DE2404913A1 - PROCESS FOR THE PRODUCTION OF ALPHA, GAMMA -DIAETHYLENIC KETONS - Google Patents

Description

Dr. F. Zumsiein sen. - Dr. Ξ. Assmann 2 A O 4 9 1 Dr. R. Koenigsberger - Dipi.-Phys. R. Holzbauer - Dr. F. Zurnstein

PATENT LAWYERS

TELEPHONE: COLLECTIVE NO. 22 5341 ₈ MUNICH 2.

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Societe des Usines Chimiques RhSne-Poulenc, Paris / France

Process for the preparation of o6, y-diethylenic ketones

In the perfumery industry, the Jonons take an important one Place. It would be difficult today to find a perfume composition that does not contain ionone. You know more than a hundred Jonone. Most frequently used are the ß-ionon, oC-ionon, the methyljonones and the irons. The ß-ionone is also a common one intermediate used in the synthesis of vitamin A.

The importance of the ionons is reflected in that in the literature attempts to find suitable manufacturing processes. All economic processes use as raw material the citral or the dehydrolinalool and lead to ionones via pseudojonones as intermediate products. So condensed the citral with acetone or methyl ethy! ketone and cyclized the pseudo-jonon to jonon. The dehydrolinalool is also left act after a Carroll reaction on ethyl acetate with the formation of pseudojonon, which one then cyclized. It is also known that the condensation of citral with 2-ethoxy-propene to a triethoxylated derivative of the Pseudojonons, which in turn leads to pseudojonons (US ~ PS 3 109 861) ο The pseudo-jonon is also used as a starting point of dehydrolinalool and methyl acetoacetate or diketene

4 09833/1041

here. The rearrangement of the dehydrolinalool acetate to the enolic acetate of citral, followed by a reaction with acetone and Rearrangement of the by condensation of a. Ketal or an enol ether Aheni ketone formed with dehydrolinalool (US-PS 3,029,287) both lead to pseudojonon.

The β-ionone is obtained, for example, by cyclizing the pseudo-ionone in the presence of an acid.

It should be noted that in both cases of the β-ion and the pseudo-ion the Λ 5 double bond conjugated to the carbonyl group Has transconfiguration. This is the normal form. One imagines that the cis - ^ configuration of the pseudo-jonon is theoretical would be possible, however, little v / ah rs before in borrowed and unstable is. In fact, all attempts to prepare the cis isomer have failed (Chem. Soc. (1965), page 5528). Regarding the configuration of the Δ 5 double bond, there are two cis isomers possible.

ο-λ / ^Η

-R

R-CH ₀

R-H.

cis - Δ 3, trans -Δ 5

R β (CH ₃ ), - C = CH-CH ₂ -

cis -Δ 3 1 ice -Δ 5

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Although the ice-cream pseudo-jonon was not made, one can the cis-ß-ionone in a different way starting from the 2,6,6-trimethy! -cyclohexanone produce, which is reacted with acetylene to form trimethyl-äthinyl-cyclohexanol, which is in turn subjected to a Grignard reaction according to the following route:

HG S CH

Pd / C

CS CHgBr ^

C S CH

CH ₃ MgBr

cis-ß-ionon

The cis-c6- or ß-ionones can also be obtained by means of ultraviolet radiation the trans-o6 - or ß-ionons obtained.

It is believed that the cis -β-ionone is in equilibrium with a pyran structure.

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This has been reported in J. Am. Chem. Soc. 88, 619-20 (1966). Recently, Martell et al (J. Org. Chem. _3Z> 2992, 1972) have also shown that the Λ 3-cis ionone exists in equilibrium with the pyran form. Buchi and Wang (HeIv. Chem. Acta 160 , 1339, 1955) have described the preparation of the cis - <? G ion starting from the trans isomer by irradiation. Since the cis-ß-ionone is obviously present at least to a certain extent in the open-chain structure and the equilibrium is stored in such a way that the mixture behaves as if it were entirely in open-chain form, it is not necessary in the present description to maintain the pyran structure, so that this is not mentioned in the following.

It has now been found that the previously unknown and unstable cis-A3 pseudo-jonons based on Dehydrolinalool and its homologues can be produced by reaction with an isoalkenyl ether, also known as Alkyl- [alken (2) -yl (2)] -oxide denote (cam) in the presence of compounds selected from copper (II) sulfate, copper (II) nitrate and the metal salt amine complexes. In addition, it appears that of the two possible cis-Δ3 isomers, i.e. cis-Δ 3-cis / l -5- and cis- ^ 3-trans-A5, there is only one and the interpretation the analytical results allow the conclusion to be drawn about the presence of the cis-Δ3-trans-A5 isomer.

It is completely surprising that the invention Process the cis-A.3 isomer is obtained, since all other known processes (such as that of US Pat. No. 3,029,287), which start from dehydrolinalool and its homologues, to trans-Δ 3-pseudo-jonones to lead. It appears that the metal derivatives used are the reason for this remarkable result and that these compounds also produce the cis-Δ3 isomer allow in a single step.

One can convert the eis-A3 pseudo-jonon into cis-jonon, which is in equilibrium with the Λ-pyran form and to trans-ionone can be isomerized. You can also use the Eis-A3 pseudo-jonon Isomerize to the trans - ^ \ 3-pseudo-jonon and the latter can be converted into

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the trans-ionon be transferred.

Also, according to one embodiment of the invention, the dehydrolinalool or one of its derivatives is allowed to act on an alkylisopropenyl (or isobutenyl) oxide in the presence of a member of the group of copper sulfate, copper nitrate and the metal salt / amine complexes to form the corresponding pseudoionones or to obtain pseudomethylionones in general in the form of their A 3-cis isomers. The alkyl radical of the oxide preferably has 1-4 carbon atoms. The radicals substituting the dehydrolinalool include alkyl, alkenyl, cycloalkyl and cycloalkenyl radicals. The alkyl and alkenyl radicals can have up to 30 carbon atoms and the cycloalkyl and cycloalkenyl radicals from 3 to 30 carbon atoms: the lower alkyl and alkenyl homologues, the alkyl radicals with 1-4 carbon atoms and the alkenyl radicals with 2-4 carbon atoms are preferred. While some of the trans-Δ 3 isomer is obtained, the cis-A 3 isomer is generally produced as the predominant portion.

The eis-Λ3 pseudo-jonons and the cis-Δ 3-pseudomethyljonons open a convenient and direct way to .Manufacture the corresponding cis-ionones and cis-methyljonones.

The cis-Δ3-pseudo-ionons and the cis-Δ 3-pseudomethylionons can be isomerized to their trans- / \ 3-1 sorting, which lead to known ions and methyionons.

According to a more general feature of the invention is this implementation with some acetylenic tertiary alcohol of general formula (1-ethynyl-carbinole)

OH

R'- C C Ξ CH

R "

feasible _:. wherein

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(a) R ^{1 is} selected from the group consisting of the radicals of the formula

wherein R ₁ , R ~ and R-. are selected from the group of hydrogen, alkyl radicals with 1-4 carbon atoms and alkenyl radicals with 2-4 carbon atoms.

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(b) R "is selected from the group of alkyl radicals with 1-4 Carbon atoms' and of the alkenyl radicals with 2-4 carbon atoms .

In the event that the isoalkenyl ether is an isopropenyl ether, the course of the reaction according to the invention can be represented by the following scheme Σ:

Scheme I.

R = alkyl with 1-4 carbon atoms

OH

C - C = CH

ir

R * -

HHO

Isopropenyl ether

C = CH-C = C-C R "

o £ ~ jf-diethylenic ketone.

Is the isoalkenyl ether an isobutenyl ether or a higher one
Alkenyl ether, the condensation reaction proceeds according to the
following Scheme II with the formation of several Oi, / -diethylenic ketones.

Scheme II

OH

Rt. * »C -. C »CH R "

OK

sobuteny lather

R * C «CH - C = b ⁵ - C -

^, ^ - diethylenic ketone I. HHO

I ι II

Rt_ C = CH-C = CC-CH ₂ - I R "

oC, y'-diethylenic ketone II

A09833 / 1 OAI

The class of acetylenic tertiary alcohols with the structure des Dehydrolinalool is an example. The Dehydrolinaloole, to which the process according to the invention can be applied correspond to the general formula:

R ₄

where R. ,, R ~, R-, and R., which can be the same or different, represent alkyl radicals with preferably 1-4 carbon atoms or alkenyl radicals with preferably 2-4 carbon atoms, where 3L ·, IL, u ²¹ ^ ^ 3 can also be hydrogen atoms. In the event that the isoalkenyl ether is an isopropenyl ether, the predominant part is generally an cis- / ± 3-pseudojonon according to the following scheme III:

Scheme III

Dehydrolinalool or homolog

- OR

Isopropenyl ether

R, eis-Δ3 pseudo-jonon

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Reaction (b) - isomerization

Eis- A3 pseudo-jonon

trans-A3 pseudo-jonon

Reaction (c) - Cyclization

eis-Δ 3-pseudo-jonon

^u l

ice-CoU-, ß-, 3 ^

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If the isoalkenyl ether is an alkenyl radical with more than 3 carbon atoms, several isomeric eis-A3 pseudo-jonons are obtained in this way; the reaction can be illustrated by Scheme IV below.

Scheme IV

Reaction Ca) - condensation

R and R ₅ = alkyl

Dehydrolinalool
or homologous

higher alkenyl ethers

^R 2

cis-Δ 3-isoalkyl pseudo-jonone

cis - Δ 3 - normal alkyl pseudo-jonone

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404913

Reaction (b) - isomerization to trans-Δ 3 isomers

cis- IS 3-isoalkyl pseudo-jonone

^LV 5

cis-Δ 3-normal-alkyl pseudo-jonone

Isoalkyl pseudo-jonone normal-alkyl-pseudojonon

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- 12 reaction (c) - cyclization

and or

ice pseudo jonon

eis-A 3-normal-alkyl pseudo-jonone

H H

and or

cis-isoalkylionone

cis-normal-alkyl ionone

The process according to the invention can be applied to isoalkenyl ethers, in which Rr is a radical greater than the methyl radical, such as the ethyl, propyl and isobutyl radical, although the process is of particular economic interest when the radical R _{5 is} a methyl radical.

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The expressions "cis-A3-pseudo-jonon", "cis-A3-isoalkyl-pseudo-jonone" and "cis-A3-normal-alkyl-pseudo-jonone" are used to denote the compounds corresponding to the above formulas. Similarly, the terms "cis-ionone" and "cis-alkylionone" are used to denote the cis-ionones in the formulas presented above. It can be seen, however, that the isopropenyl ethers give pseudo-jonones and that the isobutenyl ethers give cis-A3-methyl-pseudo-jonones. The cis-alkyl pseudojonones exist in iso- and normal-forms. By cyclizing, the pseudo-jonons or the alkyl-pseudo-jonones result in the mixtures of cis-oi /, β- and J "-ionons and of cis-alkylionons ₀

It goes without saying that when Rp and R- are both low Are alkyl groups, the isomeric a-ionones do not exist.

In the course of the addition of the isoalkenyl ether to the tertiary acetylenic carbinol, the substituent R of the isoalkenyl ether is converted into the corresponding alcohol, which is normally is caught by the excess isoalkenyl ether «,

If the radicals R ^, Rp and R _{3 represent} a hydrogen atom and the radical R _{4 represents} a methyl radical, the acetylenic alcohol is dehydrolinalool. The condensation of the dehydrolinalool with an isopropenyl ether gives the cis-Δ3-pseudojonone and the condensation of the dehydrolinalool with isobutenyl ethers gives the cis- Δ 3-methyl-pseudojonone in the two iso- and normal forms.

The derivatives and homologues of dehydrolinalool give the corresponding pseudo-jonones and the cis-Δ 3-methyl-pseudo-jonones in the same way in the iso and normal forms.

The process according to the invention can be applied to the following tertiary Apply acetylenic carbinols:

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OH

OH

OH

OH

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The latter lead to the following eis-oC-ionons, if one Isopropenyl ether used according to scheme I and then cyclized:

H H

40 9833/1 OAl

IsO-C ₄ H ₉

For the Pall that Rp and R ^ are both alkyl radicals, for example with the carbinol of the formula

the corresponding cis-ionones only exist in the ß- and 5 -forms, i.e.

and

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These tertiary acetylenic alcohols lead to the following cis-isomethyl-6-ionones, if one is used according to scheme II Isobutenyl ether used and then cyclized:

R,

4 O 9 8 3 3/1 O ά. 1

The inventive method is also applicable to the three tertiary acetylenic alcohols of the following formulas can be used:

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The process according to the invention is carried out in the presence of copper (II) sulfate, Copper (II) nitrate or a metal salt amine complex carried out.

The metal salt amine complex has an unknown structure, may but by an empirical formula

I ²

. Y

can be defined in which:

a) MY is the metal salt, where M is the metal and Y is the anion of the salt. For example, one can use the copper, Name chromium and silver salts;

b) Rj, R ₂ and R ₃ j, which are identical or different, represent monovalent hydrocarbon radicals having 1-30 carbon atoms or hydrogen. ·

Two of these radicals can form a divalent hydrocarbon radical, the heteroatoms, such as nitrogen, oxygen or may include sulfur (e.g. of the morpholine or thiazole type) or may include three of these Hydrocarbon residues become a single one diminish the divalent radical, as in the case of pyridine ^

c) η is the number of amine groups in the complex and is in the range from 0.01 to 50, preferably from 1 to 6, but does not necessarily represent a molar relationship.

It is understood that the number of metal atoms M and the anions Y are in equilibrium in the metal salt depending on their valencies.

Regarding the amines one can name: the methylamine, butylamine, decylamine, diethylamine, dipropylamine, dibutylamine, dioctylamine,

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the aniline, para-toluidine, meta-toluidine, trimethylamine, triethylamine, Ethyldimethylamine, decyldipropylamine, N-methylaniline, Cyclohexylamine, cyclopentylamine, methylcyclohexylamine, morpholine, pyridine, pyrazine, piperidine, pyrimidine, quinoline, isochino- lin, thiazole, triazole, oxazole and the pyrrole.

The metal salt-amine complexes are prepared by reacting the amine with a compound of the metal. The liquid amine can serve as the reaction medium. You can also use water to dissolve the Add metal derivative if the latter is soluble in water. You can also use a lower aliphatic alcohol instead of the Use solvent.

Any metal salt can be used. The accessible effective salts are generally those in which the anion Y is chlorine, bromine, iodine, nitrate or sulfate.

The effectiveness of the metal salt-amine complex is surprising, since the amine alone does not have a catalytic effect and the metal salts for the most part do not have a sufficient catalytic effect However, even if the metal salt is a catalyst by itself such as copper sulfate, the effectiveness will be greatly multiplied by the amine.

The percentage of the amine is not critical and need not be stoichiometric if a complex is certain. This is probably due to the fact that the excess of the metal salt or amine which cannot be complexed may be present. The catalyst can have a nitrogen content of 1 - 30% exhibit. For an optimal effect, however, a proportion which corresponds to a value for η of 1 to 4 is preferred.

The catalyst content can be very low. A level as low as 1 % is effective, but better results are obtained with levels of 1-5%. You can use a content of over 5%, for example up to about 10%; however, this does not seem to bring any advantages corresponding to the amount of catalyst used.

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In the case of copper (II) nitrate, it has been shown that low Catalyst amounts from about 0.1 to 3.5% the formation of the cis isomer favor, while amounts in the order of 3.5-10% favor the formation of the trans isomer. It is possible that high copper (II) nitrate concentrations cause isomerization favor the cis connection to the trans connection.

The reaction time usually varies between 0.2 hours and 3 days, depending on the reaction components, the intensity of the Drilling, furnace temperature and catalyst content. In general the reaction is complete after 2 to 40 hours.

The reaction temperature is the most general criterion. The reaction generally proceeds at temperatures from 80 to 150 ^° C. and preferably from 85 to 125 ° C. At temperatures below 80 ° C., the reaction very frequently does not proceed at a sufficiently high rate. Above 125 °, only the trans-A3 isomer is produced, and the side reactions tend to reduce the yield of the trans isomer.

However, in the case of copper nitrate, the reaction can occur spontaneously Use room temperature and the heat generated is sufficient to achieve a sufficient degree of conversion without heating, although heating can increase this degree of conversion. In the case of copper nitrate, temperatures between 10 and 45 ° C, preferably work between 15 and 38 ° C, but you can also as with the other catalysts of the group up to 125 or 150 ° C.

Because of the low boiling point of the isoalkenyl ether, the reaction is preferably carried out in a closed vessel good stirring carried out. However, when using copper (II) nitrate at a low temperature, you can also use it in an open Working container.

The reaction proceeds better and with a better yield if one works without a solvent. In the presence of solvents the reaction always takes place, but with reduced efficacy

^prey 409833/1041

It appears that the catalyst operates preferentially in the presence of a high concentration of the reactants.

After its isolation, the cis-A 3-pseudoionone can be cyclized to form ionone or alkylionone in the presence of an acidic cyclizing agent. The procedure is analogous using the usual working conditions and using the acids usually used under similar circumstances, for example phosphoric acid in the presence of a suitable solvent under heat or an acetic acid / sulfuric acid mixture at low temperature.

By direct cyclization of the cis- Δ 3-pseudo-jonone in the presence of strong acids, a mixture can be obtained which contains large amounts of cis - (# /. ~ ₇ ß- and <^ -) - ionone. The cis (ocß- and y) -Jonone have entirely different odor characteristics that completely and clearly different from those of the trans - ^ - _y ft and f-ionones are and find in perfumes application.

One can use the eis - / ^ 3 pseudo-jonon under different conditions Isomerize to the trans-Ä3-pseudo-jonone. In the presence of catalysts the isomerization generally takes place at room temperature, but higher temperatures can also be used Apply up to about 150 C. Very low levels of catalyst are effective. So you can with catalyst contents of 0.2 to 0.4% isomerize completely. It is also possible to use higher percentages, for example up to 10%, but these are not noticeable Improvement occurs.

Elemental halogens are preferred as isomerization catalysts Form, such as bromine and iodine. Iodine is preferably used in a solvent which is inert to iodine, such as ethyl ether or isopropyl ether, to facilitate contact with the cis pseudo-jonon or the alkyl pseudo-jonon.

In general, any acid, base, acid salt or basic salt can be used as the isomerization reagent. as

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Acids can be called sulfonic acids, p-toluenesulfonic acid and octanesulfonic acid; the carboxylic acids such as formic acid, acetic acid, trichloroacetic acid and propionic acid; the inorganic Acids such as nitric acid, phosphoric acid, sulfuric acid and hydrochloric acid, the Lewis acids such as boron fluoride. The hydroxides of sodium, potassium and ammonium can be named as bases, and silver nitrate can be named as salts.

It is also possible to isomerize by means of ultraviolet radiation. It works at room temperature and for a relatively short time, for example 0.2 to 10 hours, and at temperatures of 25 to 150 ^° C.

Even heating to an elevated temperature in the absence of catalysts and a range from 125 to 150 C can alone lead to isomerization of cis- ^ 3- to trans-A3-pseudo-jonone.

The following examples serve to illustrate the invention:

Example 1 '

45.6 g (0.299 mol) of dehydrolinalool, 64.8 g (0.894 mol) of 2-methoxypropene and 0.9 g are placed in a pressure-resistant glass vessel (5.6 χ 10 mol) anhydrous copper (II) sulfate. One brings Place a magnetic stir bar, close the bottle and immerse it in an oil bath heated to 85 to 89 ° C while stirring.

It is kept at this temperature for 39 hours; gas-liquid chromatography of the product obtained shows that it consists essentially of cis-pseudo-jonone. It is therefore not necessary to continue the reaction. The heterogeneous brown reaction mass is filtered while warm through a bed of Celite with the aid of benzene and the solvent is stripped off in vacuo. A rapid distillation at a pressure of 0.5 mm Hg and a temperature at the column head 74-160 ° C (temperature of the mass 91 to 190 ⁰ C) results in 3.7 g of a residue and 59.4 g of distillate. The gas-liquid chromatography of the distillate shows the following results:

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7th % , 4 % traces _} 2 % O 86

Light parts
Dehydrolinalool

unidentified
Products

eis-Δ 3-P seudoj onon

trans-Δ 3-pseudo-jonon

(cis-A5) 1.5 %

trans-Δ 3-pseudo-jonon

(trans-Δ 5) 3.7%

heavy proportions 1.1%.

The cis-Δ3 pseudoionone not correspond to the gas-liquid chromatography retention time of trans-ZI3-isomers cm in 6.36 or 8.23 minutes on a column of 10% Carbowax 2OM at 190 ⁰ C of 304 length and 0.64 cm in diameter (and at a capacity of about 100 cm / min). Under the same conditions, the cis / \ 3 isomer is eluted in 5.4 minutes. The eis-A3 isomer has a Λ at 292 (E =; 18400) in hexane and a Λ at 300 (E = 17200) in ethanol. The index n- is 1.5251. The infrared spectra of the ice-A 3- and trans-pseudoionones A 3 are different, and their nuclear magnetic resonance spectra.

IR spectra

Cis-Δ3 pseudo-jonon Trans-Δ3- (cis- and trans-A5) -

Pseudo-jonons (mixture of nerolid and geranylid acetones)

1690 cm strong 1674 era " ¹ strong 1627 strong 1634 strong 1578 strong 1595 strong 1433 middle 1447 middle 1380 middle 1363 medium to strong 1356 strong 1255 strong 1253 medium to
weak 1162 medium to weak 1177 strong 974 medium to strong 967 middle 757 nothing 757 middle 409833 / 1041

Nuclear magnetic resonance spectrum of eis-Λ3-pseudoionon

Doublet centered at 1.6 ppm, 6 isoprenylmethyl protons.

Non-symmetrical doublet centered at about 1.85 ppm, 2 methylene * ^ rotons.

Singlet at about 2.1 ppm, 3 methyl ketone protons. Locked in into the methyl ketone singlet, centered at about 2.15 ppm, 2 methylene protons. Far, at around 5.1 ppm centered singlet, 1 vinyl proton.

Doublet centered at about 5.8 ppm (J = 11 Hz), 1 vinyl proton.

Triplet centered at 6.6 ppm (shoulder at 11.5 cps), 1 vinyl proton.

Doublet centered at about 7.15 ppm (J about 11.5), 1 vinyl proton.

The amount of cis-pseudoionon produced (52.4 g = 0.273 mol) represents a yield of cis-pseudojonon of 91.4% The total yield of cis and trans pseudo-jonons is 96.8%.

Example 2

Example 1 is repeated, but working at 91 ° C. for 21 hours. A yield of 92.9 % cis-pseudojonon is obtained and the total yield of cis- and trans-pseudojonon is 95.2%.

The isolated product shows on gas-liquid chromatography the following composition:

Wt%

Dehydro.linalool 2.0

Cis-Δ3 pseudo-jonon 90.6

Trans- Λ3 pseudo-jonon (cis-A 5) 0.6

A trans-3-pseudoionone (trans-Λδ) 1.4

heavy proportions 1.1 unidentified compounds

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Example 3

In a pressure-resistant vessel equipped with a magnetic stirrer, 61.2 g of dehydrolinalool, 86.5 g of 2-methoxypropene and 1.2 g of anhydrous pulverized copper (II) sulfate are introduced. Man The mixture is stirred for 20.5 hours in an oil bath at 85-89 ° C., after which the brownish reaction mixture is cooled, then with the aid of Benzene is filtered to obtain the catalyst and the light fractions are removed by stripping off in vacuo. The rapid distillation at 1.4 to 0.9 mm Hg (temperature at the top of the column 67 to 114 ° C., temperature of the mass 104 to 122 ° C.) gives 79.2 g of distillate and 4.9 g of residue. The distillate has the following composition (analysis by gas-liquid chromatography):

Wt%

Easy proportions 7.1

unidentified 0.7

Cis A3 pseudo-jonpn 83.7

Trans-Δ 3 pseudo-jonon

({\ 5 , cis- and trans-) 8.3

heavy parts 0.2

Yield: 85.7 % cis- A3-pseudojonon 94.5% Δ3-pseudojonon.

Example 4

0.3 g of copper (II) sulfate recovered from a previous experiment, 15.2 g of dehydrolinalool and 21.6 g of 2-methoxypropene are placed in a pressure-resistant vessel. The mixture is heated with stirring to 83 to 89 ° C. for 13 hours, then cooled, filtered and washed with water, whereupon the light components are evaporated at 50 ° C. and 40 mm Hg. The rapid distillation of the flashing back oil at 1 to 0.5 mm Hg and 60 to 138 ° C in the top of the column (100 to 180 ° C in bulk) gives 18.1 g of a yellow oil containing 0.04 g of dehydrolinalool, Contains 15.4 g of cis- Δ 3-pseudo-jonon and 0.8 g of trans-Δ3-pseudo-ion.

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Example 5 Cis-Δ 3-isomethyl-pseudoionone

A pressure-resistant vessel is charged with 15.2 g of dehydrolinalool, 36.4 g of a mixture of 2-ethoxy - / \ 1-butene and 2-ethoxy - / \ 2-butene and 0.3 g of anhydrous pulverized copper (II) sulfate . The mixture is stirred at a temperature of 87 to 89 ° C. for 70.3 hours, then cooled and filtered through a bed of celite with the aid of cyclohexane. The organic layer is washed twice with an equal volume of water and dried over sodium sulfate, and the light components are removed by stripping off in vacuo. The rapid distillation of the remaining oil at 0.4 to 0.8 mm Hg and a temperature in the top of the column of 34 to 114 ° C (temperature in the mass 64 to 180 ⁰ C) gives 17.5 g of a yellow oil, the 51.1% of a mixture of 3-methyl-cis- / 3-pseudo-jonone and 1-methyl-cis- ^ 3-pseudo-ion and 9.5 % of a mixture of trans- ^ 3-, cis- and trans-Δ 5 -Methyl pseudo-jonons contains.

Example 6

In a pressure-resistant glass vessel equipped with a magnetic stirrer, 15.2 g of dehydrolinalool, 21.4 g of 2-methoxypropene and 0.3 g of copper (II) nitrate trihydrate are introduced. By stirring The salt is dissolved in the mixture, an exothermic reaction takes place and the solution turns brown. Gas-liquid chromatography shows that at this moment about 40% cis - / ^ 3 pseudo-jonon have formed. One warms them up The reaction mixture was then heated to 90 ° C. for 17 hours. After cooling and washing with water, the mixture is concentrated by evaporation in a vacuum. The remaining oil is rapidly distilled at 0.8 mm Hg and a temperature at the top of the column of 38 to 160 ° C., 18.2 g of distillate and 1.7 g of residue being obtained. Gas-liquid chromatography of the distillate shows that there are 6.53 g of dehydrolinalool, 8.01 g of cis-Δ3-pseudo-jonone and contains 0.71 g of trans-Λ3-pseudo-jonon.

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Example 7

15.2 g of dehydrolinalool, 21.4 g of 2-methoxypropene and 0.3 g of pulverized copper (II) nitrate trihydrate are placed in a pressure-resistant glass vessel equipped with a magnetic stirrer. The whole thing is stirred. . As the salt dissolves, the color of the mixture turns brown, while an exothermic reaction takes place in a few minutes. The mixture is left to stand for one hour, after which analysis by gas-liquid chromatography shows the presence of about 40-50% of condensation products (mainly cis-Δ3-pseudo-jonone). The reaction mixture is then immersed in a 90 ° C. oil bath for 70 minutes. After cooling, the mixture is washed with water, the light components are drawn off in vacuo and the residue is rapidly distilled at 1 mm Hg and a temperature at the top of the column of 60 to 191 ° C. 16.3 g of distillate and 3.5 g of residue are obtained in this way. Analysis by gas-liquid chromatography shows that the distillate 7.78 g dehydrolinalool, 5.8 g of ice - contains /) i3-pseudoionone and 1.03 g of trans-3-fa pseudoionone.

Example 8

In a pressure-resistant glass vessel equipped with a magnet stirrer, 15.2 g of dehydrolinalool, 21.4 g of 2-methoxypropene and 0.3 g of powdered copper (II) nitrate trihydrate are introduced. After an initially exothermic reaction, the resulting homogeneous mixture is left with stirring for 17 hours at room temperature stand. The mixture is washed with water, the light components are drawn off in vacuo and the oil that remains is distilled off rapidly below 1 mm Hg at a temperature at the top of the column of 68 to 214 ° C. 16.2 g of distillate and 2 g of residue are obtained in this way. Gas-liquid chromatography of the distillate shows a content of 8.2 g of dehydrolinalool, 6.05 g of cis-A 3-pseudoion and 0.79 g trans- / ^. 3 — pseudo jonon.

Example 9

In a two-necked flask of 100 cm, equipped with a magnetic stirrer he, a thermometer, a dropping funnel and a cooling bath,

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15.2 g of dehydrolinalool and 0.99 g of powdered copper (II) nitrate trihydrate are introduced. 21.6 g of 2-methoxypropene are then added dropwise over the course of one and a half hours, the temperature being kept between 10.degree. And 20.degree. Stirring is continued for 15 hours at room temperature, and the final brown solution is washed three times with about 75 cm of water, each washing solution itself being extracted with cyclohexane. Combine the organic layers, dry them over sodium sulfate and remove the solvent in a vacuum of about 40 mm Hg. The rapid distillation of the remaining oil at 1.5 to 0.3 mm Hg and a temperature of 40-140 ° C in the column head (70 to 200 ⁰ C in the mass) yields 14.8 g of distillate and 5.8 g of residue. The gas-liquid chromatographic analysis of the distillate shows a content of 9.04 g of dehydrolinalool and traces of cis- / S 3-pseudojonone and 3.85 g of trans-. / \ 3-pseudojonone.

Example 10

In a pressure-resistant vessel equipped with a magnetic stirrer, 15.2 g of dehydrolinalool, 21.6 g of 2-methoxypropene and 30 mg of copper (II) nitrate trihydrate are introduced. One stirs at room temperature for 16 hours and then for 93 hours at 50 ° C.

A further 30 mg of copper (II) nitrate trihydrate are introduced and the mixture is stirred at 50 ° for 20.5 hours.

Finally, it brings a final portion of 30 mg of cupric nitrate trihydrate, and stirred for 7 hours at 50 ⁰ C. At this time, the reaction mixture is dark brown in color and contains no insolubles.

The mixture is poured into 50 cm of cyclohexane and washed three times 75 cm of water (each wash water is extracted with cyclohexane itself). You combine the organic layers, you dry them over sodium sulfate and draws the solvent at about 40 mm Hg away.

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The distillation of the remaining oil at 1 to 1.3 mm Hg and a temperature of 60 to 109 ° C. in the top of the column (temperature of the mass 80 to 156 ° C.) gives 13.3 g of distillate and 5.8 g of residue. The gas-liquid chromatographic analysis of the distillate shows 4.79 g of dehydrolinalool, 4.65 g of ice-Ä3-pseudoionone and 0.32 g of trans-Δ 3-pseudoionone.

Example 11

6 g of anhydrous copper (II) sulfate are dissolved in water and 27.7 g of quinoline are added, which immediately leads to the formation of a clear-green precipitate. 100 cm of methanol are added and the slurry is filtered. The filter cake is washed with methanol and the clear green solid is allowed to air dry. Analysis of the solid found 17.6% copper, 6.81 % sulfur, 48.99% carbon, 3.81 % hydrogen and 6.50 % nitrogen.

15.2 g of dehydrolinalool are placed in a pressure-resistant vessel,

21.6 g of 2-methoxypropene and 0.3 g of the above catalyst. The magnetic rod stirrer is added, the vessel is closed and immersed in an oil bath heated to 90 ° C. for 4.2 hours. The oily mixture obtained is washed with water. The light components are removed by distillation at 44 mm Hg at 60 ⁰ C and the residual brown oil is distilled quickly at 1.2 to 1.5 mm Hg and a temperature at the column head of from 40 to 22O ° C. 1.1 g of residue and 17.9 g of distillate are obtained in this way.

The distillate contains 0.48 g of dehydrolinalool, 15 g of cis-Ä3-pseudojonon and 1 g of trans-Δ3 pseudo-jonon.

Example 12

3 g of anhydrous copper (II) sulfate are placed in a bottle with stirring and 30 g of diethylamine. After stirring the mixture for 4 days at room temperature, the solid is filtered off, wash it with ethyl acetate and air dry it. A blue powder is obtained (elemental analysis: 8.15% hydrogen,

33.07 % carbon, 9.41% nitrogen and 25.9% copper).

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15.2 g of dehydrolinalool, 21.6 g of 2-methoxypropene and 0.3 g of the above catalyst are placed in a pressure-resistant vessel · Add the magnetic stir bar, close the vessel and it is immersed in an oil bath heated to 90 ° C. for 3.75 hours. The brown, practically homogeneous mixture is washed with it Water. The light components are drawn off in vacuo and the mixture is distilled the remaining oil at 1 mm Hg and a temperature in the top of the column of 40 to 174 ° C (temperature of the mass 80 to 200 ° C). 14.9 g of distillate and 4.3 g of residue are obtained in this way. The distillate contains 0.8 g of dehydrolinalool, 3.8 g of cis-43-pseudo-jonone and 5.3 g of trans-Α3-pseudo-jonone.

Example 13

A pressure-resistant vessel equipped with a magnetic stirrer is charged with 30 g of triethylamine and 3 g of anhydrous copper (II) sulfate. The mixture is stirred for 21.5 hours at 90 ° C. and then the clear green precipitate is filtered off, the filter cake is washed with ethyl acetate and dried in the air. The catalyst contains 3.14% nitrogen, 15.42 % carbon and 4.44 % hydrogen.

15.2 g of dehydrolinalool are placed in a pressure-resistant vessel,

21.6 g of 2-methoxypropene, 0.3 g of the above catalyst and a magnetic stir bar, closes the vessel and immerses it in an oil bath at 90 ^° C. for 2.5 hours while stirring. The practically homogeneous reaction mixture is cooled and washed with water. The volatile components are driven off by stripping off in vacuo and the remaining oil is rapidly distilled at 1.1 to 1.5 mm Hg and a temperature at the top of the column of 40 to 135 ^° C. (temperature of the mass 80 to 190 ^° C.). This gives 18.5 g of distillate and 0.7 g of residue.

The distillate contains 1.7 g of dehydrolinalool and 15.72 g of condensation product. The direct yield is around 82% and the actual yield is 92.4%.

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Example 14

6 g of copper (II) sulfate are dissolved in water and 16.8 g of pyridine are added dropwise, while stirring and cooling. After finished Addition, the mixture is stirred for one hour and ethanol is added. The sky-blue precipitate is filtered off and washed with

·· V 9 | Tl C L 6 JlJ I i iJ J, \ i ^ s *

Ethanol and dried IhnV5rs "" Z "a constant weight. Elemental analysis reveals 10.35 % nitrogen, 33.68 % carbon, 3.97 % hydrogen and 17.9% copper.

Bring 15.2 g of dehydrolinalool into a pressure-resistant glass vessel, 21.6 g of 2-methoxypropene and 0.3 g of the above catalyst and a magnetic stir bar, closes the vessel and It is immersed in an oil bath at 90 ° C. with stirring for 17.5 hours. The practically homogeneous reaction mixture is cooled and washed with water. The volatiles are removed in vacuo and the remaining oil is rapidly heated to 0.5-3.9 mm Hg and a temperature in the top of the column of 75 to 142 C (temperature of the mass 125-163 ° C) distilled. 18.2 g of distillate are obtained in this way and 1.6 g of residue.

The distillate contains 0.8 g of dehydrolinalool, 12.1 g of ice-Δ3-pseudo-jonone and 3.2 grams of trans- ^ 3 pseudo-jonon.

Example 15

6 g of copper (II) sulfate are dissolved in water, 16.8 g of pyridine are added dropwise with stirring and the reaction mixture obtained is left to stand for 1 hour at room temperature while stirring. The sky-blue solid is filtered off, washed with ethyl acetate and air-dried for 15 hours. Elemental analysis reveals 4.55% nitrogen, 20.86 % carbon, 2.75% hydrogen, and wet analysis reveals 25.6% copper and 6.3% water.

15.2 g of dehydrolinalool, 21.6 g of 2-methoxypropene and 0.3 g of the above catalyst are placed in a pressure-resistant vessel a; a magnetic stir bar is added, the vessel is closed and

4 0 9 8 3 3/1041

immerse it in an oil bath for 1 hour and 50 minutes while stirring 9O ° C. The practically homogeneous reaction mass is cooled and washes them with water. The light fractions are driven off by stripping off in vacuo and the oil that remains is distilled off Schnell. at 0.6 to 1.1 mm Hg and a temperature at the top of the column of 30 to 121 ° C (100 to 160 ° C ii so 16 g of distillate and 5.7 g of residue.

head from 30 to 121 ° C (100 to 160 ° C in the mass). You get

The distillate contains 6.7 g of cis-4,3-pseudojonone and 5.6 g of trans-A 3 pseudo-jonon.

Example 16

4 g of Cr (NO ₃ ) ₃ .9HpO are introduced into 50 cm of hot methanol and then 4.8 g of pyridine are added. A vacuum of 30 mm Hg is applied to the dark blue solution for 68 hours at room temperature. 4.9 g of gray crystals are obtained in this way. Elemental analysis reveals 13.40% nitrogen, 41.88% carbon, 3.62% hydrogen and 8.14 % chromium.

15.2 g of dehydrolinalool, 21.4 g of 2-methoxypropene and 0.3 g of the above catalyst are placed in a pressure-resistant vessel which is lined with glass on the inside. A magnetic bar is added and the mixture is stirred at 90 ^° C. for 2 hours, then the brown-salmon-pink reaction mixture is filtered, washed with water and a vacuum of 40 mm Hg is applied at 60 ° C. Rapid distillation of the remaining brown oil at 0.8 mm Hg and a temperature at the top of the column of 53 to 154 ° C. (temperature of the mass 70 to 190 ° C.) gives 14.9 g of distillate and 0.7 g of residue.

Gas-liquid chromatographic analysis of the distillate shows that there are 6.12 g of dehydrolinalool, 6.85 g of cis-A3-pseudo-jonone and contains 1.49 g of trans- ./ \ 3-pseudo-jonon.

Example 17

4 g of Cr (NO ₃ ) ₃ .9H ₂ O are dissolved in 50 cm hot methanol and then 4.8 g of pyridine are added. You add to the received

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dark blue solution, a vacuum of 40 mm Hg for 68 hours at room temperature and thus receives 4.9 g of gray crystals. By Elemental analysis shows 13.4o% nitrogen, 41.88% carbon, 3.62% hydrogen and 8.14% chromium.

A pressure-resistant vessel lined on the inside with glass is charged with 15.2 g of dehydrolinalool, 21.4 g of 2-methoxypropene and 0.3 g of the catalyst obtained above. It also adds a magnetic stir bar added, the mixture stirred for 18 hours at 90 ⁰ C, then the mixture filtered, washed with water and evaporated at 40 mm .hg and 60 C. The rapid distillation of the residual oil under 0.8 mm Hg and at a temperature in the top of the column between 54 and 135 ° C (65-200 ° C in the mass) gives 16.6 g of distillate and 0.6 g of residue. Analysis by gas- liquid chromatography shows 8.03 g of dehydrolinalool and 8.22 g of condensation product.

Example 18

_ 3

6 g of copper-III sulfate are dissolved in 20 cm of water and then 20 g of aniline are added dropwise with stirring. The yellow solid obtained is filtered off, washed quickly with methanol and air-dried to constant weight. The elemental analysis shows that the catalyst contains 7.62 % nitrogen, 3.92% hydrogen and 41.59 % carbon, while the wet analysis allows the determination of 18.4 % copper.

15.2 g of dehydrolinalool, 21.4 g of 2-methoxypropene and 0.3 g of the above catalyst are introduced into a pressure-resistant vessel lined with glass on the inside. The magnetic stir bar is also used and the mixture is heated to 90 ^° C. for 4.8 hours while stirring. The reaction mixture is cooled and washed three times with an equal volume of water (each wash water is extracted with cyclohexane), the organic layers are combined, drier over sodium sulfate and the solvent is removed in vacuo. By rapid distillation of the residue below 0.4 to 1 mm Hg and at a temperature in the top of the column between 50 and 150 ° C

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(Temperature of the mass 85 to 200 ° C.) one receives 17.3 g of distillate and 2.5 g of residue.

The distillate contains 0.42 g of dehydrolinalool, 10.8 g of ice-Δ3-pseudpionon and 3.8 g of trans-Δ 3-pseudo-jonon.

Example 19

3.6 g of copper (II) chloride are dissolved in 20 cm of water. 16.8 g of pyridine are added dropwise with stirring. A blue color is formed immediately. Methanol is added to precipitate the complex, the complex is filtered, washed three times with methanol and air-dried. A clear blue powder is obtained in this way. The catalyst contains (elemental analysis) 13.40% nitrogen _; 41.88 % carbon, 3.62% hydrogen and 23.2% copper.

15.2 g of dehydrolinalool, 21.6 g of 2-methoxypropene and 0.3 g of the above catalyst are introduced into a vessel. A magnetic stir bar is also used and the mixture is stirred for 54.5 hours at 90 ° C. The practically homogeneous brown solution is cooled and washed three times with an equal volume of water (each wash water is itself extracted with cyclohexane). Combine the organic layers and dry them over sodium sulfate and remove the solvent in vacuo. (Up to 140 ⁰ C in the mass 57), one obtains 15.5 g of distillate and 2.7 g of a residue by distillation of the residual brown oil at 0.8 mm Hg and a temperature at the column head 50-124 ° C.

The distillate contains 11.1 g of dehydrolinalool, 1.74 g of ice-Δ 3-pseudo-jonone and 0.12 g of trans- Λ3-pseudojonon (gas chromatographic Analysis).

Example 20

3 g of CuSeO _{4 are dissolved} in 5 cm of hot water and 8 cm of methanol are added. A bodice forms on it. 4.8 g of pyridine are added while heating. A dark blue one is obtained

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3 solution and then gradually adds 200 cm of methanol and 500 cm of acetone. The pale blue flakes obtained are filtered off, washed with methanol and then with ether and air-dried for 15 hours, a clear blue powder being obtained. This powder contains 5.82% nitrogen, 25.8% carbon, 2.94 % hydrogen and 20.4% copper (elemental analysis).

15.2 g of dehydrolinalool, 21.4 g of 2-methoxypropene and 0.3 g of the above catalyst are introduced into a vessel. A magnetic stir bar is also used and the mixture is heated to 90 ^° C. for 49.5 hours. The mixture is cooled, extracted with water, the washing water is extracted with cyclohexane, the organic layers are combined, dried over sodium sulfate and the light components are drawn off in a vacuum. The remaining oil is rapidly distilled below 0.8 mm Hg at a temperature in the top of the column of 50 to 181 ° C. (temperature in the mass 86 to 220 ° C.).

13 g of distillate and 1.4 g of residue are obtained in this way.

The distillate contains 11 g of dehydrolinalool, 0.94 g of ice - / ^ _- 3-pseudo-jonone and 0.27 g of trans-Δ 3-pseudo-jonone (gas-liquid chromatographic analysis). The direct yield is 6.6 %, the actual yield 23%.

Example 21

6.5 g of copper (II) nitrate trihydrate and then 16.8 g of pyridine are introduced into 20 cm of methanol. The blue-violet precipitate obtained is washed with methanol and then dried in air for 15 hours. It contains 11.66 % copper, 16.75% nitrogen, 4.13% hydrogen and 47.87% carbon (elemental analysis).

15.2 g of dehydrolinalool, 21.4 g of 2-methoxypropene and 0.3 g are placed in a pressure-resistant vessel lined with glass on the inside of the above catalyst. You then place one

409833/10 4 1

Magnetic stir bar and stir the mixture for 3.2 hours at 90 ° C. After cooling, the cloudy brown solution is washed with water (the wash water is also extracted with cyclohexane), combine the organic layers, dry them over sodium sulfate and drives off the volatile components in a vacuum. Distillation in vacuo as in Example 20 gives 17.6 g of distillate and 1.5 g residue.

The distillate contains 4.47 g of dehydrolinalool, 11.16 g of cis-A3-pseudojonon and 1.33 g of trans-Δ3-pseudojonon (gas-liquid- ^ chromatographic analysis).

Example 22

3.6 g of copper (II) chloride are dissolved in 20 cm of water and 16.8 g of pyridine are then added dropwise with stirring. Methanol is added to the blue solution, which gives a blue solid precipitate which is filtered off, washed three times with methanol and air-dried to constant weight. The clear blue powder obtained contains 23.2 % copper, 13.40% nitrogen, 41.88% carbon and 3.62 % hydrogen (elemental analysis).

A pressure-resistant interior is lined with glass Vessel 15.2 g of dehydrolinalool, 21.4 g of 2-meth'oxy-propene and 0.3 g of the above catalyst. A magnetic stir bar is also used and the mixture is stirred for 28.3 hours at 120 ° C. The dark brown, cloudy solution obtained is washed with water and dried over sodium sulfate and rapidly distilled in vacuo below 0.8 mm Hg at a temperature at the top of the column of 53 to 198 ° C (in the mass 68 to 212 ° C). 15.6 g of distillate and 0.8 g of residue are obtained in this way. The distillate contains 11.8 g dehydrolinalool, 1.56 g Eis-A. 3-pseudojonon and 0.14 g trans-Δ. 3 pseudo-jonon.

Example 23

3 g of Cu (BP ₄ ) and then 9.6 g of pyridine are introduced into 15 cm of hot methanol. After cooling, a precipitate is obtained, which is washed with ethanol and then with ether and air-dried. 1.7 g of a micro-

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crystalline purple powder. The catalyst contains 10.8% copper, 10.07% nitrogen, 3.75% boron, 43.30% carbon and 3.79% hydrogen (elemental analysis).

15.2 g of dehydrolinalool, 21.4 g of 2-methoxypropene and 0.3 g of the above catalyst are introduced into a pressure-resistant vessel lined on the inside with glass. A magnetic stir bar is also used and the whole is heated to 90 ° C. for 19.8 hours while stirring. The resulting cloudy, dark brown mass is filtered off, washed with water (the wash water itself is extracted with cyclohexane) and the volatile components are driven off in vacuo . (60 to 190 ⁰ C in the mass) is obtained 19.2 g of distillate and 1.8 g of residue was purified by rapid distillation at 0.5 mm Hg and at a temperature in the top of the column between 40 and 150 ° C.

The distillate contains 11.46 g of dehydrolinalool and 2.63 g of condensation products (gas-liquid chromatographic analysis).

Example 24

6 g of silver nitrate are dissolved in 10 cm of water and then 22.4 g of pyridine are added dropwise with stirring. A vacuum of 40 mm Hg is applied to the clear solution obtained for 3 days. White crystals are thus obtained. The crystals are washed with ethyl acetate and then dried in air until the weight is constant, ie up to 11 g. The crystals contain 26.67 % silver, 36.15 % carbon, 12.94 % nitrogen and 2.99 % hydrogen (elemental analysis).

15.2 g of dehydrolinalool, 21.4 g of 2-methoxypropene and 0.3 g of the above catalyst are introduced into a pressure-resistant vessel lined with glass on the inside. In addition, a magnetic stir bar is used and the whole is heated to 90 ^° C. for 16.1 hours while stirring. At the end of the heating, the reaction medium is homogeneous. The black and cloudy final mixture is filtered off, washed with water and the volatile components are stripped off in vacuo. By rapid distillation

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below 0.5 to 0.2 mm Hg at a temperature in the top of the column of 50 to 120 ° C (65 to 160 ⁰ C
sti11at and 1 g of residue.

50 to 120 ° C (65 to 160 ⁰ C in the mass) you get 15.8 g of distilled

The distillate contains 11.04 g of dehydrolinalool and 5.3 g of condensation product.

Example 25

6 g of copper (II) sulfate are dissolved in water and then added 16.8 g of pyridine are added dropwise with stirring and cooling. After stirring for 1 hour, ethanol is added to precipitate the complex to, filter this and wash it with ethanol. Air drying gives 8.2 g of a sky-blue powder which Contains 17.9% copper, 9.38% sulfur, 10.35% nitrogen, 3.97% hydrogen and 33.68% carbon (elemental analysis).

15.2 g of dehydrolinalool, 21.4 g of 2-methoxy-butene (2) and 0.3 g of the above catalyst are placed in a pressure-resistant vessel lined with glass on the inside. A magnetic stir bar is used and the mixture is stirred for 17 hours at a temperature between 83 and 92.degree. After cooling, the mixture is filtered and the resulting brown hazy solution, washed with water (the washing water is itself extracted with cyclohexane) and ver _r drives the volatiles in vacuo. The rapid distillation of the brown oil obtained below 0.8 mm Hg and at a temperature in the Kölonnenkopf between 48 and 205 ° C (51 to 225 ° C in the mass) gives 13.5 g of distillate and 1.2 g of residue.

The distillate contains 3.77 g of dehydrolinalool and 4.77 g of a mixture of 3-methyl-cis-Ä 3-pseudojonon, 1-methyl-cis-A 3-pseudojonon and a mixture of trans-Δ · 3-methyl pseudo-ions.

Example 26

Man.bringt 3 g of powdered copper (II) sulfate in 30 g of n-propylamine and stir the mixture for 4 days at room temperature. After filtering, the solids are washed with ethyl acetate and then dries to constant weight. 7.9 g are obtained in this way

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dark blue crystals containing 33.07% carbon, 9.41% nitrogen and 8.15% hydrogen.

One brings in a pressure inventory lined with glass on the inside Vessel 15.2 g of dehydrolinalool, 21.6 g of 2-methoxypropene and 0.3 g of the above catalyst. You then place one Magnetic stir bar and stir the mixture for 12.8 hours at 120 C. The cloudy, dark brown reaction mixture is filtered and washed with water (the washing water itself is extracted with cyclohexane) . The organic layers are combined, dried over sodium sulfate and the light components are removed in vacuo. By rapid distillation of the brown oil obtained at 0.7 to 1 mm Hg and a temperature at the top of the column of 40 to 125.degree (80 to 190 ° C in bulk) 15.2 g of distillate and 1.5 g of residue are obtained.

The distillate contains 8.4 g of dehydrolinalool, 5.1 g of cis-Δ. 3 pseudo-jonon and 0.5 g of trans-Δ3 pseudo-jonons.

Example 27

6 g of copper (II) sulfate are dissolved in 20 cm of water and then 20 g of aniline are added dropwise with stirring. The yellow solid is filtered off, washed quickly with methanol and dried in air to constant weight. The catalyst contains 7.62 % nitrogen, 3.92% hydrogen and 41.59% carbon (elemental analysis) and 18.4% copper (wet analysis).

Place in a pressure-resistant vessel lined with glass 15.2 g of dehydrolinalool, 21.4 g of 2-methoxypropene and 0.3 g of the above catalyst. A magnetic stir bar is also used and then the mixture is heated to 90 ° C. for 4.8 hours while stirring. The mixture is cooled and washed three times an equal volume of water (the water is extracted with cyclohexane) and combine the organic layers, dry them over sodium sulfate and then pulls off the solvent in vacuo. By rapid distillation at 0.4 to 1 mm Hg and at a temperature in the top of the column of 50 to 150 ° C. (85 to 200 ° C. in bulk), 18.9 g of distillate and 1.2 g of residue are obtained.

409833/10 4 1

The distillate contains 0.3 g dehydrolinalool, 13.8 g cIs-Ä. 3-pseudo-jonon and 1.6 g of trans-Δ 3-pseudo-jonon. This gives a direct yield of 87.2 % and an actual yield of 88.9 %.

Example 28

3 g of Cu (BP ₄ ) ₂ and 12.1 g are placed in 14 cm ^{3 of hot methanol}
Triethylamine. The mixture is stirred for 18 hours at room temperature. The precipitate obtained is filtered off and
washes it successively with methanol and ether. One dries
the obtained pesticides in the air and receives 1.1 g of one
sky blue powder.

In a pressure-resistant vessel lined with glass on the inside
15.2 g of dehydrolinalool, 21.4 g of 2-methoxypropene and 0.3 g of the above catalyst are introduced. A magnetic stir bar is also used and the whole is stirred for 17 hours at 90 C.
The cloudy brown mixture is filtered off, washed with water and the volatile components evaporated in vacuo. The quick one
Distillation of the remaining oil at 0.3-0.8 mm Hg
and a temperature at the top of the column of 35 to 130 ° C. (60 to 180 ° C. in bulk) gives 17.2 g of distillate and 1 g of residue. The distillate contains 4.07 g of condensation product and 11.1 g
Dehydrolinalool (gas-liquid chromatographic analysis).

Example 29

Cis-Ä4-3-keto-7-methyl-octadiene- (4,6) and cis Δ -3-2-keto-3,6-dimethylheptadiene- (3,5)

8.4 g of 3-hydroxy-3-methyl-butyne- (1), 30.3 g of a mixture of 2-ethoxy-1- and
- / X 2-butenes and 0.3 g of anhydrous powdered copper (II) sulfate. The mixture is heated to 85 to 90 ^° C. for 151 hours, while stirring. It is then cooled and filtered with the aid of cyclohexane. The filtrate is washed three times with water, dried over sodium sulfate and attracted

409833/1 041

finally the light parts at 40 mm Hg. The rapid distillation at 1 to 0.3 mm Hg and a temperature at the top of the column from 38 to 120 ° C (56 to 160 ° C in the mass) gives 12.4 g of a yellow oil which contains 3.3% 3-methyl-butyne-Cl) -ol- (3), .61.8% cis- ^ 4-7-methyl-octadien- (4,6) -one- (3) and cis-Δ 3-3,6-dimethyl-heptadien- (3,5) -one- ( 2) contains.

Example 30

8.4 g of 2-methyl-butyn- (3) -ol- (2), 21.6 g of 2-methoxypropene and 0.3 g of copper (II) sulfate are placed in a pressure-resistant vessel equipped with a magnetic stirrer. The mixture is heated to 90 ^° C. for 157.3 hours, cooled, filtered, washed with water and the volatile components removed in vacuo. Rapid distillation gives 10.2 g of distillate and 2.4 g of residue. The residue contains 0.9 g of starting alcohol, 8.2 g of 2-keto-6-methyl-A3-cis-A 5-heptadiene and 1.5 g of 2-keto-6-methyl-A. 3-trans - / \ 5-heptadiene. The yield of methylheptadienes is 78%, the infrared spectrum of the product shows the simultaneous presence of cis- and trans-heptadienones.

Example 31

18 g of a mixture of 3-propyl-7-methyl-3-hydroxy-octyne- (1) -en (6) are placed in a pressure-resistant vessel equipped with a magnetic stirrer. and 3,7-dimethyl-4-ethyl-3-hydroxyoctyne- (1) -en (6), 22 g of 2-methoxy-propene and 0.3 g of copper (II) sulf at a. The mixture is heated to 85 to 90 ° C. for 289 hours, cooled and filtered, and the volatile components are driven off in vacuo. Rapid distillation gives 7.1 g residue and 13.9 g distillate. The distillate contains 2.1 g of starting alkynols and 9.1 g of a mixture of 2-keto-6-propyl-10-methyl-undecatriene- (3,5,9) and 2-keto-7-ethyl-6,10-dimethyl-undecatriene- (3,5,9). The infrared analysis shows the presence of the two cis and trans pseudo-jonons.

Direct yield 41.3 %
actual yield 44.3 %.

409833/1 0 Λ 1

Example 32

14.6 g of a mixture of 3,4,7-trimethyl-3-hydroxy-octyne- (1) -en (6) and 3-ethyl-7-methyl-3-hydroxy-octyne are placed in a pressure-resistant vessel - (l) -en- (6), 21.6 g of 2-methoxy-propene and 0.3 g of copper (II) sulfate. After the mixture has been heated to a temperature of 85 to 89 ° C. for 14 hours with stirring, it is filtered, washed with water and the volatile components are driven off at 40 mm Hg at room temperature. Rapid distillation below 0.4 to 0.6 mm Hg at a temperature in the top of the column of 32 to 122 ° C. (82 to 160 ° C. in bulk) gives 18.6 g of a yellow oil, which is 15 g of 6-ethyl -lO-methyl-2-keto-cis - / ^ 3-5,9-undecatriene and cis-A3-7-methyl-pseudojonon, 1 g of the corresponding trans- / \ 3-isomers and 0.5 g of starting alkynols.

The actual yield of cis -A3 product is 85.7% and the actual yield of cis-A3 and trans-A3 is 91.3%.

-1 -1 The product has the infrared bands at 1690 cm, 1629 cm

-1
and 1578 cm, which confirms the Δ 3-cis constitution.

Example 33 Cis-A 3-6-ethyl-7,1O-dimethyl-2-keto-undecatriene- (3,5,9)

9 g of 3-ethyl-3-hydroxy-4,7-dimethyl-octyne- (1) -en (6), 12.4 g of 2-methoxypropene and 0.15 g are placed in a pressure-resistant vessel Copper (II) sulfate. The mixture is heated to 88 ° C. for 32.5 hours with stirring, then cooled, washed with water and the light components evaporated in vacuo. By rapid distillation of the residual oil at 1 mm Hg and a temperature at the column head 66-180 ⁰ C (temperature of the mass 99-210 ⁰ C) to obtain 21.8 g of an oil which was 21.1% of the Ausgangsalkinols, 55, 3% cis-Δ3-6-ethyl-7,10-dimethyl-undecatriene- (3,5,9) and 6.3% trans- ^ 3-6-ethyl-7, -10-dimethyl-2-keto- contains undecatriene- (3,5,9). The direct yield is 50% and the actual yield is 62.4 %.

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-i -i

The product has the infrared bands at 1690 cm, 1627 cm and 1578 cm ", which confirms the / \ -3 constitution.

Example 34 Cyclization of cis-A3-pseudo-ionone to pC-ionone

In a three-necked flask equipped with a mechanical stirrer, a reflux condenser, a nitrogen inlet and a thermometer, 15 g of cis- / L3-pseudojonone (86.5 % cis-A3-pseudoionone, 5.8% trans - / \ 3- Pseudojonon), 15 g of cyclohexane and 750 mg of 85% phosphoric acid. The mixture is heated under reflux (81 to 84 ° C) for 14 hours, cooled,

3 3

washes with 200 cm of water and 100 cm of an aqueous saturated sodium bicarbonate solution. Thereafter drying the solution over sodium sulfate, the solvent is removed in vacuo and distilled rapidly at 1.2 to 1.5 mm Hg and a temperature at the column head 66-110 ⁰ C (87 to 160 ° C in the mass). This gives 7.1 g of a pale yellow oil which contains 10.5% cis-ß-ionon, 2.4% cis-c (, - ionon, 40.8% trans- <% -ionon and 12.8% contains trans-ß-ionone.

Example 35 Cyclization of eis-A 3-pseudo-ionone to ß-ionone

A mixture of 52.5 g of 95% strength sulfuric acid and 22.5 g of acetic acid is cooled to 9 ° C. 15 g of cis-pseudojonone (83.7 % cis-Λ 3, 8.3 % trans - / ^ 3) are then added dropwise, with sufficient stirring, while maintaining the temperature between 13 ° C and 13 ° C. This addition lasts 40 minutes. Immediately thereafter, the reaction mixture is poured into a with stirring

3 · ■ 3

Mixture of 80 cm of ether and 300 cm of ice water. One washes the organic layer with a saturated aqueous solution of sodium bicarbonate, dried over sodium sulfate and concentrated by suction in a vacuum. By rapidly distilling the remaining oil at 1 mm Hg and a temperature of 82 to 172 ° C in the top of the column (91 to 2O4 ° C in the mass) is obtained

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10.5 g of a yellow oil containing 22 % cis-06-ionone, 38.5 % cis-β-ionone, 1.1% trans- oL -ionone and 22.1 % trans-β-ionone. 1 cm of the above distillate is treated with 1 cm of a solution of 5 % iodine in isopropyl ether. An oil is obtained in this way which contains 8.4 % ice-O ^ -ionone, 2.6% cis-β-ionone, 2.6 % trans-06 ion and 72.7 % trans-ß-ion (gas-liquid chromatographic analysis) contains.

Example 36

4.8 g of an oil, the 3 g of cis-A3-pseudojonon, are placed in a flask and contains 1.5 g of trans-Δ3 pseudo-jonon. One holds the flask under a nitrogen atmosphere and then adds 0.3 g of copper (II) nitrate trihydrate and then stirred for 24 hours at room temperature. The mixture is then diluted with cyclohexane, washed with water and dried over sodium sulfate and ^ draws the solvent off in a vacuum of 40 mm Hg.

A rapid distillation of the remaining oil from 0.5 to 0.2 mm Hg and a temperature of 60 to 1o4 ° C (pot temperature 103-160 ⁰ C) yields 3.8 g of distillate and 1.3 g of residue.

The distillate contains traces of eis-Δ3-pseudojonon and 3.24 g trans-Λ 3-pseudo-jonon (gas-liquid chromatographic analysis) .

Example 37

10 g of cis-Δ 3-pseudo-jonone (86.2% ice, 5.2 % trans) and 0.4 g of a 5% iodine solution in isopropyl ether are placed in a vessel. The mixture is left to stand at room temperature for 2.1 hours. The isopropyl ether is then drawn off in vacuo and the remaining oil is distilled under 0.3 to 1 mm Hg at a temperature in the top of the column of 70 to 130 ° C. (temperature in the mass 96 to 168 ° C.). 0.8 g of residue and 9.2 g of distillate are obtained in this way. By gas-liquid-chromato-

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graphic analysis one finds that the starting mixture and the Distillate have the following compositions:

Weight percent

eis trans light heavy parts

Starting mixture 86.2 5.2 7.9 1.1

Distillate 5.4 87.2 5.6 1.8

Example 38

Mix 5 g ice / \ 3 pseudo-jonon (86.2% cis-Λ 3 and 5.2% trans-A3) and 0.1 g of a solution of 0.25 g of sulfuric acid in 5 g of methanol. The whole is left for 3 hours at room temperature

3
stand. Everything is poured into 40 cm of a saturated sodium carbonate solution. The organic layer is extracted with benzene and washed with water. The solvent is removed in vacuo and the residue is rapidly distilled at 0.2 to 0.5 mm Hg and a temperature at the top of the column of 76 to 156 ° C. (temperature in the mass 85 to 205 ° C.). This gives 0.5 g of residue and 3.7 g of distillate (9.3% ice-^ 3 and 86.6% transÄ 3), which gives a direct yield of 68.3% and an actual yield of 74.2% is equivalent to.

Example 39

Mix 1 g of Eis-A3 pseudojonon (86.2% cis-Λ 3 and 5.2% trans Δ-3) with 0.2 g of a solution of 0.25 g of p-toluenesulfonic acid in 5 g of methanol. The homogeneous mixture is left to stand for 3 hours at room temperature and a gas-liquid chromatographic method is carried out Analysis of the mixture by. The following results are obtained at different response times:

Duration of the reaction % relative % relative in hours in cis in trans

0 94.2 5.7

0.25 29.7 70.3

0.75 10.7 89.2

1.5 6.1 93.9

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Example 40

The pseudo-jonon is heated with 1.5 g of glacial acetic acid during 12.5 hours at 62 to 68 ° C. The distribution of the iso mers is measured at different times of the reaction by gas flow liquid chromatography.

The following results are obtained:

Reaction time % relative % relative in hours in ice in trans O 93.7 6.1 8th 20.4 79.3 12.5 6.9 93.1 Example 41

1 g of 6,10-dimethyl-undecatriene-cis - / \ is mixed. 3-5,9-on- (2) and

3 1 g of a solution of 1 g of sodium hydroxide in 25 cm of methanol. It is left to stand at room temperature for 5.25 hours. as The function of the reaction time gives the gas-liquid chromatographic Analysis of the following results:

Reaction time
in hours % relative
in ice % relative
in trans 0
(from 0.5 to 1 minute) 93.7
45.7 6.1
54.3 0.88 18.8 81.2 5.25 7.4 92.6 Example 42

A drop of boron fluoride etherate is added to 1 g of ice-3-pseudo-jonone and left to stand at room temperature for 22.3 hours. The following results are obtained as a function of the reaction time:

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- 48 - 2404913 % relative % relative in trans in ice 6.1 93.7 30th 70 51 . 49 74.8 25.2

Reaction time
in hours

0
1

5.5
22.3

Example 43

Mix 1 g of ice cream. 3-pseudojonon with 1 g of a solution of

3 1 g of silver nitrate in 4 g of water and 25 cm of methanol. One lets Stand at room temperature for 21.8 hours. As a puncture of the reaction time the following results are obtained:

Reaction time
in hours % relative
in ice % relative
in trans 0 93.7 6.1 1.7 80.3 19.7 21.8 12.6 77.4 Example 44

Isomerization of cis-Δ 3-pseudo-jonone to trans- A. 3-pseudoionone and cyclization to β-ionone

A. 1.2 g of a solution of 5% iodine in isopropyl ether are added to 15 g of eis-A 3-pseudojonone (89.7% cis-Δ 3 and 2% trans-Δ 3) and the whole is left for 50 minutes at room temperature stand. A further 0.2 g of the solution of iodine in isopropyl ether is then added. After 20 minutes, a further 0.2 g of the solution of iodine in isopropyl ether is added and finally, after 20 minutes, the solvent is removed in vacuo.

B. In a 100 cm ^ flask equipped with a thermometer and a magnetic stirrer, 52.5 g of 95% sulfuric acid and 22.5 g of acetic acid are introduced. It is cooled to 12 ° C. and added dropwise the UI obtained in the course of Step A with stirring

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for 1 hour and at a temperature between 10 and 18 C. 10 minutes after the addition of the oil is complete, the

q 3

Mixture in 300 cm of water and 50 cm of benzene, while stirring,

The organic layer is separated and washed at 40 cm a saturated sodium carbonate solution in 100 cm of water and

with 50 cm of water. The solvent is removed in vacuo and the remaining oil is rapidly distilled at 1 to 2 mm Hg and a temperature of 65 to 142 ° C. (temperature in the mass 95 to 212 ° C.). 1.2 g of residue and 11.9 g of distillate are obtained in this way. The direct yield of β-ionone is 43.2 %, the actual yield 67.7%. According to gas-liquid chromatographic analysis, the starting product and the distilled product have the following compositions:

Ingredients Original product in % Distillate in%

Dehydrolinalool 2 A. 0.7 cis-Δ 3-pseudo-jonon 89 traces trans- Δ 3-pseudo-jonon 2 41.7 ß-Jonon - Λ 49.5 not identified 1 3.9 Example 45 Isomerization of cis-A 3-pseudoionone to trans- and cyclization to β-ionone -Δ 3-pseudoionone

5 g of cis-Δ3-pseudo-jonone (83.7 % cis - / \ 3, 8.3 % trans-A.3) are treated for 2.3 hours at a temperature of 95 to 120 ° C. with 0.5 g of acetic acid. At the same time, a mixture of 17.5 g of 95% sulfuric acid and 7 g of glacial acetic acid is cooled to 4 ° C. and the previous acetic acid / pseudojonone mixture is added dropwise over a period of 47 minutes while stirring, keeping the temperature between 4 and 18 ° C. . The mixture is then poured into water and extracted with benzene. The benzene extract is washed successively with water, a saturated aqueous sodium carbonate solution and again with water, whereupon it is concentrated in vacuo. By rapid distillation

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of the residue at 1.5 mm Hg and a temperature at the top of the column from 30 to 122 ° C (temperature in the mass 92 to 185 ° C) one receives 4.1 g of distillate which contains 84.8% ß-ionon.

Yield: 70 %.

Example 46

5 g of cis-pseudo-jonone (77.4% cis- ^ 3 and 22.6% trans- / \ 3) and 95 g of toluene are placed in a pressure-resistant metal vessel equipped with a magnetic stirrer. The mixture is heated to 150 ° C. for 23.1 hours. This gives a mixture of 20.4 % ice-Δ 3-pseudo-jonon and 79.5 % trans-Α 3-pseudo-ionone (gas-liquid chromatographic analysis).

Example 47 Isomerization under the influence of ultraviolet rays

2 g of ice-Δ3 pseudo-jonon of 91.8% (8.3 % trans-A3) are applied to a watch glass of 160 mm and irradiated for 18 hours at 27 ° C. with the aid of a germ-resistant CE lamp G15 T8, which in 15 watt Rad-I-Airco device is installed (0.36 Amp., 118 and AC, 181-15 unit).

After 18 hours of irradiation, the percentage of cis - / \ 3-ionone 6.3% and that of trans-Δ 3-ionone 93.7%.

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Claims (5)

Claims 1.) Process for the production of oG-j ^ diethylenic ketones, characterized in that at a temperature below 150 ° C an acetylenic tertiary alcohol with an alkyl- [aücen (2) - -yl (2)] - ätlier converts in the presence of a catalyst which from the group of copper (II) sulfate, copper (II) nitrate and the Metal salt / amine complexes is chosen. 2.) Process for the production of cis-Δ3-trans-Ä 5-pseudo-jonons and eis-4 3-trans-A 5-pseudomethyljononen according to claim 1, characterized in that the dehydrolinalool on an alkyl isopropenyl ether or on an alkyl isobutenyl ether "at a temperature below 125 ⁰ C can act. 3.) Cis-Δ3-trans-A5-pseudo-jonons and cis-Δ 3-trans-Λ-5-pseudomethyljonones. 4.) Use of the cis-Δ 3-trans- & 5-pseudo-ionons and the cis- A 3-trans-Δ5-pseudomethyljonones according to claim 3 for the production of trans-A3-pseudo-ionons or trans-Δ3-pseudomethyljonons by treatment with a cis -trans isomerization catalyst or by UV irradiation or by thermal treatment between 125 and 150 ⁰ C. 5.) Use of the cis- Λ 3-pseudojonones and the cis-Δ 3-pseudomethyljonones according to claim 3 for the preparation of cis-ionones or of cis-methylionones by treatment with a cyclization catalyst. 409833/1041