DE2643062A1 - METHOD FOR PREPARING 4- (4'-METHYL-4'-HYDROXYAMYL) -DELTA 3-CYCLOHEXENCARBOXALDEHYDE AND MIXTURES CONTAINING THE ALDEHYDE, AND USES OF THE ALDEHYDE - Google Patents

Description

Applicant: International Flavors & Fragrances Inc.

Process for the preparation of 4- (4'-methyl-4 ¹ -hydroxyamyl ) -Λ ^ -cyclohexencarboxaldehyd and mixtures which contain the aldehyde and use of the aldehyde

The invention relates to a process for the preparation of 4- (4'-methyl-4'-hydroxyamyl) - Δ ^ -cyclohexencarboxaldehyde and mixtures which contain a major proportion of the aldehyde, as well as the use in perfumery, the process under relative mild conditions and gives good yields. The invention also relates to a process for the preparation of an intermediate product, namely 4- (4'-methylr y- pentenyl) - Δ -cyclohexene-carboxaldehyde and mixtures which contain a major proportion of this aldehyde and which is suitable for the preparation of the first-mentioned compound.

The 4- (4'-methyl-4'-hydroxyamyl) - Δ ^ -cyclohexenecarboxaldehyde is also referred to herein as "Lyral" and the intermediate 4- (4'-methyl-3'-pentenyl) -Λ -oyclohexenecarboxaldehyde is also referred to herein as "Myrac aldehyde".

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In general, the process according to the invention proceeds according to the following scheme:

C-

Lewis acid 'catalyst

HO,

Lewis acid catalyst

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It was surprisingly found that Myreenol the formula

with acrolein of the formula

CHO

Il

can be reacted under mild conditions in the presence of at least one of the specific catalysts zinc chloride, zinc bromide, aluminum chloride, ethylaluminum chloride and tin chloride, the Diels-Alder product 4- (4'-methyl-4 ¹ -hydroxyamyl) - Λ -eyelohexencarboxaldehyde in good yields and is obtained in a relatively short time.

Similarly, myrcene was found to have the formula

reacted with acrolein under mild conditions in the presence of at least one of the specific catalysts zinc chloride, zinc bromide, aluminum chloride, ethylaluminum chloride and tin chloride and the Diels-Alder product 4- (4'-methyl-4 ¹ -hydroxyamyl) - Δ -eyelohexencarboxaldehyde in good yields within can be obtained in a relatively short time.

According to the invention, it is therefore intended to create a process for the production of mixtures which make up a major part

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4- (V -Methyl-4'-hydroxyaryl) - Λ -eyelohexencarboxaldehyd, which is characterized by the following process steps:

Thoroughly mix the acrolein with kyrcenol

1. In the presence of a catalyzing amount of a Lewis acid catalyst from the group:

Zinc chloride; Tin chloride; Zinc bromide; Aluminum chloride; Ethyl aluminum chloride (C ₂ H ₁ -AlCl ₂ );

or a mixture of two or more of the Lewis acids;

2. at a temperature in the range of about -20 ° C up to about 100 ° C; and

J5. a pressure of about 1 atm. up to about 100 atm.

Depending on the catalyst used, the product obtained is a mixture of compounds with the following structural formulas:

CHO

and

OH

in various isomeric amounts. From a perfumery standpoint from and with regard to the aroma it is particularly desirable to prepare a mixture which has a maximum amount of

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4- (4'-Methyl-4'-hydroxyamyl) - Λ -cyclohexencarboxaldehyd der Formula _

contains.

The following tables show the isomer amounts of the compound:

in relation to those of the compound:

produced both by the "thermal" process according to US Pat. No. 2,947,778 and also by the catalytic according to the invention Procedure.

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Table 1

Proportion of the compound type of reaction

the proportion of the compound

"Thermal" method according to

U.S. Patent 2,947,780 (Example V, 2.5: 1

below)

Zinc chloride catalyzed process according to the following

Examples 1-5, 9: 1

Tin chloride catalyzed process according to the following

Example 4, 28: 1

The molar ratio of acrolein: myrcenol is suitably in the range from about 10: 1 to about 1:10, with a Ratio of about 1: 1 is most preferred.

The reaction temperature varies from -20 ° C to 100 ° C, however, the preferred temperature range is a function of the catalyst used and therefore depends on it, For example, if zinc chloride or zinc bromide is used, the reaction temperature can be between 20 and 80.degree vary, particularly preferably between 40 ° to 50 ° C. In the case of tin chloride, aluminum chloride and ethylaluminum chloride the usable temperature range is -20 ° C up to 50 ° C, preferably 0 to 10 ° C.

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It has been found that certain Lewis acid catalysts are not usable for the process according to the invention, for example titanium tetrachloride or boron trifluoride etherate.

One of the particular advantages of the method according to the invention is the fact that only moderate temperatures are required to achieve good yields and satisfactory reaction times to achieve. At the abovementioned moderate temperatures, the reaction times are between about 1 hour to to 10 hours. In general, it is preferred to carry out the reaction over a period of about 7 to 9 hours.

The amount of catalyst used varies from about $ 0.2 to about $ 10, based on the reaction mass, and depends on the temperature and the reaction time. An amount of 1 to 2%, based on the total weight of the reactants used, is particularly preferred.

The reaction can also be carried out under pressure. Since, however, unlike the known processes, they are no special Requiring high pressure techniques, it is preferably carried out at atmospheric pressure.

Another advantage is that no special regulations have to be observed when mixing the reactants. It does not matter in which order the reactants are added; indeed, the myrcenol, acrolein and the catalyst can also be added at the same time. However, it has been found that in order to achieve the highest possible yield, the catalyst should first be mixed with the myrcenol. The acrolein is then added with sufficient stirring, for example by means of a metering pump over a period of 3 to 6 hours. The reaction temperature% uv is kept in the desired range during this entire period.

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The product obtained can be mixed with salt solutions, such as NaCl solutions, washed to facilitate the separation of the reaction product from the catalyst and a preliminary purification of the product. The product recovered from the reaction mixture is then purified in a conventional manner and / or isolated, for example by distillation, extraction, preparative chromatography and the like. Particularly preferred cleaning is done by vacuum distillation. Furthermore, additives such as antioxidants can be used on petroleum based oils, tr! alkanolamines and the like are used will. Triethanolamine and calcium carbonate are preferred A means of flushing out traces of acid before or during the distillation.

It is also possible, but not absolutely necessary, to carry out the reaction in the presence of a liquid carrier material perform. When such a carrier is used, it is preferably a solvent for the reactants and the reaction product. It must be inert under the reaction bonds. Preferred carrier materials are methylene dichloride, Toluene, benzene, diethyl ether, other ethers, esters, nitriles, nitro compounds and chlorinated solvents, in particular halogenated mononuclear aromatic hydrocarbons such as dichlorobenzene and the like. The amount of used The carrier can be from zero to about 300 grams per mole of myrcenol vary in the reaction mixture, with 250 g per mole of myrcenol to be favoured.

The advantages of the manufacturing process according to the invention

of reaction products, which are a major part of the

"5
4- (4'-methyl-4'-hydroxyamyl) - Δ -eyelohexenecarboxaldehyde

are therefore the following:

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1. The reaction can take place in standard kettles or standard facilities without devices for applying pressure or for continuous flow;

2. The reaction can be carried out at moderate temperatures;

3. A large quantity can be processed, with one high conversion rate and high yields can be achieved;

4. The unpleasant and harmful odor and the toxicity of acrolein can be eliminated by the method according to the invention easily suppressed;

5. The isomer ratio of the compound

to the connection

is in favor of the former connection

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compared to the "thermal" Diels-Alder reaction for the preparation of reaction products with a high proportion of 4- (4'-methyl- ¹ ! - '-hydroxyamyl) - A -cyclohexenecarboxaldehyde.

According to the invention, Lyral can also be prepared from myracaldehyde of the formula

in which the formyl group is in position "4" or in both position "4" and in position "5". The reaction occurs by direct hydration or by hydrohalogenation to form a halide (hydrohalogen myracaldehyde), which is then either (i) hydrated, or (ii) the halide portion by a carbalkoxy group replaced and this is then hydrolyzed.

It was also found within the scope of the invention that myracaldehyde the formula

in which the formyl group is attached in the "4" position or in both the "4" and "5" positions can be used to form isomers directly into a mixture (sometimes hereinafter referred to as "Lyral" ) to hycüM ^ ire which contains a predominant amount of 4- (4'-methyl-4 ¹ -hydroxyamyl) -Δ - ^ - cyclohexenecaroxaldehyde. An acidic hydrate agent is used, such as:

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(a) A mixture of at least one protonic acid and at least one miscible with water

organic solvents;

(b) An ion exchange resin or a mixture of Ion exchange resins;

(c) an acidic polymerization catalyst or a mixture of such catalysts; or

(d) Aktij ^ fourth clay or a mixture thereof Clays.

However, one of the following acidic hydrate agents is preferred

(i) mixture of lower alkanoic acids (e.g. formic acid and acetic acid) and p-toluenesulfonic acid;

(ii) Mixture of 30 $ aqueous sulfuric acid and Tetrahydrofuran;

(iii) mixture of sulfuric acid and dimethylformamide;

(iv) mixture of 50 $ sulfuric acid and tetrahydrofuran;

(v) mixture of 65 $ sulfuric acid and acetic acid;

(vi) mixture of methanesulfonic acid and tetrahydrofuran;

(vii) sulfonated copolymer of styrene and divinylbenzene;

(viii) Mixture of (a) sulfonated copolymers of styrene and divinylbenzene and (b) lower alkanoic acid;

(ix) activated alumina absorbent;

(x) silico-phosphoric acid polymerization catalyst; or

(xi, mixture of aqueous hydrochloric acid and a lower alkanol.

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Myracaldehyde itself can be obtained by intimately mixing acrolein and myrcene in the presence of a catalytic amount of a Lewis acid -Catalyst are produced, the zinc chloride, tin chloride, zinc bromide, aluminum chloride, ethylaluminum chloride, or may be a skeleton of two or more of these Lewis acids, at a temperature in the range of about -20 ° C up to about 100 ° C and a pressure of about 1 atm. up to about 100 atm.

The acrolein: myrcene molar ratio is about 10: 1 up to about 1:10, preferably about 1: 1.

The preferred temperature range is a function of the one used Catalyst. In the case of zinc chloride or zinc bromide as the catalyst, the reaction temperature is in the range between 20 ° C to 80 ° C, the most favorable temperature range at 40 ° to 50 ° C. Tin chloride, aluminum chloride and ethyl aluminum chloride require a temperature in the range from -20 ° C to 50 ° C, preferably 0 to 10 ° C.

One of the most prominent advantages of this process is that only moderate temperatures are required in order to obtain good yields and satisfactory reaction times. At the abovementioned moderate temperatures, the reaction times are from about 1 to 10 hours, it being generally preferred to carry out the reaction within 7 to 9 hours. The amount of catalyst varies from about 0.% to about 10 $, based on the reaction mass, and depends on the temperature and the reaction time. An amount of catalyst of 1 to 2 #, based on the total weight of the reactants used, is preferred. The reaction can be carried out under pressure, but since it does not require any special high pressure techniques, as is the case with the known processes, it is preferably carried out at atmospheric pressure. It is also advantageous that no special regulations have to be observed when mixing the reactants, these can

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, ίο *

added in any order or at the same time. It has been found that it can achieve the highest yields it is advisable to first mix the catalyst with myrcene and then add the acrolein while stirring well. This addition can, for example, by means of a metering pump in one Period of time from 3 to about 6 hours, with the reaction temperature is kept in the desired temperature range.

The reaction of myracaldehyde and the acidic hydrate agent takes place at a temperature which can vary from 0 ° C to 120 ° C and depends on the catalyst system used. An example of the sulfonated copolymer of styrene and divinylbenzene (containing about K% divinylbenzene) is that of the Dow Chemical Company known under the trademark Dowex 50W-X4. An example of an activated alumina adsorbent is Piltrol 105 (Trade Mark), which has the following properties:

Analysis of the particle size

By roller (10 L / min. Air speed)

0-5 / U, wt % 8

0-20 ya, wt % 43

Tyler standard screen table
through 100 meshes,

(0,147mm mesh size) wt -.% 100 through 200 mesh,

(0,074mm mesh size) wt -.% 95 325 by meshes,
(0.044mm mesh size) wt -.% 78

Bulk density, g / cc 0.67284

Free moisture, weight -. 15%

Free and combined moisture, wt % 21

(Loss at 926 ° C / I7OO ⁰ F /)

Effective surface (BET method), SqM / gm. 300

Acidity , phenolphthalein, mg.K0H / gm 4.8

Filter speed , cc / min. 38

Sealing against oil leakage, wt. % 35

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An example of a silico-phosphoric acid polymerization catalyst is the product known under the name UOP-SPA-2 from Universal Oil Products Company of Des Piaines, Illinois.

The response time is primarily a function of four variables:
, (1) reaction temperature;

(2) desired conversion;

(3) the hydrajic agent used; and

(4 ·) Concentration of the hydrate agent in the Reaction mass.

In general, higher reaction temperatures are shorter Effect response times. Reaction temperatures too high and / or reaction times that are too long, however, cause a reduction in the conversion, although this is due to decomposition products. Higher concentrations of hydrate agents in the Reaction masses shorten the reaction time for a given conversion of the desired "Lyral" reaction product. Therefore the reaction time can vary from 1 to 48 hours.

It has been found that this in the process according to the invention to be used hydrate agent surprisingly extremely is specific. Numerous hydrate agents or hydration systems are unusable, for example;

64% sulfuric acid; 50% sulfuric acid; 30 # sulfuric acid;

65% sulfuric acid-tetrahydrofuran mixture; 50% sulfuric acid-dimethylformamide mixture;

and

Methanesulfonic acid.

The concentration of the hydrate agent in the reaction mass varies from about $ 3 (when this agent is used as a polymerization catalyst used - such as silico-phosphoric acid) up to about 5Q & if hydrate means like a

p-Toluenesulfonic acid-arneic acid mixture or a p-toluenesulfonic acid-acetic acid mixture can be used. Are preferred based on the reaction mass, 3 to 10 wt -.% Polymerization catalyst (eg Silieo-phosphoric acid) or cation exchange resin (such as sold under the Wz known Dowex 50W-X4.) Grade or activated toner Dead sorbent (such as that known under the Wz Filtrol. 105). The hydrate-medium is also based on the reaction mass, preferably in an amount of about 25 to 60 wt -.% Is added, for example, 65 ^ sodium aqueous sulfuric acid-acetic acid mixture, or 50 ^ sodium aqueous sulfuric acid-tetrahydrofuran mixture, or 30 # sulfuric acid-dimethylformamide mixture, or p-toluenesulphonic acid-formic acid mixture, or methanesulphonic acid-tetrahydrofuran mixture.

The ratio of protonic acid to secondary solvent, e.g., sulfuric acid, methanesulfonic or p-toluenesulfonic acid: tetrahydrofuran, dimethylformamide or acetic acid, is preferably from about 1: 5 to about 5x1 on a dry basis and weight: weight.

In summary, the advantages of the process according to the invention for producing a product with a major proportion of 4- (4'-methyl-4'-hydroxyamyl) - / \ -cyclohexencarboxaldehyde are as follows:

1) The reaction can be carried out in standard vessels or vessels be carried out without a pressure device, batchwise or continuously;

2) The reaction can take place at moderate temperatures;

3) It gets high throughput, high conversion and high yield achieved;

4) The unpleasant odor and the toxicity of certain Diels-Alder reagents, such as acrolein, do not occur, as is the case with known Diels-Alder reactions; and

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Problems caused by the smell of morpholine or others Amines - which used to protect the carboxaldehyde during hydration; were used - as well as when removing Such amines occur from the reaction mass are completely eliminated.

According to a third embodiment of the invention, it has been found that myracaldehyde's formula

wherein the pormyl group is bonded in the "4" position or both in the "4" position and in the "5" position, initially with HCl or HBr can be hydrohalogenated to give hydrohalogen myracaldehyde of the formula

to form, wherein X is chlorine or bromine and wherein the Formy! Group in position "4" or both in position "4" and Position "5" sits, this aldehyde is then either (i) hydrolyzed with a base, for example with alcoholic Alkali metal carbonates, bicarbonates and / or hydroxides or their mixtures; or (ii) is reacted, the halogen group being replaced by a carbalkoxy group (e.g. acetate) is replaced and this reaction is carried out with the help of an alkali metal alkanoate, which has the general formula

«7 η fl ft 1 R / 1 1 9 7

has, " % tf _%

where R is lower alkyl and M is an alkali metal, such as sodium acetate, mean to form a compound of the formula

which in turn with a base, for example aqueous alcoholic Alkali metal hydroxide is hydrolyzed under reflux.

The reaction sequence is as follows:

, Cl

Cl

^ isopropiirtol /

r ;

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The hydrohalogenation is carried out using anhydrous hydrogen chloride or hydrogen bromide in an inert solvent, like glacial acetic acid. The reaction temperature is between 0 and 30 ° C., preferably 10 ° to 15 ° C. Am atmospheric pressure is most convenient, but higher pressures can also be used, thereby reducing the reaction time can be shortened. The range of weight ratios of myracaldehyde: hydrogen halide, HCl or HBr, can vary from 10: 1 up to 1: 1, with the preferred weight ratio being about 5: 1. The area of Myracaldehyde: solvent weight ratios are 1: 1 up to 1:10, preferably 1: 5.

After the reaction has ended, the reaction mass is worked up, by pouring it onto crushed ice and extracting, for example, the hydrochloromyracaldehyde, and with an inert and volatile extraction solvent, like diethyl ether. The hydrochloromyracaldehyde has the formula

'5 μ

The extract is made with an inert desiccant, such as anhydrous Magnesium sulfate, dried and the solvent removed. The hydrochloromyracaldehyde is then preferably hydro lysed or reacted with a carbalkoxylating agent to the corresponding acetate of the formula

which is then hydrolyzed.

7.0 9 8 1 5/1 1 9 7

The hydrolysis of the hydrochloromyracaldehyde or hydrobromycaldehyde is carried out in the presence of an aqueous base such as an alkali metal carbonate, bicarbonate or hydroxide, for example sodium bicarbonate, potassium bicarbonate, sodium hydroxide, lithium hydroxide or potassium hydroxide. It is carried out in an inert organic solvent, for. For example, isopropanol, at a temperature of between 50 ° and 120 ° C, preferably at the reflux temperature of the reaction mass (8o - 85 ⁰ C in the case of a 50: 50 water: isopropanol Hydrolysemaium). The weight ratio of water: inert organic solvent can vary from 1: 5 up to 5: 1, with the preferred ratio being 1: 1. The base: water weight ratio can vary from 1:25 up to 1: 2, with the preferred weight ratio being 1:10.

In order to replace the halogen group with an ester group, the hydrochloromyracaldehyde or the hydrobromyracaldehyde is used reacted with the carbalkoxylating agent, which is an alkali metal salt a lower alkanoic acid in an aqueous medium. Sodium acetate or potassium acetate, for example, are suitable in an inert solvent such as toluene or xylene and it is carried out at reflux temperatures. This reaction is preferably carried out in the presence of a phase converter, the one or more organic quaternary ammonium salts can be. Specific examples of such phase converters which can be used according to the invention are:

Tricaprylmethylammonium chloride, Cetyltrimethylammonium bromide and benzyltrimethylammonium hydroxide.

709815/1197

^ 64-3062

J ».

In general, the most preferred have phase converters the following basic formula:

R ¹ -

R ¹

-1 +

-R ¹ 2

wherein at least one of Rj, Rg, R-4 and R ^ Cg-C ^ Cg-C ₁₀ aralkyl, Cg-CgQ-alkyl, Cg-C- ^ - alkaryl and Cg-C ₂₀ -alkenyl. The remaining R ', R4 and BJ are methyl, ethyl, n-propyl, i-propyl, 1-butyl, 2-butyl, 1, -Methyl-2-propyl, 1-pentyl or 1-octyl groups. Z ~ is an anion like chloride, bromide or hydroxide.

The hydrolysis of the resulting carbalkoxylate to form Lyral is preferably made by heating the carbalkoxylate in aqueous alcoholic base, expediently aqueous rr.ethanolic sodium hydroxide solution, passed under reflux leads.

When the reaction is complete, Lyral becomes the formula

wherein the formyl group is in the "4" position or in both the "V" and "5" positions, with an inert, volatile one Extraction solvent, such as diethyl ether, extracted.

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-ar-

The extract is dried, stripped from the solvent, preferably under reduced pressure, and the "crude" Lyral obtained is fractionally distilled.

The mixture prepared according to the invention, the 4- (4'-methyl-4'-hydroxyamyl) -tl -cyclohexenearboxaldehyd can be mixed with one or more perfume additives, e.g. B. alcohols, other aldehydes, nitriles, esters, cyclic esters, as well as natural essential oils, can be blended to by combined and complementary scent notes of the individual components to create a pleasant and desired scent, in particular and preferably lilacs, flowers, ferns, floral fragrances and roses. Such perfume compositions usually contain (a) the main note or "bouquet" or basis of the composition; (b) Modifiers that round off the main grade and complement; (c) Fixatives containing fragrances that give the perfume a special note during all stages of evaporation to lend; and substances that delay evaporation; and (d) top notes traditionally of low boiling, come from freshly smelling substances.

In the case of perfume compositions, it is the individual components that contribute to the particular fragrance characteristics of the compositions wearing. But the overall effect of the perfume composition is at least determined by the sum of the effects of each component certainly. So that can the 4- (4'-methyl-4'-hydroxyamyl) -Δ -eyclohexencaroxaldehyd-containing mixture for this purpose to change, modify or enhance the aroma characteristics of a perfume composition, namely by particularly emphasizing or masking the olfactory reaction imparted by other components.

The effective amount of that prepared according to the invention in perfume compositions and in perfumed articles and colognes Mixture depends on many factors, not least the other components, their proportions and their own effects must be taken into account.

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It was found that the mixture containing 4- (4'-methyl-4'-hydroxyamyl) - i \ -cyclohexencarboxaldehyde can already be used in amounts of $ 0.01 or even less (for example $ 0.005) For example, to give soaps, cosmetics or other products a sweet aromatic scent reminiscent of lilacs and lilies, or to intensify, improve or modify the scent. The amount added can be up to $ 70 of the fragrance component and depends on the cost, the nature of the end product, the desired effect and the particular fragrance sought «,

The mixture according to the invention can be used alone or in perfume compositions or as a fragrance component in detergents and soaps, room sprays and deodorants, perfumes, colognes, toilet water, bath additives such as bath oils and bath salts, hair preparations (such as hair lacquers, brillantines, pomades and shampoos), cosmetic preparations (such as creams , Deodorants, hand lotions and sun protection creams) as well as in powder (such as talc, dusting powder, face powder and the like). As a fragrance component, just 1% of the mixture is sufficient to give a pleasant lilac-lily note, for example a preparation with lily, lumen, fern, bouquet and rose fragrances. Generally no more than $ 8 of the mixture is needed based on the final product.

The perfume composition or fragrance component can contain a carrier for the mixture produced according to the invention. This carrier can be liquid, for example a non-toxic alcohol or a non-toxic glycol or the like, or an absorbent solid such as a gum (e.g. gum arabic), or a capsule material (such as gelatin).

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. re·

The inventive method is based on the following Examples 1 to 15 explained in more detail.

Example 6 illustrates the Thermal Diels-Alder reaction according to the method of US Pat. No. 2,947,780.

Examples 7 to 15 illustrate the usefulness of the product prepared according to the invention in perfumery.

All parts and percentages are given by weight, unless stated otherwise.

Examples 1, 2 and 3

6600 (42.8 mol) of myrcenol and 90 g (0.66 mol) of myrcenol Given zinc chloride.

The resulting mixture was heated to 45 ° C and the heating jacket removed. With good stirring, 2400 g (42.8 mol) of acrolein were added over a period of time with the aid of the metering pump added from 5 to 6 hours. The reaction temperature thereby became maintained at 45 ° to 50 ° C. using a cooling bath.

After the exothermic reaction subsided, the heating mantle was put on again and the reaction mass during Maintained for 2 hours at a temperature of 45 ° to 50 ° C. The reaction mixture was then transferred to a separatory funnel brought, at 60 ° C with 4500 ml of a 10 ^ -igen aqueous sodium chloride solution and then with 4500 ml 10- # igenr washed with aqueous sodium carbonate.

A yield of 8928 g of crude product was obtained in these process steps. The analysis of this product by internal gas-liquid chromatography gave 88.8 # 4- (4'-methyl-4 ^f -hydroxyamyl) - / \ -cyelohexenecarboxaldehyde and by area normalization 9.2 $> myrcenol. This means an 86.5 ^ conversion

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and essentially a $ 100 chemical yield of 4- (4 '-methyl-4 ^f -hydroxyamyl) - ^ -cyclohexenecarboxaldehyde based on myrcenol.

Two further experiments were carried out using different zinc chloride concentrations than in Example 1. A summary of these two experiments as well as experiment No. 1 is shown in Table II below.

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Table II

Myrcenol weight (MoI)

6600 g (42.8)

2633 g (17.1)

2002 g (13)

Respondents

2400 g (42.8)

912 g (16.3)

728 g (13)

Acrolein «^ * ₂

Weight (mol) weight (weight #) '

88 g (1 %)

50 g

54.6

(2Si)

Analysis of washed raw material

4- (4 ^l -Methyl-4'r hydroxyamyl) - Δ 2-cyclohexencaxfexalde-

hyd ^ myrcenol%%

Weight (weight) (weight) conversion yield

8928g

3633g 2847g 88.8 (7928g)

85.9 (3138 g)

83.1 (2366 g)

a: Based on the total amount of reactants

9.2
(821 g) 87 5 100
(estimated) 10.5
(384 g) 85 4th 100
(estimated) 9.2
(262 g) 86 9 100
(estimated) te

The gas-liquid chromatography profile for the reaction product according to Example 1 is shown in Figure 1 of the drawings. The main peaks are "A" ($ 9.3) and "B" ($ 90.3). The examination conditions: 500 'χ 0.03 "Carbowax 2OM coated tubular Stainless steel column calibrated from 80 ° to 130 ° C at 2 ° C per minute.

The infrared spectrum of the reaction product is shown in FIG

and the NMR spectrum shown in FIG.

Example 4

Into a 2 liter reaction flask equipped with a mechanical stirrer, thermometer, filling funnel and reflux condenser were 5 * 2 g of SnCl ^ and 300 g of toluene filled with stirring and the obtained Mixture cooled to 3 ° C. 168 g (3 mol) of acrolein dissolved in 100 g of toluene were added with vigorous stirring, and over a period of 5 minutes, the reaction temperature being kept at 3 ° C. During 4 hours were 320 g (2 mol) of myrcenol were added with stirring while the temperature of the reaction mass was maintained in the range from 2 ° to 5 ° C became.

Then 200 g of ice were added together with 300 g of water and the mixture was stirred for 15 minutes. The phases separated. the aqueous phase was extracted with a 100 ecm portion of toluene and the organic layers were combined and washed with two 100 ecm portions of saturated sodium chloride solution. 1 g of 2,6-di-tert-butyl-4-methylphenol, known as the trademark Ionol, and 10 g of triethanolamine were added to the washed organic solution, which was rapidly distilled through a short column without fractionation. The distillate was at 14 ° to 153 ° C and 1.4 to 3.9 mm Hg collected and then fractionated in a 12 "χ 1" Goodloe column and thereby obtained 276 g of the product (boiling point 125 ° to 126 ° C / 0.7 mm Hg).

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The gas-liquid chromatography profile (conditions as in Example 1) for the _{product obtained from the SnCl 2} -catalyzed reaction of myrcenol and acrolein is shown in FIG. 2 of the drawings. The tips are "A" ($ 2.5) and "B"

Example 5

2500 g of toluene and 52.5 g of anhydrous tin chloride were placed in a 22 liter reaction flask equipped with a thermometer, air-driven stirrer, two filling funnels, reflux condenser and cooling bath. One of the hopper was 27.5 mole) acrolein in 25OO g of toluene charged with 3850 g (25.0 mol) myrcenol and the other hopper with a solution of 15 ² K) g (. The contents of the flask were stirred and cooled to 0 ° C. About 10 $ of the acrolein solution was added and then the contents of the two funnels were added simultaneously at about the same rates over 5 hours. After about 40 # of the addition, gas-liquid chromatography showed the reaction to be slow. Therefore an additional 52.5 g of the catalyst was added. The reaction temperature was kept at 0 ° to 5 ° C. for almost the entire time of the addition and then for a further hour. The reaction mass was then held at 5 ° to 12 ° C. for 45 minutes. A solution of 50 g of sodium hydroxide in 1 liter of water was added, followed by 5 g of 2,6-di-tert-butyl-4-methylphenol (trade mark Ionol), with thorough stirring. Then the mixture stopped to sit. The aqueous phase was extracted with 1200 g of toluene and the organic layers were combined and washed twice with 1 liter portions of saturated sodium chloride solution. After adding 75 g of triethanolamine, the mixture was distilled without fractionation. The distillate collected at a vapor temperature of 155 ° to 163 ° C. and a pressure of 0.8 to 1.1 mm Hg was fractionally distilled in a 12 "χ 1" Goodloe column and 3000 g of product were obtained. The boiling point was 133 ° to 135 ⁰ C at 0.5 to 0.9 mm Hg.

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2ü43062

Example 5 (A) * 3 * "

Production of Lyral from Myrcenol and Acrolein using an aluminum chloride catalyst

A mixture was poured into a 250 ecm flask equipped with a stirrer, condenser, thermometer, dropping funnel and drying tube given from 0.5 g of aluminum chloride (0.0037 mol) and 10 ecm of toluene. A mixture of 20 g (0.35 mol) of acrolein and 50 g (0.32 mol) of myrcenol was added dropwise over 1 1/4 hours added to the aluminum chloride-toluene mixture while maintaining the temperature of the reaction mass at 0 ° C. To this A dry ice isopropyl alcohol bath was used for this purpose. After the addition was complete, the reaction mass was stirred at a temperature of 0 ° to 20 ° C. for 30 minutes. Then were 30 ecm of water and then 50 ecm of diethyl ether are added. The resulting organic layer was with two 50 ecm Servings of saturated sodium bicarbonate solution and then with washed two 50 ecm portions of water. The so washed organic Layer was dried over anhydrous magnesium sulfate, filtered and concentrated.

Gas-liquid chromatography (conditions: SF-96 column calibrated at 100 ° to 200 ° C at 8 ° C / min.) resulted in the formation of 73 * 9 $ lyral and 0.4 $ myracaldehyde. It also didn't show $ 25.0 converted myrcenol.

The gas-liquid chromatography profile is shown in FIG. 5B Drawings shown. A reference profile illustrating a pre-made mixture of lyral and myracaldehyde is shown in Fig. 5A shown.

The product obtained was fractionally distilled using Lyral with an S
mm Hg

Lyral with a boiling point of 155 ° to 155 ° C at 0.5 to 0.9

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Example 5 (B)

Production of Lyral from acrolein and myrcenol using an ethylaluminiuro / chloride catalyst

A mixture was poured into a 250 ecm flask equipped with a stirrer, condenser, thermometer, dropping funnel and drying tube from 1.0 g (0.008 mol) of ethylaluminum chloride and 10 ecm of toluene given. A mixture of 20 g (0.25 mol) of acrolein and 50 g (0.32 mol) of myrcenoi was added dropwise over 11/4 hours added, the temperature being kept at 0 ° C. A dry ice isopropyl alcohol bath was used for this purpose. After completion the addition was the reaction mixture at a temperature stirred from 0 ° to 20 ° C for 30 minutes. Then there were 30 ecm of water and then 50 ecm of diethyl ether was added. The organic layer formed was separated from the aqueous layer and with two 50 ecm portions of saturated sodium bicarbonate solution and then washed with two 50 ecm portions of water. The organic layer thus washed was dried over anhydrous magnesium sulfate, filtered and concentrated.

Gas-liquid chromatography (conditions: SF-96 column calibrated at 100 ° to 200 ° C at 8 ° C / min.) yielded 78.2 $ Lyral and $ 1.2 myraealdehyde. It also showed $ 19.7 unreached Myrcenol.

The gas-liquid chromatography profile is shown in Figure 5C. A reference profile of a prefabricated mixture of lyral and myraealdehyde is shown in Figure 5A.

The product obtained was fractionally distilled and Lyral with a Si < mm Hg.

Lyral having a boiling point of 133 ° to 135 ⁰ C at 0.5 to 0.9

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Example 6

575 g of myrcenol, 4 ^ 2 g of acrolein and 10 g of hydroquinone were placed in a reaction vessel which was sealed tightly. The reaction mixture was heated to 150 ° C. for 4 1/2 hours with stirring. After the reaction kettle had cooled down, the mixture contained therein was removed and fractionally distilled in vacuo. After a first run of unreacted inert isomeric C ₁₀ alcohols, 640 g of the product were obtained, which had a boiling point of 126 ° to

C at 2 mm Hg. Another distillation gave 442 g of product with a boiling point of 120 ° to 122 ° C at 1 mm Hg, a refractive index of 20 ° C, 1.4915; specific gravity at 20 ° C, 0.9941; maximum ultraviolet absorption, 292 m, u. The product showed 99.6 # aldehyde by oximation test. Weight yield = $ 56.8 based on the myrcenol used. The product was 4- (4 ^L -methyl-4 ^L -hydroxyamyl) - Δ eyelohexenecarboxaldehyde. It had a very sweet, lilac-lily-aromatic scent.

The gas-liquid chromatography profile (conditions as in example I) obtained by the thermal, non-catalyzed reaction of myrcenol and acrolein is shown in Figure 3 of the drawings illustrates and shows two major peaks, "A" ($ 27.8) and "B" (69.7 *).

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Example 7 * 3 ··

A perfume composition of the "Fougere" type was prepared:

Parts by weight of ingredients

50 cinnamon alcohol

40 ambrite musk

5 vanillin

80 coumarin

10 oak moss resinoid

125 linalool

150 linalyl acetate

50 benzyl acetate

70 phenyl ethanol

Bergamot oil lavender oil

50 Geranium Oil (Bourbon)

50 sandalwood oil E.I.

5 eugenol

15 isoeugenol

20 amyl salicylate

20 benzyl salicylate

20 Connection established

according to Example 1, which has a major proportion of 4- (4 »-Methy1-4 · -hydroxyamyl) -A Contained 3-cyclohexenecarboxaldehyde

1010

The product according to Example 1 gave the "Pougdre" composition a very sweet / lilac-lily-like aromatic fragrance.

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2843062

Example 8

A "rose" type perfume composition was prepared.

Parts by weight

20th

10 10 50 40

1030

Components

20th Phenylethylphenyl acetate 40 Phenylethyl salicylate 150 Geraniol 240 Phenylethanol 150 Citronellol 20th Sandalwood oil E.I. 75 Nonanediacetate - 1.3 50 Geranyl acetate 20th Ger any 1 pheny Iac e ta t 20th Citronellyl formate 25th Phenylethyl acetate 60 Phenylethyl propionate 20th Pheny! Acetaldehyde $ 50 in

Diethyl phthalate

Phenyl acetaldehyde 1,3 butylene glycol acetal

Eugenol

Methyl-iso-eugenol

alpha-hexyl cinnamaldehyde

Product manufactured according to example 3 * the main part -, 4? - (4-Methyl-4'-hydroxyamyl) - A ->. eyelohexenearboxaldehyde contains

This "rose" perfume had a sweet floral aroma that came through the addition of the product from Example 3 had been increased.

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Example 9

A "bouquet" type perfume composition was prepared:

Parts by weight

20th

40

100

80

130

40 30 80 80 80 100 25 15 40 60 20

50

5 5

Components

Ambri musk Heliotropin Benzyl acetate

4-tert-butylcyclohexyl acetate

alpha-hexylcinnamaldehyde alpha-amylcinnamaldehyde Linalyl acetate Terpineal geranyl acetate Linalool

alpha-methylionone Methyl-iso-eugenol Isoeugenol Geraniol

Phenylethanol styrallyl acetate vetiveryl acetate 10-undecene-l-al

Product prepared according to Example 4, which contained 4- (4 · -Meihyl-4'-hydroxyamyl) - Λ 2-cyclohexenecarboxaldehyde.

10,000

The product according to Example 4 gave this "bouquet" perfume a sweet lilac and lily shade. The same results were obtained achieved when the product according to Example 4 is produced by one of the products according to Examples 5 * 5 (A) or 5 (B) has been replaced.

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Example 10 ^%

Manufacture of a cosmetic powder preparation

In a ball mill, 100 g of talcum powder were mixed with 0.25 g of the mixture prepared according to Example 1, which contained a major proportion of 4- (4'-methyl-4'-hydroxyamyl) - ^ d -cyclohexenecarboxaldehyde. The powder was an excellent one
sweet, lilac and lily aroma.

Example 11 Perfumed liquid detergent

Samples of "concentrated liquid detergents were used
a sweet, lilac-lily scent that was $ 0.10,
0.15 # or 0.20 $ of the mixture prepared according to Example 6
contained. Corresponding amounts of the den
4- (4'-methyl-4'-hydroxyamyl) - A -cyclohexenecarboxaldehyde
containing mixture added to the liquid detergent and mixed with this homogeneously. All samples had one
sweet, lilac and lily seasoning, the intensity increasing with increasing concentration of the mixture containing the aldehyde.

Example 12 Production of a cologne and handkerchief perfume

A mixture according to Example 2 prepared containing the 4- (4'-methyl-4'-hydroxyamyl) - containing A. -cyclohexencarboxaldehyd, was in a concentration of 2.5 $ in sodium 85 # aqueous ethanol in a cologne and a concentration of 2Ο5έ (in 95 ^ aqueous ethanol) added. Both the colognes and the handkerchief perfume were given a distinctive and specific sweet lilac and lily flavor and a corresponding scent

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Example 13 * <%

Production of a cologne and handkerchief perfume

The perfume composition from Example 9 was placed in a colognes at a concentration of $ 2.5 in 85 # ethanol, and in a handkerchief perfume at a concentration of $ 20 (in 95 # aqueous ethanol) admixed. The usage

of the 4- (4 ^l -Methyl-4 ^f -hydroxyamyl) - / \ -cyclohexencarboxaldehyde containing mixture from Example 9 gave both the colognes and the handkerchief a distinctive and certain strong "bouquet" aroma with sweet, lilac-lily Grades.

Example 14 Making a soap preparation

100 g of soap flakes were mixed with 1 g of a mixture prepared according to Example J and containing 4- (4'-methyl-4 ^l -hydroxyamyl) - / \ ^ -cyclohexenecarboxaldehyde until a completely homogeneous mass was formed. The perfumed soap preparation had an excellent, sweet, lilac and lilac aroma.

Example 15 Manufacture of a detergent preparation

100 g of detergent powder were mixed with 0.15 g of the mixture prepared according to Example 4 until it was homogeneous Mass was formed. This preparation had an excellent sweet lilac and lilac flavor.

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The following examples 16 Ms 47 are working examples other aspects of the invention which are presently preferred practices. Examples 22 to 30 and 35 to 44 illustrate the usefulness of the product produced according to the invention in perfumery.

The examples show AK procedure followed for the preparation of mixtures with a high proportion of a mixture of 3- and 4- ^(4-f -Methy1-4' hydroxyamyl) - Δ -cyclohexencarboxaldehydj but these attempts were unsuccessful.

Example A

Attempt to prepare a mixture of 3- and 4- (4'-methyl- 4'-hydroxyamyl ) - A -cyclohexenecarboxaldehyde

50 g of concentrated sulfuric acid were dissolved in 50 g of water, the resulting 50 ^ sulfuric acid solution is cooled to 20 ° C and placed in a 250 ml reaction flask, the one with stirrer, thermometer, reflux condenser and funnel was provided. In the course of 1 hour, 60 g Myracaldehyde of the formula

admitted.

The reaction mixture was stirred at a temperature of 20 ° to 25 ° C. for 5 hours. Gas-liquid chromatography, NMR and IR analyzes confirmed that no conversion to 3- or 4- (4'-methyl-4'-hydroxyamyl) - / \ -cyclohexencarboxaldehyde had taken place. The same procedure was repeated, but using a temperature of 50 ° to 55 ° C

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Υ ».

became. There was no reaction. The same procedure was repeated once more at a temperature of 75 ° C, however, no reaction was observed either.

Example B.

Attempt to produce a mixture of 3- and 4- (4'- Methyl-4'-hydroxyamyl) - Ä -eyelohexencarboxaldehyde

In a 500 ml equipped with a stirrer and thermometer Reaction flasks were given the following reactants:

Components

Myracaldehyde water

Tetrahydrofuran

While stirring, 20 g of concentrated sulfuric acid were added, the temperature of the reaction mass was kept at 25 ° C. and further touched. There is no reaction.

The same procedure was followed at a reaction temperature carried out at 50 ° C. But there was no reaction here either.

A third experiment was made at a reaction temperature of 70 ° C. and with 30 g of concentrated sulfuric acid. A conversion between 2% and 5% to a mixture of 3- and 4- (4'-methyl-4 ^l -hydroxyamyl) -Δ -eyclohexencarboxaldehyd was found.

Examples C through K.

In the following examples, given mixtures were intimately mixed under the specified conditions. But in no case was 3- or 4- (4'-methyl-4 ^t -hydroxyamyl) - Δ cyclohexenecarhoxaldehyde formed:

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- aer-

example
C.

Reaction mixture

4 g myracaldehyde 2.5 g water g tetrahydrofuran 0.5 g concentrated Sulfuric acid

Reaction conditions

Reflux 5 hours

4 g myracaldehyde 4 g water 10 g tetrahydrofuran 2 g concentrated Heavy isic acid reflux for 5 hours

75 g 64 # sulfuric acid 25 g myracaldehyde -20 ° C
2 hours

5 g myracaldehyde

1 g of tetrahydrofuran

5 g of 64 # sulfuric acid

20 g myracaldehyde 5 g dimethylformaide 5 g water 5 g concentrated Sulfuric acid reflux at 120 ° C minutes

55 ° C
Minutes

2.5 g myracaldehyde 1.0 g dimethylformaide 0.5 g concentrated sulfuric acid 50 ° C

Minutes

1 * 5 g myracaldehyde

1.0 g dimethylformamide

0.5 g 50 # sulfuric acid 50 ° C
Minutes

1.5 g myracaldehyde

1.0 g dimethylformamide

0.5 g of 50 # sulfuric acid at 28 ° C
Minutes

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Example 16

Preparation of a mixture of 3- and 4- (4'-methyl-4'-hydroxyamyl) - Δ -cyclohexencarboxyaldehyde

Reaction:

wT

H ₂ O

IH ⁺ ]

)H

The following substances were mixed with one another in a fitted with a thermometer, magnetic stirrer and reflux condenser:

Ingredients quantity

Myracaldehyde 100 g

Water 50 g

Cation exchange resin (sulfonated copolymer from styrene and divinylbenzene,

containing 4 # divinylbenzal monomer units, manufactured by the Dow Chemical Company of Midland, Michigan;

Moisture content: 65.8 #;

Sieve fineness: DIN 20 - 40j Trademark: Dowex R 50W-X4 10 g

Samples were taken every 30 minutes or every hour and analyzed to be the percentages of a mixture of 3- and 4- (4'-methyl-4'-hydroxyamyl) -Δ - to determine cyclohexenecarboxaldehyde. Analysis was by gas-liquid chromatography (SE-30 column). The following table gives the Time, temperature and percentage of reaction product to:

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Time
hours temperature
⁰ C 4- (4'-methyl-4'-hydroxy-
amyl) - ^ 3-cyclohexene
carboxaldehyde - % O 22nd —— 1 23 0 2 90 0 Previous year 95 1.2 4th 95 1.8 VJl 100 2.8 6th 100 2.8 7th 100 2.8 8th 100 2.8 9 100 2.3 10 100 2.8 11 100 2.8 12th 100 2.8 22nd 21 4.9 * 24 24 4.8 26th 25th 4.6 29 1/2 64 5.4 27 1/2 103 9.1 31 1/2 100 3 * 7 33 1/2 100 2.0 35 1/2 100 0.1 36 1/2 100 complete
decomposition

* At this point, 40 g of 90% formic acid were used added to the reaction mass.

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Example 17

Preparation of a mixture of 3- and 4- (4'-methyl-4'-hydroxy-amyl) - Λ 3-oyclohexenearboxaldehyde

Reaction:

H ₂ O

)H

185 g of a 33 # aqueous sulfuric acid solution were placed in a 1 liter reaction flask equipped with a stirrer, thermometer, filling funnel and reflux condenser and this was heated to 40.degree. Over 11/2 hours, 220 g of myraealdehyde were added through the funnel, the temperature being kept at 40 ° C. This reaction mixture was kept at 43 ° C. for 14 hours and then it was determined by gas-Plussig chromatography that a 1.5% mixture of 3- and 4- (4'-methyl-4'-hydroxyamyl) -Δ ^ -eyclohexencarboxaldehyde had been formed was. The reaction mixture was then kept at a temperature in the range from 43 ° to 45 ° C. for 14 hours, after which it was found that a 2.8% mixture of ^{3- and 4- (4 f} -methyl-4'-hydroxyamyl) - Δ ^ -cyclohexencarboxaldehyd was formed. Another 8 hours at 24 ° C gave 4.0 # mixture. At this point in time, a further 100 ml of tetrahydrofuran were added and this reaction mixture was heated under reflux at 75 ° to 75 ° C. for 12 hours. At the end of this reaction time, a mixture of $ 13.9 was found.

The reaction mass was then washed with water and then with saturated aqueous sodium carbonate solution. The solvent was removed in vacuo and the residue was determined by gas-liquid chromatography as a 14.8 # mixture of 3- and 4- (4'-methyl-4 ¹ -hydroxyamyl) - A -eyelohexenearboxaldehyde.

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Example 18

Hi.

Preparation of a mixture of j5- and 4- (4'-methyl-4 ^! -Hydroxy amyl) -Δ -cyclohexencarboxaldehyde

Reaction:

H ₂ O

In one with a stirrer, thermometer, filling funnel and reflux condenser equipped 1-liter flasks were given the following substances:

Components

p-Toluenesulfonic acid

90 ^ aqueous formic acid

lot

38 g l80 g

The mixture was stirred until completely dissolved. After the reaction mass had cooled to 7 ° C, the addition of myracaldehyde began, a total of 300 g over a period of 2 1/2 hours, with the temperature "" being maintained between 5 ° and 10 ° C. The gas-liquid chromatography carried out thereafter showed the formation of approximately 10 # mixture of 3- and 4- (4 ^t -methyl-4 ^l -hydroxyamyl) - ₎ ^ ⁵ -cyelohexenearboxaldehyde. The reaction mass was then heated to 24 ° C. and held at this temperature for 4 hours, after which the mixture was determined. After cooling the reaction mass to 9 ° C., 50 g of water were added! Stirred for an hour, the temperature being kept at 9 ° to 10 ° C. Thereafter, 30.7 # mixture was found. Further stirring for 9 hours at 20 ° to 23 ⁰ C showed no visible change in the © * percentage. The reaction mixture was then washed with water and saturated aqueous sodium carbonate solution and the solvent was stripped off. In the crude residue were 49 * 8 # mixture of 3- and 4- (4 ^l -Methyl-4 ^l -hydroxyamyl) - ^ l ^ -cyclohexencarbox-

Example 19

Preparation of a mixture of 3- and 4- (4'-methyl-4'-hydroxyamyl) - A -cyclohexenecarboxaldehyde

Reaction i

)H

H ₂ O

[H ⁺ J

In one with a stirrer, thermometer, filling funnel and reflux condenser The 500 ml reaction flask was filled with the following substances:

Ingredients quantity

water
Myracaldehyde

Silico-phosphoric acid polymerization catalyst - UOP-SPA-2 (the Universal Oil Prod. Corp. of Des Piaines, 111)

50 g 250 g

10 g

- The reaction mixture was mixed for 2 hours at room temperature. During this time no mixture of 3- and 4- (4 ^f -methyl-V-hydroxyamyl) - Λ -cyelohexencarboxaldehyde had formed. The mixture was then heated to 50 ° C. and the reaction mixture was kept at this temperature for 2 hours, but even now no formation of the desired mixture was found. After the reaction mass had cooled, 50 g of formic acid were added, namely at room temperature and stirred at this for 8 hours. The mixture was then heated to 70 ° C. and this temperature was maintained for 4 hours. After refluxing for 11 hours, gas-liquid chromatography gave 9 # of the mixture 3- and 4- (4 ^f -methyl-4 ^f -hydroxyamyl) -A ⁵ -cyclohexenecarboxaldehyde.

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-Vf-

Example 20

Reaction:

In one with a stirrer, thermometer, filling funnel and reflux condenser stocked 500 ml reaction flasks were as follows Substances given:

Components

Piltrol 105

(Activated alumina adsorbent from Filtrol Corporation, which has the following properties: Particle size:

by rolling (10 l / min. air speed)
0-5 / U, wt % 8

0-20 / rev, ""

by Tyler Standard DIN 40 wt.% DIN 80 100 "" 95 DIN 100 "" 78

Quantity 10 g

Bulk density 0.67284 50 g g / ccm % 15 250 g free moisture, wt. free and com combined humidity, Wt. % (Loss 21 at 926 ^ό C) OfI. area _{or similar} 300 (BET method) πΓ / g Phenolic acidity 4.8 thalein mg KOH / g Filter speed. 38 ccm / min. 35) oil retention, wt. % water Myracaldehyde

The reaction mixture was stirred at room temperature for 2 1/2 hours, but no formation of the mixture was observed thereafter.

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After stirring under reflux for 7 hours, gas-liquid chromatography gave a 1% mixture of J> - and 4- (4'-methyl-4 * -hydroxyamyl) -Zi - ^ - cyclohexenecarboxaldehyde. The addition of 100 ml of tetrahydrofuran and stirring for 5 hours at room temperature brought no visible change in the concentration of the mixture. The reaction mixture was then refluxed for 2 hours, then 50 g of formic acid were added and the mass was kept at room temperature for 12 hours, after which time the mixture was found to be 1.5%. After a further 4 hours of refluxing, the content of the mixture rose to 1.9 $. At this point, 100 g of acetic acid were added and the mass was stirred at room temperature for 2 1/2 hours. But even this measure brought no change in the ^ content of the mixture. Only after a further 7 1/7 hours of refluxing could a concentration of k% of the desired product be determined. The catalyst was then filtered and the reaction mixture was washed until neutral. The analysis showed

18.0 $ solvent

76 % myracaldehyde

4 % mixture of 3- and 4- (4'-methyl-4'-

hydroxyamyl) - £ ± 5-cyclohexenecarboxaldehyde.

Example 21

In one equipped with a stirrer, thermometer and reflux condenser The following substances were introduced into the 500 ml reaction flask:

Ingredients quantity

Myracaldehyde 100 g

Acetic acid 100 g

Sulfuric acid (64 #) 50 g

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reaction time temperature Min. ° C 15th 78 75 40 195 33 300 33

Samples of the reaction mixture were taken at the specified time intervals. The following table gives the # content of 4- (4'-methyl-4 ^t -hydroxy- cyclohexenearboxaldehyde determined by analysis:

(through range normalization)

33 58 69 73.7

After the reaction had ended, the composition contained (internal standard): _Q ^ _solvent

6.1 % myracaldehyde

$ 10.2 Desired mixture of

3- and 4-14'-methyl-4 ^t -hydroxyamyl) - / \ 3 -eyelohexenearboxaldehyde

Example 22

The following substances were introduced into a 500 ml reaction flask equipped with a stirrer, thermometer and reflux condenser:

Ingredients quantity

Myracaldehyde 100 g

Acetic acid 100 g

p-toluenesulfonic acid 10 g

The reaction mass was stirred at room temperature and samples were taken at different time intervals, different ^ contents of the desired product, namely a mixture of 3- and 4- (4'-methyl-4 ^f -hydroxyamyl) -Δ -cyclohexencarboxaldehyde were determined, such as the following table shows:

709815/1 19f

Response time min.

30th

210

% of the desired product

5.6 14.8 21
22.6

10 g of water were added to the reaction mass and the mixture was stirred for a further half an hour. According to this, 18.9% of a mixture of 3- and 4- (4'-methyl-4 ^f -hydroxyamyl) -> / \> -cyclohexencarboxaldehyde were formed. After stirring for a further 4 hours at room temperature, 28% of the mixture were found in the reaction mass (on a solvent-free basis). Gas-liquid chromatography showed the following raw information:

$ 91.6 solvent 5.3 $ myracaldehyde

$ 2.6 Mixture of 3- and predominantly- * 4- (4'-methyl-hydroxyamyl) - Δ cyclohexenecarboxaldehyde

This mixture was distilled from the reaction mass and used in the following examples:

Example 23 Components A "Fougdre" perfume preparation Cinnamon alcohol Parts by weight Ambrite musk 50 Vanillin 40 Coumarin 5 Oak moss resinoid 80 Linalool 10 Linalyl acetate 125 Benzyl acetate 150 Phenylethanol 50 Bergamot oil 70 Lavender oil 100 150

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^ 643062

Port setting example 23 ö

Parts by weight Components 50 Geranium Oil (Bourbon) 50 Sandalwood oil E.I. 5 Eugenol 15th Isoeugenol 20th Amyl salicylate 20th Benzyl salicylate 20th Product manufactured

Example 16, which is a major portion of a mixture of 3- and 4- (4'-Me ethyl-4'-hydroxyamy1) -

Δ 3-cyclohexenecarboxal-

contains hyd

This product gives the "Fougere" perfume a very sweet, Lilac-lilies aromatic fragrance.

Example 24 ·.

A rose perfume was made from the following ingredients Parts by weight of ingredients

20th Phenylethylphenyl acetate 40 Phenylethyl salicylate 150 Geraniol 240 Phenylethanol 150 Citronellol 20th Sandalwood oil E.I. 75 Nonanediol diacetate - 1.3 50 Geranyl acetate 20th Geranyl phenyl acetate 20th Citronellyl formate 25th Phenyl ethyl acetate ^; 60 Phenylethyl propionate 20th Phenvlacetaldehyde 50 $ i

Diethyl phthalate 709815/1 197

Continuation of example 24

Parts by weight

Components

20th Pheny! Acetaldehyde 1,3- butylene glycol acetal 10 Eugenol 10 Methyl isoeugenol 50 alpha-hexyl cinnamaldehyde 40 Product manufactured na

Example 18, which is a major part of a Geraisches from 3- and 4- (4'-Methy1-4'-hydroxyamyl) -Δ Contained 3-cyclohexenecarboxaldehyde.

1030

This "rose" perfume had a sweet floral aroma that passed through the addition of the product from Example 18 was increased.

Example 25

A "bouquet" perfume was made from the following ingredients:

Parts by weight

Components

20th Ambrite musk 40 Heliotropin 100 Benzyl acetate 80 4-tert-butylcyclohexyl acetate 130 alpha-hexyl cinnamaldehyde 40 alpha-ΑmyIcinnamaldehyde 30th Linalyl acetate 80 Terpineol 80 Geranylace did 80 Linalool 100 alpha methyl ionone 25th Methyl isoeugenol 15th Isoeugenol

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Continuation of example 25

Parts by weight Components 40 Geraniol 60 Phenylethanol 20th Styrallyl acetate 50 Vetiveryl acetate 5 10-undecene-l-al 5 Product manufactured

Example 19 with a major portion of a mixture from 3- and 4- (4'-Methy1-4'-hydroxyamyl) - ^ \ 3-cyclohexenecarboxaldehyde

1000

The product from Example 19 gave the "bouquet" perfume a sweet lilac-lily nuance.

Example 26 Manufacture of a cosmetic powder

In a ball mill, 100 g of talcum powder were intimately mixed with 0.25 g of the mixture which contained 3- and a major part 4- (4'-methyl-4 ^? -Hydroxyamyl) - / \ -cyclohexenecarboxaldehyde (Example 16). The powder had an excellent, sweet, lilac and lily flavor.

Example 27 Perfumed liquid detergent

Concentrated liquid detergents with a sweet, lilac and lily scent were made that cost $ 0.10; 0.15 $ and 0.20 # of the mixture according to Example 21, which consisted of 3- and predominantly 4- (4'-methyl-4'-hydroxyamyl) - / \ "-cyclohexenecarboxaldehyde. The seasoning additive was mixed homogeneously with the liquid detergent. All samples produced in this way

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had a sweet, lilac-lily-spicy note, with the intensity r. increased with higher concentrations of the mixture mentioned.

Example 28 Production of a cologne and handkerchief perfume

A mixture consisting of 3- and predominantly 4- (4'-methyl-4'-hydroxyamyl) - Λ -cyclohexencarboxaldehyde, prepared according to Example 17, was in a concentration of 2.5 $ in 85 ^ strength aqueous ethanol in a cologne and at a concentration of $ 20 in 95 ^ -igera aqueous ethanol put into a handkerchief perfume. The mixture gave both the colognes and the handkerchief perfume a distinct, sweet, lilac-lily-spicy note.

Example 29

The procedure was as in Example 28, but instead of the mixture according to Example 17, the mixture according to Example 9 was added to the colognes and the handkerchief perfume in the concentrations mentioned. The use of the mixture from 3- and 4- (4'-methyl-V-hydroxyamyl) - Δ ^ -cyclohexenecarboxaldehyde in the composition from Example 24 contributed to a pronounced and distinctly strong "bouquet" aroma sweet, lilac-lily notes.

Example 30 Manufacture of a soap composition

100 g of soap chips were with 1 g of the mixture 3- and 4- (4'-methyl-4'-hydroxyamyl) -Δ -cyclohexencarboxaldehyd from Example 18 mixed until a substantially homogeneous mass is formed was. The perfumed soap composition had an excellent sweet, lilac-lily flavor.

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Example 31 Production of a detergent composition

100 g detergent powder were mixed with 0.15 g of the mixture 3 and 4- (4'-methyl-4'-hydroxyamyl) - / \ -cyclohexencarboxaldehyde, prepared according to Example 19, mixed until a substantially homogeneous mass was formed. This composition had a excellent, sweet, lilac-lily aroma.

Example 32 Part A :

Into a 250 ml reaction flask equipped with a stirrer and thermometer the following substances were introduced:

Ingredients quantity

Sulfonated copolymer

from styrene and divinylbenzene,

containing 4 # divinylbenzene monomer units;

Moisture content: 65, J>%; Sieve fineness: DIN 20 - 40,

Wz.Dowex® 50W-X4 100 g

Myracaldehyde 100 g

Acetic acid 100 g

The reaction mixture was left for 33 hours at room temperature touched. Samples taken were checked for the presence of a mixture of 3- and 4- (4'-methyl-4'-hydroxyamyl) -Δ -cyclohexenecarboxaldehyde analyzed. The dates are as follows:

Time of the sample- % Lyral in the withdrawal: hours of reaction mass

9 8th 22nd 16 33 22.5

The reaction product was filtered, neutralized and fractionally distilled. The lyral passed over at 14 ° to 153 ° C. and 1.4 to 3.9 mm Hg. The distillate collected in this way was then fractionated in a 12 "χ 1" Goodloe column and concentrated

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Obtained product whose boiling point was 125 ° to 126 ° C and 0.7 mm Hg.

part B

The procedure of Part A was repeated with the exception of Temperature and reaction time. The work was carried out at 60 ° to 62 ° C. for 3 1/2 hours. The following table gives the response times the temperatures as well as the ^ proportions of Lyral.

Time temperature percent

45 min. 61 ° C 19 * 5 #

2 1/2 hours 60 ° C 7 ', <#

3 1/2 hours 61 ° C $ 3.5

Part C.

Continuous hydration. of myracaldehyde using sulfonated! Copolymer of styrene and divinylbenzene, known as Dowex (^) 50W-X4 .

A solution was made up of the following ingredients: Ingredients Amount

Myracaldehyde 500 g

Acetic acid 1000 g

deionized water 180 g

50 g of the copolymer (Dowex® ) (preferably washed with 200 g of 10% sulfuric acid and rinsed with deionized water) were placed in a chromatography column jacketed with cooling water. (20 mm) rinsed in using 80 # acetic acid. The column was then rinsed with 500 g of 80 # acetic acid. Due to gravity, the myracaldehyde / acetic acid / water solution then flowed through the chromatography column, the temperature of which varied between 26 ° and 50 ° C. for 6 hours. The following table gives the reaction time, temperature of the column and the percentage of Lyral in the eluate and its total weight;

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Time

temperature

Myracaldehyde ratio

Lyral

Weight of eluate

30 min. 2 hours 4 hours t> hours 6 hours

26 ° C 56 ° C 27 ° C 27-49 ⁰ C 50 ° C

O O O

11: 1 12.65: 1

68 g 72 g 30 g 8? g 90 g

Part D:

The procedure in Part C was repeated with the exception the temperature of the chromatography column, which was between 50 ° and 60 ° C. The following results were achieved:

Time temperature 50 ° ⁰ C relationship
Myracaldehyde 1 1/2 hours 57-60 55 ° C. 20: 1 5 hours C. 25: 1 4 hours 20: 1 Part E:

Lyral

Weight of eluate

125 g 98 g

The following components were placed in a reaction flask (250 ml) equipped with a stirrer and thermometer:

Ingredients quantity

G
G
G

Myracaldehyd Dowex® 50W-X4 glacial acetic acid

The reaction mixture was stirred at room temperature for 48 hours during which time no lyral was formed. Then was Heated to 60 ° C for 7 hours.

A 20 ecm sample was removed and placed in a separatory funnel given. 100 ml of water and 50 ecm of benzene were added to this sample, and the mixture obtained was shaken vigorously and the water phase is separated from the resin / oil layer. The oil layer

709815/1197

was with a sodium bicarbonate solution until neutral washed and dried over anhydrous magnesium sulfate. Then the benzene was evaporated and the oil layer through preparative gas-liquid chromatography analyzed. The relationship Lyra! : Myracaldehyde was 4 ^, 5: 54.6.

The gas-liquid chromatography profile is shown in FIG Drawings reproduced.

Part F:

The following reactants became a 2 liter reaction flask equipped with a stirrer, thermometer and reflux condenser brought in:

Ingredients quantity

Myracaldehyde I96 g (1 mole)

Dowex® ^l 50W-X4 583 g

Water 217 ml

The reaction mixture was heated to 60 ° C. and kept at this temperature for 89 hours, with constant stirring. A 20 ecm sample was then taken and 100 ml of water and 50 ecm of benzene were added in a separating funnel. The mixture was shaken vigorously and the oil phase separated. After the oil phase was dried over anhydrous magnesium sulfate, it was placed in a "Rinco" evaporator evaporated at 50 ° C. Gas-liquid chromatography and IR analysis gave Lyral $ 29.4. The relationship Lyral: myracaldehyde was 32.5: 64.2.

Figure 7 of the drawings shows the gas-liquid chromatography profile of the product obtained.

Part G:

In one with stirrer, thermometer, reflux condenser and one Nitrogen blanketed 2-liter reaction flasks were added the following reaction participants brought in:

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Ingredients quantity

Myracaldehyde 196 g

DowexS ^ 50W-X4 533 g Water 67 ml

Glacial acetic acid 13O g (3 mol)

The reaction mixture was heated to 60 ° C. with stirring and kept at this temperature for 48 hours. A 20 ecm sample was then taken and treated further in accordance with the process steps in Part F. Gas-liquid chromatography, IR and spectral analyzes gave 8.0 $ Lyral. The myracaldehyde: lyral ratio was 87.7: 8.0. Figure 8 shows the gas-liquid chromatography profile of the reaction product at the end of the 48 hours.

Part H:

In one with a stirrer, thermometer, reflux condenser and nitrogen blanket The following reaction participants were introduced into the 2-liter reaction flask provided:

Ingredients quantity

Myracaldehyde 196 g

Dowex® 50W-X4 620 g

Acetic acid 180 g (3 mol)

The reaction mixture was heated to 60 ° C. with stirring and kept at this temperature for 48 hours. The reaction mass was then treated further in accordance with the process steps in Part F. Gas-liquid chromatography, IR and MS analyzes gave $ 25.3 of Lyral. The ratio of lyral: myracaldehyde was 24.8: 74.9. Figure 9 shows the gas-liquid chromatography profile of the reaction product at the end of the 48 hours.

0 9 815/1197

Part One:

In a 2 liter reaction flask equipped with a stirrer, thermometer and reflux condenser, feeble reactants became brought in:

Ingredients quantity

Myracaldehyde 98 g (0.5 mol)

DowexvS ^ 50W-X4 620 g

Glacial acetic acid 240 g (4 mol)

The reaction mixture was heated to 60 ° C. and kept at this temperature for 24 hours. The reaction mass was then treated further in accordance with the process steps in Part F. Gas-Plüssig chromatography, IR and MS analyzes showed $ 3.6% by-product with a ratio of lyral: myracaldehyde of 33 * 6: 57 * 2. Fig. 10 shows the gas-liquid chromatography profile of the reaction product after 24 hours.

Example 33

A clear, single-phase solution of 90 S myracaldehyde, 100 g acetic acid and 18 g deionized water. This solution was mixed with 20 g of the cation exchange resin from Rohm and Haas Company, Philadelphia, known as "amberlyst 15". This cation exchange resin is a copolymer of styrene and divinylbenzene, the monomer units of divinylbenzene being the same as the monomer units of styrene.

The reaction mixture was at temperatures from 25 ° to 80 ° C heated while stirring. Samples were taken at various time intervals and examined for the content of Lyral. The following table shows the reaction times, temperature and the amount of Lyral formed:

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Time hours temperature C. and Percentage 2 1/2 hours 25-65 ° C. 3.2 # 3 1/2 hours 65-64 ° C. 21 0 4th 1/2 hours 64-65 ° C. $ 29.3 5 hours 65-85 ° C. 5 1/4 85-86 ° 14.30
(through internal
Standards) 36.90
(by area
normalization)

After adding 100 g of toluene, the reaction mixture was washed with water and saturated sodium carbonate solution. Then was evaporated and distilled to give a Lyral with a boiling point of 133-135 ° C at 0.5-0.9 mm Hg became.

example ~ $ K

In one equipped with a stirrer, thermometer and reflux condenser The following reactants were introduced into the 500 ml reaction flask:

Ingredients quantity

Myracaldehyde 200 g

300% aqueous

Sulfuric acid 160 g

Dimethylformamide 50 g

The reaction mixture was from 25 ° C to reflux temperature (117 ° C) heated and refluxed for 5 hours. Then a further 100 g of dimethylformamide were added and samples were taken at different times and analyzed for Lyral by gas-liquid chromatography. the Results are:

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CC,

Time temperature Lyral
Percentage 1 1/2 hours 117 ° C 4.0 # 3 1/4 hours 115 ° C 4.6 # 5 hours 114 ° C 2.8 * Example 35 Reaction:

HC 1 / H ₂ O.

Isopropatiol

CHO

HO

CHO

In one equipped with a stirrer, thermometer and reflux condenser 250 r.l reaction flask became the following reactants brought in:

Components

lot

Myracaldehyde

1 molar hydrochloric acid

Isopropanol

The reaction mixture was heated under reflux and with a stirrer for 4 hours.

19.2 g (0.1 mol) 100 ml (0.1 mol) 100 ml

100 ml of water were then added and the aqueous layer thus formed was extracted with free 50 ml portions of diethyl ether. The ether extracts were poured together and mixed with three 50 ml portions of saturated sodium bicarbonate solution and then washed with three 50 ml servings of water. The ether extracts were washed with anhydrous magnesium sulfate, filtered and concentrated. Gas-liquid chromatography showed a Ratio of $ 49 myracaldehyde to $ 47 lyral. The amount of Lyral formed was confirmed by IJMR and MS analyzes.

The gas-liquid chromatography profile is shown in FIG.

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- β ¹ ?.

represents. The Lyral - a mixture of 3- and 4- (4'-methyl-4 'hydroxyaryl) - ^ -cyclohexencarboxaldehyd) was then distilled from the reaction mixture and used in the following examples 3ό to j ?9 used.

The lyral thus produced had that shown in FIG NMR spectrum and the IR spectrum shown in FIG on. For the myracaldehyde, the NMR spectrum is shown in FIG and the IR spectrum shown in FIG.

example 36

A "Fougere" perfume was produced:

Parts by weight of ingredients

30 40

125

150

100

150

15 20 20 20

Cinnamon alcohol

Ambrite Musk Vanillin

Coumarin

Oak moss resinoid Linalool

Linalyl acetate Benzyl acetate

Phenylethanol Bergamot oil Lavender oil 45/47 Geranium Oil (Bourbon) Sandalwood Oil E.I.

Eugenol

Isoeugenol

Amyl salicylate benzyl saclicylate.

Product made according to Example 35 * das a major proportion of 4- (4 · -Methyl-4'-hydroxyamyl) -Δ ^ -cyclohexencarboxaldehyde contained

1010

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This compound from Example 35 gave the perfume a one very sweet, lilac-lily aromatic fragrance.

Example 37

A rose perfume was made from the following components: each component

Phenylethylphenyl acetate

Phenylethyl salicylate

150 geraniol

240 phenyl ethanol

150 citronellol

20 sandalwood oil E.I.

Nonanediol diacetate - 1.3

50 geranyl acetate

20 geranyl phenyl acetate

20 citronellyl formate

25 phenyl ethyl acetate

60 phenylethyl propionate

Pheny! Acetaldehyde $ 50

in diethyl phthalate

Pheny! Acetaldehyde 1,3 -

butylene glycol acetal

10 eugenol

10 methyl isoeugenol

alpha-hexyl cinnamaldehyde

Product made after

Example 35> comprising a major proportion 4- (4'-methyl-4 ^t hydroxyamyl) - ^ 3-cyclohexene carboxaldehyde and a minor proportion of 3- (4'-methyl-4'-hydroxyamyl) A ^ -cyclohexencarboxaldehyd contained

1030

The product from Example 35 enhanced the sweet floral aroma of the rose perfume.

70981 5/1197

example Jd

A "bouquet" perfume was made from the following ingredients:

3 weight parts

20th Ambrite musk 40 Heliotropin 100 Benzyl acetate 80 4-tert-butylcyclohexyl- acetate 130 alpha-hexyl cinnamaldehyde 40 alpha-amylcinnamaldehyde 30th Linalyl acetate 80 Terpineol 80 Geranyl acetate 80 Linalool 100 älpha-methylionone 25th Methyl isoeugenol 15th Isoeugenol 40 Geraniol 60 Phenylethanol 20th Styrallyl acetate 50 Vetiveryl acetate 5 10-undecene-l-al 5 Product made nac

1000

Example 35 with a major proportion of 4- (4'-methyl-4'-hydroxyamyl) - / ^ - ^ - cyelohexencarboxaldehyde and a small proportion of 3- (4'-methyl- · * ¹ -hydroxyamyl) - ./ \ 3- cyclohexenecarboxaldehyde

The addition of this product «gave the" bouquet "perfume a sweet, lilac-lily nuance.

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Example

Manufacture of a cosmetic powder

In a ball mill 100 grams of talcum powder was mixed with 0.25 g of the mixture of 3- and predominantly 4- (4'-methyl-4'-hydroxyamyl) - l \ -cyciohexencarboxaldehyd according to Example 35 mixed. This powder had an excellent sweet, lilac and lily flavor.

Example 40 Perfumed liquid detergent

Concentrated liquid detergents with a sweet, Lilac-Lily Fragrance made $ 0.10; $ 0.15 and $ 0.20, respectively the mixture of 3- and predominantly 4- (4'-methyl-V-hydroxyamyl) -Δ -cyciohexencarboxaldehyd according to Example 35 contained. The additive was mixed homogeneously with the liquid base material. All samples produced in this way had a sweet, lilac-lily flavor, the intensity increasing with increasing concentration.

Example 41 Production of a cologne and handkerchief perfume

A mixture containing 4- (4 '-Met hy I -4' -hydroxyamyl) - ^ \ -cyciohexencarboxaldehyde, prepared according to Example 35 *, was added to a cologne in a concentration of 2.5 $ in 85% aqueous ethanol and added to a handkerchief perfume at a concentration of $ 20 (in $ 95 aqueous ethanol). Both the eau de Cologne and the handkerchief perfume received a pronounced and specific sweet, lilac-lilac flavor.

Example 42

The compound prepared according to Example 38 became a cologne in a concentration of $ 2.5 in $ 85

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aqueous ethanol; and a handkerchief perfume in one Concentration of $ 20 (in 95 # aqueous ethanol) added. Both preparations received a distinctive and specific strong bouquet aroma with sweet lilac and lily notes.

Example 43

100 g of soap chips were with 1 g of a 4- (4'-methyl-V-hydroxyaryl) - ^ - ^ - cyclohexenecarboxaldehyde containing mixture, prepared according to Example 35, up to an essentially homogeneous mass mixed. The perfumed soap had an excellent sweet lilac and lily aroma.

example

100 g detergent powder containing sodium benzene sulfonate, were mixed with 0.15 g of the mixture prepared according to Example 35 until an essentially homogeneous mass was educated. This composition had an excellent sweet lilac-lily flavor.

709.8 1 5/1 197

St.

Example 43

Manufacture of Lyral by hydrochlorination of Myrac and subsequent hydrolysis

Reaction:

, Ct

WaHCO ₃

(A) hydrochlorination

40 g of anhydrous hydrochloric acid was poured into a cooled one (10-15 ° C) solution of 200 g of myracaldehyde in 1000 g of glacial acetic acid poured over the course of an hour. The reaction mixture turned 15 Stirred for hours at 10 ° to 15 ° C. and then poured over 2 kg of crushed ice. It was extracted with diethyl ether that Extracts washed with sodium carbonate solution and dried over anhydrous Dried magnesium sulfate. After removing the diethyl ether in vacuo, 225 g of crude hydrohalogenated product were obtained (Hydrochloromyracaldehyde) which was hydrolyzed without further treatment.

7 0 9 8 15/1197

(B) hydrolysis

The crude hydrohalogenated product (hydrochloromyracaldehyde) was stirred for 10 hours under reflux at 30 ° to 85 ° C. in a mixture of 1000 g v / water, 1000 g isopropanol and 100 g sodium bicarbonate. The reaction mixture was then diluted with 1000 g of water and extracted with diethyl ether. The ¹ diethyl ether extracts were dried over anhydrous magnesium sulfate and the diethyl ether was then removed in vacuo (0.5 atm.). What remained was an oil which was carefully distilled, 5 g of Lyral with a boiling point of l ~ $ k- to 135 ° C. at 1 mm Hg being obtained. The yield was $ 25, based on the starting material myracaldehyde.

Example 46

Production of Lyral by hydrochlorination of myracaldehyde and subsequent hydrolysis

Reaction:

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(A) hydrochlorination

This is carried out as in Example 45.

(B) hydrolysis

The crude hydrohalogenated product was refluxed for 10 hours at 80 ° to 85 ° C in a mixture of 1000 g Water, 1000 g of isopropanol and 90 g of potassium hydroxide were stirred. Then the reaction mass was diluted with 1000 g of water, extracted with diethyl ether and the diethyl ether extracts dried over anhydrous magnesium sulfate. After removing of the diethyl ether in vacuo left an oil which was carefully distilled, yielding 56 g of Lyral with a boiling point passed from 1 ^ 4 ° - 135 ° C at 1 mm Hg. The yield of $ 26 is based on the myracaldehyde.

Example 47

(i) Manufacture of myracaldehyde hydrochloride

A solution of 1000 g of myracaldehyde in 2500 g of toluene was cooled to -20 ° C. 200 g of anhydrous were added to this solution Hydrogen chloride gas bubbled in over a period of 5 hours, the temperature being maintained at -10 ° to -20 ° C became. The reaction mixture was left to stand at room temperature for 3 days. After removing the toluene under reduced pressure left 1140 S of crude myracaldehyde hydrochloride.

(ii) Solvolysis of myraoaldehyde hydrochloride

(a) A solution of 100 g of myracaldehyde hydrochloride in a mixture of 100 g of water and 500 g of isopropanol was used for 2 hours stirred at 80 ° C with 50 g of sodium acetate. After diluting with water, extracting with ether and removing the solvent 90 g of a product containing 35 # Lyral were obtained.

709815/119 *

254-3062

(b) A solution of 100 g of myracaldehyde hydrochloride in 250 g of toluene was stirred under reflux for 3 hours with 50 g of anhydrous sodium acetate and 1 g of tricapryymethylammonium chloride (aliquot ^>J>^>) . Washing with water and evaporation of the toluene gave 95 g of a product which contained 50% of lyral acetate. The hydrolysis of this acetate to form lyral was carried out by refluxing the crude product in aqueous • methanolic sodium hydroxide solution.

(c) A mixture of 100 g of myracaldehyde hydrochloride, 500 g of isopropanol and 25 g of sodium hydroxide was refluxed Heated for 2 hours and then poured over crushed ice. After extracting with ether and removing the ether, 85g of a crude product containing $ 45 Lyral.

709815/1197

Brief summary of the drawings . Show it:

1 shows the gas-liquid chromatography profile of the reaction product from the reaction catalyzed with zinc chloride between myrcenol and acrolein according to Example Ij

2 shows the gas-liquid chromatography profile of the reaction product from the reaction catalyzed with zinc chloride between myrcenol and acrolein according to Example 4;

3 shows the gas-liquid chromatography profile of the reaction product from the non-catalyzed thermal Diels-Alder reaction of myrcenol and acrolein according to Example 6;

4 shows the IR spectrum of the product from Example 3; 5 shows the NMR spectrum of the product from Example 3; Figure 5A is a reference profile of gas-liquid chromatography

a pre-made mixture of lyral and myracaldehyde;

5E shows the gas-liquid chromatography profile of the reaction product from Example 5 (A) j

5C shows the gas-liquid chromatography profile of the reaction product from Example 5 (B);

6 is a gas-liquid chromatography profile of the reaction product from Example 32, Part E;

7 is a gas-liquid chromatography profile of the reaction product from Example 32, Part F;

8 is a gas-liquid chromatography profile of the reaction product from Example 32, Part G;

9 shows a gas-liquid chromatography profile of the reaction product from Example 32, Part Hj

10 is a gas-liquid chromatography profile of the reaction product from Example 32, Part I;

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11 is a gas-liquid chromatography profile of the reaction product from Example 35;

12 shows the NMR spectrum for the Lyral prepared according to Method according to example 35;

Fig. 13 is the NMR spectrum prepared for the myracaldehyde according to the method according to Example 35;

14 shows the IR spectrum for the Lyral produced after Method according to example 35; and

15 the IR spectrum for the myracaldehyde prepared according to the procedure according to example 35 »

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Claims (2)

P_a ten t_a n_s p_r_ü c h_e 1. A process for the preparation of a composition which has, as a main component, a compound of the general formula in which Y is one of the groups: CH; or represents, where Q is one of the following groups: 709815/1197 ORiGlNAL INSPECTED Chlorine or bromine; and R is a lower alkyl group, characterized by one of the following Reaction processes: I. Thoroughly mix acrolein of the formula CHO with myrcenol of the formula OH 709815/1197 being the reaction (i) In the presence of a catalytic amount of a ¹ Lewis acid catalyst, such as ZnXp, SnX ₂ ,, AlX ,, AIR X or mixtures of two or more of the Lewis acids, where X is chlorine or bromine, R is an alkyl group, m + η = 3, or m = 1 or 2 and η = 1 or 2, (ii) at a temperature in the range of from about -20 to about 100 ° C and (iii) at a pressure of about 1 to 100 atmospheres. is carried out and the acrolein: myrcenol molar ratio is about 10: 1 to about 1:10 and about 0.2 to about 10 wt. % Lewis acid catalyst, based on the total weight of acrolein and myrcenol, are used; II. Thorough mixing of myracaldehyde of the formula ■ CHO with an acid acting as a hydrate agent, the Aldehyde group is not reacted and during the reaction free aldehyde is present; or III. Thorough mixing of myracaldehyde of the formula CIIO with a hydrohalogenating agent which is either hydrogen chloride or hydrogen bromide, a compound of the 7 0 9 815/1197 formula • V. & t- is formed, wherein X is chlorine or bromine and the formyl group is either in position "4" or the hydrohalogenated aldehyde is a mixture of "4" and "5" position isomers, then either (a) the hydrohalogenated aldehyde thus formed with a hydrolysis agent or (b) with a carbalkoxylating agent unoccupied and a myracaldehyde carbalkoxylate is formed that will be the formula wherein R is a lower alkyl group, then this myracaldehyde carbalkoxylate is treated with a hydrolyzing agent, the aldehyde group not converted, but a free aldehyde during the hydrohalogenation, the carbalkoxylation and the Hydrolysis is; 7098 15/1197 IV. Thoroughly mixing acrolein with myrcene, starting the reaction (i) in the presence of a catalytic amount of a Lewis acid catalyst, such as ZnXp, SnXu, ADU, AIR X or mixtures of two or more of the Lewis acids, where X is chlorine or bromine, R is an alkyl group, m + η = 3, or m = 1 or 2 and η = 1 or 2 mean, (ii) at a temperature ranging from about -20 ° C to to about 100 ° C and (iii) at a pressure of from about 1 to about 100 atmospheres. is carried out and the acrolein: myrcene molar ratio is about 10: 1 to about 1:10 and about 0.2 to about 10 wt. % Lewis acid catalyst, based on the total weight of acrolein and myrcene, are used. 2. The method according to claim 1 for the preparation of a mixture which contains a major proportion of a compound of the formula: wherein the formyl group is either in position "4" or in both position "4" and in position "5" and wherein Y is either 7 0 9 8 15/1197 or is, where acrolein of the formula 'OH with a compound of the general formula: is intimately mixed and the reaction (i) in the presence of a catalytic amount of a Lewis acid catalyst, how ZnClp, SnCl ^, ZnBr ₂ , AlCl ,, C ₂ ILAlCl ₂ or a mixture of two or more of these Lewis acids (ü) at a temperature in the range from about -20 ° to to about 100 ° C and (iii) at a pressure of from about 1 to about 100 atmospheres. is carried out, wherein the molar ratio acrolein: myrcene is about 10: 1 to 2u about 1:10 and about 0.2 to to about 10 wt .- ^ of the Lewis acid catalyst, based on the total weight. Acrolein and myrceri, can be used. 70981 5/1197 Λ- Use of a product produced according to claim 1 or 2 in a perfume preparation, where appropriate at least an additive such as a natural perfume oil, a synthetic one Perfume oil, an alcohol, an aldehyde, a ketone, an ester or a lactone is added. 9,815/1 197