DE2102856A1 - Allyher bonds - Google Patents

Description

Dr. {no. A, ν mi = 'he yard Dr. Frani Lederer

PATENT AWARDI

Jan. 21, 1971

RAN 6101/55

F. Hoffinann-La Roche & Co. Aktiengesellschaft, Basel / Switzerland

AlIy! Connections

The invention relates to new AlIy! Compounds of the general formula

-4m i ~

η 1 * 5

where R _{1 is} methyl or Ae thy I, R ₂ , R 'and R, hydrogen, methyl or ethyl, Ru is hydrogen or methyl, R _1. » Rg and R- hydrogen, lower alkyl, lower alkenyl, lower

Alkynyl, lower aryl or lower aryl-lower alkyl, 109832/1785

Hof / 11/12/70

where the lower aryl radicals optionally with halogen, lower alkyl, lower alkenyl, lower alkynyl, lower Alkyloxy, lower alkenyloxy, lower alkynyloxy, lower alkylenedioxy or nitro can be substituted, X is a Oxymethylene group in which the methylene group is still may carry a methyl group or ethyl group or an oxycarbonyl group, and in and η the number Designate O or 1.

The invention further relates to a process for the preparation of compounds of general formula I. The inventive process St ⁴ characterized in that a) a compound of general formula

γ D -p

/ ν Λ ^ U * ^ y ^ .Fv ^ s. J ^ i

RR ¹

m I-

where R-, R, R 'R ,, Rw R (-> R5 »Ry» X » Formula I have given meaning,

epoxidized to a compound of general formula I, or

b) a compound of the general formula

and η the in

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R,

where R ₁ , R ₃ , R ^, R-., R ^, Rc, R _fi , R ₇ , X, m and η have the meaning given in formula I and Z is chlorine, bromine or iodine,

converted into an epoxy of the general formula I, or

c) a compound of the general formula

IV

_lm L— -in

with a compound of the general formula

where in the formulas IV and V R., ^R ₂ * ^R 2 ' ^R V ^R 4 * ^R R ^{f R} fi' R ₇ , m and η have the meaning given in formula I, one of the symbols K and J chlorine, bromine or

Iodine and the other a hydroxyl group and Rg hydrogen 109832/1785

or Rg and r £ together form an additional carbon-carbon bond mean,

to a compound of the general formula

where R, R, R ^, R ^, R ^, Rf-, R ^, Ry, Rg, m and η die in the formulas IV and V have the meaning given and R in the formulas IV and VI are hydrogen or methyl or AethyI mean

implements, or

d) a compound of the general formula

R.

VII

R.

wherein R ^, R ₂ , R, R. and m have the meaning given in formula VI,
with a compound of the general formula

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VIII

where R is lower alkyl or phenyl, which may optionally have a lower alkyloxy or halogen substituent, and R_, R-, R_, R _Q and R ^{f are} the in

5 ο 7 ο 2

Formula VI have given meaning to a compound of the general formula

wherein R., R ₀ , R _x , R,., R, -, R, -, R ", R _fl , R 'and m have the meaning given in formula VI, reacts, or

e) in the event that in formulas VI and IX Rq and r! mean an additional carbon-carbon bond, such a compound is _{partially hydrogenated to a compound of the general formula I r} wherein R ^ is hydrogen.

Preferred process end products are compounds of the formula I in which R _{1 is} methyl or ethyl, R ₂ , R ^ ^{and R} 3 are hydrogen,

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Methyl or ethyl, R ^ hydrogen or methyl, R, R ^ and R "hydrogen, lower alkyl, lower alkenyl, lower alkynyl, lower aryl or lower aryl-lower alkyl, the lower aryl radicals optionally with halogen, lower alkyl, lower alkyloxy or nitro can be substituted and X is an oxymethylene group in which the methylene group can also carry a methyl group or ethyl group, or an oxycarbonyl-P group, and m and η denote the number O or 1. Particularly preferred are compounds of the general formula I in which R .. methyl or ethyl, R ", R 'and YL · hydrogen, methyl or ethyl, R. hydrogen or methyl, R, R ^ and R" are hydrogen, lower alkyl, lower Alkenyl, lower alkynyl, lower aryl, where the lower arm radical can optionally be substituted by halogen, nitro, lower alkyl or lower alkyloxy, X is an oxymethylene group in which the methylene group can also carry a methyl or ethyl group, or an oxycarbonyl group, and m and η denotes the number O or 1. Particularly preferred compounds are:

1- (Allyloxy) -4,5-epoxy-1,5-dimethyl-hexane 1- (Allyloxy) -6,7-epoxy-3,7-dimethyl-2-octene 1- (Allyloxy) -10, II-epoxy-3,7, II-trimethyl-2,6-dodecadiene 1- (Allyloxy) -10, II-epoxy-3,7,11-trimethy1-2,6-tridecadiene l- (Allyloxy) -10, ll-epoxy-3,7,10, ll-tetramethyl-2,6-dode-

cadiene

1- (Allyloxy) -10, ll-epoxy-7-ethyl-3,11-dimethy1-2,6-

tridecadiene

1- [1- (3,4-methylenedioxy-phenyl) allyloxy] -6,7-epoxy-

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3,6,7-trimethyl-2-octene

10, ll-epoxy-3.7 »10» ll-tetramethyl-2,6-dodecadienoic acid allyl ester

10, ll-epoxy-3,7, H-trimethyl-2,6-dodecadienoic acid allyl ester

10, ll-epoxy-7-ethy 1-3,11-dinie thy 1-2,6-tridecadienoic acid allyl ester

6,7-epoxy-3,7-dimethyl-2-octenoic acid allyl ester 1- (1,1-Dimethyl-allyloxy) -6,7-epoxy-3,7-dimethyl-2-octene

10, ll-epoxy-3,7,11-trimethyl - [(3-methyl-2,4-pentadieny1} · oxy] -2,6-dodeeadiene

10, ll-epoxy-3,7,11-trimethyl - [(3-raethyl-2-penten-4-ynyl} · oxy] 2,6-dodecadiene

10, ll-epoxy-3,7 »H -trimethyl-2,6-dodecadienoic acid (3-methyl-2-pentene-4-inyl) ester

Particularly preferred starting materials in the invention Procedures are:

Allyl {1,5-dimethyl-4-hexenyl) ether allyl (3,7-dimethyl-2 _r 6-octadienyl) ether 3,7, ll-trimethyl-2,6,10-dodecatrienoic acid allyl ester 3 , 7,11-trimethyl-2,6,10-trldecatrienoic acid allyl ester

3,7-Dimethyl-2,6-octadienoic acid allyl ester (3,7-dimethyl-2,6-octadienyl) - (l, l-dimethyl-allyl) -ether

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Allyl (3.7 * 10, ll-tetramethyl-2,6,10-dodecatrienyl) ether allyl (3.7 _J ll-trimethyl-2,6,10-dodecatrienyl) ether allyl (3.7 , ll-trimethyl-2,6,10-tridecatrienyl) ether (3-methyl-2, ^ - pentadienyl) - (3,7, ll-trimethyl-2,6,10-

dodecatrienyl) ether.

ίο—

Allyl (7-ethyl-3, ll-dimethyl-2,6, / fcridecatrienyl) ether.

The term "lower alkyl" includes both straight chain as well as branched hydrocarbon radicals with 1-6 carbon

k stoffatoraen, such as methyl, ethy1, propyl, isopropyl and the like. The lower alkyl groups in the alkoxy groups are of the same type. Examples are: the methoxy group, the Ethoxy group, the propyloxy group and the isopropyloxy group. The terms "lower alkenyl" and "lower alkynyl" include both straight and branched chain hydrocarbon radicals having 2-6 carbon atoms. Examples are: Vinyl, allyl, butenyl, pentenyl, ethynyl, propargyl, butynyl. The alkenyloxy and alkynyloxy groups are of the same type.

| Examples include: vinyloxy, allyloxy, ethinyloxy,

Propargyloxy, etc. The term "lower aryl" includes aromatic hydrocarbons having 6-12 carbon atoms such as Phenyl, tolyl, naphthyl, etc. The term "halogen" includes the four halogen atoms fluorine, chlorine, bromine and iodine, unless expressly stated otherwise. The term "oxymethylene group, in which the methylene group is still a methyl group

ßio or ethyl group can carry "represents the formula -CHO-,

wherein R is hydrogen, methyl or ethyl. The expression "Oxycarbonyl group" stands for the formula -COO-,

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In one embodiment of the method according to the invention a compound of the general formula II becomes a compound in an inert solvent with a peracid of the general formula I epoxidized. For this purpose, a compound of formula II in an inert solvent, in particular in a halogenated hydrocarbon such as chloroform or carbon tetrachloride, preferably methylene chloride, dissolved, and in a temperature range between 0 and room temperature with a peracid, such as Performic acid, peracetic acid, perbenzoic acid, perphthalic acid or pertungstic acid, preferably m ^ chloroperbenzoic acid, treated,

In a further embodiment of the process according to the invention, a compound of the general formula III is converted into an epoxide of the general formula I. For this purpose, the terminal halohydrin of the general formula HI for the case that X is an oxymethylene group which can carry a methyl or ethyl group, in an alkanol, preferably in methanol, and for the case that X is an oxycarbonyl group, in one Ether, preferably diethyl ether, dissolved and in the former case mixed with an alkali metal alcoholate, preferably sodium methylate, and in the latter case with powdered alkali metal hydroxide, preferably potassium hydroxide. The epoxide of the general formula I is thus obtained in a smooth reaction.

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This embodiment of the process according to the invention offers the advantage that, in the case of esters and ethers, only the terminal double bond is epoxidized. The reaction of compounds of the general formula II which have more than one double bond, on the other hand, is generally not selectively converted into the corresponding epoxide with peracid, but rather a mixture of epoxides is obtained which is separated by chromatography in a manner known per se can be.

In a further embodiment of the invention Process, the reactants of the general formulas IV and V are in an inert organic solvent, such as benzene, Toluene, Dloxan, 1,2-Dimeth-xyäthan or preferably tetrahydrofuran, dissolved and with the addition of an aprotic solvent, particularly preferably hexamethylphosphoric triamide, on one

Temperature range between 0 and the boiling point of the solvent in question is cooled or heated. A particularly preferred reaction temperature is 70, since under this condition the reaction components dissolved in tetrahydrofuran can be refluxed. The reactant that carries the hydroxyl group is converted into an alkali metal salt before the reaction. The alcohol is converted into the corresponding alkali metal salt in a manner known per se in an inert solvent by the action of a corresponding base or an alkali metal, for example by the action of sodium hydride on the alcohol in tetrahydrofuran as the solvent.

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In a further embodiment of the invention Process is a carbonyl compound of the general formula VII with a phosphine oxide of the general formula VIII to one Compound of the general formula IX implemented. This reaction takes place in the presence of a base, preferably in the presence an inert organic solvent, e.g. in the presence of sodium hydride, in a solvent such as benzene, toluene, Dimethylformamide, tetrahydrofuran, dioxane or 1,2-dimethoxyethane or in the presence of an alkali metal alcoholate in an alcohol, e.g. in the presence of sodium methylate in Methanol, in a temperature range between 0 and room temperature. In a particularly preferred embodiment For example, a compound of formula VII with a phosphine oxide of formula VIII in the presence of 2 moles of sodium hydride reacted in absolute tetrahydrofuran, with excess sodium hydride before working up by adding of an absolute alkanol is destroyed.

In a further embodiment of the process according to the invention, compounds of the general formulas VI or IX, in which Rn and BX denote an additional carbon-carbon bond, are partially hydrogenated. For this purpose, such a compound is dissolved in an inert solvent, preferably high-boiling Peferolether, and in the presence of a partially inactivated catalyst (for example a lead / palladium catalyst deactivated with quinoline HeIv.

Chim. Acta. J £>, 446 (1952); Hoppe-Seylers Z. physiol. Chem.

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29 * 3 , 290 (1935)) partially hydrogenated.

Some of the starting materials of the general formula II used in the process according to the invention are new and can be made by several processes. For example, compounds of the formula II in which X has the meaning Oxymethylene is present, can be prepared by adding a compound of the general formula IV, which replaces the epoxy oxygen carries an additional carbon-carbon bond and wherein K is a bromine atom or a hydroxyl group, with a compound of the general formula V, wherein J eiii Hydroxyl group or a halogen atom in which the Η atom of the hydroxyl group has been replaced by an alkali metal, implements. This reaction can be carried out in an inert organic solvent such as benzene, toluene, dioxane, 1,2-dimethoxyethane or tetrahydrofuran at a temperature lying between 0 and the boiling point of the solvent in question

take place. An aprotic solvent such as hexamethylphosphoric acid triamide is preferably added.

Compounds of the formula II in which X is oxycarbonyl can be prepared, for example, by using a compound of the general formula VII which has an additional carbon-carbon bond in place of the epoxy oxygen carries, reacts with a phosphine oxide of the general formula VIII. This implementation is expedient in the presence of a base, preferably in the presence of one

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inert organic solvent, e.g. in the presence of Sodium hydride in a solvent such as benzene, toluene, Dimethylformamide, tetrahydrofuran, dioxane or 1,2-dimethoxyethane or in the presence of an alkali metal alcoholate in an alkanol, e.g. in the presence of sodium methylate in Methanol, carried out in a temperature range between 0 and room temperature.

Another way to make connections of the formula II, in which X is oxycarbonyl, consists in the esterification of an acid of the formula

m i_ —in

COOH

where R ₁ , R _? , R- ,, Rj ,, m and η have the meaning given in formula I,

with an alcohol of the formula V, in which J is a hydroxyl group. For this purpose, the acid of formula X in one inert solvents, for example petroleum ether, benzene, hexane, etc., to which an acid binder is added, such as Pyridine, triethylamine, quinoline, etc., preferably in pyridine with a halogenating agent such as thionyl chloride, Phosphorus trichloride, thionyl bromide, phosphorus oxychloride,

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- 14 - 2102858

preferably thionyl chloride, converted into the corresponding acid halide. The acid halide is converted with the selected alcohol in an inert solvent such as benzene, toluene, hexane, isooctane, chloroform, carbon tetrachloride or ethylene glycol dimethyl ether in the presence of an acid binder such as pyridine, triethylamine, quinoline, etc., preferably pyridine, to give the desired allyl or propargyl ester - k sets. The propargyl ester can be partially hydrogenated to a compound of the formula II.

Starting compounds of the general formula III are prepared by ^ ^"r Getting Connected tpp of the general formula hydroxyhalogeniert to a compound of general formula III II. For this purpose, the compound in question is suspended in water and an amount of an inert solvent, for example dioxane or 1,2-dimethoxyethane, preferably tetrahydrofuran, is added to produce a homogeneous, concentrated solution. If, for example, a compound of the formula III is sought in which Z is bromine,

o N-bromosuccinimide is added in portions to such a solution in a temperature range between 0 and room temperature. If compounds of the formula III are sought in which Z is chlorine or iodine, then N-chloro-succinimide or N-iodo-succinimide are used accordingly. A particularly preferred temperature range for

ο ο The implementation of this reaction is between 0 and 5.

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The compounds of the formula I obtained are obtained as a mixture of cis / trans isomers. The mixture can e.g. Adsorption on a material with selective activity can be separated into the isomeric forms. The mixture of isomers is for example dissolved in an inert organic solvent, e.g. in hexane, ether or ethyl acetate and adsorbed on silica gel. The isomers adsorbed in different zones can be mixed with one of the solvents mentioned above or solvent mixtures are eluted and isolated. The isomer mixture can also be fractionated in individual cases Distillation or, if appropriate, also by preparative Oaschromatography or preparative thin-layer chromatography be separated.

The process products of the formula I are suitable for Control of pests. In contrast to most of the pesticides known to date, which are used as contact and Food poisons kill, paralyze or drive away, attack animals the compounds of the formula I which can be prepared according to the invention into the hormonal system of the animal organism. In the case of insects, for example, the transformation to the imago, the Deposition of viable eggs and the development of deposited normal eggs are disturbed. The generation sequence will interrupted and the animals are killed indirectly. The process products are practically non-toxic for vertebrates. the The toxicity of the compounds of the formula I is over 1000 mg / fcf

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Body weight. The new connections will also be easy reduced. The risk of an accumulation is therefore excluded. Accordingly, the products of the process can be safely aur Control of pests in animals, plants and supplies can be used.

The products of the process are particularly suitable for controlling invertebrates, such as arthropods and nemathodes, in particular insects, such as, for example, Tenebrio k molitor, Tineola biselliella, Carpocapsa pomonella, Leptinotarn? decemlineata, Calandra granaria, Dysdercus cingulatus or Ephestia kllhniella. As will be explained in more detail below in an exemplary experimental report, genligt generally already an active ingredient concentration of 1O ~ ⁵ to 1O ~ g / cm in order to ensure the desired effect.

Test report Ovizlde effect in Ephestia kühniella

| Rondelles (10 cm) of cotton fabric are made with

acetone solution of the active ingredient drizzled and carefully dried. For each variant, 30-60 freshly laid eggs of the flour moth are placed on the discs and hatched in a small plastic cage at 25 ^° C. and high humidity.

The effect of the substances can be seen in the earlier or later death of the embryos in the egg or when they hatch.

The results are expressed in % egg mortality.

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—Χ 2

The dosage is given in: 10 g active ingredient / om substance Dosage 3 therefore means: 10 g / cm

Conc.

10 "" ^x g wst./cro ⁴

Wst. = Preparation (active ingredient),

Tenebrio molitor

Egg mortality

preparation dosage) in % ι
1- (allyloxy) -6,7-epoxy-3,7-
dimethyl-2-octene 3
4th 100
100 6,7-epoxy-3,7-dimethyl-2-
cis / trans-octenoic acid-allyl
ester 4th
5 100
100
100 10, ll-epoxy-3.7 # ll- ^ i * ⁿ ethyl-
2-cis / trans, 6-cis-dodecadiene
acid- (trans-3-methyl-2-pentene »·
4-ynyl) ester 3
4th
5 100
100
100

Tenebrio molitor dolls is an acetone solution of the active ingredient (Wst) of known concentration applied to the abdomen (ventral). The so treated pupae are 10 days leave in Petri dishes at room temperature and then examine whether the pupae have developed into adult animals, The activity of the active ingredient is given in percent inhibition of the development of adult animals (API) (with a given Concentration)*

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Preparation (Wst)

1- (Allyloxy) -10,11-epoxy-3.7 _T ll-trimethyl-2-cis / trans, 6-cis-dodecadiene

Conc. AFI g Wst / doll in %> 10 ~ ⁶ 100 10-7 100 10-8 100 5.10-9 100 2.10-9 6o 10-9 15th

The active ingredients can, for example, in the form of emulsions,

" Suspensions, dusts, solutions or aerosols can be used. In special cases, the objects to be protected, eg food, seeds, textiles, can be impregnated directly with the active ingredient in question or with a solution of the active ingredient. The active ingredient can also be in a form are used that are only affected by external influences, e.g. in contact with moisture or

only releases the active substance in the animal body itself. The compounds of the formula I are sprayed in a concentration of 0.01 $ to 0.5 # *, preferably 0.1 #.

The following examples illustrate the invention. All temperatures are given in Qrad Celsius.

example 1

2.4 g of sodium hydride (50% nujol suspension) are added Washed twice with hexane, covered with 10 ml of absolute tetrahydrofuran and 11 »9 β with stirring and until cooling 10, ll-Epoxy-3,7,11-triaethyl-2-oia ^ jran *, 6-eia-dodeoadien-I-ol

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in 10 ml of absolute tetrahydrofuran was added dropwise and stirring was continued for 1 hour at room temperature. Under ice cooling are after each other 7 g of allyl bromide and 20 ml of hexamethylphosphoric acid tri-

O
amide was added dropwise and the mixture was stirred at 5 ° C. for a further 3 hours. The cooled reaction mixture is poured onto ice water, extracted exhaustively with hexane, the combined hexane extracts are washed with saturated sodium chloride solution, dried over sodium sulfate, filtered and evaporated. Chromatography on silica gel with hexane / ethyl acetate (4: 1) yields pure 1- (allyloxy) -10,11-epoxy-3,7, ll-triraethyl-2-cis / trans, $ - cis-dodecadiene. A sample

ο - ^ is distilled in the bulb tube. Boiling point approx. 120/10 Torr.

τξ ° = 1.4785

Example 2

To a solution of 73 g of 3-bromo-2,6,10 ^ trimethyl-12 - [{trans-3-methyl-2-penten-4-ynyl) -oxy3 ~ 6 ~ cis, 10-cis / transdodecadiene-2 -oil in 95.5 ml of absolute methanol is under A solution of 4.4 g of sodium in 95.5 ml of absolute methanol was added dropwise to ice cooling and the mixture was then stirred for a further 0.5 hours. The reaction mixture is poured onto ice water, with ether exhaustively extracted and as described in Example 1, worked up. By chromatography on silica gel with hexane / ether (4: 1) becomes pure 10, ll-epoxy-3,7, ll-trimethyl-1- [(trans-3-methyl-2-pent * n-4-ynyl) -oxy] -2-cis / trans , 6-cls-dodecadiene obtained, which is disintegrated in the distillation in a high vacuum

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puts. A sample is distilled in a bulb tube; Boiling point approx. -145 ° Ao " ³ Torr .; n ^ ° = 1.4974.

The starting material can be produced as follows:

39 g sodium hydride (50 # Lge Nujol suspension) are washed twice with hexane, covered with 400 ml of tetrahydrofuran and with stirring and ice-cooling 78.2 g of trans-3-methyl-2-penten-4-yn-1-ol was added dropwise and the mixture was stirred for a further 1 hour at room temperature. Then are under ice cooling successively 232 g of 2-cis / trans, 6-cis-farnesyl bromide and 270 ml of hexanemethylphosphoric acid triamide were added dropwise and the mixture was stirred at 50 ° for 3 hours and as described in Example 1, worked up. Chromatography on silica gel with hexane / ether (97.5: 2.5) gives pure (trans-3-methyl-2-penten-4-ynyl) - (3,7, ll-trimethyl ~ 2-cis / trans, 6-cis, 10-dodecatrienyl) ether obtain. A sample is distilled in a bulb tube, boiling point approx. 120-127 ° / 0.OOI5 Torr; n | °. 1.5012

To a homogeneous solution of 134 g of (trans-3-methyl-2-penten-4-ynyl) - (3.7 * ll-trimethyl-2-cis / trans, 6-cis, 10-dodecatrienyl) ether in 1300 ml of tetrahydrofuran and 208 ml of water, 89.3 g of N-bromosuccinimide are added in portions while cooling with ice added, stirred for a further 4 hours with ice cooling and worked up as described in Example 1. By chromatography on Kieeelgel with hexane / ether (4: 1) pure 3-bromo-2,6,10-

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trimethyl-12 - [{trans -3-methyl-2-penten-4-ynyl) -oxy] -6-cis, 10-cis / trans -dodecadien-2-ol obtained, which sioh decomposes in the distillation in a high vacuum, n ^ = 1.5213 (sample in High vacuum dried at 50 for 3 hours).

Example 3

For a solution of 6 g of 10, ll-epoxy-3,7,11-triraethyl- 1 - [( trans-3-methyl-2-penten-4-ynyl) -oxy] -2-cis / trans> 6- cis-dodeeadiene {prepared according to Example 2) in 60 ml of high-boiling petroleum ether, 0.6 ml of quinoline and 0.6 g of Lindlar catalyst are added and hydrogenated until the theoretical amount of hydrogen is absorbed, the catalyst is filtered off and evaporated. To remove the quinoline, the reaction mixture was chromatographed on silica gel with hexane / ether (4 si) and a sample was distilled in a bulb tube. 10,1-epoxy-3,7,11-trimethyl- [{trans-3-methyl-2,4-pentadienyl) -oxy] -2-ois / trans, 6-cisdodecadiene is obtained. Boiling point approx. 120 ° / 10 "" ^ Torr. n | ° = 1.4967.

example k

0.5 ml quinoline and 0.5 g Lindlar catalyst are added to a solution of 5 g of 1- (propinyloxy) -6,7-epoxy-3,7-dimethyl-2-cis / trans-octene in 50 * nl high-boiling petroleum ether given, hydrogenated until the theoretical amount of hydrogen is absorbed and, as described in Example 3, worked up. 1- {Allyloxy) -6.7 ~ epoxy-3.7 ~ difiethyl-2-cis / tran8-octene boils at 68 /0.08 Torrj -1.4632. 1Ö9832 / 178S

Example 5

To a solution of 33 Allyl-O ^ g of 6-octadienyl) ether in 35 ° ^m l of methylene chloride under ice-cooling 43.3 g of Ni-chloroperbenzoic acid was added portionwise and stirring was continued for 2 hours under ice cooling, then diluted with 250 ml methylene chloride and washed successively with ice-cold ^ Washed in sodium hydroxide solution and saturated sodium chloride solution, dried over sodium sulfate, filtered and evaporated. Chromatography on silica gel with hexane / ether (4: 1) and subsequent distillation gives pure 1- (allyloxy) -6,7-epoxy-3f7-din> ethyl-2-cis / trans-octene; Boiling point 70-72 ° / oil torr. n ^ ° = 1.4633

The starting material can be produced as follows:

48 g sodium hydride (50% Nujol suspension) are used Washed twice with hexane and then overweighted with 500 ml of absolute tetrahydrofuran. While stirring and 58 g of allyl alcohol are added dropwise to ice cooling and the mixture is stirred at room temperature for 1 hour. Be under ice cooling successively 220 g of 2-cis / trans-Qeranylbromid and 400 ml of hexanemethyl phosphoric acid tri amide was added dropwise and the mixture was refluxed for 3 hours. Then as in Example 1 indicated, worked up and fractionally distilled. Boiling point 51 ° / 0.15 Torr, n ^ ° «1.4695.

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Example 6

To 9.3 g of 2-cis / trans-geranic acid allyl ester in 100 ml of methylene chloride, 9 S m -chloroperbenzoic acid (93%) are added in portions with ice-cooling and the mixture is stirred for a further 2 hours with ice-cooling, diluted with 100 ml of methylene chloride and then first Washed with ice-cold sodium hydroxide solution and then with saturated sodium chloride solution, dried over sodium sulfate, filtered and evaporated. Chromatography on silica gel with hexane / ether (4: 1) and subsequent distillation gives pure 6,7-epoxy-3,7-dimethyl-2-cis / trans-octenoic acid allyl ester * boiling point 81-84 ° / O.O5 Torr, r? ° = 1.4728.

The starting material can be produced as follows:

To a solution of 25.2 g of Oeranic acid and 13.5 g Pyridine is dissolved in 150 ml of absolute ether while cooling with ice 20.2 g of thionyl chloride were added dropwise and the mixture was stirred at room temperature for 1 hour with exclusion of moisture. The unusual one Pyridine hydrochloride is quickly filtered off with suction and washed with hexane and the reaction solution evaporated in vacuo. That unpurified geranic acid chloride is in 100 ml of absolute Benzene added and while cooling with ice to a solution of 9.3 g of allyl alcohol and 13 * 5 S pyridine in 200 ml of hexane and 80 ml of benzene were added dropwise and stirring was continued for 1 hour at room temperature. The reaction mixture is diluted to ice cold Poured hydrochloric acid, separated the organic phase and the

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aqueous-hydrochloric acid phase extracted twice with hexane. The combined organic phases are washed successively with saturated sodium bicarbonate solution and saturated sodium chloride solution until neutral, dried over sodium sulfate, filtered off and evaporated. Chromatography on silica gel with hexane / ether (9: 1) and subsequent distillation gives pure 2-cis / trans-queranic acid allyl ester; Boiling point 70 ° / 0.01 Torr, n ^ ⁰ = 1.4800.

Example 7

To 12.6 g of 3,7,11-trimethyl-2-cis / trans, 6-trans, 10-dodecatrienoic acid (trans-3-methyl-2-penten-4-ynyl) ester in 120 ml of methylene chloride are added 10.3 S m -chloroperbenzoic acid were added in portions to ice cooling, the mixture was stirred for a further 2 hours with ice cooling and worked up and chromatographed as described in Example 6. The pure 10,1-epoxy-3,7ill-triroethyl-2-cis / trans, 6-trans-dodeoadienoic acid (trans-3-methyl-2-penten-4-ynyl) ester obtained boils in the bulb tube with decomposition at about 150 ^o / 10 "" * ^ Torr .; n _D = I.5020.

The starting material can be produced as follows:

24.6 g of 3,7 »H-trimethyl-2-cis / trans, 6-trans, 10-dodecatrienoic acid chloride in 70 ml of absolute benzene are cooled with ice to a solution of 9.6 g of trans-3-methyl-2-penten-4-inl-ol and 8.15 ml of absolute pyridine in 200 ml of hexane and 55 ml

109832/1785

absolute benzene was added dropwise, stirring was continued for 1 hour at room temperature and as described in Example 6, second section, worked up and chromatographed. A sample of the pure 3-7jII-trimethyl-2-cis / trans, 6-trans, 10-dodecatrienoic acid {trans-3-methyl-2-penten-4-ynyl} ester boils in the spherical tube at about 130 ° / lo "* ^ Torr. n ^ ° = I.5098.

Example 8

To 12.5 g of (3,7-dimethyl-2,6-octadienyl} - (1,1-dimethyl-2-propenyl) ether 11.5 S of m-chloroperbenzoic acid are added in portions in 130 ml of methylene chloride while cooling with ice and the mixture was stirred for 2 hours, then with 130 ml of methylene chloride diluted and washed successively with ice-cold 1 η sodium hydroxide solution and saturated sodium chloride solution, over sodium sulfate dried and evaporated. The residue is chromatographed on silica gel with hexane-ether (9 * 1). What is obtained is pure 6,7-rEpoxy-3,7-dimethyl-1- [(1,1-dimethyl-2-propenyl) -oxy] -2-octene. Boiling point 80 ° / 0.15 Torr. n ^ ° = 1.4619

The starting material can be produced as follows:

9.6 g sodium hydride (50% Nujol suspension) Washed twice with hexane, covered with 80 ml of absolute tetrahydrofuran and, while cooling with ice, 17.2 g of 2-methyl-3-buten-2-ol added dropwise in 150 ml of absolute tetrahydrofuran and

1 09832 / 178S

Stirred for 1 hour at room temperature. Then 23 g Geranyl bromide and then, with occasional ice cooling, 80 ml of hexamethylphosphoric acid triaraide were added dropwise and the mixture

Heated to reflux for 2 hours. The cooled reaction mixture is poured onto saturated sodium chloride solution and worked up as described in Example 1 and chromatographed on silica gel with hexane-ether (95: 5). The {317-dimethyl-2,6-octadienyl) - (1,1-dimethyl-2-propenyl) ether boils at 58-59 ° / O.O8 Torr. . 1.4673-

Example 9

To 3.8 g of 3,6,7-trimethyl-l- [(oc-vinylpiperonyl) oxyl-2-cis / trans, 6-octadiene in 40 ml of methylene chloride, 2.5 g of m-chloroperbenzoic acid ( 93%) was added and the mixture was stirred for a further 2 hours while cooling with ice. W The reaction mixture is then diluted with 40 ml methylene chloride and washed with ice-cold Add sodium hydroxide solution and saturated brine, and dried over sodium sulfate evaporated. Chromatography on silica gel with hexane-ether (4: 1) gives pure 6,7-epoxy-3,6,7-trimethyl-l [(> * .- vinylpiperonyl) oxy] -2-cis / trans-octene. A sample boils in the bulb tube at approx. 135 ° / O.OO1 Torr, n ^ ^v = 1.5250.

The starting material can be produced as follows:

109832/1785

4.4 g of sodium hydride (50 $ Nujol suspension) are used washed with hexane, with 40 ml of absolute tetrahydrofuran covered and with ice cooling 16 g <* - ethynylpiperonyl alcohol in 120 ml of absolute tetrahydrofuran was added dropwise and stirring was continued for 1 hour at room temperature. Then be one after the other with ice cooling 21 g 3j6,7-Ti'imethyl-2-cis / trans, 6-octadienyl-1-bromide and 40 ml hexamethylphosphoric acid triamide added dropwise and stirred for 1 hour at room temperature, poured onto saturated sodium chloride solution, exhausting with ether extracted, the ether solution washed with saturated sodium chloride solution, dried and evaporated. By chromatography on silica gel with hexane-ether (9: 1) is pure 3> 6,7-trimethyl-1- [ (oc-äthinylpiperonylJexyl ^ -cis / tranSjö-octadiene

20th

obtain; n ^ = 1.5366.

To 6.6 g of 3,6,7-trimethyl-1 - [{o <.- äthinylpiperonyl} oxy] -2-cis / trans, 6-octadlene in 60 ml of high-boiling petroleum ether-ethyl acetate (3il) 0.7 ml of quinoline and 0.7 g of Lindlar catalyst given and hydrogenated until the theoretical amount of hydrogen is absorbed. Then the catalyst filtered off and the reaction solution successively with ice-cold, aqueous In hydrochloric acid, with sodium bicarbonate solution and saturated Washed brine and dried over sodium sulfate and evaporated. By chromatography on silica gel with hexane ether (85s15) pure 3,6,7-trimethyl-1- [(<* - vinylpiperonyl) oxy] -2-cis / trans, 6-octadlene. One

109832/1785

The sample boils in the spherical tube at approx. Ö2 ° / 6 Torn η _β = 1.43ÖÖ.

Example 10

To 12 g of allyl (1,5-dimethyl-4-hexenyl) ether in 120 ml 14.6 g of m-chloroperbenzoic acid (93%) are added in portions with stirring and with ice-cooling, and methylene chloride Stirred for 1 hour while cooling with ice. The reaction mixture ™ is then diluted with 120 ml of methylene chloride and Washed with ice-cold sodium hydroxide solution and saturated sodium chloride solution, dried over sodium sulfate and evaporated. Chromatography on silica gel with hexane-ether (9: 1) gives pure 2,3-epoxy-2-methy 1-6- (2-allyloxy) -heptane. Boiling point approx. 8o ° / O.OO5 Torr. n ^ ° = I.5230.

The starting material can be produced as follows:

9.6 g sodium hydride (50% Nujol suspension) Washed with hexane, covered with 100 ml of absolute tetrahydrofuran and, with ice cooling, 25.4 g of 6-methyl-5-hepten-2-0I added dropwise and stirred for a further 1 hour at room temperature. Then 24.2 g of allyl bromide and 70 ml of hexainethylphosphoric acid triamide are added dropwise one after the other with ice cooling, Stirred for 16 hours at room temperature, poured onto ice water, exhaustively extracted with ether, with saturated sodium chloride solution washed and evaporated. By chromatography

109832/1785

Silica gel with hexane-ether (9: 1} and subsequent distillation pure allyl (1,5-dimethyl-4-hexenyl) ether is obtained. Boiling point 63-64 ° / 7 Torr. n | ° = 1

Example 11

0.6 ml are added to a solution of 5 * 8 g of l- (propinyloxy) -10, ll-epoxy-3,7ilO, ll-tetramethyl-2,6-dodecadiene (cis / trans mixture) in 60 ml of high-boiling petroleum ether Quinoline and 0.6 g of Lindlar catalyst are added and hydrogenated until the theoretical amount of hydrogen is absorbed, the catalyst is filtered off and evaporated. To remove the quinoline, the reaction mixture is chromatographed on silica gel with hexane / ether {4 * 1) and distilled. 1- (Allyloxy) -10, ll ~ epoxy-3.7-10, ll-tetramethyl-2,6-dodecadiene (cis / trans mixture) is obtained. Bp. 115-116 ° c / 0.035 Torr n ^ ° * 1.4779.

Example 12

To a solution of 10 g of 3-bromo-2,6,10-trimethyl-12-allyl oxy-6,10-dodecadien-2-ol (cis / trans mixture) in 14 ml abs. Methanol becomes a solution of 645 mg sodium under ice cooling in X4 ml abs. Methanol is added dropwise and the mixture is then stirred for a further 60 minutes. The reaction mixture is poured onto ice water, exhaustively extracted with ether and worked up as described in Example 1. By chromatography on silica gel

109832 / im

with hexane / ether (4: 1) pure l- (allyloxy) -10, ll-epoxy-3, 7, ll-trimethyl-2,6-dodecadiene (cis / trans mixture) is obtained. Bp 99-100 ° c / 0.002 torr, n ^ ⁰ = 1.4751.

The starting material can be produced as follows:

4.8 g of sodium hydride (50 # strength Nujol suspension) are washed twice with hexane, with 57 ml of abs. Tetrahydrofuran Uber- ψ coated and then added dropwise 5.8 g of allyl alcohol with stirring under ice cooling, and the mixture weitergerUhrt 1 hour at room temperature, then added dropwise under ice-cooling successively 28.5 g of farnesyl bromide (cis / trans mixture) and 4o ml Hexamethylphosphoreäuretrlamid and 2 h stirred at room temperature and, as described in Example 1, worked up. Chromatography on silica gel with hexane / ether (9: 1) gives pure allyl (j5,7,11-trimethyl-2,6,10-dodecatrienyl) ether (cis / trans mixture). 94-95 ° C / O, OOl Torr. n ^ ° = 1.4807.

To a homogeneous solution of 14.5 g of allyl (3 * 7, H-trimethyl-2,6,10-dodecatrienyl) "- ether (cis / trans mixture) in 155 ml of tetrahydrofuran and 25 ml of water are cooled with ice 12.4 g of N-bromosuccinimide were added in portions, the mixture was stirred for a further 6 hours with ice cooling and as in Example 1 described, worked up. Chromatography on silica gel with hexane / ether (4il) gives pure> bromo-2,6,1O-trimethyl-12-allyloxy-6,10-dodecadien-2-ol (oie / trans mixture)

109832/1785

2102858

PO

hold, ηJ = 1.5022.

Example 13

A solution of 9.33 g of 4-bromo-3 # 7, H-trimethyl-13-allyloxy-7, ll-tridecadien-3-ol (cis / trans mixture) in 16 ml of absolute methanol is added while cooling with ice of 650 mg of sodium in 16 ml of absolute methanol are added dropwise and the mixture is then stirred for a further 60 minutes. The reaction mixture is poured onto ice water, extracted exhaustively with ether and worked up as described in Example 1. By chromatography on silica gel with hexane / ether (4: 1) pure l- (allyloxy) -10, ll-epoxy-3,7, ll-trimethyl-2,6-tridecadiene (cis / trans mixture) is obtained, bp approx. 120 ° c / 0.005 Torr (Kugelrohr) n £ ^u = 1.4768.

The starting material can be produced as follows:

4.5 g sodium hydride (5Q Nujol suspension) Washed twice with hexane, covered with 17 ml of absolute tetrahydrofuran and, with stirring and cooling, 20.2 g 3 # 7, ll-trimethyl-2,6,10-tridecatrien-l-ol (cis / trans mixture) added dropwise and the reaction mixture for 1 hour at room temperature stirred further. Then inter ice cooling one after the other 10.9 g of allyl bromide and 34 ml of hexamefchylphosphoric acid triamide added dropwise and stirred for a further 16 hours at room temperature and as described in Example 1, worked up. By

109832/1785

Chromatography on silica gel with hexane / ether (4: 1) gives pure allyl (3,7 »11-trimethy1-2,6,10-tridecatrienyl) ether (cis / trans mixture). Bp 87 ° C / 10 ~ ^ Torr, n ^ ⁰ = 1.4813-

To a homogeneous solution of 13 »8 g of allyl (3» 7 »H-trimethyl-2,6,10-tridecatrienyl) ether (cis / trans mixture) in 145 ml of tetrahydrofuran and 23 ml of water are cooled with ice 8.9 g of N-bromosuccinimide were added in portions, the mixture was stirred for a further 6 hours with cooling in an electric conditioner and as in Example 1 described, worked up. Chromatography on silica gel with hexane / ether (4: 1) gives pure 4-bromo-3,7, H-trimethyl-13-allyloxy-7, ll-tridecadien-3-ol (cis / trans mixture)

20th
obtain. n_ = 1.5035

Example 14

To a solution of 5.08 g of 4-bromo-7-ethyl-3, ll-dimethyl-13-all ^ loxy-7, ll-tridecadien-3-ol (cis / trans mixture) in 8.5 rr. l of absolute methanol is added dropwise under Eisklllrilung a solution of '' ho ng sodium in 8.5 ml of absolute methanol and then weitergerlihrt 60 minutes. The reaction mixture is poured onto ice water, extracted exhaustively with ether and worked up as described in Example 1. Chromatography on silica gel with hexane / ether (4: 1) gives pure 1- (allyloxy) -10,1-epoxy-7-ethyl-3, H-dimethyl-2, etridecadiene (cis / trans mixture). Bp approx 125 ° c / 0.001

Torr. n ^ °. 1.4772.

109832/1785

The starting material can be produced as follows:

2.44 g sodium hydride (50% Nujol suspension) Washed twice with hexane, covered with 11 ml of absolute tetrahydrofuran and, with stirring and ice cooling, a Solution of 12.7 g of 7-ethyl-3, ll-dimethyl-2,6,10-tridecatrienl-ol (cls / trans mixture) in 11 ml of absolute tetrahydrofuran was added dropwise and the mixture was stirred for a further 1 hour at room temperature. Then 6.5 g of allyl bromide and 20 ml of hexamethylphosphoric acid triamide are successively added while cooling with ice added dropwise, stirred for 4 hours at room temperature and, as described in Example 1, worked up. By chromatography on silica gel with hexane / ether (4: 1) is pure allyl (7-ethyl-3, ll-dimethyl-2,6,10-tridecatrieny1) ether (cis / trans mixture). Bp 93 ° C / O, 001 torr. n ^ ° = 1.4800.

To a homogeneous solution of 8.34 g of allyl (7-ethy 1- ^ 5,11-dimethyl-2,6,10-trideeatrienyl) ether (cis / trans mixture) in oil 2 ml of tetrahydrofuran and 13 ml of water under ice cooling ^l j, 2. g of N-bromosuccinimide were added in portions, the mixture was stirred for a further 6 hours with ice cooling and worked up as described in Example 1. Chromatography on silica gel with hexane / ether (4: 1) gives pure 4-bromo-7-ethyl-3, ll-dimethyl 13-allyloxy-7 * ll-trldecadien-3-ol (cis / trans mixture) . n_ = 1, ^ 019.

109832/1785

Claims (1)

-3 V Patent application Kyfter drive for the production of compounds of the general formula R, η R _r ¹ W? ι wherein R is methyl or ethyl, R, R ^ and R is hydrogen, methyl or ethyl, R. is hydrogen or methyl, R, R, - and R _{7 is} hydrogen, lower alkyl, lower alkenyl, lower alkynyl, lower aryl or lower aryl-lower alkyl, where the lower aryl radicals can optionally be substituted with halogen, lower alkyl, lower alkenyl, lower alkynyl, lower alkyloxy, lower alkenyloxy, lower alkynyloxy, lower alkylenedioxy or nitro, X is an oxymethylene group in which the methylene group is still a methyl group or ethy! group can carry or an oxycarbonyl group and m and η denote the number O or 1, characterized in that one 1098 3 2/1785 a compound according to the general formula a R. N I. m / ^R 7 ^{n dle in} wherein R ₁ , ^R ₂ ' ^R 2 * ^R 3' ^R V ^{R |} =>^'R6' is ^R 7 ^{'X' meters} have formula I specified, epoxidized to a compound of general formula I, or b) a compound of the general formula Rl: -in the η R III wherein R ₁ , R ₃ , R ^, R ₅ , R ^, R ₅ , r ^ r _{Xj m υηύ n have the} meaning given in formula I and Z is chlorine, bromine or iodine, converted into an epoxy of the general formula I, or c) a compound of the general formula -in the 10 109832/1785 with a compound of the general formula where in the formulas IV and VR ₁ , R ₃ , R ₂ '* Ky R4 »R ^» R ₇ , m and η have the meaning given in formula I, one of the symbols K and J chlorine, bromine or - iodine and that others are a hydroxyl group and Rq is hydrogen or Rg and R ^ together represent an additional carbon-carbon bond, to form a compound of the general formula wherein R ₁ , R ₃ , JR, R., R, R ^, R, Rg, R ^ m and η have the meaning given in the formulas IV and V and R ₁₀ in the formulas IV and VI are hydrogen, methyl or ethyl mean,
implements »or 109832/1785 2102858 a compound of the general formula -4m VII in which R, R, R, R. and m have the meaning given in formula VI,
with a compound of the general formula VIII in which R is lower alkyl or phenyl, which may optionally have a lower alkyloxy or halogen substituent, and R ₁ ^, R ^, R_, R ₀ and R 'denote in 5 ο 7 ο Formula VI have given meaning to a compound of the general formula wherein * R ,, R., Ti _t R ,, R, Rg, R 'and m die in 109832 / 178S Formula VI have the meaning given, converts, or e) in the event that in the formulas VI and IX R _Q and R ' ö 2 mean an additional carbon-carbon bond, such a compound to a compound of the general Formula I in which R 'is hydrogen, partially hydrogenated. 2. The method according to claim 1, characterized in that a compound of formula II with performic acid, Peracetic acid, perbenzoic acid, perphthalic acid, pervungstic acid or converts m-chloroperbenzoic acid. 3. The method according to claim 1 or 2, characterized in that that a compound of the formula II is reacted with m-chloroperbenzoic acid. 4. The method according to claim 1, characterized in that that a compound of the formula III, in which X is an oxymethylene group, which can carry a methyl group or an ethyl group, means with a basic agent, preferably Sodium methylate. 5. The method according to claim 1, characterized in that that a compound of the general formula III, in which X is an oxyoarbonyl group, with an alkali metal hydroxide, preferably potassium hydroxide. 109832/1785 -39- 2102858 6. The method according to claim 1, characterized in that a compound of the general formula IV with a Compound of general formula V in an inert organic solvent, preferably tetrahydrofuran, in the presence of a aprotic solvent, preferably hexamethylphosphorus o acid triamide, in a temperature range between O and the Brings boiling point of the solvent to implement. 7. The method according to claim 1, characterized in that that a carbonyl compound of the formula VII with a phosphine oxide of the formula VIII in an inert organic Solvent in the presence of a base in a temperature range ο
between 0 and room temperature to implement. 8. The method according to claim 7 »characterized» characterized that dioxane or tetrahydrofuran is used as the inert solvent and sodium hydride is used as the base. 9. The method according to claim 1, characterized in that Allyl 1,5-dimethyl-4-hexenyU ether Allyl (3,7-dimethyl-2,6-octadienyl) ether 3.7 ml-trimethyl-2,6,10-dodecatrienoic acid allyl ester 3 * 7 * II-trimethyl-2,6,10-tridecatrienoic acid allyl ester 3,7-Dimethyl-2,6-octadienoic acid allyl ester (3,7-Dimethyl-2,6-octadienyl) - (1,1-dimethyl-allyl) -ether 109832/1785 Allyl (5 * 7 * 10, ll-tetramethyl-2,6,10-dodecatrienyl) ether Allyl (3,7,11-trimethyl-2,6,10-dodecatrienyl) ether Allyl (3,7,11-trimethyl-2,6,10-tridecatrienyl) ether (3-methylr-2,4-pentadieny l) -0.7 t 11-trimethy 1-2,6,10- dodecatrienyl) ether 10-allyl- (7-ethyl-3,11-dimethy1-2,6 ^ tridecatrienyl) ether, is used as a starting material. 109832/1785 10. Process for the manufacture of pesticides, characterized in that one or more allyl compounds of the general formula wherein Κ _χ methyl or ethyl, R ₂ , R ^ and R, hydrogen, Methyl or ethyl, R ^ hydrogen or methyl, R, R ,, and R_ hydrogen, lower alkyl, lower alkenyl, ο / lower alkynyl, lower aryl or lower aryl-lower alkyl, where the lower aryl radicals can optionally be substituted with halogen, lower alkyl, lower alkenyl, lower alkynyl, lower alkyloxy, lower alkenyloxy, lower alkynyloxy, lower alkylenedioxy or nitro, X is an oxyethylene group, in which the methylene group can also carry a methyl group or an ethyl group or an oxycarbonyl group and m and η denote the number 0 or 1, inert as active ingredients, suitable for combating pests, solid or conventional per se in such agents adds to liquid carriers. 109832/1785 11. The method according to claim 10, characterized in that one or more ally! Compounds of the formula I in claim 10, wherein R _{1 is} methyl or ethyl, R ₂ , R 'and R, hydrogen, methyl or ethyl, R ^ hydrogen or Methyl, ^R , -> ^R £ and R hydrogen, lower alkyl, lower alkenyl, lower alkynyl, lower aryl or lower aryl-lower alkyl, where the lower aryl radicals can optionally be substituted with halogen, lower alkyl, lower alkyloxy or nitro, X is a Oxymethylene group, in which the methylene group can also carry a methyl group or ethyl group, or an oxycarbonyl group and m and η denote the number 0 or 1, solid or liquid carriers which are inert as active ingredients, suitable for combating pests and which are customary in such agents inflicts. 12. The method according to claim 10, characterized in that one or more allyl compounds of the formula I in claim 10, wherein R, methyl or ethyl 1, R _? , R 'and R are hydrogen, methyl or ethyl, R. are hydrogen or methyl, R, R ^ and R "are hydrogen, lower alkyl, lower alkenyl, lower alkynyl, lower aryl, the lower aryl radical optionally with halogen, nitro, lower alkyl or lower alkyloxy, X is an oxymethylene group in which the methylene group can also carry a methyl group or ethyl group, or an oxycarbonyl group and m and η denote the number 0 or 1, as active ingredients inert, suitable for combating pests in such agents common solid or liquid carriers. adds. 10 9 8 3 2/1785 13. The method according to claim 10, characterized in that that one or more allyl compounds of the formula XI wherein R, ^R 2 * ^R 2 ' ^R V ^{VSCla n in the} Formula I have given meaning and R is hydrogen, Means methyl or ethyl, inert as active ingredients for pest control suitable solid or liquid carriers customary in such agents are added. 14. The method according to claim 10, characterized in that one or more allyl compounds of the formula R. R, R. 1 t XII wherein R ₁ , R ^ R ^, R ^, R ^, RR ^, R and m have the meaning given in formula I, inert as active ingredients for pest control 109832/1785 suitable solid or liquid carriers customary in such agents. 15. The method according to claim 10, characterized in that that one l- (allyloxy) -5> 6-epoxy-6-methyl-heptane or 1- (AlIyI-oxy) -10, ll-epoxy-5,7 * 10, ll-tetramethyl-2,6-dodecadiene solid or liquid which are inert as an active ingredient, suitable for combating pests and which are customary in such compositions Carriers inflicts. 16. The method according to claim 10, characterized in that one l- (allyloxy) -6,7-epoxy-3,7-dimethyl-2-octene as Active ingredient inert, suitable for combating pests, solid or conventional per se in such agents adds to liquid carriers. 17. The method according to claim 10, characterized in that 10, ll-epoxy-3,7 »ll-trimethyl-2,6-dodecadienoic acid allyl esters inert as active ingredient, suitable for combating pests, which are customary in such agents adds to solid or liquid carriers. 18. The method according to claim 10, characterized in that 10, ll-epoxy-3,7, ll-trimethyl - [(3-methyl-2,4-pentadienyl) oxy] -2,6-dodecadiene or 1- (allyloxy) -10, ll-epoxy-7-ethyl- "5, lldimethyl-2,6-tridecadiene inert as active ingredient, suitable for the control of pests, per se in such agents conventional solid or liquid carriers. 109832/1 785 19. The method according to claim 10, characterized in that that one l- {allyloxy) ~ 10, ll-epoxy-3,7, ll-trimethyl-2,6-tridecadiene inert as an active ingredient, suitable for combating pests, customary per se in such agents adds to solid or liquid carriers. 20. The method according to claim 10, characterized in that one l- serve as active ingredient inert, suitable for the control of pests, solid or conventional per se in such agents adds to liquid carriers. 21. The method according to claim 10, characterized in that 10, ll-epoxy-3,7 * ll-trimethyl-i * [{3-methyl-2-pentene-4-ynyl} -oxy] -2,6 -dodecadiene inert as an active ingredient, suitable for the control of pests, see in such Adding agents to conventional solid or liquid carriers. 22. The method according to claim 10, characterized in that one lOill-Epoxy- ^ iTjU-trifliethyl ^ je-dodecadienoic acid (3-methyl-2-pentene-4-ynyl) ester inert as an active ingredient, suitable for the control of pests, per se in such Adding agents to the usual solid or liquid carriers. 109832/1785 23 · The method according to claim 10, characterized in, that one 6,7-epoxy-3 # 7- <uniethyl-2-octenoic acid allyl ester as Active ingredient inert, suitable for combating pests, solid or conventional per se in such agents liquid carrier. 24. The method according to claim 10, characterized in that l- (l, l-dimethyl-allyloxy) -6,7-epoxy-3,7-dimethyl-2-oetene inert as an active ingredient, suitable for combating pests, customary per se in such agents adds to solid or liquid carriers. 25. The method according to claim 10, characterized in, that one l- [l- (3,4-methylenedioxy-phenyl) allyloxy] -6,7-epoxy-3,6,7-triraethyl-2-octene inert as an active ingredient, suitable for the control of pests, per se in such Adding agents to conventional solid or liquid carriers. 109832/1785 2102858 26. Pest control agent, characterized in that that there is one or more allyl compounds of the general formula where R _{1 is} methyl or ethyl, R, R ^ and R, hydrogen, methyl or ethyl, R. is hydrogen or methyl, R, R> - and R is hydrogen, lower alkyl, lower alkenyl, lower alkynyl, lower aryl or lower aryl lower alkyl, where the lower aryl radicals can optionally be substituted with halogen, lower alkyl, lower alkenyl, lower alkynyl, lower alkyloxy, lower alkenyloxy, lower alkynyloxy, lower alkylenedioxy or nitro, X is an oxyraefehylene group in which the methylene group is also a methyl group or ethyl group can carry, or denote an oxycarbonyl group and m and η denote the number O or 1, contains. 27. The pesticide as claimed in claim 26, characterized in that it contains one or more allyl compounds of the formula I, in which R is methyl or ethyl, R, R 'and R, hydrogen, Methyl or ethyl, R. hydrogen or methyl, R, R, and R_ hydrogen, lower alkyl, lower alkenyl, lower 109832/1785 Alkynyl, lower aryl or lower. Aryl-lower alkyl, where the lower aryl radicals can optionally be substituted with halogen, lower alkyl, lower alkyloxy or nitro, X is a Oxymethylene group in which the methylene group is still one Can carry methyl group or ethyl group, or denote an oxycarbonyl group and m and η denote the number 0 or 1, contains. 28. Pesticide according to claim 26, characterized in that it contains one or more allyl compounds of the formula I, in which R is methyl or ethyl, FU, R 'and R is hydrogen, Methyl or ethyl, R, hydrogen or methyl, R, R ^ and R_ hydrogen, lower alkyl, lower alkenyl, lower alkynyl, lower aryl, the lower aryl radical optionally may be substituted by halogen, nitro, lower alkyl or lower alkyloxy, X is an oxymethylene group in which the Methylene group can still carry a methyl group or ethyl group, or an oxycarbonyl group and m and η denote Number denotes 0 or 1, contains. 29. Pesticide according to claim 26, characterized characterized in that it is one or more allyl compounds of the formula 109832/1785 - II ₉ - 10 R, XI where R ₁ , R ₉ ) Ro * R _X »Rj ₁ * R ₁ - * R-, R m and η have the meaning given in formula I and R _{10 are} hydrogen, methyl or ethyl,
contains. 30. Pesticide according to claim 26, characterized in that it contains one or more allyl compounds the formula XII wherein R ₁ , R ₂ > R2, Rj, .R4, R5, R ^, Κγ and m have the meaning given in formula I, contains. 31. Pesticide according to claim 26, characterized in that it is l ~ (allyloxy) -4,5-epoxy-1,5-dimethylhexane contains. 109832/1785 32. Pesticide according to claim 26, characterized in that it is l- (allyloxy) -6,7-epoxy-3,7-dimethyl-2-octene contains * 33 · Pesticide according to claim 26, characterized in that it is 30, XL-epoxy-3,7, ll-trimethyl-2,6-dodecadienoic acid allyl ester contains. 34. Pesticide according to claim 26, characterized marked that it is 10, ll-epoxy-3,7iH-trimethyl- [(3-methyl-2 _> 4-pentadienyl) -oxy] -2,6-dodecadiene. 35. Pesticide according to claim 26, characterized in that it is 1- (allyloxy) -10,11-epoxy-3,7 * H-trimethyl-2,6-tridecadiene contains. 36. Pesticide according to claim 26, characterized in that it contains 1- (allyloxy) -10, ll-epoxy-3, 1, 11-trimethyl-2,6-dodecadiene. 37. Pesticide according to claim 26, characterized in that it is 10, ll-epoxy-3,7 »11-trimethyl- [(3-methyl-2-penten-4-ynyl) -oxy] -2,6-dodecadiene. 38. Pesticide according to claim 26, characterized in that it 10, ll-epoxy-3,7, ll-trimethyl- 109832/1785 2,6-dodecadienoic acid {3-methyl-2-penten-4-ynyl} ester. 39. Pesticide according to claim 26, characterized characterized as being 6,7-epoxy-3,7-dimethyl-2-octenoic acid allyl ester contains. 40. Pesticide according to claim 26, characterized characterized that it is l- (l, l-dimethyl ~ allyloxy) -6,7-epoxy-3,7-dimethyl-2-octene contains. kl. Pesticide according to claim 26, characterized in that it contains 1- [1- (3,4-methylenedioxy-phenyl) allyloxy] -6,7-epoxy-3,6,7-trimethyl-2-octene. 42. Pesticide according to claim 26, characterized in that it is l- (allyloxy) -10, ll-epoxy-3,7,10, Contains ll-tetramethyl-2,6-dodecadiene. 4). Pesticide according to claim 26, characterized characterized in that it is l- (allyloxy) -10, ll-epoxy-3,7, lltrimethyl-2,6-tridecadiene contains. 44. Pesticide according to claim 26, characterized in that it is l- (allyloxy) -10, ll-epoxy-7-ethyl-3, ll-dimethyl-2,6-tridecadiene contains. 109832/1785 formula 45. Use of Ally! Compounds of general ^R l 4 J- wherein R _{n is} methyl or ethyl, R ^, R 'and R, hydrogen, 1 d. 2 5 Methyl or ethyl, R ₁ ^ hydrogen or methyl, R, R ^ and R_ hydrogen, lower alkyl, lower alkenyl, ■ lower alkynyl, lower aryl or lower aryl-lower alkyl, the lower aryl radicals optionally with halogen, lower alkyl, lower Alkenyl, lower alkynyl, lower alkyloxy, lower alkenyloxy, lower alkynyloxy, lower alkylenedioxy or nitro can be substituted, X is an oxymethylene group in which the methylene group can still carry a methyl group or ethyl group, or an oxycarbonyl group and m and η are the number 0 or 1, as a pesticide. 46. Use of allyl compounds of general Formula I in claim 45, wherein R, methyl or ethyl, R, R ' and R is hydrogen, methyl or ethyl, Hydrogen or and R "hydrogen, lower alkyl, Methyl, R ^, lower alkenyl, lower alkynyl, lower aryl or lower aryl-lower alkyl, the lower 109832/1 785 Aryl radicals optionally with halogen, lower alkyl, lower Alkyloxy or nitro can be substituted, X is an oxymethylene group in which the methylene group is still a methyl group or can carry an ethyl group, or an oxycarbonyl group mean and ra and η denote the number 0 or 1, for the purpose stated in claim 45 * 47. Use of allyl compounds of the general formula I in claim 45, in which R, methyl or ethyl, R ~, R 'and R ~ are hydrogen, methyl or ethyl, Ru is hydrogen or methyl, Rp., R ^ - and R ₇ Hydrogen, lower alkyl, lower alkenyl, lower alkynyl, lower aryl, where the lower aryl radicals can optionally be substituted with halogen, nitro, lower alkyl or lower alkyloxy, X is an oxymethylene group in which the methylene group can also carry a methyl group or ethyl group, or denote an oxycarbonyl group and m and η denote the number O or 1, for the purpose indicated in claim 45. 48. Use of ally! Compounds of the general formula R » wherein R ₁ , R, 4 m B, ; hq ►n R "XI 5 2 , R ₄ , R ₅ , R ₆ , R ₇ ^{m and n the ln} formula 109 & 32/1785 have given meaning and R is hydrogen, methyl or ethyl,
for the purpose specified in claim 45. 49. Use of ally! Compounds of general formula where R, j Rp, RA, R ,, Rw Rc, Rg, R ₇ and m have the meaning given in the formula,
for the purpose specified in claim 45. 50. Use of 1- (allyloxy) -4,5 ~ epoxy-1,5-diinethylhexane for the purpose specified in claim 45. 51. Use of 1- (allyloxy) -6,7-epoxy-3,7-dlmethyl-2-octene for the purpose stated in claim 4 5. 52. Use of 10, ll-epoxy-5,7, llr-trimethyl-2,6-dodecadienoic acid allyl ester for the purpose specified in claim 45. 53. Use of 10, II-epoxy-3,7, H-trimethyl- [(3-109832 / 1785 methyl-2,4-pentadienyl) -oxy] -2,6-dodecadiene to the claim 45 stated purpose. 54. Use of 1- (allyloxy) -10, ll-epoxy-3>, 7, ll-trimethyl-2,6-tridecadiene or 1- (allyloxy) -10, ll-epoxy-7-ethyl-3, ll-dlmethyl-2,6-tridecadiene for the purpose specified in claim 45. 55. Use of 1- (allyloxy) -10, H-epoxy-3,7 * 11-trimethyl-2,6-dodecadiene or l- (allyloxy) -10, ll-epoxy-5,7,10, ll-tetramethyl-2,6-dodecadiene for the one indicated in claim 45 same purpose. 56. Use of lOjll-Epoxy-Jjt / ll-trinjethyl-l-Ci3- "ethyl-2-penten-4-ynyl} -oxyJ-2,6-dodecadiene for the purpose stated in claim 45" 57 «Use of 10, ll-epoxy-3,7, ll-trimethyl-2,6-dodecadienoic acid (3-methyl-2-penten-4-ynyl) ester for the in Claim 45 stated purpose. 58. Use of 6,7-epoxy-3,7-dimethyl-2-octenoic acid allyl ester for the purposes indicated in claim 45. 59. Use of l- (l _# l-dimethyl-allyloxy) -6,7-epoxy-3,7-dimethyl-2-octene for the purpose stated in claim 45, 60. Use of l-El- (3,4-methylenedioxy-phenyl} allyloxy] -6,7-epoxy-3,6,7-triaethyl-2-octene for the claim 45 specified purpose. 10 9 832/1785 61. Compounds of Formula -Jm J- where R is methyl or ethyl, R, R ^ and R, hydrogen, Methyl or ethyl, R. hydrogen or methyl, R, R-- and R "hydrogen, lower alkyl, lower alkenyl, ο / lower alkynyl, lower aryl or lower aryl-lower alkyl, the lower aryl radicals optionally with halogen, lower alkyl, lower alkenyl, lower Alkynyl, lower alkyloxy, lower alkenyloxy, lower alkynyloxy, lower alkylenedioxy or nitro can be, X is an oxymethylene group in which the methylene group is still a methyl group or ethyl group can carry, or mean an oxycarbonyl group and m and η denote the number 0 or 1. 62. Compounds of the formula I in claim 61, wherein R is methyl or ethyl, R ₂ , R2 and R, hydrogen, methyl or ethyl, R ^ is hydrogen or methyl, R, R ^ and R_ is hydrogen, lower alkyl, lower alkenyl, lower Alkynyl, lower aryl or lower aryl-lower alkyl, where the lower aryl radicals can optionally be substituted with halogen, lower alkyl, lower alkyloxy or nitro, X is an oxymethylene group in which the methylene 109832/1785 group noon can carry a methyl group or an ethy group, or an oxyaarbonyl group and m and η the number O or denote 1. 63 * Compounds of the formula I in claim 6l, wherein R _{1 is} methyl or ethyl, R2, R2 and R3 are hydrogen, methyl or ethyl, R ₁ , hydrogen or methyl *, R_, R, - and R "are hydrogen, lower alkyl, lower alkenyl , lower alkynyl, lower aryl, where the lower aryl radicals can optionally be substituted by halogen, nitro, lower alkyl, or lower alkyloxy, X is an oxymethylene group in which the methylene group can still carry a methyl group or ethyl group, or an oxycarbonyl group and m and η denote the number 0 or 1. 64. Compounds of Formula —Im i_ wherein R ₁ * ^R ₂ * ^R ₂ * ^R 3> ^R 4 * ¹ V ^R 6 ^JR 7 * ^{m and n have the} meaning given in formula I in claim 6l and R _{10 is} hydrogen, methyl or ethyl. 109832/1785 65 · Compounds of the formula R. 00. R, XII wherein R-, R_, ROiR ^ jRw, Rp. , R ^, R ₇ and m have the meaning given in formula I in claim 6l . 66. 1- ( Allyloxy ) -4,5-epoxy-1,5-dimethyl-hexane. 67. 1- ( allyloxy) -6,7-epoxy-3,7-dimethyl-2-octene. 68. 10, II-epoxy-3,7, II-trimethyl-α ^ -dodecadienoic acid allyl ester. 69. 10,11-epoxy-3,7,11-trimethyl - [(3-aethyl-2,4-pentadienyl) -oxy] -2,6-dodecadiene. 70. 1- (Allyloxy) -10, ll-epoxy-3,7,11-trimethyl-2,6- tridecadiene. 71. 1- (Allyloxy) -10, II-epoxy-3 * 7, H-trimethyl-2,6-dodeoadiene. 109832/1785 72. 1- (Allyloxy) -10, II-epoxy-3,7,10, II-tetramethyl-2,6-dodecadiene. 75. 1- (Allyloxy) -10, ll-epoxy-7-ethyl-3, ll-dimethyl-2,6-tridecadiene. 74. 10, ll-epoxy-3,7, ll-trimethyl-l-i (3-methyl-2-penten-4-ynyl) -oxy] -2,6-dodecadiene. 75, 10, ll-epoxy-3,7, ll-trimethyl-2,6-dodecadienoic acid (3-methyl-2-pentene-4-ynyl) ester. 76. ö ^ -Epoxy - ^^ - dimethyl - ^ - octenoic acid allyl ester. 77. 6,7-epoxy-3,7-dimethyl-l - [(l, l-dimethyl-2-propenyl) oxy] -2-octene. 78. 6,7-epoxy-3,6,7-triethyl-1 [(a-vinylpiperonyl) -oxy3-2-cis / trans-octene. 79. 2,3-epoxy-2-methyl-6- (2-allyloxy) heptane.