DE2166152A1 - NEW ETHERS - Google Patents

Description

CIBA-GEIGYAG, CH-4002 Basel

CiBA-GEIGY

2156152

Dr. F. Zumstein Sr. - Dr. E. Assmann Dr.fLKovnigsborgor - Dipl. Phyo. R. Holzhauer

Dr. F. Zumstein j Jn. ., _ Patent Attorney «

Mixing 2, Braubausstrafi · 4 / UI

Case 5-7200 / H-2 / A / B Germany

( Elimination; from P 21 44- 954.7-42)

New ethers

The present invention relates to new terpene aryl ethers, their preparation and agents for influencing them the development of insects containing these compounds as an active ingredient. The new compounds correspond to the formula

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wherein Z ₁ and Zp are a carbon-carbon bond or together are an oxygen bridge,

R and Rp each methyl or ethyl Z, and Z ₁ , together a carbon-carbon bond or 'each hydrogen or

Z-, Z ", Z, and Z ₁ . each mean hydrogen. The compounds of the formula deserve special mention because of their action

C = CH

(ID

wherein R, methyl or ethyl and z 'and Z * ₂ mean a carbon-carbon bond or an oxygen bridge. 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 reactants involved can be used:

X ⁺ HO

-CH ₂ -CaCH

base

-> CK,

, O-CH ₂ -C = CH

309810/1 151

GH,

j- C / sCxi

selective epoxy ding agent

O CD QO

3)

? ■,

^) CH ₃

5) CK

'R,

-C5CH

.Xr

O-CH ₂ -C = CH

Acid acceptor

-CH ^ -CsCH

Acid-

accep "tor

Oxidizing agents

1 X)

-CH ₂ -C = CH

X stands for halogen, preferably chlorine or bromine. The reactions 1) and 3) i, ie the reactions with the mixtures of geometric isomers of the reactive allylic halides with the desired phenol, are carried out in a solvent such as 1,2-dimethoxyethane, tetrahydrofuran, dioxane, dimethylformamide, dimethyl sulfoxide, sulfolane or a dialkyl ether, but preferably in 1,2-dimethoxyethane by slowly adding an equivalent of an acid acceptor such as alkali or alkaline earth hydroxides, alkali or alkaline earth carbonates, alkali alkoxides or alkali hydrides with stirring at room temperature and optionally subsequent heating. The terpene aryl ethers are isolated then by known techniques, where alkali is to be understood in particular as sodium and potassium, and alkaline earth is to be understood as calcium.

Reactions 2) and 6) - i.e. the transfer of the terpenoid Aryl ethers in their 6,7-epoxy derivatives are preferably converted with cooling in an inert solvent such as a chlorinated hydrocarbon, carried out with an epoxidizing agent such as a peracid. Applying one mole of a peracid will result in of the steric factors predominantly formed the 6,7-epoxy derivatives. The 6,7-epoxy derivatives can also be mixed with N-bromosuccinimide of water with a solvent such as tetrahydrofuran, 1,2-dimethoxyethane, dioxane or tert-butanol in a homogeneous or heterogeneous phase and subsequent treatment of the intermediate bromohydrin with an alkaline agent such as alkali carbonate, alkali hydroxide

3 0 9 8 10/1151

or an alkali alkoxide. Among alkali are in particular Understand sodium and potassium.

The term "peracid" is primarily used for lower Peralkanoic acids with 1 to 6 carbon atoms, such as peracetic acid, as well as aromatic peracids such as perbenzoic acid, monoperphthalic acid, but especially understood m-chloroperbenzoic acid. As a basic Reagents for converting a bromohydrin into the 6,7-epoxy derivative alkali carbonates, alkali hydroxides and alkali alkoxides come into play Consideration.

The conversion after the equation 5) λ i.e. e.g. the reaction a non-allylic aliphatic halide with a desired one Phenol is preferably carried out in the presence of at least one mole of an alkali or alkaline earth carbonate, as well as with or without a catalysis Amount of an alkali iodide in a solvent such as acetone, 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 hydroxide in a solvent such as dimethylformamide, dimethyl sulfoxide, sulfolane or 1,2-dimethoxyethane between 0 and 100 ° C.

Another synthesis variant is the implementation of a 1- (4-hydroxy) phenoxy-3i7-dialkyl-2,6 ~ octa ~ or nona-diene with a propargyl halide (in the presence of a base, e.g. a tertiary Amines, alkali carbonates or alkali hydroxides), to a phenol

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dieters, highlighting the formula I:

Similarly, the 1- (4-hydroxy) -phenoxy-3i7-dialkyl-6-octene or 6-nonene compounds to form phenol dieters.

CH

./N ₁ -O-CH _n -CsCH

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The phenol diether obtained in this way can then be used with an epoxidizing agent can be converted into the 6,7-epoxy derivatives in the cold in an inert solvent.

In the preparation of the compounds of the formula I ₃ , all possible geometric isomers are formed as a result of the allyl halides used for the synthesis. The compounds described represent mixtures of the geometric isomers as they arise in the synthesis.

The active ingredients of the formula I are suitable for combating a wide variety of animal and vegetable pests, especially for combating insects. In contrast to most of the previously known insecticides, which are available as contact or Food poisons kill, paralyze or drive away the animals quickly, affect 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 holometabolites) disturbed. The generation sequence is interrupted and the animals are thus killed indirectly. For warblers, the connections are of formula I practically non-toxic. In addition, these compounds are easily broken down, so no accumulation is possible.

The new terpenoid aryl ethers can mainly be used to combat the following pests of plants, stored products and hygiene become: Against insects of order and families:

309810/1151 BAD ORfGfNAL

Orthoptera

Isoptera
Hemiptera

Colebptera

Lepidoptera

Acrididae

Gryllidae

Blattidae

Kalotermitidae

Miridae

Piesmidae

Lygaeidae

Pyrrhocoridae

Pentatomidae

Cimicidae

Reduviidae

Jassidae

Eriosomatidae

Leccaniidae

Carabidae

Elateridae

Co ccinellidae Tenebrionidae

Dermestidae

Cucujjidae

Chrysomelidae

Curculionidae

Scolytidae

Scarabaeidae

Pyralidae

Phyticidae

Pyraustidae

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• - Crambidae

Tortricidae Galleriidae Lyonetiidae Yponomeutidae Plerldae Plutellidae Lymantriidae Noctuidae

Dlptera Culicidae

Simullidae Tipulidae

The compounds of the formula I can be used alone or together with suitable carriers and / or additives will. Suitable carriers and additives can be solid or liquid and correspond to the substances customary in formulation technology such as natural or regenerated substances ^, solvents, dispersants, Wetting, adhesive, thickening, binding and / or fertilizers.

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For application, the compounds of the formula I can be converted into dusts, emulsion concentrates, granules, dispersions, Sprays, solutions or slurries in the usual formulation, which is part of general knowledge in application technology will. Furthermore, there are "cattle dips", i.e. cattle baths, and "spray races", i.e. spray courses in which aqueous preparations used to mention v / earth.

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

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. solid processing forms: dust, grit,

Granules, coated granules, impregnation granules and homogeneous granules liquid processing forms:

a) dispersible in water

Active ingredient concentrates: wettable powders,

Pastes, emulsions;

b) Solutions

The active ingredients are mixed with solid carriers for the production of solid processing forms (dusts, grit) Carrier materials include, for example, kaolin, talc, Bolus, loess, chalk, limestone, lime grit, "attapulgite, dolomite, diatomaceous earth, precipitated silica, alkaline earth silicates, sodium and potassium aluminum silicates (feldspar and mica), calcium and Magnesium sulfate, magnesium oxide, ground plastics, fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, ground vegetable products such as cereal flour, Tree bark flour, wood flour, nut shell flour, cellulose powder, residues of plant extracts, activated charcoal, etc., each separately or as mixtures with one another.

Granules can be produced very easily by dissolving an active ingredient of the formula I in an organic solvent and applying the solution obtained in this way to a granulated mineral, for example attapulgite, SiO _p , granicalcium, bentonite, etc. and then evaporating the organic solvent again.

Polymer granules can also be produced by combining the active ingredients of the formula I with polymerizable

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BATH ORIGINAL

Compounds are mixed (urea / formaldehydeJ dicyandiamide / Formaldehyde; Melamine / formaldehyde or other), whereupon a gentle Polymerization is carried out, from which the active substances remain unaffected, and granulation during the gel formation is made. It is cheaper to use finished, porous polymer granules (Urea / formaldehyde, polyacrylonitrile, polyester and others) with a specific surface and favorable, predictable Adsorption / desorption ratio with the fluidized substances e.g. to impregnate in the form of their solutions (in a low-boiling solvent) and to remove the solvent. Such Polymer granules can also be in the form of micro-granules with a bulk density of preferably 300 g / liter to 600 g / liter be applied with the help of atomizers. Can atomize be carried out over large areas of crops with the help of airplanes.

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 and cationic active substances Substances are added that, for example, improve the adhesive strength of the active ingredients on plants and plant parts (adhesive and adhesives) and / or ensure better buildability (wetting agents) and dispersibility (dispersants).

For example, the following substances come into question: Οΐβΐη / Lime mixture, cellulose derivatives (methyl cellulose, carboxymethyl cellulose), Hydroxyethylene glycol ethers of mono- and dialkylphenols with 5-15 ethylene oxide residues per molecule and 8-9 carbon atoms

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BAU ÖÄ ⁿ

in the alkyl radical, lignin sulfonic acid, its alkali and alkaline earth salts, Polyethylene glycol ether (Carbowax), fatty alcohol polyglycol ether with 5-20 ethylene oxide residues per molecule and 8-l8 carbon atoms in the. • Fatty alcohol part, condensation products of ethylene oxide, propylene oxide, Polyvinylpyrrolidones, polyvinyl alcohols, condensation products of urea / formaldehyde and latex products.

Active ingredient concentrates dispersible in water, i.e. wettable powders, pastes and emulsion concentrates "represent. Agents that can be diluted with water to any desired concentration. They consist of active ingredient, carrier, optionally additives stabilizing the active substance, surface-active substances and antifoams, and optionally Solvents.

The wettable powders and pastes are obtained by mixing the active ingredients with dispersants and in powder form Carriers mixed and ground in suitable devices until homogeneous. Examples of carriers are used those mentioned above for the solid work-up forms in question. In some cases it is advantageous to use mixtures of different 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 lignin sulfonic acid, further alkylarylsulfonates, alkali and alkaline earth metal salts of dibutylnaphthalene sulfonic acid, fatty alcohol sulfates, v / ie salts of sulfated hexadecanols, heptadecanols,

3 09810/1151 BAD ORfGWAL.

Octadecanols and salts of sulfated fatty alcohol glycol ethers, the sodium salt of GLe ylmethyltauride, ditertiary ethylene glycols, Dialkyldilaurylammonium chloride and fatty acid alkali and alkaline earth salts.

Silicone oils, for example, come in as antifoam agents Question.

The active ingredients are mixed, ground, sieved and passed with the additives listed above in such a way that the wettable powders are solid .; Proportion does not exceed a grain size of 0.02 to 0.04 and in pastes, of 0.03 m ^m "For the preparation of emulsion concentrates and pastes organic solvent and water are dispersants such as those listed in the preceding sections used. For example, alcohols, benzene, xylenes, toluene, dimethylsulfoxide and mineral oil fractions boiling ^{in the range from 120 to 350 ° C. come into consideration as solvents.} The solvents must be practically odorless, non-phytotoxic and inert to the active ingredients.

The agents according to the invention can also be used in the form of Solutions are applied. For this purpose, the active ingredient or several active ingredients of the general formula I are grounded in suitable organic Solvents, solvent mixtures or water dissolved, aliphatic and aromatic solvents can be used as organic solvents Hydrocarbons, their chlorinated derivatives, alky! Naphthalenes, Mineral oils can be used alone or as a mixture with one another.

The content of active ingredient in the agents described above is between 0.1 and 95 ^, it should be mentioned that in the Application from the aircraft or by means of other suitable application devices Concentrations up to 99.5 # or even more pure

30981 0/1151 BAD ORiGJNAL

■ "- 15 -

Active ingredient can be used.

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

Dust i To produce a) 5 and b) 2 dusts, the following substances are used!

a) 5 parts of active ingredient
95 parts of talc;

b) 2 parts of active ingredient

I part of highly disperse silica, 97 parts of talc.

The active ingredients are mixed and ground with the carrier materials ".

Granules: The following substances are used to produce 5% granules:

—5 parts of active ingredient

0.25 part of epichlorohydrin,
"- -: 0j25 parts of cetyl polyglycol ether,

3.50 parts of polyethylene glycol
91 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 and cetyl polyglycol ether are added. The solution obtained in this way is sprayed onto kaolin and then the acetone is evaporated in vacuo, wettable powder: The following ingredients are used to produce a) 40%, b) and c) 25% d) 10% wettable powder:

3 0 9 8 10/1151

- X6 -

a) 40 parts of active ingredient

5 parts of lignin sulfonic acid sodium salt, 1 part of dibutylnaphthalenesulfonic acid sodium salt, Parts of silica;

b) 25 parts of active ingredient

4.5 parts calcium lignosulfonate,

1.9 parts of champagne chalk / hydroxyethyl cellulose mixture (l: l),

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

c) 25 parts of active ingredient

2.5 parts of isooctylphenoxy-polyoxyethylene-ethanol, 1.7 parts of Champagne chalk / HydroxyäthylceΙΐμίοεε-

Mixture (1: 1),
8.3 parts sodium aluminum silicate,

16.5 parts kieselguhr,

46 parts of kaolin;

d) 10 parts of active ingredient

3 parts mixture 'of the sodium salts of saturated

Fatty alcohol sulfates,

5 parts of naphthalenesulfonic acid / formaldehyde condensate, Share kaolin.

The active ingredients are intimately mixed with the additives in suitable mixers and put on appropriate mills and Grind rollers. You get wettable powder, which can be mixed with water

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Allow suspensions to be diluted to 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 of Fatty alcohol polyglycol ether and alkylarylsulfonate calcium salt,

40 parts of dimethylformamide, • 43.2 parts of xylene;

b) 25 parts of active ingredient

2.5 parts epoxidized vegetable oil,

10 parts of an alkylarylsulfonate fatty alcohol poly

glycol ether mixture, 5 parts of dimethylformamide, 57.5 parts of xylene.

Such concentrates can be diluted with water / water emulsions of any desired concentration. Spray: The following ingredients are used to produce a 5% spray: 5 parts of active ingredient,
1 part epichlorohydrin, 94 parts gasoline (boiling limits ΙβΟ -19O ⁰ C);

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• Other biocidal active ingredients or agents can be added to the agents described. So can the new funds In addition to the compounds of general formula I mentioned, for example insecticides, fungicides, bactericides, fungistats, bacteriostats. Contains nematocides or herbicides to broaden the spectrum of activity.

example 1

la) to a solution of 15.2 g of 4-propargyloxyphenol (boiling point 92-932 / 0.0

20th
Torr; n_: 1.5625) in 150 ml of pure 1,2-dirne thoxyethane was added 21.7 S of 1-bromo-317-dimethyl-2,6-octadiene and the dropwise addition began immediately afterwards at 20-22 ° C. with stirring a solution of 6.4 g of 85% potassium hydroxide in 100 ml of absolute ethanol. The addition of the potassium hydroxide solution (duration approx. 8 hours) was regulated in such a way that the reaction mixture always remained slightly alkaline (pH approx. 8-9). After the addition of the base, the mixture was stirred for a further 16 hours at room temperature, then heated to 70 ° C. for one hour, then cooled and the precipitated potassium bromide was filtered off. The filtrate was concentrated to about 50 ml, taken up in a diethyl ether-hexane mixture (1: 4), washed three times with 30 ml of 10% aqueous potassium hydroxide solution and then with water until neutral. The organic phase was dried over sodium sulfate and the solvents were distilled off in vacuo. The remaining l- (4-propargyloxy) -phenoxy-3,7-dimethyl-2,6-octadiene was purified by chromatography on silica gel (activity III) with an ether-hexane mixture (1: 5)

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cleaned. n_: Γ, 5316. This ether can also be obtained by high vacuum distillation getting cleaned.

Analogously to Example la) can be prepared from 3-Propargyloxyphenol (b.p .: 84-85 ° / 0.02 torr; n ^ °: 1.5640) and l-bromo-3 _J> 7-dimethyl-2-octadiene, 6 _J

pn

l- (3-propargyloxy) phenoxy-3 _J 7-dimethyl-2,6-octadiene (η _β : 1.5326] as well as from 4-propargyloxyphenol and l-bromo-3,7-dimethyl-2,6-nonadiene the 1- (4-propargyloxy) -phenoxy-3i7-dimethyl-2., 6-nonadiene produced

20th
(η _β : 1.5301).

The one for the production of 1- (4-propargyloxy) -phenoxy-3 * 7-dimethyl-2,6-octadiene The 4-propargyloxyphenol used can be produced in the following masses: -

To the mixture of 220 g hydroquinone, 305 g anhydrous potassium carbonate, 7 * 3 g finely powdered potassium iodide in 700 ml acetone, under "a nitrogen atmosphere, it was added dropwise with stirring the boiling point of acetone within 2 hours. 165 g of propargyl chloride. It was then refluxed for a further 14 hours. The reaction mixture was then with 800 ml Acetone diluted, filtered clear and the filtrate concentrated. The residue was taken up in 1500 ml of toluene and the toluene solution was washed repeated with 200 ml of 40-50 warm water each time, after drying the toluene solution over sodium sulfate and adding something Active charcoal was filtered off and the solvent was removed from the piltrate in vacuo freed and the residue dissolved in 1000 ml of ether. The ethereal solution was three times with 200 ml of 30% ice-cold sodium hydroxide solution

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BATH ORIGINAL

and then washed twice with water. The combined aqueous alkaline phases were then washed twice with a little ether. The aqueous-alkaline phase, which contains the sodium salt of 4-propargyl-oxyphenol was left with vigorous stirring • to the mixture 1000 ml of chloroform, 1 kg of ice and 600 ml concentrated Hydrochloric acid flow in. The phases were separated, the aqueous-hydrochloric acid phase was washed again with Chlorofrom, the combined chloroform phases were washed briefly with water, dried over sodium sulfate and the solvent was distilled off. Of the The residue was then fractionally distilled in vacuo, whereby the colorless 4-propargyloxyphenol with bp 92-93 // O, O4 Torr was obtained.

Ib) To a mixture of 16.4 g of l - {- 4-hydroxy) phenoxy-3,7-dimethyl-2,6-octadiene and 13 * 8 g of anhydrous potassium carbonate in 70 ml of acetone were at the boiling point of acetone and 9.6 g of propargyl bromide were added dropwise under a nitrogen atmosphere within 30 minutes. After the propargyl bromide had been added, the mixture was refluxed for a further 8 hours. For work-up, the sediment was filtered off, the residue was washed out repeatedly with diethyl ether and the solvents were removed from the piltrate in vacuo. The oily residue was taken up in diethyl ether-hexane (1: 4), washed three times with 10 ^ strength potassium hydroxide solution and then with water. After drying the organic phases over sodium sulfate and suctioning off the solvent in vacuo, the 1- (4-propargyloxy) phenoxy-3,7-dimethyl-2,6-octadiene was as described under

PO section, a) specified further purified. n ": 1.5315

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^{The 1- (1} I-hydroxy) -phenoxy - ^ * T-dimethyl- ^ ö-octadiene used as starting product in Example Ib) can be prepared as follows: To a solution of 165 g of hydroquinone in 2000 ml of 1,2-dimethoxyethane 326 g of 1-bromo-3j7-dimethyl-2,6-octadiene and the solution of 95 g of approx. 90% potassium hydroxide in 1200 ml of absolute ethanol were added dropwise uniformly from two dropping funnels within 10 hours, while stirring at room temperature so that the reaction mixture always reacted slightly alkaline. The mixture was then stirred for a further 5 hours at room temperature and 3 hours at 50.degree. The entire reaction was carried out under a nitrogen atmosphere.

For work-up, after the reaction mixture had cooled, the precipitated potassium bromide was filtered off, the solvent removed in vacuo, the residue taken up in 1600 ml of η-hexane and extracted four times with approx. 200 ml of 20% aqueous potassium hydroxide solution. The combined aqueous-alkaline phases were washed twice more with a little η-hexane. The aqueous-alkaline solution was then diluted with about 1500 ml of water and exhaustively with diethyl ether extracted. The combined ethereal extracts were washed with a very little water, dried over sodium sulfate and the ether is distilled off. What remains after a while crystalline-solidifying 1- (4-hydroxy) -phenoxy-3j7-dimethyl-2,6-octadiene was distilled in vacuo for further purification (boiling point: 140-142-0.05 Torr) and then crystallized from pentane. M.p. 45-47 ^.

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lc) To a solution of 5 * 77 g of 1- ( ¹ I-propargyloxy) -phenoxy-3,7-dimethyl-2,6-octadiene in 55 ml of dichlorine than was added at -2 ° to 0 ° C with stirring Solution of 4.1 g of 86% m-chloroperbenzoic acid in 40 ml of a dichloromethane-ether mixture (9 ^ 1) was added dropwise within 4 hours. After a further 14 hours of stirring at 0 ° to 2 ° C., the reaction mixture was diluted with η-hexane, washed three times with 40 ml of 10% aqueous potassium hydroxide solution at about 5 ° C. and then washed neutral with water. After the organic phase had been dried over sodium sulfate, the solvent was distilled off in vacuo and the product was purified by chromatography on silica gel (activity III) (eluent: diethyl ether-hexane 1: 3) whereby the pure, colorless 1- (4-propargyloxy) phenoxy was obtained -6,7-epoxy-3i7-dimethyl-

OQ

2-octene received. n _D : 1.52β3.

Example 2

A mixture of 18.7 g of l-bromine ^^ - dimethyl-ö-octene, 11.2 g of 4-propargyloxyphenol, 12 g of anhydrous, powdered potassium carbonate, 1 g of finely powdered potassium iodide and 60 ml of methyl ethyl ketone was at 70 for 48 hours g stirred. The reaction mixture was then filtered off, the filtrate was concentrated, then washed neutral with 10 ^ iger ice-cold potassium hydroxide solution and then with water. After drying the organic phase over sodium; sulfate, the solvent was distilled off in vacuo and the 1- (4-propargyloxy) phenoxy-317-dimethyl-6-octene was purified by chromatography on silica gel. Eluent: diethyl ether-hexane 1:10). njf: 1.5142.

3 0 9,810 / 1 1 51

The l- (4-propargyloxy) -phenoxy-3,7-dimethyl-6-octene obtained in this way can be converted into the 1- (4-propargyloxy) phenoxy-6 _i 7-epoxy-3j7 with 3-chloroperbenzoic acid analogously to Example 2 -dimethylojQtan, (nj: 1.5115).

The following compounds are also produced analogously to Examples 1 and 2:

(C-C- means carbon-carbon bond: -0- oxygen bridge).

^R l ^R 2 y · y
Z ₁ , z ₂ Z ₂ = H Zy Z 4th Z ₄ = H Physical data 1.5301 C ₂ H ₅ CH ₃ -C-C- Z ₂ = H -C-C- Z ₄ = H 1.5245 C ₂ H ₅ CH ₃ -0- -C-C- Z ₄ = H 20th
ⁿ D ^: 1.5143 OH ₃ CH -C-C- Z ₃ = H; Z ₄ = H η ^20
n D * 1.5115 CH ₃ OH ₃ -0- Z ₃ = H; Z ₄ = H η? ⁰ · CH ₃ CH ₃ Z ₁ = H; Z ₃ = H; Z ₄ = H C ₂ H ₅ CH ₃ Z ₁ = H; Z ₃ = H; C ₂ H ₅ CH ₃ -C-C- Z ₃ = H; C ₂ H ₅ CH ₃ -0- Z ₃ = H;

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Example 5

10 larvae Dysdercus fasciatus, the 8-10 days before adult moult were treated topically with acetone solution at a concentration of 5 7 · The test animals were then kept at 28 ° C and 80-90 $ relative humidity. as Putters received the Dysdercus fasciatus larval meal from pre-swollen Cottonseed.

After about 10 days, i.e. as soon as the control animals moult had completed, the test animals were examined. In addition to normal adults and dead larvae, special forms such as extra larvae were found (Larvae with an additional larval moult) and adultoids (adults with larval characteristics). The special forms were about non-viable developmental stages that occur in normal development s cycle cannot be found.

The following table shows the number of normal adults that were found at the initial concentration: A = normal adults C = adultoids
B = extra larvae D = dead larvae.

link Amount of active ingredient
in 7 Dysdercus fasciatus B. C. D. 1- (4-propargyloxy) -phenoxy-
6,7-epoxy-3,7-dimethyl-2-octene
1- (4- »propargyloxy) -phenoxy-
6, f-epoxy-3,7-dimethyl-2-nonene 5
0.5
5 A. 3
7th 7th
9
3 1

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2186152

link Amount of active ingredient
in Ύ Dyad out B. - fasicätus D. A. 9 C. 1 1- (4-propargyloxy) -phenoxy-
6, f-epoxy-3j 7-dimethyl-ootane 5
0.5 10 - control - 1Ö -

Example 4-

10 fresh pupae from Dermestes lardarius each were topical with Active ingredient solutions in acetone treated »The pupae were then at Maintained 28% and 80-90 $ relative humidity.

After approx. 10 days, i.e. as soon as the control animals reach the pupae when adults had left the test animals were examined. Adultoids were found alongside normal adults and dead pupae (Adults with larval characteristics).

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

A = normal adults
C = adultoids
D = dead dolls.

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link Amount of active ingredient
in 7 Demiested LärdärlUs Ö D. ί- (4 ^ PrOp'argyloxy) -phenoxy * -
6,7-epoxy-, 3 j7-dimethyl-2-
octeri 5 ·
0.5 A. 10
9 1- (4-propargyloxy) -phenoxy-
6, - f »et> öxyr3i 7-dimethyi-> 2-
norieii 5
0> 5 1 10
10 1- (4-propargyloxy) -phenoxy-
öif-öpöxy- ^ iT'-ditnethyl ^ ööfcafi 5 ■ 9 control 1 10

Example 5

10 fresh dolls from Tenebrio molitor would be topical with each Treated active ingredient solutions in acetone. The pupae would then be at 28 ι And kept $ 80-90 relative humidity.

After approx. 10 days> i.e. as soon as the control animals remove the pupal shell when adults had left, the test animals would be examined. Ma found raising normal adults and dead pupae adultoids (Adülte miü Lärvehmerktnaleh).

The aedultoids are not viable ent ^ stages of development that cannot be found in the normal development cycle are.

A = normal adults
C = adultoids

D = dead dolls.

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COPY

link , 7- Amount of active ingredient
in 7 Tenebrio C. molitor 7- 5
0.5 A. 8th
10 1- (4-propargyloxy) phenoxy-6
3> 7-dimethyl-2-nonene 5
0.5 10
10 1- (4- propargyloxy) -phenoxy-6,
epoxy-3,7-dimethyl-2-octene control 10 D. 2

Example 6

10 fresh pupae of Leptinotarsa decemlineata were treated topically with solutions in acetone. The dolls were then at
28 ^ and 80-9O ^ relative humidity.

After approx. 10 days, that is, as soon as the control animals reach the pupae
when adults had left 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 cannot be found in the normal development cycle. A = normal adults
C = adultoids
D = dead dolls.

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COPY

2166Ί52

Amount of active ingredient
in 7 - Leptinotarsa
decemlineata C. D. 1- (4-propargyloxy) -phenoxy-
G ₃ 7-epoxy-3,7-dimethyl-2-
octen 5
0.5 A. 9
8th 1
2 control 10

3098 10/1151

Claims (10)

Claims • 1-, compounds of the formula -CH-CsCH Z and Z are a carbon-carbon bond or together an oxygen bridge, Around each methyl or ethyl, 2L · and Zu together form a carbon-carbon bond or each is hydrogen or Z _n , Z ^, Z-. and Zi ₁ each represent hydrogen. 12 3 4 2. Compounds according to claim 1 of the formula O-CH ₂ -C = CH 3 0 9 8 10/1151 wherein R, methyl or ethyl and Z * and Z 'are a carbon-carbon bond or mean an oxygen bridge. 3. Compound according to claim 2 of the formula H- 4. Compound according to claim 2 of the formula CH 5. Process for the preparation of compounds of the formula ~ O-CH -C = CH 3 0 9 8 10/1151 wherein Z and Zp a carbon-carbon _{bond or together an oxygen bridge, R 1} and R each methyl or ethyl, Z_ and Zu together a carbon-carbon bond or each hydrogen or Z ₁ , Ζ », Z-. and to each denote hydrogen, characterized in that one is a halide of the formula R, wherein X is halogen, preferably chlorine or bromine, with a phenol of the formula where R, Rp, Z, Z, Z ^. and Z ^ have the meaning given above, in the presence of an acid acceptor or that one is a phenol of the formula 3 0 9 8 10/1151 with a »halide of the formula X-CH ₂ -C = CH, where X is halogen, preferably chlorine or bromine, is converted or that one is a compound of the formula -CH-CSCH wherein R-, R_, Z and Z ^ have the meaning given above in one indifferent solvent with an epoxidation agent! implements. 3098 10/1151 6. Insecticidal agent which, as the active component, is a compound of the formula -O-CH-C ^ CH where Z_ and Z are a carbon-carbon bond
or together an oxygen bridge,
R .. and R_ each methyl or ethyl, together a carbon-carbon bond or each hydrogen or Z ₇ . and Z, Zp, Z ₇ . and each mean hydrogen contains. 7. Means according to claim 6, which as active
Component a compound of the formula wherein R is methyl or ethyl and Z ¹ and Z ^! mean a carbon-carbon bond or an oxygen bridge contains. 309810/1151 8. Means according to claim T ₃ which, as the active component, is the compound of the formula contains. 9. Means according to claim 7 * which as an active component the compound of the formula ·. contains. 3.35 / YES / sl 309810/1151 Case 5-7200 / 1 + 2 / A / B Germany 1?. July 1972 Test report 10 larvae of Dysdercus fasciatus, which 8-10 days before the. Standing adult molt, were topically treated with acetone solution in a concentration of 5 7 · The test animals were then kept at 28 ° C and 80-90 $ relative humidity. The Dysdercus fasciatus larvae received meal from pre-swollen cotton seeds as putters. After about 10 days, i.e. as soon as the control animals have fully moulted, the test animals were examined. Man found, 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). The special forms were non-viable stages of development in the normal development cycle cannot be found. The following table shows the number of normal adults, which were at the specified concentration. 309810/1 1 51 if, link Dysdercus fasciatus
Number of Norraa adults 1- (4-propargyloxy -) - phenoxy-6,7-epoxy-
317-dimethyl-2-octene 0 1- (4 ~ propargyloxy) -phenoxy-6 , 7-epoxy-
3,7-diethyl-2-nonene 0 1- (4-propargyloxy) -phenoxy-6,7-epoxy-
3,7-dimethyl-octane 0 1- (4-propargyloxy) -phenoxy-3i 7-
diraethyl-2,6-octadiene 0 1- (4-propargyloxy) -phenoxy-3,7-
dimethyl-6-octene 0 Farnesyl acid methyl ester
(known from J.Insect.Physiol. JL ^
(1) 72-94 (1969) 8th 3098 10/1151