DE1138037B - Process for the preparation of 10-trans, 12-cis- or 10-cis, 12-cis-diene- (10, 12) -olen- (1) - Google Patents

Description

GERMAN

PATENT OFFICE

F 30904 IVb / 12 ο

REGISTRATION DATE: 2. A PRIL 1960

NOTICE
THE REGISTRATION
ANDOUTPUTE
EDITORIAL: OCTOBER 18, 1962

The diene- (10,12) -olen- (l) are effective sexual attractants of insects. So is z. B. the 10-trans, 12-cis-hexadecadiene- (10,12) -ol- (l) in the silk moth Bombyx mori is the most effective of the four possible isomers. For its specific effectiveness as an insect attractant, it was found that geometric configuration of the double bonds is of crucial importance.

The present invention is a process for the preparation of 10-trans, 12-cis or 10-cis, 12-cis-diene- (10,12) -olen- (l) of the general formula I or II:

(CHs) ₈ -CH ₂ OH I.

Method of manufacture

from 10-trans, 12-cis- or 10-cis,

12-cis-diene- (10,12) -olen- (l)

Applicant:

Paint factories Bayer Aktiengesellschaft,
Leverkusen

Dr. Ernst Truscheit, Leverkusen,

Dr. Karl Eiter, Cologne-Stammheim,

Dr. Adolf Butenandt and Dr. Erich Hecker,

Munich,
have been named as inventors

H'

- CH ₂ OH

c = c;

II

wherein R is a saturated or unsaturated straight-chain or branched aliphatic or cycloaliphatic Rest means.

The process allows the preparation of sterically uniform diene- (10,12) -ole- (l).

It has been found that sterically uniform diene- (10,12) -ole- (l) which either have the 10-trans, 12-cis- or have the 10-cis, 12-cis configuration, can be obtained by using a decanal of the formula

R '- (CHb) ₈ -CHO

in which R 'denotes a carboxyalkyl or an acyloxymethylene group, with a triarylphosphine carbalkoxymethylene to form a mixture of trans- and cis-dodecene (2) acid (1) alkyl esters of the formula
R '- (CH ₂ ) ₈ -CH = CH-COO- alkyl

converts the isomer mixture obtained in this way, optionally after saponification, separates the sterically uniform trans- or cis-compound with a complex metal hydride to the trans- or cis-dodecen- (2) -diol- (l, 12) reduced, this partially oxidized to dodecen- (2) -ol- (12) -al- (l), the same optionally acylated and with a phosphor-ylene of the general formula

ff ~ * TT \ t> / ~ * Τ-Γ Ό

in which R is a saturated or unsaturated, straight-chain or branched aliphatic or cycloaliphatic Remainder means converts and, if necessary, saponifies the reaction product under alkaline conditions.

The process steps can be represented by the following equation:

R '- (CH ₂ ) ₈ -CH = O + (C ₆ Hs) ₃ P = CH-C-OR "III IV

209 677/330

"· \ 3 0
I ₁ OR " 1 138 037 ^ c = C
/ \ VI C- C HIGH ₂ - (CH ₂ ) ₈ 4th - (CHA ' I. !! + R '- (CH ₂ ) / I ^LiAiH * 1 ^Χ Η ^Η \ / \ / ^{Η Η} χ OH ^X C-OR "+ (C ₆ Hs) ₃ P R ' ν ^ CH ₂ i
O - (CH ₂ ) / ^Χ Η / ^Η ) c-c ( ^ CH ₂ OH HIGH ₂

VII VIII

MnO,

CC X ^{C = C} \

HIGH ₂ - (CH ₂ ) / H HIGH ₂ - (CHa) ₈ CH = O

IX X

I + (C ₆ Hs) ₃ P = CH-R I

\ XI *

H, H

H / ^C - ^C \. ^H \ / ^H

> = ^C \ ^R / ^{C = C} \ / ^R

HOCH ₂ - (CH ₂ ) / H HOCH ₂ - (CH ₂ ) ₈ ^ C = C.

H H

I II

+ (C ₆ Hs) ₃ P = 0 + (C ₆ Hs) ₃ P = O

wherein R has the meaning given above, are separated during lization. But you can also do that

R 'saponify the group 50 isomer mixture under alkaline conditions and the thereby

obtained dodecen- (2) -diacids- (l, 12) by fract-

0 separated crystallization.

1 In the second stage, the trans- or the cis- CO alkyl or -CH ₂ -O acyl dodecene (2) diacid (l, 12) or their dialkyl esters

55 (V or VI) with a complex metal hydride, e.g. B.

and R "denotes alkyl. Lithium alanate (lithium aluminum hydride) or Na-

In the first stage z. B. a decanal (IO) - trium borohydride, in the presence of a solvent

acid (l) -alkyl ester (III) in a manner known per se (e.g. ether, tetrahydrofuran, dioxane or their

with a triarylphosphine-carbalkoxymethylene (e.g. mixtures) at temperatures from -20 to + 100 ° C,

IV), which is obtained from a triaryl-carbalkoxymethyl- 60, preferably 40 to 50 ° C, to trans- or cis-Dode-

phosphonium bromide and aqueous sodium hydroxide solution erzen (2) diol (l, 12) (VII or VIII) reduced,

holds, to a mixture of trans- and cis-dodecen- In the third stage, the trans- or the cis-

(2) diacid (l, 12) dialkyl esters (V and VI) implemented. Dodecen- (2) -diol- (l, 12) (VII or VIII) without

This reaction is preferably carried out in a special benzene cleaning process with active manganese (IV) oxide

Solution at the boiling point. The resulting iso- 65 to the corresponding dodecen- (2) -ol- (12) -al- (l) (IX

Merengenisch can be oxidized by fractional distillation or X). It is convenient per mole

or in the case of dodecene (2) diacid (l, 12) di-dodecene (2) diol (l, 12) 4 to 20, preferably 8 to

methyl ester preferably by fractional crystalline 15 mol manganese (IV) oxide in the presence of 1000

5 6

up to 5000, preferably 3000 to 4000 parts by volume divide decanal (10) acid (l) methyl ester (prepared from a solvent (e.g. petroleum ether [bp 30 to J. Am. Chem. Soc, 48, p. 1074 [1926]) in 60 Vo-50 ⁰ C], η-hexane, cyclohexane, benzene, diethyl ether by volume add to absolute benzene and heat the or mixtures of these solvents) per mole of Do reaction mixture for 6 hours in a nitrogen decene (2) - diol- (l, 12) to be used. The reaction 5 atmospheres on the reflux condenser to boiling. This is performed at temperatures of -20 to + 100 ° C, pre-reaction mixture (the Do- 5O ⁰ C Kp. 30 to preferably + 10 to + 3O ⁰ C is performed.) Is treated with petroleum ether, cooled to about 0 ° C , the auskristaldecen- (2) -ol- (12) -al- (l) is sucked off from the reaction mixture lized triphenylphosphine oxide (72 parts by weight) by extraction with one of the above and with petroleum ether (bp 30 to 50 ⁰ C) gel solvent, preferably diethyl ether, isolated and wash OK. The solvent is evaporated from the filtrate under reduced pressure via the sodium bisulfite addition compound. The residue can be cleaned. is again diluted with petroleum ether (b.p. 30 to 50 ° C),

In the fourth stage, the trans- or the ice- the solution is cooled, a further 11 parts by weight of tri-

Dodecen- (2) -ol- (12) -al- (l) (IX or X), optionally phenylphosphine oxide, are suctioned off and again

by acylation (preferably with acetic acid 15 with petroleum ether (bp. washed 30 to 5O ⁰ C). We

anhydride at temperatures around + 8O ⁰ C) with a total of 83 parts by weight (99% of theory)

Phosphorus-Ylene of the general formula XI in counter-triphenylphosphine oxide. After one of the filtrate,

Was a solvent (e.g. diethyl ether, Tetra combined with the washing solutions, the solvent

hydrofuran, dioxane, petroleum ether [bp. 30, has evaporated to 5O ⁰ C] under reduced pressure, receives

η-hexane, cyclohexane, benzene) at temperatures of 20 one as residue in quantitative yield 77 Ge

- 30 to + 3O ⁰ C implemented. The phosphor-ylene of the weight parts of trans- and cis-dodecen- (2) -diacid- (l, 12) -

General formula XI is known to consist of dimethyl ester as a colorless liquid, which soon becomes too

a corresponding triarylphosphonium halide solidifies to a crystal slurry. Fractional crime

and a proton acceptor (e.g. methyl, butyl, crystallization from η-hexane is obtained from it

Phenyllithium, lithium, sodium acetylide, an Al- 25 52 parts by weight (67.5% of theory) trans-dodecene

Potash or alkaline earth metal alcoholate or amide) in (2) diacid (l, 12) dimethyl ester of melting point 33 to 35 ° C.

Presence of a solvent produced. Suitable The infrared absorption spectrum has characteristic

Triarylphosphonium halides are e.g. B. the methyl, static absorptions at 1735 cm " ¹ («, ß-saturated

Ethyl, n- or isopropyl, n- or isobutyl, propene ester carbonyl), 1725 cm- ¹ (α, β-unsaturated ester

(2) -yl- (l>, butene- (2) -yl- (l>, 3-methylbutene- (2) -yl- (l) -, 30 carbonyl), 1650 cm- ¹ (conjugated to the carbonyl group

Penten- (2) -yl- (l) -, penten- (3) -yl- (l) -, 3,7-dimethyl-alloyed double bond), 977 cm- ¹ (symmetrically di-

octadiene- (2,6) -yl- (l>, cyclopentylmethyl-, cyclohexyl- substituted

methyl-, [cyclopenten-ilO-ylJ-methyl-, [cyclohexene;

(1 ') -yl] -methyl- or the P' ^ '. Ö'-trimethylcyclohexene CH-C Η-trans ethylene bond

(l ') - yl] methyl triphenylphosphonium bromide, iodide 35 ^CH ~ ^{CM trans} atnylene bond).
or chloride.

The 10-trans is obtained from the reaction mixture, analysis: C ₁₄ H ₂₄ O ₄ (molecular weight 256.34).

12-cis- or the 10-cis, 12-cis-diene- (10,12) -ol- (l) Calculated C 65 59 ° / H 9 44 ° / ·

(I or II) or their acylate after suctioning off the ßerecnnei ... ^ oopy / ₀ , ti ^ ₀ '. ⁰ '

^{formed triarylphosphine oxide} containing lower 40 S eIunaen ··· -JJSo / "JJJ ₀ /

Impact and evaporation of the solvent - ^ "'^ ^{/ o} ' ^{n y} ' ^{4 / / o} ·

Impact and evaporation of the solvent won. The compounds of the saponification according to the invention are 5 parts by weight of the trans process can be purified by distillation. Dodecene (2) diacid (1,12) dimethyl ester, dissolved in

You can also proceed in such a way that first a 20 parts by volume of ethanol with the solution of 2.7 gel acyloxydecanal (10) (III) in 45 parts by weight of potassium hydroxide known per se in 10 parts by volume of water with a triarylphosphine-carbalkoxymethylene ser and 20 parts by volume of ethanol for 1 hour under stick (z. B. IV), which is z. B. from a triaryl carbide heated to boiling on the reflux condenser. Alkoxymethyl-phosphonium bromide and aqueous Na- obtained after working up about 4.2 parts by weight of tronlauge, to a mixture of trans- and (95% of theory) trans-dodecene (2) diacid (l, 12) cis- 12 Acyloxydodecen- (2) -säure- (l) alkyl ester (V or 50, mp. 168-169 ⁰ C (from ethyl acetate). The Infra-VI). This reaction and the subsequent red absorption spectrum has characteristic Ab isomer separation are carried out as described above by- Sorptions at 1705 cm- ¹ («, / ^ - saturated acid, carbonyl), 1690 cm- ¹ («, ^ - unsaturated acid carbonyl),

Then the trans or the cis - ^ - acyloxy 1645 cm " ¹ (double conjugated to the acid carbonyl

dodecene (2) acid (l) alkyl ester (V or VI) or 55 bond) and 982 cm- ¹ (symmetrically disubstituted, if necessary, the trans- or the cis-12-hydroxy

dodecenoic (2) acid (I) or their alkyl esters, such as,.

already described above, reduced, the same ^CH = CH-trans-ethylene bond).

Products are obtained, which are then as described *

are further processed. 60 Analysis: C ₁₂ H ₂₀ O ₄ (molecular weight 228.29).

Example 1 Calculated ... C 63.13%, H 8.83%, O 28.04%;

^p found ... C 63.14%, H 8.81%, O 27.80%.
a) trans-dodecene (2) diacid (l, 12) dimethyl ester

.. ..., _imr . ,,. .. ". ,. ,,. , b) 12-acetoxydodecen- (2) -al- (l)

100 parts by weight of triphenylphosphine 65 ' ^J ww are dissolved

carbomethoxymethylene (prepared according to Angewandte To a solution of 10.3 parts by weight of lithium chemistry, 71, pp. 271, 272 [1959]) in 300 parts by volume of alanate in 580 parts by volume of absolute ether is left absolute benzene, adds the solution of 60 weight- with stirring in a nitrogen atmosphere to the

Solution of 48 parts by weight of trans-dodecen- (2) -diphenylphosphonium bromide. 25 of these (l, 12) dimethyl esters are added in 270 parts by volume of absolute parts by weight in 300 parts by volume of absolute petroleum ether in such a way that the reaction mixture (boiling point 30 to 50 ° C.) is suspended. Boils vigorously in this suspension. To complete the reaction the solution is from 4.1 parts by weight of the reaction mixture is heated for a further 1 hour at 5 n-butyllithium in 50 parts by volume of absolute petroleum reflux condenser to boiling at 2O ⁰ C. Thereafter, the ether (boiling point 30 to 50 ° C.) is stirred in under nitrogen, excess lithium alanate with 8.2 parts by volume . parts by weight of trans-12-acetoxydodecen- (2) -al- (l) in

The reaction mixture is (decomposed Kp. 30 to dilute sulfuric acid, the organic 5O ⁰ C) at 0 ° C with ice-cold io 100 parts by volume of absolute petroleum ether extracted with ether with vigorous stirring at -20 ° C in approximately proportion, the ether phase is washed successively with 1 to 2 hours added, whereupon the reaction diluted sulfuric acid, water and sodium hydro- mixture gradually decolorized. It is washed for 1 hour with carbonate solution, over sodium sulfate - 20 ° C., 2 to 3 hours at ⁰ ° C. and finally dried and the solvent is finally stirred for a further 3 hours at + 20 ° C. The resulting reduced pressure is evaporated. The un- precipitate of triphenylphosphine oxide and Lifähr 35.5 parts by weight of trans-dodecen- (2) -diol- (l, 12) thium bromide is suctioned off and washed with petroleum ether of a waxy consistency, which is immediately washed further. The filtrate will be working with the washing solutions. The solution of 35.5 parts by weight is combined, the solvent is evaporated under reduced trans-dodecene (2) diol (1.12) in 600 parts by volume and the residue is distilled in a high vacuum of solid ether with 150 parts by weight of active. 12.5 parts by weight (71.5% of the manganese (IV) oxide about 12 hours based on spatial theory) of 10-trans, U-cis-1-acetoxyhexadecadiene temperature are obtained. Thereafter, the solid (10, 12) with a boiling point of _{0> 1} 140 to 142 ° C, n'S = 1.4703; Sucked off proportions and washed several times with ether. A _max = 232 ταμ (ε = 21000). The infrared absorption The washing solutions combined with the filtrate are 25 spectrum shows characteristic absorptions when evaporated in vacuo. 26 weight- 1735 cm- ¹ (ester carbonyl), 981 cm- ¹ , 943 cm- ¹ (ice, parts of trans-dodecen- (2) -ol- (12) -al- (l) are obtained as colorless fluids- trans- conjugated diene) 718 cm " ¹ [(CH ₂ W ₄ ]. fluid that can be used for acetylation without further purification. For saponification, 40 parts by weight of 10-trans,

be dissolved in 60 parts by volume of acetic anhydride. ^ -cis-l-Acetoxyhexadecadien-flOjlZ), dissolved in 160 Vo-This solution is after 1 hour of heating in 30 lum parts of ethanol, with a solution of 11.2 Ge-80 ° C for a further 10 hours at room temperature weight parts in potassium hydroxide 48 parts by volume of washing and then at 0 ° C with ice-water and water and 320 parts by volume of ethanol for 45 minutes under sodium hydrogen carbonate. After the nitrogen has ended, the mixture is heated on the reflux condenser. Thereafter, the organic components are neutralized from the alcohol, largely etherified under reduced pressure. Evaporated from the dried over sodium sulfate, the residue is diluted with water and the ether phase is reduced to the solvent. organic fraction etherified. The ether phase evaporates under pressure. The residue obtained is, for example, dried over sodium sulfate and 30 parts by weight of crude product are evaporated from it in vacuo. The residue is taken up in petroleum ether high vacuum distillation 22 parts by weight (49% of the (boiling point 30 to 50 ° C.) and the theoretical mixture, based on the trans-dodecene-40 used, is ^{cooled to 0} ° C. The (2) - diacid (l, 12) dimethyl ester) pure trans-12-acetal solid fractions are suctioned off, and the filtrate oxydodecen- (2) -al- (l) of _{boiling point 0j08} 130 to 134 ⁰ C; the solvent becomes rfg = 1.4600 under reduced pressure; X _max = 222 ΐημ (ε = 16000). The infra evaporated. 30 parts by weight are obtained (87% of the red absorption spectrum shows the characteristic Ab theory) of 10-trans, 12-cis-hexadecadiene (10,12) -ol- (l) sorptions at 2700 cm- ¹ (hydrogen atom of Al-45 of bp _Oi001 132 to 134 ⁰ C, nf = 1.4799, dehyde group). 1732 cm- ¹ («, ^ - saturated ester carbonyl X _max = 232 ΐημ (ε = 21500). The infrared absorption nyl), 1684 cm- ¹ («, / ^ - unsaturated aldehyde carbonyl), spectrum shows characteristic absorptions at 1630 cm- ¹ (conjugated to the aldehyde carbonyl Double 3300 cm ^-1 (hydroxyl group), 1052 cm- ¹ (CO-valence), bond) and 972 cm ^"1 (symmetrical disubstiutierte 979 cm" ^1, 943 cm ^"1 (cis, trans-conjugated diene ),

50 718 cm ^-1 [(CH ₂ ) ^ ₄ ].

CH = CH-trans -ethylene bond). Analysis: C ₁₆ H ₃₀ O (molecular weight 238.42).

i Calculated ... C 80.60%, H 12.69%, O 6.71%;

Analysis: C ₁₄ H ₂₄ O ₃ (molecular weight 240.34). found ... C 80.53%, H 12.63%, O 6.71%.

Calculated C 69 96 ° / H 10 07 ° / · ⁵⁵ The »attractant unit« (LE) (after A. But en andt

ppfnnHpn r mno / w mm ο / and employees, »Journal for Nature Research«, 14b,

found ... C 69.77 J ₀ , H 10.02 / ₀ . _§ ^ _ß ^ ^ _{manufactured lo} . _{tranS5 12} . _cis .

c) 10-trans, 12-cis-hexadecadiene- (10,12) -ol- (l) hexadecadiene- (10,12) -ol- (l) was used in the behavioral test

determined on male silk moth (Bombyx mori) to the mixture of 40 parts by weight of triphenyl 60 10 ¹³ y, phosphine, and 50 parts by weight of n-butyl bromide is Example 2

heated with stirring in a nitrogen atmosphere. , _ _TT,,,, ". .. _{ίΛ s}

The initially clear solution solidifies at + 7O ⁰ C. The trans-12-Hydroxy-dodecen- (2) -saure- (l)

The mixture is heated to 110 ° C for 1 hour and the according to that described in Example 1 under a)

Reaction mass digested with benzene in the cold. The 6g process are 65 parts by weight of triphenylphosphine

Solid fractions are sucked off, first with benzene and carbäthoxymethylene in 250 parts by volume absolute

then washed with petroleum ether (bp 30 to 50 ° C). Benzene with 40 parts by weight of l-acetoxydecanal (10)

About 40 parts by weight of n-butyl-tri- [prepared by ozonizing 1-acetoxyundecene

(10) in acetic acid]. 51 parts by weight of triphenylphosphine oxide (98% of theory) are obtained in quantitative yield 53 parts by weight of trans- and cis-12-acetoxydodecen (2) acid (1) ethyl ester.

For saponification, 30 parts by weight of the ester fraction of boiling point _{0) 005} 145 to 147 ° C (n ² g - 1.4552 to 1.4566), dissolved in 120 parts by volume of ethanol, with the solution of 15 parts by weight of potassium hydroxide in 60 parts by volume of water and 120 parts by volume of ethanol heated for 30 minutes on a reflux condenser in a nitrogen atmosphere. The alcohol is largely evaporated under reduced pressure. The residue is dissolved in water and this solution is acidified with dilute phosphoric acid in the cold. The precipitated solid components are extracted with ether and the combined ether extracts are dried over sodium sulfate after washing with sodium chloride solution. After evaporation of the ether under reduced pressure, 22 parts by weight (97% of theory) of a colorless crystal pulp are obtained, from which 14.5 parts by weight (64%) by fractional crystallization from an ether-petroleum ether (b.p. 30 to 50 ° C) mixture of theory) of trans-12-Hydroxydodecen- (2) -säure- (l); mp. 72-73 are obtained ⁰ C. The infrared absorption spectrum shows characteristic absorptions at 3400-3100 cm " ¹ (hydroxycarboxylic acid), 1695 cm" ¹ (oc, /? - unsaturated ^{acid carbonyl), 1650 "1} (double bond conjugated to the acid carbonyl) and 976 cm" ¹ (symmetrically disubstituted

CH = CH-trans -ethylene bond).

Analysis: C ₁₂ H ₂₂ O ₃ (molecular weight 214.31).

Calculated .... C 67.25%, H 10.35%, 0 22.40%; found .... C 67.30%, H 9.83%, 0 23.10%.

40

Example 3
10-trans-, 12-cis-tetradecadiene- (10,12) -01- (l)

To a suspension of 14 parts by weight of ethyltriphenylphosphonium bromide (prepared according to Ang. Chemie, 71 [1959], p. 271) in 120 parts by volume of absolute ether, the solution of 2.5 parts by weight of n-butyllithium in 40 parts by volume of absolute ether is left in a Flow in a nitrogen atmosphere at room temperature. After about 1 hour stirring at 0 ⁰ C 8.5 parts by weight of trans-12-Acetoxydodecen- (2) -AL- (l) dissolved in 30 parts by volume of absolute ether was added.

The reaction mixture is allowed to react for a few more hours at 0 °, then the precipitate formed of triphenylphosphine oxide and lithium bromide is filtered off with suction and washed with ether. The united with the washings filtrate is concentrated under reduced pressure and (30 Kp. To 5O ⁰ C) was added to the residue with petroleum ether. The triphenylphosphine oxide precipitated in this way is filtered off with suction and the residue from the evaporation of the filtrate is distilled in a high vacuum. About 6 parts by weight (about 67% of theory) of 10-trans-, 12-cis-1-acetoxytetradecadiene (10.12) with a _{boiling point of} 125 to 130 ° C., n% ° = 1.4660 are obtained.

For saponification, the solution of 5 parts by weight of the 10-trans, 12-cis-1-acetoxytetradecadiene (10,12) obtained in this way in 18 parts by volume of ethanol is mixed with the solution of 1.4 parts by weight of potassium hydroxide in 5 parts by volume of water and 36 parts by volume of ethanol 1 Heated to the boil in a nitrogen atmosphere on the reflux condenser for an hour. After the ethanol has evaporated under reduced pressure, the residue is diluted with water and the organic fraction is extracted with ether. After drying the ether phase over sodium sulfate, the ether is evaporated and the residue is treated with 30 to 40 parts by volume of petroleum ether (bp. 30 to 5O ⁰ C) was added. The mixture obtained is ^{cooled to 0 °} C. and the precipitate formed is filtered off with suction.

After evaporation of the solvent from the filtrate, 3.7 parts by weight (89% of theory) of 10-trans, 12-cis-tetradecadiene- (10,12) -ol- (l), bp. _{0 001} 95 to 100 ⁰ C; n ² S = 1.4798, l _max = 230 ΐημ (e = 20,000). The infrared absorption spectrum shows characteristic absorptions at 3250 cm " ¹ (hydroxyl group), 1058 cm ^-1 (C - O valence), 981 and 945 cm ^-1 (cistransconjugated dienes), 711 cm ^-1 [(CH ₂ ) _{M> 4} ].

The LE according to "Zeitschrift für Naturforschung", 14b, p. 283 (1959), of the 10-trans, 12-cis-tetradecadiene- (10,12) -ol- (l) produced in this way was tested in the behavior test on the male silk moth (Bombyx mori) determined to be 100 γ .

Example 4
10-trans-, 12-cis-octadecadiene- (10,12) -ol- (l)

According to the information in Example 3 are implemented: 12 parts by weight of n-hexyl triphenylphosphonium bromide (produced by fusing triphenylphosphine with 1-bromohexane) in 90 parts by volume of absolute ether with a solution of 1.8 parts by weight of n-butyllithium in 30 parts by volume of absolute ether and one Solution of 6.6 parts by weight of trans-12-acetoxydodecen- (2) -al- (l) in 25 parts by volume of absolute ether. About 5.5 parts by weight (about 65% of theory) of 10-trans, 12-cis-1-acetoxyoctadecadiene (10.12) of boiling point ₀₀₁ 125 to 140 ° C., n% ° = 1.4640 are obtained.

By saponification of 5 parts by weight of 10-trans, 12-cis-l-acetoxyoctadecadiene (10,12), dissolved in 20 parts by volume of ethanol, with 1.3 parts by weight of potassium hydroxide, dissolved in 5 parts by volume of water and 30 parts by volume of ethanol, 4 are obtained 2 weight parts of crude 10-trans, 12-cis-Octadecadien- (10,12) -OL- (l), which is incorporated in 30 to 40 parts by volume of petroleum ether (bp. 30 to 50 ⁰ C). After cooling the mixture prepared in this way to 0 ^° C., suctioning off the precipitate formed, evaporating the solvent and distilling the residue in a high vacuum, 3.5 parts by weight (81% of theory) of 10-trans, 12-cis-octadecadiene (10 , 12) -ol- (l) of bp. _Oi001 120 to 130 ° C (air bath temperature), tfg = '1.4760, hmax = 231 πιμ (ε = 19 500). The infrared absorption spectrum shows characteristic bands at 3300 cm ^-1 (hydroxyl group), 1058 cm ^-1 (C-O valence), 982 and 946 cm ^-1 (cis, trans-conjugated dienes), 719 cm ^-1

Analysis: Ci ₈ H ₃₄ O (molecular weight: 266.47).
Calculated .... C 81.12%, H 12.88%;
found .... C 80.93%, H 13.13%.

The LE according to "Zeitschrift für Naturforschung", 14b, p. 283 (1959), of the 10-trans, 12-cis-octadecadiene- (10,12) -ol- (l) produced in this way, was tested in the behavior test on the male silk moth (Bombyx mori) determined to be 10 ~ ^e y.

209 677 / Ϊ30

Claims (3)

ϊ 138 G37 11 12 Example 5 game Ib)] shows the infrared absorption spectrum of the λ · τ-, j / -ν, j · ·· / -1 i "\ j ·, .ι τ χ cis-12-Acetoxydodecen- (2) -al- (l) no absorption, a) cis-dodecen- (2) -disaure- (l, 12) -dimethylester ^J wwf The mixture of c) cis, cis-hexadecadiene- (10,12) -ol- (l) obtained according to Example l, a) trans- and cis-dodecen- (2) -diacid- (l, 12) -dimethyl- 5 The ester is dissolved in η-hexane, the solution is cooled to 0 ^° C. 5 parts by weight of n-butyl-triphenylphosphonium and the precipitated crystals are filtered off with suction. The filtrate obtained in this way is cooled to -20 ° C. and suspended in 30 parts by volume of absolute ether. At room temperature, the mixture is then suctioned off under the crystal slurry at -20.degree. Stirring the filtrate in a nitrogen atmosphere, the solvent is evaporated and the return io 0.8 parts by weight of n-butyllithium in 10 parts by volume was fractionated in a high vacuum: the fraction of absolute ether flow. After about an hour from bp O ₁ O ₀₁ 125 to 127 ° C, n% ° = 1.4540, the solution of cis-dodecen (2) diacid (l , 12) -dimethylester. The 3 parts by weight of cis-12-acetoxydodecen- (2) -al- (l) in the infrared absorption spectrum shows characteristic 20 parts by volume of absolute ether. After 3 hours of absorption at 1733 cm ^-1 (α, β-saturated ester-15 digem stirring the reaction mixture at -10 ° C carbonyl), 1722 cm ^-1 (α, / 9-unsaturated ester carbonyl) the precipitate of triphenyl and 1641 cm " ¹ (phosphine oxide and lithium bromide conjugated to the carbonyl group sucked off and with a double bond; this band is washed compared to the ether. . Im evaporated for the symmetrical 20 pressure and the residue to remove disubstituted further small proportions of triphenylphosphine oxide with Petroleum ether (boiling point 30 to 50 ° C) added. After this ι suction of the precipitate, the filtrate is CH = CH-ethylene bond evaporates and the residue is distilled in a high vacuum. j 25 2.4 parts by weight (68.5% of theory) are obtained cis ^ is-1-acetoxyhexadecadiene-ilO, ^) of bp. _OiOO1 120 characteristic area [e.g. B. 977 cm ^"1, s. Example to 125 ° C, X = _ma x 233 πιμ. The infrared absorption 1, a)] there is no absorption. Deviating from the spectrum, it shows characteristic bands at 1738 cm- ¹ Infrared absorption spectrum of the trans isomer be (ester carbonyl) and 721 cm ^-1 [(CH ₂ ) ^ ₄ ]. Character if that of the cis isomer has a characteristic absorbency for trans, trans or cis, trans absorption at 820 cm- ¹ . conjugated dienes in the range of 1000 to 900 cm " ¹ Analysis: C ₁₄ H ₂₄ O ₄ (molecular weight 256.34). ^fel like ^en · ... ,,. _T .. _{o n} . _u ' j i4 24 4 ν 6> j _For saponification, the solution of 2 weight Calculated C 65.59%. Ή 9.44%, O 24.97%; divide cis, cis-l-acetoxyhexadecadiene- (10,12) into 8 vol- found ..... C 65.54%, H 9.69%, 0 25.05%. ₃₅ lumteilen ethanol at 0 ⁰ C and the solution of 0.6 parts by weight of potassium hydroxide in 2.5 parts by volume of b) cis-12-Acetoxydodecen- (2) -al- (l) water and 15 parts by volume of ethanol mixed and leave about 10 hours at room temperature. There- According to the method described in Example 1 under b), the ethanol under reduced pressure is 12 parts by weight of cis-dodecene (2) - 40 largely evaporated and the residue with diacid (l, 12) dimethyl ester in 70 parts by volume of abso water diluted. The organic fraction is etherified from lute ether with a solution of 2.6 parts by weight, the ether phase is concentrated after drying over lithium alanate in 140 parts by volume of absolute ether sodium sulfate and treated with petroleum ether (b.p. 30 to about 8.6 parts by weight of cis-dodecene (2) -diol- (l, 12) up to 50 ° C) diluted. The mixture is cooled to ⁰ ° C. and this is reduced with 38 parts by weight of active 45 and the precipitated solid components are filtered off with suction. The manganese (IV) oxide in 150 parts by volume of absolute ether filtrate is evaporated and the residue is selectively oxidized. About 6.4 parts by weight of high vacuum are obtained. About 1.4 gecis-dodecen- (2) -ol- (12) -al- (1) are obtained, which acetylates ice, cis-hexadecadiene with 15 parts by volume of acetic anhydride without further parts by weight (82% of theory) , 12) -ol- (l) of bp _M01 120 ° C (air bath temperature). The high vacuum distillation of the raw product 5 ° nf = 1.4780, X _ma x = 233 ΐημ (ε = 15,000). The infrared gives about 5.2 parts by weight [47% of theory, red absorption spectrum shows characteristic bands based on the cis-dodecene (2) -di used at 3300 cm ^-1 (hydroxyl group), 1053 cm ^-1 (C - O- acid- (1,22) dimethyl ester] cis-12-acetoxydodecene (2) valence) and 720 cm- ¹ [(CH ₂ ) ^ ₄ ]. Absorptions in the Al (l), bp. _{0, 06135-138} ° C, n = 1.4580% °. The range from 1000 to 900 cmr ¹ (characteristic of infrared absorption spectrum shows characteristic 55 trans, trans and ciSjtrans conjugated dienes) are absent. Absorptions at 2710 cm " ¹ (hydrogen atom of the
Aldehyde group), 1736 cm " ¹ («, / S-saturated ester carbonyl), 1687 cm- ¹ (ix, _J e-unsaturated aldehyde carbonyl), PATENT CLAIMS: 1633 cm ^-1 (double bond conjugated to the aldehyde carbonyl; weaker than the corresponding 60 1. Method trans-10 for the preparation of 12-cis-absorption of the trans isomer). In the field of labeled for or 10-cis, 12-cis-diene (10,12) -olen- (l), characterized symmetrically disubstituted in that a decanal the formula R '- (CH ₂ ) ₈ -CHO CH = CH-ethylene bond 65 I wherein R 'is a carboxylalkyl or an acyloxy methylene group means having a triaryl characteristic absorption [e.g. B, 972 cm- ¹ , see bisphosphine-carbalkoxymethylene for a mixture of trans- and cis-dodecene (2) acid (1) alkyl esters of the formula R '- (CH ₂ ) S -CH = CH- COO - alkyl converts, the isomer mixture obtained in this way, optionally after saponification, separates the sterically uniform trans- or cis-compound with a complex metal hydride to the trans- or cis-dodecen- (2) -diol- (l, 12) reduced, this partially oxidized to dodecen- (2) -ol- (12) -al- (l), the same optionally acylated and with a phosphorus-ylene the general formula (C ₆ H ₅ ) ₃ P = CH-R in which R is a saturated or unsaturated, straight-chain or branched aliphatic or cycloaliphatic Remainder means converts and, if necessary, saponifies the reaction product under alkaline conditions. 2. The method according to claim 1, characterized in that one decanal (10) acid (l) alkyl ester. with a triphenylphosphine-carbomethoxymethylene to the mixture of trans and cis-dodecene (2) diacid (l, 12) dimethyl ester, the isomer mixture thus obtained through fractional crystallization separates the sterically uniform trans or cis compound with a complex metal hydride, especially lithium alanate or sodium boranate, to trans- or cis-dodecen- (2) -diol- (l, 12) reduced, this with manganese (IV) oxide to the corresponding dodecen- (2) -ol- (12) -al- (l) oxidized and the same acetylated with acetic anhydride and with a phosphor-ylene to l-acetoxy-10-trans-, 12-cis- or 10-cis-, 12-cis-diene- (10,12) converts and this is saponified under alkaline conditions. 3. The method according to claim 1, characterized in that l-acetoxydecanal (lO) with a triphenylphosphine-carbalkoxymethylene to a mixture of trans- and cis-12-acetoxydodecen (2) acid- (1) -alkyl ester converts, this mixture is saponified under alkaline conditions, the 12-hydroxydodecen- (2) -acids- (l) obtained in this way separates by fractional crystallization, this optionally after esterification with a complex metal hydride, in particular lithium alanate or sodium boranate, reduced to trans- or cis-dodecen- (2) -diol- (l, 12), this is oxidized with manganese (IV) oxide to the corresponding dodecen- (2) -ol- (12) -al- (l), the same acetylated and with a phosphor-ylene of the general formula (C ₆ H ₅ ) ₃ P = CHR in which R is an aliphatic or cycloaliphatic radical, for l-acetoxy-10-trans-, 12-cis-diene- (10,12) or 1-acetoxy-10-cis, 12-cis-diene- (10,12) and this is saponified under alkaline conditions. © 209 677/330 10.62