DE2750206A1 - NORBORNAN DERIVATIVES, PROCESS FOR THEIR PRODUCTION AND THEIR USE AS ORGANOLEPTIC SUBSTANCES - Google Patents

Description

Applicant: International Flavors & Fragrances Inc.,

521 West 57th St. New York, N.Y. IQOI9 - V.St.A.

Norbornane derivatives, process for their preparation and their use as organoleptic substances

It has been found that with one or more substituted norbornane derivatives of the general formula

New solid and liquid foods, chewing gum, medical products and toothpastes as well as spices can be created whose aroma is fruity, spruce / green, wine-like, fruit ester-like, reminiscent of cedarwood, flowery, woody, balsamic-resin-like, sweet, fruity-berry-like , berry-like incense-like, minzartig, en balsam, blueberries, spruce

809-21 / 0723

_ _r _

reminiscent, green-fruity and / or spruce needle / green and spruce-like, eugenol / cloves, aromatic spicy, fruity, wine-like, sweet, banana-like, ester-like, balsamic-resin-like, woody, incense-like, on warm ones Tea-like, flowery, cedar-like, rose-like, berry, reminiscent of tea, astringent, bitter, camphor-like green / earthy, green, mint-like, earthy, reminiscent of beetroot, have flavors reminiscent of natural balsam, balsam resin-like, rum-like and / or blueberries. Further The norbornane derivatives can be used as additives for tobacco, tobacco substitutes and used as tobacco flavorings and new preparations of these products are being created that prevent smoking a sweet, woody, fruity, cooling aroma and in the main stream have sweet taste and spice characteristics reminiscent of natural tobacco when smoked. Also suitable the norbornane derivatives for perfume preparations, colognes and perfumed articles, which they give an intense and pleasant, tender, melon-like, sweet, woody, fruity, aromatic-spicy (nutmeg, pepper), herbaceous, fir balm, Thuja-like, reminiscent of cedar leaves, camphor-like, musty, mint-like, freshly cut spruce Reminiscent, wormwood and mugwort-like, natural cresol resin and borneol resin aroma with a strong St. John's wort-like aroma cedar leaf-like, earthy and camphor-like undertones.

In the structural formula of the norbornane derivatives shown above, each dashed line means a carbon-carbon single bond or a carbon-carbon double bond, with the proviso that at least one of the dashed lines is a carbon-carbon single bond. Further, η is 0 or 1, with the proviso that η is 1 when both dashed lines are single bonds and η is 0 when one of the dashed lines represents a double bond. R ₁ is either hydrogen, a lower alkyl or a lower alkylidene group and R ₂ is either hydrogen or a

809821/0723

lower alkyl group, Y means

10

or

• ("eis" and / or "trans";

and Q is hydrogen or the hydroxyl group, where when Q is hydrogen, Z is one of the groups

O R-

Y '

OH

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or

means - and

when Q is hydrogen, Z is the group -CH ₂ -, η = O and R. is lower alkylidene. IU and R ₂ are each an alkyl group, R ₁ , Rg and R 0 are each identical or different substituents, namely hydrogen or a lower alkyl group. Rq and Rq taken separately are the same or different.? lower alkyl groups, or taken together they are lower alkylene. The dotted line means a carbon-carbon single bond or a carbon-carbon partial double bond and each wavy line represents either exo or endo isomers.

The derivatives are suitable as additives or seasonings in foods, Chewing gum, toothpastes, medicinal products, perfume preparations, perfumed articles, colognes as well Tobacco and tobacco substitutes.

Unless otherwise stated, the herein indicated mean carbon-carbon double bonds referring to an "eis" isomer, a "trans" isomer, or a mixture of "eis" and "trans" isomers on the carbon-carbon double bond.

The new norbornane derivatives according to the invention can preferably can be produced by one of several processes:

(1) In one of the processes, a compound or a mixture of compounds of the formulas

or

(endo) (exo)

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wherein the dashed line represents a carbon-carbon single bond or a carbon-carbon double bond dung represents " with an aldehyde of the formula

ΊΟ

is reacted, where R ₁ and R _{10 are} the same or different alkyl groups or hydrogen - as defined above - represent.

This results in a mixture of compounds, the two of them Have structural formulas:

to

The compounds obtained can be used because of their organoleptic properties or they can be further reacted

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-fi-

using either a Grignard reagent, RgMgX, or an organic lithium reagent, such as RgLi (where ta

8 is a lower alkyl group, for example methyl, ethyl, 1-propyl-2-propyl, 1-butyl, 2-butyl, 2-methyl-1-butyl or 2-methyl-2-butyl is) with subsequent hydrolysis to form the tertiary alcohol of one of the formulas:

or by reducing the carbonyl group and / or a (or several) of the carbon-carbon double bonds around the secondary alcohol or ketone to form one of the formulas:

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and

or by rearrangement of the carbon-carbon double bond into the rare chain «whereby compounds of the formula are formed:

10

wherein R 1 and R. _{Q represent} the same or different groups such as hydrogen or a lower alkyl group, the dotted line is a carbon-carbon single bond or a carbon-carbon double bond, and wherein each broken line is LIn. means a carbon-carbon single bond or a carbon-carbon double bond, with the proviso that at least one of the dashed lead lines is a carbon-carbon single bond.

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-jar-

(2) Another process involves oxidizing camphene to form camphene oxide the formula

to manufacture.

The camphene oxide then becomes the aldehyde (3,3-dimethylnorbornane-2-carboxaldehyde) converted that to the formula

having.

The aldehyde is made with a Grignard reagent of the formula

or an organic lithium reagent of the formula

reacted, wherein X is a halogen atom such as chlorine, bromine or iodine. The metal-organic compound obtained has the formula

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or

This compound is then hydrolyzed to give the corresponding alcohol of the formula

to form, which then as so loher because of its organo leptic Properties is used or further treated. It can be oxidized or reduced to either the unsaturated Ketone or the saturated alcohol su form, as it is with first described method (1) is explained. The ketone and the alcohol are of the form Int

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respectively·

IO

ιΟ

These products can be used as such because of their organoleptic properties. But if in the side chain If an unsaturated bond is present, this double bond can be displaced and a compound of the formula

or

("eis" and / or "trans" isomer) 10 are formed.

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Another method is to use an aldehyde of the formula

with a Grignard reagent of the formula

MgX

or an organic lithium reagent of the formula

reacted »in which η« is 0 or 1;

An organic metal compound of the formula

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or

educated. This compound is then hydrolyzed to produce the saturated alcohol of the formula

manufactured. This alcohol can be considered as such because of its organoleptic nature Properties used or it can be oxidized and the ketone of the formula formed

or it can be esterified to give an ester of the formula

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to form * where R ₁ , Rg vmd R, the same or different groups «namely hydrogen or an alkyl group and η ο is 0 or 1 ·

(4) A Grignard reagent of the formula

MgX

where X is chlorine «bromine or iodine« with camphene oxide formula

be mixed (the "endo", the ⁿ exo ^tt or a

Mixture of the "endo" or "Exo" forms). The organometallic salt formed is hydrolyzed using acid. the The reaction sequence shows the equation:

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A /

MgX

(5) In another method, a compound, namely 2-acetyl-3 # 3-dimethyl-5-norbornene, is represented by the formula

added to acetaldehyde and converted according to the reaction equation:

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where X is a halogen »for example chlorine, bromine or iodine, It becomes a compound of the formula

educated,

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Al

(6) In another process, 2-acetyl-3 »3-dimethylnorbor ■ nan the formula

to an allyl halide of the formula

\O

¹ I-

J.

and R,

or both

given, wherein either each group R ₁ , R ₂ and R, _Q groups are hydrogen or a lower alkyl group and X is a halogen atom, ie chlorine, bromine or iodine. The reaction takes place in the presence of a base such as an alkali metal hydroxide, and a "Phasenumwandler" - or in the presence of a base such as an alkali metal hydride in the presence of a ^w Phasenumwandlers "to prepare compounds of the following formulas:

IO

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and

IO

wherein R ₁ , Rg, R ^, R |, Rg and R ^ _{0 represent} the same groups, namely hydrogen or a lower alkyl group - or different of these groups. The mixture obtained can be used as such because of its organoleptic properties or it can be broken down into its constituent parts, which in turn serve as organoleptic substances. On the other hand, the mixture or its components can be treated by rearrangement of a carbon-carbon double bond and / or by reducing the keto group to form a hydroxyl group - or by reducing one or more carbon-carbon double bonds using hydrogen.

(7) Another possibility is the conversion of 2-acetyl-3,3-dimethylnorbornane or 2-acetyl-3,3-dimethyl-5-norbornene with dialkyl carbonate, whereby a ketocarboxylic acid ester is formed will. Using a base, the enolate is formed, which is reacted with an allyl halide. The received substituted ketocarboxy! acid ester is saponified and a salt made of ketocarboxylic acid, which is then decarboxylated, according to the reaction sequence:

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♦ R ₄ OC-OB ₄

M ₁ H

• λ

•1·

■, o «

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wherein Rg is a lower alkyl group and R ₁ and R _{2 are} the same or different groups, namely hydrogen or a lower alkyl group. M ₁ and M ₂ are the same or different alkali metals. The ketone obtained can be used as such because of its organoleptic properties or it can be treated further in accordance with the process steps explained in processes (1) to (5).

(8) In this process, 2-acetyl-3,3-dimethylnorbornane becomes or S-AcylOO-dimethyl-S-norbornene of the general formula:

wherein Rg represents a lower alkyl group, with an allylic Grignard reagent of the formula:

HgX

or an allylic lithium reagent of the formula

wherein X is a halogen atom, namely chlorine, bromine or iodine, implemented and an organometal! compound of the formula:

ι ο

or

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2750208

manufactured. This compound is then mixed with aqueous mineral acid hydrolyzed and the corresponding tertiary alcohol of the

formula

OH

educated.

Each of the methods briefly outlined above is explained in more detail below.

Procedure (1)

The reaction of the aldehyde of the formula

•O

with 2-acetyl-3,3-dimethylnorbornane or 2-acetyl-.j5,> - dimethyl-5-norbornene is preferably in the presence of either a base such as alkali metal ethoxide (e.g. NaOH) or a mixed catalyst carried out from boron oxide and boric acid, an alkenoyl norbornane or norbornene derivative of the formula

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4?

is formed wherein one of the dashed lines denotes a carbon-carbon double bond and the other denotes a single bond; the dotted line represents a carbon-carbon single bond or a double bond; R. and R, _{Q are} the same or different groups namely hydrogen or lower alkyl groups. For example, when acetaldehyde is reacted with 2-acetyl-5 »3-dimethylnorbornane, 2- (trans-2-butenoyl) -3,3-dimethylnorbornane is formed. This reaction is preferred at a temperature in the range of 120 ° C up to 200 ° C over a period of 3 to 10 hours. The molar ratio of 2-acetyl-3,3-dlmethylnorbornane (or norbornene) aldehyde is preferably 1: 1 or is slightly larger than 1: 1. If an alkali metal hydroxide catalyst is used »If the molar ratio of base: acetyl norbornane or norbornene from 1: 1 up to 20: 1. If a mixed catalyst "boron oxide: boric acid" is used "the molar ratio of aldehyde: boron oxide is preferably about 2: 1 or greater than 2: 1 "with the particularly preferred molar ratio of boron oxide: boric acid between 5: 1 and 10: 1, especially others between 6: 1 and 8: 1. The reaction temperature is in the range of 120 ° to 180 ° C and the reaction is carried out in one Autoclave carried out at autogenous pressure. The product obtained can be considered as such because of its organoleptic properties used or it 'can be treated further. So it can with an RgMgX (e.g. CH, MgBr) Grignard reagent or RgLi «where Rg is a lower alkyl group. It will worked in a solvent (e.g. tetrahydrofuran or diethyl ether) and then subjected to acid hydrolysis (e.g. dilute HCl). On the other hand, it can be used with hydrogen as Reducing agents and a hydrogenation catalyst - such as £ 5 palladium-on-carbon or Raneynlckel - welter reduced will. Instead of boric acid: boron oxide catalyst can also only boron oxide can be used «and then« when at a temperature between 170 ° and 185 ° C and at a pressure in the car claves between 2.8 and 7 at are worked.

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Procedure (2)

The camphene epoxide is produced by reacting camphene with a peralkanoic acid oxidizing agent, for example peracetic acid or perpropionic acid. The reaction is preferably carried out at a temperature of from ⁰ to 80 ° C. (preferably 40 ° to 60 ° C.) in the presence of a solvent which is inert towards the reactants or the reaction product. One such inert solvent is methylene chloride. Other suitable solvents are benzene, toluene, xylene and cyclohexane. The camphene: peracetic acid molar ratio is preferably somewhat less than 1: 1, since it is desirable that all of the camphene is converted. After the reaction has ended, the excess peracetic acid is neutralized and the camphenoxide can be isolated or the reaction product can be used as such for the further reaction. For economic reasons, the reaction product is preferably used as such - and the camphene oxide is not first purified.

The product obtained is then converted into the aldehyde by heating with MgClp or MgBr ₂ , which is then prepared with a Grignard reagent of the formula:

or an organic lithium reagent of the formula:

is mixed.

X is a halogen atom such as chlorine, iodine or bromine and R. and R ₂ are the same or different groups, namely hydrogen

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or a lower alkyl group. It is preferred that the Grignard reagent and the aldehyde are dissolved in respective solvents prior to mixing. Suitable solvents are tetrahydrofuran, diethyl ether and Serbian of tetrahydrofuran or diethyl ether with benzene, toluene, xylene or cyclohexane. The reaction is preferably carried out in a temperature range of 50 ° up to 100 ° C. at atmospheric pressure, preferably in the range from 65 ° to 70 ° C. The resulting organometallic compound is then treated with aqueous acid, preferably a aqueous protonic acid, such as hydrochloric acid or phosphoric acid, hydrolyzed at a pH of the solution of about 1. The alcohol obtained, the hydrolysis product, is then treated with an appropriate inert extraction solvent, such as benzene, Toluene or xylene, and then extracted by evaporation or fractional distillation isolated. The alcohol obtained can as such because of its organoleptic properties in perfumery, as a flavoring for food, for chewing gum, medicinal products or types of tobacco or as a condiment for Tobacco are used. But it can also be treated further, and may be oxidized or reduced.

An appropriate oxidizing agent such as "Jones reagent", sodium dichromate-sulfuric acid mixture, pyridinium chlorochromate or a chromium trioxide-acetic acid-water mixture, is used to form the corresponding ketone. the

Oxidation occurs at temperatures between -10 ° C and + 50 ° C

carried out. When using the "Jones reagent" the preferred temperature is about -5 ° C.

It is noteworthy that oxidation systems such as dimethyl sulfoxide-acetic anhydride or copper chromite are not resulting oxidation.

The ketone obtained can be hydrogenated, for example with a palladium catalyst or a palladium-on-carbon catalyst, a saturated ketone being formed, for example according to the reaction equation:

80982170723

Ύ>

PA

H.

On the other hand, the ketone can be used as such because of its organoleptic properties.

The hydrogenation is preferably carried out at temperatures in the range from about 20 ° C. up to 100 ° C.

Procedure (3) ·

BeJ. the reaction of 3,3-dimethylnorbornane-2-carboxaldehyde with the Grignard reagent of the formula:

MgX

or the hydrocarbyl lithium compound of the formula:

Li

wherein η = 0 or 1, one or both groups of R. or R _{2 represent} hydrogen or a lower alkyl group, and X represents a halogen atom such as chlorine, bromine or iodine, the reaction conditions are essentially the same as those in FIG

Procedure (2). Likewise, the stages of recovery of the products are essentially the same. The alcohol obtained has the
Formula:

ⁿ R,

EAR'

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It can be used as such because of its organoleptic properties used or it can be oxidized to a ketone, operating as in process (2). It can also be esterified and thereby an ester of the formula

form where R-. Is hydrogen or a lower alkyl group. Esterifying agents are alkanoic anhydrides, such as acetic anhydride, proprionic anhydride, butyranhydride; mixed anhydrides such as acetic propionic acid anhydride; Acyl halides such as Acetyl chloride, propionyl chloride, acetyl bromide, propionyl bromide, n-butanoyl chloride, i-butanoyl chloride, n-pentanoyl chloride, n-octanoyl chloride and n-lauroylchlorld.

Method (4) ;

The reaction with the allylic Grignard reagent takes place at a temperature between 25 ° and 50 ° C in the presence of a Solvents which are inert towards the reactants, such as, for example, diethyl ether or tetrahydrofuran. The arignard reagent is first used in the presence of the same solvent made by reacting magnesium with an allyl halide will. Allyl chloride, allyl bromide or allyl iodide are suitable. Camphenoxide previously mixed with additional allyl chloride is used added to the Grignard reagent. The organometallic salt has formed after a period of between 2 and 10 hours at 40 ° C

The reaction time is a little shorter at higher temperatures.

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- 96 -

The hydrogenation of the organometallic salt to the tertiary alcohol Nornornanol derivative takes place at a temperature in the range between 20 ° to 60 ° C using a mineral acid such as hydrochloric acid, sulfuric acid, phosphoric acid or paratoluenesulfonic acid. It is worked in excess of water, which is one of the reactants.

After completion of the reaction, the reaction product is concentrated and the desired product is fractionally distilled at a low pressure (between approximately 1 to 10 mm Hg).

Method (5); The reaction goes as follows:

Methyl aniline is combined with methyl magnesium halide (chloride, bromide or iodide), each reactant preferably in an appropriate solvent, such as benzene / tetra-

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hydrofuran, tetrahydrofuran or diethyl ether is dissolved. A ratio of methyl aniline: methyl magnesium halide of 1: 1 is preferred. The reaction temperature for formation the connection:

is preferably from -5 ° C to about 40 ° C, in particular 20 ° to 30 ° C. The reaction of the abovementioned compound with Acetaldehyde is preferably carried out in the presence of an appropriate solvent, such as benzo1 / tetrahydrofuran, tetrahydrofuran or diethyl ether at a temperature in the range from -5 ° C to 20 ° C. The hydrolysis to form the keto alcohol takes place with a mineral acid »such as dilute aqueous hydrochloric acid, sulfuric acid or phosphoric acid or another protonic acid, such as Paratoluenesulfonic acid · The temperature of the hydrolysis is preferably 0 ° C. Used for dehydration. a mild dehydration tion agent, such as a mixture of acetic anhydride and sodium acetate at a temperature in the range of 80 ° to 150 ° C for a period of 1 to 5 hours. The dehydration can also be mi a strong acid in a refluxed one inert solvent, for example a benzene paratoluene sulfonic acid mixture can be carried out. After finishing this In the reaction, the excess of dehydrating agent, e.g. acetic anhydride, is destroyed and the reaction product is isolated. At this Only the "trans" isomer is formed in the reaction. If the starting material "endo" is 2-acetyl-3,2-dimethyl-5-norbornene is also the final product is an "endo" isomer. For the same reason, the end product is an "exo" isomer if that is the starting product "exo" is 2-acetyl-3,3-dimethyl-5-norbornene. When the final product is to be isolated, standard techniques are used to for example fractional distillation and, if desired, preparative gas-liquid chromatography.

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Method (6);

The reaction of 2-acetyl-3 »3-dimethylnorbornane with the allyl chloride derivative takes place after first the enolate of 2-acetyl-3,3-dimethylnorbornane was made, namely:

A hydride such as sodium hydride and potassium hydride is preferably used to form the enolate. It will then be with an ally! halide of the formula:

reacted, wherein R, and R _{2 are} the same or different

Groups, namely hydrogen or lower alkyl groups, and X represents a halogen atom such as chlorine, bromine or iodine. Further, a similar result can be obtained when an alkali metal hydroxide is used in the presence of a phase converter. The reactants and the base are in two immiscible phases and the phase converter phase can consist of one or more quaternary salts. Examples of such phase converters used in the method according to the invention are:

Tricaprylmethylammonium chloride;

Cetyltrirr.ethylammonium bromide; and benzyl trimethyl ammonium hydroxide.

Most preferred phase converters have the following general principles Formula:

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JS

'14'

Ί.2

wherein at least one of the groups R ₁₁ * ^R i2 * ^R 13 ^{and R} 14 is a Cg-C ₁ ^ aryl-j Cg-CjQ-aralkyl-; Cg-C ₂₀ -AIlCyI-;

- Or Cg-C ₂₀ -alkenyl group and the rest

^R l2 * ^R 13 * ^R l4 represent ^an alkyl group, namely methyl,

Ethyl, n-propyl, i-propyl, 1-butyl, 2-butyl, l-methyl-2-propyl, 1-Pentyl and 1-Octyl · Z ~ is an anion, such as chloride, bromine or hydroxide Furthermore, this process works in a cheap solvent

XO 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 and o-dichlorobenzene.

The method (6) is carried out at a temperature in the range of about 10 ° C up to about 150 ° C, preferably 50 ° to 120 ° C. The reaction time is inversely proportional to the reaction temperature, longer reaction times being required at lower temperatures. Thus, the reaction time ranges from about 30 minutes to about 10 hours.

The molar ratio of 2-acetyl-5 # 3-diraethylnorbornane ι ally! Halide is 0.5! 1.5 up to 1.5: 0.5, preferably 1: 1 up to 1: 1.2.

The amount of "phase converter" in the reaction mixture, based on the amount of 2-acetyl-3,3-dlmethylnorbornane can be from 0.5 g Phase converter per mole of norbornane derivative up to 25 g per mole are sufficient. An amount from 2.5 g up to about 7.5 g is preferred

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Phase converter per mole of norbo man derivative.

This method (6) is preferably carried out at atmospheric pressure, because this is the most comfortable condition to work with. However, lower or higher pressures can also be used without affecting the yield of the desired reaction product would be adversely affected.

Procedure (7) :

The first product is that produced by the reaction of the dialkyl carbonate is formed with 2-acetyl-2, J5-dimethylnorbornane in the presence of an alkali metal hydride, namely according to the following Reaction equation:

Close

where Rg is an alkyl group with 1 to 8 carbon atoms, mostly However, ethyl is. The reaction is preferably carried out under reflux, an inert to the reactants Solvents such as benzene. Toluene or xylene is used. The molar ratio of norbornane derivative: dialkyl carbonate is preferably 1: 2, but can vary from 1: 1 to 1: 5. The base: dialkyl carbonate ratio is preferably 1: 1.

The reaction of the ß-ketocarboxylic acid ester obtained with the Ally! Halide of the formula: R,

wherein X is a halogen, such as chlorine, bromine or iodine and R., R ₂ and R are the same or different groups, namely hydrogen or lower alkyl - is in the presence of approximately one

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Equivalents of a base such as alkali metal hydride or alkali metal alkoxide or hydroxide in the presence of an appropriate solvent. A phase converter can also be used.

The ketocarboxylic acid ester derivative has the following structural formula:

This ketocarboxylate is a new type of compound. Ss is then saponified in a conventional manner, for example with an aqueous base such as aqueous sodium hydroxide or Potassium hydroxide. The alkali metal salt obtained has the formula!

wherein M is an alkali metal. It is neutralized and decarboxylated at the same time, using aqueous mineral acid such as sulfuric acid or aqueous hydrochloric acid. The received Reaction product has the formula:

^R 10

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(a mixture of "cis" and "trans" isomers, where R, and R represent an alkyl group). It can be seen because of its organoleptic properties Properties used as such or it can be used with hydrogen and a catalyst such as palladium, palladium on carbon or Raney nickel. This creates the carbon-carbon double bond in the side chain reduced to a carbon-carbon single bond, a compound of the formula:

10 is formed.

Both the unsaturated ketone and the saturated ketone can - if desired - with an alcohol or glycol in the presence of sulfuric acid or hydrochloric acid, with a ketal according to the reaction:

2R _g OH

or R ₉ OH

R ₉ ¹ OH

or

J (OH)

is formed.

Rg and R 'represent any other alkyl groups when separated be taken. When taken together they are lower alkylenes, ζ. B. ethylene. The dashed line means

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a carbon-carbon single bond or a carbon-carbon double bond. On the other hand, either Ketone can be converted into the corresponding oxime by Hydroxylamine or hydroxylaminehuresalfc, such as hydroxylamine or Hydrochloride is used «where an oxime of the formula:

is formed. These ketals and oximes also have useful organoleptic properties.

Method (8) t In the reaction of 2-acyl-3,3-dimethylnorbornane or the

2-Acyl-3,3-dimethyl-5-norbornene with the Grignard reagent from Formula

wherein R ₁ , R ₂ and R ₁₀ , taken separately, are hydrogen or a lower alkyl group, and X is a halogen such as chlorine, bromine or iodine, the reaction conditions are substantially the same as those in process (2). This also applies to the stages of extraction. Rg of the compound of the general formula:

809821/0723

is a lower alkyl group such as methyl, ethyl, n-propyl, i-propyl, η-butyl, i-butyl, n-pentyl or n-octyl. The received Alcohol has the formula:

and can be esterified, the process steps according to process (3) being suitable.

Specific examples of those produced by the above-mentioned methods Connections are summarized in the following table:

Table I.

Name and structural formula of the compound

Use (perfume, flavoring and / or tobacco)

2 (2-butenoyl) -3,> dimethylnorbornane

(ice and. trans)

Perfumery; sweet, woody, fruity, aromatic spicy (nutmeg, pepper), herbaceous aroma with nuances of spruce needles.

fruity, spruce needle / wine-like aroma with on

Spice:
green,

Spruce resin reminiscent of ^ ugenol / cloves, aromatic, spicy, fruity, wine-like taste nuances.

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¹ M.

Table I continued

Name and structural formula of the compound

2- (3'-butenoyl-3,3-dimethylnor- bornan

Use (Parf Uir.erIe, seasoning and / or tobacco)

Perfumery ; fruity, herbaceous, spruce-like aroma with St. John's wort or mugwort character and spruce balm characteristics.

Spice; fruity-ester-like, floral, woody aroma reminiscent of cedarwood, with a sweet, fruity, banana-like, ester-like aroma reminiscent of balsamic wood resin, spruce spice character.

methyl-2-norbornane methanol

Perfumery; sweet, woody, thujone-like aroma with fighter-like nuances reminiscent of St. John's wort or mugwort, cedar leaves and spruce.

Spice; sweet, fruity-berry aroma with woody, incense-like, floral nuances reminiscent of warm tea and spicy character reminiscent of incense and cedarwood with rose-like, berry and tea-like nuances.

Tobacco ; sweet, woody, fruity, cooling aroma and taste, both before and during smoking.

Ctf-methallyl-3,3- dimethyl-2-norbornane

Perfumery ; fruity, musty, sweet, woody, minty aroma with nuances that smell of freshly cut spruce / pine.

Seasoning ; Incense and wood aroma with incense * and wood spice and astringent and bitter notes.

endo-2- (2'-butenoy1) -3 » 3-d ime thy1-5-norms

(ice and trans) perfumery ; Woody, spruce-like, natural aroma with fruity, aromatic, spicy, cresyl-like, borneol-like nuances and a definite berry top note.
Spice; Balsam, blueberry, spruce-pure unfruit and wood aroma with natural balsam, balsam resin, spruce-wood and blueberry spice characteristics

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ti

Table I continued

Name and structural formula of the compound

Mixture of 2-acetyl-2-allyl-3ij5-dirr.eth.ylnorbornane and 3,3-dimethyl-2- (V-pentenoyl) norbornane

Use (perfumery, seasoning, and / or tobacco)

Perfume ; Camphor-like, woody, fruity (orange) aroma with green, spruce-like undertones.

2- (cis-2'-butene-l ¹ -oyl) -3,3-dimethylnorbornane

Perfumery: incense, spruce, fruit with floral, berry and cologne nuances.

3,3-dimethyl-2- (4'-pentenoyl) norbornane

Parf üjr.erie : sweet, fruity, lichen balsam-like, flowery aroma with woody and banana-like notes.

Seasoning ; sweet, fruity, banana-like, green, woody, spruce-like aroma reminiscent of apple juice with berry, spruce-like, oriental-like and woody spicy character.

3,3-dimethyl-2-pentanoylnorbornane

Perfumery : sweet, fruity, spruce oalsam-like aroma with floral (ylang, jasmine) and berry notes.

Seasoning ; sweet, fruity / berry-like, raspberry-like, woody and plum-like aroma with sweet, fruity / berry-like, raspberry-like, valerian oil-like, woody and plum-like spicy characteristics.

3/3-dimethyl-C \ - propyl-2-norbornane methanol

Perfumery : camphor-like, woody, green aroma with mint nuances.

Seasoning ; sweet, delicate spruce-like, fruity, berry-like, valerian oil-like, woody aroma with sweet, delicate spruce-like, evergreen valerian oil-like, fruity berry-like and astringent spice characteristics.

809821/0723

- jr -

Table I continued

Name and structural formula of the compound

2-butyryl-3,3-dimethylnorbornane

Use (perfumery, seasoning and / or tobacco)

Perfumery : sweet, spruce-like, fruity, fighter-like aroma.

Seasoning ; sweet, delicate, spruce-like, fruity, pine balsam needle oil. Blueberry, wood and strawberry aromas with sweet, delicate spruce-like, blueberry, juniper, strawberry and astringent nuances.

Mixture of 3 »3-Dimethy1-2 (4'-methyI-

4'-pentenoyl) norbornane and

3,3-dimethyl-2-acer

tyl-2 (2'-methy1-2'-

propenyl) norbornane

Perfumery ; fruity, woody, deeply tuned but long-lasting aroma.

Spice; Camphor-like, woody and mint-like aroma with a strong, cooling nuance and a. strict, woody and minty spicy character.

Tobacco ; woody aroma before and when smoking with sweet, aromatic, spicy, floral nuances.

2-acetyl-2-methallyl-3,3-dimethylnorbornane

3,3-dimethyl-2- (2-methallyl-4 ^f methyl-4'-pentenoyl) norbornane

Mixture of 3f3-dimethyl-2- (4'-methyl-2 ^f -pentenoyl) -norbornane and

3,3-dimethyl-2- (4 ^f -methy1-3'-pentenoyl) -norbornane and

3,3-dimethyl-2- (4'-methyl-3-methoxypentenoyl) norbornane

Perfumery ; Deep, sweet, camphor-like, woody (cedarwood) aroma with green, herbaceous and spruce-like nuances.

Perfumery; Deep, green, woody, herbaceous aroma with waxy nuances.

- perfumery ; long-lasting, excellent fruity and berry aroma.

Seasoning ; fruity, raspberry-like, sweet aroma with a green nuance and a fruity, raspberry-like and green spice with a bitter nuance

Tobacco ; sweet, fruity, raspberry-like aroma before smoking and a sweet, fruity, raspberry aroma with green notes when smoking - in the tobacco and also in the filter.

809821/0723

Table I continued

Name and structural formula of the compound Uses (perfumery, seasoning and / or tobacco

Mixture of 3 * 3-dimethyl-2- (V-

methyl-2'-pentenoyl) -5-norbornene and 3,> dimethyl-2-

(4'-methyl-3-pentenoyl) -5- norbornene and 3,3-dimethyl-2- (4'-methyl-5-methoxy-pentenoyl) -5-norbornene

Perfume : fruity, berry-like aroma.

Seasoning ; sweet, fruity aroma reminiscent of red currant jam with citrus, ion, berry, spruce needle-like, biting nuances and a fruity, currant and berry jam-like spice, with green nuances reminiscent of fresh raspberries and pines.

Tobacco t has a sweet, floral and green aroma before smoking and a sweet, fruity, floral aroma when smoking in the main and side stream.

O < -ethyl-. 3,3-dimethyl-2-norbornane methano1

Perfumery : mint-like, sweet, fruity, woody aroma with a certain wormwood character and more. herbaceous and spruce needle-like nuances.

Spice : sweet, woody and mint-like aroma with green and earthy nuances and a woody, green, mint-like spice with aromatic, spicy, earthy, cooling nuances reminiscent of beetroot. Tobacco : sweet, woody, spruce aroma and a strong cooling effect when used in the filter. The aroma and effect are present both before and during smoking. It also reduces the sharpness and gives the tobacco a fresh effect.

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- 39 -

Table I continued

Name and structure formula of the connection

Of-A lly 1-OC -3,3-trimethyl-2-norbornane methanol

3,> trimethyl-5- norbornene-2- methanol

Use (perfumery, seasoning and / or tobacco

Perfume Ü.T.erie ; low-pitched, sweet, woody (cut spruce) note.

Seasoning ; Sweet, earthy, spruce-like aroma reminiscent of cedarwood with sweet, fruity, blueberry-like spice reminiscent of cedarwood with nuances of patchouli and walnut.

Perfumery ; Sweet, mint-like, fruity, slightly melon-like, woody aroma.

Wort t spruce-like, fruity, woody, patschull-like, carrot-like, walnut aroma with a sweet, fruity, woody, kämpfd-like, carrot-like, patchouli-like, walnut-like and astringent spicy note reminiscent of dried apples

If the norbornane derivatives according to the invention are used as seasoning additives for food, they also serve

Ingredients added jointly to these derivatives for changing, modifying, improving or enhancing the organic properties of the treated products.

"Change" as the terms used herein, "modify" and ⁿ "reinforcing means in the various forms that a relatively tasteless substances is given a Würzcharakter, or that an existing WUrzcharakterl-35 is amplified stic, for example when the natural wort insufficiently is, or that the already existing flavor impression is modified in its quality, in its character or in its taste.

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The terms mentioned are also related in a similar way used with condiments per se.

The term "strengthen" means that a flavoring or flavoring characteristic or note is intensified without the quality of these properties being changed, d. H. it no additional spicy note is given.

Food is understood to mean solid and liquid products, which do not necessarily have to have any nutritional value. This subheading essentially includes soups, conventional foods, beverages, Dairy products, sugar confectionery, vegetables, grains, soft drinks, snacks, ready meals and the like.

The medical products can also be solid or liquid and include ingestible preparations with medicinal content, such as cough syrups, cough drops, aspirin, and chewable medicinal tablets.

"Chewing gum" are preparations made from a substantially water-insoluble, chewable gum composition, such as chicle, or theirs Substitutes such as jelutong, guttakay, gum or certain edible natural or synthetic resins or waxes. This rubber mass plasticizers, for example glycerol, seasonings, for example one or more of the derivatives according to the invention can be used and also sweeteners such as sugar, including cane or beet sugar, dextrose and / or artificial sweeteners such as cyclamates or saccharin, can be added. Other additives can also be used.

Additives or flavoring auxiliaries such as can be used together with the norbornane derivatives according to the invention are known. It is necessary that they are harmful ise edible and therefore not toxic or in any other W _e, this being the organoleptic properties is also important in terms.

809821/0723

Such substances are generally used as seasoning auxiliaries or to be referred to as carrier substances and in the broadest sense they include stabilizers »thickeners, wetting agents, surface-active agents, conditioning agents or other seasonings or Flavor enhancers.

The stabilizers include preservatives such as sodium chloride; Antioxidants, e.g. Calcium and sodium ascorbate, ascorbic acid, butylated hydroxyanisole (mixture of 2- and ^ -tert-butyl ^ -hydroxyanlsol, butylated hydroxytoluene (2,6-tert-butyl-4-methylphenol), propyl gallate and the like; Sequestrants, e.g. citric acid.

To'den thickeners include carriers, binders, Protective colloids, suspending agents, emulsifying agents 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; Gelatine, substances containing protein; Lipids; Carbohydrates; Starches, pectins and emulsifiers, for example Kono and Diglycerides of fatty acids, skimmed milk powder, hexoses, pentoses,

Disaccharides such as sucrose corn syrup and the like.

Wetting agents or surface active agents include emulsifying agents, e.g., fatty acids such as caprylic acid, caprylic acid, palmitic acid, myristic acid and the like. Mono- and diglycerides of fatty acids, lecithin, defoaming agents and seasoning dispersants such as sorbitan monostearate, potassium stearate, hydrogenated Tallow alcohol and the like.

Conditioning agents include, for example, bleaching agents and ripening agents such as benzoyl peroxide, calcium peroxide, hydrogen peroxide, and the like; Starch modifiers such as peracetic acid, succinic anhydride, and the like, buffering agents and neutrals dissolving agents such as sodium acetate, ammonium bicarbonate, ammonium phosphate, citric acid, lactic acid, wine vinegar and the like; Dyes, e.g. B · carminic acid, cochineal, gymnast

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Ht

and turmeric and the like; Solidifying agents, such as aluminum sodium sulfate, Calcium chloride and calcium gluconate; Texturizers and anti-caking agents, e.g. B. aluminum calcium sulfate and tribasic calcium phosphate; Enzymes; Yeast nutrients such as calcium lactate and calcium sulfate; Nutrient additives, e.g. iron salts such as ferric phosphate, ferrogluconate and the like, riboflavin, vitamins, zinc sources such as zinc chloride, Zinc sulfate and the like.

Other condiments and condiment enhancers include aldehydes, esters, natural oils, alcohols, sulfides, ketones, lactones, carboxylic acids and hydrocarbons such as heliotropin, terpinenol-4, Benzaldehyde, anisaldehyde, phenylacetaldehyde, benzyl format, benzyl acetate, cis-2-hexenyl benzoate, methyl hexanoate, hexanal, Eucalyptol, eugenol, acetaldehyde, ethyl acetate, ethyl butyrate, turpentine gum oil, limonene, camphor gum, isobornyl acetate, borneol, Cinnamaldehyde, cuminaldehyde, furfural, methyl cinnamate, cassia oil, vanillin, maltol, parahydroxybenzyl acetone, dimethyl sulfide, of-ionone, acetic acid, isobutyl acetate, acetone, butyric acid, formic acid, Valeric acid, amyl acetate, amyl butyrate, anethole, benzyl salycilate, diacetyl, dimethyl anthranilate, ethylmethylphenyl glycidate, Ethyl succinate, ethyl valerate, geraniol, cis-3-hexen-l-ol, 2 »hexenyl acetate, 2-hexenyl butyrate, hexyl butyrate, 4- (p-hydroxyphenyl) -2-butanone, ß-ionone, i-butyl cinnamate, jasmine, lemon oil, Methyl butyrate, orris root butter, rose absolute, terpenyl acetate, V'-undecalactone, vanilla and alcohol.

The special wort additive can be either solid or liquid, depending on the desired physical form of the end product, e.g. B. a food. He must in any case (i) be organoleptically compatible with the inventive

JO norbornane derivative and may have its organoleptic properties neither cover nor spoil with regard to the aroma or the taste, (ii) not with the norbornane derivative according to the invention react and (iii) create an environment in which the Norbornane seasoning used according to the invention disperses or can be mixed homogeneously with this. The selection also depends

809821/0723

one or more of the auxiliaries and their amount of the precise organoleptic character of the desired end product away. As a result, the choice will vary depending on the

ni. food, chewing gum, medicinal product or the Toothpaste, i.e. the substances, their flavoring and / or aromatic effects should be influenced. If it is a matter of normally solid substances, the components are selected in such a way that also these result in solid substances in the end product, for example various cellulose derivatives.

The amount of the norbornane derivative according to the invention used as a seasoning can vary within wide ranges and depends on the organoleptic effects desired in the end product. So larger quantities will be required if that is to be seasoned Food is relatively tasteless. Against it nismatically small amounts, if only an inadequate natural amount There is a bad taste or insufficient natural aroma that is merely intended to be enhanced. In any case, it must the amount is sufficient to achieve the desired organoleptic properties in the end product. So it should be too low

Avoid quantities but also do not add too large quantities

will. In any case, it would be uneconomical and in the case of too much flavoring can also disturb the flavor-flavor balance and the flavoring effect can be impaired.

It has been found that when it comes to food, chewing gum preparations as well as medical preparations and toothpastes, the amount of the norbornane derivative or derivatives between 0.5 T / Mi11. and 100 T / Mill., Based on the total preparation. As already mentioned, higher concentrations are not recommended as they will not produce positive results. if the norbornane derivative according to the invention is used in a seasoning preparation, it must be in sufficient quantity in this be present in order to achieve the appropriate seasoning effect in the end product.

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so

Seasonings which contain one or more norbornane derivatives according to the invention are contained therein in a concentration of preferably 0.1% by weight up to about 15% by weight , based on the total weight of the seasoning preparation.

The seasoning preparations can be produced using conventional methods, such as those used for cake dough, Fruit drinks and the like are common. The ingredients are in the appropriate proportions in a mixer processed to achieve the desired consistency, homogeneity of dispersion, etc. On the other hand, the seasonings in the form of powders by mixing the norbornane derivative with, for example, gum arabic, gum tragacanth, carrageenan and the like, then spray drying the mixture to obtain the comminuted solid.

However, solid substances can also be mixed with one another right from the start such as starch, sugar and the like.

The preferred additives for the seasonings using the norbornane derivatives according to the invention are: heliotropin, terpinenol-4; Benzaldehyde; Anisaldehyde; Phenylacetaldehyde; Benzyl format; Benzyl acetate; cis -3-hexenyl benzoate; Methyl hexanoate, hexanal; Euciyptol; Eugenol; Acetaldehyde; Ethyl acetate; Ethyl butyrate; Turpentine gum oil; Limonene; Camphor gum; Isobornyl acetate; Borneol; Cinnamaldehyde; Cuminaldehyde; Furfural; Methyl cinnamate; Cassia oil; Vanillin; Maltol; p-hydroxybenzyl acetone; Dimethyl sulfide; cf-ionone; Acetic acid; i-butyl acetate; Acetone; Butyric acid, formic acid; Valeric acid; Amyl acetate; Amyl butyrate, anethole; Benzyl salicylate; Diacetal; Dimethyl anthranilate; Ethyl methylphenyl glycidate; Ethyl succinate; Ethyl valerate; Geraniol; cis -3-hexen-1-ol; 2-hexenyl acetate; 2-hexenyl butyrate; Hexyl butyrate; 4- (p-hydroxyphenyl) -2-butanone; ß-ionone, i-butyl cinnamate; Jasmine, lemon oil; Methyl butyrate, methyl caproate; Methyl disulfide; Methyl p-naphthyl ketone; Irris butter; Rose absolute; Terpene acetate; ^ - undecalactone; Vanilla; and alcohol.

809821/0723

With the norbomane derivatives according to the invention, a Organoleptically improved smoking tobacco can be produced, either the tobacco itself or corresponding tobacco spices being formed. It was found that with the Seasonings Problems that have arisen to date with regard to the specific desired sweet, woody, spruce-like and fruity seasoning characteristics of natural tobacco - namely before smoking, when smoking in the main stream and in the side stream - as well as the cooling effects can be switched off. the The flavoring properties of tobacco are created, strengthened, modified or intensified and improved and at the same time kept at the desired uniform level, independently of the variations of the tobacco ingredients in the mix.

According to the invention also improved tobacco additives and Process created in which various desired natural aromatic tobacco seasoning characteristics with sweet, woody, spruce-like, cooling and fruity notes are given, which can be easily varied and controlled to achieve the desired uniform flavoring characteristics. 20th

Tobacco «in particular smoking tobacco or a corresponding one

Tobacco substitute (e.g. dried lettuce leaves) becomes a flavor and seasoning additive added as an active ingredient of a or contains more of the additives according to the invention.

In addition to the norbornane derivative, others can also be used Flavor additives are added, either alone or mixed with the norbornane derivative. Such additives are for example:

1. Synthetic fabrics ; ß-ethyl cinnamaldehyde; Eugenol; Dipentene; Damascenon, Maltol, Ethylmaltolj if-ündecalacton; cT-decalactone; Benzaldehyde, amyl acetate, ethyl butyrate; Ethyl valerate; Ethyl acetate; 2-hexenol-1; 2-methyl-5-isopropyl-1,2-nonadien-8-one; 2,6-dimethyl-2,6-undecadien-1,3-one; 2-methyl-5-isopropyl acetophenone; 2-hydroxy-2,5 # 5 # 8a-tetramethyl-1- (2-hydroxyethyl) -decahydronaphthalene; Dodeoahydro ^ a ^ fe ^ a-tetramethylnaphtho- (2, lb) -furan; 4-hydroxyhexanoic acid, i'-lactone; and polyisoprene

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Hydrocarbons as described in Example 5 of U.S. Patent 3,589,372 are described;

2. Natural oils; Celery seed oil; Coffee extract; Bergamot oil; Cocoa extract; Nutmeg oil; and origanum oil.

A flavor and seasoning concentrate that contains one or more norbornane derivatives according to the invention - and if desired one or more of the above-mentioned additives - contains the smoking tobacco itself, the filter, or the wrapping sheet or paper. The smoking tobacco can be cut, dried, for Packing compressed, mixed or a tobacco substitute (e.g.

Lettuce leaves). The proportions of seasoning additives vary Depending on the taste, a reinforcement or at all an award of natural and / or sweet notes, and / or cooling notes and / or fruity notes and / or woody notes is desired. It has been found to be satisfactory Results are achieved when the weight percentage of the total amount is 50 T / Mill. up to 1500 T / Mill. (0.015 # to 0.1550 norboman derivative amounts to. It has also been found that satisfactory results are obtained when the weight fraction the total amount of Korbornan-Derviat, used as seasoning material used is 1500 to 1500 T / Mill (0.15 # - 1.5 #).

The aromatic substance can be in any tobacco or tobacco product be added in an appropriate manner. So can the norbornane derivative alone or with the appropriate additives in a suitable solvent such as ethanol. Diethyl ether and / or Dissolve another volatile organic solvent and dry the resulting solution on the one pressed into the pack or the mixed tobacco can be sprayed or the tobacco can be immersed in the solution. Under certain conditions it can the seasoning also for example by a brush or a roller on the wrapping paper or the wrapping sheet for the Smoking tobacco is applied and the filter can be sprayed, dipped in or coated with it.

It can also be only a part of the tobacco or the tobacco

809821/0773

S3

substitute can be treated with the seasoning preparation. In such a case, the tobacco should contain the norbornane derivative in excess contained in the tobacco product compared to the final amount, so that the corresponding seasoning effect is ensured in the final product.

In a specific embodiment according to the invention, an aged, dried and cut Burley tobacco is mixed with a 20 # ethyl alcohol solution of 2- (2-butenoyl) -3,3-dimethylnorbornane of the formula:

sprayed at an amount that is 800 T / M'ill. weight des 2- (2-butenoyl) -3,3-dimethylnorbornane on a dry basis im Final product results. Then the alcohol is evaporated and the Tobacco made into cigarettes. The pleasant aroma of cigarettes is in both the main and side streams determine when the cigarette is being smoked. The aroma is described as sweet, aromatic, tobacco-like with sweet and fruity notes.

The norbornane derivatives according to the invention are particularly suitable for the treatment of smoking tobacco, such as cigarette tobacco, cigarettes rent tobacco and pipe tobacco, but other tobacco products, such as those made from tobacco dust, can also be used with the Seasonings are refined. You can also use the filter tips (e.g. cellulose acetate filters), where sweet, woody, spruce-like and / or cooling effects are desired, seam pastes, packaging materials and the like, as they are used with tobacco products, the seasonings according to the invention are applied.

809821/0723

The norbornane derivatives according to the invention are also suitable for the perfumery and you can use one or more perfume additives, such as hydrocarbons, alcohols, ketones, aldehydes, nitriles, esters, lactones or cyclic esters, Acetals, ketals synthetic essential oils and natural essential oils oils are mixed so that the combinedon scents of each Components result in a pleasant and desired fragrance note, in particular as woody and / or spruce-like and / or can be called earthy. Contain such perfume preparations usually (a) the main note or "bouquet" or cornerstone of the composition; (b) modifier representing the main note round off and accompany them; (c) Fixatives that contain fragrances that affect the perfume during the entire period of evaporation give a special touch and delay evaporation; and (d) top notes, which usually consist of low-boiling, fresh smelling substances.

In perfume preparations, it is the individual components that contribute to the particular fragrance characteristics, but the overall effect is at least the sum of all components. For example, one or more of the norbornane derivatives according to the invention can be used to change, modify or enhance the aroma characteristics of a perfume preparation, for example by utilizing the odor reaction of another component in the preparation or by reducing it.

The effective amount of the norbornane derivatives according to the invention in perfume preparations and in perfumed articles depends on many factors, including other constituents, their proportions and the desired effects. It has been found that even as little as $ 0.01 - or even less (e.g. 0.005Ji) of the norbornane derivative can suffice to create sweet , spruce-like, woody, flowery, aromatic, spicy, pine balsam-like, fruity fragrances with St. John's wort-like , berry, evergreen-like, cedar leaf-like, earthy and tobacco-like nuances of perfumed articles such as soaps, detergents (including anionic, non-ionic and

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cationic) or other products. It can furthermore, up to 70Si of the fragrance component can be used, with the cost, the nature of the end product, the desired effect and the particular fragrance intended must always be taken into account.

The norbornane derivatives according to the invention are suitable - either alone or together with other ingredients in perfume preparations - for cleaning agents, detergents, soaps, room sprays and deodorants, perfumes, colognes, toilet water, Bath preparations, such as hair lacquers, brillantines, pomades and shampoos; cosmetic preparations such as creams, deodorants, hand lotions and face protection creams; Powders such as talc, body powder, face powder and the like. Even Vf> of the norbornane derivatives are sufficient to give wood-like perfume preparations an intensive To give a spruce note · In general, more than "% of the norbornane derivatives, based on the end product, are required to achieve the desired effect.

In addition, the perfume preparations or fragrance compositions contain a carrier substance for the norbornane derivative. These The carrier substance can be a liquid such as a non-toxic alcohol, a non-toxic glycol or the like. On the other hand, it can be an absorbent solid such as a Gum (e.g. gum arabic), or an encapsulating substance (e.g. gelatin).

The above statements show that the norbornane derivatives according to the invention are suitable for a large number of consumer articles Seasoning can be used, in particular to change the organoleptic properties of these articles, to modify or to enhance and improve.

The following examples 1 to 13, 17 »191 to 31» 61 and 62 serve for a more detailed explanation of the process for the preparation of the norbornane derivatives according to the invention

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20th

The following Examples 14 to 16, 13, 32 to 60 and 63 bis 71 explain specific uses of the inventive Compounds with regard to their organoleptic properties.

The proportions are given in parts by weight and ^ unless expressly stated otherwise.

example 1 Preparation of 3,3-dimethyl-2-norbornancarboxaldehyde

Reaction:

Procedure:

The following components were placed in a 3 liter flask equipped with a stirrer, filling funnel, reflux condenser and thermometer:
Camphene 6805ε) 500 g

Methylene chloride 500 ecm

Sodium carbonate 500 g

The slurry was stirred while adding 600 ecm peracetic acid (40 #) during a period of t> Hours were added.

The temperature rose until the mixture reached the reflux temperature

ture had reached (at the beginning at 44 ° C and was 48 ° C

after completion of the addition) .The course of the reaction was indicated by gas-liquid chromatography. After all of the peracetic acid had been added, the mixture was stirred for 2 hours.

The salts formed were removed by filtration, the methylene chloride was drawn off and 500 ecm of benzene added.

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The mixture was azeotroped using a water trap was used to remove traces of water. After all of the water was removed the mixture (670 g) was ready for the next level. Samples were examined by dissolving the salts in water and separating the organic layer and washed several times with water. Gas-liquid chromatography (Conditions: 10 'χ 1/8 "SE-J50 column, programmed at 80 - 200 ° at 8 ° C per minute) yielded 26 # benzene, 9,6j6 tricyclics and 6l, 2 # camphenoxide, resulting in a yield of 408 g of camphene oxide, or 92Ji corresponds to theory.

50 g of magnesium bromide were added and the mixture for 4 hours heated under reflux. After that, a gas-liquid chromatography analysis showed (10 * χ 1/8 Carbowax 2OM column, programmed from 80 - 220 ° C at 8 ° C / minute) the complete conversion of camphene oxide to 3 "5-di" methyl-2-norbornancarboxaldehyde.

Example 2 Production of Qi -Allyl - ^^ - dimethyl ^ -norbornanmethanol

Reaction:

Procedure:

55 g of magnesium turnings (2.26 mol) and 1 liter of anhydrous tetrahydrofuran were introduced into a 3 liter reaction flask equipped with a stirrer, reflux condenser, thermometer, dropping funnel and an N _{2 outlet.} The device was covered with dry N ₂ and 2 moles of allyl chloride (152 g, 162 ml) were added to the addition funnel. From this io ecm were added at once,

809821/0723

with stirring. Once the reaction started (exotherm to 30 ° C), the contents of the flask to 0 ° C (dry ice-isopropyl alcohol bath) was cooled and the rest of the allyl chloride was added over 3 hours while the temperature was maintained at 0 ° to 5 ⁰ C . After the addition was complete, the contents of the flask were stirred for an additional hour while warming to 22 ° C at room temperature. The Grignard solution was decanted from the excess magnesium into another reaction flask and 330 g of a solution of 3,3-dimethyl-2-norbornancarboxaldehyde in benzene - prepared according to Example 1 - (62% aldehyde by gas-liquid chromatography range normalization) during added over a period of 1 hour. The reaction was exothermic and the temperature rose until the solution came to reflux (65 ° -70 ° C). After the addition was complete, the mixture was heated and refluxed for an additional half hour. The Grignard complex was hydrolyzed by adding about 400 ecm of 15 # HCl to a pH of 1 -. The aqueous layer was separated off and extracted with 200 ecm of benzene. The combined organic layers were drawn off on a rotary evaporator and the residue passed through a column packed with stones after adding 30 g of the preparation known under the trademark PrimoIv- ^ at 70 ° to 77 ° C at 0.2-0.25 distilled mm Hg pressure. 206 g of the product were obtained. In gas-liquid chromatography (conditions: 10 'χ 1/8 "SE-30 column, programmed at 80-220 ° C. at 8 ° / tain.), This essentially resulted in a peak. It corresponded to a yield of 92 $ of theory based on 3,3-dimethyl-2-norbornanarboxaldehyde addition. This tip consisted of a compound of the formula:

- ⁵⁰

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SS

NMR data:

O.92 ppm singlets, methyl protons

(5H each) O.98

1.0-2.4 Complex signals 2H 4.85-5.2O Multiplet, CH = CH ₂ IH 5.68-6.O8 Multiplet, CH = CH ₂

MS data :

m / e = 69, 55, 41, 111, 67, 109 IR data :

cm " ¹ 3475 (-0H), 3079 (CCH = CH ₂ )

The NMR spectrum is shown in FIG. 1 and the IR spectrum in FIG.

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CO

Example 3

Production of 2- (3-butenoyl) -3,3-dimethylnorbornane under Use of a sodium dichromate-sulfuric acid-benzene

oxidizing system

Reaction:

Procedure:

Sulfuric acid (60 ecm, 110 g) was slowly added to 300 ml of water while stirring. After the solution had cooled to room temperature, 300 ecm (263 g) of benzene and 50 g of C { -Allyl ^^ - dimethyl ^ -norbornanmethanol were added. The mixture was stirred at room temperature and 20 g of sodium dichromate was added. After 1 hour a second 20 g portion was added. After stirring for an additional hour, the layers were separated. The benzene layer was washed with saturated NaHCO, solution and then with water. The solvent was removed and the residue was rapidly distilled and two fractions collected. The first fraction had a boiling range of 65 ° to 97 ° C at 1.2 mm Hg and weighed 2.5 g. The second fraction had a boiling range of 97 ° to 99 ° C at 1.0 mm Hg and weighed 39.1 g, which corresponded to a yield of 80 # of theory.

The second fraction consisted primarily of a compound of the formula:

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10

This compound was purified by column chromatography on a silicon acid column (deactivated by adding 5 # water) cleaned. It was with a mixture of 2 # diethyl ether in Isopentane diluted. Thus, from 1.5 g of this second fraction, after removing the solvent, 1.0 g of a UI was obtained, which has been distilled in a micro-still, wherein pure 2- (3-butenoyl) -3,3-dimethylnorbornane (i) was obtained, which had the following spectral characteristics:

(i) Structural forms:

15th

20th

NMR data;

O . ppm

0.95 1.0 1.18 1.24

interpretation Methyl singlet

(endo and exo isomers)

1.0-2.5 0
η
C-CH ₂ -CH ^ H ₂ Complex signals 3.12 CH ₂ -CH-CH ₂ Doublets of quartets 6.1
6.9 Multiples

MS data t

m / e = 123, 41, 67, 81, 39 »151

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fairy

IR data;

cm "I72O (normal carbonyl)

The NKR spectrum for this compound is in Fig. 5 and that IR spectrum shown in Fig. 6.

When either crude or purified 2- (3-butenoyl) -3,3-dimethylnorbornane is subjected to gas-liquid chromatography, a second material is found. This was collected and identified as cis -2- (3-butenoyl) -5,3-dimethylnorbornane (ii) of the following formula:

( cis isomer)

NMR data : interpretation

O , PPm

0.96 methyl singlet

1.20 (endo and exo isomers)

1.88 CH,

^N _c _ '~ ³ doublet of triplets

1.0-2.5 complex signals

6.12 ^ C = C ^X

yf ⁿ h multiplet

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MS data:

m / e4l, 69, 125, 67, 81, 108, 123

IR-Da ten t

cm 1685 (conjugated carbonyl)

5 The NMR spectrum is in Fig. 3 and the IR spectrum is in Fig. 4 shown.

Examples 4 to

Oxidation and attempted oxidation of O (-Allyl- ^, 3-dlmethyl-2-norbornanmethanol

10 Various oxidizing agents were used. The following Examples as given in Table Ia show under “Results” in which reactions 2- (3-butenoyl) -3,3-diir.ethylnorbornane was formed and in which “no reaction” was recorded became·

Table Ia

Example amount no. Alcohol

Respondents

Oxidizing agent

and

conditions Results

50 g

Ig 10 g

Jones reagent at room temperature

(60 ocm) / benzene (300 ecm); Room temperature - 2 hours the

10 ml of dimethyl sulfoxide / 5 g of acetic acid anhydride at 60 ° C

Copper chromite

(lg) / 2000 c - 1 hour

Mixture of many products

Successful Oxidation; 50 # conversion to ketone.

No reaction No reaction

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Table Ia continued

example lot Oxidizing agent Results No. alcohol and Reaction conditions Attendees 8th 5 g Pyridine chloride 50 # conversion chromate (8.5g) to ketone manufactured after Corey, Tetrahedron Letters, Jl, 2647, 1975); Met-iylenedi- chorid (50 ecm); Room temperature; 1 hour 50 # conversion 9 5 g Chromium trioxide (2.5g) / to ketone. - acetic acid

(5ml) / water (50ml); Room temperature; 1 hour

10

15 g

Jones reagent (25 ml) (prepared according to Example 4) / acetone (15 ml), -5 ^b C; 2 hours

$ 90 conversion to ketone.

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Example U

Preparation of endo-2- (trans-2-butenoyl) -3,3-dimethyl-5 norbornen

Reaction:

Ho 0 «

In a with condenser, thermometer, mechanical stirrer and cooling bath (Trockenels-isopropyl alcohol) three-necked flask were added 3M methyl magnesium chloride in tetrahydrofuran and 666 g (* 0 mole 3). A solution of 321 g (3 »0 mol) of methyl aniline in 300 ml of benzene was added over a period of 30 minutes

809821/0723

added, the reaction temperature being kept at 20 ° to 30 ° C. The reaction was exothermic and methane gas was evolved. After the evolution of gas had ended, a solution of 510 g (3 * 0 mol) of endo-2-acetyl-3 »3-dlmethyl-5-norbornene (produced by an AlCl, catalyzed reaction of cyclopentadiene and mesityl oxide, according to US Pat. PS 3,852,358) in 300 ml of benzene was added, the temperature being kept at 20.degree. To 30.degree. The mixture was stirred at room temperature for 1 hour and then cooled to 0 ° C. At this temperature, 132 g (3 * 0 mol) of acetaldehyde in 300 ml of benzene were added over a period of 30 minutes. After a further 30 minutes at 0 ° C., 600 g of 37 # HCl, diluted with 1200 ml of water, were added. After standing at 0 ° C for 15 minutes, the layers were separated. The organic layer was washed twice with water and dried over MgSOh. The solvent was evaporated keeping the temperature of the liquid below 45 ° C. The residue was then combined with 600 ml of acetic anhydride and 150 g of sodium acetate, stirred and heated to 100 ° C for 2 hours. The mixture was then cooled to 80 ° C., washed with water, saturated with NaHCO, solution and dried over MgSO ^. The product was distilled without fractionation and thereby, 204 g of an oil obtained, the boiling point was 70 ° C (1.0-1.5 mm Hg) to 130 ⁰ C ·. This reaction mass contained about $ 50 starting ketone and a mixture of reaction products. The main product was purified by redistillation by subsequent preparative gas-liquid chromatography on a 6 ^f χ 1/4 "column packed with 10 # Carbowax 2OM iaiiert. On the basis of its NMR spectrum, the product consisted predominantly of the endo isomer

The NMR spectrum is in Fig. 7 and the IR spectrum in Fig. 8 shown.

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Example 12

Production of 2- (2-butenoyl) -3 »3-dlmethylnorbornane (predominantly the "trans" isomer)

Reaction:

The following substances were introduced into a 2 liter autoclave:

Ingredients quantity

2-acetyl-3,3-dimethylnorbornane 644 g (4 KoI)

Acetaldehyde 132 g (3 mol) Boron oxide 105 g (1.5 mol) Boric acid 12 g (0.2 mol)

The autoclave was closed and the contents at 3 hours ! 5 autogenous pressure heated to 150 ° C. The contents of the autoclave were then cooled to room temperature and filtered. The filter cake was washed with 250 ml of cyclohexane and the filtrate rapidly distilled through a 2 "column after 20 g of the under de.n trademark Prlmoivfy and 0.1 g of the under the trademark ΙοηοχΦ) known preparations had been added. There were 649 g of oil at 77 ° to 129 ° C and a pressure of 2.7 - 4.0 mm Hg collected. This substance was then fractionally distilled on a 12 "χ 1" Goodloe SauIe, after again Primoiv / and lonoxvfy had been admitted. At 73 ° to 78 ° C at one pressure from 3.3-4 mm Hg, 490 g of oil were collected. The received

809821/0723

Product, as far as its fragrance properties are concerned, had a sweet, woody, fruity, aromatically spicy and herbaceous one Aroma with nuances of pine needles. As far as the seasoning characteristics concerned, it had a fruity, spruce needle / green, wine-like aroma with a pine, eugenol / clove, spice, Fruit and wine-like seasoning.

The NTIR, IR and MS analyzes confirmed the structural formula this connection:

NMR data

ei, ppm 0.82 0.95 1.16 1.20

Inte rpre tat ion

Singlet methyl protons (endo and exo isomers)

1.28 = CH-CH, Doublet of doublets 1.0-2.5 Complex signals 6.1
6.7 H ^N Kultiplett IH each

MS data :

m / e = 69, 41, 125, 59, 67, 108

IR data :

cm "1690 (conjugated carbonyl)

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The NMR spectrum is in Fig. 9 and the IR spectrum is in Fig. 10 shown.

Example 13 Production of 2- (2-butenoyl) -3 »3-dimethylnorbornane

Reaction:

The following substances were placed in a 2 liter autoclave:

Ingredients quantity

2-ethyl-3,3-dimethyl-

norbornane 830 g (5 KoI)

Acetaldehyde 88 g (2 KoI) Boron oxide 50 g (0.71 mol)

The autoclave was sealed and heated the contents at ⁰ to I70 I85 ⁰ C and held for 2 hours at this temperature, during this time the pressure in the autoclave was 3 * 50 atm. After the 2 hours the reaction mass was cooled to room temperature and decanted. After adding 20 g of the product known under the trademark PrimolGV and 0.1 g of the product known under the trademark Ionoxv ^, the resulting liquid was rapidly ^{distilled through a 2 n} column, in the range from 77 ° to 129 ° C and a pressure of 2, 7-4.0 mm Hg 625 g of a crude product was collected. To this was again PrimolS / and Ionox v- ^ added and then fractionally distilled, through a 12 "χ 1" Goodloe column at 73 ° to 78 ⁰ C and a pressure of 3 # 3 -. 4 mm Hg The main peak was collected on a gas-liquid chromatography column and a product

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the formula:

as obtained by gas-liquid chromatography, IR and NKR analysis was confirmed.

The product had a fruity aroma with penthouse and musty nuances as far as the fragrance properties were concerned. As for the taste, it became fruity and berry Aroma with waxy, berry, sour and bitter spice characteristics' noted.

example

Blueberry seasoning preparation Parts by weight The following mixture was produced: 3.0 Components 0 * 2 Heliotropin 1.5 Terpinenol-4 (10 # in 95 #
aqueous non-denatured ethanol) 0.2 Benzaldehyde 0.4 Anisaldehyde 0.5 Phenyl acetate aldehyde 2.0 Benzyl format 0.5 Benzyl acetate 2.0 cis -3-hexenyl benzoate (10 # in
95 ^ aqueous non-denatured
Alcohol) 1.0 Methyl hexanoate 0.5 Hexanal 0.2 Eucalyptol {1% in 95% aqueous
undenatured alcohol) Eugenol

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Ingredients Parts by weight acetaldehyde 3.0

Ethyl acetate 21.0 Ethyl butyrate 26.0 Propylene glycol 38.0

. 100.0

This preparation was divided into 2 servings. 2- (2-butenoyl) -3 # 3-dimethylnorbornane was added to the first portion in an amount of \%. The second portion was examined without any additive. The norbornane derivative was prepared according to Example 12. Both portions were mixed with water (100 parts per million). The portion flavored with 2- (2-butenoyl) -3 * 3-dimethylnorbornane had a much stronger wine, fruit and spruce character and is very similar to the flavor of wild blueberries. It is therefore preferable to the unseasoned portion.

Example 15 Lichen needle oil preparation The following ingredients were mixed together: Components weight point

Turpentine gum oil '100 limes 70

Rubber camphor 10 Isobornyl acetate 50

Borneol 30

2- (2-butenoyl) -3 # 3 ^ imethylnorbornane (manufactured according to example 12) 40

Mixture of 2- (3-butenoyl) -3 »3-dimethylnorbornane and 2- (2-butenoyl) -3,3-dimethylnorbornane (prepared according to Example 3) 100 Ol-allyl-3,3-dimethyl-2-norbornane-methanol (manufactured according to example 2) 70

The 2- (2-butenoyl) -3 »3-dimethylnorbornane prepared according to Example 12 gave the preparation a green, melon-like, herbal, ozone-like and delicate character of spruce needles,

809821/0723

namely in the middle part of the aroma profile and when drying out.

The mixture of 2- (2-butenoyl) -3 »3-dimethylnorbornane and 2- (3-butenoyl) -3,3-dimethylnorbornane, prepared according to the example 3 awarded the for this spruce needle oil preparation so substantial sweet, light, melon-like, herb-like increase in the spiciness.

The i ^ -Allyl-3,! 5-dimethyl-2-norbornanmethanol, prepared by Example 2 gave the sweet woody, melon-like note reminiscent of cut wood to the drying aroma.

10 Example 16

Seasoning use of M-allyl-3 ^ 3-dimethyl-2-norbornane methanol

The following basic mixture of a cinnamon preparation was made:

Ingredients 15 cinnamaldehyde

Eugenol

Cuminaldehyde

Furfural

MethyIc innamat 20 cassia oil

This mixture was divided into two portions. To the first portion were 5 # of the O ^ -allylj5,3-dimethyl-2-norbornanmethanol prepared according to Example 2 admitted. The second serving remained without any additive. The norbornane methanol imparted to the preparation a character more reminiscent of cinnamon bark, both in aroma as well as in taste. In addition, the aroma was more woody / sweet. It was preferred to the unseasoned preparation. The comparison was made in water with an added amount of 10% of the wort.

Parts by weight VJl 70 0 15th VJl 1 0, 5, 8th,

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- 67 -

Example 17 Production of iX-ethyl-j ^ -dlmethyl ^ -norbornaniiiethanol

Reaction:

η, ο-

Into a 2 liter equipped with a stirrer, thermometer, condenser, nitrogen inlet and dropping funnel. Reaction flasks were 129 ecm of a 2.9 molar solution of ethylmagnesium chloride in tetrahydrofuran. After 20 minutes, 19.0 g 3,3-Dimethyl-2-norbornancarboxaldehyde was added with stirring.

The reaction was exothermic. The reaction mass was then refluxed for Z> hours and then cooled to room temperature. Then 100 ecm of saturated ammonium chloride solution were added. The organic layer was extracted with 500 ecm diethyl ether and the extract concentrated and distilled through a micro-Vigreux column after adding 3 g of PrimolΦ ^.

The MS, NMR and IR analyzes of the distilled product, whose boiling point was 85 ° C at 1.5 mm Hg, confirmed the formula:

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NMR data:

ppm interpreter

⁹⁶ singlets according to dimethyl

1.02

1.04 triplet -CH ₂ -CH-,

1.0 - 2.4 multiplet

-CH ₂ - and -CH

5.5 multiplet

MS data:

m / e = 67, 41,121,31, 59, 182 (rigid tip)

From a food flavoring standpoint, this product had a sweet, woody, minty flavor with camphor-like greens and earthy nuances and a woody, green, mint-like spicy note with reminiscent of spices, earthy, cooling, reminiscent of beetroot and camphor-like nuances, in an amount of 5 T / MiH. As for the perfumery Interestingly, this product had a musty, sweet, fruity, woody aroma with a St. John's wort character.

This seasoning has a special meaning when used in Tobacco filter seasonings, which it gives a cooling effect with sweet, woody and spruce-like pods, namely both before smoking and while smoking. The quantities are very small, namely 10 microliters for a 10 ^ solution are added to the filter.

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is

The NMR spectrum is in Fig. 11 and the IR spectrum in Fig. shown.

Example 18

Use of Q'-ethyl-3 * 3-dimethyl-2-norbornanmethanol The following raspberry preparation was made:

Components parts by weight

Vanillin 2

Maltol 4

p-hydroxybenzyl acetone 5

Dimethyl sulfide 1 Of - Ionon (1O # in propylene glycol) 2 Ethyl butyrate '6 Ethyl acetate 16 Isobutyl acetate 14 Acetic acid 10 Acetaldehyde 10 Propylene glycol 930

1000

This preparation was divided into two servings. 0.3 # 0 ^ ethyl-3 # 3-dimethyl-2-norbornannethanol were added to one portion - prepared according to Example 12 - added. The second serving remained unsorted. The two servings were in water in one Quantity of 50 T / Ml11. examined. It was found that the the portion containing the norbornane methanol according to the invention had a taste more reminiscent of ripe raspberries and a woody raspberry stone character than the second serving. It was unmistakable that the flavored sample left a much more natural and characteristic raspberry impression.

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/ ν

Example 19 Production νοη <λ -Methallyl - ^, ^ - dimethyl-2-norbornanmethanol

Reaction:

In one with a stirrer, condenser, nitrogen inlet, thermometer 3 liter reaction flask equipped with a dropping funnel, 24 g of magnesium with just enough tetrahydrofuran were introduced, that the magnesium was covered. 2 ml (about 20 ecm) methallyl chloride was then added to start the reaction to put. As soon as the reaction ran, it became 500 ecm of tetrahydrofuran and 90.5 g of methallyl chloride were added dropwise over 2 hours, the mixture being kept at reflux became. After the addition was complete, the reaction mixture was refluxed for an additional hour. Afterward 50 g of norbornanaldehyde - prepared according to Example 1, dissolved in 100 ecm of toluene - were added over the course of 20 minutes. Thereafter was refluxed for a further 2 hours. The reaction product was then cooled to room temperature and 100 ecm saturated aqueous ammonium chloride solution added. The reaction mass was then extracted with diethyl ether and the ether extract concentrated. The concentrate was at an 8 "χ 1 1/2" Column packed with porcelain pieces after adding 5 g Primolv / distilled.

The product obtained in this way had a boiling point of 100.degree at 2.0 mm Hg and examined by NMR, IR, MS and UV analyzes. It became the formula

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confirmed.

NMR data:

ppm

0.94 1.0

Singlet

interpretation

according to Dinethy1

1.77 singlet

^C »3

1.0 - 2.4 multiplet

-CH ₂ - and.-CH-

4.72 multiplet

CH ₂

MS data ;

m / e = 69, 4l, 55, 45, 69, 208 (trunk-tip)

The product obtained had a musty, sweet, woody, Mint-like aroma with an intense nuance reminiscent of freshly cut spruce / balsamic.

The NMR spectrum is shown in Fig. 13 and the IR spectrum in Fig. shown.

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Example 20

Preparation of 2- (V-Hethyl-2'-pentenoyl) -3,3-dlmethylnorbornane

Reaction:

The following ingredients were introduced into a 3 liter reaction flask equipped with a stirrer, thermometer, reflux condenser, filling funnel and nitrogen inlet: Ingredients Amount

Methanol 500 g "

Potassium hydroxide 56 g

Toluene 50 g

2-acetyl-3,3-dimethylnorbornane 500 g

The reaction mixture was refluxed for 1 hour and then 240 g (3.3 mol) of isobutyraldehyde during one A period of 20 minutes was added. After the addition was complete, the mixture was stirred at a temperature of 72 ° C. for a further 4 hours. Then 50 g of concentrated HCl were added. The reaction mixture was then mixed with 1 liter of water and 500 ml of toluene, The aqueous phase was extracted with a 250 ml portion of toluene and this toluene was combined with the organic layer. This extract was washed as follows: Two 250 ml

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> s

27SÖ206

Portions of water, a 500 ml portion of 5% sodium bicarbonate solution and a 250 ml portion of saturated sodium chloride solution. The crude product was then freed from the solvent in a Buchi evaporator and the withdrawn crude product after the addition of 25 g Primol ν and 1 g Ionox (Jy an The distillate was rapidly distilled in a 2 "column. The distillate was in a 12" Goodloe column

distilled after the addition of J> 0 g pritnol.

and 1 g of Ioriox ^ feactiert

The gas-liquid chromatography, NMR, IR and MS analyzes showed that the product obtained is a mixture of three compounds existed, the structural formulas of which look like this:

OCH,

The gas-liquid chromatography profile is shown in FIG.

The NMR spectrum of the mixture of the above three compounds is shown in Fig. 17 and the IR spectrum in Fig. 17.

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KO

The NI-iH spectrum of the Jemish of the ketones of the formulas:

is shown in Fig. 18 and the IR spectrum in Fig. 19,

The NKR spectrum of the compound of the formula:

so the keto ether,

Is shown in Fig. 20 and the IR spectrum in Fig. 21,

Structure determinations
I. Mixture of A and B

IR data:

-1

1618 cm ", 1705, 1698

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NMR data (CDCl ₃ ): interpretation!

ΡΡΠ »

⁶ · ⁷⁰ doublet of doublets JL J

(JSi Iß Hz, 7Hz) | rC

η η

6.00 doublet of doublets P ^H

(yes; 6 Hz, 1 Hz)

⁵ · ²⁸ Second triplet

(YES 6 Hz)

³ · ⁰³ Broad doublet

(J »6 Hz)

1.74, 1.63 °

Broad singlets ^ Jl

^a 2

1.23, 0.87, 0.33 singlets

CH.

Doublet J ^ C Hz)

Comparison of the integrals for the signals at 6.70 and 6.00 ppm with the signal at 5.28 ppm shows that the ratio of A / B is about 1/1.

809821/0723

II. Connection C MMR data :

ppm interpretation

5.50 IH multiplet ₀

CH ₂

two
Singlet

(asymmetrical center)

I.23 3H singlet

₁₀ 0.85 3H singlet

O.89 6h doublet CH,

(J »5 Hz)

IR date :

The total mixture of the three compounds in fraction 12 has a fruity, raspberry-like, sweet aroma with a green nuance and a fruity, raspberry-like, green spicy character with a bitter nuance at 5 T / Mill. The mixture of the ketones A_ and β has from the point of view perfumery has a long, fruity, berry-like flavor Aroma with chocolate-like, aromatic-spicy, wine-like, sweet, balsamic, fruity, banana-like, raspberry-like, zir.t-like, ion-like, musty, flowery, woody, salicylic, nuances reminiscent of elemi resin.

809821/0723

-W-

When used with tobacco, it has a sweet, fruity , raspberry-like, green aroma before smoking and gives the tobacco smoke a sweet, fruity , green taste when used in an amount of 200 to 500 T / taill. is added to the tobacco .

example 21 Procedure to Preparation of 2- (4'-methyl-2'-pentenoyl) -3,> dlmethyl-5-

norbornen

Reaction:

56 g of potassium hydroxide in 500 g of methanol were introduced into a 3 liter reaction flask equipped with a stirrer, thermometer, reflux condenser and filling funnel. While the Methanol / KOH solution was kept at 2 ° to 4 ° C, became a Solution of 500 g (3 mol) of 2-acetyl-3 # 3-dimethyl-5-norbornene, 240 g (3.3 mol) of isobutyraldehyde and 50 g of toluene were added from the feed funnel over a period of 35 minutes.

The reaction mixture was then stirred at 2 ° to 4 ° C. for 1 hour and then refluxed at 71 ° to 73 ° C. for 12 hours. It was then cooled and the reaction product was placed in a separating funnel and mixed with 1 liter of water and 500 ml of toluene

809821/0723

- 73 -

mixed. The ν: us sr i (right layer was separated a ':: ~ and with one 250 ml of rcrtion toluene extracted. The organic layer became rr.it give the toluene extract: .usa: r.: r.en £ e and gev: ash as follows: a 500 ml Port ic η water, a SOG ml Fortion of a 5 # Sodium bicarbonate solution and a 500 ml serving of a saturated aqueous! latrium chloride lüoung. The organic raw product v; was withdrawn from Lo3ung3r.itte 1 and after adding 25 g of Prir.ol and 1 g of Ionol * - * rapidly distilled. The distillate was then

Fractionally distilled in a 12 "GoodICe-CiIuIe.

The read liquid chromatography, IR, KMR and KS analyzes he indicated that the product obtained was an Irish made up of three (3) compounds, the formulas of which were as follows:

The las liquid chromatography profile of this mixture is in Flg. ? 2 shown.

This Glemisch had a food flavoring point of view siJsses, an rote <Tohannisceer .-. ar: .-, elade erinr.eri: des, fruc: itiges Aroma with citrus- and ionon-like, burnt, spruce needles reminiscent and piquant! nuances and a fruity, spicy character reminiscent of red Johann is little berry lade with grin fresh raspberries and spruce reminiscent of I. 'nuances.

809821/0723

- rs -

From the point of view of perfume, this mixture had a fruity, berry-like ai? o; r.a. In tobacco v: ar the aroma before smoking sweet, bloomy and green. When smoking, sweet, fruity and slightly floral nuances emerged.

The three compounds were separated in a Sas liquid chromatography column (conditions: 5 'x 1, ^{/ J} * ^W & / ί SZ-JO column, free 200 ° C isothermal).

The KT-'iR spectrum for the mixture of the compounds of the structural formulas

Spectral acts for the flesantcemic IR data :

1620 ⁰ ^ ¹ , 1705, 1635, 1660

KTlR data: Doublet of duplicates interpretation ppm (J & 16 Hz, 7Hz) H 6.74

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--θβ -

Ϊ7 / .Β. -Data ; continuation

P pm 5.95-6.50

Kultiplett

interpretation

O H

VSc

broad triplet

H H

1.73

1.66

broad

Singlets

1.04, 0.81, 0.79

Singlets

Doublet (Js-6 Hz)

3.BO 3. ^ 0

Sinclettes

O-C! F

(asymmetrical

Center)

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Example 22

Production of 2- { l-Hydroxybutyl) - ^,. ~> rilr.ethylnorbornane and 2-butyryl-3, ^ - dircethylnorbornane

Response : Part A

part B

toj

Part A

In one equipped with a RUhi ^ r, thermometer and reflux condenser 200 ecm flasks were 15 C dimethylnorbornancarboxaldehyde, prepared according to Example 1, and 50 ecm diethyl ether brought in. During 15 minutes, 50 ecm were read from n-propy! magnesium chloride (2.2 molar in diethyl ether) added. The reaction mixture was refluxed for 1/2 hour, after which a gas-liquid-chronato ^ raphie analysis the complete implementation of norbornanearboxaldehyds ar.eeijte. The reaction mass obtained was then washed with saturated aqueous ammonium chloride solution; hydrolyzed. Then -was

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- 82 -

Added water to dissolve the salts. The aqueous phase was extracted with 50 cc diethyl ether and the ether extract was combined with the organic phase and drawn off. The product obtained was distilled in a micro-Vigreux column and thereby obtained 13.3 g in 5 fractions, boiling point 79 ° to 62 ° C at 1 mm Hg.

Data:

ppm

10

15th

0.88 1.02

lr.01

1.25

interpretation

Singlets, according to dimethyl protons (2 sets; 2 isomers exo and endo)

1.06 Triplet CH ₅ -CH ₂ - 2.34-1.32 Methylene and methine
Protons 3.56 Multiplet I.
HC-Ο
Ι 1.13 Singlet OH

IR data ;

950, 1005, 1055, HOO, 1355, 1375, 1455, 2860, 2920, 2950, 336Ο cm " ¹

20 MS data ;

m / e = 41, 155, 55, 67, 43, 27; Stem tip = I96

The NMR spectrum is in Fig. 25 and the IR spectrum is in Fig. 26 shown.

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part B

A 2.5 g portion of the distillate obtained in Part A was dissolved in 10 ecm of acetone and the solution was cooled to 0 ° to 5 ° C. while a "Jones reagent", prepared according to Example 4, was added dropwise (a total of 2 ml required). The aJis liquid chronatography analysis showed that one (1) product was formed. 25 ecm of water were added to the reaction mass and the aqueous phase was extracted with diethyl ether. The diethyl ether extract and the organic phase were combined and washed with saturated sodium chloride solution. The washed organic solution was drawn off and distilled on a micro-Vigreux column to give 1.5 g of a product
Distilled pressure.

Product were obtained. It was measured at 90 ° C and 1.0 mm Hg-

The NMR, IR and MS analyzes showed that the product 2-butyryl-3 * 3-dimethylnorbornane was.

ΝΤΕ data:

<T, pm Triplet interpretation 0.84
0.90
0.95
1.14
1.31 -CH ₂ CH- ,; -CH ,; endo and
exo isomers 1.0-1.06 Multiplets 2.3 O
Il
-C-CH ₂ -CH ₂ - IR data:

1700 cm " ¹ (C = O)

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MS data ;

m / e = 123, 43, 41, 127, 27, 67; Trunk tip = 194

The IIMR spectrum is in Fig. 27 and the IR spectrum in Fig. 23 shown.

Example 23 Production of 2-Dutyroyl-3,3-diraethylnorbornane

Reaction:

The following ingredients were placed in a 250 ecm Parr shaker brought in:

Ingredients quantity

2- (trans-2-butenoyl) -3,3-dlme thylnorbo man,
produced according to Example 12 90 g

555 palladium on carbon 1 g

catalyst

The shaker was sealed and then with hydrogen pressurized, up to 3.5 at, and periodically the pressure increased over a period of 7 hours to keep it at 3.5 atm. The temperature of the reaction mixture remained at 25 ° C. After the 7 hours, the shaker was turned off opened and the contents filtered. 5.0 g PrinolLx and 0.1 g IonolViy were added to the piltrate. The mixture

809821/0723

- ΑΓ

was then distilled in a 1.20 m Vigreux column and 47 g of an oil collected. - Boiling point 93 ° to 95 ° C at 3 * 0 now Hg

The NMR, IR and MS analyzes showed that it was a compound of the following formula:

HO

NMR -Data : O\. ppm

0.85 0.96 1.14 1.22

Shifts

Singlet, 2 sets, (2 isomers)

0.89 (t) CH ₅ -CH ₂ - 2.08-1.46 Methylene and t'ethine
Protons 2.50 Diffuse triplet
Protons o ( carbonyl

IR data : 1100, III5, I29O, I36O, 1400, 1455, I7OO, 2940 cm

-1

MS data:

m / e «123, 41, 43, 127, 27, 151J Stammspitze»

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

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Example 24 Production of 2- (4'-pentenoyl) -3>,? - dirr.ethylnorbornane

Reaction:

In a nit stirrer, thermometer, reflux condenser, filling funnel and a nitrogen inlet of 500 ml reaction flask equipped with a suspension of 48 g of 55% sodium hydride and? 50 ml of toluene introduced. Under a nitrogen blanket were 166 g (1 mol) of 2-acetyl-3,3-dimethylnorbornane during added over a period of 5 minutes. The reaction mixture was refluxed for 70 minutes and then to 45 ° C chilled. Within 15 minutes, allyl chloride (76g, 1 mol) and tricaprylmethylarTuT.onchlorid (4 g) (known as the trademark Aliquat 3J56 ^ - ^ from General Mills Chemical Inc.) added and the mixture was then stirred at 60 ° C. for 12 hours.

The resulting suspension was left to settle and then filtered through glass wool. The filtrate was washed with water, the solvent was removed on a rotary evaporator and a white, milky oil was obtained. Gas-liquid chromatography gave three peaks. The gas-liquid chromatography profile (conditions: 3 ¹ χ 1/4 "SE-30 column, programmed

809821/0723

isothermal at 200 ° C; 40 ml / foinute) is shown in FIG. 31.

The IC-IR, IR and MS analyzes confirmed that three compounds of the following formula were formed:

The compound of the formula:

had the following KS data :

m / e = 123, oil, 67, 55, 151, 108, 33; Steel point = 206

ppm

0.83 1.22

Singlet singlet

interpretation

like dimethyl group

4.92 5.05 5.12

-CH = CH ₂

5.65-5.95

-CH ₂ -CH = CH ₂

The NMR spectrum is shown in FIG.

The compound of the formula:

had the following NMR -Data :

809821/0723

- .88 -

ό,

.pm

1.04 Singlet 1.02

interpretation

gene dimethyl group

2.05 Singlet O üi'rO J = 7Hz doublet -CH ₂ -CH = CH ₂ 4.92
5.96 Multiplet
Multiplet -CM = CH ₂ 5.3-5 .8 multiplet -CH ₂ -CH = CH ₂

The Ι, Ί-IR spectrum of this compound is shown in Fig. 33, 10 The compound of the formula:

/ jSt- ¹

had the following ^ -! R data ; 'J, PPm

0.88 singlet 1.20 singlet

interpretation

like dimethyl group

4.92-5.14 multiplet

5.5-5.9 multiplet

-CH = CH ₂

The IIMR spectrum is in Fig. 34 and the IR spectrum is in Fig. 35 shown.

20 The IR data ; I700 cm " ¹ (C = O); I635 cm" ¹ (C = C)

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- rock

From the point of view of perfumery, the product has a camphor-like, woody, fruity (orange) aroma with green, spruce-like undertones.

A procedure similar to that described above was carried out, with the exception that a molar equivalent of sodium hydroxide was used in place of sodium hydride. The result was that the same three joints were formed in the following percentages and proportions.

Structural formula

percent

relationship

1.5

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Example 25 Preparation of 2- (4'-pentenoyl) -3,3-dirr: ethylnorbornane

Response: Part A

Response: Part B

t.'aH

EtO -? - o- _st

H .

"OEt

' ^ OEt (1) MaH H
C- " (2) H (3) KaOH (4) HCl

Part A:

In one with nitrogen inlet, thermometer, reflux condenser The following compounds were introduced into the 3 liter reaction flask equipped with a stirrer:

Sodium hydride (55Ji) 88 g

Diethyl carbonate 2% g

Benzene 1 liter

The mixture was refluxed under a nitrogen blanket

warmed up.

Over a period of 30 minutes, 2-acetyl-3 »3-dlmethylnorbornane added and then refluxed for a further 40 minutes. 200 ml were then added to the reaction mass

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Acetic acid and then 1 liter v / ater added. The organic Phase was separated and the crude product obtained was rapidly distilled in a 2 "column and 205 g of Cl were collected: Boiling point 80 ° to 160 ° C at 1 mm Hg.

(H)

After adding 5 g of Pritnol ^ the distillate was on a 12 "xl" Goodloe still fractionated. Yield were 119 g of product, boiling point 109 ° to 127 ° C at 1.2 trjn Hg.

NT-IR analysis indicated that the distilled product had the structural formula

exhibited.

NMR data :
S , ppm

0.92 singlet 1.22 singlet

interpretation

according to Dimethy! group

1.24 (J = 7Hz) triplet

-CH ₂ CH,

Singlet

> COOEt

4.18 (J = 7Hz) quartet

-OCH ₂ CH,

The NMR spectrum is shown in Fig. 36 and the IR spectrum is shown in Fig. 37 .

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IR data:

1650 -C = C- (m)

I7OO CO (strong)

17Ö0 0

C-O eth. (strong)

MSr data :
m / e = 103, 123, 109, 107, 29, 41; Trunk tip = 233

part B

100 g of toluene were mixed with 24 g (0.55 mol) of sodium hydride and heated to 60 ° C, in a with stirrer, thermometer

and reflux condenser equipped 500 ecm reaction flask. Over 80 minutes, the carbocethoxy compound prepared in Part A was added to the totuene / sodium hydride mixture. After completion of the addition and it Ketocarboxylsäureesters a mixture I ^ of 38.5 g allyl chloride and 7 g Tricaprylmethylammonchlorid (Aliquat 336v- ') was added over a period of 20 minutes while the reaction mixture to 8o ° C.

Then 50 ml of 50% sodium hydroxide solution and 50 ml of water are added and the mixture is then refluxed for 2 hours. 100 ml v / ater was added to dissolve the precipitated precipitate. When 110 ml of 20% hydrochloric acid was added, CO ₂ gas developed.

The product obtained was rapidly distilled at 100 ° C. and 2 mm Hg pressure, and the distillate, after adding 10 g of PrimolCJund

(n)

Ig Ionox ^ - / fractionally distilled, taking an oil with a Boiling point of 90 ° C at 1 mm Hg was obtained.

The NT-IR and IR analyzes confirmed the structural formula

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The NMR spectrum is shown in FIG. 38.

NMR data : Q, ppm interpretation

0.88 singlet _{according to} dimethyl group

1 .22 singlet

4.92-5.12 multiplet -CH = CH ₂

5.65-5.95 multiplet -CH ₂ -CH = CH ₂

The IR spectrum is shown in FIG. 39.

IB data t

I63O (C = C), I7OO cm " ¹ (C = O)

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275Ö2D6

ηοο

Example 36 Production of 2-pentanoyl-3,3-dinethylnorbornane

Reaction:

H.

Pd

10'g of the 2- (V-pentenoyl) -3i3-dimethylnorbornane prepared in Part B of Example 25 and 50 ml of isopropyl alcohol were placed in a Parr shaker along with 0.5 g of a palladium catalyst brought in. The shaking machine was closed and brought to a pressure of 2.0 ^ at with hydrogen .- This pressure was held for 2 hours, and hydrogen supplied when it was necessary. The temperature of the reaction mass remained at 25 ° C. It was then filtered, the solvent evaporated and the product by preparat! ve Gas-liquid chromatography isolated.

the

NMR, MS and IR analyzes confirmed the structural formula:

This compound had a sweet, berry-like, tangerine-orange aroma with nuances of spruce.

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- 99 - 404

NMR data:

<L

ppm

1.86 singlet 2.24 singlet

interpretation

according to Dimethy! group

O .88 (j ^ 6Hz) Triplet -CHpCH, 2 .30 (J # 7Hz) Triplet O
Il
'^ CH ₂ CH ₂ CH ₃ 2 .30 Singlet

MS data :

m / e = 123, 41, 67, 81, 57, 103j stem tip = 208 IR data :

1700 cm " ¹ (^ C = O)

The NMR spectrum is in Pig. 40 and the IR spectrum is in Fig. 41 shown.

Example 27

Production of ^ f-Methallyl-Cy, 3 _< 3 ".trlmethyl-5-norbornen-2-methanol

Reaction:

MgCl

(1) Kther

(2) H ₃ O ⁺

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In one with reflux condenser, thermometer, stirrer, dropping funnel 1 liter reaction flask equipped with a nitrogen inlet, 12 g (0.5 mol) of magnesium turnings and 250 ecm of anhydrous were removed Given diethyl ether. 45.3 g (0.5 mol) Methallyl chloride added. This Grignard solution was 30 minutes stirred and 28 g of 2-acetyl-3,3-dimethyl-5-norbornene for 20 minutes admitted. The mixture was stirred under reflux for 30 minutes and then by adding saturated ammonium chloride solution hydrolyzed. The organic layer was washed with water and dried over magnesium sulfate. The reaction product was then filtered and the solvent evaporated to give 40 g of an oil which was deposited on a micro-Vigreux column after adding 5 g of Primol ^ and a trace of IonoxS- ^ fractionated was distilled.

The MS, IR and NMR analyzes confirmed that the obtained Compound had the structural formula:

NMR data r interpretation

(if ppm
1.40-0.97 methyl protons

1 .86 .48 olefinic
ring = C-CH, 2 .36-1 .78 Methylene and methine
Protons 4th .84-4 12th -C = CH ₂ 6th 24-1. Protons from the norbornene

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IR data:

700, 830, 1030, 1320, 1560, 1450, 2350, 3500 cm " ¹ .

The NMR spectrum is in Fig. 42 and the IR spectrum is in Fig. 43 shown.

Example 28 Production of ^ i-Allyl »Of, 3 ^ 3-trlmethyl-g-norbornanmethanoI

Reaction;

Components

2-acetyl-3,3-dimethyl-

norbornane 23.5 g (0.17 mol)

Magnesium 12.0 g (0.5 mol) Allyl chloride 33.25 g (0.5 mol)

anhydrous ether 200 ecm

The magnesium shavings were placed in a 1 liter three-necked flask and 200 ecm of anhydrous ether was added. To the Formation of the Gridnard reagent were about to start 6 ecm of allyl chloride added. After the start of the reaction was the remaining allyl chloride dropwise over a period of time mes of 2 hours added under gentle reflux. After Been After the addition, the mixture was refluxed for a further hour. Then 28.5 g of 2-acetyl-3,3-diniethylnorbornane were during Added 20 minutes. This reaction was very exothermic. After the addition was complete, reflux was continued for 1 hour warmed up. The preparation was carried out by hydrolysis with NH ^ Cl solution, filtering and separating the layers. The organic Layer was washed over with two 200 ecm portions of water MgSO ^ dried, filtered and concentrated, leaving 34 g of one Oil were obtained which, after distillation, had a yield of

80982170723

15th

lull

26 g of a product resulted which had a boiling range of 90 to 105 ° C at 1 to 2 mm / lg pressure.

LT S data:

shift

ü, ppm

1.06 1.10 1.20 1.24 1.26 1.30

Methyl protons

2.13-1.56
2.32 Methylene protons 5.16-5.00 H
-C = CH ₂ 6.03-5.64 HC = CHp

IR data ;

910, 1035, 1160, 1200, 1250, 1300, 1330, 1360, 1335, 1460, 2860, 2940, 3070, 3 ^ 80 cm " ¹ .

The NMR spectrum is in Fig. 44 and the IR spectrum in 45 shown.

Example 29 Preparation of C7f-allyl- / 7 \ .3> 3-trlmethyl-5-norbornene-2-methanol

Reaction:

H.

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The following components were placed in a 1 liter three-liter nlokolberi equipped with a stirrer, thermometer, cooler, drying tube and nitrogen inlet:

Ingredients quantity

2-acetyl-5,5-dimethyl-5-

norbornene 29.2 g (ö, 17 KoI)

Magnesium. 12.0 g (0.5 tfol)

Allyl chloride 53.25g (0.5 mol)

anhydrous fither 200 ecm

The reaction was carried out under the same conditions like that in Example 23. The preparation was carried out by hydrolysis with an NH ^ Cl solution, filtering and separating the Layers. The organic layer was made with two £ 00 ecm servings Washed water, dried over MgSO ^, filtered and concentrated to give 57 g of a crude product.

This was distilled on a Klkro-Vigreux column after 5 g Primol ^ and traces of Ionox ™ was added. There were 25 g oil, boiling range from 90 ° to 93 ° C at 1.0 to 1.6 nm Hg Pressure, received.

NMR patents t

Q , ppm interpretation

I.58-0.94 riethyl protons

2.40-1.50 ^ ethylene and methine
Protons 5.20-5.00 HC = CH ₅ 6.02-5.66 HC = CH ₂ 6.28-6.04 Borne olefinic
Protons

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IR data ;

710, 910, 995, 1035, Il4o, 125G, 1 * 25, 1560, 1460, 1635, 2960, 3060, 3470 cm " ¹ .

The KI-IR spectrum is in Fig. 46 and the IR spectrum in Fig. 47 shown.

Example 30

Production of Oj -Methallyl- Ό ( 3,3-trlrr, ethyl-2-norbornanmethano l

Reaction:

In one with stirrer, Therir.orr.eter, condenser, drying tube and nitrogen inlet Equipped 1 liter three-necked flask, the following components were introduced:

Ingredients quantity

2-acetyl-3,> dimethyl-

norbornane 28.5 g (0.17 mol)

Magnesium 12.0 g (0.5 mol)

Methallyl chloride 45.27 g (0.5 mol)

The reaction was carried out under the same conditions as in Example 23. The work-up was carried out by hydrolysis with an NH ^ Cl solution, filter and separate the layers. After removing the Löcunssriittels 34 g elnos product remained, after adding 5g Prir.olCL ^ and a trace of Ionox ^ on one Micro-Vigreux column was distilled.

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- .131 -

NKR data :

C ',

ppm

1.27-1.06

Interpretation of methyl protons

1.86 3 HC-
I. 2.12-1.32 -CH ₂ - + 4.74-4.94 I.
-C = CH ₂

IR data :

880, 1080, 1105, 136O, 1330, 1455, I630, 2860, 2940, 3500 cm " ¹ .

The NMR spectrum 1st in Fig. 48 and the IR spectrum in Fig. K? shown·

Example 31 Preparation of 3 * 3-Dwgthyl-2- (4-methyl-4-pentenoyl) -norbornane

Reaction:

toluene

(A)

^(c)

(B)

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A suspension of 146 g of l! Atriu: i.hydriri (5f - ^ - ige mineral oil dispersion) in 1500 g of toluene were heated to 100 ° C and a solution of 5CO g of 2-acetyl-3,3-dimethylnorbornane in 50 g Toluene was added over a period of 1 hour. The mixture was stirred at 100 ° to 103 ° C until no hydrogen gas more was developed (total amount of gas development = 66 liters at 1 at).

A solution of 230 g of methallyl chloride in 250 g of toluene was then added at 100 ° to 105 ° C. over the course of 1 hour. The mixture was stirred at 100 ° to 110 ° C. for a further 14 hours and then cooled to room temperature. It was then washed several times with water and the solvent was removed at atmospheric pressure. The solvent-free product was rapidly distilled through a short column at reduced pressure and the distillate carefully fractionated in a 12 "χ 1" Goodloe column, (i) 214 g of an oil, boiling range 100 ° to 111 ° C at 0.9 mm Hg was obtained. The gas-liquid chromatography profile is shown in FIG. 50 and turns out to be a mixture of (A) 3,3-dimethyl-2- (4'-methyl-4 ^l- pentenoyl) norbornane and (B) 2 -Acetyl-2-methallyl-3,3-dimethylnorbornane in a ratio of about 3: 1. (ii) 78 g of an oil, boiling point 122 ° C at 0.8 mm Hg, which turns out to be essentially pure (C) 3, ^ - dimethyl-2- (2 ^f -methallyl-4'-methyl-4 ^l - pentenoyl) norbornane was the third product obtained.

The N ¹ MR data for compound A were:

Ci, ppm Interpretation of structural forms 1

If

4.70 Kultiplett

I.74 common singlet

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Tj > ppm

1.24 0.86

Interpretation S ingle tt

Structural formula

CH,

IR godparents ; (A) cm " ¹

The NMR spectrum of Compound A is shown in FIG. 51 and the IR spectrum in FIG. 52.

Str uk door f orr.e 1

NMR data . ppm for connection (B) T .82
.67 interpretation 4th
4th wide singlet

H H

2.09

Singlet

^C «3

I.69

1.10

wide singlet

Singlet

IR data (B) 1690 cm " ¹

The NMR spectrum of the compound (B) is shown in Fig. 53 and the IR spectrum in Fig. 54.

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NMR data for compound (C) :

C, ppm Interpre tat ion Structural formula 4.77 Kultiplett I.76
1.63 2 wide singlets 1.22
p.87 2 singlets NCH ₃ IR data (C):

1695 cm ' ¹

The NMR spectrum of the compound (C) is in Fig. 55 and that IR spectrum shown in Fig. 56.

The mixture of compounds H

had, from the standpoint of its use as a flavoring, in one Lot of 10 T / foil., A camphor-like, woody, mint-like Aroma with a strong cooling nuance, which makes it suitable for dentifrices, mouthwashes and the like. The tobacco imparts the mixture in an amount of 200 T / foill. cooling and floral notes, although we smoke the tobacco. For perfumery purposes it has a fruity, woody note that surprisingly lasts for a very long time.

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The compound of the formula:

had a deep-voiced, sweet, fight-like, cedarwood-like feel Aroma with notes reminiscent of green herbs and spruce when considered for perfumery purposes.

The compound of the formula:

has, also from the point of view of the parforery, a deeply starred, Sweet, herbaceous aroma reminiscent of green wood.

Example 32 Manufacture of a cosmetic powder

In a ball mill, 100 g of talcum powder with 0.25 g of the Compound from Example 15 mixed. This powder mixture had an excellent spruce needle aroma with green, rr.elon-like, Herbaceous, delicate characteristics reminiscent of cut wood.

Example 33 Perfumed liquid detergent

Concentrated liquid detergents (lysine salt of n-dodecylbenzenesulfonic acid, particularly in US Pat. No. 3,9 ^ 8,813 described) with intense spruce needle aroma notes.

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The detergents contained 0.10 ^; 0.15 # and $ 0.20 the Perfume preparation from Example 15. The individual constituents were each mixed homogeneously with one another. All samples of the Dissolvents had an intense spruce needle arc green, melon-like, herbaceous, delicate characteristics reminiscent of cut wood, whereby the intensity with higher concentrations increased.

Example? 4

Hera division of a cologne and a handkerchief perfume The preparation from Example 15 was added in a concentration of 2.5 # in 85% aqueous ethanol to a cologne, which thereby has a pronounced and specific spruce needle scent with green, melon-like, herbaceous, delicate and cut Received notes reminiscent of wood. The preparation from Example 15 was added in a concentration of 20 # (in 95 # oil according to uässrlgen ethanol) to a handkerchief perfume, which thereby received a pronounced and starry spruce needle scent with green, melon-like, herbaceous, delicate and cut wood-like characteristics .

Example 35 Making a soap preparation

100 g of soap chips were mixed with 1 g of the perfume preparation from Example 15 until the cash register was homogeneous. the perfumed side had an excellent spruce needle scent with green, melon-like, herbaceous, delicate and cut Characteristics reminiscent of wood.

Example 36 Manufacture of a cosmetic powder

ICO g of talcum powder were mixed with 0.25 g of the .30 compound from Example 12 in a ball mill. This powder mixture had an excellent spruce needle aroma with sweet, woody, fruity, aromatic-spicy (nutmeg, pepper) and herbaceous characteristics.

809821/0723

Example 37 Perfumed liquid detergent

Concentrated liquid cleaning agents (lysine salt vcn n-Dodecylbenzenesulfonic acid, US-F3 3,943,318) rides you intense spruce needle aroma produced by 0.10 pounds; £ 0.15 and 0.20 # of the perfume preparation from Example 12 were added. The ingredients were each mixed until the mass was homogeneous. The detergents all had an intense one Pichtennade laroma with external, woody, fruity, aromatic and spicy (Nutmeg, pepper) and herbaceous characteristics. The intensity increased with increasing concentration.

Example 38

Making a cologne and a handkerchief perfume Ur.z .

For a Kölnischvxasser, 2.5 # of the compound from the example 12 added in 85 # aqueous ethanol, which thereby a pronounced and specific spruce scent with sweet, woody, fruity, aromatic-spicy (nutmeg, pepper) and herbaceous characteristics.

The same compound (Example 12) was made into a handkerchief perfume at a concentration of 20 # in 95% aqueous ethanol admittedly, it has a pronounced and specific spruce flavor with sweet, woody, fruity, aromatic and spicy scent. (Nutmeg, pepper) and herbaceous characteristics.

Example 39
Making a soap preparation

100 g of soap chips were mixed with 1 g of the perfume preparation Example 12 mixed homogeneously. The so scented soap had someone. excellent spruce scent with sweet, woody, fruity aromatic-spicy (nutmeg, pepper) and herbaceous characteristics.

809821/0723

Example 40 Manufacture of a cosmetic powder

100 g of talcum powder were mixed with 0.25 g of the preparation according to Example 3 in a ball mill. This powder mix had an excellent scent of pine needles with fruity, herbaceous, St. John's wort and fir balsam-like characteristics.

Example 41 Manufacture of a liquid cleaning agent

There were concentrated detergent (lysine salt of n-Dcdecylbenzolsulfonsäure as in Example 37) ^m i ^ a more intense. Spruce needle! Aroma produced by adding to samples of the detergent £ 0.10; 0.155? and 0.20 ;? the perfume preparation according to Example 3 were added. The components v.-urden each homogeneously mixed. All samples had an intense aroma of spruce with fruity, herbaceous, St. John's wort and fir balsam-like characteristics. The intensity increased with higher concentrations.

Example 42
Manufacture of a cologne and a handkerchief par for

The preparation from Example 3 was in a concentration of 2.5 ^ in 85 ^ aqueous alcohol to a cologne and at a concentration of 20% in 95% aqueous ethanol added to a handkerchief perfume. In both cases there was a pronounced and specific scent of pine needles with fruity, herbaceous, St. John's wort and fir balsam-like characteristics awarded.

Example 43

Making a soap preparation
ICO g of soap chips were homogeneously mixed with 1 g of the perfume

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device from example 2 mixed homogeneously. The perfumed soap had an excellent spruce needle scent advises fruity, herbaceous, St. John's wort and fir baisam articen characteristics.

Example 44

Making a cosmetic powder

In a ball mill, 100 g of talc powder with 0.25 g of the Preparation according to 3 example 2 mixed. This powder mixture had an excellent pichtennadelaror.a with sweet, woody, thujone-like, St. John's wort-like, reminiscent of 2 leather leaves and camphor-like characteristics.

Example 45 Perfumed liquid detergents

Concentrated liquid detergents (lysine saline -crj n-dodecylbenzenesulfonic acid as in example yj) with an intense spruce needle aroma were produced, in the. C, 10>ü; 0.15 $ and 0.2C ^ of the perfume preparation from Example 2 for samples of the Reini-u.-.

medium were added. The ingredients were mixed homogeneously.

They all had an intense spruce needle aroma with sweet, Woody, thujone-like, St. John's wort-like, cedar leaf-like and camphor-like characteristics. As usual the intensity increased with increasing concentrations.

Example 46 Manufacture of a cologne and a handkerchief perfume

The preparation from Example 2 v: urde in a concentration of 2.5 $ in 85% aqueous ethanol to a cologne and at a concentration of $ 20 in 95 pound ethanol to one. Handkerchief perfume added. The preparation gave the eau de Cologne and the handkerchief perfume a distinctive and famous Spruce needle scent with sweet, woody, thujone-like, St. John's wort-like, cedar leaf-like and camphor-like Characteristics.

809821/0723

Example 47 Making a soap preparation

100 g of soap chips were mixed homogeneously with 1 g of the preparation from Example 2. The soap received an excellent Spruce needle scent with sweet, woody, thujone-like, St. John's wort-like, characteristics reminiscent of cedar leaves and camphor-like characteristics.

Example 43 Perfumed liquid detergents

Ice were concentrated liquid detergents (as in example 37) with an intense spruce needle aroma. Samples of the detergent were added to 0.105 & j 0.15 # and 0.20 # the preparation from Example 19 was added. The 'ingredients were mixed together homogeneously. All rehearsals were intense Spruce needle aroma with fresh, musty, sweet, woody, minty nuances and with freshly cut spruce / resin reminiscent characteristics. The intensity increased with higher concentrations.

Example 49
Production of a cologne and handkerchief perfume

The preparation from Example 19 was used in a concentration of 2.5 $ in 8% aqueous ethanol to make a cologne and at a concentration of $ 20 in 95% aqueous ethanol given to a handkerchief. The preparation gave the eau de Cologne and the handkerchief perfume a distinctive and certain spruce needle scent with fruity, musty, sweet, woody, minty, freshly cut spruce / resin reminiscent characteristics.

Example 50
Making a soap preparation

100 g of soap schnitzel were made with 1 g of the perfume preparation

809821/0723

Example 19 mixed homogeneously. The side so perfumed had an excellent Fidttennadel smell with fruity, musty, sweet, woody, mint-like and characteristics reminiscent of freshly cut oak / resin.

Example 51 Manufacture of a cosmetic powder

In a ball mill, 100 g of talc powder were mixed with 0.25 g of the preparation from Example YJ . The powder mixture had an excellent spruce needle aroma with musty, sweet, fruity, woody and vermouth-like characteristics.

example 52 Perfumed liquid detergents

Concentrated liquid detergents (such as Example 37) were made with an intense spruce needle laroma, Indian. to samples 0.10 ^; $ 0.15 and $ 0.20 ^ of the perfume preparation Example 17 were added. The components were each mixed together homogeneously. All samples had an intense spruce needle aroma with musty, sweet-fruity, woody and wormwood-like characteristics, the intensity increasing with higher concentrations.

Example 53

Production of a cologne and a handkerchief parfti

The preparation from Example 17 was added at a concentration of 2.5 # in 85 # aqueous ethanol to a cologne and at a concentration of 20 # in 95% aqueous ethanol to a handkerchief. The preparation gave the eau de Cologne and the handkerchief perfume a distinctive and definite spruce needle scent with musty, sweet-fruity, woody and vermouth-like characteristics.

609821/0723

Example 54 Manufacture of a soap preparation

100 g of soap chips were mixed with 1 g of the perfume preparation Example 17 mixed homogeneously. Who had so scented soap an excellent spruce needle scent; it musty, sweet-fruity, woody and wormwood-like characteristics.

Example 55 Manufacture of a cosmetic powder

In a ball mill, 100 g of talcum powder with 0.25 g of the Preparation from Example 11 mixed. This powder mixture had an excellent spruce needle aroma with woody, spruce-like, natural-looking nuances with fruity, aromatic, spicy, cresyl-like, borneol characteristics with a defined berry top note.

Example 56 Perfumed liquid detergents

There were concentrated liquid detergents like in the Examples 37 * 41 etc, except that the Perfume preparation from Example 11 in concentrations of 0.10 ^, $ 0.15 and $ 0.20 was added. The detergents produced in this way all had an intense spruce needle aroma with woody, spruce-like, natural nuances with fruity, aromatic-spicy, cresyl-like borneol characteristics and a definite berry top note. The intensity increased with it higher concentrations.

Example 57 Manufacture of a cologne and a handkerchief perfume

The preparation from Example 11 was used in a concentration of 2.5 $ in 85% aqueous ethanol to make a cologne and at a concentration of 20 # in 95 # aqueous ethanol given to a handkerchief. Both the cologne and

809821/0723

the handkerchief perfume had a pronounced and definite quality Pine needle scent with woody, spruce-like, natural-looking nuances with fruity, aromatic-spicy, cresyl-like nuances Borneol characteristics and a definite berry top note.

Example 58 Making a soap preparation

100 g of soap chips were mixed with 1 g of the perfume preparation Example 11 mixed homogeneously. The perfumed soap had an excellent scent of pine needles with woody, spruce-like, natural-looking nuances with fruity, aromatic- spicy, ci'esylartlgen, borneol characteristics and one definitive berry head note.

Example 59 Tobacco filter

In a 20 mm cellulose acetate pilter was £ \ -Ethyl-3,3-dlmethyl-2-norbornanmethanol in an amount of 1000 T / kill. (10 microliters of a 10% lgin solution of norbornane methanol were used to Filter added) introduced. The filter was then attached to a cigarette from a well-known cigarette manufacturer on the market.

Variety (such as (1) Marlboro (5J (2) WinstonLJ or (3) Viceroy®) and a "Kentucky 1A3" comparative cigarette (manufactured by the University of Kentucky) attached. The following results were found:

1 · Both types of cigarettes had a sweet, woody appearance when the norbornane methanol additive was added to the filter when smoked spruce-like aroma with a pleasant cooling effect and noticeably reduced sharpness when compared to untreated filter cigarettes.

2. Both cultivars of cigarettes with a filter treated with norbornane methanol additive showed a lower degree of "Heat" and conveyed a "fresh" Taste.

809821/0723

Example 6o

Sodium borohydride reduction of 2- (2-butenoyl) - ' -, ^ - dinethyl norbornane

Reaction:

NaBH

In a 500 ecm equipped with a stirrer, cooler and thermometer Three-necked flasks were 82 g (4 ^ mol) of a product, the more than 90 $ '2- (trans-2-butenoyl) -3,3-dimethylnorbornane (prepared according to Example 12), and introduced 250 g of anhydrous methanol. During 1 hour 7 g of sodium borohydride were added while the reaction mixture was maintained at 25 ° to 26 ° C.

It was then stirred for 3 hours at 25 ° to 28 ° C, after which more 7 g of sodium borohydride were added. The reaction mixture was stirred for a further 3 hours until there was no change in the gas-liquid chromatography profile was to be determined. The resulting mixture was then placed in a 1 liter flask and the methanol evaporated, leaving a pulp. This was mixed with 500 ml of water and this mixture with 150 ml of cyclohexane extra * here. The cyclohexane extract was rapidly distilled at 100 ° to 115 ° C., working in vacuo at 2.4 to 2.6 mm Hg and the solvent was removed. After adding 5 g Primoiv ^ and 0.1 g Ionol ^ was fractional distilled, and on an 8-plate Vigreux column, at 11) ° to 120 ° C vapor temperature and 2.7 to 4.4 mm Hg pressure (reflux ratio 20: 1). Ten (10) fractions were collected, of which fractions 2 to 8 were used as seasonings and fragrances.

809821/0723

The product obtained was primarily a mixture of three (3) compounds of the formulas:

CH

which were confirmed by NT-IR, IR and MS analyzes.

The mixture was evaluated at 10 # in undenatured ethanol and from the point of view of perfumery had sweet spruce-like, Bornyl acetate-like, berry and somewhat woody notes.

From the point of view of the spicy character it had an aromatic-spicy, valerian oil-like, calamus-like, spruce needle-like, IQ herbaceous and fruity aroma with a valerian oil-like, calamus-like, spruce needle-like, herbaceous and fruity spicy character at 1 T / Wed11. .

The resulting mixture is suitable as food condiments, invigorating condiments, spruce needle condiments and condiments for a drink made from the roots of various herbs (root beer flavors).

The gas chromatography MS profile of the compound of the formula

is. shown in FIG. 57 .

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The GC-MS profile of the compound of the formula:

is shown in FIG. 53.

The GC-MS profile of the compound of the formula

is shown in FIG. 59.

The GC-KS profile of the gene of remaining in the reaction product Connections are shown in FIG.

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275Ö2Ö6

Example 61 Preparation of 3 _f ^ -dimethyl-2 (;? - butenyl) norbornanol-2

Reaction:

MgCl

-H

164 g of magnesium and 985 g of tetrahydrofuran were placed in a 12 liter reaction kettle. While the magnesium / tetrahydrofuran mixture was being stirred, 20 g of allyl chloride were added and the temperature of the reaction mixture was raised to 40.degree. A mixture of 2410 g of camphen oxide (43 £ in benzene solution) and 520 g of allyl chloride were slowly added and the reaction mixture was kept at a temperature of 35 ° to 40 ° C. by cooling from the outside. The allyl chloride and that Camphene oxide was added over a period of 7 hours. Then 10 grams of magnesium was added and one (1) more Stirred for an hour while the reaction mixture was kept at 40 ° C. by external cooling. The reaction mixture was then cooled to room temperature and held there for 15 hours.

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Then 6.3 liters of water were mixed with 170 g of concentrated 9J5 # iger Mixed sulfuric acid. The 3 * 8 liter reaction product was added to the sulfuric acid solution, whereupon the temperature rose from 20 ° C to 40 ° C. The resulting mixture was one Emulsion, and in order to separate the phases of the emulsion, became a Solution of 178 g of concentrated sulfuric acid and 1200 ml of water added. The water layers and organic layers were separated and the organic layer washed with 1 liter of water containing 5 g concentrated sulfuric acid, washed. The organic layer was then rotovaped and thereby 1249 g of a product obtained, which on an 8 "loodloe column fractional distillation was carried out after 41 g of Prlmolv-x 'had been added had been. Ej the following fractions were collected:

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fraction Steam temp,
(ο C) Liquid vacuum • • weight No. 43-60 temp. (° C) now ed (K) 1 60 124-122 3 - 2 65 111 2 - 3 76 108 1 - 4th 80 115 1 ι · 5 91 118 1 1.5 - 6th 91 122 1 1 - 7th 90-95 121 1 2 18.9 8th 101 128-126 3 2 3.7 9 103 · 123 3 2 26.4 10 103 123 3 2 28.3 11 101 123 3 2 37.8 12th 86 124 T 3 2 23.4 13th 88 124 1 2 41.5 14th 88 124 1 38.4 15th 91 124 1 31.6 16 93 125 36 17th 86 126 76.5 18th 102 122 81.3 19th 88 125 59.3 20th 88 125 75.9 21 88 125 64.1 22nd 88 127 60.3 23 93 134 44.5 24 161 40.1 25th 196 40.2

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- J20 -

Fractions 12-23 are essentially all product and were combined to give 633 grams of good material became.

NMR data:

a ', ppm interpretation

0.89 (s, 3H)

0.95 (s, 3H) 0.95-2.5 (m, 12H) 4.85 (m, 2H) 5.85 (m, IH)

MS data ;

ra / e = 55, 41, 111, 69, 43

The NMR spectrum is in Fig. 61 and the IR spectrum in Fig. 62 shown.

Example 62

Seasoning preparation using the product from Example 61 The following cinnamon base seasoning was produced:

Ingredients Parts by weight cinnamaldehyde 70

Eugenol I5

Cuminaldehyde 1.0

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Components 1φ * Weight point

Furfural 0.5

Methylcinnamate 5.0

Cassia oil 8.5

Total 100.0

The fraction 5 was in an amount of 5 # in this seasoning

mixture and gave it a character more reminiscent of the cinnamon bark, both in aroma and taste furthermore the aroma was more woody and pungent. The spicy mixture was preferable to the unseasoned one.

Example 63

A perfume preparation was made from the following ingredients:

Components parts by weight g

n-decylaldehyde I.

n-dodecylaldehyde 2

Methylnony / acetaldehyde 0.5

Linalool 50 linalyl acetate .70

Phenylethyl alcohol 100 Petitgraln 3A 20 Bergamot oil 30

0 (-Methyllonone 25

3,3-Dlmethy1-2 (3-butenyl) norbornano1-2

produced according to example 61 10

Cyclocated bicyclo c-12 product

manufactured according to Can-PS 854 225 5

Isobornyl cyclohexyl alcohol. ok Benzyl acetate 25

2-n-hepty / cyclopentanone 5

Total 353.3

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This mixture has been evaluated and it has been found that the natural spruce needle quality imparted to it was fuller and more persistent. This basic mixture can be mixed with aqueous ethanol blended, chilled and filtered to make a finished cologne to manufacture. This has a sweet, woody, thujone-like aroma with strong, fir balsam, St. John's wort, cedar leaf, spruce, earthy and camphor-like nuances. The basic mix Can also be used to perfume soaps or other toiletries such as lotions, aerosols, sprays and the like be used.

Example 64 Manufacture of a cosmetic powder

In a ball mill, 100 g of talcum powder with 0.25 g of 3,3-dimethyl-2 (^ - butenyl) norbornano-2 - prepared according to Example 61 - mixed. The powder mix was excellent sweet, woody, thujone-like aroma.

example $ 6 Perfumed liquid detergents

Concentrated liquid cleaning agents (such as example yi> ² H etc.) with a sweet, woody, thujone-like aroma were produced by adding 0.1OJi, 0.15 # and 0.20 # 3,3-dimethyl- 2 (; 5-butenyl) norbornanol-2 were added. All samples had a sweet, woody, thujone-like scent, the intensity increasing with increasing concentration.

Example 66 Production of a cologne and handkerchief perfume

3,3-Dimethyl-2 (3-butenyl) norbornanol-2 from Example 61 was in an amount of $ 2.5. in 85 # aqueous ethanol to one Eau de Cologne and in the amount of $ 20 in 95 # aqueous Ethanol is added to a handkerchief perfume, which thereby

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a pronounced and certain sweet, woody, thujone-like Received scent.

Example 67 Production of a cologne and handkerchief perfume

The preparation from Example 61 was in a concentration from 2.5 # in 85 # aqueous ethanol to a colognes and at a concentration of $ 20 in 95 ^ aqueous Ethanol added to a handkerchief perfume. The use of j5,3-dimethyl-2 (2-butenyl) norbornanol-2 in the preparation from Example 61 lent a distinctive and starry, sweet, woody, thujone-like aroma with strong fir balsam, St. John's wort, cedar leaves, pichten, earthy and camphor notes.

Example 68
Making a soap preparation

100 g of soap chips was mixed with 1 g of ^, 3-dimethyl-2 (^ - butenyl) norbornanol-2 from Example 61 mixed homogeneously. The one so perfumed Soap had an excellent sweet, woody, thujone-like flavor.

Example 69 Preparation of a detergent mixture

100 g of a detergent powder (lysine salt of n-dodecylbenzenesulfonic acid according to US Pat. No. 3,948,818), 0.15 g of I3,3 ^ bimethyl-2 (3-butenyl) norbornanol-2 from Example 61 were homogeneous mixed. This product had an excellent sweet, woody, thujone-like flavor.

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-730

example

It was found that the compound 3 »3-dimethyl-2 (3-butenyl) norbornanol-2 advantageously with the following herbal mixture can be used when added at a concentration of 15 wt.

Components jewel parts Eichenr.oos absolutely
505 in diethyl thalate 20th C \ -Methyl-3,4 -. Ethylenedi.oxy-
hydroc innarcatalcehyd 10 Methyl dihydrojasmonate 100 Coumarin 20th Ke'ton Musk 8o Isocyclocitral ($ 10 in diethyl
phthalate) 10 · Galbanum oil (10 ^ in diethyl phthalate) 6th Rosemary oil 10 Spruce needle oil 60 Tannenbaisarn absolute (10 $ in
Diethyl phthalate) 10 Bergamot oil 60 Benzyl acetate 320 Linalool 30th Indole (10 # in diethyl phthalate) 6th Undecalactone ($ 10 in diethyl phthalate) 12th Ylang Ylang oil 32 lemon oil 14th 3,3-dimethyl-2 (3-butenyl) nor-
bornanol-2 - manufactured close to Bei
game 61 150

total

1000

The addition of 15 # 3,3-dimethyl-2 (3-butenyl) norbornanol-2 conferred the mixture has a rich woody thujone-like nuance. The fragrance character the perfume was significantly improved by this addition. The fragrance was rounded and was more complete.

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The compound 3 * 3-Diroethyl-2 (3-butenyl) norbornanol-2 used advantageously in many types of preparations and added in concentrations from 10 μl up to 50 μl. Higher Concentrations can be used to achieve specific effects.

Brief description of the drawings

Show it:

Fig. 1 shows the NMR spectrum of the compound of the formula

prepared in Example 2;

Flg. 2 the IR spectrum of the compound according to Flg. 1, Flg. 3 the NMR spectrum of the cis isomer of the formula

produced according to example 3j

4 shows the IR spectrum of the compound according to FIG. 3; Flg. 5 the NMR spectrum of the compound of the formula

produced according to example 3;

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6 shows the IR spectrum of the compound according to FIG. 5; 7 shows the NKR spectrum of the compound of the formula

prepared according to Example 11;

8 shows the IR spectrum of the compound according to FIG. 7;

9 shows the NMR spectrum of fraction 7 from Example 12, which is predominantly a compound of the formula

contains;

Flg. 10 the IR spectrum of the fraction according to FIG. 9;

Flg. 11 the NMR spectrum of fraction 5 from Example 17, which is a compound of the formula

FIG. 12 the IR spectrum of fraction 5 according to FIG. 11;

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-733

13 shows the NMR spectrum of the fraction ρ from Example I9 which contains the compound of the formula

14 shows the IR spectrum of fraction 5 according to FIG.

the gas-liquid chroniatography profile of the mixture from Example 20;

Fiß. 16 shows the Nl-H spectrum of the mixture of three O) compounds in fraction 12 from Example 20, the compounds having the following form:

(A)

(B)

(C)

Flg. 17 the IR spectrum of fraction 12 according to FIG. 18;

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18 shows the NMR spectrum of peak 1 of fraction 13 from Example 20, a mixture of two (2) ketones of the formula;

(A)

(B)

Flg. 19 the IR spectrum of the tip 1, fraction 18 according to FIG. 18;

20 shows the NMR analysis of the keto ether, prepared according to Example 20 - formula:

OCH.

(O

21 shows the IR spectrum of the keto ether according to FIG. 20;

22 shows the gas-liquid chromatography profile of the mixture of ketones and keto ethers, prepared according to Example 21, with the formulas:

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OCH.

Flg. 23 the NMR spectrum of the ketone-keto ether mixture according to FIG. 22;

Flg. 24 the IR spectrum of the ketone-keto ether mixture according to FIG. 22;

Flg. 25 is the NMR spectrum of the compound of the formula

prepared according to Part A of Example 22 (fraction 4); 26 shows the IR spectrum of the compound according to FIG. 25; Flg. 27 is the NMR spectrum of the compound of the formula

prepared according to Part B of Example 22 (fraction 2);

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-Χίο -

Flg. 28 the IR spectrum of the compound according to FIG. 27;

29 shows the NMR spectrum of fraction 4 from Example 2J>, a compound of the formula

Flg. 30 the IR spectrum of the compound according to FIG. 29;

Fig. ^ L the gas-liquid chromatography profile of the mixture, prepared according to the method of Example 24, which contains the compounds of the following formulas :

'O

Fig. 32 is the NMR spectrum of the compound of the formula

prepared according to Example 24;

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Fig. 33 is the NMR spectrum of the compound of the formula

prepared according to Example 24; Fig. 34 is the NMR spectrum of the compound of the formula

prepared according to Example 24; Flg. 35 the IR spectrum of the compound according to FIG. 34;

Flg. 36 the NMR spectrum of the compound prepared according to Part A of Example 25, having the formula

Flg. 37 the IR spectrum of the compound according to FIG. 36;

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"3 Z

Fig. 38 is the NMR spectrum of the compound prepared in Part B of Example 25, having the formula

Flg. 29 the IR spectrum of the compound according to FIG . 40 the NMR spectrum of the compound of the formula

. M O

prepared according to Example 26;

41 shows the IR spectrum of the compound according to FIG. 40; Figure 42 is the NT-IR spectrum of the compound of the formula

OH

prepared according to Example 27; 43 shows the IR spectrum of the compound according to FIG. 42; Flg. 44 is the NMR spectrum of the compound of the formula

J ^0H

prepared according to Example 28;

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45 the IR spectrum of the compound of the formula

prepared according to Example 28; Fig. 46 shows the NMR spectrum of the compound of the formula

prepared according to Example 29;

47 shows the IR spectrum of the compound according to FIG. 46; Fig. 48 is the NMR spectrum of the compound of the formula

prepared according to Example 30; Flg. 49 the IR spectrum of the compound according to FIG. 48;

Flg. 50 the gas-liquid chromatography profile of the mixture (i) of the reaction product from Example 31, boiling range 100 ° to 111 ° C. / 0.9 mm Hg;

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- IJWT -

5 * the NMR spectrum of the compound of the formula

prepared according to Example 31;

ft. 52 the IR spectrum of the compound according to FIG. 51; Fig. 53 shows the NMR spectrum of the compound of the formula

produced according to example Jl; Fig. 5 ** the IR spectrum of the compound of the formula

produced according to example J>1; Flg. 55 the NMR spectrum of the compound of the formula

manufactured according to the example

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56 shows the IR spectrum of the connection according to FIG. 55;

Fig. 57 ; 53 .; 2I ^and §2. show the GC-MS profiles of the compounds prepared according to Example 60.

61 shows the NMR spectrum of the norbornanol derivative according to the invention, prepared according to Example 61; and

62 shows the IR spectrum of this norbornanol derivative Example 6l.

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L e r s e i t e

Claims (1)

wherein each dashed line is carbon-carbon-7. Infachblnclunc or a Kohlenatoff-Kohlerintoff-Do ^ pelbir.rivir. ^ Means, nit the cash gift, that at least one of the dashed. Lines is a carbon-carbon single bond, '.; Orin is furthermore η = 0 or 1, with the provision that η = 1 ·, v / eii .: both dashed lines carbon-carbon single bond cind i; nd r: = 0, v; cnn one of the dashed r.ien is a carbon-carbon double bond; wherein: 'err. ° r R ^ either hydrogen or a lower alkyl group; R, .. 'hydrogen , a lower alk}'! - or a lower alkylidene group; Y represents one of the following groups or Ii R. ("eis" and / or "trans") 809821/0723 ORIGINAL INSPECTED ivorin .. '.'issutv.toi'f or the hydroxyl group, where, when ^{: is} hydrogen, Z represents one of the following groups: R. OH or and when Q is the hydroxyl group, Z is -CHp-, η = 0 and R. is a lower alkylidene group; R ^ and R ^ each represent an alkyl group, and R ₇ * H;> and R. represent either the same or different groups, namely ... hydrogen or a lower alkyl group; R and R ^, when taken separately, the
same or different lower alkyl groups, and if they
together cenorrjr.en will mean lower alkylene groups;
furthermore, the dotted line represents a carbon-carbon single bond or a carbon-carbon double bond and each wavy line represents either exo or endo isomers. Θ09821 / 0723 2. liaison; after
the formula: •. Claim 1, characterized by ^, do:; 3 them ("eis" and / or "trans") on v / eist. Compound according to Claim 1, characterized in that it has the formula: ("eis" and / or "trans") on v / eist. 4. A compound according to claim 1, characterized in that it has the formula: having. 5. A compound according to claim 1, characterized in that it the formula: on v / eist. 809821/0723 6. Compound according to claim 1, characterized in that it has the formula: having. 7. A compound according to claim 1, characterized in that it the formula: ¹ AA having. 8. Compound according to claim 1, characterized in that it has the formula: AH having. 9 · Compound according to claim 1, characterized in that it has the formula: a OH wherein the wavy lines have "exo" or "endo" configurations represent. 809821/0723 10. Use of the compounds according to one or more of the Claims 1 to 9 as a seasoning to improve or intensify or Modification of the organoleptic properties of food, chewing gourds, medicinal preparations, chewing tobacco, Toothpastes, Parfii-r.s, perfumed items, colognes, Tobacco or tobacco substitutes. 11. Use according to claim 10, characterized in that the seasoning for improving and / or intensifying the cinnamon or berry-fruity aroma and taste of a food in amounts from about 5 to about 500 T / MiH. is admitted. 12. Use according to claim 11, characterized in that the seasoning of (i) about 0.1 wt -.% To about 10 0ew.- £ at least one of the norbornane derivatives according to claim 1, the remainder of the root composition (ii ) is at least one seasoning additive that does not react with the norbornane derivative and is organoleptically compatible, namely heliotrope, terpinenol-4, benzaldehyde, anisaldehyde, pheny / acetaldehyde, benzyl format, benzyl acetate, cis-2-hexenyl benzoate, methyl hexanoate, hexanal, eucalyptol, eugenyl , Acetaldehyde, ethyl acetate, ethyl butyrate, turpentine gum oil, pimones, camphor gum, isobornyl acetate, borneol, cinnamaldehyde, cumic aldehyde, furfural, methyl cinnamate, cassia oil, vanillin, maltol, p-hydroxybenzyl acetate, amylate, amyl acetate, anylethyl acetate, anylethyl acetate, anylethyl acetate, anylethyl acetate, anylethyl acetate, butyric acid, isobornyl acetate , Diacetyl, dimethyl anthranilate, ethylmethylphenyl glycidate, ethyl succinate, ethyl valerate, geraniol, cis-3-hexen-1-ol, 2-hexenyl acetate, 2-hexenyl butyrate, hexyl butyra t, 4- (p-hydroxyphenyl) -2-butanone, ß-ionone, isobutyl cinnamate, jasmine, essential lemon iyl, methyl butyrate, methyl caproate, methyl disulfide, methyl pnaphthyl ketone, Irris butter, rose absolute, terpenyl acetate, ^ -undecalactone, vanilla or Guiacol and (iii) contains a carrier substance which neither reacts with the seasoning nor with the additive and is furthermore organoleptically compatible. 809621/0723 - -WTl - · Use after. Claim 10, characterized in that the Seasoning as a fragrance in perfumery either alone or together with one or more additives, such as natural or synthetic coloring oil, another alcohol, an aldehyde, another ketone, a nitrile, an ester, a lactone, another ketal or another acetal to a perfume, a is added to perfumed articles or a cologne. 809821/0723