DE2144936A1 - New ethers - Google Patents

Description

CIBA-GEIGYAG, CH-4002 Basel V ^ j L) / Ά ~~~ " \ 3 [LiI \ 3 T

_{r D} , _A 2H4936

Dr. Fi. n.oiiii. ".Γι ;," D: 'Λ; j. υ. u ^. ^ baiier

Di. F. To ..: Ii j JIl.

Patent Attorney 8 Munich 2, Bräuhausstrasse 4/111

Case 5-7200 / 1 + 2 / B / =

New ethers

The present invention relates to new terpene aryl ethers, their manufacture and their use to influence the development of invertebrates.

209818/1234

_a 21U936

The new compounds correspond to the formula

(I)

where Z. and Zp together form a carbon-carbon bond or together an oxygen bridge or each hydrogen, R, and R _p each methyl or ethyl, Z and Z ₂ together a carbon-carbon bond, R., hydrogen, ^c p ~ ^C S ^Alk y ^lcarbon y ¹ i carbamoyl ', C ₁ -C ₂ monoalkyl, Cp-C ^ alkenyl, Cp-C. ₂ Alkynyl or aryl carbamoyl; ^R 4 ^C 2 ~ ^C S ^{A1]: C} y ^lcairloon y ¹ > carbamoyl, C ₁ -C 4 monoalkyl- ^, Cp-C ₂ , alkenyl, Cp-C ₂ , alkynyl- or arylcarbamoyl or R ^c p- ^c c: alkylcarbonyl, carbamoyl, C ₁ -C ₂ ^ monoalkyl, C ₂ -C ₂ ^ alkenyl, Cp-C ₂ . Alkynyl- or arylcarbamoyl, R. hydrogen, Cp-Cj. Alkylcarbonyl, carbamoyl, C ₁ -C ₂ , monoalkyl-, Cp-C ₂ ^ alkenyl-, C ₂ -C ^ alkynyl- or arylcarbamoyl or Z and Z. each hydrogen and R-, and R ^ - each hydrogen, Cp- Cj. Alkylcarbonyl, carbamoyl, C ₁ -C ₂ ^ monoalkyl, ^C ₂ ~ ^c i ^ alkenyl, Cp-C ₂ , alkynyl or arylcarbamoyl.

_{In connection with the substituents R 1} and R 2 ^ mentioned under formula I, the alkyl part of the alkyl carbonyl groups is, by definition, straight-chain or branched unsubstituted or substituted.

209818/123 4

Possible substituents on these groups are, for example, halogen, such as fluorine, chlorine, bromine or iodine, C ₁ -C ₄ alkoxy, hydroxy or Cp-Cj, alkoxycarbonyl.

Examples of suitable Cp-C ₁ -alkylcarbonyl groups for R _{1 and R 2} . are: ethyl, propyl, isopropyl, n-butyl, isobutyl, sec. or tert-butylcarbonyl groups. Examples of carbamoyl groups for R, and Rj, include:

-C-NH-CH.

It J

-C-NH-C ₂ HO

dd o

-C-NH-C, H ₇ (i) ' ti Jl

-C-NH-C ₄ H ₉ (n) O

-C-NH-C ₄ H ₉ U) O

-C-NH-C, .H _n (sec.)

ti ^ y 0

-C-NH-C ₄ H (tert.) O

-C-NH-CH ₀
ti c-
O -C = CH ₀
f c-
Cl -C5CJ -C-NH-CH ₀
it <= ■
O -CH = CHCl -C-NH-CH ₀
ti c-
O -C = CH -C-NH-CH ₀
tt <-
O -C = C-CH -C-NH-CH-C = CH
ti t
O CH CH,
t J
-C-NH-C-CHCH
ti I
O CH -C-NH-CH ₀
ti d
O

-C-NH

209818/1234

-C-NH-CH ₀ -CH = CH ₀
η d. d

-C-NH-CH ₀ -C = CH ₀

I! ^ t d

O CH

Of particular importance are compounds of the formula I in which Z ₁ and Z ₀ together form a carbon-carbon bond or together an oxygen bridge, R and R _{0 are} each methyl. or ethyl, Z-, and Z ₂ , together a carbon-carbon bond, R., acetyl, propionyl, butyryl, carbamoyl, methyl-, ethyl- or phenylcarbamoyl and R ₁ , hydrogen. Examples of suitable compounds include: l_ (4_Propionyl) -phenoxy-35,7-dimethyl-2,6-octadiene-. 1- (4-propionyl) phenoxy-3,7-dimethyl-6,7-epoxy-2-octene. 1- (4-Acety1) -phenoxy-3,7-dimethy1-2-nonadiene. 1- (4- acetyl) -phenoxy-3,7-dimethyl-6,7-epoxy-2-nonene. 1- (4-N-methylcarbamoyl) -phenoxy-3j7-dimethyl-2,6-octadiene. 1- (4-N-methylcarb, amoyl) -phenoxy-3,7-dimethyl-6,7-epoxy-2-octene. 1- (4-butyryl) phenoxy-3 , 7-dimethyl-2,6-octadiene. 1- (4-butyryl) phenoxy-3,7-dimethyl-6,7- & poxy-2-octene. 1- (4-N-ethylcarbamoyl) -phenoxy-3 * 7-dimethyl-2,6-octadiene. 1 - (4-N-ethylcarbamoyl) -phenoxy-3 * 7-dimethyl-6,7-epoxy-2-octene. 1- (4-carbamoyl) phenoxy-3,7-dimethyl-6,7-epoxy-2-octene. 1- (4-carbamoyl) phenoxy-3,7-dimethyl-2,6-octadiene. 1- (4-N-phenylcarbamoyl) -phenoxy-3j7-dimethyl-2,6-octadiene. 1- (4-N-phenylcarbamoyl) -phenoxy-3,7-dimethy1-6,7-epoxy-2-octene.

209818/123 4

The compounds of the formula I are prepared in a manner known per se by the following reactions: preferably with equimolecular amounts of the starting materials; However, if desired, an excess of one or more of the involved reaction partners are applied:

HO

R-

R ₁

selective

Epoxidizing agents

CH.

3 acid

acceptor

Epoxidation R ₁ , medium

2098 18/1234

X stands for halogen, preferably chlorine or bromine. Reactions 1) and 3), "i.e. the reactions with the mixtures geometric isomer of the reactive allylic halides with the desired phenol, are in an inert Solvents such as 1,2-dimethoxyethane, tetrahydrofuran, dioxane, Dimethylformamide, dimethyl sulfoxide, sulfolane or a dialkyl ether, but preferably in 1,2-dirnethoxyethane slow addition of an equivalent of an acid reagent such as alkali or alkaline earth hydroxides, or alkali or alkaline earth carbonates, Alkali alkoxides or alkali hydrides with stirring at room temperature and, if necessary, subsequent heating carried out. The terpene aryl ether is isolated then using known techniques. -Under alkali are in particular sodium and potassium and among alkaline earth Understanding Calcium.

The reactions 2) and 6), i.e. the conversion of the terpenoid aryl ethers into their 6,7-epoxy derivatives, are preferably with cooling in an inert solvent such as a chlorinated hydrocarbon an epoxidizing agent such as a peracid. If one mole of a peracid is used, the 6,7-epoxy derivatives are predominantly due to steric factors educated. The 6,7-epoxy derivatives can also by Action of N-bromosuccinimide on the starting material to be epoxidized in a mixture of water with a solvent such as tetrahydrofuran, 1,2-dimethoxyethane, dioxane or tert.

209818/1234

Butanol preferably with cooling in homogeneous or heterogeneous Phase and subsequent treatment of the intermediate 6,7-bromohydrin with an alkaline agent such as alkali carbonate, alkali hydroxide or an alkali alkoxide. Among alkali are in particular Understand sodium and potassium.

The term "peracid" primarily refers to lower peralkanoic acids with 1 to 6 carbon atoms, such as e.g. peracetic acid, as well as aromatic peracids such as perbenzoic acid, monoperphthalic acid, but especially m-chloroperbenzoic acid Understood. Alkali carbonates are used as basic reagents for converting a bromohydrin into the 6,7-epoxy derivative, Alkali hydroxides and alkali alkoxides into consideration.

The reaction according to equation 4), ie for example the reaction of a nonallylic aliphatic halide with a desired phenol, is preferably carried out in the presence of at least one mole of an alkali or alkaline earth metal carbonate, and with or without a catalytic amount of an alkali iodide in a solvent such as acetone or methyl ethyl ketone or cyclohexanone between room temperature and the boiling point of the solvent used. The reaction can also be carried out with the aid of an alkali metal hydroxide in a solvent such as dimethylformamide, dimethyl sulfoxide, 1,2-dimethoxyethane or SuIfolan between 0 and 100 ⁰ C.

209818/123

In the preparation of the compounds of formula I form see as a result of the allyl halides used for synthesis all possible geometric isomers. The compounds described represent mixtures of the geometric Isomers represent how these arise in the synthesis.

In the case of PL · can be alkyl or arylcarbamöyl the terpene aryl ether either according to equation 1) from the allylic halide and the phenol component or else

fc by reacting a l- (4-lower alkoxycarbonyl) phenoxy-3,7-dialkyl-2., 6-octa- or nona-diene derivatives or one 1- (4-lower alkoxycarbonyl) phenoxy-6,7-epoxy-; 5,7-dialkyl-2-octene or 2-nonene derivatives with an alkyl or arylamine · lithium derivative in a suitable inert solvent can be obtained.

Furthermore, a 1- (4-Garbamoyl) -phenoxy-3,7-dialkyl ^ io-octadiene- or 2-octene or 1- (4-carbamoyl) phenoxy-3i7-dialkyl-2,6-nonadiene or 2-nee connection

P in dimethyl sulfoxide in the presence of alkali hydroxide between room temperature and 80 ⁰ C with a corresponding alkyl, alkenyl or alkynyl halide to the desired 1- (4-N-alkyl, alkenyl or alkynyl) -phenoxy ^^ - dialkyl ^ jö -octadiene or • 2-octene or 1- (4-N-alkyl, alkenyl or alkynyl) '- phenoxy- ■ 5,7-dialkyl-2,6-nonadiene or 2-nonene derivative implemented will.

The active ingredients of the formula I are suitable for combating a wide variety of animal and vegetable species

209818 / 1-234

■ pests, especially for combating insects, representatives of the order Acarina and plant-parasitic nematodes. In contrast to most of the well-known insecticides, acaricides and nematocides, which are used as contact or eaters kill, paralyze or drive away the animals quickly, influence them the active ingredients of formula I their development.

In the case of insects, for example, the moulting (in the case of hemimetabolites) or the transformation to the imago (in the case of shark metabolites) and also disrupted the development of the egg. The generation sequence is interrupted and the animals become thus killed indirectly. The compounds of the formula I are practically non-toxic for warm-blooded animals. In addition, these Connections are easily broken down, so no accumulation is possible.

The new terpenyl aryl ethers can mainly be used to combat the following pests of plants, stored products and hygiene are used: Against insects of the orders and families: Orthoptera Acrididae (e.g. Locusta, SchiStocerca)

Gryllidae (e.g. Acheta, Gryllus)

Blattidae (e.g. Blattella germanica,

Periplaneta americana, Nauphoeta cinerea)

Isoptera Kalotermitidae. (E.g. Kalotermes)

Hemiptera Miridae (e.g. Distantiella)

Piesmidae (e.g. Piesma)

Lygaeidae (e.g. Lygus)

Pyrrhocoridae (e.g. Dysdercus)

Pentatomidae (e.g. Eurydema)

209818/1234, _nr , _m ^ Cimicidae (e.g. Cimex)

Coleoptera

Lepidoptera

/ ο
Reduviidae (e.g. 2144936
Rhodinus) Jassidae (e.g. Empoasca) Eriosomatidae (e.g. Eriosoma) Lecaniidae (e.g. Coccus) Carabidae (e.g. Carabus) Elateridae (e.g. Agriotes) Coccinellidae (e.g. Epilachna) Tenebrionidae (e.g. Tribolium, Tenebrio) Dermestidae (e.g. Dermestes, Anthrenus,
Attagenus) Cucujidae ' (e.g. Oryzaephilus) Chrysomelidae (e.g. Leptinotarsa, Melasoma.
Phyllotreta) Curculionidae (e.g. Sitona, Anthonomus) Scolytidae (e.g. Scolytus) Scarabaeidae (e.g. Melolontha) Pyralidae (e.g. Diatraea) Phyticidae (e.g. Anagasta) Pyraustidae (e.g. Pyralis) Crambidae (e.g. CMIo) Tortricidae (e.g. Pandemis) Galleriidae (e.g. Galleria) Lyonetiidae (e.g. Lyonetia) Yponomeutidae (e.g. Hyponomeuta) Pieridae (e.g. Pieris). Plutellidae (e.g. Plutella) Lyraantriidae (e.g. Lymantria) Noctuidae (e.g. Spodoptera)

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21U93.6.

DIptera Culicidae (e.g. Äe'des)

Simuliidae (e.g. Simulium) Tipulidae (e.g. Chironomus), '

against acarids of families'.

Ixodidae.

Argasidae
Tetranychidäe
Dermanyssidae

and against phytopathogenic nematodes such as Aphelendoides, Ditylenchoid.es, Meloidogyne.

The compounds of the formula I can be used on their own or used together with suitable carriers and / or additives. Suitable carriers and aggregates can be solid or liquid and correspond to those in the formulation. Technically common substances such as natural or regenerated substances, solvents, dispersants, wetting, adhesive, thickening j Binders and / or fertilizers.

The agents according to the invention are prepared in a manner known per se by intimately mixing and / or grinding active ingredients of the formula I with the suitable carriers, optionally with the addition of dispersants or solvents which are inert towards the active ingredients. The active ingredients can be present and used in the following working-up forms:
solid forms of processing: dusts, grit,

Granules, coating granules, impregnation granules and

Hotnogengränul at e 209818 / 12.34

liquid processing forms:

a) dispersible in water

Active ingredient concentrates: wettable powder,

Pastes, emulsions;

b) Solutions.

For the production of solid processing forms (dust, Litter) the active ingredients are mixed with solid carriers. As a carrier, for example Kaolin, talc, bolus, loess, chalk, limestone, lime grit, ataclay, dolomite, diatomaceous earth, precipitated silica, alkaline earth silicates, Sodium and potassium aluminum silicates (feldspar and mica), calcium and magnesium sulfates, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, ground vegetable products such as grain flour, tree bark flour, wood flour, nutshell flour, cellulose powder, residues of Plant extractions, activated charcoal etc., depending on their own or as Mixtures with each other in question.

Granules can be produced very easily by adding an active ingredient of the formula I in an organic Solvent dissolves and the resulting solution on a granulated mineral, e.g. attapulgite, SiO ^, granicalcium, Applying bentonite etc. and then evaporating the organic solvent again.

209818/1234

Polymer granules can also be produced by mixing the active ingredients of the formula I with polymerizable Compounds are mixed (urea / formaldehyde j dicyandiamide / formaldehyde; Melamine / formaldehyde or others), whereupon a gentle polymerization is carried out, from which the Active substances remain unaffected, and granulation is still carried out during gel formation. Is cheaper es, finished, porous polymer granules (urea / formaldehyde, polyacrylonitrile, polyester and others) with a specific surface and a favorable, predeterminable adsorption / desorption ratio with the active ingredients, e.g. in the form of their solutions (in a low boiling solvent) to impregnate and remove the solvent. Such polymer granules can in the form of micro-granules with a bulk density of preferably 3OO g / liter to 600 g / liter with the help of Atomizers are applied. The atomization can be done over large areas of crops with the help of Aircraft are carried.

Granules are also made by compacting the carrier material available with the active ingredients and additives and subsequent chopping.

These mixtures can also contain additives stabilizing the active ingredient and / or nonionic, anionic active substances and cation-active substances are added, for example, the adhesion of the active ingredients to plants and parts of plants improve (adhesives and adhesives) and / or a

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21U936

ensure better wettability (wetting agents) and dispersibility (dispersants).

For example, the following substances are possible: olein-lime mixture, cellulose derivatives (methyl cellulose, Carboxyraethyl cellulose), hydroxyethylene glycol ethers of mono- and dialkylphenols with 5-15 ethylene oxide residues per molecule and 8-9 carbon atoms in the alkyl radical, ligninsulphonic acid, its alkali and alkaline earth salts, polyethylene glycol ethers (Carbowach & e), fatty alcohol polyglycol ethers with 5-20 ethylene oxide residues per molecule and 8-18 carbon atoms in the fatty alcohol part, condensation products of ethylene oxide, propulene oxide, Polyvinylpyrrolidones, polyvinyl alcohols, condensation products of urea-formaldehyde and latex products.

Active substance concentrates that are dispersible in water, i.e. wettable powders, pastes and emulsion concentrates are agents that can be mixed with water to any desired Concentration can be diluted. They consist of an active ingredient, a carrier and, if applicable, the active ingredient stabilizing additives, surface-active substances and antifoams and, if necessary, solvents.

The wettable powders and pastes are obtained by mixing the active ingredients with dispersants and powdery carriers mixed and / or ground in suitable devices until homogeneous. Suitable carriers are, for example, those mentioned above for the solid work-up forms. In In some cases it is advantageous to use mixtures of different

209818/1234

Use carriers. As dispersants, for example are used: condensation products of sulfonated naphthalene and sulfonated naphthalene derivatives with formaldehyde, Condensation products of naphthalene or naphthalene sulfonic acids with phenol and formaldehyde as well as alkali, ammonium and alkaline earth salts of ligninsulphonic acid, further alkylarylsulphonates, Alkali and alkaline earth metal salts of dibutylnaphthalenesulfonic acid, Fatty alcohol sulfates such as salts of sulfated hexadecanols, heptadecanols, octadecanols and salts of sulfated Fatty alcohol glycol ether, the sodium salt of oleymethyitauride, ditertiary acetylene glycols, dialkyldilaurylammonium chloride and fatty acid alkali and alkaline earth salts.

Silicones, for example, can be used as antifoam agents.

The active ingredients are mixed, ground, sieved and passed with the additives listed above in such a way that the solid portion of the wettable powders does not exceed a particle size of 0.02 to 0.04 and of the pastes 0.03 mm. To produce emulsion concentrates and pastes, dispersants such as those listed in the previous sections, organic solvents and water are used. Examples of suitable solvents are alcohols, benzene, xylenes, toluene, Dirnethylsulfoxyd and in the range of 120 to 35O ⁰ C boiling mineral oil fractions in question. The solvents must be practically odorless, non-phytotoxic and inert to the active ingredients.

209818/1234

The agents according to the invention can also be in the form of of solutions can be applied. For this purpose, the active ingredient or several active ingredients of the general formula I in suitable organic solvents, solvent mixtures or water. Aliphatic solvents can be used as organic solvents and aromatic hydrocarbons, their chlorinated derivatives, alkylnaphthalenes, mineral oils alone or as a mixture can be used with each other.

The content of active substance in the above-described w agents is from 0.02 to $ 95, it is to mention that are used in the application from the aircraft or other suitable application equipment concentrations of up to 99.5 $ or even pure active compound.

The active ingredients of the formula I can, for example, be formulated as follows:

Dust : The following substances are used to produce a) 5 and b) 2 dust:

. a) 5 parts of active ingredient

95 parts of talc;

b) 2 parts of active ingredient

1 part of highly disperse silica 97 parts of talc.

The active ingredients are mixed and ground with the carrier substances.

209818/1234

Granules ; For the production of a ^ igen granules are

the following substances are used: 5 parts of active ingredient 0.25 parts of epichlorohydrin 0.25 parts of cetyl polyglycol ether 3.50 parts of polyethylene glycol ("Carbowax") Parts of kaolin (grain size 0.3-0.8 mm).

The active substance is mixed with epichlorohydrin and dissolved with 6 parts of acetone, then polyethylene glycol is added and cetyl polyglycol ether added. The solution obtained in this way is sprayed onto kaolin and then the acetone evaporated in a vacuum.

Wettable powder : To produce a) 40 #, b) and c) 25% and d) 10 ^% wettable powder, the following ingredients are used:

a) 40 parts of active ingredient

5 parts of lignin sulfonic acid, sodium salt, 1 part of di-butylnaphthalenesulfonic acid, sodium salt 54 parts of silica;

b) 25 parts of active ingredient

4.5 parts calcium lignosulfonate

1.9 parts of champagne-chalk-hydroxyethyl cellulose mixture (1: 1)

1.5 parts of sodium dibutyl naphthalene sulfonate 19.5 parts of silica 19.5 parts of champagne chalk, 28.1 parts of kaolin;

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21U936

c) 25 parts of active ingredient

2.5 parts of isooctylphenoxy-polyoxyethylene-ethanol

1.7 parts of champagne-chalk-hydroxyethyl cellulose mixture (1: 1)

8.3 parts of sodium aluminum silicate 16.5 parts of diatomaceous earth

46 parts of kaolin;

d) 10 parts of active ingredient

~ 5 parts mixture of the sodium salts of

saturated fatty alcohol sulfates

5 parts of naphthalenesulfonic acid-formaldehyde condensate 82 parts of kaolin.

The active ingredients are in suitable mixers with the aggregates intimately mixed and ground on appropriate mills and rollers. One receives wettable powder that can be diluted with water to form suspensions of any desired concentration.

Emulsifiable concentrates : The following substances are used to produce a) 10% and b) 25% emulsifiable concentrate:
a) IO parts active ingredient

3.4 parts epoxidized vegetable oil

13.4 parts of a combination emulsifier, consisting from fatty alcohol polyglycol ether and alkylarylsulfonate calcium salt

40 parts of dimethylformamide, 43.2 parts of xylene;

209818/1234

b) 25 parts of active ingredient acid ester and 2.5 parts of epoxidized vegetable oil

10 parts of an alkylarylsulfonate fatty alcohol polyglycol ether mixture

5 parts of dimethylformamide 57.5 parts of xylene.

These concentrates can be diluted with water to prepare emulsions of any desired concentration will.

· Spray means: In order to produce a) a 5 $ ig ^s and b) 2 # strength spraying means uses the following ingredients:

a) 5 parts of active ingredient

1 part epichlorohydrin ■

94 parts of gasoline (boiling point 160 ° -19O ° C.);

b) 2 parts of active ingredient

3 parts of 4,4'-dichlorodiphenyl-trichloroethane

95 parts of kerosene.

These solutions are sprayed with pressure syringes. Solution a) is advantageous for controlling aphids used on fruit trees and other plants.

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Example 1

1- (4-propionyl) phenoxy-3,7-dimethyl-2,6-octadiene. (Active ingredient no. L)

To a solution of 30 g of 4-hydroxypropiophenone and 43 * 5 S l-bromo-3,7-dimethyl-2,6-octadiene in 320 ml of 1,2-Dirnethoxyäthan was added dropwise with stirring at room temperature within ¹ h J, the Solution of 12.8 g of approx. 86% potassium hydroxide in 200 ml of absolute ethanol. After a further 12 hours of stirring at room temperature, the mixture was ^{heated to 50 °} C. for 1 hour, cooled and the precipitated potassium bromide was filtered off. The filtrate was concentrated in vacuo, the residue was taken up in ether and washed three times each with 10% aqueous potassium hydroxide solution and water After the ether solution had been dried over sodium sulfate, the solvent was distilled off in vacuo and the 1- (4-propionyl) phenoxy-3,7-dimethyl-2,6-octadiene that remained was purified by chromatography on silica gel.

ΡΩ (eluent: ether - hexane 1: 4), n ^: 1.5370.

Example2

1- (4-propionyl) phenoxy-6,7-epoxy-3,7-dimethyl-2-octene. (Active ingredient No. 2)

The solution of 17.2 g of 1- (4-propionyl) -phenoxy-3,7-dimethyl-2,6-octadiene in 180 ml of methylene chloride was added dropwise at -2 to ⁰ ° C. within 3 hours 12.3 g of approx. 85% 3-chloroperbenzoic acid in 120 ml of methylene chloride ether (9: 1) and then stirred for a further 3 hours at ⁰ ° C. To dissolve

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2UA936

The reaction mixture was diluted with ether ^{and washed three times at 0} ° C. with ice-cold 10% potassium hydroxide solution and then washed neutral with water. After drying the organic phase over sodium sulfate, the solution. medium removed in vacuo and the 1- (4-propionyl) -phenoxy-6,7-epoxy-3,7-dimethyl-2-octene further purified by adsorption on silica gel (eluent: ether-hexane 1: 2).

n _D : 1.5326 (supercooled melt); M.p .: 54-57 ⁰ C (isomer mixture, from pentane).

Example 3

1- (4-N-ethylcarbamoyl) -phenoxy-3,7-dimethyl-2,6-octadiene (Active ingredient no.3)

To the solution of 16.5 S 4-hydroxybenzoic acid monoethylamide (H. Schönenberger et al., Arzneimittelforschung 3A, 324-328 (1964)]) and 22 g of 1-bromo-3 _i 7-dimethyl-2,6-octadiene In 150 ml of 1,2-dimethoxyethane, the solution of 6.4 g of approx. 86% potassium hydroxide in 100 ml of absolute ethanol was added dropwise at room temperature with stirring over the course of 6 hours. The mixture was then stirred for a further 16 hours at room temperature. For working up, the precipitated potassium bromide was filtered off, the filtrate was concentrated in vacuo, the residue was taken up in ether and washed three times with ice-cold 10% potassium hydroxide solution and three times with water. After the ether solution had been dried over sodium sulfate, the solvent was removed and the residue was dried completely in vacuo.

209818/1234

21U936 99.

The l- (4-N-ethylcarbamoyl) -phenoxy-; 5,7-dimethyl-2,6-octadiene thus obtained immediately became 1- (4-N-ethylcarbamoyl) -phenoxy-6,7-epoxy-3,7-dimethyl-2-octene as follows implemented,

Example 4

1- (4-N-ethylcarbamoyl) -phenoxy-6,7-epoxy-3> 7-dimethyl-2-octene (Active ingredient No. 4)

The solution was added dropwise to the solution of 15.5 g of 1- (4-N-ethylcarbamoyl) phenoxy-3-7-dimethyl-2,6-octadiene in 160 ml of methylene chloride over the course of 3 hours ^{while stirring at 0 ° C} of 10.7 g of 86 # 3-chloroperbenzoic acid in 120 ml of methylene chloride ether (9: 1). After the addition of the peracid, the mixture was ^{stirred at 0} ° C. for a further 3 hours. The reaction mixture was then diluted with ether and washed three times each with ice-cold 10 ^ iger potassium hydroxide solution and water, the organic phase was dried over sodium sulfate, the solvent was removed in vacuo and the 1- (4-N-ethylcarbamoyl) -phenoxy-6,7- epoxy-3,7 'dimethyl-2-octen on silica gel chromatography (eluent: Methylcacetat ^ exan 1: 1), mp 67-69 ⁰ C..

209 8 18/1234

2H4936

The following compounds are grounded analogously to Examples 1 to manufactured:

-C-C- means carbon-carbon bond -0- "oxygen bridge

Really
material
No. Λ ^{: B} 5 ^Η 2 J ^R l ^z r ^z 2 Z ₃ -Z ₄ physical
data 5 H -CO-CH, -C-C- -C-C- d \ j -, r - f * ~ Ci
n _D : 1,53'-8 6th H -CO-CH ^ -CH-, -O- -C-Q- n ^ ⁰ : 1.5321 7th H - ^CO - ^C 3 ^H 7 (n) -CH ^ -CH ₃ ~~ XJ \ J -C-C- njf: 1.5340 8th H -CO-C ₃ H ₇ ^ _n J -CH ₃ -CH -0- -C-C- n ^ °: 1.5287 9 H -CO-NH ₂ -CH ₃ -C-C- -C-C- M.p .: 1O5 ° '-1O8 ^Ö 10 H -CO-NH ₀ -CH ₃ " ^CH 3 -0- -C-C- M.p .: 90 ° - 92 ° 11 H -CO-NHCH.,
ϊ 0 - -CH ₃ -0- -C-C- M.p .: 97 ° - 99 ° 12th H -CO-NH- ^ "^ -CH
3 I
ί ^ -C-C- -C-C- M.p .: 116 ° -118 °
i 13th H \ -CH ^ -0-- -C-C- M.p .: 113 ° -115 °

209818/1234

Example5

10 larvae of Dysdercus fasciatus, which are 8-10 days before adult moult, were topically treated with acetone solution. The test animals were then kept at 2δ ° C and 80-90 ^ relative humidity. The Dysdercus fasciatus larvae received meal from pre-swollen cotton seeds as putters. After about 10 days, ie as soon as the control animals had completed their adult moult, the ψ test animals were examined. In addition to normal adults and dead larvae, special forms such as extra larvae (larvae with an additional larval moult) and adultoids (adults with larval characteristics) were found. The special forms were non-viable stages of development that cannot be found in the normal development cycle.

The following table shows the number of animals that are in the specified concentrations in the * found different stages of development:

A = normal adults
B = extra larvae C = adultoids
D = dead larvae

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21,936

1- (4-N-ethylcarbamoyl) phenoxy ■ 3,7-dimethyl-2, β-octadicn

5 0.5

• 1_ (4-propionyl) phenoxy-3.7
dimethyl-2,6-octadiene Active ingredient
lot
in 7. fa
A. sdercL
sciatu
Bj C. C.
C.
D. 1- (h -propionyl) -phenoxy-
6,7-epoxy-3,7-dimethyl-2-octene 5
0.5 ;
1 i
£. 10 l - '(4-N-Methylcarbamöyl) -phenoxy-
6, f-epoxy-3,7-dimethyl-2-octene 5
0.5 l
2 6
» •8th l- (4-acetyl) -phenoxy-3,7-
dimethyl-2 _J 6-nonadiene 5
0.5 t
. ·.
i
5Ϊ 5 1- (4-acetyl) -phenoxy-6,7-epoxy-
3,? - dimethyl-2-nonene Ul ever 1 l- (4-butyryl) -phenoxy-6j7-epoxy-
3,7 ~ dimethyl-2-octene 5
0.5 . J -
5 2 _r
£ 1 5
0.5 7 s
9] 1 3
!

2 8 Ij 8! 1

209818/1234

21U936

example

10 fresh pupae from Dermestes lardarius each were topical treated with active ingredient solutions in acetone. The pupae were then kept at $ 28 and $ 80-90 relative humidity. After about 10 days, i.e. as soon as the control animals left the pupal shell as adults, the test animals became examined. In addition to normal adults and dead pupae, adultoids (adults with larval characteristics) were found.

The adultoids are non-viable Developmental stages that cannot be found in the normal development cycle.

A = normal adults
C = adultoids
D = dead dolls

Active ingredient
lot
in 7 De
la
A. rrae s'
rdar:
C. 101 :it
LUS
^D. l- (4-acetyl) -phenoxy-3,7-
dimethyl-2,6 nonadrene 5
0.5 1 .
2 9
6th ..2-!
i 1- (4-acetyl) -phenoxy-3,7-
dimethyl-6,7-epoxy-2-nonene 5
0.5 10
10 I.
I.
t
i control - i
i
Ϊ

209818/1234

21U936

Example ¹ J

Ten fresh Tenebrio molitor dolls were treated topically with active ingredient solutions in acetone. The dolls were then kept at 28 ° and $ 80-90 relative humidity. After 10 days, i.e. as soon as the. Control animals have left the pupal shell when adults have left the test animals. Man found adultoids (adults with larval characteristics) in addition to normal adults and dead pupae.

Adultoids are non-viable stages of development that do not occur in the normal development cycle are found.

A = normal adults C = adultoids D = dead pupae

1- (4-propionyl) phenoxy-3,7-dimethyl-2,6-octadiene

Amount of active ingredient In 7

Tenebrio

molitor

ACD

1 - (^ - Propionyl) -phenoxy-3 * 7 * dimethyl-o, 7-epoxy-2-octene

5
0.5

1- (4-acetyl) -phenoxy-3,7-dimethyl-2, o-nonadiene

5
0.5

1- (4-acetyl) phenoxy-3,7-dimethyl-2-nonene

5
0.5

¹ I ⁷ ! ²

2 0 9 8 1 8/1

1- (4-butyryl) phenoxy-β, 7-epoxy-3 } 7-dimethyl- ^, 6-octadiene

21U936

// active ingredient

nonge

in 7

.Teriebrio molitor AJC D

control

Examples

10 fresh pupae of Leptinotarsa decemlineata were treated topically with solutions in acetone. The pupae were then kept at 28 ⁰ C and 80-90 relative humidity. After about 10 days , ie as soon as the control animals had left the pupal shell as adults, the test animals were examined. In addition to normal adults and dead pupae, adultoids (adults with larval characteristics) were found.

Adultoids are non-viable stages of development that are not in the normal development cycle can be found.

A = normal adults C = adultoids D = dead pupae

209818/1234

21U936

! active ingredient-j Lsptinatar ^ deceinlineata

in 7 A. C. D. l- (4-propionyl) -phenoxy-
3,7-dimethyl-6,7-epoxy-2-OGten VJt 9 1 l- (4-acetyl) -phenoxy-3,7-
dimethyl-2-nonadriene 5
0.5
¹ 1 9
7th l- (4-acetyl) -phenoxy-3,7-
diraethyl-6,7-epoxy-2-nonene 5
0.5 9
7th 1
3 control - 10

209818/1234

Claims (1)

21U936 Claims' ** 1. Compounds of the formula where Z ₁ and Zp together form a carbon-carbon bond or together an oxygen bridge or each is hydrogen, R ₁ and Rp are each methyl or ethyl, Z- and Z ₁ . together a carbon-carbon bond, R ^ hydrogen, C ^ -C _r alkylcarbonyl, carbamoyl, C ₁ -C ₁ , monoalkyl-., Cp-C ₁ , alkenyl, Cp-C ₁ , alkynyl or arylearbamoyl, R ₁ , C ₀ -C ₁ . Alkyl carbonyl, carbamoyl, C _{1 -C 1} , monoalkyi-, Cp-C ₁ alkenyl-, Cp-C ₁ , alkynyl- or arylearbamoyl or R 1 -C P -C _{alkyl carbonyl, CarbaraoyJ., C 1} -C ₁ monoalkyl, C ~ -C ,, alkenyl, C ₀ -C ₁ alkynyl or arylearbamoyl, R ₁ , hydrogen, Cp-Cj. Alkyl carbonyl, carbamoyl, C ₁ -C ₁ , monoalkyl, Cp-C ₁ alkenyl, C ₂ -C ₁ , alkynyl or arylearbamoyl or Z- and Z ₁ -Je hydrogen and R and Rj, each hydrogen, Cp-C ₁ . Alkyl is carbonyl, carbamoyl, C ₁ -C ₁ , monoalkyl, Cp-C ₁ , alkenyl, Cp-C ₁ , alkynyl or arylearbamoyl. 2. Compounds according to claim 1 wherein Z ₁ and Z ₂ together form a carbon-carbon bond or together an acidic bridge, R, and R ₅ , each methyl or ethyl, Z ^ and Z ₁ , together a carbon-carbon bond, R ^ 209818/1234 21U936 Acetyl, propionyl, butyryl, carbamoyl, monomethyl, monoethyl or monophenylcarbamoyl and R ₁ denotes hydrogen. 3. Compound geraäss claim 1 of the formula COC ₀ H ₁ 4. Connection according to claim 1 of FormeJ. COC ₂ H ₅ 5. Compound according to claim 1 of the formula COC ₂ H ₅ 2098 18/1234 21U936 6. Compound according to claim 1 of the formula COC ₂ H ₅ 'J. Compound according to claim 1 of the formula 5. δ. Compound according to claim 1 of the formula NV-COC ₂ H ₅ 9. Compound according to claim 1 of the formula CH 209818 / 123A 21U936 10. Compound according to claim 1 of the formula CH. COCH (n) 11. Compound according to claim 1 of the formula CO-C ₃ H ₇ (ISo) 12. Compound according to claim 1 of the formula CO-CH (iso) . Compound according to claim 1 of the formula CH CONHCH ₅ SS 20 9818/1234 Compound according to claim 1 of the formula CONHCH 15. Compound according to claim 1 of the formula CONiIC ₂ H 16. Compound according to claim 1 of the formula CH CH. , CONHC ₂ H- 17. Compound according to claim 1 of the formula CONHC ₀ H ₁ 209818/1234 - 18th link according to Claim 2H.A936 C ₂ H ₅ Γ ³ 1 of the formula CH 3 . CONHC ₂ H ₅ 19. Process for the preparation of compounds of the formula where Z, and Z ₂ together form a carbon-carbon bond or together an oxygen _{bridge or each hydrogen, R-, and R 2} each methyl or ethyl, Z-, and Z ₂ , together a carbon-carbon bond, R., hydrogen, Cg- C ^ alkylcarbonyl, carbamoyl, C ₁ -C ^ monoalkyl-, O ^ -Cu alkenyl- , Cg-C ^ alkynyl- or arylcarbamoyl, Rk Cp-C- alkylcarbonyl, carbamoyl, C ₁ -C ₁ , monoalkyl, "Cp ^ Cj, alkenyl, C ₃ -C ^ alkynyl or arylcarbamoyl or R, C ₃ -C ^ alkylcarbonyl, carbamoyl, C ₁ -C ₂ , monoalkyl, C ₂ -C ₂ ^ alkenyl, Cp-C ^ alkynyl or Arylcarbamoyl, R ₂ , hydrogen, Cp-C, -alkylcarbonyl, carbamoyl, C ₁ -C ₂ ^ monoalkyl-, Cp-C ₂ ^ alkenyl-, C ₂ -C ₂ , alkynyl- or arylcarbamoyl or Z-, and Z ₂ , per hydrogen and R-, and R ₂ ^ per hydrogen, C ₃ -Cf- alkylcarbonyl, 209818/1234 Carbamoyl, C 1 -C. Monoalkyl, ^C ₂ ~ ^C H -alkenyl, Cp-C ₂ , alkynyl or arylcarbamoyl, characterized in that a halide of the formula CH- * 2 No. ₁ wherein halogen, preferably chlorine or bromine, and "R ₁ , R 2, Z, up to To have the meaning given above, with a phenol of the formula HO wherein R ^, and R ₁ , have the meaning given above, reacts in the presence of an acid acceptor. 20. Process for the preparation of compounds of the formula 209818/1234 2U4936 wherein Z ₁ and Z ₂ together form a carbon-carbon bond or together an oxygen bridge or each is hydrogen, R, and IU are each methyl or ethyl, Z, and Z ₂ , together a carbon-carbon bond, R-. Hydrogen, Cp-Cp. Alkyl carbonyl, carbamoyl, C1 -C6. Monoalkyl, ^C 2 ** ^C 4 ^alkene y ^L * ^C ~ 2 ~ ^C 4 alkynyl or aryl carbamoyl, _R.sub.2. C ₂ -Cj- alkyl carbonyl, carbamoyl, C ₁ -C ₂ , monoalkyl, Cg-C ₂ , alkenyl-, Cp-C ₂ , alkynyl- or arylcarbamoyl or R-, Cp-Cf- alkyl carbonyl, carbamoyl, C ₁ -C ₂ , monoalkyl-, Cp-C ₂ , alkenyl-, C ₂ -C ₂ , alkynyl- or arylcarbamoyl, R ₂ , hydrogen, Cp-Cj- alkylcarbonyl, carbamoyl, C ₁ -C ₂ , monoalkyl-, Cp- C ₂ , alkenyl, C _? -C ₂ , alkynyl- or arylcarbamoyl or Z-, and Z ₂ -Je V / asterstoff and R-, and R ₂ , each hydrogen, Cp-Cj- alkylcarbonyl, carbamoyl, C ₁ -C ₂ ^ alkyl, C ₂ -C ₂ ^ alkenyl, Cp-C ₂ , alkynyl or arylcarbamoyl, characterized in that the compound of the formula wherein R ₁ to R ₂ ,, Z_ and Z ₂ , have the meaning given, in an inert solvent with an epoxidizing agent directly to the desired 6,7-epoxy derivative or a compound of the formula 209818/1234 21U936 wherein R, to R ^, Z ^ and Z ₂ , have the meaning given in a mixture of water with a suitable solvent such as tetrahydrofuran, 1,2-dimethoxyethane, dioxane or tert. Butanol, preferably with cooling with N ^ bromosuccinimide, first into the 6,7 ~ bromohydrin compound of the formula transferred and this by subsequent treatment with an alkaline agent such as alkali carbonate, Alkali alkoxide or alkali hydroxide with elimination of hydrogen bromide into a 6,7-epoxy compound of the formula 'R convicted. 2098 18/1234 21U936 21. Method according to claim 18 for production of the compounds according to claims 2 to 17. 22. The method according to claim 19 for producing the epoxides of claims 1 to 18. 23. Pesticides, which as active compo nente a compound of the formula contain, in which Z, and Zp together form a carbon-carbon bond or together an oxygen bridge or each VJhydrogen, R, and R _{2 are} each methyl or ethyl, Z-, and Z ₂ , together a carbon-carbon bond, IU hydrogen, pC, - alkylcarbonyl, carbamoyl, C, -C ₂ ^ Monoalkyl, C ₂ -C ₂ ^ alkenyl, ^C 2 ~ ^C k A ^ ¹ ^ ¹ " ^or aryl-. Carbamoyl, R ₂ , Cg-C- alkylcarbonyl, carbamoyl, C ₁ -C ₁ ^ monoalkyl, C ₂ -Cj ^ alkenyl-, Cg-C ^ alkynyl- or arylcarbamoyl or R, C ₂ -Cp. Alkylcarbonyl, carbamoyl, C, -C ^ monoalkyl-, C ₂ -C ₂ , alkenyl-, C ₂ -C ₁ , Alkynyl or arylcarbamoyl, R ₂ ^ hydrogen, C ₂ -C ^ alkylcarbonyl, carbamoyl, C ₁ -C ^ monoalkyl, C ₂ -C ₁ ^ alkenyl, C ₂ -C ₂ ^ alkynyl or aryl 209818 / 123A carbamoyl or Z-. and Z ₂ , each hydrogen and R., and R ₂ , each hydrogen, Cp-C alkylcarbonyl, carbamoyl, C, -C ^ monoalkyl-, Cg-C ^ alkenyl-, C ₃ -C ^ alkynyl- or arylcarbamoyl, together with suitable supports and / or other additives. 24. Pesticides according to claim 23, which contain a compound according to claims 2 to 18 as the active component. · 25. Use for influencing the development of invertebrates of compounds of the formula wherein Z ₁ and Z ₂ together form a carbon-carbon bond or together an oxygen _{bridge or each is hydrogen, R 1} and R _{2 are} each methyl or ethyl, Z, and Z ₂ , together a carbon-carbon bond, R, hydrogen, Cg-Cj. Alkylcarbonyl, carbamoyl, C ₁ -Cj, monoalkyl, ^C 2 ~ ^C 4 alkenyl, C ₂ -C ₂ , alkynyl or aryl carbamoyl, E ₁ , C ₂ -C "alkylcarbonyl, carbamoyl, C ₁ -C ₂ , Monoalkyl, C ₂ -C ₂ , alkenyl, C ₂ -C ₂ ^ alkynyl or arylcarbamoyl or R-, Cp-C, 2098Ί8 / 1234 -41- 2U4936 Alkylcarbonyl, carbamoyl, ^c \ ~ ^C h monoalkyl, Cp-C ₂ , alkenyl-, Cp-C ₂ , alkynyl- or arylcarbamoyl, R ₂ , hydrogen, _{O2-C 1} -alky 1 carbonyl, carbamoyl, C ₁ -C ₂ , Monoalkyl-, C ₃ -C ₂ , alkenyl-, Co ^- C ₂ , alkynyl- or arylcarbamoyl or Z-, and Z ₂ , each hydrogen and R., and R ₂ -Je hydrogen, Cp-C ₁ . Alkylcarbonyl, carbamoyl, C ₁ -C ₂ ^ monoalkyl, C ₃ -C ₂ ^ alkenyl, C ₂ -C ₂ ^ alkynyl or arylcarbamoyl. 26. Use according to claim 25 of compounds according to claims 2 to 17. 27. Use according to claim 26 for influencing the development of insects, representatives of the order Acarina and nematodes. 209818/1234