a saturated aqueous sodium bicarbonate solution, dried over sodium sulfate, initially at 3O ⁰ G evaporated under reduced pressure and then dried under high vacuum. The crude l-bromo-3,7,11-trimethyl-dodeca-2-cis / trans, 6-cis, 10-triene that remains can be used as follows without further purification

A) to the l-methoxy-3,7, ll-trimethyl-dodeca-2-cis / trans, 6-cis, 10-trien or

B) to the l-acetoxy ^^ ill-trimethyl-dodeca ^ -cis / trans, 6-cis, 10-trien

further processed v / earth. 90982 77 1624

~ ⁹ ~ 18U872

A) 350 g of l-bromine ^^ jll-trimethyl-dodeca ^ -cis / tranSjö-cis, 10-triene are converted into a solution of 32 g of sodium in 64O ml of abs. Added dropwise methanol. The internal temperature should not exceed 20 G. The reaction mixture is stirred anschlies send 16 hours at room temperature, heated for 1 hour under reflux conditions at the boiling point, then cooled, poured onto ice and exhaustively extracted with petroleum ether [boiling range 40-45 ⁰ C]. The combined extracts are washed neutral, dried over sodium sulfate and evaporated. The remaining l-methoxy-3,7, ll-trimethyl-dodeca-2-cis / trans ₁ 6-cis, 10-triene is purified by distillation. B.p .: 92-94.5 ° C / 0.15 torr. .

B) 363 g l-

10-triene together with 208 g of anhydrous potassium acetate in 24OO ml of acetone heated under reflux conditions for 24 hours.

The potassium bromide which precipitates out on cooling is filtered off. That The filtrate is evaporated. The remaining 1-acetoxy-3,7, ll-trimethyl-dodeca-2-cis / trans, 6-cis, 10-triene (226 g) after distillation boils at 116-119 ° C / O.O3 Torr.

The l-methoxy-3,7,11-trimethyl-dodeca-2-cis / trans, 6-cis, 10-triene mixture can by fractional distillation · in

l-methoxy-3,7, ll-trimethyl-dodeca-2-cis, 6-cis, 10-triene and l-methoxy-3,7, ll-trimethyl-dodeca-2-trans, 6-cis, 10-triene (B.p. 94.5 ° C / 0.15 torr.), 9 0 9 8 2 7/1624

18U872

separated, which according to one of the following Methods can be epoxidized

5 g of l-methoxy-3 ₁ 7, ll-trimethyl-dodeca-2-trans, 6-cis, 10-triene in 100 ml of methylene chloride are cooled to 0 °, 4.4 g of m-chloroperbenzoic acid are added in portions, 1- Stirred for J hours at 0, then washed successively with 1N sodium hydroxide solution and water, dried over sodium sulfate and evaporated separated by fractional distillation of portions of the corresponding 6,7-epoxy compound. Bp 93-94.5 ° C / 0.002 Torr.

The l-methoxy-3,7, ll-trimethyl-dodeca-2-trans, 6-cis, 10-triene can also be converted into the corresponding 10,11-epoxy compound with the aid of N-bromosuccinimide as follows.

In a homogeneous solution of 23 »6 g of l-methoxy-3,7,11-trimethyl-dodeca-2-cis / trans, 6-cis, 10-triene, 40 ml dist. Water and 230 ml of tetrahydrofuran are 18.6 g of N-bromosuccinimide at 0-3 ° C. added in portions within 30 minutes. The mixture will Stirred for 5 hours at 0-3 ° C., poured into 2000 ml of saturated sodium chloride solution, extracted with hexane and worked up. By Chromatography with hexane-ethyl acetate (60:40) is 17.8 g of isLnes lO-bromo-ll-hydroxy-l-methoxy ^^ H-trimethyl-dodeca ^ -

a received. Kp.
909 8 2 7/162

cis / trans, 6-cis-diene obtained. Bp 115 ° C / 0.001 Torr; n _D = 1.5216,

18U872

In a solution of 16.3 g of 10-bromo-II-hydroxy-1-methoxy-3,7, II-trimethyl-dodeca-2-cis / trans, 6-cis ~ diene in 25 ml of abs. A solution of 1.12 g of sodium dissolved in 25 ml of absolute methanol is added dropwise to methanol at 0-3 ° C. The mixture is stirred for a further 30 minutes, then poured into 100 ml of saturated sodium chloride solution, extracted with hexane and worked up. 10.4 g of pure lOjll-epoxy-l-methoxy ^^ ll-trimethyl-dodeca ^ - cis / trans, 6-cis-diene are obtained by distillation. Ep. 92-94 ° C / 0.002 Torrf j * ° - 1.4721.

Example 2

The obtained according to Example 1

l-acetoxy-3 »7, ll-trimethyl-dodeca-2-cis / trans, 6-cis, 10-triene can if desired before further processing by fractional distillation in

l-acetoxy-3f7, ll-trimethyl-dodeca-2-cis, 6-cis, 10-triene and 1-acetoxy-3 »7, ll-trimethyl-dodeca-2-trans, 6-cis, 10-trlen separated or further processed as follows;

In a homogeneous solution of 26.4 g of l-acetoxy-3 »7, ll-trimethyl-dodeca-2-cis / trans, 6-cis, 10-triene, 715 ml of tetrahydrofuran and 200 ml of water are added at 0-3 ° C. within 30 minutes 19.6 g of N-bromosuccinimide added in portions. The mixture is stirred for 5 hours, then in a saturated saline solution poured, extracted with hexane and worked up. Chromatography with hexane / ether [85sl5l on silica gel gives 22.5 g

18U872

pure lO-bromo-ll-hydroxy-l-acetoxy ^^ ll-trimethyl-dodeca-, 2-cis / trans, 6-cis-diene obtained.

In a solution of 20.7 g of 10-bromo-II-hydroxy-1-acetoxy-3,7,11-trimethyl-dodeca-2-cis / trans, 6-cis-diene in 60 ml of abs. Methanol is a solution of 2.64 g of sodium dissolved in 60 ml of abs at 0-3 ° C. for 30 minutes. Added dropwise methanol. The mixture is stirred for 30 minutes at 2 ⁰ C and 2 l / 4 hours at room temperature, poured into .a solution of sodium chloride, extracted with hexane, worked up and distilled. There are 12.8 g of 10, ll-epoxy-3 »7,11-trimethyl-dodeca-2-cis / trans, 6-cis-dien-l-ol, '

ο
Bp 99-101 C / 0.001 torr.

The same compound can also be used starting from 1-acetoxy-3,7,11-trimethyl-dodeca-2-cis / trans, 6-cis, 10-triene by. Epoxidation with a peracid to 10, ll-epoxy-l-acetoxy-3,7, lltrimethyl-dodeca - ^ - cis / transjö-cis-diene, which is then saponified to give the desired primary alcohol.

Example. ^

2.4 Natriumhyarid (50 i »in mineral oil) g are washed twice with 20 ml of hexane, after addition of abs ml 50th Dioxane cooled to 10-12 ⁰ C and treated dropwise with 11.9 g of 10,11-epoxy-3,7, ll-trimethyl-do'deca-2-cis / trans, cis-6-dien-l-ol offset

• The mixture is stirred for a further 2 hours at room temperature

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about 10-15 ⁰ C cooled, treated dropwise with 7.5 g of methyl iodide, stirred for 16 hours at room temperature, then in a ge. Poured saturated saline solution, extracted with hexane and worked up. Chromatography with hexane / 15 % ethyl acetate on silica gel and subsequent distillation give 10.5 g of pure 10, II-epoxy-1-methoxy-3,7, II-trimethyl-dodeca-2-cis / trans, 6-cis-diene obtain. Bp 92-94 ° C / 0.002 torr; n ^ = 1.4721.

Example 4

1.5 g of cis-nerolidol are dissolved in 60 ml of 5% methanol Entered sulfuric acid and left to stand for 64 hours at room temperature. The reaction mixture is then in water poured and extracted with petroleum ether [boiling range 40-60 C]. The extract is first saturated with an aqueous Sodium bicarbonate solution, then washed with an aqueous saturated sodium chloride solution, dried over sodium sulfate and evaporated. The remaining l-methoxy-3,7> 11-trimethyldodeca-2-cis / trans, 6-cis, 10-triene [Cp. 92-94.5 ° C / 0.15 Torr] can, as described in Example 1, to one of 10,11-epoxyl-methoxy-3 »7» 11-trimethyl-dodeca-2-cis / trans, 6- cis-diene and 6,7-epoxy-1-methoxy-3,7,11-trimethyl-6,7-cis-dodeca-2-cis / trans, 10-the existing mixture can be oxidized, if necessary can be separated into the individual components by fractional distillation.

909 8 27/1 62 4.

18U872

Example 5 "

9 g of l-methoxy-3,7,11-

trimethyl-dodeca-2 ~ cis / trans, 6-cis, 10-triene are introduced into 100 ml of methylene chloride, cooled to 0, and 16.4 g of m-chloroperbenzoic acid [79 ⁰ A] are added in portions with stirring. The reaction mixture is stirred for 2 hours at 0, diluted with 100 ml of methylene chloride and washed successively with ice-cold 1 η sodium hydroxide solution and a saturated aqueous sodium chloride solution, dried over sodium sulfate and evaporated. The remaining 6,7flO, ll-diepoxy-l-methoxy-3,7 »ll-IQ trimethyl-ö ^ -cis-dodec ^ -cis / trans-en is chromatographed on silica gel [eluent hexane-ethyl acetate 1: 1] cleaned. Bp. 120 ° C / 0.28 Torr; .n ^ ° = 1.4672.

Example 6

Woolen cloth discs [diameter 30 now] are made with a Solution of 10, ll-epoxy-l-methoxy-3f7, ll-trimethyl-dodeca-2-trans, 6-cis-diene soaked in acetone and populated with 10 larvae of the clothes moth [Tineola biselliella] each. The ones on untreated Larvae exposed to woolen material develop into caterpillars, which pupate undisturbed and then form moths. The larvae exposed to treated wool discs are disturbed in their caterpillar formation and pupation.

909827/1624

Control 0

-, 15 -

number
living
Caterpillars number
Hey
services 181 4872 mg of active ingredient
per full disk ■ 0
3 22nd
47 number
Butterfly. Eating rate
in % 10
1 0
3 0
35

17th

80

Example 7

Corrugated cardboard strips [20 χ 50 mm] are mixed with a solution of 10, ll-epoxy-1-methoxy-3,7,11-trimethyl-dodeca-2-trans, 6-cisdiene soaked in acetone and populated with mature larvae of codling moth [Garpocapsa pomonella]. The one on untreated Larvae exposed to cardboard crawl into the cavities of the corrugated cardboard, spin themselves and release the after 14 days Butterfly. The larvae exposed on treated cardboard are disturbed in their caterpillar formation and pupation.

mg of active ingredient per cardboard strip

Number of heads and pupae
normal dead

10 1 0.1

Control 0

0
2

5
5

Number of moths normally crippled

0 0 0

15th

1 5

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Example 8

100 g of wheat grains are mixed with a solution of 10,11-epoxy-l-methoxy-3,7, ll-trimethyl-dodeca-2-trails, 6-cis-diene soaked in acetone, dried and infected with 100 grain beetles [Calandra granaria]. The beetles are sieved off after 14 days and Observed for 6 weeks. The beetles fed untreated grains reproduce normally. The ones with active ingredient-containing grains fed beetles show clear developmental disorders.

mg of active ingredient per multiplication factor 1 g of wheat

5. 0

0.5 0.1

Control 0 6.2

Example 9 .

Young bean plants become strong with aphids [Neomyzus circumflexus] and infected with a solution of 10,11-epoxy-lmethoxy-3,7, ll-trimethyl-dodeca-2-trans, 6-cis-diene sprayed. The mortality of the lice is determined after 2 days.

Active substance concentration Mortality in%

0.1 15

0.01 8

Control O ^- 5

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Example 10

Larvae of the house fly [Musca domestica] that are ready to pupate are placed on a mixture of bran, milk powder, yeast and 10,11-epoxyl-methoxy-3,7, ll-trimethyl-dodeca-2-trans, 6-cis-diene, existing mixture set. The larvae pupate and release the flies after a few days. Larvae on inactive medium have been exposed develop normally and show no disturbance in oviposition. Larvae on active substance-containing medium have an increased mortality.

mg of active ingredient per hatching rate of oviposition cml of larval food in %

5 35 "0

Control 0 78 '46

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Example 11

Gentle Offel beetle larvae in the final instar are on two consecutive days in each case once with a 0.1 followed solution of 10, ll-üipoxy-l-methoxy-3,7 '11-trimethyl-dodeca-2-trans, 6-cis- dien sprayed in acetone and fed with potato leaves. , ■ ■

Active ingredient concentration Pupation delay metamorphosis disorder

[of every 10 animals after, [of every 10 animals not pupated for 3 days:] dead or crippled Beetle: J.

approx. 10 " ⁶ g / cm ² 5 6

0 0 0

Example 12

10 " ^x g 10, II-epoxy-l-methoxy-3,7,11-trimethyl-dodeca-2-

P trans, 6-cis-diene are dissolved in acetone and, with the aid of a precision pipette, 10 Vanessa larvae that are about to pupate are added dropwise. The course of the metamorphosis of the treated animals is compared with the metamorphosis of untreated animals.

Active substance concentration metamorphosis disorder

Doll Imago (of 10 (of 10 animals) each)

10 " ⁵ g / tier 7 3

10 " ⁶ g / tier 6 4

^ 909827/1624 ° °

Example 15

Approx. 50 eggs of the flour otty [Ephestia kühniellaj] are placed on floss papxer rondelles, with an acetone solution of a mixture of 10, ll-epoxy-1-methoxy-3 »7,11-trimethyldodeca-2-cis / trans, 6-cis- diene and ö '^ - Epoxy-1-methoxy-S ^ illtrimethyl-6,7-cis-dodeca-2-cis / trans, 10-diene sprayed and held for 4 days at 25 ⁰ G »The ovicidal effect is based on the number , normally hatched larvae determined.

Active ingredient concentration number
lier number
Larvae mortality ΙΟ "= * 56 - 0 100 10 ⁵ 65 24 63 10 " ^g 60 47 22nd 0 without acetone 52 49 6th 0 without acetone 47 43 8th 0 with acetone 49 46 7th 0 with acetone . 50 47 6th

909827/1624

Claims (23)

18U872 claims 1. Process for the preparation of epoxy compounds of the general formula in which A with B and C with D each denote an oxygen bridge, or A with B a carbon-carbon bond and C with D an oxygen bridge, or A with B an oxygen bridge and C with D a carbon-carbon bond, where in each case the biggest residues at the carbon atoms 2 and 3 c ± s / trans "= _s cis or trans and an.den carbon atoms 6 and 7 are cis-configured, characterized in _t that a compound of the formula II by exposure to methanol in the presence of an allyl rearrangement acid subordinates and converts the ether obtained in an epoxide or that a compound of formula II converted into a primary halide with allyl rearrangement and this either reacts with an alkali metal methoxide and the product obtained is converted into an epoxy, or with an alkali 90982 77 1624 COPY converts metal alkanoate and the product obtained is converted into an epoxide in any order and hydrolyzed and the primary alcohol obtained is reacted with a methyl halide, and that one. separating an obtained mixture of 6,7- and 10,11-epoxy compounds if desired. 2. The method according to claim 1, characterized in that one cis-nerolidol in the presence of an acid, preferably in the presence of sulfuric acid or p-toluenesulfonic acid, with methanol converts and the resulting 2-cis / trans, 6-cis-farnesylmethyl ~ ether converted into an epoxy. 3. The method according to claim 1, characterized in that cis-nerolidol with a phosphorus halide, primarily with Phosphorus tribromide, halogenated and the halide obtained, in particular the bromide, with an alkali metal methoxide, preferably with sodium methylate, and the ether obtained is converted into an epoxide. 4. The method according to claim I _1, characterized in that 'cis-nerolidol is halogenated with a phosphorus halide, primarily with phosphorus tribromide, and the halide obtained, in particular the bromide, with an alkali metal alkanoate in an _ω- inert solvent, primarily with potassium acetate in acetone. o ■ co sets the ester obtained, in particular the acetate, in any ^ * Sequence converted into an epoxy and hydrolyzed and the obtained _> ten alcohol in the presence of a base in an inert solution ^ ° medium, mainly in the presence of sodium hydride in dioxane, with a methyl halide, in particular with methyl iodide, reacts » COPY T8U872 5. A process for the preparation of pesticides, characterized in that one Bpoxyverbindungen the general formula ^A viii CH ₂ OCH in the A with B and C with D an oxygen bridge each, or A with B a carbon-carbon bond and C with D an oxygen bridge, or A with B. is an oxygen bridge and C with D is a carbon-carbon bond denote, with the largest residues on carbon atoms 2 and 3 cis / trans, cis or trans and on the carbon atoms 6 and 7 are cis-configured, as an effective base component, for combating k Adds solid or liquid carriers which are suitable per se in such agents to pests. 6. The method according to claim 5 »characterized in that 10, ll-epoxy-1-methoxy-3» 7, ll-trimethyl-dodeca-2-cis / trans, 6-cis-diene used as an effective ingredient. 7. The method according to claim 5, characterized in that one 10, ll-epoxy-1-methoxy-3,7, ll-trimethyl-dodeca-2-trans, 6-cisdiene used as an effective ingredient. 909827/1624 '** " 18H872 93 8. Pesticide, characterized in that it is a Bpoxyverbindungen of the general formula in which A with B and C with D each have an oxygen bridge, • 5 or A with B a carbon-carbon bond and G with D an oxygen bridge, or A with B an acid bridge and C with D a carbon-carbon bond lean, where the largest Eesi © βά carbon atoms 2 and 3 are cis / traas = y © is- or trans- as tlsa carbon atoms δ tsad 7 eis ^ koafigi / ^ ieE "· ¹ "? "^. - · ΐ ₉ hats 9 β pesticides according to claim 8, characterized gelceimseicliiietg that the active substance is 10,11-Bpoxy-lmethoxy ^ fTffll-trimethyl-dodeca-Z-cis / trans ^ ö-cis-dien contains. 10. Pesticides according to claim 8, characterized characterized as having the active substance 10,11-epoxy-l-iBethoxy Contains 3,7, ll-trimethyl-dodeca-2-trans, 6-cis-diene. 909827/1624 18U872 11. Use of epoxy compounds of the general formula I D in the A with B and C with D an oxygen bridge each, or A with B a carbon-carbon bond and 0 with D an oxygen bridge, or A with B. .an oxygen bridge and C with D a carbon-carbon bond denote, with the largest residues on carbon atoms 2 and 3 cis / tear, ice or trans and on the carbon atoms 6 and 7 are cis-configured, ... as a pesticide 12. Use of 10, ll-epoxy-1-methoxy-3,7,11-trimethyl dodeca-2-cis / trans, 6-cis-diene for the purpose specified in claim 11. 13. Use of lO ^ l-epoxy-l-methoxy-jJ ^ ll-trimethyl dodeca-2-trans, 6-cis-diene to that given in claim 11 Purpose. 909827/1 62A 18U872 [14.! Epoxy compounds of the general formula ^A -. . CH ₂ OGH ₃ in which A with B and C with D each denote an oxygen bridge, or A with B a carbon-carbon bond and C with D an oxygen bridge, or A with B an oxygen bridge and 0 with D a carbon-carbon bond, where in each case the I largest radicals on carbon atoms 2 and 3 are cis / trans, cis or trans and on carbon atoms 6 and 7 are cis-configured. 15. lOjllcis / trans, 6-cis-diene. 16. 10, II-epoxy-1-methoxy-3,7, II-trimethyl-dodeca-2-cis, 6-cis-diene. 17. 10,1-Bpoxy-1-methoxy-3,7> II-trimethyl-cLodecai-2-trans, 6-cis-diene. 18. 6,7-Bpox3i ^r -l-methoxy-3,7,11-trimethyl-6,7-cis-dodeca-2-cis / trans, 10-diene. 909827/1624 _β . 18U872 19. 6,7-Epoxy-1-methoxy-3,7,11-trimethyl-6,7-cis-dodeca-2 ~ cis, 10-diene. 20. 6,7-3poxy-1-methoxy-3 »7,11-trimethyl-6,7-cis-dodeca-2-trans, 10-diene. 21. 6.7; 10, ll-Diepoxy-1-methoxy-3,7,11-trimethyl-6,7-cisdodec-2-cis / trans-ene. 22. 6.7; 10, ll-Diepoxy-1-methoxy-3,7,11-trimethyl-6,7-cisdodec-2-cis-en. 23. 6.7; 10, ll-Diepoxy-1-methoxy-3,7, ll-trimethyl-6,7-cisdodec-2-trans-ene. 909827/162 A