DE2000274A1 - Methyl and Aethyl esters of 10-epoxy-7-ethyl-3,11-dimethyl-2,6-tridecadienoic acid and process for their preparation - Google Patents

Description

RING. F. WtTKSTStOVV

S MUNICH 90 SCHWEIGE RSTRASSE » 32 06 91

IHI. IKG. D. BKlIRSXS FATBXTjHfVTiLTI

1E-57 272

Description of the patent application.

John Ä, Findlay, 682 George Street, Fredericton Province of New Brunswick _f Canada

concerning:

Methyl and ethyl esters of 1Q-epoxy-7-ethyl-3,11-dimethyl- _2T 6-tridecadienoic acid and process for their preparation,

The invention relates to a process for the preparation of the methyl and ethyl esters of 10-epoxy-7-ethyl-3,11-dimethyl-2,6-tridecadienoic acid and to the intermediates used in this preparation. The methyl and ethyl esters of 1O-epoxy-7-ethyl-3 _J-11 diiaethyl _2-l 6-tridecadiensäurenach of the invention may by the formula

COQH:

I.

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are reproduced, in which R denotes the methyl group or the ethyl group.

The compound of formula I in which R is the methyl group can occur in several isomeric forms, one of which is identical to the juvenile hormone, isolated by Roller et al. from Hyalophora eecropia (J. Insect Physiol. Vol. 11, p. 1185 (1965), Life Sci. Vol, 4, p. 1617 (1965) and Proceedings of the International Symposium on Insect Endocrinology, Brno, Czechoslovakia, 1966, Academic Press Inc., New York) and its constitution was elucidated by Roller et al. (Angew. Chem. Intern. Ed. Engl. Vol. 6, p. 179 (1967).

Pas from Roller et al. isolated juvenile hormone is of particular Interest because it evidently shows the maturation and normal development of the sexually mature insect (Imago) controls from the larva. In the normal life cycle of the insect, the juvenile hormone must be in the immature stage that is, young larvae must be present if they are to go through the normal stages of larval development. However, may the juvenile hormone will no longer be present when the raw, i.e. old, larva has metamorphosed into sexually mature Insect is supposed to go through. The presence of the juvenile hormone at this stage of development of the insect prevents this Formation of the sexually mature animal capable of reproduction and when the eggs come into contact with the juvenile hormone advised, normal embryonic development is prevented. These facts are of great importance in combating of insect populations and to date five different synthesis options for the juvenile hormone are known become:

-j-

⁰⁰⁸¹² »'"' * ORK ₃ (NAL

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Dahm et al., J. Am. Ghem. Soo. Vol. 89, p. 5292 (1967); Dahm et al., Life Sci. Ed. 7, p. 129 (1968)} Corey et al., J. Am. Chem. Soc. Vol. 90, p. 5618 (1968); Zurflüh et al., Ibid. 90: 6224 (1968) Johnson et al., Ibid. "Vol. 90, p. 6225 (1968)

The aim of the invention is a simpler and more effective process for the preparation of the juvenile hormone and its ethyl analogue.

The compounds of the formula I according to the invention have the biological effectiveness of the juvenile hormone and are useful means for the control of insect populations a .. In particular, these compounds show when they are according to the pharmacological methods customary in enthymology Tests are checked, for example according to the modified Tenebrio test, as described by Roller et al. in Life Sei. Vol. 4, P. 1617 (1965) describes the expected useful activity of the juvenile hormone. The compounds according to the invention of Formula IX (below) show the same type of biological activity, but somewhat less Dimensions. After administration to test insects in the manner described above, the compounds of the present invention act of formulas I and IX the formation of a typical doll skin over the area of the shelf.

For the control of insect populations you can use the compound grues Compounds of the formula I in the form of liquid sprays, or dissolved in appropriate solvents are used, for example lipophilic solvents such as vegetable or mineral oils are suitable for this or hydrocarbon solvents, excluding those

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Hydrocarbon solvents that are less than 7 carbon atoms show ^ or solvents which both have lipophilic and hydrophilic properties, for example lower aliphatic ketones or polyvalent ones Alcohols} the active ingredients can also be dissolved in a lipophilic solvent as indicated above and then together with appropriate surface-active agents, such as emulsifiers and / or detergents and other suitable agents Excipients are brought in the form of aqueous emulsions. You can also get them in the form of dusts use in conjunction with suitable solid supports. All of these agents can contain 0.1 to 100 mg of active ingredient per 1 liquid preparation or per kg of solid preparation and are based on that of Insect infested areas or plants applied.

According to the invention, the compounds of the formula I are prepared as follows: 3 ~ methyl-1-penten-3-ol (II), obtained from 2-bitanone and sodium acetylide and subsequent partial reduction, is mixed with ethyl vinyl ether to give the corresponding o & Ethoxyethyl ether (III) condensed. This is heated with a catalytic amount of phosphoric acid and provides 5-methyl-4-hepten-1-al (IV), this aldehyde is reacted with an ethylmagnesium halide Eum 7-methyl-6-nonen-3-ol (V), which in turn eu 7-meth _v l-6-nonen-3-one (VI) is oxidized. This ketone is treated with the ylide, which is formed from 4-oxopentyl-1-triphenylphosphonium iodide-ethylene ketal (VII) with the aid of sodium methylsulfynyl-carbanion produced from sodium hydride and dimethyl sulfoxide, and after cleavage of the shielding ketal group 6 provides -Athyl-1O-methyldodeca-5i9-dien-2-one (VIII). The 4-oxopentyl-1-triphenyl-phosphonium iodide-ethylene ketal used here is produced from 5-chloro-2-pentanone: this is

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next converted into 5-iodo-2-pentanone; this will be with Ethylene glycol converted to 5 ~ iodine-2-pentanone-ethylene ketal, which on treatment with Triphenylphosphi'n the desired 4-oxopentyl-1-triphenylphosphonium iodide-ethylene ketal gives. .

The 6-ethyl-10-methyldodeca-5- _t 9-dien-2-one (VIII) obtained is treated with the anion obtained from a dialkylcarbomethoxymethyl or a dialkylcarbethoxymethyl phosphonate containing 1-4 carbon atoms in the alkyl groups. These latter compounds are conveniently prepared from methyl or ethyl chloroacetic acid ester and de :, corresponding trialkyl phosphite, the alkyl groups of which each contain 1-4 carbon atoms, and the anion of these compounds is prepared with the help of an alkali metal alcoholate containing 1 to 4 carbon atoms or with the help of a Alkali hydride obtained. The reaction gives methyl or ethyl 3,11-dimethyl-7 ~ ethyl trideca-2,6,10-trienoate (IX); these compounds are converted into the corresponding 10-epoxy derivatives with a K-halosuccinimide and then with alkali isopropylate, resulting in the corresponding methyl or ethyl 1O-Bpoxy-7-ethyl-2,1,1-dimethyl-2,6-tridecanedienoate (I).

The compounds according to the invention can, as is readily apparent, occur in numerous isomeric forms, The invention does not relate to the separation of these isomers, which is carried out in a manner familiar to the person skilled in the art can be.

The main advantage of the method according to the invention lies in that commercial starting substances are used as the starting point, the desired end products in good yield can be obtained and the synthesis involves relatively few steps

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includes, in contrast to the methods previously described in the literature. In view of the great importance of insect hormones, especially the juvenile hormone, as Means for controlling insect populations provides a practical manufacturing method, as is shown in the the following will be described in more detail, special advantages.

According to the invention, 3-methyl-1-penten-3-ol of the formula II is obtained by reacting 2-butanone with sodium acetylide in liquid ammonia and then reducing the acetylenic alcohol obtained, 3-methyl-1-pentyn-3-ol with hydrogen and Lindlar's catalyst, described in HeIv. Chim. Acta, Vol. 35, p. 446 (1952), condensed with ethyl vinyl ether in molar excess in the presence of phosphoric acid. Preferably, in this reaction with 88% commercial phosphoric acid in catalytic amounts of about one part per 250 parts of alcohol, a molar ratio of 3-methyl-1-penten-3-ol to ethyl vinyl ether of about 1: 2, at temperatures of 40 ⁰ C to the boiling point of the mixture and with reaction times of 2 to 24 hours.

In this way the ct. Ethoxyethyl ether of 3-methyl-1-penten-3-ol of the formula III obtained, which is purified by distillation.

This latter compound is heated in a closed vessel in the presence of catalytic amounts of phosphoric acid and provides 5-methyl-4-hepten-1-al of the formula IV Parts of the CM-Ä'thoxyäthyläthers of 3-methyl-1-penten-3-ol used, worked at temperatures in the range of 100-200 ⁰ C and reaction times of 5-60 min. The connection you want

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remains in the residue after the reaction mixture has been neutralized and the highly volatile components have been stripped off. It can be purified by distillation, but this cleaning is not required and the compound may as obtained from the reaction mixture immediately so, will continue to _use% n.

5-Methyl-4-hepten-1-al · is used with a Grignards reagent for Brought implementation, made from an ethyl halide, preferably ethyl bromide and magnesium in diethyl ether has been; the Grignard adduct obtained is decomposed with ammonium chloride in the usual way and the reaction mixture undressed with ether. The ether extracts are washed with water and dried and the solvent is evaporated; it remains 7-methyl-6-nonen-3-ol of the formula V, which without further purification can be used in the following stage.

The compound V is oxidized to 7-methyl-6-nonen-3-one of the formula VI. Preferably this 8nChromsäure a trace of sulfuric acid in acetone solution (Jones' reagent) temperatures are 0 applied to 3O ⁰ C and reaction times of 0.5-24 hours containing. To isolate the compound from the reaction mixture, it is diluted with water, extracted with ether, the ether extracts are washed neutral, dried and the solvent is evaporated. The purification is preferably carried out by chromatography, in particular on silica gel.

The 7-methyl-6-nonen-3-one obtained is made with the 4-Oxopentyl-i-triphenyl-phosphonium-iodide-ethylene ketal der Formula VII treated ylide which is obtained by containing the latter compound with an alkali metal alcoholate 1 to 4 carbon atoms or treated with an alkali hydride in a common solvent. That

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^ -Oxopentyl-i-triphenylphosphonium iodide-ethylene ketal is prepared by first adding commercially available 5-chloro-2-pentanone in a solvent with a molar Excess of sodium iodide ^ * the corresponding 5-iodo-2-pentanone is implemented. Preferably, three equivalents of sodium iodide are used in this reaction, as Acetone solvent is used and the mixture is refluxed for 0.5 to 2 hours.

The 5-iodo-2-pentanone obtained is ketalized by adding it to "a water-immiscible solvent." a molar excess of ethylene glycol in the presence Treated a small amount of an acid catalyst and the water formed continuously from the reaction mixture is separated. Preference is given to three equivalents of ethylene glycol and 0.1 equivalent of p-toluenesulfonic acid used, benzene as solvent and a water separator used as part of the device and the reaction mixture Refluxed for 8 to 24 hours.

5-iodo-2-pentanone äthylenketal is reacted with a molar excess of triphenylphosphine at temperatures of 50 to 15O ⁰ C in an inert solvent to give 4-oxopentyl-i-triphenylphophoniumiodid äthylenketal. Preferably, 1.1 equivalents of triphenylphosphine and benzene are used as the solvent and the reaction is carried out at the reflux temperature of the mixture, whereupon the desired compound crystallizes out of the reaction mixture in sufficient purity for immediate further use.

In the above reaction, the ylid is preferably prepared in situ in dimethyl sulfoxide solution by first adding about 1 mol equivalent of sodium hydride to an excess of the solvent, the sodium methyl

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Then a solution of 4-oxopentyl-i-triphenylphosphonium iodide-ethylene ketal in dimethyl sulfoxide is added under nitrogen at a temperature of 15 to 35 ° C. After stirring for 5 to 30 minutes, the desired ylide has formed. To this solution of the ylid, 0.5 to 1.0 molar equivalents, preferably 0.6 idol equivalents, of 7-methyl-6-notene-3-one "are added and the mixture is kept at temperatures from 2O ⁰ O to the boiling point of the mixture for 3 Stirred for 24 hours. It is then diluted with water, extracted with a water-immiscible solvent, preferably with n -]? Entane and the solvent is evaporated or drawn off, leaving a residue that is 6-ethyl-10-methyldodeoa-5,9 ~ dien-2-one ethyl ketal is identified. This compound is preferably not isolated, but the residue obtained is treated directly in an inert water-immiscible solvent, preferably in tetrahydrofuran with an acid, preferably dilute aqueous hydrochloric acid. The ketal group is split off and 6-ethyl-10-methyldodeca-5,9-dien-2-one of the formula VIII is obtained.

This compound is treated with the anion obtained from a dialkylcarbomethoxymethyl or dialkylearboethoxymethylphosphonate, preferably diethyl carbometboxymethyl phosphonate made from methyl chloroacetate and triethyl phosphite according to the P.O. Orofts in quart. Rev. Ohem. Soc., 12, 341 (1958) described method, by the action of about the equivalent amount of an alkali hydride in one inert solvents or duroh exposure to about the equivalent amount of a corresponding alkali metal alcoholate contain 1 to 4 carbon atoms in an inert solvent will be produced. This anion formation is preferred

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wisely caused by equivalent molar amounts of the corresponding dialkylcarbomethoxymethyl or dialkylcarbethoxymethyl phosphonate, preferably diethylcarbomethpxymethyl phosphonate, are mixed with sodium hydride in benzene and the reaction mixture is ^{stirred at temperatures of 10 to 50 0} C until the sodium hydride has dissolved. The alkyl groups of the above compounds contain 1 to 4 carbon atoms.

When W Zugahe of 6- ethyl-10-methyldodeoa-5,9-dien-2-one with the anion solution prepared as described gives the corresponding methyl or ethyl ester of 3,11-dimethyl-7-ethyl-1,6 trideca _T , 10-trienoic acid of the formula IX. If the anion formed from diethyl carbomethoxymethyl phosphonate is used as the reaction partner, methyl 3,11-dimethyl-7-ethyltrideca-2,6,10-trienoate is formed, while the anion formed from diethylcarbethoxymethylphosphonate produces ethyl 3,11-diraethyl-7 ethyl trideca-2,6,10-trienoate. Preferably, in this reaction, the reaction mixture at temperatures of 10-50 ⁰ C θ hours to 6 days is stirred, then diluted with water, extracted with a water-immiscible solvent and the crude compound ohromatographisoh, worzugsweise purified on Silioagel.

The methyl and ethyl esters of the formula IX can, if desired, are converted into one another: this is how methyl 3,11-dimethyl-7-ethyl-trideoa-2,6,10-trienoate is formed with a molar excess of an alkali hydroxide, preferably with 55 · Potassium hydroxide in methanol to give the free 3,11-dimethyl-7-ethyl-trideoa-2,6,10-triene acid hydrolyzed and theeae with Diazoethane to ethyl 3,11-dimethyl-7-ethyl-trideoa-2,6,10-trienoate interesterified. The same procedure can auoh

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can be applied to a given ester of the formula IX to clean. So if one of the impure methyl 1-3,11-dimethyl; * 7-ethyl-trideca-2,6,10-trienoate goes out, this hydrolyzed as above and treated the trienoic acid obtained with diazomethane, a pure sample of the methyl ester of the formula'IX obtained.

In the last stage of the synthesis according to the invention, the methyl or ethyl 3 »11-dimethyl-7-ethyl-trideca-2,6,10-trienoates are converted into the desired methyl or ethyl-10-epoxy-7-ethyl-3,11 -dimethyl-2,6-tridecadienoate of the formula I converted. For this purpose, the ersteren.Verbindungen are treated with a molar excess of N-halosuccinic acid imide in solution in a mixture of 1.5 to 4 parts of dimethoxyethane and one part of water, then the reaction product is treated with a molar excess of an alkali isopropylate, all of these reactions at temperatures of from - 10 ⁰ C to + 1O ⁰ C and reaction times of 20 to 120 minutes according to the above-mentioned procedure of Corey et al. be performed. Preference is given here to using 1.1 equivalents of N-bromosuccinic acid imide, a 3: 1 mixture of dimethoxyethane and water as solvent and 1.2 equivalents of sodium isopropoxide, and reaction ^{temperatures close to 0} ° C. and reaction times of 60 min. The desired methyl or ethyl esters of 10-spoxy-7-ethyl-3,11-dimethyl-2,6-tridecadienoic acid obtained are preferably purified by chromatography on silica gel or clay.

The invention is illustrated further by the following formulas _v and examples,

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II.

VI.

acetone

EtMgBr, ether

.

IV;

1) NaH, DMSO

2) H ⁺ , XHF

• I ^vm

NaH, benzene, (E tO), PCH ₉ COOR

Ii

COOR

IX.

COOR

974

Et = C ₂ H ₅ - 12-

1A-37 272

example Λ_

A) 3-methyl-1-pentyn-3-ol

A solution of 27.6 g of sodium in 2 1 of liquid ammonia was saturated with acetylene, the saturated solution was added 2-butanone 72.1 g in 300 car ether and the mixture was stirred for 8 hours at -40 to -35 ⁰ C ; the ammonia was then allowed to evaporate. The residue was diluted with water, extracted with ether, the ether solution was washed, dried and evaporated; the residue was distilled ■ Λ and gave the title compound, which was at 121 ⁰ C.

^C ^ 3600; 2970; 2930; 2875 cm "¹; T ^{0Ι> 01} 3 7.55; 8.35;

8.51; 8.96.

B) 3-methyl-1-penten-3-ol (II)

A solution of 9.8 g of 3-methyl-1-pentyn-3-ol prepared as above in an equal volume, petroleum ether, was mixed with 0.42 g of quinoline and 0.75 g of Lindlar catalyst. The mixture was shaken in a hydrogen atmosphere at atmospheric pressure for 18 hours, after which time hydrogen was taken up. The mixture was filtered and the solvent evaporated; Distillation of the residue gave the title compound with boiling point 116 ⁰ C ₅ ° V ^ _χ 3 3600; 2970; 2925; 2875; 1675 cm "! ^ CDCl _{3 4ι38} .4 _ι7 5. ^ _{91. 8t73; 9 | 13} .

C) a-ethoxyethyl ether of 3-methyl-1-penten-3-ol (III)

To a mixture of 25 g (0.25 mol) of 3-methyl-1-penten-3-ol and 38 g (0.53 mol) of ethyl vinyl ether was added 0.1 g of orthophosphoric acid. The mixture was refluxed 19 π, neutralized with 0.25 cnr triethylamine and reduced Distilled pressure; the title compound went at boiling point 7O.5 ° C /

x 3310; . _13th

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23 mm Hg about; -J ^ ax ^{3 2975; 2925; 287} ^ ^{; 1640; 1140; 11} ° ^5; 1075; 1040 cm ^"1;... ^ CDCl ₃ ^ ₇₅ ^ ₄₉ ^ ₆₉ g ^ _Jn one of these operation carried out according to test the yield was 91.2% of theory..

Example 2

5-methyl-4-hepten-1-al (IV)

13.1 g (0.076 mol) prepared according to Example 1 of the a-Äthoxyäthyläthers of 3-methyl-1-penten-3-ol were heated with a drop of 88% orthophosphoric acid in a sealed glass tube for 1/2 hour at 15O ⁰ C . The mixture was neutralized with 3 drops of triethylamine and evaporated under reduced pressure at room temperature; the title compound was obtained as a light yellow clear liquid with b.p. 60 to 62 ⁰ C / 14 mm Hg; V 5 ° Ϊ3 2960?; 2925; 2870; 2720; 1720;

ι PDC ¹ T max
1680 cm; - ^ ^X 3 0.29; 4.98; 8.41, and also detected by vapor chromatography. In an experiment carried out according to this procedure, the yield was 54.5% of theory.

Example 3

7-methyl-6-nonen-3-ol (V)

8.13 g (0.0644 mol) of 5-methyl-4-hepten-1-al prepared according to Example 2 was dissolved in 3 volumes of dry ether and added dropwise to one with cooling in an ice bath Grignard reagent prepared from 1.72 g (0.0708 mole) magnesium and 8.6 g (0.0779 mole) ethyl bromide was. The mixture was refluxed for 1 hour and then poured into an ice-cold solution of 5.7 β ammonium chloride in 150 cm * of water poured out. The ether layer was separated and the aqueous phase extracted twice with ether. The combined ether solutions were washed neutral, over anhydrous

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fsr

Sodium sulfate dried and evaporated; the title compound remained as a pale yellow liquid with a boiling point of 206 ^° C .; ^{0 CDG1}

g g g p

3620; 2970; 2940; 2875; 1660 cm "¹; * £ ^CDG1 3 4.90; 6, -50; 8.35; 9j04; m / e 156; 138. In an experiment carried out according to the above procedure, the yield was 95% of theory.

Example 4

7-methyl-6-nonen-3-one (VI)

1.0 g (0.0064 mol) of 7-methyl-6-nonen-3-ol prepared according to Example 3 was dissolved in twice the volume of acetone and the solution was cooled in an ice bath. Jones' reagent was added dropwise until an orange color persisted, the mixture was stirred in an ice bath for 1/2 hour, diluted with an equal volume of water and extracted 4 times with ether; the ether extracts were washed with 5% sodium bicarbonate solution, dried over anhydrous magnesium sulfate, filtered and evaporated; a clear, light yellow liquid remained, which was chromatographed as 75 g silica gel, eluting with ether / petroleum ether (15 ^ 85). The title compound was obtained as a colorless liquid, V ⁰ S 2965; 2925; 2870; 1710 cm "¹; f ^aDC1 3 5.05; 7.64; 8.39;

your
9.04; m / e 154 and also characterized by 2,4-dinitrophenylhydrazone with melting point 48 to 49 ° C.

In an experiment carried out according to this procedure, the yield was 79 % of theory.

Be. game 5

4-oxopentyl-i-triphenylphosphonium iodide ethylene ketal _; (VII) A) 5-iodo-2-pentanone

4.82 g (0.04 mol) of commercially available 5-chloro-2-pentanone and: '18 _v 0g

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4b

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Sodium iodide (0.12 mol) was dissolved in 100 cm * acetone and refluxed for 1 hour. The acetone was drawn off, the residue was dissolved in water and extracted twice with ether. The combined ether extracts were washed iodine-free with 0.1N sodium thiosulphate solution, dried over anhydrous magnesium sulphate, filtered and evaporated; the title compound remained as a pale yellow liquid, - ^ 3

PTPl

g _ma ^

2955; 1710 cm ~ ', r ^{OJJ X} 3 6.81; 7.44; 7.87; 8.00. A sample was purified by distillation to Kp °> 4 ⁰ C / 14 mm Hg, but decomposition occurred partly in the distillation and the main mass of the compound produced was therefore used without further purification in the following stage.

In an experiment carried out in this way, the yield was 58% of theory.

B) 5-iodo-2-pentanone ethylene ketal

68 g (0.12 mol) of 5-iodo-2-pentanone prepared as above, 6.1 g (0.032 mol) of p-toluenesulfonic acid and 51.8 g (0.96 mol) of ethylene glycol were combined with 800 cnr of benzene in a with a water separator device is heated under reflux for 1 d. The reaction mixture was then cooled, diluted with 1.250 liters of 5% strength sodium bicarbonate solution and extracted twice with 625 cubic meters of ether each time. The combined ether extracts were washed iodine-free with 400 cm * 0.1N sodium thiosulphate solution, dried over sodium sulphate, filtered and evaporated. The residue was distilled under reduced pressure, the title compound passed over at 76 ° C./0.05 mm Hg ; Vf ⁰ JJj ^ 2955; 1375; 1115 cm "¹; r ^CDC1 3 6.06; 6.75; 8.21; 8.69.

In an experiment carried out in this way, the

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²⁷²

Yield 100% of theory

O) 4-oxopentyl-1-triphenylphosphonium iodide ethylene ketal

11.2 g (0.429 mol) triphenylphosphine was dissolved in 35 cnr benzene and 10 cnr benzene was distilled off to remove any traces of water present. Then 10.0 g (0.039 mol) of 5-iodo-2-pentanone-ethylene ketal prepared as above were added and the mixture was refluxed for 1 hour. The title compound crystallized out of the reaction mixture, was filtered off and washed with dry ether, boiling point 210 to 215 ° C., V ^C ^ 3 1435, 1110 cm " ¹ .

In an experiment carried out in this way, a yield of 74% of theory was found. achieved.

Example 6

6-ethyl-10-methyldodeca-5,9-dien-2-one (VIII)

202 mg of sodium hydride (4.83 mmol, 56.8% suspension in mineral oil) were ^{stirred with 4 cm ^ dimethyl sulfoxide at 75 to 80 0} O for 45 minutes under nitrogen. During this time hydrogen was evolved. The mixture was cooled to room temperature and treated with 2.76 g (5.32 mmol) of 1-triphenylphosphonium iodide-ethylene ketal prepared according to Example 5 in 8 cnr dimethyl sulfoxide. This mixture was stirred under nitrogen for 15 minutes at room temperature. Thereupon, 5 ⁰⁰ mg (3.22 mmol) prepared according to Example 4 7-methyl-6-nonen-3-one in 1.5 cm ^ dimethylsulfoxide added and the mixture under nitrogen for 6 h at room temperature and then overnight at 80 ⁰ C stirred. It was then diluted with 80 cm ^ of water, 4 times with about half the volume each time

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ORIGINAL INSPECTED,

AK

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n-pentane extracted, the η-pentane extracts were washed with water, dried with anhydrous magnesium sulfate, filtered and finally the n-pentane was stripped off; 6-ethyl-10-methyldodeca-5,9-dien-2-one-ethylene ketal "^ ^C m ° x ^{5 1650; 1} ^ 5 °; 1375; 945 cm"¹; t ^{/ CDG1} 3 4.90; 6.06; 8.39; 8.67; 9.02.

• χ

This compound was dissolved in 10 cm of tetrahydrofuran and treated with 10 cnr of 3% aqueous hydrochloric acid; the mixture was stirred at room temperature overnight, the tetrahydrofuran was stripped off under reduced pressure and the mixture was extracted with three equal volumes of ether. The combined ether extracts were washed neutral with water, dried over anhydrous magnesium sulfate, filtered and evaporated. The residue was chromatographed on a column of 35 g of silica gel, eluting with ether / petroleum ether (1: 9). The title compound was obtained as a light yellow liquid, - ^ ° ^ 3 2930; 1710; 1660 cm " ¹ , £ ^{0Ι) 01} 3 5.02; 7.65; 7.89; 8.36; 9.05; m / e 222.

In an experiment carried out according to this procedure, the yield was 84 % of theory.

B is ρ ie 17

Methyl 3.11 "dimethyl 7-ethyl trideca-2,6,10-trienoate (IX) A) Diethyl carbomethoxymethyl phosphonate

According to the PC Crofts in Quart. Rev. Chem. Soc. . Procedure described Vol 12, p 341 (1958), 1.9 g (0.11 koi) and methyl chloroacetate g (0.10 mol) Triäthylphosphlt heated at a bath temperature of 16.6 Bueammen 160 ⁰ C overnight; the reaction mixture was distilled under reduced pressure which

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Title compound passed over at 90 ° C / 0.2 mm Hg, V ° ^ i3 2980; 1735 cm "¹; ti 3 5.85; 6.28; 7.06; 8.65. In an experiment carried out according to this procedure, the yield was 94.7 % of theory.

In the same way, ethyl chloroacetate was used as the starting compound Obtained diethylcarbethoxymethylphosphonate.

B) methyl 3,11-dimethyl-7-ethyl trideca-2,6,10-trienoate

15 mg (0.357 mmol, 56.8% suspension) of sodium hydride was suspended in 1 cnr dry benzene, 75 mg (0.357 mmol) of diethyl carbomethoxymethylphosphonate obtained above were added dropwise, and the mixture was stirred at room temperature until it was clear. Then 53 mg (0.238 mmol) of 6-ethyl-IO-methyldodeca-5,9-dien-2-one prepared according to Example 6 were added and the mixture was stirred at room temperature for 4 days. Then it was diluted with the same volume of water, extracted with ether, the ether extracts were washed neutral, dried over anhydrous magnesium sulphate and evaporated; an oily residue remained which was purified by chromatography on a column of 20 g of silica gel. Elution with ether / petroleum ether (1: 9) gave the title compound as a colorless oil, V ^C ™? I3

ι pump max

2915; 1720; 1645 approx ^{. 1} ; * ⁰ ^ 4.35; 4.97; 6.32; 7.81; 8.32; 9.04; m / e 278.

In an experiment carried out according to this procedure, a yield of 85.5% of theory was found. achieved.

The title compound could also by hydrolysis and then Re-esterification can be purified as follows: The crude • compound (100 mg) was dissolved in 5% methanolic potassium hydroxide solution (10 cnr) dissolved, the mixture refluxed overnight

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keep, evaporated under reduced pressure, with 1% aqueous hydrochloric acid was added until the mixture was slightly acidic and then extracted with ether. The ether extracts were washed neutral, dried over anhydrous magnesium sulfate, filtered and evaporated. The residue off 3,11-dimethyl-7-ethyl-2,6,10-tridecatrieoic acid dissolved in a 1: 1 mixture of ether and methanol (5 cnr) and mixed with diazomethane until the yellow coloration no longer disappeared. The mixture was evaporated under reduced pressure and the residue is chromatographed on silica gel as above. The pure title compound had the same physical properties Constants as given above.

According to the procedure described in the first part of this example, diethylcarbethoxymethylphosphonate was used as starting material ethyl ^ iH-dimethyl ^ -äthyltrideca-2,6,10-trienoate obtain. The following procedure could also be used to produce this connection: A sample of Methyl 3,11 -dimethyl ^ -äthyltrideca ^, 6,10-tri enoate (29 mg, 0.1 mmol) was mixed with 0.2 cnr 1N methanolic sodium hydroxide solution Treated at room temperature for 2 hours, the mixture neutralized, extracted with ether, the ether extract neutral washed, dried over anhydrous magnesium sulfate and the ether evaporated; the 3,11-dimethyl-7-ethyl-2,6,10-tridecatrienoic acid remained, which was treated with diazoethane.

Example 8 Hethyl-IO-epoxy ^ -äthyl ^ ii-dimethyl ^ je-tridecadienoate (I),

. 40 mg (0.144 mmol) of methyl 3,11-dimethyl-7-ethyltrideca-2,6,10-trienoate prepared according to Example 7 were in 2 cm * one

Φ * 009829/1974

ORiGlNALlNSPECTED

20GQ274

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3: 1 mixture of 1,2-dimethoxyethane and water dissolved, ^{cooled to 0} ° C. and mixed with 28 mg (0.158 mmol) of N-bromosuccinimide. The mixture was ^{stirred at 0} ° C. for 1 hour, the solvent was stripped off under reduced pressure, the residue was dissolved in n-pentane, the solution was dried with anhydrous magnesium sulfate, filtered and the solvent was finally stripped off. The residue was treated with a solution of 4 mg of sodium metal in 2 cm of anhydrous isopropanol at ⁰ ° C. and stirred ^{at 0} ° C. for 1/2 hour. The solvent was removed under reduced pressure. The residue was taken up in anhydrous ether, the sodium bromide was filtered off and the solution was evaporated. The pale yellow oily residue was purified by chromatography on clay plates which had been developed with ether / petroleum ether (2: 3); the title compound was obtained as a clear, colorless oil, V ° Soi3 2950; I7IO; 1645 cm " ¹ , r ^CDC1 3 4.38; 4.86;

IUoI-A.

6.35; 7.47; 7.82; m / e 294.

In an experiment carried out according to this procedure, the yield was 51 % of theory.

Ethyl was in the same way when using 3,11-dimethyl-7-äthyltrideca-2,6,10-trieonat Also the corresponding ethyl-IO-epoxy ^ -äthyl ^ ii-dimethyl ^ jö-tridecadienoate as starting material obtain.

Fat deprived marriage

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Claims (3)

Claims 1./Methyl and ethyl esters of 10-epoxy-7-ethyl-3, ll-Lj * imethyl-2,6-tridecadienoic acid the formula COOK wherein R denotes the methyl group or the ethyl group. 2. Process for the preparation of the compounds according to claim 1, characterized in that one 3-methyl-l-penten-3-ol with ethyl vinyl ether in the presence a catalyst to the / ethoxyethyl ether of 3-methyl-1-penten-3-ol converts the compound obtained heated in the presence of a catalyst, the resulting 5-methyl- * i - hepten-l-al with a methylmagnesium halide brings to implementation and the reaction mixture decomposes, the 7-methyl-6-nonen-3-ol obtained in this way oxidized to 7-methyl-6-nonen-3-one, this ketone with the from ^ -oxopentyl-l-triphenylphosphonium iodide-ethylene- " Ylid produced ketal to form 6-ethyl-10-methyldodeca-5 | 9-dien-2-one ethyl ketal reacts, the shielding ketal group is split off with acid, the 6-ethyl-10-methyldodeca-5,9-dien-2-one obtained with the from a dialkyloarbomethoxymethyl or Dialkyloarböthoxyjnethylphosphc ^ tit, 009819/1974 INSPECTED lA-37 whose alkyl groups contain 1 - M carbon atoms, the anion produced is reacted in an inert solvent to form the methyl or ethyl ester of 3 »ll-diniethyl-7-ethyl-trideca-2,6,10-trienoic acid, whereupon the ester obtained is first reacted with an N-halosuccinic acid imide in a mixture of Dimethoxyathan.und water and then treated with an alkali metal isopropoxide and finally the resulting methyl or ethyl ester of 10-epoxy-7-ethyl-3, ll-dimethyl-2,6-tridecadienoic acid is isolated and optionally purified . 3. The method according to claim 2, characterized in that the catalyst used is phosphoric acid used. k. Use of the compounds according to Claim 1 for controlling insect populations. aQ9829 / 1974