DE2166152C3 - Propargyloxyphenyl terpene ether - Google Patents

Description

D-CH ₂ -C = CH (D

H ₃ CZ ₁ '

0-CH ₂ -C = CH (Π)

No. ₄ 35

in which Ri is methyl or ethyl and Z ' ₂ and Z' _{2 are} a carbon-carbon bond or an oxygen in which bridge.

The preparation of the compounds of formula I Zi and Z ₂ together form a carbon-carbon bond in a manner known per se by means of the following

formation or an oxygen bridge, reactions, preferably with equimolecular men-

R ₁ and R _{2 are} each methyl or ethyl, the starting compounds; as desired can Z ₃ and Z4 together form a carbon-carbon bond, however, an excess of one or more of the

application or one hydrogen atom or one of the reactants involved:

A / \ A / \ A

H ₃ CX + HO

O-CH ₂ -C = CH

H ₃ C

R ₂

base

H, C

O-CH ₂ -C = CH

selective epoxidizing agent

H, C

Q-CH ₂ -C = CH

Q-CH ₂ -C = C

Ai / \ X / \

H ₃ CX -I- HO

Q-CHj-C = CH

base

R.

H ₃ C

Ο — CH ₂ -C = CH

X + HO

^R i ^R :

O-CH ₂ -C = CH

Acid acceptor

5) R ₁

H ₃ C

- »H ₃ C
Ο — CH ₁ -C =

X + HO

H ₁ C

Acid acceptor

Ο -CH ₂ -C = CH

Q-CH ₂ -C = CH

Epoxidizing agents

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

Reactions 2) and 6), i.e. H. the conversion of the terpenoid aryl ethers into their 6,7-epoxy derivatives, are preferably cooled in an inert solvent such as a chlorinated hydrocarbon, with an epoxidizing agent, e.g. B. carried out a peracid. When using a mole of a peracid are due to steric factors

Q-CH ₂ -C = CH

H, C

mainly the 6,7-epoxy derivatives formed The 6,7-epoxy derivatives can also be used with N-bromosuccinimide in a mixture of water with a solvent such as tetrahydrofuran, 1,2-dimethoxyethane, or dioxane tert.ButanoI in homogeneous or heterogeneous phase and

subsequent treatment of the intermediate bromohydrin with an alkaline agent such as Alkali carbonate, alkali hydroxide or an alkali alcoholate can be obtained. Among alkali are in particular Understand sodium and potassium.

The term "peracid" primarily refers to lower peroxyalkanoic acids with 1 to b carbon atoms, such as peracetic acid and aromatic peracids such as perbenzoic acid, monoperphthalic acid, especially but understood m-chloroperbenzoic acid. As a basic

Reagents *. For converting a bromohydrin into the 6,7-epoxy derivatives come alkali carbonates, alkali hydroxides and alkali alcoholates into consideration.

The implementation according to Geleichu.ig 5), d. H. z. B. the Reaction of a nonallylic aliphatic halogen

Nids with a desired phenol is preferably carried out in the presence of at least one mole of an alkali or Alkaline earth carbonates and in the presence or absence of a catalytic 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 metal hydroxide a solvent such as dimethylformamide, dimethyl sulfoxide, sulfolane or 1,2-dimethoxyethane between 0 and 100 ° C.

OH Another synthesis variant is the implementation of a 1- (4-Hydroxy) -phenoxy-3,7-dialkyl-2,6-octa- or nonadiene with a propargyl halide (in the presence a base, e.g. B. of a tertiary amine, of alkali carbon ■ natcn or alkali hydroxides), to a phenol diether of formula I should be emphasized:

O -C ^- H, - C = CH

H., C

C)

Analogously, the! - ("l-llydroxyl-phnoxy-.lT-diilkyl-fi-octcn- or o-noncn-compounds to phenol. diiithers. implemented.

R.

Orthoptera

Isoptera
Hemiptera

Acrididae

Gryllidae

Blattidae

Kalotermitidae

Miridae

Piesmidae

Lygaeidae

Pyrrhocoridae

Pentatomidae

Cimicidae

Reduviidae

Jassidae

Eriosomatidae

Leccaniidae

R.

R.

0 --- C ¹ H, C = CH

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

In the preparation of the compounds of the formula I, the compounds used for the synthesis are formed as a result Allyl halides all possible geometric isomers. Make the connections described 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 species vegetable pests, in particular for combating insects. Unlike most of the previous ones known insecticides which, as contact or food poisons, quickly kill, paralyze or drive away the animals, the active ingredients of the formula I influence their development.

In the case of insects, for example, the moulting (in the case of hemimetabolites) or the transformation into an imago (with holometabols) disturbed. The generation sequence is interrupted and the animals thus become indirect killed. The compounds of the formula I are practically non-toxic for warm-blooded animals. Also, these Connections are easily broken down, so no accumulation is possible.

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

Coleoptera

Lepidoptera

Diptera

C)

Carabidae

Elateridae

Coccinellidae

Tenebrionidae

Dermestidae

Cucujjidae

Chrysomelidae

Curculionidae

Scolytidae

Scarabaeidae

Pyralidae

Phyticidae

Pyraustidae

Crambidae

Tortricidae

Galleriidae

Lyonetriidae

Yponomeutidae

Pieridae

Plutellidae

Lymantriidae

Noctuidae

Culicidae

Simuliidae

Tipulidae

The compounds of formula I can stand alone or together with suitable carriers and / οί'.τ aggregates. Suitable carriers and aggregates can be solid or liquid and correspond to those customary in formulation technology Substances, e.g. B. natural or regenerated substances, solvent, dispersing, wetting, adhesive, thickening, Binders and / or fertilizers.

For application, the compounds of the formula can be used to form dusts, emulsion concentrates, granules, Dispersions, sprays, solutions or slurries in the usual formulation used in application technology is part of general knowledge. Furthermore, there are "cattle dips", i. H. Cattle baths, and Mention should be made of “spray races”, i.e. spray courses in which aqueous preparations are used.

The means according to the invention are produced in 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 which are inert towards the active ingredients or solvents. The active ingredients can be in the following working-up forms and can be used:>

fixed forms of processing:

Dusts, grit, granulates (coating granulates, impregnation granulates and homogeneous granulates);

liquid processing forms: '"

a) Active substance concentrates dispersible in water:
Wettable powders, pastes, emulsions;

b) Solutions:

For the production of solid reprocessing forms (dusts, grit), the active ingredients are treated with '' mixed solid carriers.

Granules can be produced very easily by adding an active ingredient of the formula I to an organic Solvent dissolves and the solution thus obtained on a granulated mineral, for. B. attapulgite, SiO ?, granicalcium, Applies bentonite and then evaporates the organic solvent again.

It is also possible to prepare polymer granules by using the active ingredients of the formula I with> -> polymerizable compounds are mixed (urea / formaldehyde; dicyandiamide / formaldehyde; Melamine / formaldehyde or others), after which a gentle polymerization is carried out from the the active ingredients remain unaffected, and still jo granulation is carried out during gel formation. It is cheaper to use ready-made porous polymer granules (Urea / formaldehyde, polyacrylonitrile, polyester and others) with a certain surface and favorable, predeterminable adsorption zOesorp- r, tion relationship with the active ingredients z. B. in the form of their solutions (in a low-boiling solvent) impregnate and remove the solvent.

Granules are also available by COMPACTER the support material with the active compounds and additives and w followed by shredding.

These mixtures can also contain additives stabilizing the active ingredient and / or non-ionic, anion-active substances and cation-active substances are added, which, for example, affect the adhesive strength of the active substances Improve plants and parts of plants (adhesives and adhesives) and / or better wettability (Wetting agents) and ensure dispersibility (dispersants).

Active ingredient concentrates dispersible in water, d. H. in Wettable powders, pastes and emulsion concentrates are agents that can be mixed with water to any desired level Concentration can be diluted. They consist of an active ingredient, a carrier and, if appropriate, the active ingredient stabilizing additives, surface-active substances and anti-foaming agents, and optionally Solvents.

The wettable powders and pastes are obtained by mixing the active ingredients with dispersants and powdery Carriers mixed and ground in suitable devices until w> to homogeneity.

The active ingredients are mixed, ground, sieved and passed with the additives in such a way that the The solid part has a particle size of 0.02 to 0.04 for wettable powders and not 0.03 mm for pastes For the production of emulsion concentrates and pastes, dispersants, organic Solvents and water used Examples of solvents are alcohols, benzene, xylenes, Toluene, dimethyl sulfoxide and in the range of 120 and 350 ° C boiling mineral oil fractions in question. the Solvents have to 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. To do this, the active ingredient or are several active ingredients of general formula I in suitable organic Solvents, solvent mixtures or water. The organic solvent used can be aliphatic e and aromatic hydrocarbons, their chlorinated derivatives, alkylnapthalenes, mineral oils alone or used 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 when applying from an airplane or by means of other suitable application devices, concentrations of up to 99.5% or even more pure Active ingredient can be used.

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 dispersed silica
97 parts of talc

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

granules

The following substances are used to produce 5% granules:

5 parts of active ingredient
0.25 part epichlorohydrin
0.25 part of cetyl polyglycol ether
3.50 parts poly ethylene 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 is Polyethylene glycol and cetyl polyglycol ether added. The solution obtained in this way is sprayed onto kaolin and then the acetone evaporated in vacuo.

Wettable powder

The following ingredients are used to produce a) 40%, b) and c) 25%, d) 10% wettable powder used:

a) 40 parts of active ingredient

5 parts of lignin sulfonic acid sodium salt
1 part dibutylnaphthalenesulfonic acid sodium

salt
54 parts of silica

b) 25 parts of active ingredient

4.5 parts calcium lignosulfonate

13 parts of champagne chalk / hydroxyethyl cellulose mixture (l : 1)

1.5 parts of sodium dibutyl naphthalene sulfonate
194 parts of silica
19.5 parts of Champagne chalk
28.1 parts of kaolin

Active ingredient Isooctylphenoxy-polyoxyethylene-etha- nol Champagne chalk / hydroxyethyl cellu- Iose mixture (l: 1) Sodium aluminum silicate Kieselguhr Kao'in Active ingredient Mixture of the sodium salts of saturated ten fatty alcohol sulfates, Naphthalenesulfonic acid / formaldehyde Pv (Jl IUC I ι Λα I
kaolin c) 25 parts 2.5 parts 1.7 parts 8.3 parts 16.5 parts 46 parts d) 10 parts 3 parts 5 parts 82 parts

The active ingredients are intimately mixed with the additives in suitable mixers and mixed with the appropriate Grind mills and rollers. You get wettable powders, which can be mixed with water to form suspensions allow to dilute the desired concentration.

Emulsifiable concentrates

The following substances are used to produce a) 10% and b) 25% emulsifiable concentrate used:

a) OK parts Active ingredient 3.4 parts epoxidized vegetable oil 3.4 parts of a combination emulsifier, best starting from fatty alcohol polyglycol ether and Alkyl aryl sulfonate calcium salt 40 parts Dimethylformamide 43.2 parts Xylene b) 25 parts Active ingredient 2.5 parts epoxidized vegetable oil 10 parts of an alkylarylsulfonate fatty alcohol poly glycol ether mixture 5 parts Dimethylformamide 57.5 parts Xylene

Any desired emulsions can be obtained from such concentrations by dilution with water Concentration can be established.

Sprays

The following ingredients are used to make a 5% spray:

5 parts of active ingredient
1 part epichlorohydrin
94 parts gasoline (boiling limits 160-! 90 ⁰ C)

Other biocidal active ingredients or agents can be admixed with the agents described. So can the new ones Agents other than the compounds of general formula I mentioned, for example insecticides, fungicides, Bactericides, fungistats, bacteriostats, nematocides or contain herbicides to broaden the spectrum of activity.

example 1

. la) To a solution of 15.2 g of 4-Propargyloxyphenol (bp 92-93 ° C / 0.04 torr; η Γ: 1.5625) in 15OmI pure 1,2-dimethoxyethane was added 21.7 g of L- Bromo-3,7-dimethyl-2,6-octadiene and then immediately began at 20-22 ⁰ C with stirring with the dropwise addition of 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 base addition was 16 hrs. At room temperature v, stirred -jiter, then heated for one hour at 70 ⁰ C, then cooled and filtered from the precipitated potassium bromide. 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% strength aqueous potassium hydroxide solution and then with water until neutral. The organic phase was dried over sodium sulfate and the solvents in

distilled off in vacuo. The remaining 1- (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). η : 1.5316. This ether can also be produced by high vacuum

r> distillation.

Analogously to example la), l- (4-propargyloxy) phenoxy-3,7dimethyl-2,6-nonadiene can be prepared from 4-propargyloxyphenol and l-bromo-3,7-dimethyl-2,6-nonadiene (n : 1.5301).

2 (i The one for the preparation of 1- (4-propargyloxy) -phenoxy-3,7-dimethyl-2,6-octadiene The 4-propargyloxyphenol used can be prepared as follows:

To the mixture of 220 g of hydroquinone, 305 g of anhydrous potassium carbonate, 7.3 g of finely powdered

r, potassium iodide in 700 ml of acetone, under a nitrogen atmosphere, 165 g were added dropwise with stirring at the boiling point of acetone within 2 hours Propargyl chloride. The mixture was then refluxed for a further 14 hours. Then the

jo reaction mixture diluted with 800 ml of acetone, clear filtered 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 sulphate

jj fat and with the addition of some activated charcoal was filtered off, the filtrate in vacuo from the solvent freed and the residue dissolved in 1000 ml of ether. The ether solution was three times with 200 ml of 30% ice-cold caustic soda and then twice with water

4 (washed i. The combined aqueous alkaline phases it was then washed twice more with a little ether. The aqueous alkaline phase, which the sodium idl of the

T-r ι υμαι gjri-OAjjJiicnOiä cüiiiäii, iiCu ΪΤιοΓ »ΓιϋΓι Ur.tCT

vigorous stirring to the mixture of 1000 ml

4> chloroform, 1kg ice and 600 ml more concentrated Hydrochloric acid flow in. The phases were separated, the aqueous hydrochloric acid phase again with chloroform washed, the combined chloroform phases washed briefly with water, over sodium sulfate

dried in and the solvent was distilled off. The residue was then fractionated in vacuo distilled, whereby the colorless 4-propargylphenol from Bp 92-93 ° C / 0.04 torr.

Ib) To a mixture of 16.4 g of 1- (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 under a nitrogen atmosphere 9.6 g propargyl bromide dripped within 30 minutes After the addition of the propargyl bromide

b0 mids were refluxed for a further 8 hours. To the Work-up was filtered off from the sediment, the filter residue washed out repeatedly with diethyl ether and the filtrate was freed from the solvents in vacuo. The oily residue was dissolved in diethyl ether-hexane (1: 4) added, washed three times with 10% potassium hydroxide solution and then with water. After drying the organic phases over sodium sulfate and suctioning off the solvent in the

The 1- (4-propargyloxy) -phenoxy-3,7-dimethyl-2,6-octadiene was further purified in vacuo as indicated under section a), η : 1.5315.

The 1- (4-hydroxy) -phenoxy-3,7-dimethyl-2,6-omdiene used as the starting product in example b) can be prepared as follows: Added dropwise to a solution of 165 g of hydroquinone in 2000 ml of 1,2-dimethoxyethane 326 g of l-bromo-3,7-dimethyl-2,6-octadiene and the solution of 95 g of approx. 90% potassium hydroxide in 1200 ml of absolute ethanol are added evenly from two dropping funnels while stirring at room temperature, in such a way that the reaction mixture always reacted slightly alkaline. The mixture was then stirred at room temperature for 5 hours and at 50 ^° C. for a further 3 hours. The entire reaction was carried out under a nitrogen atmosphere.

After the reaction mixture had cooled down from the precipitated potassium bromide, it was worked up filtered off, the solvent removed in vacuo, the residue taken up in 1600 ml of η-hexane and extracted four times Tiit approx. 200 ml of 20% strength aqueous potassium hydroxide solution. The combined aqueous alkaline phases it was washed twice with a little η-hexane. Then the aqueous alkaline solution with about 1500 ml Diluted water and exhaustively extracted with diethyl ether. The combined essential extracts were washed with very little water, dried over sodium sulfate and the ether was distilled off. What remains after some time, 1- (4-hydroxy) -phenoxy-3,7-dimethyl-2,6-octadiene solidifies in a crystalline manner was distilled for further purification in vacuo (boiling point: 140-142 ° C / 0.05 Torr) and then from pentane crystallized. M.p. 45-47 ° C.

Ic) The solution of 4.1 g was added to a solution of 5.77 g of 1- (4-propargyloxy) phenoxy-3,7-dimethyl-2,6-octadiene in 55 ml of dichloromethane at -2 to 0 ° C. with stirring 86% m-chloroperbenzoic acid in 40 ml of a dichloromethane-ether mixture (9: 1) was added dropwise within 4 hours. After stirring for a further 14 hours at 0 to 2 ° C., the reaction mixture was diluted with η-hexane, washed three times at about 5 ° C. with 40 ml of 10% strength aqueous potassium hydroxide solution and then with water until neutral. Nacn ucni l fm-Micu uci vjtganiSCucii ι uüSC over sodium sulfate, the solvent was distilled off in vacuo and the product was purified by chromatography on silica gel (activity III) (eluent for diethyl ether-hexane 1: 3) whereby the pure, colorless l- (4- Propargyloxy) phenoxy-6,7-epoxy-3,7-dimethyl-2-octene, η : 1.5263.

Example 2

A mixture of 18.7 g of l-bromo-SJ-dimethyl-ö-octene, 11.2g 4-propargyloxyphenol, 12g anhydrous, powdered potassium carbonate, 1 g of finely powdered potassium iodide and 60 ml of methyl ethyl ketone was 48 hours. stirred at 70 g. Thereafter, the reaction mixture was

filtered off, the filtrate concentrated, then with IO% ice-cold potassium hydroxide solution and then washed neutral with water. After drying the organic phase over sodium sulfate, the solvent was distilled off in vacuo and the 1- (4-propargyloxy) phenoxy-3,7-dimethyl-6-uctene purified by chromatography on silica gel. Eluent: diethyl ether-hexane 1:10). π: 1.5142.

The l- (4-propargyloxy) -phenoxy-3,7- <dimethyl-6-octene obtained in this way can be converted into l- (4-propargyloxy) -phenoxy-6,7-epoxy with 3-chloroperbenzoic acid analogously to Example 2 3,7-dimethyloctane are transferred, (n : 1.5115).

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

O CH, -Ch-CH

H, CZ ₁

Z, O

(C-C— means carbon-carbon combination: - O - oxygen bridge.

Ri JiI C ₂ II, R ₂ Z ₁ ; Z ₂ Zj: Z ₄ Physical 1.530! C ₂ H ₅ data 1.5245 CH, 1.5143 I, CII, -C-C- -C-C- »■ ο ■ 1.5115 CH., -O- -C-C- nil ' : CH, -C-C- Zj = H: Z ₄ = II ng : CII, -O- Z, = H; Z ₄ = H n% ' :

The experiments described below show the effect of the compounds of the formula I.

1) 10 larvae of Dysdercus fasciatus, the 8-10 days before

.40 of the adult moult were topically treated with acetone solution in a concentration of 5 γ. The test animals were then at 28 ° C and

Ov / —WfU iciauvci i_iuiiicu \ .imgficii gciiaiicn. / -via J'ulici

received the Dysdercus fasciatus larvae 'v'hrot from

• n pre-soaked cottonseed.

After about 10 days, i.e. H. once the control animals had fully moulted, the test animals became examined Besides normal adults and dead larvae, special forms such as extra larvae (larvae with an additional larval moult) and adultoids (adults with larval characteristics). With the special forms they were non-viable developmental stages that did not occur in the normal development cycle are found.

The following table shows the number of normal adults in the specified Concentration found:

link

Active ingredient - Dysdercus fasciatus
amount in y _{A ß}

1 - ^ - PropargyloxyJ-phenoxy-oJ-epoxy-

3,7-dimethyl-2-octene

M4-propargyloxy) phenoxy-6,7-epoxy-3,7-dimethyl-2-nonene

Definition link

Active ingredient Dysdercus fasciatus amount in y _A "~

r \ ρ L

H4-propargyloxy) phenoxy-6,7-epoxy-5 3,7-dimethyl-octane 0.5

Control -

2) Each 10 fresh pupae from Dermestes lardarius were topical with active ingredient solutions in acetone Treated The pupae were then kept at 28 ° C and 80-90% relative humidity.

After about 10 days, i.e. H. as soon as the control animals are When adults had left the doll shell, they became the Test animals examined In addition to normal adults, adultoids were found on dead pupae (adults with

10

Larval characteristics).

The adultoids are non-viable stages of development that occur in normal Development cycle cannot be found.

A = normal adults Dolls.

Adultoide D = dead link

Active ingredient Dermestes Lardarius amount in γ. ~

l- (4-Propargy! oxy) -phenoxy-6,7-epoxy- 5 1 10 3J-dimethy! -2-octem 0.5 9 1- (4-propargyloxy) -phenoxy-6,7-epoxy- 5 10 3,7-dimethyl-2-nonene 0.5 1 10 l- (4-propargyloxy) -phenoxy-6,7-epoxy- 5 9 3,7-dimethyl-octane 10 control _

3) 10 fresh Tenebrio molitor dolls were treated topically with active ingredient solutions in acetone Dolls were then kept at 28 ° C and 80-90% relative humidity.

After about 10 days, i.e. H. as soon as the control animals the -to When adults had left the pupae, the test animals were examined. One found next to normal Adults and dead pupae adultoids (adults with

Larval characteristics).

The adultoids are viable stages of development that occur in the Development cycle cannot be found.

to not normal

A = normal adults Dolls.

C - = Adultoide D - dead link

WirkstolT- Tenebrio molitor amount in γ A. C. 5 8th 0.5 10 5 10 0.5 10

I - (4-propargyloxy) phenoxy-6,7-3,7-dimethyl-2-nonene

1- (4-propargyloxy) phenoxy-6,7-epoxy-3.7-dimethyl-2-octene

control

10

4) 10 fresh pupae of Leptinotarsa decemlineata were given topical solutions in acetone treated. The dolls were then kept at 28 ° C and 80-90% relative humidity.

After about 10 days, i.e. H. as soon as the control animals die When the adults had left the doll envelope, the test animals were examined. One found next to normal Adults and dead pupae adultoids (adults with

Larval characteristics).

The adultoids are non-viable stages of development that occur in normal Development cycle cannot be found.

A - normal adults Dolls.

Adultoide D - dead

030 238/117

21
17th 66 152 Leptinotarsa
A. 18th D. Active fault
amount in j> clecemlineata
C. ! H4-propargyloxy) -phenoxy-6,7-epoxy-
3,7-dimethyl-2-octene 5
0.5 9
8th

control

Test report

10 larvae of Dysdercus fasdatus, which are 8-10 days before adult moult, were topically treated with acetone active ingredient solution in a concentration of 5 y. The test animals were then kept at 28 ° C. and 80-90% relative humidity. The Dysdercus fasciatus larvae received meal of pre-swollen cottonseed as food.

After about 10 days, i.e. H. as soon as the control animals die Have completed adult moult, the test animals were examined. One found in addition to normal adults and Dead larvae special forms such as extra larvae (larvae with an additional larval moult) and aduitoids (Adults with larval characteristics). The special forms were non-viable stages of development that did not occur in the normal development cycle are found.

The following table shows the number of normal adults in the specified Concentration found.

link

Dysdercus fasciatus Number of normal adults

H4-propargyloxy) phenoxy-6,7-epoxy-3,7-dimethyl-2-octane 1- (4-propargyloxy) phenoxy-6,7-epoxy-3,7-dimethyl-2-nonene i-14-propargy! oxy) -phenoxy-o, 7-epoxy-3,7-dimethyl-octane 1 - (4-propargyloxy) phenoxy-3,7-dimethyl-2,6-octadiene 1- (4-propargyloxy) phenoxy-3,7-0 dimethyl-6-octene

Farnesyl acid methyl ester

so (known from J. Insect. Phy siol. 15 [1] 72-94 (1969])

Claims (4)

Patent claims:
I. Propargyloxy terpene ether of the general formula O — CH, - C = CH Ri R ₂ / ' / k / \ A / \ H ₃ CZ ₁ Z ₃ TO in which Z, and Z ₂ together are a carbon-carbon _{bond or an oxygen bridge, R 1} and R _{2 are} each methyl or ethyl, Z ₃ and Z ₄ together form a carbon-carbon bond or a hydrogen atom each or Z ₃ and Ζ »each mean a hydrogen atom. 2. H'l-propargyloxyJ-phenoxy-SJ-dimethyl-oJ-epoxy-octen- ^) of the formula O-CH ₂ -C = ECH CH ₃ CH. " H ₃ C ₀ 'O 3. 1- (4-propargyloxy) -phenoxy-3,7-dimethyl-6,7-epoxy-nonene (2) of the formula O-CH ₂ -C = CH C ₂ H ₅ CH ₃ H ₃ C 4. Process for the preparation of compounds according to claim I, characterized in that one a halide of the general formula in a manner known per se H ₃ CZ ₁ Z ₃ X Z ₂ Z ₄ in which R ₁ , R ₂ , Z ₁ , Z ₂ , Z ₃ and Z _{4 have} the meaning given in claim 1, and X denotes halogen, preferably chlorine or bromine, with hydroquinone mono-propargyl ether of the formula O-CH ₂ -C = HCH in the presence of an acid absorber or that one converts a phenol of the general formula OH HjC Z ₁ with a halide of the general formula X-CH ₂ -C = CH in which X is halogen, preferably chlorine or bromine, or that one is a compound the general formula Q-CH ₂ -C = CH in which R ₁ , R ₂ , Z ₃ and Z _{4 have} the meaning given in claim 1, is reacted with an epoxidizing agent in an inert solvent. 5. Insecticidal agent containing a compound according to claim 1 as an active ingredient. The invention relates to Propargyloxyphenylterpen- 20 Zi, Z2, ether, their production and means for influencing Z ₃ and Z ₄ each mean a hydrogen atom. Development of insects that use these compounds as Contain active ingredient, according to the above patent, because of their effect are particularly noteworthy Sayings. the compounds of the general formula The new connections correspond to the general 25 a formula