DE2700688A1 - CARBONYL COMPOUNDS, THE PROCESS FOR THEIR PRODUCTION AND THEIR USE AS PERFUMES TO INFLUENCE THE AROMA AND TASTE OF FOOD, TOBACCO, BEVERAGES AND FOR PERFUMES AND PERFUMED ARTICLES - Google Patents

Description

Patent attorneys

Dipl.-Chem. I. SCHULZE Dipl.-Ing. E. GUTSCHER

Gaisbergstrasse 3 69OO HEIDELBERG 1 phone 23269

27ÜÜ688

Abs. Dipl.-Chem. I. Schulze, Dipl.-Inq E. Gutscher, patent attorneys Giiisborgstrasse 3. 69CO Heidelberg 1

OUR SIGN:
YOUR SIGN:

3088

Applicant: International Flavors & Fragrances Inc., 5? 1 West 57th Street, New York, NY 10019, V.ST.A.

Carboxyl compounds, processes for their preparation and their use as Seasonings to influence the aroma and taste of food, tobacco, Beverages and for perfumes and perfumed articles.

The invention relates to methods of reacting with a first specific group of carbonyl compounds either (i) organic halogen compounds or (ii) aldehydes to form a second specific group of carbonyl compounds to form whose molecular weight is greater than that of the first group of carbonyl compounds. The implementation runs according to the general formula:

3 /

709829/1 O

Boron oxide

Boric acid

mixture

wherein each of the groups P ₁ = C and F ₂ = C is alkylidene, alkenyl, alkadlenyl, cycloalkyl, cycloalkenyl, or each of them completes a cyclic group; in which furthermore R _{11 is} hydrogen, an alkyl, alkenyl or methylene group; R ₁ ^ can be hydrogen, an alkyl, alkenyl, methylene or alkylidene group; where O (represents a reaction accelerator such as a quaternary ammonium salt or toluene and the dashed line is a covalent bond or no bond. When the dashed line is a covalent bond, each of the groups P ₁ = C and Fp ^ completes ^a cyclic group. When X _{11 is} chlorine or bromine, then R _{12 is} benzyl, prenyl, allyl or methallyl, on the other hand, when X _{11 is} an oxocarbonyl ^{, Rip ^ ii is an acyclic aldehyde.}

If R., with
R ₁₁ and R

_{12 is} identical, then is is hydrogen.

identical with

If R _{11 is} hydrogen then ask

and

F ₂ = C

acyclic alkylidene, acyclic alkenyl, acyclic alkadienyl, Cycloalkyl, cycloalkenyl, substituted cycloalkyl or substituted cycloalkenyl and the dashed line is not a bond.

If R _{11 is} the methyl group, then each of the groups F ₁ = C and F ₂ = C means cycloalkyl, the dashed line does not represent a bond, either (i) R ₁ ^ is the methyl group, R _{1, hydrogen and R 10 are} identical with R ₁ , or (ii) R ₁ ,

is hydrogen,

is hydrogen and R, u is one of the

, u

Groups of the following general formula

R,

or

Ο Ι

I?

12th

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If R ,. Methylene of the formula

-CH ₂ -is then complete each of the groups

31

and

R ₁₄ F ₂ = C

denotes a cyclopentenyl ring and the dashed line means a carbon-carbon double bond.

If R- ,, is not hydrogen but a different substituent, then R, -, can represent two groups bonded to the carbon atom, (i) R ^ ₁ and (ii) R ₁₂ ; On the other hand, R, u can be the same substituent as R ,, and R ₁₂ and R, -, is identical to R ^ ₁ *

If desired, the substances obtained in this process can be reduced by hydrogenation with a corresponding hydrogenation catalyst.

With the method described, new chemical compounds are created the general formula

if.

rc

manufactured

in which the group

C = F-

represents a cycloalkyl group or a cycloalkenyl group which has six carbon atoms and may be substituted or unsubstituted, wherein (i) R _{2 is} hydrogen and R _{22 represents} a carbon atom which is represented by an or

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-K-

two of the following groups is substituted:

CH ₂ ,

or

CM,

(where Rp ^, an alkyl group such as ethyl, alkenyl or alkylid) or (ii) Rp _{2 is} a methyl group or hydrogen and R _{21 is} allyl or methallyl of the formulas:

CH ₂ ,

or

mean or the group

C = F,

represents an acyclic hydrocarbyl group, in which case the compound is 2,4,7-trimethyl-2,6-octadienal.

Generally speaking, it is an object of the invention to provide alpha, beta-unsaturated aldehyde compounds with allyl halides or with benzyl halides in the presence of an inert alkali metal hydroxide solvent and in the presence of a "phase transfer agent" to implement. In general, you can

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4 $ 27UU688

Process according to the invention by the following reaction formula illustrate:

R ₁ X + R - C - C = CC * MOH ^ R - CC CC

^{1 2} HHR

wherein one of the dashed lines represents a double bond and the other dashed line represents a single bond. R ₁ is an allyl or benzyl group, Rp is an alkyl, aryl, alkenyl or alkoxyalkyl group and R-, and R ^, each represent hydrogen or an alkyl group, with the proviso that when R-, an alkyl group is, the dashed line between the ß carbon atom and the % carbon atom is a double bond and then, when R ^ is hydrogen, one of the dashed lines represents a double bond, where X is chlorine or bromine and K is an alkali metal.

More precisely, the process according to the invention relates to alkylation of alpha-, beta-unsaturated aldehydes with reactive Ally! Halides or Benzy! Halides under the Exposure to a base, bringing the reactants and the base into two immiscible phases, namely one organic phase and either (i) an aqueous basic phase or (ii) a solid basic phase, the reactants being essentially completely in the organic phase and the base is essentially completely contained in the second (i) or (ii) phase. This two-phase system becomes a "phase transfer agent" (phase converter) such as one or more organic quaternary ammonium salts is added.

Examples of such phase converters are: tricaprylmethylammonium chloride; Cetyltrimethylammonium bromide and Benzy 1 trimethyl ammonium hydroxide.

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The preferred phase converters have the following general principles formula

M4 '

—N-

42

^ 4 ^ 5 ^unc ^

wherein at least one of the groups Rj. ,, Riip

^C 6 "" ^C 14 " ^aryl * Cg-CjQ-aralkyl, Cg-C ^ -alkyl, or Cg-Cp ₀ alkenyl and the other of Rh ₂ *% 3 ^{and R} ii4 an alkyl group, such as methyl, ethyl, n- Propyl, i-propyl, 1-butyl, 2-butyl, 1-methyl-2-propyl, 1-pentyl and / or 1-octyl and z "denotes an anion such as chloride, bromide or hydroxide.

This step of the inventive method is in one cheap solvent carried out which is inert to the reaction system, for example toluene, benzene, o-xylene, m-xylene, p-xylene, ethylbenzene, η-hexane., cyclohexane, Methylene chloride or o-dichlorobenzene.

The reaction temperature is between about 10 ° C. up to about 150 ° C., preferably 50 ° to 120 ° C. The reaction time is inversely proportional to the reaction temperature, with lower temperatures requiring a longer reaction time. This ranges from about 30 minutes to about 10 hours.

The ratio (mol) of alpha-, beta-unsaturated reactants to the allyl or benzyl halide compounds is 0.5: 1.5 up to about 1.5: 0.5 »preferably alpha-, beta-unsaturated aldehydes to allyl or 3enzyl halides 1: 1 up to about 1: 1.2.

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The molar ratio of base to allyl or benzyl halides in the reaction mass can range from about 0.75: 1 to to about 1.5 J 1 », preferably 1: 1 to about 1.2: 1.

The amount of "phase transfer agent" in the reaction mass, based on the amount of alpha-, beta-unsaturated aldehydes can be from 0.5 g / mole of aldehyde up to 25 g of "phase transfer agent" per mole of aldehyde, preferably about 2.5 to about 7.5 g per mole of alpha-, beta-unsaturated aldehyde.

The reaction is preferably carried out at atmospheric pressure, as this is the most convenient condition. However, lower or higher pressures can also be used without the Yield of the desired reaction product would be adversely affected.

The invention is explained in more detail with the aid of a few examples. It is particularly noted that the reaction products can be used as such because of their organoleptic properties. But you can also use conventional separation processes, for example fractional distillation, can be isolated.

2 _J 5-dimethyl-2-propenyl-hex-4-enal

CHO

CH-Cl

^{2 CH0} CHO

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2-methyl-2-benzyl-pent-3-enal

<δ>

Π "B C-c C

HI
CHO

+ small amounts of isomer analogs to (I)

2-butenyl-2-ethyl-5-methyl-hex-4-enal

'CHO 2

CBO

+ small amounts of isomer analogs to (I)

2-Benz: - l-2-ethyl-hex-5-enal

CHO

ClIO

CH ₂ Cl

+ small amounts of isomer analogs to (I)

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2-prenylcitral

CHO

CH ₂ Cl

+ small amounts of isomer analogs to (I)

2-prenylnonenal

H ₂ Cl

CHO

+ small amounts of isomer analogs to (I)

The base used for the reaction is not critical, it is preferred but are sodium hydroxide and potassium hydroxide.

Those produced by these process steps according to the invention Compounds are useful ingredients for making perfume compositions. For example, 2,5-dimethyl-2-propenyl-hex-4-enal a bitter, green, ζitrus-like, Carvone-like, sweet, carvone-like note and a lavender-like nuance. 2-Benzyl-2-ethyl-hex - ^ - enal a sweet, flowery one

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and rose-like note. 2-butenyl-2-ethyl-5-methyl-hex-4-enal has a green, sweet, tomato-like aroma with a lemon character and a rose-like, floral note. 2-Methyl-2-benzyl-pent - ^ - enal has a sweet, fruity, citrus-like, floral, green aroma. Has 2-prenylcitral a sweet, green, orange-like aroma with woody, citrus and resinous notes. In tobacco, in the main stream at Smoking, 2-prenylcitral has a spicy, coriander-like aroma and a woody effect in the side stream. As a food seasoning 2-prenylcitral has a sweet, coriander-like, spicy and citral character.

2,4,7-Trimethyl-2,6-octadienal is a new compound. In terms of flavoring properties, it has a lemon-like, citral-like, mandarin aroma with a tangerine nuance and a lemon-mandarin flavor with a tangerine nuance at an amount of 0.2 T / ml11. Your threshold is 0.05 T / Mill. This compound is suitable for changing, strengthening or modifying the wort or the aroma of citrus fruits, especially lemon, or of foods flavored with citrus fruits or lemon.

There is another aspect of the method according to the invention in the reaction of J-methylcyclopentenone-2 with cis-pent-2-enyl-1-halide in the presence of one or more inert solvents, aqueous alkali metal hydroxides and in the presence of one or more "phase transfer agents". The reaction is carried out in a two phase system. It is through the following Reaction form illustrates:

WHERE.

wherein X is chlorine or bromine and M is an alkali metal.

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In other words, this process stage according to the invention relates to the alkylation of 3-methylcyclopentenone-2 under Action of a base, whereby the reactants and the base are brought into two immiscible phases, namely one organic phase and either (i) an aqueous basic phase or (ii) a solid basic phase, the reactants essentially completely in the organic phase and the base essentially completely in the second (i) or (ii) phase are included. A phase converter, such as one or more organic quaternaries, is used to this two-phase system Ammonium salts, added.

Examples of such phase converters are tricaprylmethylammonium chloride;
Cetyltrimethylammonium bromide; and benzyl trimethyl ammonium hydroxide.

The preferred phase converters have the general formula

⁸ I.

NO

^R 3.

wherein at least one of the groups R ₁ , Rp, R-. and Rl is a Cg-C, aryl, C ₆ -C ₁₀ aralkyl, Cg-C ^ -alkyl, Cg-C ^ -aralkyl or Cg-C ₂₀ -alkenyl and the other R ₂ * R- * and R ^ - An alkyl group, such as methyl, ethyl, n-propyl, i-propyl, 1-butyl, 2-butyl, 1-methyl-2-propyl,. 1-pentyl or 1-octyl and Z ~ is an anion such as chloride, bromide or hydroxide.

This process step is done in a cheap solvent carried out which is inert to the reaction system

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and for example toluene, benzene, o-xylene, m-xylene, p-xylene, Ethylbenzene, η-hexane, cyclohexane, methylene chloride or o-Dlchlorbenzol can be.

The reaction temperature is between about 10 ° C. up to about 150 ° C., preferably 30 to 120 ° C. The reaction time is inversely proportional to the reaction temperature, with lower temperatures requiring a longer reaction time. This ranges from about 30 minutes to about 10 hours.

The molar ratio of 3-methylcyclopentenone-2 to cis-pent-2-enyl-1-halide is 0.5: 1.5 up to about 1.5: 0.5, preferably from about 1: 1 to about 1: 1.2.

The molar ratio of base to cis-pent-2-enyl-1-halide can vary in the range from about 0.75: 1 to about 1.5: 1, preferably from about 1: 1 to about 1.2: 1.

The amount of phase converter in the reaction mixture, based on to the amount of 3-methylcyclopentenone-2 can be from about 0.5 grams per mole of 3-methylcyclopentenone-2 up to about 25 grams per mole vary, with about 2.5 g to about 7.5 g phase converter per mole of 3-methylcyclopentenone-2 being preferred.

The reaction is preferably carried out at atmospheric pressure since this is the most convenient condition. But it can lower or higher pressures can also be used without adversely affecting the yield of the desired reaction product would.

The invention also relates to the preparation of the compounds 1-acetyl-1 (methallyl or allyl) -3,3-dimethylcyclohexane and 1- (2-methallyl or allyl) -5-methyl-4-pentenoyl) -3,3-dimethylcyclohexane the general formula:

¹ R, Ra,
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wherein one R, or or both Rp and / or R ^, allyl or methallyl and the other R ₁ or R ₂ and / or R, are hydrogen. These compounds, which contain l-acetylO ^ -dirnethylcyclohexane derivatives of the formula mentioned, are suitable as seasonings for perfumes, perfumed articles, foods, medicinal products, tobacco varieties and tobacco seasonings. They enhance or intensify orange spiciness by giving the aroma of pineapple, allyl caproate, galbanum, wood, fat, sweetness, fruits, citrus fruits with green notes and have rose-like, iononic, oriental, wood-like, sweet, fruity, zltrus-spicy characteristics, especially when used with groceries, chewing gum and medicinal products.

The compounds of the general formula:

are also able to determine the aroma characteristics of perfume compositions and perfumed articles to modify and enhance and give them a sweet, earthy, animal, green, herbaceous, melon-like and fruity aroma with pineapple-like, amber-like, galbanum-like, ginger-like and to give citrus-like nuances as well as tobacco / animal notes.

The compounds of the general formula:

wherein one of the R ₁ group or one or both of the Rp and / or Rz group is methallyl or allyl and the other R ₁ - or Rp group is hydrogen, are obtained by reacting acetyl- ^ i ^ -dimethylcyclohexane with a methaiIy ! halide

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or an allyl halide in the presence of a base such as alkali metal hydroxide or potassium t-butoxide, and in the presence of a third compound which is either a tertiary amine, toluene, t-butanol or a crown ether (or various mixtures of these compounds) can be, as follows referred to as "reaction accelerator", prepared according to the formula:

ff,

where R is allyl or methallyl and X is chlorine or bromine. The properties of the reaction product depend mainly on the reaction accelerator used, namely what the Isomer ratios of the reaction products concerns. Hence, if the crown ethers have the general formula:

ff ^z - ° \ r for LJ

L.z-oU

wherein ZC, -C ₁ , lower alkylene, for example methylene or ethylene, N from J5 up to 8, P and Q denote _{the same or different groups-C 1 -Cj 1} , lower alkylene or o-phenylene group, such as compounds the general formula

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(Dibenzo-18-crown-6) and used as a promoter, the reaction product consists essentially of those products in which the methallyl or allyl substituent is in the "1" position on the ring, namely

Crown ether

wherein R ^ is methyl or hydrogen and M is an alkali metal. However, if a phase changer is used as a reaction promoter is used, several by-products are formed:

Phase converter

MOH

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wherein Ru is methyl or hydrogen and X is chlorine or bromine.

If a tertiary amine, or toluene, or t-butanol are used as the reaction promoter, the reaction proceeds as follows:

where R _{1 is} methyl or hydrogen and X is chlorine or bromine. Examples of tertiary amines which can be used according to the invention are trimethylamines, triethylamines, dimetbylaminoäthyId ime thylamine.

These process steps are carried out in an inexpensive solvent which is (a) opposite to the reaction system is inert and (b) also serves as a reaction promoter. Such solvents include toluene, benzene, o-xylene, m-xylene, p-xylene, ethylbenzene, η-hexane, cyclohexane, methylene chloride dichlorobenzene, t-butanol and crown ether, such as benzo-18-crown-6.

It is carried out at a temperature in the range of about 10 ° C up to about I50 ⁰ C, preferably 50 ° to 120 ° C. The reaction time is inversely proportional to the reaction temperature, with lower reaction temperatures requiring longer reaction times. A reaction time of about 30 minutes to about 10 hours can therefore be expected.

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Regardless of which reaction promoter is used, the molar ratio of l-acetyl-jJ ^ -dimethylcyclohexane to Allyl halide or methallyl halide 0.5: 1.5 up to 1 * 5: 0.5 »preferably 1: 1 up to about 1: 1.2.

The molar ratio of base to give allyl halide or methallyl halide to base may be in the range of about 0.75 to 1 to about 1.5: 1 * preferably 1: 1 to about 1.2: vary. 1

The method is preferably carried out at atmospheric pressure, as this is the most convenient working condition. But lower or higher pressures can also be used, without adversely affecting the yield of the desired product.

The base used is critical and sodium hydroxide, potassium hydroxide or potassium t-butoxide are preferred.

According to the invention it has been found that with 1-acetyl-J5 ^ -dime thy lcyclohexane derivatives of the formula

wherein one of the dashed lines is a carbon-carbon single bond or a carbon-carbon double bond and the other dashed line a carbon-carbon -Single bond and R denotes hydrogen or methyl, a new flavoring for solid and liquid foods, Chewing gum, medicinal products, toothpastes and seasoning compositions have been created for this purpose, the sweet, fruity, raspberry-like, woody, lemon-like, spruce-like, iononic-like, blueberry-like and floral aroma characteristics as well as sweet, raspberry-like, lemon-like, sweet-fruity, berry-like, spruce-like, flowery, ionon-like and has nutmeat-like seasoning characteristics. Perfume compositions, colognes and perfumed articles

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lend the compounds fruity, woody, spruce-like aromas with floral nuances and a light chocolate undertone sound.

The l-acetyl-j ^ J-dimethylcyclohexane derivatives can preferably by reacting l-acetyl- ^ j ^ -dimethylcyclohexane with an aledhyd of the formula:

r ^t:

be prepared, where a compound of the formula:

in which one of the broken lines is a carbon-carbon double bond and the other broken line is a carbon-carbon single bond. It is carried out in the presence of an inorganic base or a mixture of boron oxide (B ₂ O-,) and boric acid. The product obtained is either used because of its organoleptic properties or it is reduced with hydrogen and a compound of the formula:

formed, in which R is hydrogen or methyl. The first reaction with aldehyde of the formula

¹ H.

is at a temperature of about 20 ° C up to about 160 ° C carried out when the catalyst is an inorganic base,

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such as an alkali metal hydroxide, for example potassium hydroxide, sodium hydroxide and lithium hydroxide, or an alkaline earth metal hydroxide, such as barium hydroxide or lithium hydroxide is used. If the catalyst is a mixture of boric acid (HBO,) and boron oxide, the reaction temperature is about 100 ° C up to about 200 ° C.

The reaction time is inversely proportional to the reaction temperature. When a mixture of boric acid and boron oxide is used the reaction time varies between 2 and 10 hours. At higher temperatures, the reaction time is around 1 to 8 hours.

When using an inorganic base, the molar ratio of inorganic base to 1-acetyl-j}, 3-dimethylcyclohexane from 0.1: 1 to 2: 1, preferably 1: 1. When using a mixture of boric acid and boron oxide varies the molar ratio of boron oxide to 1-acetyl-3,3-dimethylcyclohexane from 0.5: 1 to 1.5: 1 »preferably 1: 1. The concentration of boric acid in the reaction mass can from Ig up to 80g per mole of aldehyde of the formula

vary. ^

In all cases the molar ratio of aldehyde can be of the formula

j ^{H: 1} - ^A cetyl-3,3-dinethyl-I cyclohexane

vary from 1: 1 up to about 5: 1, with a molar ratio of 2: 1 is preferred.

Both reactions are preferably carried out in the presence of an inert solvent,

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The reduction to the formation of the connection:

is preferably inert in the presence of solvents such as isopropyl alcohol, psig Hydrierdrucken of between 50 and 150, at temperatures between 25 ° and I5O ⁰ C and using a hydrogenation catalyst such as 5 $ palladium-on-carbon, rhodium, platinum and Raney nickel . The reaction time varies inversely with the reaction temperature and pressure. Lower pressures and temperatures require a longer reaction time, which can vary from 1 hour to 5 hours.

The reaction sequence can be represented as follows:

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Examples and organoleptic properties of compounds, which have been prepared by the above process are given in Table I:

Surname

Table I.

Structural forms1 Organoleptic properties:

Spice

Scent

Mixture of l- (j5,3-dimethylcyclohexyl) -4-methyl-cis-2-penten-1-one, 1- (3,3-dimethylcyclohexyl) -4-methyltrans-2-penten-l-one, and 1- (3,> dlmethylcyclohexyl) -4-methyl-3-penten-l-one

sweet, woody, raspberry-like, Lemon and spruce-like aroma with a sweet, raspberry-like flavor and lemon-like spicy character at 1.0 ppm

fruity woody, spruce-like aroma with St. John's wort-like, floral nuances and light chocolate -Undertone

Mixture of l- (2,3-dimethylcyclohexyl) - ^c is-2-penten-l-one /! - (3,3-dimethylcyclohexyl) -trans-2-penten-l-one) and 1- (3,3 -dimethylcyclohexyl) -3-penten-1-one

sweet, raspberry-like, fruity, spruce-like, floral, iononic-like aroma with sweet, sweet-fruity, raspberry-like, redberry-like, spruce-like, flowery and ionon-like Seasoning characteristics

sweet, fruity woody (spruce) with pineapple galbanum, hexalone grades

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Surname

Structural formula

Organoleptic properties:

Spice

Scent

3,3-dimethyl-1- (4-methylvaleryl)
cyclohexane

sweet, spruce, blueberry-like, woody aroma character with sweetness, spruce-like, fruity, nut-like characteristics.

low-pitched, sweet, woody, somewhat chocolate-like.

It was also found that the compound 1-butanoyl-3,3-dimethylcyclohexane the formula:

with good success for new perfume compositions, colognes and perfumed items can be used to make this one to give fruity, berry and herbaceous aromas with green and tobacco nuances.

This compound is preferably prepared by reacting 1 ~ acetyl-j5-3-dimethylcyclohexane with acetaldehyde in the presence of an inorganic base or a mixture of boron oxide (B ₂ OO and boric acid, a compound of the formula

709829/1% 72

(Mixture of "cis" and "trans" isomers) and a compound the formula:

can be obtained. The product obtained is reduced with hydrogen and a compound of the formula

educated.

The first reaction with acetaldehyde is carried out at a temperature of about 20 ° C to 160 ° C when used as a catalyst an inorganic base such as an alkali metal hydroxide such as potassium hydroxide, sodium hydroxide and lithium hydroxide, or an alkaline earth metal hydroxide such as barium hydroxide or lithium hydroxide is used. When the catalyst a mixture of boric acid (HBO ^) and boron oxide is at a temperature in the range of about 100 ° C up to 200 ° C worked.

The reaction time is inversely proportional to the reaction temperature. When a mixture of boric acid and boron oxide is used the response time is between 2 and 20 hours. At higher temperatures it varies between 1 and 8 hours.

When using an inorganic base, the molar ratio of inorganic base to 1-acetyl-3,3-dimethylcyclohexane varies from 0.1: 1 to 2 : 1, a molar ratio of 1: being preferred. With a mixture of boric acid and boron oxide

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is the molar ratio of boron oxide to 1-acetyl-J ^ -dlmethylcyclohexane 0.5: 1 up to 1.5: 1, preferably 1: 1. The concentration of boric acid in the reaction mixture varies from Ig to 80 g per mole of acetaldehyde.

In all cases, the molar ratio of acetaldehyde to 1-acetyl 1-3,3-dimethylcyclohexane can vary from 1: 1 bJs to about 3 '· 1, with a molar ratio of 2: 1 being preferred.

The reactions can be carried out with or without an inert solvent. When using boric acid or boron oxide is preferably carried out without a solvent. In the case of an inorganic basic catalyst, a Solvent used, for example methanol, ethanol or isopropanol.

The reduction to the connection:

is expediently carried out in the presence of inert solvents, such as isopropyl alcohol. The Hydrierdrucke range between 50 and 15 psig and temperatures between?. [° and 150 ° C. The hydrogenation catalysts are $ 5 Fa] L-Kiium on carbon, rhodium, platinum and Raney nickel.

The sequence of actions can be represented as follows:

+ CH, -

Reduction

middle

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wherein one of the dashed lines is a carbon-carbon double bond and the other dashed line represents a carbon-carbon single bond.

The invention also includes the compounds 1- (2-propenyl) -3- (4-methyl-3-pentenyl) -Δ -eyelohexen-1-carboxaldehyde and 1 - (2-propenyl) -4- (4-methyl-3-pentenyl) -A -eyelohexene-1-arboxaldehydes the general formula:

wherein the carboxaldehyde group either on the o (-carbon- or is bonded to the β-carbon atom of the cyclohexenyl group; Process for their preparation and their use as organoleptic Fabrics.

The connections with the formulas:

the mixtures made by the formula:

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are suitable for strengthening or enhancing cocoa buttery types Seasonings, apricot, peach, milk and coconut seasonings to make these sweet, fatty, cocoa butter-like, green / grassy, milk-like, diacetyl-like, apricot-like and carrot-like aroma characteristics fatty, cocoa-buttery, green / grassy, milk-like, diacetyl-like, peach and coconut flavoring characteristics to rent.

The compounds 1- (2-propenyl) -3- (4-methyl-2-pentenyl) -cyclohexene-1-carboxaldehyde and 1- (2-propenyl) -4- (4-methyl-3-pentenyl) -A -eyelohexen-1-carboxaldehyde are also suitable for modifying or improving the fragrance characteristics of perfume compositions and perfumed articles to which they are attached give sweet, fruity, lavender-like notes with citrus-like, floral and balsamic nuances.

Tobacco and tobacco seasonings give the compounds 1- (2-propenyl) -3 - (^ - methyl-2-pentenyl) -A -eye lohexene-1-carboxaldehyde and 1- (2-propenyl) -4- (4-methyl-3-pentenyl) - Δ eyelohexene-1-carboxaldehyde Cocoa-like, strongly sweet and creamy oily notes.

The compounds l- (2-propenyl) -3 - (^ - methyl-5-pentenyl) - _ii / \ eyelohexen-1-carboxaldehyde and l- (2-propenyl) -4- (4-methyl-3-pentenyl) - ^ -cyclohexen-l-carboxaldehyde are made by reacting myracaldehyde of the formula:

with an allyl halide in the presence of an inert solvent and an alkali metal hydroxide and a phase converter manufactured. The reaction is carried out in a two-phase system as illustrated, for example, by the following reaction formula

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OGK

₀ -i_ - ι _ÜWH __ ^

wherein the carboxaldehyde group on the «^ carbon or am ß-carbon atom is bonded; X is chlorine or bromine and M is an alkali metal.

The reactants and the base are brought into two immiscible phases, namely an organic phase and either (i) an aqueous basic phase or (ii) a solid basic phase, with the reactants being essentially completely in the organic phase and the base being essentially completely are included in the second phase. To this two-phase system, a phase converter, for example, one or more organic quaternary Ammoniumsalzverbin extension (s) such as t

Tricapryl methylammonium chloride;

Ce ty1trime thylammonium chloride j

Cetyltrimethylammonium bromide; and

Benzyltrimethylammonium hydroxide

Tertiary amines , such as

Trimethylamine;

Triethylamine; and

Dimethyl (dimethylaminoethyl) amine.

Crown ether , like

l8-crown-6 of the formula:

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Dibenzo-18-crown-6 of the formula:

Γ \ Γ \

The most preferred phase converters or phase transfer agents have the general formula:

-N-

M 3

M 2

wherein at least one R ^ _{1 1,} R ₁ ^ _2, R ^ ₂ and R ₂ ^ Cg-C ^ Cg-CjQ aralkyl, Cg-C ₂₀ -A lkyl, Cg-C ^ Cg alkaryl and _C-2 Q -Alkenyl and the other R ₂ ^ ₂ , R ₂ ^ and R ^^ alkyl, such as methyl, ethyl, n-propyl, i-propyl, 1-butyl, 2-butyl, 1-methyl-2-propyl, 1- Pentyl or 1-octyl, and Z ~ is an anion such as chloride, bromide or hydroxide.

The process is carried out in an inexpensive solvent which is inert to the reaction system, for example Toluene, benzene, o-xylene, m-xylene, p-xylene, ethylbenzene, n-hexane, Cyclohexane, methylene chloride or o-dichlorobenzene.

The reaction temperature is in the range of about 10 ° up to about 150 ° C, preferably 50 ° to 120 ° C. The reaction time

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is inversely proportional to the reaction temperature, with lower Temperatures require longer reaction times, generally between 20 minutes and about 10 hours.

The molar ratio of myracaldehyde to allyl halide is from about 0.5: 1 * 5 up to 1.5: 0.5 * preferably 1: 1 up to 1: 1.2.

The molar ratio of base to allyl halide is about 0.75: 1 up to about 1.5: 1, preferably 1: 1 up to 1.2: 1.

The amount of phase converter in the reaction mixture, based on the amount of myracaldehyde, can vary from 0.5 g up to about 25 g per mole of myracaldehyde, the preferred range being about 2.5 g up to about 7.5 g.

The reaction is preferably carried out at atmospheric pressure since this is the most convenient condition. But it can also lower or higher pressures can be used without adversely affecting the yield of the desired reaction product would.

The base used is critical. Sodium hydroxide is preferred and potassium hydroxide.

The terms "change" and "modify" as used herein are to be understood to mean that given a relatively tasteless product or substance a spicy character or a spicy note or one already existing seasoning is strengthened or the seasoning or the aroma impression is supplemented in order to increase the organoleptic character modify. The with the inventive seasonings to Modifying substances or substances are generally referred to as consumables.

As used herein, the term "increase" is intended to be so be understood that an already existing wort

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and or Aroma "nuance" or "Note" is / intensified in a seasoning composition for food or the food, without changing the nature or quality of nuance or note to be changed.

The term "food" or "food", as used herein includes both solid and liquid ingestible materials for man or animals, which usually have nutritional value, but not one like this must have. Such foods or foods include fruit juices, meats, roasts, soups and convenience foods, vegetables, snacks and the like, dog and cat foods, other veterinary products and the like.

If the 2,4,7-trimethyl-2,6-octadienal prepared according to the invention is used in a seasoning composition for food or food , it can be combined with conventional seasonings or auxiliaries. Such additional or seasoning auxiliaries are known and described in detail in the literature . Such additives must of course be fit for consumption and consequently not toxic or otherwise harmful. However, there are numerous substances that meet these requirements and they generally include other seasonings, carriers, stabilizers, thickeners, surface-active substances, conditioning agents and seasoning intensifiers.

Examples of preferred seasoning additives are: natural orange oil; Acetaldehyde; Ethyl acetate; Ethyl butyrate; Propanal; Trans-2-hexenal;

Trans-2-ethylidene-cis-3-hexenal; 2-ethylidene-6-methyl-cis-3-heptenal; and cis-2-ethylidene-cis-; 5-hexenal.

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The 2,4,7-trimethyl-2,6-octadienal or compositions containing this compound can be mixed with one or more Carriers are combined in order to be suitable as an additive for the particular product to be seasoned. Such carriers can be edible or other harmless substances, such as ethyl alcohol, propylene glycol, water and like that. Other carriers are gum arabic, carrageenan, other gums, and the like. The 2,4,7-trimethyl-2,6-octadienal can be incorporated into the carrier by conventional methods such as spray drying, drum drying and the same. The carrier substances also include those that can be used as capsule material to protect the To wrap seasoning. When the carrier is an emulsion, the seasoning composition can also contain emulsifiers such as mono- and diglycerides of fatty acids and the like. With such carrier substances, the desired physical form of the Composition are made.

The amount of 2,4,7-trimethyl-2,6-octadienal used must be be sufficient to produce the desired flavoring characteristics. On the other hand, the amount should not be too large used as this is not only wasteful and uneconomical, but in some cases it can be too large Adding the seasoning and / or other organoleptic properties of the product to be seasoned affect and the balance disturb. The amount added varies depending on the end product, which is already at the beginning in the food or foodstuff available amount and type of seasoning, the further process and further treatment, which the food or Food is subject to regional or other significant factors, eventual storage and the prevailing conditions Conditions of treatment before consumption, such as baking, roasting, etc.

It has been found that good results are obtained when the final product is about 0.08 T / mill. up to about 250 T / Mill.

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Contains 2,4,7-trimethyl-2,6-octadienal. More precisely, for food or foodstuffs, about 0.15 t / Mi11. up to 50 T / Mill. achieved good results and the flavoring characteristics increased or modified. In some cases, an Amount from about 0.2 up to 10 T / Mill. to 2,4,7-trimethyl-2,6-octadienal positive citrus-like flavoring properties in the end product. All parts, proportions and percentages are in Expressed weight, unless expressly stated otherwise

The amount of 2,4,7-trimethyl-2,6-octadienal used can vary over a wide range. So about 1 up to 80 or 90 $ of the total amount of seasoning is added, Generally speaking, amounts range from about $ 2 to about $ 20 the connection proved to be particularly favorable.

With regard to the perfume properties, this compound has an excellent lemon-citrus character which is suitable is to impart lemon nuances to citrus-like perfume compositions and essential oils.

Compounds of the general formula:

wherein one R. or both R ₂ and / or R, methallyl or allyl and the other R, or R ₂ and / or R, is hydrogen (herein as "the l-acetyl-j ^ J-dimethylcyclohexane derivatives of the invention" are used as seasoning additives for food. The nature of the additives added to these derivatives also serve to “change, modify, enhance or increase the organoleptic properties of the food treated with them.

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The "medicinal products" mentioned herein include both solid and liquid substances that can be ingested and are non-toxic such as cough syrup, cough drops, aspirin, and chewable medicinal tablets.

"Chewing gum" is understood to mean a substance which is an essentially water-insoluble, chewable plastic gum compound, such as chiale, or its substitutes, such as jelutong, guttakay, gum or certain edible natural ones or synthetic resins or waxes. The gum base may contain plasticizers or tenderizers, for example glycerin; a seasoning mixture, the l-acetyl- ^ i ^ -dimethylcyclohexane derivatives according to the invention contains; and also sweeteners, such as sugar, including sugar, or dextrose and / or artificial sweeteners such as cyclamates or saccharin are added. If desired, other additives can also be added will.

Substances that are used as additives or seasoning auxiliaries are known and adequately described in the relevant literature. You have to be tolerable and accordingly be non-toxic and must not otherwise be harmful, and in particular the organoleptic properties of the do not adversely affect the final flavor and / or the flavor of the seasoned product. These substances include whole generally stabilizers, thickeners, surfactants, conditioning agents, other condiments and seasoning intensifiers.

Stabilizers include preservatives such as sodium chloride; Antioxidants, such as calcium and sodium ascorbate, Ascorbic acid, butylated hydroxy anisole (mixture of 2- and 2-tert-butyl-4-hydroxy anisole), butylated hydroxytoluene (2,6-di-tert-butyl-4-methylphenol), propyl gallate, and the like; and sequestering agents such as citric acid.

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Thickening agents include carriers, binders, protective colloids, suspending agents, emulsifiers and the like, for example agar-agar, carrageenan; Cellulose and cellulose derivatives, such as carboxymethyl cellulose and methyl cellulose "natural and synthetic gums, such as gum arabic, Gum tragacanth; Gelatin, proteinaceous substances; Lipids; Carbohydrates; Starches, pectins and emulsifiers, for example Mono- and diglycerides of fatty acids, skimmed milk powder, hexoses, pentoses, disaccharides, for example sugar cane syrup and the same.

Surface-active substances include emulsifiers, for example fatty acids such as capric acid, caprylic acid, palminic acid, Myristic acid and the like, mono- and diglycerides of fatty acids, lecithin, antifoams and dispersants for the condiment such as sorbitan aronostearate, potassium stearate, hydrogenated tallow alcohol and the like.

Conditioning agents include compounds such as bleaches and Aging agents, for example benzoyl peroxide, calcium peroxide, Hydrogen peroxide and the like; Starch modifiers, such as peracetic acid, sodium chlorite, sodium hypochlorite, Propylene oxide, succinic anhydride and the like; Buffers and neutralizing agents, e.g. sodium acetate, ammonium bicarbonate, Ammonium phosphate, citric acid, lactic acid, vinegar and the like; Dyes, for example carminic acid, Cochineal, gymnast and turmeric and the like; Firming agents such as aluminum sodium sulfate, calcium chloride and calcium gluconate; Structuring agents, anti-sticking agents, for example aluminum calcium sulfate and trivalent calcium phosphate; Enzymes; Yeast substances such as calcium lactate and calcium sulfate; Nutritional additives, such as iron salts, such as Ferric phosphate, ferrogluconate and the like, riboflavin, vitamins, zinc sources such as zinc chloride, zinc sulfate and the like.

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Other seasonings and seasoning intensifiers are organic acids, for example acetic acid, formic acid, 2-hexenoic acid, benzoic acid, n-butyric acid, caproic acid, caprylic acid, cinnamic acid, isobutyric acid, isovaleric acid, alpha-methyl butyric acid, Propionic acid, valeric acid, 2-methyl-2-pentenoic acid, and 2-methyl -> - pentenoic acid, ketones and aldehydes and ketals and Acetals thereof, for example acetaldehyde, acetophenone, acetone, acetylmethylcarbinol, acrolein, n-butanal, crotonal, diacetyl, 2-methylbutanal, beta, beta-dimethylacrolein, methyl-n-amyl ketone, n-hexenal, 2-hexenal, isopentanal, hydrocinnamaldehyde, cls-3-hexenal, 2-heptanal, nonylaldehyde, 4- (p-hydroxyphenyl) -2-butanone, alph-innon, beta-ionon, methyl-3-butanone, benzaldehyde, Damascenone, damascone, acetophenone, 2-heptanone, o-hydroxyacefcophenone, 2-methyl-2-hepten-6-one, 2-octanone, 2-undecanone, 3-phenyl-4-pentenal, 2-phenyl-2-hexenal, 2-phenyl -> - pentenal, furfural, 5-methylfurfural, cinnamaldehyde, cis-ethylidene-cis-3-hexenal, cis-ethylidene-trans-3-hexenal, cis-ethylidene-trans-2-heptenal, cis-ethylidene-trans-3-heptenal-diethylacetal, cis -3-ethylidene-4-octenal, beta-cyclohomocitral, 2-pentanone, 2-pentenal and propanal; Alcohols, such as 1-butanol, benzyl alcohol, 1-borneol, trans-2-buten-1-ol, Ethanol, geraniol, 1-hexanal, 2-heptanol, trans-2-hexenol-l, cis-3-hexen-l-ol, 3-methyl - ^ - buten-l-ol, 1-pentanol, l-penten-3-ol, p-hydroxyphenyl-2-ethanol, isoamyl alcohol, Isofenchyl alcohol, phenyl-2-ethanol, alpha-terpineol, cis-terpineol, Hydfcat, eugenol, linalool, 2-heptanol, acetoin; Esters, such as butyl acetate, ethyl acetate, ethyl acetoacetate, ethyl benzoate, Ethyl butyrate, ethyl caprate, ethyl caproate, ethyl caprylate, Ethyl cinnamate, ethyl crotonate, ethyl formate, ethyl sobutyrate, Ethyl isovalerate, ethyl laurate, ethyl myristate, ethyl alpha-methylbutyrate, Ethyl propionate, ethyl salicylate, trans-2-hexenyl acetate, Hexyl acetate, 2-hexenyl butyrate, hexyl butyrate, Isoamyl acetate, isopropyl butyrate, methyl acetate, methyl butyrate, Methyl caproate, methyl isobutyrate, alpha-methylphenyl glycidate, Ethyl succinate, isobutyl cinnamate, cinnamyl formate, methyl cinnamate and terpenyl acetate; Hydrocarbons, such as

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Dimethylnaphthalene, dodecane, methyldiphenyl, methylnaphthalene, myrcene, naphthalene, octadecane, tetradecane, tetramethylnaphthalene , tridecane, trimethylnaphthalene, undecane, caryophyllene, 1-phellandrene, p-cymene, 1-alpha-pinene; Pyrazines, such as 2, j5-dimethylpyrazine, 2,6-dimethylpyrazine, 2-ethyl - ^, 5 »6- trimethylpyrazine, jJ-ethyl ^^ - dimethylpyrazine, 3-isoamyl-2,5-dimethylpyrazine, S-isoamyl ^^ dimethylpyrazine, 2-isoamyl-3,5 »6-trimethylpyrazine, isopropyldimethylpyrazine, methylethylpyrazine, tetramethylpyrazine, trimethylpyrazine; essential oils such as jasmine absolute, cassia oil, cinnamon bark oil, rose absolute, iris absolute, lemon oil, Bulgarian rose oil, yara yara and vanilla; Lactones, such as c -nonalactone; Sulphides, for example methyl sulphide and other substances such as maltol, acetoin and other acetals (e.g. 1,1-diethoxyethane, 1,1-dimethoxyethane and dimethoxymethane).

The seasoning auxiliaries can be used in either the solid or liquid state, depending on the desired physical form of the end product. In any case, they must (i) be organoleptically compatible with the l-acetyl - ^ - ^ - dimethylcyclohexane derivatives and not mask or destroy their organoleptic properties (aroma and / or taste); (ii) be inert towards the l-acetyl- ^ O-dimethylcyclohexane derivatives and do not react with them; and (iii) be able to create a condition in which the compounds can be dispersed, admixed or otherwise incorporated in such a way that a homogeneous medium is produced. Furthermore, the choice of one or more of the auxiliaries and the amount used depends on the precise organoleptic character of the end product. So these criteria vary depending on the food, the chewing gum, the medicinal preparation or the toothpaste for which the seasoning and / or flavoring is to be used in order to impart, modify, change or increase the flavoring and / or the flavor. In the manufacture of solid products, solid compositions are normally chosen, such as various cellulose derivatives.

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The amount used as a seasoning of the inventive l-Acetyl- ^ i ^ -dimethylcyclohexane derivatives can be used in a wide range vary and depends on the desired organoleptic effects. So in the cases larger quantities may be required in which the food to be seasoned is relatively tasteless, while relatively low Quantities are sufficient to reinforce existing, albeit not strong, natural spicy and aromatic notes. What is essential is that the amount added must be sufficient to change the organoleptic characteristics of the composition modify or increase.

Too large quantities should be avoided, as these are not only uneconomical, but in extreme cases that too Disturbing the spice-aroma balance and thus the opposite of what is desired is achieved.

It has been found that the effectively effective amounts of l-acetyl - ^^ - dimethylcyclohexane derivatives in the range of 0.5 T / toill. up to about 100 T / Mill., based on the total product to be seasoned vary. Concentrations in excess of the stated maximum amount are not recommended since they do not improve the organoleptic properties.

Seasoning compositions for food produced according to the invention contain the l-acetyl - ^^ - dimethylcyclohexane derivative in concentrations of from about 0.1 to about 15% by weight based on the total weight of the seasoning composition.

The composition can be prepared by any conventional working method, such as with Dough mixers or devices, such as for making fruit drinks. The components can be in a corresponding Mixer to the desired consistency, homogeneity of the dispersion, etc. are mixed together. On the other hand you can Seasoning compositions in the form of crushed solids by mixing 1-acetyl-jJi ^ -dimethylcyclohexane derivatives

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with, for example, gum arabic, gum tragacanth, carrageenan and the like, and then spray drying. Ready-made seasoning mixes in powder form, e.g. a fruit seasoning mix, are made by mixing the dried solid components such as starch, sugar and the like and the l-acetyl-3i3-dimethylcyclohexane derivatives in one Dry mixer manufactured. The mixing process is carried out until the appropriate degree of evenness is reached.

The novel l-acetyl-3 '3-dimethylcyclohexane derivatives are preferably used with the following additives I p-Hydroxybenzylaceton, geraniol, cassia oil, acetaldehyde, maltol, Äthylmethylphenylglycidat, benzyl acetate, dimethyl sulfide, eugenol, vanillin, caryophyllene, methyl cinnamate, guiacol, Äthylpelargonat. Cinnamaldehyde, methyl anthranilate, 5-methylfurfural, isoamyl acetate, cis-ethylidene-cix-3-nexenal, cis-ethylidene-trans-3-hexenal, cis-ethylidene-trans-3-heptenal, cis-ethylidene-trans - ^ - heptenal- diethyl acetal, cis-3-ethylidene-4-octenal, isobutyl acetate, cuminaldehyde, alpha-ionone, cinnamyl formate, ethyl butyrate, methyl cinnamate, acetic acid, gamma-undelactone, naphthyl-ethyl-ether, diacetyl, furfural, ethyl acetate Dimethylpyrazine, 2-ethyl-3-methylpyrazine, 3-phenyl-4-pentenal, 2-phenyl-2-hexenal, 2-phenyl-2-pentenal, J-phenyl - ^ - pentenal diethylacetal, damascone (l-crotonyl-2, 2,6-trimethylcyclohex-1-one), damascenone (l-crotonyl-2,2,6-trimethylcyclohexa-1,5-diene), beta-cyclohomocitral (2,2,6-trimethylcyclohex-l-encarboxaldehyde), isoamyl butyrate , cis-3-hexenol-1, 2-methyl-2-pentenoic acid, elemicin (4-allyl-1,2,6-trimethoxybenzene), isoelemecin (^ -propenyl-l ^ o-trimethoxybenzene) and 2- (4- Hydroxy-4-methylpentyl) norbornadiene, prepared by the method of US Patent Application 461,703, filed April 17 1974.

The 1-acetyl-3,3-dimethylcyclohexane derivatives and one of or several additives for perfume ingredients, for example

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Alcohols, aldehydes, ketones, terpene hydrocarbons, nitriles, esters, lactones, natural essential oils and synthetic ones Essential oils can be mixed together so that the combined fragrances of the individual components make one pleasant and desired fragrance, especially and preferably Petitgrain. Such perfume compositions usually contain (a) the main note or "bouquet" or Cornerstone of the composition; (b) modifiers that round off and accompany the main note; (c) fixatives that Contain fragrances that give the perfume a special note during the entire evaporation stage, and the also contain substances that delay evaporation; and (d) top notes, usually from low boiling, come from freshly smelling substances.

In perfume combinations, it is the individual components that contribute their own particular odor characteristics, but the total effect of the perfume composition is at least the sum of the effects of all components. So can the l-acetyl-J ^ -diroethylcyclohexane derivatives according to the invention used to change, modify or increase the aroma characteristics of a perfume composition, for example by taking advantage of or attenuating the odor effect of another component of the composition.

The effective amount of the l-acetyl - ^^ - dimethylcyclohexane derivatives in perfume compositions or perfumed articles depends on numerous factors, not the least of which is other ingredients, their proportions and effects, as well as the desired end effect. It was found that an amount as low as $ 0.01 or even less (e.g. 0.005 #) 1-acetyl-3 * ^ - dimethylcyclohexane derivatives is sufficient, around soaps, cosmetic products or other preparations, green, fruity, aldehyde-like notes with galbanum, ginger and To give citrus nuances.

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Up to $ 70 of the seasoning components can be used where for the amount used the costs, the nature of the end product, the desired effect of the end product and the particular preferred fragrance is decisive.

The inventive l-acetyl - ^^ - dimethylcyclohexane derivatives - alone or together with other ingredients for perfume compositions - can be used as an odor component for perfumed articles, for example in detergents and soaps, air fresheners and deodorants; Perfumes, colognes; Toilette; Bath additives such as bubble baths or bath salts; Hair preparations such as hair lacquers, brillantines, pomades and shampoos; cosmetic preparations such as creams, deodorants, hand lotions and sunscreen creams; Powders such as talc, body powder, face powder and the like. If the compounds are used as odor components, \% _t is sufficient to give nuances of ginger, citrus and galbanum to the petitgrain aroma. In general, no more than yf> of the l-acetyl - ^^ - dimethylcyclohexane derivatives are required, based on the end product of the perfume composition.

The l-acetyl- ^ J-dimethylcyclohexane derivatives can also with a carrier can be used. This can be liquid, for example a non-toxic alcohol or a non-toxic glycol or the like. The carrier substance can also be a solid with absorbent properties, such as gum (e.g. gum arabic) or a capsule material (such as gelatin) around the To envelop the flavoring component.

The l-acetyl- ^ J-dimethylcyclohexane derivatives are also capable Adding certain spicy and aromatic notes to tobacco seasonings or - if they are already present in small quantities - to strengthen them.

The terms "altering" and "modifying" as used herein can also be used in connection with tobacco condiments,

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suggest that mild tobacco varieties, tobacco substitutes or tobacco flavorings give certain flavoring characteristics or flavoring notes or reinforce existing flavoring properties or can be added to modify the character or taste of the end product.

“Increase” is understood to mean that one or more taste and / or aroma nuances that are found in tobacco, the tobacco substitute or the tobacco seasoning is already present, is intensified, but without affecting the type or quality of the Aroma or taste is changed.

According to the invention additives for tobacco products are supplied, which improve their organoleptic properties, eliminating specific problems that have arisen up to now, to create green, sweet, fruity, floral nuances reminiscent of Virginia tobacco that are used in the tobacco before smoking as well as in the main and side streams during smoking and at a desired uniform level remain, no matter how the tobacco ingredients vary in the mix.

The tobacco additives according to the invention impart to the types of tobacco green, sweet, fruity, floral and reminiscent of Virginia tobacco Nuances that can be easily varied and controlled in order to achieve the desired uniform flavoring characteristics obtain.

To achieve this, the tobacco material or a tobacco substitute is used (for example, dried lettuce leaves) a flavoring and seasoning additive is added as an active component Contains 1-acetyl-j ^ -dimethylcyclohexane derivatives.

In addition to 1-acetyl- ^ O-dimethylcyclohexane derivatives, Still other seasoning and flavoring additives can be added to the tobacco products, either separately or mixed with them the l-acetyl - ^^ - dimethylcyclohexane derivative. Such additives are:

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I. Synthetic fabrics ; ß-ethyl-cinnamaldehyde, eugenol, dipentene, damascenone, maltol, Äthylir.altol, delta-undecalactone, delta-decalactone, benzaldehyde, amyl acetate, ethyl butyrate, ethyl valerate, ethyl acetate, ß-cyclohomocitral, 2-hexenol, 2-hexenol isopropyl-l, j5-nonadien-8-one, 2,6-dimethyl-2,6-undecadien-10-one, 2-methyl-5-isopropy! acetophenone, 2-hydroxy-2,5 * 5 * 8a- tetramethyl-1- (2-hydroxyäthy1) -decahydronaphthalin, Dodecahydro- ^ a, 6,6,9a-tetramethylnaphtho- (2,1-b) -furan, 4-hydroxy-hexanoic acid, gamma-lactone and polyisoprenoid hydrocarbons, described in Example V of U.S. Patent J> 589,372 (June 29, 1971); and

II. Natural oils ; Celery seed oil, coffee extract, bergamot oil, cocoa extract, nutmeg oil and origanum oil.

A flavor and spice concentrate, the l-acetyl-J ^ -dimethylcyclohexane derivatives and optionally contains one or more of the above-mentioned additives, the tobacco, the filter or added to the sheet or paper wrapping material. The smoking tobacco can be cut, dried, pressed and be mixed. The addition quantities of the seasoning additives vary according to the desired taste. But it was found that to increase naturally present spicy notes and / or sweet notes, or to add these to the tobacco, quantities of between 25O T / Mill. up to I500 T / Mill. ($ 0.025 to 0.15 $) * n l-acetyl-J ^ -dimethylcyclohexane derivatives - based on the active ingredients - get good results. Furthermore, amounts by weight between 25OO and 10,000 T / Mill. (0.25Jg to 1.5 $) of the l-acetyl-2, dimethylcyclohexane derivatives Proven to be beneficial when used alone as condiments.

The flavoring can be added to the tobacco in any of the conventional ones Wise to be admitted. So can the l-acetyl - ^, 3-dimethylcyclohexane derivative alone or with other additives in an appropriate solvent, for example ethanol, pentane, Diethyl ether and / or other volatile organic solutions

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medium and the solution is either pickled and Pressed tobacco can be sprayed on or the tobacco can be immersed in the solution. Under certain conditions, the Solution with an appropriate device, such as a brush or a roller, applied to the sheet or paper envelope will. On the other hand, the filter can also be soaked with the solution by spraying it on, applying it or by dipping the filter.

Furthermore, only part of the tobacco or the tobacco substitute can also be used treated and then mixed with other types of tobacco. In this case, the l-acetyl-3,3-dlmethylcyclohexane derivatives containing seasonings are used in excess, so that the right one in the end product Concentration is present.

In a specific example according to the invention, an aged, pickled and cut Burley house tobacco was included a 20 ^ strength ethyl alcohol solution of 1-acetyl-1 ^ -dimethylcyclohexane derivatives in an amount sprayed to produce a tobacco preparation that is 800 T / Mill. (Weight) 1-acetyl-3,3-dimethylcyclohexane derivatives contained on a dry basis. Then the alcohol was evaporated and the tobacco closed Processed cigarettes. These cigarettes had a desired and pleasant aroma (increased smoke body feeling in the mouth with intensified tobacco-like notes and pleasant aromatic nuances), both in the main stream when smoking as was noticeable in the side streams. This aroma has been given green, sweet, fruity, floral and virginia tobacco reminiscent nuances awarded, and these before and during smoking in the main and side streams.

The seasoning according to the invention is particularly suitable for the production of smoking tobacco, such as cigarette tobacco, cigar tobacco and pipe tobacco, but it can also be used for other tobacco products from pressed tobacco dust.

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Likewise, the l-acetyl - ^^ - dircethylcyclohexane derivatives the material of the filter tip, the seam paste, the packaging material and the like. You can also use certain tobacco substitutes, i. H. Tobacco substitutes more natural or of synthetic origin (e.g. dried lettuce leaves) can be added. As a result, under the The term "tobacco" means everything that can be used for smoking.

The l-acetyl- ^ j ^ -diniethylcyclohexane derivatives according to the invention can consequently change, modify or increase the sensory properties, such as smell, taste and / or flavoring can be used in a wide variety of consumer items.

The l-butanoyl - ^^ - dimethylcyclohexane according to the invention and one or more perfume additives, for example alcohols, aldehydes, nitriles, esters, cyclic esters (or Lactones), as well as essential natural oils, can be mixed together to get through the combined fragrance notes of each Components to form a pleasant and desired fragrance, in particular amber fragrances. Such perfume compositions usually contain (a) the main note or "bouquet" or cornerstone of the composition; (b) modifiers to round off and accompany the main note; (c) Fixatives that contain fragrances, which the Adding a special touch to perfume during all stages of evaporation, "and substances that delay evaporation; and (d) Top notes, which are usually low-boiling, fresh-scented substances.

In the case of perfume compositions, it is the individual component that gives the olfactory characteristics. But the overall effect of the perfume composition is at least the sum of the effects of all ingredients. So can l-butanoyl-j5, J5-dimethylcyclohexane can be used to change, modify or change the aroma of a perfume composition

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to increase this, for example by exploiting the effect of another component of the perfume composition or is attenuated.

The effective amount of 1-butanoyl-; 5,3-dimethylcyclohexane in perfume compositions as well as in perfumed articles and colognes depends on numerous factors, not least on other constituents, their quantities and the desired effects in the end product. It has been found that perfume compositions cost as little as $ 0.01 - or even less (e.g. $ 0.005) - 1-butanoyl- ^ O-dirnethylcyclohexane is used Can be used to make soaps, cosmetics or other products a fruity, berry, herbaceous aroma with green and tobacco-like To give nuances. The amount used can be up to $ 70 of the seasoning component and depends on the cost The nature of the end product, the desired effect of the end product and the intended flavoring.

The inventive l-butanoyl - ^^ - dimethylcyclohexane can alone or together with other ingredients in perfume compositions as a seasoning component in detergents, soaps, Air fresheners and room sprays, perfumes, colognes, Toiletries, bath preparations, hair preparations such as hair varnishes, Brillantine, Pomades, and Sha ^ pOos; cosmetic preparations, such as creams, deodorants, hand lotions, and sunscreen creams; Powders such as talc, body powder, face powder and the like be used. Already 1 $ of l-butanoyl- ^ i ^ -dimethylcyclohexane is sufficient as an odor component to make ambergris to give an intense herbaceous note. In general, no more than 3 $ of the compound, based on the end product, needed in the perfume composition.

The l-butanoyl-j ^ jJ-dimethylcyclohexane as an additive for perfume compositions can be used together with a carrier. This can be liquid, for example a non-toxic one Alcohol, a non-toxic glycol, or the like. The carrier substance can also be an absorbent

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solid containing shafts, such as gum (e.g. gum arabic) be or consist of substances that encapsulate the seasoning as capsule material (e.g. gelatine).

The erf indungsgemässe l-butanoyl ^ j ^ -dimethylcyclohexan can be used for a wide variety of Koß'umstoffen as a seasoning for altering, modifying or enhancing the Würzwirkung be used.

When inventive l- (2-propenyl) - (4-methyl-3-pentenyl) -Δ -eyelohexen-1-carboxaldehyde as a food seasoning are used, the additives used with these compounds also serve to improve the organoleptic properties change, modify or increase the treated food.

The specific seasoning aid chosen can be solid or liquid and depends on the desired physical shape of the end product. Such a seasoning aid for food must in any case (i) be organoleptically compatible with the ingredients and neither mask nor destroy their organoleptic properties (aroma and / or taste); (ii) it must not react with the compounds according to the invention, namely the 1- (2-propenyl) - (4-methyl-2-pentenyl) - Δ -eyelohexene-1-carboxaldehydes; and (iii) needs to create such a state that the l- (2-propenyl) - (4-methyl-3-pentenyl) -Δ cyclohexene-l-carboxaldehyde dispersed or may be mixed so that a homogeneous mass is obtained. And their proportions - - outside the selection of one or more Würzhilfen or additives depends on the desired organoleptic character of the final product from. So when Würzzusammensetzungen the selection of the ingredients according to the food, chewing gum, medicinal product or toothpaste so the product, the flavor and / or aroma will depend awarded modified to be changed or improved. In the case of solid products, substances are usually selected that produce solid substances themselves, such as various cellulose derivatives.

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The amount of l- (2-propenyl) - (4-methyl-3-pentenyl) - Zl -eyelohexen-Ιο used in the various cases ar boxaldehyde can vary within wide limits and depends on the desired organoleptic effects. crisper Quantities are necessary where the food to be seasoned is relatively mild and bland, while less seasoning is required, where the natural flavor and aroma should be increased. What is important is that such a lot is added, which actually has the required and desired effect. Excess amounts are useless, firstly because they cause higher costs and in extreme cases disrupt the spice-aroma balance and thus the opposite is achieved.

It has been found that the l- (2-propenyl) - (4-methyl-3-pentenyl) -Δ -cyclohexen-l-carboxaldehyde as a seasoning for food, chewing gum, medical products and toothpastes in amounts between 0.5 T / million. up to about 100 T / Mill., based on the total composition, usable are. Larger concentrations are usually not recommended as they do not increase the organoleptic properties cause. In cases where the l- (2-propenyl) - (4-methyl-3-pentenyl) -Δ ^ -cyclohexen-l-carboxaldehyde to the food as an integral component of a seasoning composition is added, it is of course important that the total amount of the seasoning composition is sufficient to one effective concentration of l- (2-propenyl) - (4-methyl-3-pentenyl) -A -cyclohexen-l-carboxaldehyde in food.

Seasoning compositions prepared according to the invention contain the l ~ (2-propenyl) - (4-methyl-5-pentenyl) - Δ -cyclohexene-carboxaldehydes preferably in concentrations of about 0.1 to about 15% by weight, based on the total weight of the seasoning composition.

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The composition described can be produced by conventional methods, for example in devices for kneading dough or for producing fruit juices. The ingredients can simply be mixed together until the desired consistency, homogeneity of the dispersion, etc. is achieved. Seasoning compositions in the form of granules or powder, i.e. in solid form, can be prepared by mixing the l- (2-propenyl) - (4-methyl-3-pentenyl) - / \ -eyelohexen-1-carboxaldehydes with, for example, gum arabic, gum tragacanth, Carrageenan and the like and then spray drying to form the solid. Spice mixtures in powder form, e.g. fruity powder mixtures are made by mixing dried solids, for example starch, sugar and the like and one or more of the compounds l- (2-propenyl) - (4-methyl-3-pentenyl) -A -eyelohexen-1- carboxaldehyde is prepared in a dry blender until the required degree of uniformity is achieved j.

The 1- (2-propenyl) - (4-methyl-3-peritenyl) - / \ -eyelohexen-1-carboxaldehydes can be combined with the following additives: p-hydroxybenzyl acetone, geraniol, cassia oil, acetaldehyde, Maltol, ethylmethylphenylglycidate, benzyl acetate, dimethyl sulfide, eugenol, vanillin, caryophyllene, methyl cinnamate, Guiacol, ethyl pelargonate, cinnamaldehyde, methyl anthranilate, 5-methylfurfural, isoamyl acetate, isobutyl acetate, cuminaldehyde, alpha-ionone, cinnamyl formate, ethyl butyrate, methyl cinnamate, Acetic acid, gamma-undecalactone, naphthyl ethyl ether, diacetyl, Furfural, ethyl acetate, anethole, 2,3-dimethylpyrazine, 2-ethyl-3-methylpyrazine, 3-phenyl-4-pentenal, 2-phenyl-2-hexenal, 2-phenyl-2-pentenal, J-phenyl - ^ - pentenal diethylacetal, damascone (l-crotonyl-2,2,6-trimethylcyclohex-l-one), damascenone (l-crotonyl-2,2,6-trimethylcyclohexa-1,5-diene), beta-cyclohomocitral (2,2,6-trimethylcyclohex-l-en-carboxaldehyde), Isoamyl butyrate, cis-3-hexenol-l, 2-methyl-2-pentenoic acid, Elemecin (4-allyl-1,2,6-trimethoxybenzene), Isoelemecin (4-propenyl-1,2,6-trimethoxybenzene) and 2- (4-hydroxy-4-methylpentyl) norbornadiene, made according to US patent application 461 703 of April 17, 1974.

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The 1- (2-propenyl) - (4-methyl - ^ - pentenyl) - A -cyclohexene-1-carboxaldehydes can with one or more perfume auxiliaries, for example alcohols, aldehydes, ketones, Terpine hydrocarbons, nitriles, esters, lactones, natural essential oils and synthetic essential oils be mixed so that the combined fragrance notes of the individual components have a pleasant and desired spicy character result, preferably rose fragrances. Such perfume compositions usually contain (a) the main note or that "Bouquet" or the cornerstone of the composition; (b) modifiers, which round off and accompany the main note; (c) Fixatives that contain fragrance substances that add to the perfume give a special note during all stages of evaporation and also contain substances that cause evaporation delay; and (d) top notes, which are typically low-boiling, fresh-scented substances.

In perfume compositions it is every single component which contributes to the special smell characteristics, but the overall impression of the perfume composition is at least that Sum of the individual effects of all components. The inventive 1- (2-propenyl) - (4-methyl-3-pentenyl) -Z \ -cyclohexene-1-carboxaldehydes can be used to alter the aroma characteristics of a perfume composition modify or increase it, for example by taking advantage of or dampening the odor reaction caused by others Components of the composition.

The 1- (2-propenyl) - (4-methyl-5-pentenyl) -2 ^ ^ -cyclohexene-1-carboxladehydes are effective in perfume compositions, perfumed products and in colognes and the amount required depends on several factors, for example of the other ingredients, their proportions and the desired effects of the end product. It has been found that amounts as low as $ 0.01 - or even just $ 0.005 - are enough to give soaps, cosmetics, or other products a sweet, fruity

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and lavender-like notes with citrus and balsam nuances to lend. Up to $ 70 of the seasoning component can be used The costs, the nature of the end product, the desired effect and the special flavoring note are decisive are.

The l- (2-propenyl) - (4-methyl-3-pentenyl) -Δ -cyclohexene-l-carboxaldehydes can be used alone or together with other ingredients in perfume compositions as Fragrance component in detergents, soaps, air fresheners and deodorants, perfumes, cologne, toilet water,

Bath preparations, such as varnishes, brillantines, pomades and shampoos; in cosmetic preparations such as creams, deodorants, hand lotions and sun protection creams; Powders such as talc, body powder, face powder and the like can be used. A quantity of only 1 $ of the l- (2-propenyl) - (4-methyl-5-pentenyl) - Λ ^ -cyclohexene-l-carboxaldehydes is enough to give rose preparations an intense flowery note. In general, no more than yfc of 1- (2-propenyl) - (4-methyl-3-pentenyl) -Z! \ -Cyclohexene-carboxaldehydes, based on the end product, are required for perfume compositions.

The 1- (2-propenyl) - (4-methyl-3-pentenyl) - / \ -eyelohexene-1-carboxaldehydes can also be used for perfume compositions with a carrier that is liquid, such as an alcohol, non-toxic alcohol -toxic glycol or the like. On the other hand, the carrier substance can also be a solid; for example gum (such as gum arabic) or substances that are suitable for coating the seasoning (e.g. gelatine).

The l- (2-propenyl) - (4-methyl-3-pentenyl) -Δ ^ -cyclohexen-l-carboxaldehyde can therefore be used for a variety of consumer products to make their organoleptic To change, modify or increase properties. They are also suitable for making different types of tobacco to give certain spicy and aromatic notes and / or -

709 8 29/1072

if these are already present to a certain extent to be strengthened. This is an organoleptically improved Smoking tobacco and additives created for it, with specific desired woody-cocoa and cocoa broth-like flavoring characteristics in natural Burley tobacco - as well as sweet and creamy-oily nuances - can be produced or enhanced. Included is it possible to keep and control the organoleptic properties at a desired uniform level, regardless of whether the tobacco components vary in the mixture or not.

The l- (2-propenyl) - (4-methyl-3-pentenyl) -A , -eyelohexene-1-carboxaldehydes according to the invention can be added to smoking tobacco or a corresponding substance or tobacco substitute (eg dried lettuce leaves) alone or together with other ingredients . Such components are:

I. Synthetic fabrics ; ß-Ä'thyizirr.taldehyd, eugenol, dipentene, damascenone, maltol, Äthylrnaltol, delta-undecalactone, delta-decalactone, benzaldehyde, amyl acetate, ethyl butyrate, ethyl valerate, ethyl acetate, beta-5- cyclohomocitral, 2-hexenol, 2-hexenol isopropyl-1,3-nonadien-8-one, 2,6-dimethyl-2,6-undecadien-10-one, 2-methyl-5-isopropylacetophenone, 2-hydroxy-2,5,5-8a-tetramethyl- 1- (2-hydroethyl) -decahydronaphthalene, dodecahydro-3a, 6,6,9a-tetramethylnaphtho- (2, lb) -furan, 4-hydroxyhexanoic acid, gamma-lactone, polyisoprene hydrocarbons described in Example V of the US PS 3 589 372 of June 29, 19.71 J and

II. Natural oils ; Celery seed oil, coffee extract, mountain ganotte oil, cocoa extract, nutmeg oil and origan oil.

A flavor and seasoning concentrate that contains l- (2-propenyl) - (4-methyl-3-pentenyl) -Δ -cyclohexene-1-carboxaldehyde - and, if desired, one or more of the above-mentioned seasoning additives - Contains, can be added to the smoking tobacco, the filter or the wrapping sheet or paper. As usual the tobacco can be cut, pickled, pressed, it can be a tobacco blend or processed tobacco material or

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Tobacco substitutes (e.g. lettuce leaves) or mixtures thereof can be used. The added amounts of seasoning additives can be varied according to the taste. With regard to the natural and / or sweet notes to be enhanced or given , it has been found that satisfactory results are obtained when 250 T / Wed 11th up to 1500 T / Mil .. (0.025 # to 0.15 #) of the active ingredients, based on the total sum of the l- (2-propenyl) - (4-methyl-2-pentenyl) -A - cyclohexene-l-carboxaldehydes to be added to smoking tobacco . It has also been found that good results are achieved when the weight proportions of the l- (2-propenyl) - (4-methyl-3-pentenyl) - ^ -cyclohexene-l-carboxaldehydes in the entire seasoning material between about 2500 and 10,000 T / Wed 11. (0.25 # to $ 1.5).

The 1- (2-propenyl) - (4-methyl-5-pentenyl) - Δ ^ -cyclohexene-lcarboxaldehydes - alone or together with seasoning additives - can be in an appropriate solvent, such as ethanol, pentane, diethyl ether and / or other volatile organic Dissolved solvents and the solution either sprayed onto the pickled, pressed and mixed tobacco or dipped into the solution. Under certain circumstances, such a solution can be applied to the paper or sheet wrapping for the tobacco by means of an appropriate device, for example a brush or a roller. It can also be added to the filter material, being sprayed or brushed onto it or the filter material being immersed in the solution.

It can also be just part of the tobacco or the tobacco substitute are treated with the seasoning, in which case the concentrations are higher because this treated amount is used for this purpose is to be mixed with untreated tobacco. In this case, too, it must be ensured that the required amount of seasoning substance is present in the end product.

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One trial was aged, pickled, and cut Burley house tobacco with a 20% ethyl alcohol solution the l- (2-propenyl) - (4-methyl-3-pentenyl) -tA -cyclohexene-1-carboxaldehydes sprayed in such an amount that the tobacco composition is 800 parts by weight / mill. the Seasoning substance, based on dry weight. The alcohol was then evaporated and the tobacco made into cigarettes. The cigarettes treated in this way had a desired and pleasant aroma (improved smoke body feeling in the Mouth with heightened tobacco-like notes and pleasant aromatic nuances), which both in the main flow during smoking as well as in the side streams. This aroma has been described as having more body, More tobacco-like, more aromatic, slightly oily and slightly cocoa-like and cocoa-broth-like, creamy-oily and heavy had sweet notes.

The l- (2-propenyl) - (4-methyl-j5-pentenyl) - Δ ^ -cyclohexen-Ιο arboxaldehydes are particularly suitable for smoking tobacco, such as cigarette, cigar and pipe tobacco, as well as tobacco products, which are made from recycled tobacco dust. You can choose the filter material, the seam paste, the packaging material and the like can be added.

The invention is illustrated by the following exemplary embodiments explained in more detail.

All parts and percentages are expressed by weight unless expressly stated otherwise.

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example 1 Preparation of 2,5-dimethyl-2-propenyl-hex-4-enal

In one with a stirrer, thermometer, reflux condenser and funnel A solution of 72 g sodium hydroxide in 72 g water was added to the 1 liter reaction flask provided. to 80 g of toluene and 5 g of tricaprylmethylammonium chloride (ALIQUAT 336® from General Mills Chemicals, Inc.) and then heated to 75 to 80 ° C with stirring, a solution of 200 g of 2-kethylpent-2-enal and 210 g of the reaction mixture was added over a period of 6 hours Added prenyl chloride. After the 6 hours, the reaction mixture was stirred at 75 to 80 ° C. for a further 4 hours. After the For 4 hours the organic layer was separated, washed neutral and the solvent evaporated.

The remaining oil was then distilled in a 12 "Vigraux column after adding 10 g of PrimolW and 1 g of Ionox ^. The fractions removed from the column were as follows:

fraction
No. Steam temperature
temperature ( ⁰ C) River.Terno.
( ⁸ C) * vacuum
mm Hg weight
(G) 1 64-75 93-110 44-44 24.4 2 115 123 44 23.9 3 118 131 44 52.3 4th 119 139 44 52.8 5 121 168 44 39.7 6th 138 190 44 17.2

Fractions 2 to 5 were collected and placed on a 12-plate Vigreaux column at a reflux ratio of 12: 1 after the addition of 8 g Primol ^ V and 0.4 g ΙοηοχΦ. The fractional distillation dates were as follows:

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fraction
No. Steam temp.
(° C) Liquid temp.
(ο C) vacuum
mm Hg weight
(G) 1 55-58 106 44-44 1.1 2 68 108 '44 3.3 3 94 109 32 4.2 4th 108 111 .38 3.0 5 112 112.5 38 5.2 6th 112 113 38 6.6 7th 115 115 38 7.3 8th 114 115 38 8.3 9 114 ' 116 38 8.6 10 115 118 . 38 11.3 11 115 110 38 8.5 12th 115 118 38 9.1 13th 115 120 38 8.0 14th 115 120 38 8.1 15th 116 120 38 11.0 16 117 120 28 IC.4 17th 117 120 38 9.2 18th 118 120 38 4.7 19th 112-114 122-123 38-38 4.7 20th 114 131 38 ' * 10.5 21 120 151 38 9.0 22nd 123. 230 38 5.5

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Fractions 10 to 19 were determined using gas-liquid chromatography, as well as the NMR and IR analyzes and found that the main corr that was 2,5-dimethyl-2-propenyl-hex-4-enal. This connection had a tart, green, citrus-like, cake-like, sweet, carvone-like note with a lavender-like nuance.

Example 2 Preparation of 2-methyl-2-benzyl-pent-2-enal

In one with a stirrer, thermometer, reflux condenser and funnel A solution of 72 g sodium hydroxide in 72 g water was added to the 1 liter reaction flask provided. 80 g of toluene and 5 g of tricaprylmethylanunonium chloride were added to this NaOH solution added and the mixture heated to 75 to 80 ° C. This temperature was held for 6 hours and during this period, a solution of 200 g of 2-methylpent-2-enal and added 255 g of benzyl chloride. The reaction mixture was stirred for a further 6 hours, the temperature was kept in the range of 75 to 80 ° C. The reaction mixture was then refluxed for 2 1/2 hours, to cause the remaining benzyl chloride to react. The organic layer was separated, neutral washed and the solvent removed.

The remaining oil was distilled in a 3 "immersion column after 14 g Primol ^ and 1 g Ionox ^ had been added . The distillation data are as follows:

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fraction
No. Steam temp.
(OC) Fluss.TemD.
(° c) ■ vacuum
mm Hg weight
(S) 1 79-100 137-142 50-50 8.9 2 113 152 50 18.1 3 150 165 50 27.7 4th 166 121 50 47.8 5 168 180 50 59.6 6th 170 185 . " 50 48.8 7th 172 218 50 37.8 8th 175 . 242 50 22.1 9 200 250 50 8.3

Fractions ^ to 8 were collected and after addition
_ _o and 0.5 g of IonoxU in a 10 "column

(Reflux rate 9: 1) distilled. The dates of this fractional distillation were as follows:

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fraction
No. Steam temp.
(ο C) Flow temp.
(OC) vacuum
mm Hg weight
(S) 1 90-94 116-117 3.0-3. 0 2.7 2 103 118 3.0 5.8 3 109 118 3.0 · 6.3 4th 114 118 3.0 7.9 5 112 117
• 2.9 10.2 6th 113 117 3.0 15.2 7th 113 118 3.0 14.7 8th 113 118 3.0 14.0 9 . 113 118 3.0 14.3 10 113 118 3.0 15.5 11 113 119 3.0 13.2 12th 113 120 3.0 14.2 13th 113 120 3.0 10.6 14th 113 124 3.0 15.0 15th 116 135 3.0 14.1 16 119 172 3.0 1-3.9 17th 124 196 3.0 7.4 18th 118 250 3.0 6.0

Fractions 6 to 8 were collected and with the aid of gas-liquid chromatography and NMR and IR analyzes was examined to find that the product obtained was 2-methyl-2-benzyl-pent-3-enal. It had a sweet, fruity, citrus-like, flowery green aroma. The IR spectrum of this compound (fraction 5) is shown in FIG.

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Example 3

Production of 2-prenyl-citral - (;;, 7-dimethyl-2 (3-methyl- 2-butenyl) 2,6-octadienal)

In one with cooler, stirrer, thermometer, heating jacket and A 1-liter reaction flask equipped with a funnel was added to a solution of 61 g of sodium hydroxide in 61 g of water. 61 g of toluene and 13 * 6 g were added to this NaOH solution Tricapryl-methyl-ammonium chloride added. The mixture was heated to reflux (102 ° C) and while the The toluene-sodium hydroxide mixture refluxed for 1 hour, a solution of 215 g Citral and 153 g prenyl chloride added. After completion After the addition, the reaction mixture was refluxed for a further hour. Then 200 ml of water were added, the reaction mixture was stirred for 15 minutes and then placed in a separatory funnel. The organic layer was separated off, washed neutral and the solvent removed.

The remaining oil was after the addition of 10.9 g and 1 g of Ionox ^ at 2.5 mm Hg through a 6 "Vigreaux column distilled. The data of the fractional distillation are as follows:

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raktior
No. ι steam temp.
(ο C) River.Terno.
(ο C) " weight
(G) 1 51 106 8.0 2 64 134 11.1 3 102 133 10.1 4th 118 138 13.1 5 122 141 15.1 6th • 125 148 32.8 7th ^ 127 154 23.7 8th 127 159 24.0 9 135 176 19.9 10 142 184 15.4 11 164 195 24.2

Fractions 5 to 9 were collected and, after the addition of 3 g Primol ^ y and 0.5 g Ionox ^ in an 8-plate Vigreaux column distilled. The data of the fractionated Distillation were the following:

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fraction
No. Steam temp.
(° c) Flow temp.
(° C) vacuum
mm Hg weight
(ß) 1 107-139 150-156 3.1 4.8 2 141 155. 3.0 4.8 3 143 155 3.0 5.8 4th 144 156 3.0 8.1 5 144 157 2.6 7.5 6th 144 160 2.6 11.1 7th 140 162 2.5 7.0 8th 144 176 2.4 8.7 9 146 214 2.4 7.3 10 138 250 2.4 6.1

Fractions 3 to 8 were collected and analyzed by NMR, IR and gas-liquid chromatography analyzed. It was confirmed that the product was 2-prenylcitral. These Compound had a sweet, creamy, orange-like note with woody, citrus-like, and resinous nuances.

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example Preparation of 2-butenyl-2-ethyl-5-methyl-hex-4-enal

In a 1 liter equipped with a stirrer, thermometer, cooler, filling funnel, heating jacket and temperature monitor The reaction flask became a solution of 72 g of sodium hydroxide and given 72 g of water. Then 81 g of toluene and 5 g Tricapryl-methyl-ammonium chloride added and the mixture heated to 75 to 90 ° C. with stirring. Over a period of 6 hours, a solution of 252 g of 2-ethylhex-2-enal and 215 g of prenyl chloride were added, the temperature being kept at 75 to 80 ° C. After completion After the addition, the reaction mixture was stirred at 75 to 80 ° C. for a further 4 hours. The organic layer was then separated, washed neutral and the solvent removed, after adding 13 g of PrimolO 'to the remaining oil

was measured at 2.5 mm Hg in a rapid

Column rapidly distilled, the following fractions were obtained :

fraction
No. Steam temp.
(° O Flow temp.
(° O weight
(K) 1 40 57 14.8 2 47 62 22.9 3 51 58 15.4 4th 54 71 18.0 5 58 73 23.4 6th '67 83 17.9 7th . 80 "89 13.4 8th 83 92 26.6 9 05 92 22.3 10 85 94 19.0 11 85 99 18.5

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r action
No. Steam temp.
(ο c) Flow temp.
(OC) weight
(S) 12th 87 98 16.8 13th 94 119 26.9 14th 130 160 19.5 15th 195 250 22.8

Fractions 5 to 14 were collected and redistilled, at 2.5 mm Hg and a reflux ratio of 9: 1 on a plate Vigreaux column after 5.1 g PrimolLy and 0.5 g Ionoxv / had been added. The following fractions were won:

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Fraction steam temp. No. ( ^δ C)

1 44 2 50 3 93 4th 96 5 97 6th 95 7th 92 8th 96 9 88 10 89 11 83 12th 85 13th 85 14th 85 15th 85 16 85 17th 93 IS • 96

Flow temp.
(O ρ \
\ W weight
(S) 88 Cl 95 6.9 117 13.7 119 9.2 116 10.4 114 10.4 110 11.5 110 16.9 105
105 10.1
10.9 105 9.9 106 9.3 112 . 11.2 115 11.1 132 6.6 143 4.3 171 3.4 250 3.8

Fractions 3 to 16 were collected and examined by gas-liquid chromatography, NMR and IR analyzes to confirm that it was the obtained compound

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2-butenyl-2-ethyl-1,5-methyl-hex-4-enal of the general formula

CHO

acts. This compound had a green, sweet, tomato aroma with a citrus character and a flowery rose-like one Note that, after drying out, was even more reminiscent of roses.

Example 5 Preparation of 2-benzyl-2-ethyl-hex-3-enal

A solution of 85 g of sodium hydroxide in 100 g of water was placed in a 1 liter reaction flask equipped with a condenser, stirrer, thermometer, filling funnel, heating mantle and temperature monitor. 100 g of toluene and 5 g of tricaprylmethylammonium chloride were then added and the reaction mass was heated to 70 ° C. with stirring. The reaction mixture was kept at this temperature for 5 hours and during this time a mixture of 252 g of 2-ethylhexenal and 235 g of benzyl chloride was added. After the addition was complete, the reaction mixture was stirred at 70 ° C. for a further 4 hours. After this period the reaction mixture was cooled to 25 ° C and 300 ml of water was added. The organic layer was separated off, washed neutral and, after adding 15.7 g of Primol ™ and 2 g of Ionox® · 'to the oil obtained, toluene was stripped off and the product obtained was rapidly distilled over at 2.5 mm Hg. The following fractions were obtained:

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Fraction steam temp.
No. C C) 47-48 River. Θγγιό.
(O c) weight
(S) 1 113 110-80 106.9-30.6 2 120 117 31.5 3 121 127 55.7 4th 122 123 49.4 5 122 123 49.2 6th 125 123 39.0 7th 126 125 33.9 8th 138 133 50.8 9 225 164 25.3 10 Fractions 2 ^ to 9 205 15.8 from 9.6 were collected and after adding κ Primoivfy and 0.8 κ Ionox ^ became the mixture

at 2.5 mm Hg and a reflux ratio of 9: ι on a 12 plate Vigreaux column distilled and following Factions won:

fraction
No. Steam temp,
(ο C) Liquid temp.
(° c) weight
(S) 1 38 107 7.2 2 38 124 6.5 3 86 150 9.2 4th 117 141 7.1 5 117 141 12.8 6th 117 141 13.8

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Steam temp.
(O C) U 2700688 fraction
No. 117 Liquid temp.
(O r> \
\ W weight
(G) 8th 117 142 13.6 9 117 142 14.9 10 117 142 11.2 11 118 138 13.0 12th 118 139 12.9 13th 113 146 13.5 14th 120 148 14.1 15th 121 150 15.8 16 121 151 14.8 17th 121 154 14.7 18th 121 154 14.2 19th 121 154 14.8 20th 121 154 15.3 21 123 154 13.9 22nd 125 163 6 .. 6 23 118 175 11.4 24 132 188 7.0 25th 250 7.7

Fractions 7 to 19 were collected and analyzed by gas-liquid chromatography, IS and mass spectral analyzes examined and confirmed that it is 2-benzyl-2-ethyl-hex-3-enal acts. There was a sweet, floral, rose-like note to this compound.

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TJ

Example 6 Manufacture of 2-prenylnonenal

In one with a cooling bath, thermometer, condenser, stirrer, and filling funnel and temperature monitor equipped 500 ml reaction flask was a solution of 30.5 g sodium hydroxide in 30.5 g Given water. Then there were 30.5 g of toluene and 6 g of tricaprylmethylammonium chloride added and the mixture cooled to 30 ° C. This reaction mixture was added over a period of time a solution of 110 g of 2-nonenal and 45 g of prenyl chloride was added over a period of 11/2 hours. This was followed by 1 hour stirred at 27 ° C and then added 100 ml of water. The organic layer was separated, washed neutral and the Solvent removed.

The oil obtained was after the addition of 3.5 g of PrimolüVund 1 g of IonoxViy distilled through a 12 "Vigreaux column. The Distillation dates were as follows:

fraction
No. Steam temp.
(° c) Flow temp.
( ⁰ C) vacuum
mm Hg weight
(R) 1 138 163 0.8 8.6 2 151 180 0.8 10.3 3 175 193 0.8 8.0 4th 192 210 0.7 10.4 5 200 225 1.9 12.1

The NMR, IR and mass spectral analyzes confirmed the compound 2-prenylnonenal of the general formula

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CHO

(Mixture of isomers)

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Example 7 Orange terpeneless perfume composition

The following mixture was produced:

Components

Alcohol C- (n-nonanal) alcohol C ₁

Alcohol C ₁

Aldehyde C aldehyde C aldehyde C Citral

Methyl anthranilate neryl acetate geranyl acetate terpenyl acetate Nerol

Terpineol Geraniol Linalool Linalyl-a ceta £

(n-decanal) (n-dodecanal) (n-nonanal) (n-decanal) (n-dodecanal)

Parts by weight

2

5 10

20 40 15

In the alternative, one of the connections

(2,5-dimethyl-2-propenyl-hex-4-enal; 2-methyl-2-benzyl-pent-3-enalj

(ii

(iii

(iv

2-prenylcitral;

2-butenyl-2-ethyl-5-methyl-

hex-4-enal;

(v) 2-benzyl-2-ethyl-hex-3-enal; or (vi) 2-prenylnonenal

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2,5-dimethyl-2-propenyl-hex-4-enal; 2-methyl-2-benzyl-pent-3-enal; 2-prenylcitral; 2-butenyl-2-ethyl-5-methyl-hex-4-enal; 2-benzyl-2-ethyl-hex-3-enal; and 2-prenyl non-2-enai gave the perfume composition a distinct green, citrus-like, fruity, floral note, with the Orange note has been increased.

Example 8 reaction:

CHO CH ₀ Cl

: ho

A solution of 720 g of sodium hydroxide and 720 g of water was placed in a 12 liter reaction flask equipped with a stirrer, thermometer, reflux condenser and filling funnel. To this mixture, 800 g of cyclohexane and 50 g of tricaprylmethylammonium chloride were added. The mixture was heated to a temperature between 75 and 80 ° C. with stirring and a solution of 2000 g of 2-methylpent-2-enal and 2100 g of prenyl chloride was added over a period of 6 hours. After these 6 hours, the reaction mixture was stirred at 75 to 30 ° C. for a further 4 hours. The organic layer was then separated off, washed neutral and the solvent was stripped off. After adding 82.0 g of Primol ^ and 6g of Ionox ^, the oil obtained was subjected to rapid distillation and the following fractions were obtained:

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fraction
No. Steam temp.
( ⁰ C) River .Terno.
( ⁵ C) vacuum
mm Hg Oewicht
(ß) 1 42-65 100-100 120-95 24.7 2 75 100 87 34.8 3 80 102 87 41.7 4th 87 102 75 82.7 5 90 102 . 64 94.9 6th 88 105 59 121.1 7th 94 114 58 133.8 8th 108 125 58 179.4 9 120 130 56 165.2 10 122 132 . 57 161.5 11 124 134 57 199.5 12th 125 136 57 197.4 13th 127 139 57 182.3 14th 129 145 57 Ϊ98.5 15th 133 157 57 173.1 16 144 185 57 165.8 17th 172 , 212 57 99.0 18th 179 215 55 35.1

Fractions 4 to 17 were collected and g at a Good loe column after addition of 5 Ionox ^ and 63 g of distilled again. A reflux ratio of 9: 1 was used. The distilled fractions were as follows:

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action steam temp. Flow temp. Vacuum no. Γ C)

1 49-55 2 59 3 60 4th 60 5 66 6th 100 7th 113 8th 118 9 118 10 / 95-100 11 ICS 12th 100 13th 99 14th 99 15th 104 16 108 17th 106 18th 105 19th 105 20th 105 21
22nd 1C5
• 105 23 105 24 107 25th 112

üss.temp.
(° c) vacuum
mm Hg Weighted 96-97 50 14.2 100 • 50 27.9 104 50 40.6 109 50 45.5 120 50 85.6 124 50 56.5 125 50 27.0 125 50 27.5 125 50 '89.4 110-110 25-27 22.0 113 30th 51.8 109 • 26 74.9 109 26th 79.0 109 2G 73.0 110 26th 63.1 113 25th 83.8 113 26th 73.4 111 26th 82.3 112 25th 82.4 112 25th 83.5 112 25th 89.7 116 25th 98.4 119 25th 92.0 124 25th 91.1 131 25th 92.8

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fraction
No. Steam temp.
(° C) Flow temp.
(° c) vacuum
mm Hg weight
(S) 26th 114 145- 25th 91.5 27 316 170 20th 48.6 28 12ί 192 20th 36.5 29 OK 216 15th 31.8 30th 147 250 15; 22.7

Fractions 24 to 27 were pooled and after addition of 10 g PrimolliV and 0.3 g ΙοηοχΟ 'on a 12 "Vigreaux column, provided with heating jacket and fraction separator, distilled. The data of the factions were as follows:

Fraction steam temp. Flow temp. Vacuum weight reflux no. (° C) (° C) mm Hg (g) ratio

1 83-85 98-98 15-14 2.0 14: 1 2 86 99 14th 9.0 14: 1 3 86 99 12th 10.5 14: 1 4th 86 99 12th 8.1 14: 1 5 86 99 12th 8.5 14: 1 δ. 88 99 · 12th 14.4 14: 1 7th 85 99 12th 7.3 14: 1 8th 85 99 12th 6.2 14: 1 9 85 99 12th 11.3 14: 1 10 85 99 12th 11.3 14: 1 11 85 99 12th 14.1 14: 1 12th
13th 85
■ 4
85 99
102 12th
12th 15.4
14.5 14: 1
14: 1

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Fraction steam temp. Flow temp. Vacuum weight reflux no. ( ^δ C) (° C) mm Hg (g) ratio

14th 83-85 99-101 10-10 4.8 12: 1 15th 90 104 12th 8.3 12: 1 16 89 104 13th 9.9 12: 1 17th 82 104 12th 7.0 12: 1 18th 87 105 12th 12.8 12: 1 19th 90 105 11 11.2 12: 1 20th 92 105 11 9.6 12: 1 21 94 105. 11 8.6 12: 1 22nd 94 105 11 11.9 12: 1 23 94. 105 11 15.8 12: 1 ¹ 24 94 105 11 16.9 12: 1 25th 94 105 11 14.6 12: 1 26th 94 105 11 15.8 12: 1 27 94 105, 11 14.4 12: 1 28 94 119. 11 8.4 12: 1 29 100 140 11 3.7 12: 1 30th 108 220 11 5.7 12: 1

Fraction 26 of the distillate was analyzed on a gas-liquid chromatography column (Conditions: 1/4 "χ 10 '; 5 # Carbowax 2OM / absorbed on Chromasorb G / column, programmed at 10 ° C / minute from 80-220 ° C), chromatographed and a main component determined by 9O #. purity. The NMR, mass spectrum and IR analyzes showed that this major component Was 2,4,7-trimethyl-2,6-octadienal.

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The NMR spectrum for fraction 26, main peak, is in Fig. 2 shown. The IR spectrum for fraction 26, major peak, is shown in FIG.

Example 9 Tangerine and orange seasoning composition

An orange seasoning was made by mixing the following ingredients:

Components parts

Natural orange oil

acetaldehyde

Ethyl acetate

Ethyl butyrate

Propanal

Trans-2-hexenal

Ethyl alcohol (95 #)

Fusel oil 0.05

Propylene glycol 24.65

This mixture was designated as Wort "A".

A second mixture - wort "B" - was prepared by adding 2,4,7-trimethyl-2,6-octadienal, prepared according to Example 8 (1 # in ethanol) to a portion of wort ¹¹ A ".

Each seasoning mix "A" and ¹¹ B "was added in an amount of about 57 g per 3 * 785 l (2 ounces per gallon) of 32 ° Baume sugar syrup to make a syrup which, when diluted with water, makes a drink The Spice Mix "A ⁿ spiced drink was an acceptable orange drink of good character, flavor and intensity.

The drink mixed with the ¹¹ B "spice mixture had a much better orange character with new tangerine, orange and lemon nuances.

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Example 10 Manufacture of cis-jasmone

In one with heating jacket, condenser, stirrer, thermometer and Funnel-equipped 250 ml reaction flask was added added a solution of 21.3 g of sodium hydroxide and 21.3 g of water. 20 g of toluene and 1.5 g of tricaprylmethylammonium chloride (ALIQUAT 336 vV, from General Mills Chemicals, Inc.) * were then added and the reaction mixture was heated to reflux (102 ° C.) and a mixture for 1 hour from 35 g of cis-pent-2-enyl-1-chloride and 24.5 g of 3-methylcyclopentenone-2 added under reflux. The reaction mixture was refluxed for a further 4 hours and then mixed with 100 ml of cold water and placed in a separatory funnel.

The organic layer was separated, washed neutral and the solvent evaporated.

The oil obtained was retained before distillation mixed with the reaction product from Example 2 will.

Example 11 Manufacture of cis-jasmone

A Solution of 106.5 g of sodium hydroxide in 106.5 g of water and then 100 g of toluene and 7 * 5 g of tricaprylmethylammonium chloride added. The mixture was heated to reflux and a mixture of 122.5 g of 3-methylcyclopentenone-2 for 1 hour and 175 g of cis-pent-2-enyl-1-chloride were added. Afterward the reaction mixture was refluxed for a further 2 hours and then 250 ml of water were added. The mixture was placed in a separatory funnel.

The organic layer was separated, washed neutral and the solvent ob ^ * * © ^ «^.

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ti

The oil obtained was mixed with the product from Example 1 combined and this mixture 17 g Primol ^ 'and 7 g Triethanolamine added. The mixture was quickly distilled over and the following fractions were obtained:

Fraktioi
No. ι steam temp.
(ο C) Flow temp. vacuum
mm Hg weight
(S) .3 1 43-120 91-159 2.6 27 .0 2 125 162 2.6 19th .3 3 167 185 2.6 18 .4 4th 184 201 2.5 19th 4th 5 203 217 2.5 16. 9 6th 220 240 2.5 26th

Fractions 1, 2 and 3 were combined and fractionally distilled after addition of 2 g Primol® and Ionox ^ on a 12 plates Vigreaux column. The following fractions were won:

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SO

fraction
No. Steam temp.
(° c) Flow temp.
(° c) vacuum
mm Hg weight
(G) 1 53 107 3.5 . 4.8 2 36 100 1.0 4.5 3 72 120 0.8 3.1 4th 80 121 0.8 4.0 5 80 123 1.0 4.9 6th 78 122 1.2 4.2 7th 79 128 1.2 3.8 8th 79 137 1.2 4.6 9 79 144 1.2 3.9 10 87 151 1.2 2.3 11 9> 159 1.2 4.1 12th 98 174 1.2 3.8 13th 112 182 1.2 2.4 14th 120 204 1.2 1.9 15th 125 250 1.2 2.6

Fractions 6 to 9 were combined, analyzed and evaluated. The NMR, IR and mass spectrum analyzes gave cis-jasmone of the formula:

and the rest trans- jasmine. The NMR spectrum is shown in FIG. 4 and the IR spectrum is shown in FIG.

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Example 13
Jasmine perfume

27ÜÜ688 3t

The following mixture was produced:

Components parts by weight

Para-cresol *

Acetyl-m.ethyl-anthrani.late 20

Farnesol ⁴

Cis -3-hexenyl benzoate ³⁰

Nerolidol ³⁰

Indole ^15th

Eugenol ²⁰

Benzyl alcohol ⁴⁰

Methyl linoleate ⁴⁰

Jasmine lactone * ²⁰

Dihydromethyl jasmonate 1 °

Linalool 150

Benzyl alcohol ⁴⁰⁰

Abietyl alcohol ¹⁵⁰

Cis jasmone (manufactured according to Example 11; United
Parliamentary groups 6 to 9)

The cis-jasmone produced according to Example 11 gave the Jasmine preparation that is so important for a jasmine perfume green, sweet, celery-like note.

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example 14th

Manufacturing of 1-acetyl-3 »3-dimethyl- (2-propenyl) cyclohexane

Reaction :

ÜÜÜ

.AliquatVi / 336 toluene

To a slurry of l-acetyl - ^^ - diniethylcyclohexan (462g, 5 mole) of granulated sodium hydroxide (l8O g, 4.5 mol), Aliquat ^R ^ ^{56 (1021} ^ P ¹ Vlmethylammoniumchlorid) ₍₂ 4 g) and toluene ( 200 g) were added 222 g (3.8 mol) of allyl chloride over a period of 15 minutes with stirring and at a temperature of 70 ° C. The mass was heated to reflux for 7 1/2 hours, at the end of which time the temperature rose to 83 ° C. After the mass had cooled , 1 liter of water was added with a stirrer. The organic phase of the reaction mixture was washed twice with water and distilled through a 12 " χ 1/2" Goodloe column, which was equipped with an automatic reflux head. The reflux head was set at 19: 1 (85 ° C, 2.7 mm Hg). There were 275 g of a compound of the formula

obtained (56 # conversion), 40g of the compound had the formula:

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Yield) and 147 g of l-acetyl - ^^ - dimethylcyclohexane.

If sodium hydride is used instead of sodium hydroxide, a compound of the formula

educated.

The NMR spectrum of the compound

is shown in FIG. 6 and its IR spectrum in FIG.

The NMR analysis is as follows:

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S, T / taiii.

0.74 (
0.90 (s, 3)

Explanation of methyl groups "A"

2.14 (s, 3) 4.8 - * 5.1 (m, 2)

»Oll

CH -, - group B CHg group C

5.4 -> 5.8 (m, 1)

The IR analysis is as follows:
C = O; 1690 cm " ¹
C = C; I66O

The mass spectral analysis is as follows: m / e = 95, 94, 69, 41, I09, 55, 194 (output peak)

The NMR spectrum for the compound:

is shown in FIG. The NMR analysis is as follows:

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, T / frill. 0.90 (s, 3 0.93 (s, 3

Explanation

Methyl groups "A ¹

2 , 2 - ♦ 2.65 (m, 5) CH ₂ • s "B" and H _c 4th , 60 -5.12 (m, 2) CH ₂ lljjtl 5 , 50 -5.95 (m, 1)

The mass spectral analysis is as follows:

m / e = 69, Hl * 55 * 41, 83, 139, 194 (output peak)

The NMR spectrum of the compound with the formula

(Stereo structure unknown)

(made using sodium hydride) is shown in FIG. 1 and the IR spectrum in FIG. 10.

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The NMR analysis is as follows:

f>

(Stereo structure unknown)

T / garbage.

Explanation
Methyl groups "A"

scattered allyl H resonances

Ht ₃ II

2.08 (d, 1) small connection J = (Hz) CH, "B '

The IR analysis is as follows: 1600 cm "¹; C = C
1700; C = O

The mass spectral analysis is as follows: m / e = III, 69, 55, ² U, ¹ V, 57, 290 (output peak)

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Example 15

A perfume composition was prepared by mixing the following components:

Components. lot

n-decylaldehyde 1 n-dodecylaldehyde 2 Methylnonylacetaldehyde 0.5 Linalool 50 Linalyl acetate 70 Phenylethyl alcohol 1 100 Petitgrain SA 20th Bergamot oil 30th alpha-methylionone 25th l-acetyl-3,3-dimethyl- (2-propenyl)
cyclohexane, prepared according to
Example 14 10 cyclized bicyclo C-12 compound,
produced according to Example 4 of
CAN-PS 854 225 (2O.IO.7O) 5 Isobornyl cyclohexyl alcohol 10 Benzyl acetate 25th 2-n-heptylcyclopentanone 5

This mixture has been evaluated and it has been found that there is a high degree of fullness and aftereffect in its new natural amber quality. The basic composition

mixed ^
Can be cooled with aqueous Alkonol / T and filtered to produce a finished cologne. This has an amber aroma that tends towards a woody amber note. The base composition can also be used to perfume soap or other toilet articles such as lotions, aerosols, sprays and the like.

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Example 16 Manufacture of a cosmetic powder preparation

In a ball mill, 100 g of talcum powder were mixed with 0.25 g of 1-acetyl-3,3-dimethyl- (2-propenyl) cyclohexane (Example 14) mixed. This powder mix had an excellent woody, earthy, amber flavor.

Example 17 Perfumed liquid detergent

Concentrated liquid detergents with woody, earthy and amber-like aromas (the detergents from the lysine salt of n-dodecylbenzenesulfonic acid according to the US Pat. No. 3,948,818) containing 1-acetyl-3 * 5-dimethyl- (2-propenyl) cyclohexane (Example 14) were made by homogeneously mixing the two ingredients. Due to increasing concentrations of 1-acetyl-3,3-dimethyl- (2-propenyl) cyclohexane) the woody, earthy, amber aroma has been intensified.

Example 18 Production of a cologne and handkerchief perfume

1-acetyl-3 »3-dimethyl- (2-propenyl) cyclohexane (Example 14) were at a concentration of $ 2.5 in 85 # aqueous Ethanol added to a cologne. The concentration for the handkerchief perfume was 20Ji (in 95 # aqueous Ethanol). Both the cologne and the handkerchief perfume received a clear and specific woody, earthy, amber aroma.

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Example 19 Manufacture of a cologne and a handkerchief perfume

The compound from Example 2 became a cologne at a concentration of 2.5 $ in 35 # aqueous ethanol and added to a handkerchief perfume at a concentration of 20Ji in 9556 aqueous ethanol. The connection 1-acetyl-3,5-dimethyl- (2-propenyl) cyclohexane in the compound of Example 15 gave a distinct and distinct strong woody, earthy, amber aroma note to both that Eau de Cologne as well as the handkerchief perfume.

Example 20 Manufacture of a soap composition

100 g of soap chips were mixed with 2 g of the compound from Example 15 until an essentially homogeneous one Mass was formed. The soap perfumed in this way had an excellent amber aroma with intense woody and earthy nuances.

Example 21 Making a DeterKenz Composition

100 g of a detergent powder (lysine salt of n-dodecalbenzenesulfonic acid known from US-PS 3,948,818) were 0.70 g the compound from Example 15 mixed until a homogeneous mass was formed. This composition was excellent Amber aroma with intense earthy and sweet woody nuances.

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Example 22 4Φ0

Raspberry spice mixture

The following basic mixture of a raspberry spice was made:

Components Parts by weight Vanillin 2.0 Maltol 5.0 p-hydroxybenzyl acetone 5.0 alpha-ionone ($ 10 in propylene glycol) 2.0 Ethyl butyrate 6.0 Ethyl acetate 16.0 Dimethyl sulfide 1.0 Isobutyl acetate 13.0 acetic acid 10.0 acetaldehyde 10.0

Propylene glycol 930.0

To half of this mixture was 2.0 # 1-acetyl-3,3-dimethyl- (2-propenyl) cyclohexane added and this mixture with a mixture without l-acetyl-3,3-dimethyl- (2-propenyl) compared cyclohexane. 0.015έ (100 parts / million) of each of the two test mixtures was added to water and examined .

It was found that the seasoning mixture with l-acetyl-3,3- (2-propenyl) cyclohexane Significantly sweeter aromas and a sweet raspberry, raspberry seed _- *.-like and sweet aftertaste and mouthfeel, properties that the base mix lacked. It follows that the 1-acetyl-3,3-dimethyl- (2-propenyl) cyclohexane the spice rounds off and contributes to a very natural fresh aroma and taste, like her can be found in fully ripe raspberries. The seasoning mixture with the seasoning additive according to the invention is therefore much better than the basic mix without additives.

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Example 23 A powder-seasoning mixture

20 g of the seasoning mixture from Example 22 were dissolved in a solution emulsified from 300 g acacia gum and 700 g water and the Emulsion with a "Bowen" dryer (laboratory model) (7.36 rtr / Min. Air and an inlet temperature of 260 ° C, an outlet temperature of 93 ° C and a speed of 50,000 rpm spray-dried.

B Persistently aromatic seasoning mixture The following mixture was prepared

Components parts by weight

Liquid raspberry seasoning

from example 22 20

Propylene glycol 9

(Silica made by the
Cabot Corporation, 125 High Street, Boston, Mass. 02110;
Physical characteristics: ₂

Surface area: 200 m / g

Nominal particle size: 0.012 ai

Density:. (2.3 lbs / 6u.ft.) 5.00 0 * 037 g / ccm

The Cab-0-Sil was made from the liquid raspberry spice mixture Example 22 dispersed with vigorous stirring until a viscous liquid was formed. The seasoning mixture A was then in an amount of 71 parts by weight to the viscous liquids given and this stirred at 25 ° C. After 30 minutes, a dry free flowing seasoning powder was obtained which persisted was spicy.

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Example 24

10 parts by weight of 50 Bloom pig skin gelatin were added to 90 parts by weight of water at a temperature of about 65 ° C. and the mixture was stirred until the gelatin was completely dissolved. After cooling the solution to about 48 ° C 20 parts by weight of the liquid seasoning mixture were added in Example 22, then homogenized, and an emulsion was formed, the particle size was in the range of 2-5 m. This mixture was kept at about 48 ° C so that the gelatin would not gel.

A coacervate was formed by adding 40 parts by weight of a 20 # solution of sodium sulfate. The addition was made slowly and evenly. In doing so, the gelatin molecules deposited evenly around each oil droplet as a core.

Gelling was effected by pouring the heated coacervate mixture into 1000 parts by weight of a 7 # aqueous sodium sulfate solution at 18 ° C. The resulting thickened coacervate _{could be} filtered and washed with water at temperatures below the melting point of the gelatin to remove the salt.

The filtered cake was in this example by washing with 200 parts (weight) of a 37 ^ formaldehyde solution in Water hardened. The cake was then washed to remove the residual formaldehyde.

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- ie -

Example 25

100 parts by weight of chicle were mixed with 4 parts by weight of the seasoning mixture from Example 24. To this mixture , 300 parts of sucrose and 100 parts of corn syrup were added. Was mixed in a ribbon blender with isolier th side walls, such as those sold by Baker Perkins Co..

The resulting chewing gum was cut into strips 2.54 cm wide and 0.254 cm thick and the length was 7 * 62 cm. While chewing this gum had a pleasant, long- lasting raspberry flavor.

Example 26 chewing gum

100 parts by weight of chicle were mixed with 18 parts by weight of the seasoning mixture from Example 25 and 300 parts of sucrose and 100 parts of corn syrup were added. It was mixed as in Example 25.

The chewing gum cut into strips had a pleasant, long-lasting raspberry flavor.

Example 27 Toothpaste preparation

The following separate groups were made from different components:

Parts by weight of ingredients

Group "A"

30,200 glycerin

15 x 325 distilled water

• 100 sodium benzoate

• I25 saccharin sodium

• 400 stannous fluoride

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group "B" 12,500
57,200 group "C" 2,000 group "D" 1,200 100.00 (Total Procedure:

⁴ IOH

Components

Calcium carbonate

Dicalcium phosphate (dihydrate)

Sodium N-Lauroyl Sarcosinate (foaming agent)

Seasoning mixture from example 23

1. The ingredients of group "A" were stirred and heated to 71 ° C. in a kettle surrounded by a steam jacket.

2. Stirring was continued for an additional 3 to 5 minutes to obtain a homogeneous To form gel.

3. The group "B" powders were added to the gel while mixing continued until a homogeneous paste was formed.

4. The seasoning mixture "D" was added while stirring, and finally the sodium n-lauroyl sarconizate.

5. The resulting slurry was mixed for 1 hour. The finished paste was placed in a three-roll mill and homogenized and finally filled into a tube.

The toothpaste obtained resulted in a pleasant raspberry flavor during normal use, which remained throughout the entire putting process (1 1/2 minutes) was very intense.

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Example 28 Chewable vitamin tablets

The seasoning mix from Example 24 became a chewable one Vitamin tablet preparation given, in an amount of 10 g / kg. The vitamin tablet preparation was made made by mixing in a Hobart mixer the following ingredients:

Vitamin C (ascorbic acid)

as an ascorbic acid-sodium ascorbate mixture 1: 1

Vitamin B, (thiamine mononitrate) as Rocoat ^ thiamine mononitrate 33 l / 3 # (Hoffman La Roche)

Vitamin B ₂ (riboflavin) as Rocoat & -Riboflavin 33 1/30 vitamin EL- (pyridoxine hydrochloride) V pyridoxine hydrochloride

as Rocoat
33 1/35 *

Niacinamide / C \

as Rocoat ViV niacinamide 33 1/30 Calcium pantothenate

Vitamin B ₁₂ (cyanocobalamin) as Merck 0.10 in gelatin Vitamin E (dl-alpha-tocopheryl acetate)

as dry vitamin E acetate 33 1/30 Roche

g / 1000 tablets 70.0

4.0 5.0

4.0

33.0 11.5

3.5

d-biotin

Approved opaque dye flavoring mixture from Example 24 Sweetener - sodium saccharin magnesium stearate as a lubricant mannitol q.s. up to

6.6 0.044 5.0 (as stated above)

1.0

20.0

500.0

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The preliminary tablets were punched out with flat punches manufactured. These tablets were then ground through a 5 DIN sieve and 13 and 5 g of dry vitamin A acetate and 0.6 g of vitamin D were added in the form of beads. The entire mixture was made 0.5 g with a concave punch Compressed tablets.

When chewing, there was a pleasant, long-lasting, steadily strong raspberry taste for a period of 12 minutes.

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- 9b -

Example 29 Production of l-acetyl-l-methylallyl-Q ^ -dimethylcyclohexane

1- (2-methylallyl-3-methyl-4-pentenoyl) - ^, 3-dimethylcyclohexane

Reaction:

Ci

ALIQUOT® 336 toluene

(Main product)

-1-

(By-product)

(By-product)

A slurry of 1-acetylO ^ -dimethylcyclohexane (624 g, 4 moles), granulated sodium hydroxide (24o _g , 6 moles), aliquot ^ 336 (tricaprylmethylammonium chloride / 35 g /), methallyl chloride (432 g, 4.8 moles) and 400 ml of toluene were refluxed for 4 1/4 hours. Then 1 liter of water was added to the cooled reaction mixture. The aqueous layer was discarded and the organic layer was rapidly distilled through a short column to give 203 g of regenerated 1-acetyl ^^ - dimethylcyclohexane, 500 g of l-acetyl> 3 »3-dimethyl-l-methallylcyclohexane and 73 g of 3» 3 -Dimethyl-l- (2-methallyl-5-methyl-4-pentenoyl) cyclohexane) (1-4 °, 3.0 mm Hg) containing 5% 3,3-dimethyl-l- (4-methyl-4- pentenoyl). A portion of the latter compound was determined by gas-liquid chromatography (l'x 1/4 "80Ji SE-30 packed column; 200 ⁰ C isothermal)

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and showed the following fragrance and flavoring properties:

Fragrance properties:

green;

herbaceous; melon-like; fruity; galbanum-like; gingery; and citrus-like.

Flavoring properties;

greasy;

Sweet;

fruity;

citrusy;

green;

vegetable-like; and waxy.

The NMR analyzes of the compounds indicated the following

• I - »» It \\

T-Mil .

0.92 (s, 3) O.94 (s, 3) Explanation of methyl groups "A"

I.7O (s, 6)

Methyl groups "C"

3.02 (quintet, 1, J = 6h) ¹¹ D

4.76 (d, 4, J_ = 8H) methyl groups "B"

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The IR analyzes gave the following data: C = O 1695 cm " ¹ C = CH ₂ 1635 cm" ¹

The mass spectral analysis showed: MW-262 (confirmed by GC-MS)

The NMR spectrum is in Figure 11 for 1-acetyl-3,3-dimethyl-1-methallyleyelohexane; the IR spectrum is shown in Fig. 12 for 1-acetyl-3 * 3-dimethyl-1-methallylcyclohexane.

The NMR spectrum for 3,3-dimethyl-1- (2-methallyl-5-methyl-4-pentenoyl) eyelohexane is shown in FIG. 13 and the IR spectrum in FIG. 14 shown.

Example 30
Reaction:

toluene

KOH

Il

A slurry of 1-acetyl-3 * 3-dimethylcyclohexane (156 g, 1 mol), potassium hydroxide (86 g, 1.5 mol) and toluene (300 ml) was heated to reflux. Methallyl chloride (135 g, 1.5 mol) was added to the thickened reaction mixture, whereupon the mass became liquid. The mixture was heated to reflux for 6 1/2 hours. After that it was at room temperature cooled and 500 ml of water added. The aqueous layer was discarded and the organic layer was distilled to regenerated l-acetyl-3 * 3-dimethylcyclohexane (86 g), l-Acetyl-3 * 3-dimethyl-l-methallylcyclohexane (67 g »containing

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- 99 -

2 $ 3 * 3-Dimethyl-1 - (4-methyl-4-pentenoyl) eye lohexane)

(NMR spectrum of Pig. 11; IR spectrum of Fig. 12 and 3,3-dimethyl-1- (4-methyl-4-pentenoyl) cyclohexane (12 g).

Example 31 reaction:

A mixture of l-acetyl - ^^ - dimethylcyclohexane (156 g, 1 mol), sodium hydroxide (60 g, 1.5 mol), methallyl chloride g, 1.5 mol) and triethylamine (10 g) was 12 hours

stirred and heated to 80 to 84 ° C. After that it was on Cooled to room temperature and added water with stirring. The aqueous layer was discarded and the organic Layer distilled. L-acetyl - ^^ - dimethylcyclohexane were obtained (62.4 g); l-acetyl-3,3-dimethyl-l- (2-methyl-2-propenyl) eyelohexane (80 g), (NMR spectrum Fig. 11; IR spectrum Fig. 12); and 3-3-dim.ethyl-1- (4-methyl-4-pentenoyl) cyclohexane (8g).

Example 32 reaction:

KO-t-Bu t-BuOH

.Cl

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A fresh solution of potassium t-butoxide was prepared by adding potassium metal (28 g, 0.72 mol) to 500 ml of anhydrous t-butanol under a nitrogen blanket. To this , l-acetyl - ^^ - dimethylcyclohexane was added and the resulting mixture was stirred at room temperature for 1 hour. Methallyl chloride (74.4 g, 0.8 mol) was then added and the reaction mixture stirred for an additional hour. It was then filtered in order to remove potassium chloride. The t-butanol was removed by evaporation on a rotary evaporator. The remaining oil was distilled to give a mixture of l-acetyl-3,3-dimethylcyclohexane, l-acetyl-5, ^ - dimethyl-l- (2-methyl-2-propenyl) eye lohexane (NMR spectrum Fig. 11 ; IR spectrum Fig. 12) and 3-3-dimethyl-1- (4-methyl-4-pen tenoyl) eyelohexane.

Example 33

Production of l-acetyl-3j3-dimethyl- (2-methyl-2-propenyl) eyelohexane

Reaction :

KO-t-Bu ^

18-crown-6 (dibenzoderivative)

A slurry of potassium hydroxide (84 g, 1.5 moles),

1-acetyl-3 » 3-dimethylcyclohexane (156 g, 1 mol), dibenzo-18-

Crowns-6 (3 g) of the formula

\ ~ y \ J

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manufactured by the Aldrich Chemical Company of Metuchen, New Jersey, and toluene (150 ml) was heated to reflux while the reaction mixture was thickened. After cooling on 70 ° C and addition of methallyl chloride (135 g, 1.5 mol), the reaction mixture became liquid. It was further refluxed Heated for hours and then cooled and water added. The aqueous layer was decanted and the organic layer was distilled and l-acetyl- ^ i ^ -dimethylcyclohexane (62 g) and l-acetyl-3,3-dimethyl-l- (2-methyl-2-propenyl) cyclohexane (83 g - NMR spectrum Fig. 11; IR spectrum Fig. 12) obtained.

Example 34

A tobacco blend was made from the following ingredients:

Components parts by weight

Bright 40.1

Burley 24.9

Maryland 1.1

Orient 11.6

Stem (flue cured) 14.2

Glycerin 2.8 water

This tobacco blend was used to make cigarettes with the following preparation:

Components weight point

Ethyl butyrate 0.05

Ethyl valerate 0.05

Maltol 2.00

Cocoa extract 26.00

Coffee extract 10.00

Ethyl alcohol 20.00

Water 41.90

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This seasoning mix was placed in model "filter" cigarettes in an amount of $ 0.1. A third of these Pro bezigaretten was in the tobacco sector with the mixture of l-acetyl-l-methallyl- ^ j ^ -dimethylcyclohexane and l- (2-methallyl-5-methyl-4-pentenoyl) -3, 3-dimethylcyc lohexane from the Example 29 in an amount of 100 t / mill. treated per cigarette. Another third of the sample cigarettes were made by treating the filter with the said

-5 Mixture prepared, in an amount of 2 10 -g and 3 χ 10 g. Comparative tests have shown that the cigarettes were treated in the tobacco and the filter in the smoke flavoring is a green, sweet, fruity, floral and reminiscent of Virginia tobacco spice and aroma nuances as well as exhibited in the main flow in the bypass, these nuances but also had before smoking.

Example 35

A tobacco blend was made from the following ingredients:

Components parts by weight

Bright 40.1 Parts by weight Burley 24.9 0.05 Maryland 1.1 0.05 Orient 11.6 2.00 Stem. (Flue cured) 14.2 26.00 Glycerin 2.8 water 5.3 From this mixture became Cigarettes made with the following seasoning mixture were treated: Components Ethyl butyrate Ethyl valerate Maltol Cocoa extract

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Parts by weight OO 10, 00 20, 90 41,

Components
Coffee extract
Ethyl alcohol
water

This seasoning mix was placed in sample "filter" cigarettes in the amount of $ 0.1. One third of the test cigarettes in the tobacco sector were treated with 1-acetyl-1-methallyl-3,3-dimethylcyclohexane, from Example 33 *, in an amount of 100 T / Mill. treated per cigarette. Another third of the sample cigarettes were treated in the filter material, namely in an amount of 2 o "- ⁵ g and 3 x 10 -g of the compound mentioned. It was found that the cigarettes treated in the tobacco and filter in the smoke wort a green, sweet, fruity, floral and spice and aroma nuances reminiscent of Virginia tobacco both in the main and in the side stream, but also had these nuances before smoking.

Example 36

A tobacco mixture identical to that in Examples 34 and 35 was made into cigarettes and treated with a seasoning mixture also specified in these examples, which was added in an amount of $ 0.1 to sample ¹¹ "filter" cigarettes.

One third of the sample cigarettes was 1-acetyl-1-methallyl-3,3-dimethylcyclohexane, produced according to Examples 30, 21 or 22 in the tobacco sector in an amount of 100 T / mill. brought in per cigarette. A further third this compound was incorporated into the filter material, and g in an amount of 2 χ 10 ^ g and 3 x 10 degrees. Comparative tests have shown that the cigarettes treated in the tobacco and filter have a green, sweet, fruity, flowery flavor and aroma reminiscent of Virginia tobacco.

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Had nuance in both the main and side stream, but also had these nuances before smoking.

Example 37 Orange seasoning

The following ingredients were mixed:

Components Parts

natural orange oil 13 * 00

Acetaldehyde 1.50

Ethyl acetate 0.10

Ethyl butyrate 0.50

Propanal 0.10

trans-2-hexenal 0.10

Ethyl alcohol (95 #) 60.00

Fusel oil 0.05

Propylene glycol 24.65

This seasoning mix was designated "A". A seasoning mix "B" was made by adding 1-acetyl-1- methallyl-3 »3-dimethylcyclohexane ($ 1 in ethanol) to seasoning mix" A "," B "in an amount of 2 parts per 100 parts" A "was added.

Each of the flavor compounds "A" and "B" has been g in an amount of 56-57 per 3 * 8 1 added to a Baume sugar syrup

together with water resulted in a drink. The seasoning mix "A" gave the drink an acceptable orange character.

However, the beverage treated with the seasoning mix "B" had better seasoning. The improvement brought about by the l-acetyl-l-methallyl-3,3- dimethylcyclohexane is due to the following reasons:

1 increase of the natural character of freshly squeezed oranges,

2. Greater depth of orange juice flavor.

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3example 38

Perfume composition Components parts

Linalool 30

Linalyl acetate 10

Terpineal-coeur 5

Nerol-coeur 10

Terpinylacetate 2

Geranyl acetate 2

Nerylacetate 2

Methyl anthranilate 1

Citral 10

n-decyl alcohol 1

n-dodecyl alcohol 5

n-dodecanal 15

n decanal 30

n-nonanol 3

n-nonanal 5

n-decyl acetate 5

n-dodecyl acetate 3

l-acetyl-l-methallyl ^^ - dimethyl-

cyclohexane (prepared according to Example 29) 5

The 1-acetyl-1-methallyl-3,3-dimethylcyclohexane imparted this terpeneless orange perfume a natural, bitter orange character.

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Example 39 reaction:

toluene

KOH

A slurry of 1-acetyl-3,3-dimethylcyclohexane (156 g, 1 mol), potassium hydroxide (86 g, 1.5 mol) and toluene (300 ml) was heated to reflux. Allyl chloride (114 g 1.5 mol) was added to the thickened reaction mass, whereupon it became more fluid. This mixture was 6 1/2 hours heated under reflux and then cooled to room temperature and treated with 500 ml of water. The aqueous layer was discarded and the organic layer was distilled, whereby 74 g of regenerated 1-acetyl- ^ i ^ -dimethylhexane, 53 g of 1-acetyl-3,3-dimethyl-1- (2-propenyl) cyclohexane, and 35 g of 3> 3-dimethyll- (4-pentenoyl) cyclohexane were recovered.

The NMR spectrum of the l-acetyl-3 * 3-dimethyl-l- (2-propenyl) cyclohexane is shown in FIG. 15 and the IR spectrum in FIG .

The NMR analysis showed:

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8. T / Mill 0.74 (s, 5th

Explanation

ITa »I

Methyl groups A

O. .90 (s, ³⁾ • (m, 2) CH -, - Group ¹¹ B " 2- 14 (s, (m, 1) Explanation 8th. T / Wed11 CH ₂ group "C" 4th 8 - »5.1 5. 4 -4 5.3

The IR analysis showed:

C = O; 1690 cm " ¹ C = Cj 1660

The mass spectral analysis showed:

m / e = 95, 94, 69, 109, 55, 194 (output peak).

The NMR analysis for 3,3-dimethyl-1- (4-pentenoyl) cyclohexane is in Flg. 17 and looks like this:

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0.90 (s, 3) methyl groups "A"

C, T-MlIl. Explanation

3.90 (s, 3) 0.93 (s, 3)

2.2 -2.65 (m, 5) CH ₂ ¹ S ¹¹ B "and H _c

4.60-5.12 (m, 2) CH ₂ "D"

5.50 -5.95 (m, 1)

The mass spectral analysis showed:

m / e = 69, 111, 55, 41, 83, 139, 194 (output peak)

Example 40 reaction:

^ v. NaOH

⁺ I I ^ - >

Cl

A mixture of 1-acetyl-3,3-dimethylcyclohexane (156 g, 1 mol), sodium hydroxide (60 g, 1.5 mol), allyl chloride (114 g, 1.5 mol) and triethylamine (10 g) was stirred and Heated to 80 to 84 ° C for 12 hours. After cooling the mass to room temperature, water was added with stirring and then the aqueous layer is discarded. The organic layer was distilled and 119 g of l-acetyl-3,3-dimethyl-

cyclohexane, 31 g of l-acetyl-3,3-dimethyl-l- (2-pentenyl) eyelohexane and 5 g of 3,3-dimethyl-1- (4-pentenoyl) eyelohexane obtained.

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The NMR spectrum for 1-acetyl-3,3-dimethyl-1- (2-propenyl) -cyclohexane is shown in FIG. 15 ; the IR-3 spectrum is shown in FIG. 16 and the NI-TI spectrum for 3,3-dimethyl-1- (4-pentenoyl) cyclohexane is shown in FIG .

example 41 ι
> ^ Κρ-t-Bu v ^ Reaction! + ^ I ^
^% I t-DuOH ' • χ: Y
O Cl Q

A fresh solution of potassium t-butoxide was made by adding of potassium metal (28 g, 0.72 mol) to 500 ml of anhydrous t-butanol under a nitrogen blanket bsrgssteXLt. To this 1-Acetyl-O ^ -dimethylcyclohexane was added to the reaction mixture and then the whole thing was stirred at room temperature for 1 hour. Then allyl chloride (63.2 g, 0.8 mol) added and stirred for a further hour. The reaction mixture was filtered to remove potassium chloride. That t ^ -butanol was driven off by evaporation in a rotary evaporator. The oil obtained was distilled and 78 g of a 13: 1 mixture of 1-acetyl-3,3-dimethyl-1- (2-propenyl) cyclohexane and 3,3-dimethyl-1- (4-pentenoyl) eyelohexane. The ratio was determined by reading a gas-liquid chromatography chromatogram certainly. (Gas-liquid chromatography conditions: 10 'χ 1/4 "10 $ SE-30 packed column, 200 ° C isothermal). 41 g of non-volatile substances fell also on.

D ^a s NMR spectrum for l-acetyl-3,2-dimethyl-l- (2-propenyl) cyclohexane 15 and the IR spectrum in Fig. 16 is shown in Fig.. The NMR spectrum for 3,3-dimethyl-1- (4-pentenoyl) cyclohexane is shown in FIG .

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-WtT-

Example 42 Production of 1-acetyl-3,3-dinethyl- (2-propenyl) eyelohexane

Reaction:

KO-t-Bu

18-J <ronen-6 (Dibenzo derivative)

A slurry of potassium hydroxide (84 g, 1.5 mol), 1-acetyl-3,3-dimethyl) cyclohexane (156 g, 1 mol), dibenzene-8-crown-6 (3 g) of the formula:

\ _ / V_y

manufactured by Aldrich Chemical Company of Metuchen, New Jersey, and toluene (150 ml) was heated to reflux, the mass becoming thick. It was cooled to 70 ° C and allyl chloride (114 g, 1.5 mol) added, causing the reaction mixture to become more fluid. It was taking another 9 hours Heated to reflux, then cooled and mixed with water. The aqueous layer was discarded and the organic Layer was distilled and thereby 24 g of 3,3-dimethylcyclohexane, 48 g of l-acetyl-3,3-dimethyl-l- (2-propenyl) cyclohexane and 90 g of non-volatile substances obtained.

The NMR spectrum for l-acetyl-3,3-dimethyl-l- (2-propenyl) -cyclohexane is in Flg. Ij? and the IR spectrum shown in FIG .

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Example 4?

Manufacture of l - (^ _f ^ -Dimethylc;, 'clohcxyl) ~ 4-n'ethyl · · cis- and trans- (2 and ^) - penten-l-one

Reaction:

NaOH

MeOU

A solution from 4? 4 g 1-acetyl - ;;, ^ - ^ 00 ml of methanol, 40 g of NaOH and 50 ml of toluene was up heated to reflux. For a period of 45 minutes 240 g of isobutyraldehyde was added dropwise. The reaction mixture was then taking an additional 90 minutes Heated to reflux, then cooled to room temperature and neutralized with hydrochloric acid. Methanol was through Distillation and the aqueous layer from the resulting two-phase system was removed by discarding. The organic Layer was washed once with water and rapidly distilled through a short column, whereby

a mixture of l- (3 * 3-dimethylcyclohexal) -4-methyl-cis_- and trans- (2 and 3) -penten-l-one (360 g, 58 $) / 112 to 117 ° C, 2.8 mm / and higher-boiling products were obtained as

OMe

have been identified.

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ORIGINAL INSPECTED

Another distillation of this mixture by a " 1 1/2 "χ 12 Goodloe column yielded the following fractions:

fraction
No. DamOftemp. Flow temp.
ro ο vacuum
mm Hg weight
(5) Reflux
relationship 1 85-101 128 2.8 6.6 9: 1 2 112 128 2.8 10.6 9: 1 3 112 128 2.8 16.6 9: 1 4th 112 132 2.8 12.9 9: 1 5 112 128 2.8 28.3 9: 1 6th 112 128 2.8 12.0 9: 1 7th 112 128 2.8 24.2 • 9: 1 8th 112 128 2.8 27.3 9: 1 9 114 134 2.8 27.1 4: 1 10 115 135 2.8 22.7 4: 1 11 115 137 2.8 26.9 4: 1 12th 115 140 2.8 25.7 4rl 13th 116 149 2.8 25.0 4: 1 14th 116 149 2.8 26.9 4: 1 15th 117 155 2.8 16.9 4: 1 16 122. 160 2.8 16.9 4: 1 17th 128 165 2.8 23.9 4: 1 18th 128 176 2.8 26.9 4: 1 19th 130 205 2.8 24.3 4: 1 20th 130 214 2.8 23.1 4: 1 21 130 219 2.8 25.5 4: 1 22nd 138 241 2.8 25.5 4: 1 23 149 250 2.8 11.7 4: 1

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Fractions 5 through 13 contained more than $ 99 of the desired product of the formulas:

and

The following fractions contained the following percentages of this mixture:

Parliamentary group no,

3 4

5-13 14 15 16 17 18

of the desired product

60 90

> 99 98 96 90 '60 20

With regard to the fragrance properties, the fractions 5 to 13 had fruity, woody, spruce needle-like aromas with St. John's wort-like, floral nuances and a light chocolate undertone.

In terms of flavoring properties, this material had a sweet, fruity, raspberry-like, woody, lemon-like, Spruce needle aroma with a sweet, raspberry and lemon flavor.

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3elsplel 44

Production of l- (3, ^ - Dimethy! Cyclohexyl) -4-methyl-cis- and trans- (2 and;?) - penten-l-one

Reaction:

CHO

HBO ₃ , B ₂ O ₃

A mixture of 1-acetyl- ^ i ^ -dimethylcyclohexane (462 g), Isobutyraldehyde (108 g), boric acid (6.2 g) and boron oxide (52 g) were stirred in an autoclave and heated to 150 ° C. for 5 hours. The solution was freed from the inorganic salts by filtration and washed three times with 10 ^ hydrochloric acid. The distillation gave 219 g of l-acetyl - ^^ - dimethyl-cyclohexane and 158 g! - (^ j ^ -DimethylcyclohexylJ ^ -methyl-cis- and trans- (2 and 3) -penten-l-one ($ 22, based on the added

thyJLcyc lohexane.

The l- (3 * 2-dimethylcyclohexyl) -4-methyl-cis- and trans- (2 and 3) -penten-l-one was determined by NMR and IR analyzes to be a mixture acts:

( ice and trans )

and

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The NMR spectrum for this mixture is in Flg. 13 and the IR spectrum shown in FIG .

The NMR analysis is as follows:

T / Wed 11 . Explanation

^{1 # 85 (s)} methyl groups "A"

1.87 (s)

CVJ CVI .62
.76 (d, J = 1 H ₂ )
(d, J = 1 H ₂ ) Methyl groups "C" % 2
2 .05
.1 (s)
(s) Methyl groups "B" 2, .5-2 ! .8 (wide multiplet) 5. .14 (d, J = 7H _Z ) CH ₂ group "Ξ" 5. , 28 (wide t, J = 71 ^) «Ρ 6th 0 and 6.28 (two multiplexes) H _Q 6th 68-6.92 (two multiplettes)

The UR analysis showed: 1665 cm " ¹

1690 (sh) 1720 (sh) 1620 cm " ¹ C = C

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Example 45

Synthesis of 1 - (^, ^ - Dimethy! Cyclohexyl) ice and trans- (2 and 3) -pent-1-one

Reaction;

ί L ^ S. + CC-CHO ^{2 S} ν, Γ Ί -

C-C = C-C-C

A mixture of 462 g of 1-acetyl- ^ i ^ -dimethylcyclohexane, 87 g of propionaldehyde, 52 g of boron oxide and 6.2 g of boric acid was heated ^{to 150 ° C. in an autoclave for 8 hours.} After cooling to room temperature, the solution was filtered and the inorganic salts were removed, the filtrate was washed once with aqueous sodium carbonate and twice with saturated salt solution. Distillation through a short column gave a mixture of 367 g of 1-acetyl- ^ i ^ -dimethyl-cyclohexane and 60 g of 1- (5, J5-dimethyl-cyclohexyl) -eis- and trans- (2 and I) -pentene -l-one ($ 20, based on the added propionaldehyde.

A portion of the distillate rich in desired products was passed through a 1.5 "x 12" Goodloe column distilled and the following fractions collected;

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fraction
No. Steam temp.
( ^δ c) River.TemO.
(OC) vacuum
mm Hg weight
(e) .2 Reflux
Proportions 1 1 55-52 105-103 2.5 10 .1 9: 1 2 52 109 2.2 11 .5 9: 1 3 60 126 2.0 5 .6 9: 1 4th 82 138 2.0 6th .0 4: 1 5 88 138 2.0 3 .3 4: 1 6th 90 140 2.0 5 .7 4: 1 7th 90 140 2.0 6th .7 4: 1 8th 90 144 2.0 6th .5 4: 1 9 90 154 2.0 6th .0 4: 1 10 95 181 2.0 7th .6 4: 1 11 93 220 2.0 2 4:

Fraction No. 7 had at 2 T / Mill. a sweet, raspberry-like, fruity, spruce needle-like, flowery, iononic aroma and a sweet, sweet-fifty, red berry, raspberry and spruce needle-like, flowery, ionon-like spice. The mixture l-O ^ -DimehtylcyclohexylJ-cis- and trans- (2 and 3) penten-1-one was determined using preparative gas-liquid chromatography evaluated and had the structural formula:

( ice and trans)

709829/107 2

The GC-MS profile of this mixture is shown in FIG. 20 , the NMR spectrum in FIG. 21 and the IR spectrum in FIG .

The NMR analysis showed:

C. , T / Mill. Explanation

1.95 (s, 6h) CH, groups "A

2. 08 (t, 3, J = ^ H ₂ ) CH, groups "B" 2. 25 (quintet, 2H, J = 8h _z ) CH ₂ groups "C" 2. 7-2.9 (broad multiplet, IH) H _D 6th 05 and 6.22 (two multiplettes) H-. 6th 75-7.05 (m, IH)

The IR analysis showed: C = O 1665 and 1685 cm " ¹ C = C 1620

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Example 4g

Hydrogenation of 1 - (;>, ^ - dimethylcyclohexyl) -4-ir.ethyl-cis and trans- (2 and pj-penten-1-one

Reaction:

V ^pd

Into a 250 ecm pair shaker was 107 g
l- (3 * 5-dimethylcyclohexyl) -4-methyl-cis- and trans- (2 and 3) penten-l-one - prepared according to Example 1 -; 1 g of a 5 $ palladium on carbon catalyst; and introduced 125 g of isopropyl alcohol. The shaker was sealed and at a pressure of 50 to 150
psig (hydrogen) heated to 125 ° C. The reaction mixture was held for about 1 1/2 hours in this pressure range and at this temperature. The reaction product was then filtered and placed in a 48 "Vigreaux column
distilled. The dates of the distillation were as follows:

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Steam temp.
(° C) - yar - vacuum
mm Hg 2700688 Reflux
relationship fraction
No. 67-89 Flow temp.
(° c) 2.2 weight
(R) 9: 1 1 91 118-126 2.2 3.8 9: 1 2 91 137 2.2 3.7 4: 1 3 91 129 2.2 7.4 4: 1 4th 91 129 2.2 8.6 4: 1 5 91 129 2.2 13.4 4: 1 6th 91. 129 2.2 14.0 4: 1 7th 91 131 2.2 15.2 4: 1 8th 94 156 2.2 14.7 4: 1 9 98 187 2.2 8.2 4: 1 10 240 3.5

With respect to a food condiment had 6 ^{v is} the fraction no. Susses a spruce needle-like, fruity, blueberry-like, woody aroma with sweet, piney, .fruchtigen, nut meat-like character.

From a perfumery standpoint, the merged had

in fractions No. 2 to 9 as a 10J6 solution / a pure alcohol a dark, sweet-woody aroma with chocolate-like nuances.

Fraction No. 7 was determined by NMR, IR and mass spectrum analyzes determined and the formula

determined.

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The NMR analysis showed:

θΓτ / trash. O.82-O.98 (m, 12H)

Explanation of CH, groups

2.43 (t, 2H,

Il Λ Η

Methylene "A

IR analysis found: 2950 cm " ¹ 2870 1700 1560 (C = O) 1390 1360

The mass spectral analysis found: 111, 41, 43, 69, 55 and 27

The NMR spectrum of this compound is shown in Fig. 23 and the IR spectrum in Fig. 24.

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Example 47 Raspberry seasoning

A raspberry spice was made from the following ingredients:

Components parts by weight

Vanillin 2.0 Maltol 5.0 p-hydroxybenzyl acetone 5.0 o (-ionone ($ 10 in propylene glycol) 2.0 Ethyl butyrate 6.0 Ethyl acetate 16.0 Dimethyl sulfide 1.0 Isobutyl acetate 15.0 acetic acid 10.0 acetaldehyde 10.0 Propylene glycol 930.0

To one half of this mixture were added 2.0 $ of the 1- (3,3-dimethylcyclohexyl) -4-methyl-cis- and trans- (2 and 3) · penten-1-one (prepared according to Example 43) was added. the Both comparison mixtures were added to water in an amount of $ 0.01 (100 parts per million) and evaluated.

The seasoning l- (3,3-dimethylcyclohexyl) -4-methyl-cis- and the sample containing trans- (2 and 3) -penten-l-one had significantly sweeter aromas and a sweet raspberry seed-like appearance and sweet aftertaste and mouthfeel, properties that the basic blend of raspberry flavoring does not exhibited. There is no doubt that the compound l- (3 * 3-dimethylcyclohexyl) -4-methyl-cis- and trans- (2 and 3) penten-1-one rounds off the spice and contributes to a very naturally fresh aroma and taste, as it is when fully ripe Raspberries can be found. As a result, the basic mix or raspberry seasoning mixed with this compound is better than those without the added seasoning

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Hf

Example 48 Raspberry seasoning

The same ingredients as in Example 47 were mixed together mixed.

To one half of this mixture was l- (3,3-dimethylcyclohexyl) -cis- and trans- (2 and 3) -penten-l-one, prepared according to Example 45, added in an amount of $ 2.0. The two Comparative products were each dissolved in water in an amount of $ 0.01 (100 tons / million) and the beverages produced in this way compared to each other. The l- (3, 3-dimethylcyclohexyl) -cis- and seasoning mix containing trans (2 and 3) penten-l-one had much sweeter aromas and a raspberry and raspberry seed-like, sweet aftertaste and a corresponding mouthfeel, which could not be found in the simple raspberry spice. It is obvious that the seasoning is added 1- (3,3-Dimethylcyclohexyl) -cis- and trans- (2 and ^) - penten-1-one the naturally fresh aroma and the naturally fresh taste rounds off and contributes to both that To evoke the aroma and taste of the fully ripe raspberries in the artificial seasoning.

Example 49 A powder seasoning mixture

20 g of the seasoning mixture from Example 4? was in a solution emulsified from ^ 00 g acacia gum and 700 g water. The emulsion was spray-dried with a Bowen dryer (laboratory model), with 7 * 36 nr / min. Air, one inlet temperature of 260 ° C, an outlet temperature of 93 ° C and a speed of 50,000 rpm.

B Persistent aromatic flavor

A seasoning mix with delayed release of the aroma was made from the following ingredients:

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Components parts by weight

Liquid raspberry spice mixture

from Example 47 20

Propylene glycol 9

Cab-O-Sil ^R M-5
(A silica made
from Cabot Corporation,
125 High Street, Boston, Mass.,
Physical characteristics: ₂
Surface area: 200 m / g
Nominal particle size: 0.012 λχ

Density: 0.037 g / ccm (2.3 lbs / cu.ft.) 5.00

The Cab-0-Sil was made from the liquid raspberry spice mixture Example 47 dispersed with vigorous stirring until viscous Liquid was formed. 71 parts by weight of the seasoning powder from part A was then stirred into this viscous liquid at 25 ° C. and after 50 minutes it was dry, free-flowing Powder formed which was persistently flavorful, d. H. exhibited delayed release of the wort.

Example 50

10 parts (by weight) of 50 Bloom pig skin gelatin was added to 90 parts by weight of water at a temperature of about 65 ° C added. The mixture was stirred until the gelatin was completely dissolved. After cooling the solution to about 48 ° C 20 parts by weight of the liquid seasoning mixture from Example 48 were added and then the solution was homogenized to a To form an emulsion whose particle size was in the range of 2 to 5 / U. The emulsion was held at about 48 ° C, so at a temperature at which the gelatin does not gel.

A coacervate was formed by slowly and evenly adding 40 parts by weight of a 20 # aqueous solution of sodium sulfate educated. During this process, the gelatin molecules were evenly deposited around each oil droplet as a core.

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The heated coacervate mixture was dissolved in 1000 parts by weight of a 7 ^ aqueous sodium sulfate solution at 18 ° C poured, whereupon the mixture gelled. To remove the salt, the gelled coacervate was filtered and washed with water washed at a temperature below the melting point of the gelatin.

In this example, the filter cake was washed with 200 parts by weight of a 57 # aqueous formaldehyde solution, to harden the filter cake. Excess formaldehyde was removed by washing.

Example 51 chewing gum

100 parts by weight of chicle were mixed with 4 parts by weight of the seasoning mixture from Example 49 and a further J500 parts Sucrose and 100 parts of corn syrup were added. Mixing was carried out with a ribbon mixer (Baker Perkins Co.) with jacketed Sidewalls.

The resulting chewing gum mixture was cut into appropriate strips that were pleasantly long while chewing had persistent raspberry flavor.

Example 52 chewing gum

A chewing gum mix was prepared as in Example 51, with the exception of the flavoring additive, which in this example consists of 18 parts by weight of the seasoning mixture from Example 50 consisted.

The resulting chewing gum mixture was cut into appropriate strips, which when chewed a pleasant, long-lasting Had raspberry wort.

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η?

Example 53 Toothpaste

The following separate groups were made up of different constituents manufactured:

Parts by weight group "A"

30th .200 .500 .000 15th .325 .200 .100 Group "C" .125 2 .400 Group "B" 12th 37

Group "D" 1,200

100.00

Components

Glycerin

distilled water sodium benzoate saccharin sodium Stannous fluoride

Calcium carbonate Dicalcium phosphate (dihydrate)

Sodium N-Lauroyl Sarcosinate (foaming agent)

Seasoning mixture from Example 49

Procedure:

1. The ingredients of group A "were stirred in a steam-jacketed kettle and heated to 71 ° C warmed up.

2. Stirring was continued for about 3 to 5 minutes to form a homogeneous gel.

3 «The powders in group" B "were added to the gel, stirring continuously until a homogeneous paste was formed.

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«J *

4. While stirring, the seasoning mixture from group "D" and finally the foaming agent from group "C" is added.

5. The resulting slurry was stirred or mixed for an additional hour. The finished paste was in Brought to a three roll mill where it was homogenized. Finally, the paste was filled into tubes.

The toothpaste produced in this way had a pleasant raspberry flavor, their intensity during the entire toothbrushing process (1 to 11/2 minutes) remained constant.

Example 54 Chewable vitamin tablets

The seasoning mixture from Example 50 became a preparation

given for chewable vitamin tablets , in an amount of 10 g / kg. The chewable vitamin tablets were made from the following ingredients, which were mixed together homogeneously in a Hobart mixer:

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Vitamin C (ascorbic acid)

an ascorbic acid sodium ascorbate

Mixture 1: 1

Vitamin B ₁ (thiamine mononitrate)

als Ro. ^ coat ^ ^y thiaminmonomitrat 33 l / 3 # (Hoffman La Roche)

Vitamin B ₂ (riboflavin)

as Ros & oat® riboflavin 33 Vitamin B, - (pyridoxine hydrochloride)

as Ro / ereoatviV pyridoxine hydrochloride 33/5

Niacinamide

as Ro / coatvS / niacinamid 33 calcium pantothenate vitamin B ₁₂ (cyanocobalamin) as Merck 6.1 $ in gelatin

g / 1000 tablets 70.0

4.0 5.0

4.0

33.0 11 * 5

3.5

Vitamin E (dl-cX tocopheryl acetate)

as dry vitamin 4-acetate 33 1/3 $ Roche

d-biotin

Approved color, seasoning mixture from Example 50, sweetener - sodium saccharin Magnesium stearate (lubricant) Mannitol q.s. up to

6.6 0.044 5.0 (as stated above)

1.0

20.0

500.0

The basic tablets were produced with a flat die and then ground through a 5 DIN sieve. 13.5 g of dry vitamin A acetate and 0.6 g of vitamin D were added as beads and the mixture is pressed into 0.5 g tablets with a concave punch

When chewed, these tablets had a pleasant, long-lasting, strong raspberry flavor that was constant over 12 minutes,

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Example 55 mixed together Blueberry fondant preparation Parts by weight There were the following components 0.25 Components 0.50 Cardamom oil 1.00 Clove oil 1.25 Galanga oil 2.50 Cinnamon oil 2.50 Coriander oil 22.00 Fennel oil 33.00 Amyl acetate Benzyl benzoate

1- (3, j5-dimethylcyclohexal) -4-

methyl cis and trans (2 and 3) -

penten-1-on - Group No. 6

from Example 4 0.1

The seasoning additive from Example 4 gives this preparation sweet, pine needle-like, fruity and woody nuances, making the taste and aroma more natural.

Example 56

The following ingredients were mixed to form a perfume composition:

Components Quantities (g)

n-decylaldehyde 1

n-dodecylaldehyde 2

Metnylnony / acetaldehyde 0.5

Linalool 50

Linalyl acetate 70

Phenylethyl alcohol 100

Petitgrain SA 20

Bergamot Oil 30

o (-Methylionone 25

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Components Quantities (g)

1- (3,3-dimethylcyclohexyl) -4-

methyl cis and trans (2 and 3) -

penten-1-one - manufactured by

Example 54 10

cyclized bicyclo C-12 material,

manufactured according to the process from

Example 4 of CAN-PS 854 225 5

Isobornyl cyclohexyl alcohol 10

Benzyl acetate 25

2-n-hepty / cyclopentanone 5

(Total)

It has been found that this mixture is rich and sustainable has natural amber quality. The base composition can be mixed with aqueous ethanol, cooled and filtered to form a finished cologne. A cologne produced in this way has an amber aroma that tends to have a woody amber note, with an excellent nuance of St. John's wort. The basic composition can also be used for perfuming soaps and other toilet articles such as lotions, aerosols, sprays and the like can be used.

Example 57 Manufacture of a cosmetic powder mixture

100 g of talcum powder were mixed with 0.25 g of l - ^^ - dimethylcyclohexylJ ^ -methyl-cis- and trans- (2 and 3) - penten-1-one from Example 44 in a ball mill. This mixture had an excellent, pine needle-like, woody, floral and fruity aroma.

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Example 53 Perfumed liquid detergent

Concentrated liquid detergents (lysine salt of n-dodecylbenzenesulfonic acid - described in U.S. Patent 3,948,818) with a pine needle-like, woody fragrance with a content of 0.10Ji; $ 0.15 and $ 0.20 of the link l-O ^ -DimethylcyclohexylJ-A-methyl-cis- and trans- (2 and 3) -pent-1-one from Example 44 were prepared by homogeneously mixing the ingredients. The intensity of the pine needle-like, Woody scent was mixed with increasing concentrations of 1- (3 * 3-dimethylcyclohexyl) -4-methyl-cis- and trans- (2 and 3) -penten-l-one increased.

Example 59 Production of a cologne and handkerchief perfume

The compound! - (^ i ^ -DimethylcyclohexylJ ^ -methyl-cis- and trans- (2 and j5) -penten-l-one from Example 44 was added in a concentration of 2.5% in 85% aqueous ethyl alcohol For the latter, in a concentration of 20% in aqueous ethyl alcohol, this compound gave both the colognes and the handkerchief perfume a distinct and definite needle-like, woody spicy note.

Example 60 Production of a cologne and handkerchief perfume

The compound 1- (3,3-dimethylcyclohexyl) -4-methyl-cis- and trans- (2 and 3) -penten-l-one from Example 56 was in a Concentration of $ 2.5 in 85 # ethyl alcohol at one Eau de Cologne and at a concentration of $ 20 in 95 # Ethyl alcohol added to a handkerchief perfume. The additive gave both products a clear and definite strong amber aroma with spruce needle-like, woody notes.

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Example 61

Making a perfumed soap

To 100 g enschn.itze Seif 1, 1 g of the compound l- (3,3-
DimethylcyclohexylJ - ^ - methyl-cis- and trans- (2 and j5) -penten-1-one given from Example 44 and the two ingredients
largely homogeneously mixed with one another. The soap produced in this way had an excellent woody, pine needle-like aroma.

Example 62

Making a Detergent composition

100 g of a detergent powder (lysine salt of n-dodecylbenzene sulfonic acid - described in US-PS 3948 8L8) were mixed with 0.15 g of the compound l- (3i3-dimethylcyclohexyl) -4-methyl-cis and trans (2 and 3) -penten-l-one mixed until homogeneous
Substance was formed. This had an excellent woody, pine needle-like aroma.

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Example 63

Synthesis of l - (^, 3-Dimethylcyclohexyl) -cis- and trans- (2 and 3) -butene-1-one

Reaction:

3C-CHO

B ₂ O ₅

H ₃ BO ₃

A mixture of 616 g of 1-acetyl-j ^ -dimethylcyclohexane (4 mol), 132 g of acetaldehyde (3 mol), 105 g of boron oxide (1.5 mol) and 12 g of boric acid (0.2 mol) was in an autoclave 3 Heated to 150 ⁰ C hours. After cooling to room temperature, the solution was filtered and the organic salts were removed. The filtrate was washed once with aqueous sodium carbonate and twice with saturated saline. Distillation through a short column gave 127.2 g of 1-acetyl-2,3-dimethylcyclohexane and 127.2 g of a mixture of l-Oj ^ -dimethylcyclohexylJ-cis- and trans-2-buten-l-one and l- OjjJ-DirnethylcyclohexylJ-J-buten-1-one.

A portion of the distillate rich in the desired products was distilled through a 1 "χ 12" Goodloe column and won the following factions:

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IIS

Fraction steam temp. Flow temp. Vacuum Weight Return Flow No. (QC) (° C) mm Hg (g) ratio

1 67-70 89-91 4.4-4.7 37.9 2: 1

2 70 95 4.9 40.9 2: 1

3 70 103 5.0 40.1 2: 1

4 74 113 5.0 29.9 2: 1

5 100 116 5.4 . 16.7 9: 1

6 102 123 4.8 17.1 9: 1

7 102 125 5.0 29.2 9: 1

8 112 131 8.2 20.7 9: 1

9 106 139 5.7 22.8 9: 1

104 154 5.2 13.3 9: 1 104 179 5.3 11.3 9: 1 100 202 5.2 6.7 9: 1

The pooled fractions 6 to 10 had one concentration of 2 T / Mill. a cedarwood-like aroma and a sweet, redberry-like, cedarwood-like spice

The mass spectral analysis showed:
180/69, 41, 39, 55, 165, 27

The NMR spectrum for fraction 9 is in Fig. 25 and that
IR spectrum shown in Fig. 26 .

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The NMR analysis gave the following data:

O.94 T / Mill. (s) gladly Dlmehtylpro tone 6 H

1 .74 - I.08 (m) - CH ₂ 0
η H - C. I. = C O
II 8th H 1 .90 (Duplicate with - C • C = C -C- AlIyI bond CH, - O
It 3 H 2 .74 (m) I. -C- HC
"I. - 1 H 6th .18 (broad doublet) 1 H

7.04-6.70 (m) 0

H 5

-C-C = C-IH

The IR analysis showed:

96Ο cm " ¹ , 1290,
I69O, 286Ο, 2940.

96Ο cm " ¹ , 1290, 136Ο, 138Ο, 1440, I625, I67O,

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Example 64

Hydrogenation of l- (3 »3-Diniethylcyclohexyl) -cis- and trans- (2 and 3) -butene-1-one

Reaction:

Into a 250 ecm Parr shaker was 107 g (6 moles) ! - (^, ^ - DimethylcyclohexylJ-cis and trans- (2 and 3) -buten-l-one from Example 1; Ig 5 # palladium on carbon catalyst and 125 S isopropyl alcohol. The shaker was closed tightly and heated to 125 ° C under a pressure of 50 to 150 psig hydrogen and then heated inside Conditions held for 1 1/2 hours. The reaction product was then filtered, and the solvent was evaporated off in vacuo and the oil obtained is distilled on an 8-plate Vigreaux column.

The dates of the distillation were as follows:

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Fraction steam temp. Flow temp. Vacuum weight reflux

No. (° C) (° C) (mm Hg) (g) ratio

1 86-89 100 4.6 9.0 11: 1

2 90 102 4.7 12.0 11: 1

3 90 102 4.6 8.8 11: 1

4 90 102 4.7 11.5 11: 1

5 90 105 4.6 14.0 11: 1

6 90 110 4.6 13.5 11: 1

7 90 113 4.6 8.4 11: 1

8 90 141 4.6 11.1. 11: 1

9 90 205 4.6 4.4 11: 1

From a perfumery standpoint, Group # 7 had one Concentration of $ 10 in pure alcohol a fruity, berry, herbaceous aroma with green, tobacco-like nuances.

The mass spectral analysis showed:
182/111, 69, 43, 41, 71, 55, 27

The NMR analysis gave for fraction 8:

0.90 T / Mill. (s) CH, - CH ₂ - 3H 0.91 T / Mill. (m) Dimethyl protons 6 H. 1.95-11.6 -CH ₂ - 10 H.

2.49 (t) 0

- CH ₂ - CH ₂ - C - 2 H

0 2.69-2.31 (m) H.

HC-C- ^x "

Example 65

A perfume composition was made from the following ingredients manufactured:

Components Quantities (g)

n-decylaldehyde 1

n-dodecylaldehyde 2

Methylnonyl acetaldehyde 0.5

Linalool 50

Linalyl acetate 70

Phenylethyl alcohol 100

Petitgrain SA 20

Bergamot Oil 30

<X-methylionone 25

1- (3,3-dimethylcyclohexy1) -

butan-1-one - manufactured by

Example 64 10

cyclized bicyclo C-12 material,

produced according to Example 4 of

CYN-PS 854 225 5

Isobornyl cyclohexyl alcohol 10

Benzyl acetate 25

2-n-heptylcyclopentanone 5

(total)

This mixture resulted in a perfume with a rich and lasting effect natural amber quality. This basic composition can be mixed with aqueous ethanol, cooled and filtered to give a finished eau-de-Cologne that has an amber aroma reminiscent of a woody amber note reminiscent, with excellent fruity and herbaceous nuances. The basic mixture can also be used to perfume soaps or other toilet articles such as lotions, aerosols, sprays and the like are used «

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example C6

Production of a cosmetic powder mixture

In a ball mill, 100 g of talcum powder with 0.25 g 1- (5 »3-Dimethylcyclohexyl) -butan-l-one from Example 64 mixed. This composition had an excellent fruity, berry, herbaceous aroma with greens and tobacco-like Nuances.

Example 67 Perfumed liquid detergent

Concentrated liquid detergents (lysine salt from n-dodecylbenzenesulfonic acid - described in US Pat. No. 3,948,818) with an herbaceous fragrance were obtained by mixing each with 0.10 #; $ 0.15 or $ 0.20 of the compound 1- (3,2-dimethylcyclohexyl) -butan-1-one made from Example 64. These mixtures all had an herbaceous flavor with green and tobacco-like nuances. The intensity of the fragrance was increased by increasing concentrations.

Example 68 Production of a cologne and handkerchief perfume

1- (3i3-Dimethylcyclohexyl) -butan-l-one prepared according to the example 64 was in a cologne at a concentration of $ 2.5 in 85 # aqueous ethanol; and in a concentration of $ 20 in 95 # aqueous ethanol. the The addition of spices gave both products a distinct and distinct herbaceous flavor.

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Example 69 Production of a cologne and handkerchief perfume

The compound l- (3,3-dimethylcyclohexyl) -butan-l-one from Example 65 was added in a concentration of 2.5% in the above aqueous ethanol to a cologne and in a concentration of 20% in 95% ethanol given a handkerchief perfume. This spice additive, together with a mixture from Example 3, gave a clear and distinct strong amber aroma with herbaceous and tobacco-like notes.

Example 70 Manufacture of a soap composition

100 g of soap chips were intimately mixed with 1 g of the compound 1- (3 * 3-dimethylcyclohexyl) butan-1-one from Example 64 g-mixed until the product was essentially homogeneous. The so scented soap had an excellent fruity, berry, tobacco-like aroma with green and tobacco-like nuances.

Example 71 Preparation of a detergent composition

100 g of a detergent powder (lysine salt of n-dodecylbenzenesulfonic acid - described in US Pat. No. 5,948,818) were with 0.15 g of the compound 1- (3,3-dimethylcyclohexyl) -butan-1-one from Example 64 mixed until homogeneous. This product had an excellent, fruity, berry, herbaceous Aroma with green and tobacco-like nuances.

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Example 72

Preparation of l-allyl-4- (4-methyl-3-pentenyl) -3-cyclohexene-1-carboxaldehyde and 1 hexene-1-carboxaldehyde

Reaction:

NaOH

Process steps:

A slurry of 289 grams of allyl chloride; 180 grams of granulated sodium hydroxide; 400 ml of toluene; 25 g of ALIQUAT 336 QP _and 576 g of a mixture of 4- (4-methyl-3-pentenyl) -3-cyclohexene-1-carboxaldehyde and 3 - (^ - methyl-3-pentenyl) -3-cyclohexene-carboxaldehyde Heated under reflux for 7 hours. Water was added to the cooled reaction mass and the organic phase formed was separated off and washed twice with water. Distillation through a short column gave an oil which contained 38I g (55 #) of the product (boiling point 140 to 144 °, 1.5 mm). It was purified by fractional vacuum steam distillation through a 1 "χ 12" Goodloe column (boiling point II3 to 120 °, 1.5 mm at a vapor rate of 1.6 ml of fl. H ₂ O / min.

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The NMR data for the mixture described above are as follows

, T / Wed 11. ι

1.08 (3, s) 1.02 O, s)

Explanation

tl_ ff

Methy! Groups a

1.79 (2, d, J = Hz)

Methylene groups (b)

9.05 (1, s)

-C-H

The Ht data of the mixture is: 1712 cm " ¹ ^ C = O

160 cm " ¹ / C = C ^

The mass spectral data are: 41, 69, 93, 39, 91, 79

The NMR spectrum of the reaction product is shown in FIG. 29 and the IR spectrum in FIG .

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Example 73

A perfume composition was made from the following ingredients:

Components Quantities (g)

n-decylaldehyde 1

n-dodecylaldehyde 2

Methylnony / acetaldehyde 0.5

Linalool 50

Linalyl acetate 70

Phenylethyl alcohol 100

Petitgrain SA 20

Bergamot Oil 30

0 (-Methylionone 25

Geraisch from l- (2-propenyl) - (4-methyl-3-pentenyl- _i A _k 3-cyclo-hexene-l-carbox-

aldehyde (s) τ from Example 72 10

cyclized bicyclo C-12 material -

produced according to Example 4 of

CAN-PS 854 225 5

Isobornyl cyclohexyl alcohol 10

Benzyl acetate 25

2-n-hepty / cyclopentanone 5

353.3 (total)

This blend had a rich and consistent natural fruity quality. The basic composition can be mixed with aqueous Ethanol can be mixed, cooled and filtered to make a finished cologne, This has a fruity aroma, which tended to have a lavender-like note The composition can also be used to perfume soap or other toiletries, such as lotions, aerosols, sprays and the like can be used.

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example Ik Manufacture of a cosmetic powder mixture

In a ball mill, 100 talc powder with 0.25 g the l- (2-propenyl) - (4-ethyl-5-pentenyl) - Δ -cyclohexenl-carboxaldehyde (e) from Example 72 mixed. This product had an excellent fruity, lavender-like note Citrus and balm nuances.

Example 75 Perfumed liquid detergents

Concentrated liquid detergents with fruity, lavender-like properties Notes and citrus and balsan nuances were created by adding and homogeneously mixing l- (2-propenyl) - (4-methyl-3-pentenyl) -A -eyelohexen-l-carboxyaldehyde (en) - (manufactured according to Example 72) - produced. These detergents all had a fruity, lavender-like note with citrus and Balm nuances. The seasoning intensity was increased with larger concentrations The detergents themselves were made from the lysine salt of n-dodecylbenzenesulfonic acid manufactured according to US Pat. No. 3,918,818).

Example 76 Production of a cologne and handkerchief perfume

1- (2-propenyl) - (4-methyl-3-pentenyl) - ^ -cyclohexene-1-carboxaldehyde from Example 72 was in a cologne at a concentration of $ 2.5 in an 85 ^ aqueous Ethanol solution; and incorporated into a handkerchief perfume at a concentration of $ 20 in 95 # aqueous ethanol. Both the cologne and the handkerchief perfume received a distinct and definite fruity, lavender-like appearance Note with citrus and balsam nuances.

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Example 77 Production of a cologne and handkerchief perfume

The composition from Example 2 was placed in a cologne at a concentration of 2.5 ^ in 85% aqueous Ethanol; and incorporated into a handkerchief perfume at a concentration of $ 20 in 85 # aqueous ethanol. The usage of l- (2-propenyl) - (4-methyl-3-pentenyl) - -cyclohexene-l-carboxaldehyde (en) in the composition according to Example 73 resulted in a distinct and certain fruity, Lavender-like note with citrus and balsam nuances.

Example 78 Manufacture of a soap composition

100 g of soap chips were mixed largely homogeneously with 2 g of the composition from Example 73. The one so perfumed Soap had an excellent fruity, lavender-like note with citrus and balsamic nuances.

Example 79 Preparation of a detergent composition

100 g detergent powder (lysine salt of n-dodecylbenzenesulfonic acid according to US-PS 3 9 ^ 8 818) were with 0.70 g of the composition from Example 73 mixed homogeneously. This mixture had an excellent fruity, lavender-like note with citrus and balm nuances.

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Example 8O Basic composition of a chocolate spice

The following ingredients were mixed:

Components parts by weight

Dimethyl sulfide 1.0

Isobutyl acetate 1.0

Isoamyl acetate 1.0

Phenyl ethyl acetate 0.5

Diacetyl (IO56 in ethanol) 0.5

Furfural ($ 50 in propylene) 0.5

Isoamyl alcohol 1.0

^ -Butyrolactone 5 * 0

Acetophenone 0.5

Benzaldehyde 1.0

Phenylacetic acid 2.0

Maltol 3.0

Acetaldehyde 2.0

Isobutyraldehyde 8.0

Isovaleraldehyde 15.0

Phenylethyl alcohol 8.0

Vanillin 15.0

Propylene glycol 40.0

100.0 (total)

15% by weight of the mixture were added to this mixture 1-Allyl-4- (4-methyl-3-pentenyl) -3-cyclohexene-1-carboxaldehyde and l-allyl - ^ - O-methyl-J-pentenylJ - ^ - cyclohexene-l-carboxaldehyde from Example 72 given. A sample of the composition contained no seasoning additive. The one mixed with the seasoning additive Serving was in an amount of 5 t / ml11. put in water and compared with the same preparation of the unseasoned portion. The seasoning added added flavor to the chocolate preparation a special spicy note and in an amount of $ 15 a characteristic cocoa butter aroma with corresponding taste characteristics was determined.

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If the connection l
Hexen-1-carboxaldehyde is added in an amount of 0.3 to the same basic composition for chocolate, a fuller, more cocoa powder-like aroma and corresponding taste notes are produced than with a composition without added spices and at an amount of 5 T / mill. in water.

Thus the l-allyl- (4-methyl-3-pentenyl) -3-cyclohexene-1-carboxaldehydes improve surprisingly and unexpectedly very beneficial the cocoa and chocolate notes as well as the Cocoa butter characteristics in chocolate.

Example 81

A. Powder seasoning mix

20 g of the seasoning mixture from Example 80 were emulsified in a solution of 200 g of acacia gum in 700 g of water. The emulsion was spray dried with a Bowen dryer (laboratory model). Was carried out with 7, 36 nr / min. Air, an inlet temperature of 260 ° C, an outlet temperature of 93 ° C and a speed of 50,000 rpm.

B. Persistent Seasoning (Delayed Release) The following mixture was prepared: Ingredients Parts by weight

Liquid chocolate spice

from example 80 20

Propylene glycol 9

Cab-0-Sil (as in Example 23

described) 5 * 00

The Cab-O-Sil was made in the liquid chocolate condiment Example 80 dispersed with vigorous stirring until a viscous liquid was formed. In this liquid were then 71 parts by weight of the seasoning powder from part A. mixed in with stirring. The temperature was 25 ° C and were stirred 30 minutes. A dry, free-flowing powder was formed

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ftf

Example 82

10 parts by weight of 50 Bloom pig skin gelatin was added to 90 parts by weight of water at a temperature of about 65 ° C. The mixture was stirred until the gelatin was completely dissolved. The solution was cooled to about 43 ° C. and 20 parts by weight of the seasoning mixture from Example 80 were added. An emulsion was formed by homogenization, the particle size of which was in the range from 2 to 5 λχ . A temperature of about 48 ° C was maintained to prevent the gelatin from gelling.

By slowly and evenly adding 40 parts by weight a 20 $ 6 aqueous solution of sodium sulfate became a coacervate educated. During this process, the gelatin molecules are deposited evenly around every oil droplet that formed a core.

This coacervate mixture was heated in 1000 parts by weight of a 7 ^ aqueous sodium sulfate solution poured at 18 ° C, whereupon gelation occurred. The gelled coacervate can be filtered and treated with water at temperatures washed below the melting point of the gelatin to remove the salt.

The filtered cake was in this example by washing with 200 parts by weight of a 37 # formaldehyde solution in Water hardened. Remaining formaldehyde was washed away.

Example 83

100 parts by weight of chicle were mixed with 4 parts by weight of the seasoning mixture from Example 81, with 500 parts of sucrose and 100 parts of grain syrup mixed. A jacketed ribbon mixer (Baker Perkins Co.) was used for this. The received The mass was cut into strips as they would be used for chewing

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rubber are common. When chewing became a pleasant, long-lasting Chocolate spices noted.

Example 84

chewing gum

100 parts by weight of chicle were mixed with 18 parts by weight of the seasoning mixture from Example 82 and a further 300 parts Sucrose and 100 parts of corn syrup were added. It was also mixed here with a ribbon mixer. The ones in strips chewing gum had a pleasant, long-lasting chocolate flavor during chewing.

Example 85 toothpaste

The following separate groups of ingredients were made:

Parts by weight of ingredients

Glycerin
distilled water

Components sodium benzoate saccharin sodium stannous fluoride

Calcium carbonate

Calcium phosphate (dihydrate)

Sodium N-Lauroyl Sarcosinate (Foaming agent)

Seasoning mixture from Example 81

group "A" "B" 30,200 15,325 Parts by weight "C" .100 .125 "D" 400 group 12,500 37,200 group 2,000 group 1,200

100.00 (total)

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Procedure;

1. The ingredients of group "A" were stirred and brought to 71 ° C in a steam-jacketed kettle warmed up.

2. Stir for an additional 5 to 5 minutes to allow a to form homogeneous gel.

J5. The group "B" powders were added to the gel, while mixing until a homogeneous paste was formed.

4. While stirring, the seasoning mixture "D" and finally the sodium N-lauroyl sarcosinate was added.

5. The obtained slurry was mixed for 1 hour, the finished paste is placed in a three-roll mill, homogenized and then filled into tubes.

The toothpaste produced in this way had a pleasant chocolate spice of constant strong intensity during normal toothbrushing the whole time (1 to 1 1/2 minutes).

Example 86 Chewable vitamin tablets

The seasoning mixture from Example 82 became a chewable vitamin tablet given in an amount of 10 g / kg. The vitamin tablets were made up by mixing in a Hobart mixer The following components are manufactured:

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g / 1000 tablets

Vitamin C (ascorbic acid)

as ascorbic acid sodium ascorbate

mixture 1: 1 70.0

Vitamin B, (thiamine mononitrate)

as Ro ^ coat ^ thiamine mononitrate

33 1/3 ^ (Hoffman La Roche) 4.0

Vitamin B ₂ (riboflavin)

as Rocoat® riboflavin 33 l / 3 # 5.0

Vitamin Bg (pyridoxine hydrochloride)

as RocoatC / pyridoxine hydrochloride
33 l / 3 #

Niacinamide ^

as Rocoat ^ niacinamide 33 1/3 # 33.0

Calcium pantothenate 11.5

Vitamin B ₁₂ (cyanocobalamin)

as Merck $ 0.1 in gelatin 3.5

Vitamin E (dl - ^ - tocopheryl acetate)
as dry vitamin E acetate 33 1/3 $ Roche 6.6

d-biotin 0.044

approved dye 5.0

Seasoning additive from Example 82 (as stated above) Sweetener - Sodium Saccharin 1.0

Magnesium stearate lubricant 20.0

Mannitol q.s. up to 500.0

First of all, tablets were produced with a flat punch and these were ground through a 5 DIN sieve. 13.5 g dry Vitamin A acetate and 0.6 g of vitamin D were given as beads added and the mixture pressed into 0.5 tablets with a concave punch.

When chewed, these tablets had a pleasant, long-lasting feel Spicy aroma of chocolate that lasted about 12 minutes.

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Example 87 Tobacco blend

The following ingredients were mixed:
Components parts by weight

Bright 40.1

Burley 24.9 Maryland 1.1

Orient 11.6

Stem (flue-cured) 14.2 Glycerin 2.8

Water 5.3

Cigarettes were made from this tobacco mixture.

The following seasoning mixture was produced:
Components parts by weight

Ethyl butyrate, 05

Ethyl valerate 05

Maltol 2.00

Cocoa extract 26.00

Coffee extract 1O, 00

Ethyl alcohol 20.00

Water ^ l »90

This seasoning mix was available in an amount of $ 1.0 at all Cigarettes made from the tobacco mixture are added. Half of the cigarettes were then with 500 or 1000 T / mill. of the mixture according to Example 1 of l-allyl-3 and 4- (4-methyl-3-pentenyl) -Z \ -eyelohexene-1-carboxaldehydes treated. The unseasoned and flavored cigarettes were then compared with each other and it was found that the Spiced cigarettes have a better smoking experience with more smoke bodies and a fuller smoky body feeling in the mouth. The tobacco-like notes were increased and the tobacco spiciness was more aromatic when smoked with cocoa liquor, sweet-rich

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and creamy-oily notes.

In addition, even before smoking, these spiced cigarettes had cocoa-like, sweet-rich and creamy-oily notes, All cigarettes were fitted with a 20 mm cellulose acetate filter.

Example 88

A slurry of 289 grams of allyl chloride; 252 grams of potassium chloride flakes; 400 ml of toluene, 40 g of 18-crown-6 of the formula

ο .0 ο \ / \ Y

and 576 g of myracaldehyde was refluxed for 3 hours. The reaction mixture was treated as in Example 1 to give 287 g of a mixture of the compounds of the following structural formulas to build:

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Example 89

A slurry of 289 grams of allyl chloride; I80 g of granulated Sodium hydroxide; 400 ml of toluene; 40 g of triethylamine; and 576 g of a mixture of myracaldehyde was 8 hours heated under reflux. The reaction mixture was treated as in Example 1 to give 240% of a mixture of compounds to form the following structural formula :.

and

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Claims (1)

Claim 1 ν Process for the production of a h ^ r.ermoiekularen carbonyl compound, characterized in that a substituted halide or substituted aldehyde with a carbonyl compound according to the reaction formula C. 11 RX / f < + Base or
Boron oxide "!
Boric acid-I
Mixture / is reacted, wherein each of the groups F ₁ = C and Fp = C is alkylidene, alkenyl, alkadienyl, cycloalkyl, cycloalkenyl or each of the groups completes a cyclic group; wherein R _{11 is} hydrogen, an alkyl, alkenyl or methylene group; R ₁ ^ hydrogen, ei'ie alkyl, alkenyl, methylene or alkylidene group can be; where O (denotes a reaction accelerator such as a quaternary ammonium salt or toluene; the dashed line can be a covalent bond or no bond at all; wherein each group F ₁ = C and Fp = C completes a cyclic group if the dashed line is a covalent bond ; wherein further R _{12 is} a benzyl, prenyl, allyl or methallyl group when X _{11 is} chlorine or bromine; or R ₁₂ Xi _{1 is} an acyclic aldehyde, where X _{11 is} an oxocarbonyl group; in which E, u is identical to R ₁₁ and R ^ _{1 are} hydrogen when R ₁ - is identical to R ₁₂ J if Hydrogen is any F ₁ = C and 709829/1072 ORIGINAL - Y an acyclic alkylidene, acyclic alkenyl, acyclic alkadienyl, cycloalkyl, cycloalkenyl, substituted cycloalkyl or substituted cycloalkenyl group and the dashed line denotes no bond; in which, furthermore, if each of the groups P - \ = C and? ₉ = ^ is a cycloalkyl group, R _{11 is} the methyl group, the dashed line is not a bond, (i) R ₁ ^ is the! - "ethyl group, R- ^ _{1 is} hydrogen and R _{12 is} identical to R ₁ - or (ii) R ₁ ^, hydrogen, R ^ ₁ hydrogen and R ^ _2. groups which have one of the structural formulas: UC H in what then, if or -Ο Ι
μ 12th the methylene group of the formula -CH ₂ - is, each of the groups: and F ₂ = C- completes a cyclopentyl ring and the dashed line represents a carbon-carbon double bond; and in which then, when R, is not hydrogen, R, - two to the C- Atom-bonded groups, (i) and (ii) R or R ₁ ^ can be a substituent which can be the same as R ₁₁ and R ₁₂ and R, ^ is identical to R ^ ₁ . 709829/1072 ORIGINAL INSPECTED 2. The method according to claim 1, characterized in that an aldehyde of the formula R ₄ M ^ R, -C C C-C ^ ir β μ ^V H is prepared by a halide of the formula R ₁ X with an unsaturated aldehyde of the formula ² H ~~ intimately mixing in the presence of an alkali metal hydroxide, an inert solvent and a "phase converter" wherein one of the dashed lines represents a double bond and the other dashed line represents a single bond; wherein R, an allyl or benzyl group, Rp an alkyl, aryl, alkenyl or alkoxyalkyl group and R, and R ₁ , hydrogen or an alkyl group, with the proviso that when R ^ is an alkyl group, the dashed Line between the ß-C atom and the YCA torn a double bond and if R, is hydrogen,
represent attachment. R, is hydrogen, one of the dashed lines is a double , The method according to claim 1, characterized in that a cis-jasmone of the formula is prepared by taking 5-methylcyclopentenone-2 of the formula 709829/1072 ORIGINAL INSPECTED- . -n with a cis-pentenal halide of the formula in the presence of a base and a "phase uniwanälcr" egg general formula N- -R is intimately mixed, wherein at least one R ^ ₁ * and R ^ Cg-C ^ -aryl, Cg-C - ^ - aralkyl, ^g ^ - ^c ₂ q Cg-C, ^ - alkaryl and Cg-Cp ₀ -Alkenyi and the other group R _{2 + 2} , R ^, and R ^ is an alkyl, such as methyl, ethyl, n-propyl, i-propyl, 1-butyl, 2-butyl, l-ethyl-2-propyl, 1-pentyl or 1-octyl and z "denotes an anion such as chloride, bromide or hydroxide and X denotes chlorine or bromine, the reaction being carried out in a liquid two-phase system. 4. The method according to claim 1, characterized in that a compound of the formula 709829/1072 OiFiIGiNAL INSPECTED where R, or one or both of R and / or R ^ groups mean allyl or methallyl and the other group of R, and R _? and / or R- represents hydrogen, v / o in the case of an allyl halide or a methallyl halide with I-acetyl-3,3-dimethylcyclohexane in the presence of (i) a base and (2) a reaction accelerator such as crown ethers, tertiary amines, toluene , t-3utanol or mixtures thereof is intimately mixed. 5. Connection established by the method according to claim 1, characterized by the general formula wherein the group C = F, a cycloalkyl group or a cycloalkenyl group having 6 carbon atoms which may be substituted or non-substituted, wherein either (i) Rp, hydrogen, and R ₂₂ ^e i ⁿ C-atom substituted by one or zv / one of the groups: or CW = CH ₃ 709829/1072 ORIGINAL INSPECTED (in which RpL is an alkyl group, such as ethyl, alkenyl or alkylidene) or (ii) Rp _{2 is} the methyl group or 'is hydrogen and Rp, an allyl or methallyl group, is one of the formulas or Ctf, represents; where the group C = F ^ _{1 means} an acyclic hydrocarbyl group, in which case the compound is 2,4,7-trimethyl-2,6-octadienal. 6. A compound according to claim 5> characterized in that it is a derivative of 1-acetyl -;), ^ - dinethylcyclohexane of the formula where one of the dashed lines is a carbon-carbon single bond or one carbon-carbon double bond and the other of the dashed lines one Carbon-carbon single bond and R is hydrogen or mean the methyl group. 7 ο compound according to claim 5 * characterized in that it is l-butenoyl- ^ i ^ -dimethylcyclohexane of the formula 709829/1072 ORIGINAL INSPECTED where one of the dashed lines is a carbon-carbon -Double bond and the other of the dashed lines represents a carbon-carbon single bond, 8. A compound according to claim b, characterized in that it 1-acetyl-3,3-diraethyl- (2-propenyl) cyclohexane of the formula is. 9. Compound or mixture of compounds according to claim L>, characterized in that they contain either l- (2-propenyl) -3- (4-methyl-3-pentenyl) -A -eye lohexene-1-carboxaldehyde or l- ( 2-propenyl) -4- (4-methyl-3-pentenyl) -J \ -eyelohexen-1-carboxaldehyde of the formula is in which the carboxaldehyde group is either on the c? {- C atom or is bonded to the ß-C atom of the cyclohexenyl group. 10. A compound according to claim 5 * characterized in that it Is 2,4,7-trimethyl-2,6-octadienal. 11. A process for preparing the compound according to claim 8, characterized in that an allyl halide with 1-acetyl-3,3-dimethylcyclohexane in the presence of a Phasenumwandlers and an alkali metal is intimately mixed. 709829/1072 ORIGINAL INSPECTED 12. A method for producing the compound according to claim ü, characterized in that an aldehyde of the formula with l-acetyl- ^ j ^ -dimethylcyclohexane in the presence of a substance the groups (i) mixture of boron oxide and boric acid or (ii) inorganic base is intimately mixed. 13. Process for the preparation of the compound according to claim 9 * characterized in that an allyl halide with myracalkdehyde is intimately mixed in the presence of a phase converter and an alkali metal hydroxide. 14. Compound of the general formula: wherein the group C = F, a cycloalkenyl group or a cycloalkenyl group with 6 carbon atoms, which can either be substituted or unsubstituted and either (i) Rp _{1 is} hydrogen and Rp _{2 is} a carbon atom, which is replaced by one or two of the groups: 709829/1072 ORIGINAL INSPECTED C- H -R CW ₃ or CK, is substituted (where R 1 is an alkyl group, four alkenyl, or alkylidene); or (ii) R _{2P is} the methyl group or hydrogen and R _{21 is} an allyl or methailyl group of one of the formulas or represent or the group C = P ^, an acyclic hydrocarbyl _____ ^ j group, in which case the compound is 2,4,7-trimethyl-2,6-octadienal. 709829/1072 Compound according to claim 14, characterized in that it a derivative of 1-acetyl -;?, J'-dimetr.ylcyclohexar. the formula is where one of the dashed lines is a carbon-carbon -Single bond or a carbon-carbon double bond and the other dashed line is a carbon-carbon single bond and R is either hydrogen or represent the methyl group. 16. A compound according to claim 14, characterized in that it is l-3utencyl-3i3-dimethylcyclchexane of the formula is where one of the dashed lines is a carbon-carbon -Double bond and the other of the dashed lines is a carbon-carbon single bond. 17. A compound according to claim 14, characterized in that it is l-acetyl-3 * 3-dimethyl- (2-propenyl) cyclohexane of the formula is. 709829/1072 ORIGINAL INSPECTED l8. A compound or a mixture of the compounds according to claim 14, characterized in that the * connections are either 1- (2-propenyl) -3- (4-methyl-3-pentenyl) -Δ -eyelohexene-1-carboxaldehyde or 1- (2-propenyl) -4- (4-methyl-p-pentenyl) - -cyclohexene-1-carboxaldehyde of the general formula are, in which the carboxaldehyde group is bonded either to or to the ß-C atom of the cyclohexenyl group. 19 · Connection according to claim 14, characterized in that it Is 2,4,7-trimethyl-2,6-octadienal. 20. Use of the prepared by the process according to claim 1 Compound or compounds as a seasoning for perfumery articles, foodstuffs or tobacco articles. 709829/1072