EP3464258A1

EP3464258A1 - Tetrahydropyranyl lower alkyl esters and the production of same using a ketene compound

Info

Publication number: EP3464258A1
Application number: EP17727194.7A
Authority: EP
Inventors: Volker Hickmann; Timon STORK; Stefan Ruedenauer; Ralf Pelzer
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2016-05-31
Filing date: 2017-05-30
Publication date: 2019-04-10
Also published as: JP7115988B2; JP2019518020A; CN109195959B; WO2017207539A1; CN109195959A; US20200325112A1; MX2018014918A; BR112018074538A2; US10981885B2; BR112018074538B1

Abstract

The invention relates to tetrahydropyranyl lower alkyl esters and particularly tetrahydropyranyl acetates, a method for producing same using ketene, and the use of same as fragrant and aromatic substances.

Description

Tetrahydropyranylniederalkylester and their preparation by means of a ketene compound

The present invention relates to Tetrahydropyranylniederalkylester and especially tetrahydropyranyl, a process for their preparation using ketene and their use as fragrances and flavorings.

BACKGROUND OF THE INVENTION For the production of consumer goods having certain organoleptic properties, that is, products having favorable olfactory (odor) or taste (gustatory) properties, a wide variety of aroma chemicals (olfactants and flavors) are considered to be the most diverse applications of these substances available. There is a continuing need for new fabrics and aroma chemicals, as well as new, better manufacturing processes that require the provision of individual aroma chemicals, e.g. B. with higher efficiency or in higher purity.

It is known, for the preparation of esters of higher alcohols, these react with carboxylic acid halides or with carboxylic anhydrides. In this way, aroma chemicals with valuable properties can be achieved, so that this synthetic route is still justified. A disadvantage of the reaction with carboxylic acid halides, however, is that during their reaction, hydrohalic acids are formed, which generally lead to corrosion problems and, in the case of tertiary alcohols, cause water splits and, as a result, in many cases polymerizations. In the reaction with carboxylic anhydrides, there is the disadvantage that equimolar amounts of the corresponding carboxylic acid are formed in the reaction mixture, which have to be separated off in the workup and their reuse can be technically complicated. A synthetic route which avoids these disadvantages is therefore to be preferred.

It is also known, for the preparation of acetic acid esters to react hydroxyl-containing compounds with ketene. For the implementation of hydroxyl-containing compounds with ketene, various catalysts can be used, for. B. Bronsted acids, such as sulfuric acid, p-toluenesulfonic acid, phosphoric acid, potassium hydrogen sulfate or Lewis acids, such as boron trifluoride or boron trifluoride etherate. However, various disadvantages are also described for the catalyzed reaction of ketenes. For example, acid catalysts in metal equipment can cause corrosion or lead to the undesirable formation of resinous contaminants. In addition, they are often difficult to separate again from the reaction mixture.

Methods and apparatus for the production of ketene are, for. In Organic Synthesis, Coli. Vol. 1, p. 330 (1941) and Vol. 4, p. 39 (1925) and in Chemiker Zeitung 97, No. 2, pages 67 to 73 (1979).

EP 0949239 A1 describes a process for the preparation of linalyl acetate by reacting linalool with ketene in the presence of a zinc salt as catalyst.

It is also known to use various substituted tetrahydropyran compounds as aroma chemicals. For example, 2,4,4-substituted tetrahydropyranyl esters of the general formula (X.1) are valuable aroma chemicals:

EP 0383446 A2 describes the synthesis and the olfactory properties of a large number of different 2,4,4-trisubstituted tetrahydropyranyl esters (X.1) in which R 'is methyl or ethyl and R "is straight-chain or branched C ₂ -C ₄ -alkyl or C2-C ₄ alkenyl stands. purpose, first 3-methylbut-3-en-1-ol is reacted with an aldehyde of formula R "-CHO in the presence of an acid catalyst, wherein a reaction mixture is obtained which is at least a 2-substituted 4-hydroxy-4-methyltetrahydropyran of the general formula (X.2) contains:

The intermediate (X.2) is then subjected to acylation by reaction with a carboxylic acid anhydride under acidic conditions.

4-Hydroxy-tetrahydropyran compounds and especially 2-substituted 4-hydroxy-4-methyl-tetrahydropyrans are also valuable compounds for use as aroma chemicals, and the skilled person are various methods for their preparation known, for example, from EP 1493737 A1, WO 201 1/147919, WO 2010/133473, WO 201 1/154330 and WO 2014/060345.

The non-prepublished WO 2016/139338 describes a process for preparing tetrahydropyranyl esters from the corresponding 4-hydroxytetrahydropyran compounds by reaction with a ketene compound.

It has surprisingly been found that certain new tetra hydropyranyl-lower alkyl, in particular tetrahydropyranyl acetate compounds show advantageous fragrance properties.

Furthermore, it has surprisingly been found that these new tetrahydropy ranyl acetate compounds can be prepared by reacting the corresponding alcohol precursors with ketene in a simple manner with very high yields and at the same time in high purity. Thus, it is possible with preference to obtain tetrahydropyranyl acetates having a higher purity and thus a better perfume quality than processes known from the prior art. This is surprising in view of the high reactivity of the ketenes used. It is known from the prior art that, as a rule, starting materials which can themselves be used as an odorant are also used to produce odorous substances. Surprisingly, the precursor of the tetrahydropyranyl lower alkyl esters (Γ) or (I), i. the respective alcohol, unsuitable as an odorant.

SUMMARY OF THE INVENTION

The invention relates to tetrahydropyranyl lower alkyl esters of the general

Formula (Γ)

wherein

R ^{1 is} hydrogen, R ^{2 is} unsubstituted or mono- or polysubstituted phenyl, where the substituents are independently selected from C 1 -C 6 -alkyl and C 1 -C 4 -alkoxy,

R ³ represents hydrogen, Ci-C ₆ alkyl or C ₃ -C ₆ cycloalkyl,

R ^{4 is} hydrogen or methyl,

R ^{6 is} Ci-Cs-alkyl,

or

R ¹ and R ² together with the atoms to which they are attached form a cyclohexane ring which is unsubstituted or monosubstituted or polysubstituted by methyl.

Another object of the invention are tetrahydropyranyl acetates of the general

Formula (I)

wherein

R ^{1 is} hydrogen,

R ² is unsubstituted or mono- or polysubstituted phenyl wherein the substituents are selected from Ci-C6 alkyl and Ci-C4-alkoxy, R ³ represents hydrogen, Ci-C ₆ alkyl or C ₃ -C ₆ cycloalkyl .

R ^{4 is} hydrogen or methyl,

or

A first preferred embodiment are compounds of the formula (Ι-Α ')

wherein

R ^{1 is} hydrogen,

R ^{3 is} hydrogen or methyl,

R ^{4 is} hydrogen or methyl,

R ^Ph1 , R ^Ph2 , R ^Ph3 , R ^Ph4 and R ^Ph5 independently of one another represent hydrogen, C ₁ -C ₆ -alkyl or C ₁ -C 4 -alkoxy,

R ⁶ is d-Cs-alkyl. A second preferred embodiment is compounds of the formula (IA),

wherein

R ^{1 is} hydrogen,

R ^{3 is} hydrogen or methyl,

R ^{4 is} hydrogen or methyl,

RP 2 _j RP 3 _i RP 4 _unc | RP 5 are independently selected from hydrogen, d-Ce-alkyl and dC ₄ -alkoxy.

A third preferred embodiment is compounds of the formula (1B)

wherein

R ³ is hydrogen, ₆ -alkyl or C ₃ -C ₆ cycloalkyl,

R ^{4 is} hydrogen,

R ^{5 is} hydrogen or methyl.

A further subject matter is a process for the preparation of compounds of the formula (I)

wherein

R ^{1 is} hydrogen,

R ^{2 is} unsubstituted or mono- or polysubstituted phenyl, the substituents being selected from C 1 -C 6 -alkyl and C 1 -C 4 -alkoxy,

R ³ represents hydrogen, Ci-C ₆ alkyl or C ₃ -C ₆ cycloalkyl,

R ^{4 is} hydrogen or methyl,

or

R ¹ and R ² together with the atoms to which they are attached form a cyclohexane ring which is unsubstituted or monosubstituted or polysubstituted by methyl, in which a) compounds of the formula (Ic)

and the compounds of the formula (Ic) are reacted with a ketene of the formula (K)

C = C = O

H

(K)

to give compounds of formula (I).

A first preferred embodiment is a process for the preparation of compounds of the formula (I-A)

wherein

R ^{1 is} hydrogen,

R ^{3 is} hydrogen or methyl,

R ^{4 is} hydrogen or methyl,

RPh2 _] RPh3 _] RPh4 _unc | RPh5 are independently selected from hydrogen, C 1 -C ₆ -alkyl and C 1 -C ₄ -alkoxy, in which

Compounds of the formula (I-Aa)

(I-Aa) with a compound of the formula (I-Ab)

to compounds of the formula (I-Ac)

and the compounds of the formula (I-Ac) with a ketene of the formula (K)

> = C = O

H

(K) to obtain compounds of formula (I-A).

A second preferred embodiment is a process for the preparation of compounds of formula (I-B)

wherein

R ³ represents hydrogen, Ci-C ₆ alkyl or C ₃ -C ₆ cycloalkyl,

R ^{4 is} hydrogen,

R ^{5 is} hydrogen or methyl, in which a) a compound of the formula (I-Ba)

0

with a compound of the formula (I-Bb)

to compounds of the formula (I-Bc)

and the compounds of the formula (I-Bc) with a ketene of the formula (K)

> = C = O

H

(K)

to give compounds of formula (I-B).

Another object of the invention is the use of compounds of formula (Γ) or (I), as defined herein, as Aromachemikalie.

Another object of the invention are flavoring and / or Duftstoffzusammen composites containing one or more compounds of formula (Γ) or (I), as defined herein, optionally at least one further, of the compounds of formula (Γ) or (I) Aromachemical and

optionally at least one diluent, with the proviso that the composition contains at least one component ii) or iii).

Another object of the invention are perfumed or flavored products containing at least one compound of formula (Γ) or (I) as defined herein or obtainable by a process as defined herein.

Another object of the invention is a process for perfuming a product in which one or more compounds of formula (Γ) or (I) as defined herein or obtainable by a process as defined herein are used.

DESCRIPTION OF THE INVENTION

Unless otherwise stated below, the term "tetrahydropyranol" denotes tetrahydropyran-4-ols, the term "tetrahydropyranyl-lower alkyl ester" tetrahydropyran-4-yl-acetate, tetrahydropyran-4-yl-propanoate and tetrahydropyran-4-yl - butanoates and the term "tetrahydropyranyl acetate" tetrahydropyran-4-yl-acetate.

Tetrahydropyranyl lower alkyl esters and tetrahydropyranyl acetates according to the invention are the compounds of the formula (II) and (I).

Unless otherwise specified below, the terms "tetrahydropyranyl lower alkyl ester", "tetrahydropyranyl acetate" or "compounds of the formula (I)" and "compounds of the formula (I)" denote both cis / trans mixtures of any composition and also the pure ones Conformational isomers and all diastereomers and optionally all enantiomers in pure form and racemic and optically active mixtures of E

If, in the following, compounds of the formula (Γ) or (I) are mentioned, only one of the isomeric forms is depicted in each case. For illustrative purposes only, the isomers of tetrahydro-4-methyl-2-phenylpyranyl acetate (IA.1) are reproduced below by way of example.

Unless the configuration of stereocenters is explicitly stated, all isomers are included. For example, the structure of formula (IA.1) includes all isomers (2R, 4R) - (IA.1), (2R, 4S) - (IA.1), (2S, 4R) - (IA.1), ( 2S, 4S) - (IA.1).

In the context of the invention, the prefix C _n -C _m indicates the number of carbon atoms which a molecule or a group designated therewith may have

In the context of the present invention, the expression Ci-C6-alkyl is unbranched and branched saturated hydrocarbon radicals having 1 to 6 carbon atoms. C 1 -C 6 -alkyl are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, (2-methylpropyl), sec-butyl (1-methylpropyl), tert-butyl (1, 1-dimethylethyl), n Pentyl, n-hexyl and the structural isomers thereof. Preferred C 1 -C 6 -alkyl are C 1 -C 4 -alkyl. In the context of the present invention, the expression Ci-C4-alkoxy is unbranched and branched saturated alkoxy having 1 to 4 carbon atoms. C1-C4 alkoxy are, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy and the structural isomers thereof.

In the context of the present invention, the expression C 3 -C 6 -cycloalkyl represents cyclic saturated hydrocarbon radicals having 3 to 6 carbon atoms. C 3 -C 6 -cycloalkyl are, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

In the context of the present invention, phenyl is unsubstituted or monosubstituted or polysubstituted, where the substituents are independently selected from C 1 -C 6 -alkyl and C 1 -C 4 -alkoxy. Preferably, substituted phenyl is monosubstituted, disubstituted or trisubstituted.

In the context of the present invention, the term lower alkyl stands for C 1 -C 3 -alkyl. C 1 -C 3 -alkyl is unbranched and branched saturated hydrocarbon radicals having 1 to 3 carbon atoms. C 1 -C 3 -alkyl are, for example, methyl, ethyl, n-propyl, isopropyl, preferred methyl and n-propyl. Lower alkyl esters denote the corresponding lower alkylcarboxylic acid esters, ie acetates, propanoates and butanoates. Preferred compounds of the formula (Γ)

are compounds in which

R ^{1 is} hydrogen,

R ^{2 is} unsubstituted or mono-, di- or trisubstituted phenyl, where the substituents are independently selected from C 1 -C 6 -alkyl and C 1 -C ₄ -alkoxy,

R ³ represents hydrogen, Ci-C ₆ alkyl or C ₃ -C ₆ cycloalkyl,

R ^{4 is} hydrogen or methyl,

R ^{6 is} methyl or n-propyl,

or

A preferred embodiment are compounds of the formula (I)

are compounds in which

R ^{1 is} hydrogen,

R ^{3 is} hydrogen, C ₁ -C ₆ -alkyl or C ₃ -C ₆ -cycloalkyl,

R ^{4 is} hydrogen or methyl,

or R ¹ and R ² together with the atoms to which they are attached form a cyclohexane ring which is unsubstituted or monosubstituted or polysubstituted by methyl. The subject of a first preferred embodiment are the abovementioned compounds of the formula (Ι-Α ') or (IA).

Preference is given to compounds of the formula (Ι-Α ') or (I-A), in which

R ^{1 is} hydrogen,

R ^{3 is} hydrogen or methyl,

R ^{4 is} hydrogen or methyl,

and wherein 2, 3, 4 or 5 of the radicals R ^Ph1 , R ^Ph2 , R ^Ph3 , R ^Ph4 and R ^{Ph5 are} hydrogen and the other radicals R ^Ph1 , R ^Ph2 , R ^Ph3 , R ^Ph4 and R ^{Ph5 are} independently selected under C 1 -C 6 -alkyl and C 1 -C 4 -alkoxy,

R ⁶ in formula (IA) is ethyl or n-propyl, preferably n-propyl.

Particular preference is given to compounds of the formula (Ι-Α ') or (I-A), in which

R ^{1 is} hydrogen,

R ^{3 is} hydrogen or methyl,

R ^{4 is} hydrogen or methyl,

and wherein 2, 3, 4 or 5 of the radicals R ^Ph1 , R ^Ph2 , R ^Ph3 , R ^Ph4 and R ^{Ph5 are} hydrogen and the other radicals R ^Ph1 , R ^Ph2 , R ^Ph3 , R ^Ph4 and R ^{Ph5 are} independently selected under methyl and methoxy,

R ⁶ in formula (IA) is ethyl or n-propyl, preferably n-propyl.

In one embodiment, the radicals R ^Ph1 , R ^Ph2 , R ^Ph3 , R ^Ph4 and R ^Ph5 which are not hydrogen are the same.

For example, the radicals R ^Ph1 , R ^Ph2 , R ^Ph3 , R ^Ph4 and R ^{Ph5 may have the} following meanings:

R ^Ph , _R Ph2 R ^Ph3 , R ^Ph4 and R ^Ph5 are hydrogen, or

R ^Ph2 , _R Ph3 R ^Ph4 and R ^Ph5 are hydrogen and R ^Ph1 is methyl, or

R ^Ph2 , _R Ph3 R ^Ph4 and R ^Ph5 are hydrogen and R ^Ph1 is methoxy, or

R ^Ph , _R Ph3 R ^Ph4 and R ^Ph5 are hydrogen and R ^Ph2 is methyl, or

R ^Ph , _R Ph3 R ^Ph4 and R ^Ph5 are hydrogen and R ^Ph2 is methoxy, or

R ^Ph , _R Ph2 R ^Ph4 and R ^Ph5 are hydrogen and R ^Ph3 is methyl, or

R ^Ph , _R Ph2 R ^Ph4 and R ^Ph5 are hydrogen and R ^Ph3 is methoxy, or

R ^Ph , _R Ph3 and R ^Ph5 are hydrogen and R ^Ph2 and R ^Ph4 are methyl; or

R ^Ph , _R Ph3 and R ^Ph5 are hydrogen and R ^Ph2 and R ^Ph4 are methoxy; or R ^Ph2 and R ^Ph4 are hydrogen and R ^Ph1 , R ^Ph3 and R ^Ph5 are methyl; or R ^Ph2 and R ^Ph4 are hydrogen and R ^Ph1 , R ^Ph3 and R ^Ph5 are methoxy.

Also particularly preferred are compounds of the formula (Ι-Α ') or (IA), wherein R ¹ , R ³ and R ^{4 are} hydrogen and the other radicals are as defined above.

Particular preference is thus given to compounds of the formula (Ι-Α ') or (IA) in which R ^{1 is} hydrogen,

R ^{3 is} hydrogen,

R ^{4 is} hydrogen,

and wherein 2, 3, 4 or 5 of the radicals R ^Ph1 , R ^Ph2 , R ^Ph3 , R ^Ph4 and R ^{Ph5 are} hydrogen and the other radicals R ^Ph1 , R ^Ph2 , R ^Ph3 , R ^Ph4 and R ^{Ph5 are the} same and selected are methyl and methoxy,

R ⁶ in formula (IA) is ethyl or n-propyl, preferably n-propyl.

Particularly preferred compounds of the general formula (Ι-Α ') or (IA) are selected from the compounds of the formulas (IA.1), (IA.2), (IA.3), (IA.4), (IA. 5), (IA.6), (IA.7), (IA.8), (IA.9) and (IA.10), where (IA.1), (IA.2), (IA.3 ), (IA.4), (IA.6) and (IA.10) are especially preferred. Particularly preferred are (I-A.1), (I-A.2), (I-A.3), (I-A.4) and (I-A.6).

(IA.3)

(Ia.10) The subject of a second preferred embodiment are the abovementioned compounds of the formula (1B).

In the compounds of the formula (1B), R ^{4 is} particularly preferably hydrogen and R ^{5 is} hydrogen or methyl, in particular methyl.

In the compounds of the formula (1B), R ^{3 is} particularly preferably hydrogen, unbranched C 1 -C 4 -alkyl, branched C 1 -C 4 -alkyl or C ³ -C 4 -cycloalkyl. In a preferred embodiment, in the compounds of the formula (1B) R ^{3 is} C ³ -C 6 -cycloalkyl, particularly preferably C ³ -C 4 -cycloalkyl, particularly preferably cyclopropyl.

In another preferred embodiment, in the compounds of the formula (1B) R ^{3 is} hydrogen, unbranched C 1 -C 4 -alkyl, or branched C 1 -C 4 -alkyl. R ^{3 is} particularly preferably unbranched C ¹ -C 4 -alkyl.

Particularly preferred compounds of the general formula (IB) are selected from compounds of the formulas (IB.1), (IB.2), (IB.3) and (IB.4), where (IB.4) is particularly preferred ,

Another object of the invention is a process for the preparation of compounds of formula (Γ) or (I). According to the invention, the compound of the formula (Γ) wherein R ^{6 is} ethyl or n-propyl, in particular n-propyl, is preferably obtained by reacting compound (Ic) with an acid chloride or anhydride.

According to the invention, the compounds of formula (I) are preferably obtained by reacting compound (Ic) with a ketene.

Another object of the invention is a process for the preparation of compounds of formula (Γ) as described above, wherein R ^{6 is} ethyl or n-propyl, in particular n-propyl, in which a ') compounds of the formula (Ic)

provides,

where R ¹ , R ² , R ³ and R ⁴ , which have the meanings given above, preferably R ^{1 is} hydrogen,

R ^{4 is} hydrogen or methyl,

especially

R ^{1 is} hydrogen,

R ^{2 is} tolyl,

R ^{3 is} hydrogen,

R ^{4 is} hydrogen,

and

b ') is reacted with a compound of the formula C2-C3-alkyl-C (= O) -X, in which X is Cl, Br or C ₂ -C ₃ -alkyl - (= O) 0,

c ') optionally subjecting the reaction mixture obtained in step b') to a separation to obtain at least one fraction.

For esterification, the compound of the general formula (Ic) can be reacted with C 2 -C 3 -alkylC (= O) -X, where X is preferably Cl, or Br. In a preferred embodiment, the compound (Ic) is reacted with butyric acid chloride. The esterification can be carried out in the presence of an esterification catalyst. As esterification catalysts customary catalysts can be used, for. For example, mineral acids such as sulfuric acid and phosphoric acid; organic sulfonic acids, such as methanesulfonic acid and p-toluenesulfonic acid; amphoteric catalysts, especially titanium, tin (IV) - or zirconium compounds, such as tetraalkoxytitans, z. As tetrabutoxytitanium, and tin (IV) oxide. The esterification catalyst is used in an effective amount, which is usually in the range of 0.05 to 10 wt .-%, preferably 0.1 to 5 wt .-%, based on the sum of acid component (or anhydride) and alcohol component.

The esterification can usually be carried out at ambient pressure or reduced or elevated pressure. Preferably, the esterification is carried out at ambient or reduced pressure.

The esterification may be carried out in the absence of an added solvent or in the presence of an organic solvent. If the esterification is carried out in the presence of a solvent, it is preferably an organic solvent which is inert under the reaction conditions. These include, for example, aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, aromatic and substituted aromatic hydrocarbons or ethers. The solvent is preferably selected from pentane, hexane, heptane, ligroin, petroleum ether, cyclohexane, dichloromethane, trichloromethane, carbon tetrachloride, benzene, toluene, xylene, chlorobenzene, dichlorobenzenes, dibutyl ether, THF, dioxane and mixtures thereof.

The esterification is usually carried out in a temperature range of 0 to 200 ° C, preferably 10 to 150 ° C. The esterification can take place in the absence or in the presence of an inert gas. An inert gas is generally understood to mean a gas which, under the given reaction conditions, does not react with the starting materials, reagents, solvents or the products formed. These include z. As nitrogen or argon.

The esterification can be carried out by addition of bases capable of intercepting HX-released acid in the reaction. Suitable bases are especially tertiary amines. In this case, 4- (dimethylamino) pyridine can be used as the esterification catalyst. Suitable amines are trimethylamine, triethylamine, tripropylamine, tributylamine, N, N-diisopropylethylamine, Ν, Ν-dimethylethylamine, N, N-dimethylisopropylamine, N-methylmorpholine, N-methylpiperidine, N-methylpyrrolidine, or mixtures thereof.

In a preferred embodiment, the solvent can simultaneously serve as a catalyst and as a base. For example, pyridine serves as a solvent, catalyst and base simultaneously. Another object of the invention is a process for the preparation of compounds of formula (I), as described above, in which

a) provides compounds of the formula (Ic) and

b) reacting the compounds of the formula (Ic) with a ketene of the formula (K) to obtain compounds of the formula (I).

Usually, in the process according to the invention, a mixture of isomers of the general formula (Ic) is reacted. It is also possible to react a single isomer of the compound (Ic). The ketene (K) is preferably produced by high-temperature pyrolysis of acetone or acetic acid at temperatures which are generally higher than 650.degree. The temperature for producing the ketene (K) is preferably in the range from 650 to 1000 ° C., more preferably from 700 to 900 ° C. In a specific embodiment, the ketene (K) is prepared under reduced pressure. The pressure is preferably in a range from about 100 to 900 mbar, particularly preferably from 300 to 500 mbar, in particular from 350 to 450 mbar. In an alternative embodiment, the ketene (K) is prepared under ambient pressure ("depressurized"). Preferably, the pressure is then in a range of about 950 to

1050 mbar.

Since the ketene compound (K) is an extremely reactive compound which is highly prone to dimerization with the formation of diketenes, in the process of the present invention, it is preferable to use a ketene compound which has been prepared only recently. The process according to the invention is particularly advantageous when using ketene (K) which has been prepared immediately before the reaction in the process according to the invention, for example by thermal cleavage of acetone, acetic acid or acetic anhydride. In a first variant of the process according to the invention, the ketene (K) is introduced into the reaction mixture below the liquid surface, so that it bubbled through the reaction mixture. Advantageously, the ketene is passed under intensive stirring into the reaction mixture, so that essentially no ketene in larger amounts into the gas phase. The pressure of the ketene (K) must be sufficiently high to overcome the hydrostatic pressure of the reaction mixture above the ketene feed, possibly assisted by an inert gas stream, for example nitrogen. The ketene (K) can be fed by any suitable means. Important are a good distribution and a fast mixing. Gassing lances, for example, which can be permanently installed, or preferably nozzles, are suitable. The nozzles may be provided at or near the reactor bottom. For this purpose, the nozzles can be formed as openings of a hollow chamber surrounding the reactor. Preferably, however, immersion nozzles are used with suitable leads. For example, a plurality of nozzles may be arranged in the form of a ring. The nozzles may face up or down. The nozzles are preferably inclined downwards. In a second variant of the process according to the invention, the ketene (K) is prepared under reduced pressure and reacted under reduced pressure with at least one tetrahydropyran-4-ol of the general formula (Ic). The pressure during the preparation and the reaction of the ketene (K) is preferably in a range from about 100 to 900 mbar, particularly preferably from 300 to 500 mbar, in particular from 350 to 450 mbar.

Methods and devices for the production of ketene (K) are z. In Organic Syntheses, Coli. Vol. 1, p. 330 (1941) and Vol. 4, p. 39 (1925) and in Chemiker Zeitung 97, No. 2, pages 67 to 73 (1979).

The reaction of tetrahydropyran-4-ol compounds of the formula (Ic) with the ketene compound (K) is preferably carried out in such a way that accumulation of the ketene compound in the reaction mixture is avoided at any time during the reaction. The reaction of the compounds of the formula (Ic) with the ketene (K) is preferably carried out in such a manner that ketenes are introduced into the reaction mixture until the compounds of the formula (Ic) have been substantially completely reacted. By "substantially reacted" is meant a conversion of at least 95%, preferably of at least 98%, and particularly preferably of at least 99%. Preferably, the reaction of compounds of formula (Ic) with a ketene (K) at a temperature in the range of 0 to 150 ° C, preferably from 10 to 120 ° C, subjected.

In a first preferred embodiment, the reaction of compounds of the general formula (Ic) with the ketene (K) takes place in the absence of an added catalyst. In a second preferred embodiment, the reaction of compounds of general formula (Ic) with the ketene (K) in the presence of a catalyst, which is preferably selected from zinc salts.

The catalyst used is particularly preferably a zinc salt of a carboxylic acid, especially a monocarboxylic acid having 1 to 18 carbon atoms or dicarboxylic acid having 2 to 18 carbon atoms. These include, for example, zinc formate, zinc acetate, zinc propionate, zinc butyrate, zinc stearate, zinc succinate or zinc oxalate. Especially preferred is zinc acetate. It is very advantageous in the process according to the invention that the catalysts generally only have to be used in very small amounts, which makes the process more cost-effective and facilitates the work-up of the reaction mixture. This applies in particular to the use of a zinc salt as a catalyst. The catalyst is preferably used in an amount of from 0.01 to 2% by weight, particularly preferably from 0.02 to 0.5% by weight, based on the total amount of compounds of the formula (Ic).

To carry out the reaction according to the invention is advantageously carried out so that one carries out this reaction in a suitable reaction vessel, which as essential ingredients a good stirring and / or mixing device, a dosing device for ketene, a heater for starting the reaction and to maintain the Reaction temperature during the post-reaction, a cooling device for removing the heat of reaction of the exothermic reaction and a vacuum pump contains.

For optimum reaction, it is advantageous that the ketene is added so that it is never present in excess in the reaction mixture, and that the reaction mixture is always well mixed. For an optimal reaction, it is furthermore advantageous to avoid too rapid metered addition of ketene and to clearly establish the end of the reaction, for example spectroscopically or by the decreasing exothermicity of the esterification or the detection of ketene at the reactor outlet can serve as criteria.

The detection of ketene succeeds, for example, by IR spectroscopy on the characteristic carbonyl. With the aid of the process according to the invention, it is possible to prepare the compounds of general formula (I) by reaction with ketene of formula (K) in a technically simple manner in high purities and still in excellent yields and space-time yields. Since the starting materials are essentially completely converted into products, the method according to the invention is characterized by a maximum atom economy.

The compositions according to the invention and the compositions obtainable by the process according to the invention are particularly advantageously suitable as fragrance or to provide a fragrance.

A first preferred embodiment of the process according to the invention is a process for the preparation of compounds of formula (I-A), as described above, in which

a) reacting compounds of the formula (I-Aa) with a compound of the formula (I-Ab) to give compounds of the formula (I-Ac) and

b) reacting the compounds of the formula (I-Ac) with a ketene of the formula (K) to obtain compounds of the formula (I-A).

Usually, in the process according to the invention, a mixture of isomers of the general formula (I-Aa) is reacted. Also, a single isomer of the compound (I-Aa) can be reacted.

The step b) according to the invention proceeds as described above. The reaction of compounds of formula (I-Ac) to compounds of formula (I-A) proceeds analogously to the reaction of compounds of formula (Ic) to compounds of formula (I).

The step a) of the synthesis of compounds of the formula (I-Ac) can be carried out by the processes known to the person skilled in the art, which are described, for example, in WO 201/154330, WO 2010/133473 and EP 1493737. The alcohol and the aldehyde are preferably used in step a) in a molar ratio of about 1 to 2 to 2 to 1, more preferably from 0.7 to 1 to 2 to 1, in particular from 1 to 1 to 2 to 1. In a specific embodiment, the alcohol and the aldehyde are used in a molar ratio of 1: 1 to 1.5: 1 in step a).

According to the invention, the reaction in step a) takes place in the presence of an acidic catalyst. In principle, any acidic catalyst can be used for the reaction in step a), ie. H. Any substance that has Brönstedt or Lewis acidity. Examples of suitable catalysts are protic acids such as hydrochloric acid, sulfuric acid, potassium hydrogensulfate, phosphoric acid, methanesulfonic acid and p-toluenesulfonic acid, acidic molecular element compounds such as boron trifluoride, zinc chloride, oxidic acidic solids such as zeolites, silicates, aluminates, aluminosilicates, clays and acidic nentauscher.

The acid catalyst used in step a) is preferably selected from hydrochloric acid, sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid and strongly acidic cation exchangers.

In a first variant, the reaction in step a) is carried out in the presence of a Bronsted acid, which is preferably selected from hydrochloric acid, sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid. In this first variant, a solvent can be used in step a), which is preferably selected from hydrocarbons and hydrocarbon mixtures. Suitable solvents are, for example, hexane, heptane, ligroin, petroleum ether, cyclohexane, decalin, toluene, xylene and mixtures thereof. Preferably, no solvent is used. The catalyst is preferably used in this first variant in an amount of 0.05 to 5 mol%, particularly preferably from 0.1 to 4 mol%, based on the aldehyde. The reaction in step a) according to this first variant preferably takes place at a temperature in the range from 20 to 120 ° C., particularly preferably from 30 to 80 ° C.

In a second variant, the reaction in step a) takes place in the presence of a strongly acidic cation exchanger. The term strongly acidic cation exchanger is understood to mean a cation exchanger in the H ⁺ form which has strongly acidic groups. The strongly acidic groups are usually sulfonic acid groups. The acidic groups are usually attached to a polymer matrix, the z. B. may be gel or macroporous. A preferred embodiment of the method according to the invention is accordingly characterized net, that one uses a strongly acidic, sulfonic acid-containing cation exchanger. Suitable strong acid cation exchangers are in the

WO 2010/133473 and WO 201 1/154330, which is incorporated herein by reference.

Suitable for use in step a) are strongly acidic ion exchangers (such as Amberlyst®, Amberlite®, Dowex®, Lewatit®, Purolite®, Serdolit®) which are based on polystyrene and the copolymers of styrene and divinylbenzene as a carrier matrix with sulfonic acid groups in H ⁺ form and with sulfonic acid groups (-SO3H) functionalized ion exchange groups. The ion exchangers differ in the structure of their polymer frameworks, and there are different gel-and macroporous resins. In a specific embodiment, a perfluorinated polymeric ion exchange resin is used in step a). Such resins are z. B. under the name Nafion ® sold by DuPont. An example of such a perfluorinated polymeric ion exchange resin is Nafion® NR-50.

Suitable commercially available strong acid cation exchangers suitable for the reaction in step a) are, for example, under the trade names Lewatit® (Lanxess), Purolite® (The Purolite Company), Dowex® (Dow Chemical Company), Amberlite® (Rohm and Haas Company), Amberlyst ® (Rohm and Haas Company). Preferred strongly acidic cation exchangers are: Lewatit® K 1221, Lewatit® K 1461, Lewatit® K 2431, Lewatit® K 2620, Lewatit® K 2621, Lewatit® K 2629, Lewatit® K 2649, Amberlite® FPC 22, Amberlite® FPC 23 , Amberlite® IR 120, Amberlyst® 131, Amberlyst® 15, Amberlyst® 31, Amberlyst® 35, Amberlyst® 36, Amberlyst® 39, Amberlyst® 46, Amberlyst® 70, Purolite® SGC650, Purolite® C100H, Purolite® C150H, Dowex® 50X8, Serdolit® red and Nafion® NR-50.

The strongly acidic ion exchange resins are usually regenerated with hydrochloric acid and / or sulfuric acid.

In a specific embodiment, in step a), the alcohol and the aldehyde are reacted in the presence of a strongly acidic cation exchanger and in the presence of water. According to a special embodiment, water is additionally added to the reaction mixture in addition to the alcohol and the aldehyde.

In a suitable embodiment, the starting materials are reacted in the presence of at least 25 mol%, preferably of at least 50 mol% of water. For example, the starting materials in the presence of 25 to 150 mol%, preferably from 40 to 150 mol%, particularly preferably from 50 to 140 mol%, in particular of 50 converted to 80 mol% of water. In this case, the amount of water used on the amount of substance of the starting material optionally used in deficiency or in the case of an equimolar conversion to the amount of one of the two.

Preferably, the reaction is carried out in the presence of about at least 3 wt .-%, particularly preferably of at least 5 wt .-% of added water. The alcohol and the aldehyde are reacted, for example, in the presence of 3% by weight to 15% by weight of water, preferably from 5% by weight to 12% by weight of water. The stated above% by weight are based on the total amount of the reaction mixture, consisting of the components alcohol and aldehyde and water.

Above the stated value, the amount of water can be chosen freely and is limited, if at all, only by procedural or economic aspects and can certainly be used in large, for example in 5- to 15-fold excess or even above. Preferably, a mixture of alcohol and aldehyde is prepared with the amount of water to be added so that the added water remains dissolved in the mixture of the alcohol and the aldehyde, i. H. there is no two-phase system.

For reacting the alcohol with the aldehyde in step a), it is possible to bring the abovementioned starting materials and optionally added water into contact with the acidic cation exchanger. Preferably, alcohol, aldehyde and optionally the added water are used in the form of a mixture in step a). The stated starting materials can be brought into contact or mixed with one another in any order.

The amount of strongly acidic cation exchanger in step a) is not critical and can be chosen freely within wide limits, taking into account the economic and procedural aspect. Accordingly, the reaction can be carried out both in the presence of catalytic amounts and in the presence of large excesses of the strongly acidic cation exchanger. The strongly acidic cation exchanger is usually employed in an amount of about 5 to about 40% by weight, preferably in an amount of about 10 to about 40% by weight and more preferably in an amount of about 10 to about 30% by weight. %, in each case based on the sum of alcohol and aldehyde used. The data refer to the ready-to-use cation exchanger, which is usually pretreated with water and accordingly amounts of up to about 70 wt .-%, preferably from about 30 to about 65 wt .-% and particularly preferably from about 40 to about 65% by weight of water may include. In particular, in the case of discontinuous process control, it is therefore unnecessary to add any additional water when carrying out the process according to the invention. The abovementioned strongly acidic cation exchangers can be used in step a) both individually or else in the form of mixtures.

In continuous operation, the catalyst loading is for example in the range of 50 to 2500 mol per m ^{3 of} catalyst and h, preferably in the range of 100 to 2000 mol per m ^{3 of} catalyst and h, in particular in the range of 130 to 1700 mol per m ^{3 of} catalyst and h , Where the molar amount in mol refers to the starting material I-Ab or I-Ba.

The reaction in step a) in the presence of a strongly acidic cation exchanger can optionally also be carried out in the presence of a solvent which is inert under the reaction conditions. Suitable solvents are, for example, tert-butyl methyl ether, cyclohexane, decalin, hexane, heptane, ligroin, petroleum ether, toluene or xylene. The solvents mentioned can be used alone or in the form of mixtures with one another. The reaction in step a) is preferably carried out in the presence of a strongly acidic cation exchanger without addition of an organic solvent.

Preference is given to reacting the alcohol with the selected aldehyde in step a) in the presence of water and in the presence of a strongly acidic cation exchanger at a temperature in the range from 0 to 70 ° C., more preferably at a temperature in the range from 20 to 70 ° C and in particular carried out at a temperature in the range of 20 to 60 ° C. This is the temperature of the reaction mixture.

The reaction in step a) can be carried out batchwise or continuously. In this case, for example, in the discontinuous case, the reaction can be carried out by initially introducing a mixture of the alcohol, the aldehyde, optionally water and optionally an organic solvent in a suitable reaction vessel and adding the acidic catalyst. After completion of the reaction, the catalyst can then be separated off from the resultant reaction mixture by suitable separation processes. The order of contacting the individual reaction components is not critical and can be varied according to the respective process engineering embodiment. If in step a) a Bronsted acid, which is preferably selected from hydrochloric acid, sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, is used as the catalyst, the separation of the Catalyst z. B. be carried out by distillation after aqueous workup or carried out directly by distillation. If a strongly acidic cation exchanger is used as the catalyst in step a), the separation of the catalyst can be carried out, for example. By filtration or by centrifugation.

In a preferred embodiment, the reaction of the alcohol with the aldehyde in step a) is carried out continuously. For example, a mixture of the starting materials alcohol and aldehyde to be reacted with water can be prepared for this purpose and this mixture continuously brought into contact with a strongly acidic cation exchanger. For this purpose, the selected cation exchanger can be introduced, for example, into a suitable flow reactor, for example a stirred reactor with inlet and outlet or a tubular reactor, and the starting materials and the water are continuously introduced into the latter and the reaction mixture is discharged continuously. The starting materials and the water can optionally be added as individual components or in the form of a mixture as described above in the flow reactor. Corresponding methods are described in the European patent applications EP 13165767.8 and

EP 13165778.5. A second preferred embodiment of the process according to the invention is a process for the preparation of compounds of the formula (I-B) as described above, in which

a) reacting a compound of formula (I-Ba) with compounds of formula (I-Bb) to give a compound of formula (I-Bc) and

b) reacting the compound of the formula (I-Bc) with a ketene of the formula (K) to obtain compounds of the formula (I-B).

In the process according to the invention, a mixture of isomers of the general formula (I-Bb) can be reacted. It is also possible to react a single isomer of the compound (I-Bb).

The step b) according to the invention proceeds as described above. The reaction of compounds of the formula (I-Bc) to give compounds of the formula (I-B) proceeds analogously to the reaction of compound of the formula (Ic) to give compounds of the formula (I).

The step a) of the synthesis of compounds of the formula (I-Bc) analogously to the step a) for the synthesis of compounds of the formula (I-Ac), as described above. Usually, the reaction takes place without the addition of an external solvent. The reaction preferably takes place at a temperature in the range from 20 to 120.degree. C., in particular from 30 to 80.degree. Furthermore, the reaction preferably takes place using a cationic ion exchanger. The reaction is particularly preferably carried out using a cationic ion exchanger without addition of an external organic solvent and at a temperature in the range from 0 to 70.degree. C., preferably from 20 to 70.degree. C. and in particular from 20 to 60.degree.

In one embodiment of the process according to the invention, compounds of the formula (I-Bb.1) are used as compound (I-Bb) in a preferred process. In this case, R ⁴ is W

In a specific variant, no isomer mixture of compounds of the formula (I-Bb.1) is used, but a single isomer or enantiomer.

The compounds of the formula (I-Bb.1) are commercially available and known by the common name isopulegol. In particular, (-) - isopulegol ((1R, 2S, 5R) -2-isopropenyl-5-methylcyclohexanol) can be used.

The compounds of the formula (Γ) or (I) are suitable as aroma chemicals. Preferred compounds of the formula (Γ) or (I) are those mentioned above.

The compounds of the formula (I) or (I) according to the invention and the compounds of the formula (I) or (I) obtainable by the process according to the invention are suitable on account of their advantageous odor properties. They are particularly advantageous as fragrances, for the provision of fragrances, as flavorings and / or for the provision of perfumed or flavored products. Preferred compounds of the formula (Γ) or (I) are those mentioned above.

This applies in particular to the compounds of the formulas (IA) and (IB), in particular to the preferred compounds of the formulas (IA.1), (IA.2), (IA.3), (IA.4), (IA. 5), (IA.6), (IA.7), (IA.8), (IA.9), (IA.10), (IB.1), (IB.2) (IB.3) and (IB.4), and especially for the compounds of the formulas (IA.1), (IA.2), (IA.3), (IA.4) and (IA.6) and (IA.7) and (IA.8) and (IA.10), more specifically (IA.1), (IA.2), (IA.3), (IA.6) and (IA.10), especially special (IA.1), (IA.3) and (IA.10).

In a further subject of the invention this applies in particular to the compounds of the formulas (IA) and (IB), in particular to the preferred compounds of the formulas (IA.1), (IA.2), (IA.3), (IA. 4), (IA.5), (IA.6), (IA.7), (IA.8), (IA.9), (IB.1), (IB.2) (IB.3) and (IB.4), and especially for the compounds of the formulas (IA.1), (IA.2), (IA.3), (IA.4) and (IA.6) and (IA.7) and ( IA.8), more specifically (IA.1), (IA.2), (IA.3) and (IA.6), especially special (IA.1) and (IA.3).

As mentioned above, the compounds of general formula (II) or (I) can be used isomerically pure or as a mixture of isomers. If the compounds of the formulas (Γ) or (I) are employed as mixture of isomers, the proportion of each isomer contained in the mixture is in each case at least 1% by weight, preferably at least 2% by weight, in particular at least 2.5% by weight. -%, Based on the total weight of the compounds of formula (Γ) or (I).

In particular, the compounds according to the invention are used in compositions which are selected from perfumes, detergents and cleaners, cosmetic agents, personal care products, hygiene articles, products for oral and dental hygiene, fragrance dispensers, fragrances and pharmaceutical agents.

A preferred object of the invention is the use of the compound of formula (I-A.1) as Aromachemikalie.

The odor of the compound of formula (I-A.1) can be described as green (int 4) and dill (int 4). In particular, this mixture has an isomer mixture of compounds of the formula (I-A.1), preferably a cis-trans mixture of (cis) - (I-A.I) and (trans) - (I-A.I). Thus, the use of compounds of the formula (I-A.1) for producing a fragrance with a green and / or dill note is particularly preferred.

The odor of green (int.4) and dill (int.4) is especially indicated by a mixture of compounds of the formulas (2R, 4R) - (IA.1), (2S, 4S) - (IA.1), (2R , 4S) - (IA.1) and (2S, 4R) - (IA.1), specifically the ratio of compounds of the formulas (2R, 4R) - (IA.1) and (2S, 4S) - ( IA.1) to compounds of the formulas (2R, 4S) - (IA.1) and (2S, 4R) - (IA.1) in the range from 1: 2 to 1: 1 and preferably in the range from 1: 1, 6 to 1: 1. Specifically, the ratio of compounds of formulas (2R, 4R) - (IA.1) and (2S, 4S) - (IA.1) to compounds of formulas (2R, 4S) - (IA.1) and (2S, 4R) - (IA.1) 1: 1, 4. A preferred subject of the invention is the use of the compound of formula (IA.2) as aroma chemical.

The odor of the compound of formula (I-A.2) can be described as flowery, grape hyacinth (int.3), sweet (int.3) and coumarin (int2); the intensity can be described as 2-3. In particular, this mixture has an isomer mixture of compounds of the formula (I-A.2), preferably a cis-trans mixture of (cis) - (I-A.2) and (trans) - (I-A.2). Thus, the use of compounds of the formula (I-A.2) for producing a fragrance with a note of flowery and / or grape hyacinth and / or sweet and / or coumarin is particularly preferred.

A preferred subject of the invention is the use of the compound of formula (I-A.3) as Aromachemikalie. The odor of the compound of formula (I-A.3) can be described as phenolic, leather and technical; the intensity can be described as 3. In particular, this mixture has an isomer mixture of compounds of the formula (I-A.3), preferably a cis-trans mixture of (cis) - (I-A.3) and (trans) - (I-A.3). Thus, the use of compounds of the formula (I-A.3) for the production of a fragrance with a phenolic and / or leather grade and / or technical is particularly preferred.

A preferred subject of the invention is the use of the compound of formula (I-A.4) as Aromachemikalie. The odor of the compound of formula (I-A.4) can be described as cresol and technical; the intensity can be described as 3. In particular, this mixture has an isomer mixture of compounds of the formula (I-A.4), preferably a cis-trans mixture of (cis) - (I-A.4) and (trans) - (I-A.4). Thus, the use of compounds of the formula (I-A.4) for producing a fragrance with a cresol and / or technical grade is particularly preferred.

A preferred subject of the invention is the use of the compound of formula (IA.6) as Aromachemikalie. The odor of the compound of formula (IA.6) can be described as flowery (int.2), honey (int.2) and iris (int.2); the intensity can be described as 1 - 2. This odor in particular comprises an isomer mixture of compounds of the formula (IA.6), preferably a cis-trans mixture of (cis) - (IA.6) and (trans) - (IA.6) in which the cis-trans Isomer enriched present. Particularly preferred is thus the Use of compounds of the formula (IA.6) for producing a fragrance with a note of flowery and / or honey and / or iris.

A preferred subject of the invention is the use of the compound of formula (I-A.7) as Aromachemikalie.

The odor of the compound of the formula (I-A.7) can be described as lilies of the valley (int.1), cresol / smoke (int.2) and / or technically (int.2). In particular, this mixture has an isomer mixture of compounds of the formula (I-A.7), preferably a cis-trans mixture of (cis) - (I-A.7) and (trans) - (I-A.7). Thus, the use of compounds of the formula (I-A.7) for producing a fragrance with a note of lily of the valley and / or cresol / smoke and / or technical is particularly preferred.

A preferred subject of the invention is the use of the compound of formula (I-A.8) as aroma chemical.

The odor of the compound of formula (I-A.8) can be described as a solvent (int.3), rubber (int.4) and / or hot angle grinder. In particular, this mixture has an isomer mixture of compounds of the formula (I-A.8), preferably a cis-trans mixture of (cis) - (I-A.8) and (trans) - (I-A.8). Thus, the use of compounds of the formula (I-A.8) for producing a fragrance with a touch of solvent and / or rubber and / or hot angle grinder is particularly preferred.

A preferred subject of the invention is the use of the compound of formula (I-A.10) as an aroma chemical.

The odor of the compound of the formula (I-A.10) can be described as natural, green, herbaceous, pertinent, cumin, fresh. This odor in particular comprises an isomer mixture of compounds of the formula (IA.10), preferably a cis-trans mixture of (cis) - (IA.10) and (trans) - (IA.IO), in which the cis-trans Isomer enriched present. Thus, the use of compounds of the formula (I-A.10) for producing a fragrance with a note of natural, green, herbaceous, spearmint, cumin and / or fresh is particularly preferred. Cis-enriched in the specification of the application designates a cis-trans ratio of at least 60:40, preferably at least 70:30.

Another object of the invention are flavoring and perfume compositions containing i) at least one compound of the formula (Γ) or (I) as defined herein, or at least one compound of the formula (Γ) or (I) obtainable in a process herein defined,

ii) optionally at least one further aroma chemical other than the compound (Γ) or (I) and

iii) optionally at least one diluent,

with the proviso that the composition contains at least one component ii) or iii). Preferred compounds of the formula (Γ) or (I) are those mentioned above. Particularly preferred compounds of the formulas (Ι-Α '), (lA) and (lB), in particular the compounds of the formulas (IA.1), (IA.2), (IA.3), (IA.4), (IA.5), (IA.6), (IA.7), (IA.8), (IA.9), (IA.10), (IB.1), (IB.2), (IB .3) and (IB.4). Especially preferred compounds are those mentioned above.

In a further aspect of the invention, the preferred compounds of the formula (Γ) or (I) are those mentioned above. Particularly preferred compounds of the formulas (Ι-Α '), (lA) and (lB), in particular the compounds of the formulas (IA.1), (IA.2), (IA.3), (IA.4), (IA.5), (IA.6), (IA.7), (IA.8), (IA.9), (IB.1), (IB.2), (IB.3) and (IB .4). Especially preferred compounds are those mentioned above.

The compositions according to the invention can be diluted as desired for use as a fragrance with at least one solvent customary in this field of application. Examples of suitable solvents are: ethanol, dipropylene glycol or its ethers, phthalates, propylene glycols or carbonates of diols, preferably ethanol. Water is also suitable as a solvent for diluting the perfume compositions according to the invention and can advantageously be used together with suitable emulsifiers. The compounds of the formula (I) or (I) according to the invention and the compounds of the formula (I) or (I) obtainable by the process according to the invention have high stability and durability.

Another object of the invention are perfumed or flavored products, which are preferably selected from perfumes, detergents and cleaners, cosmetics, personal care products, hygiene articles, oral hygiene products, fragrance dispensers, fragrances and pharmaceutical agents containing at least one compound of the invention of the formula (I) or (I) and / or at least one obtainable by the process according to the invention compound of formula (Γ) or (I).

Preferred compounds of the formula (Γ) or (I) are those mentioned above.

The compounds of the formula (II) or (I) according to the invention and / or the compounds of the formula (II) or (I) obtainable by the process according to the invention are suitable for incorporation into cosmetic compositions and consumables and / or agents, as described in US Pat Below are described in more detail, wherein the fragrances can be incorporated into the mentioned goods or even applied to such. In this context, an organoleptically effective amount, as in the context of the entire present invention, is to be understood in particular as meaning an amount which, when properly used, is sufficient to cause the consumer or consumer to have a scent impression.

As cosmetic compositions, all the usual cosmetic compositions are suitable. These are preferably perfume, Eau de Toilette, deodorants, soap, shower gel, bath gel, creams, lotions, sunscreens, compositions for cleaning and hair care, such as hair shampoo, conditioner, hair gel, hair fixative in the form of liquids or foams and more Cleaning or care preparations for the hair, compositions for decorative use on the human body, such as cosmetic pencils, for example lipsticks, lip care pens, concealers, cheek blushers, eyeshadow pencils, lip pencils, eye contour pencils, eyebrow pencils, correction pencils, sun protection pencils, Anti-acne pens and similar products as well as nail polishes and other nail care products.

The compounds of the formula (I) or (I) according to the invention and / or the compounds of the formula (I) obtainable by the process according to the invention are particularly suitable for use in perfumes, for. As Eau de Toilette, shower gels, bath gels and body deodorants.

They are also suitable for flavoring consumer goods or household goods, into which they are incorporated or applied, thereby giving them a pleasant fresh green accent. Examples of consumer goods or consumer goods are: air-deodorants (air care), cleaning or care products for textiles (especially detergents, fabric softeners), textile treatment agents such as ironing aids, cleaning agents, cleaning agents, care products for the treatment of surfaces, such as furniture, floors, kitchen equipment, glass - Washers and windows and screens, bleaching, toilet blocks, descaling agents, fertilizers, building materials, mold removers, disinfectants, car care products and the like. In this case, both a compound of formula (Γ) or (I) and a mixture of several different compounds of formula (Γ) or (I) can be used or used.

Another object of the invention are methods for perfuming, in particular for lending and / or enhancing an odor or taste, of a product in which at least one compound of formula (Γ) or (I) is used.

Preferred compounds of the formula (Γ) or (I) are those mentioned above. In one embodiment, the compound of formula (I-A.1) is used to impart or enhance a product of green and / or dill.

In another embodiment, the compound of formula (I-A.2) is used to impart or enhance a product of flowery and / or grape hyacinth and / or sweet and / or coumarin.

In a further embodiment, the compound of formula (I-A.3) is used to impart or enhance a phenolic and / or leather grade and / or technically to a product.

In a further embodiment, the compound of formula (I-A.4) is used to give or enhance technically a grade of cresol and / or technically. In another embodiment, the compound of formula (I-A.6) is used to impart or enhance a product of flowery and / or honey and / or iris.

In a further embodiment, the compound of formula (IA.7) is used to give or enhance technically a touch of lily of the valley and / or cresol / smoke and / or. In a further embodiment, the compound of formula (IA.8) is used to impart or enhance a grade of solvent, and / or gum and / or hot angle grinder to a product. In a further embodiment, the compound of formula (IA.10) is used to impart or enhance a natural, green, herbaceous, spearmint, cumin and / or fresh note to a product.

The following examples serve to illustrate the invention without limiting it in any way.

EXAMPLES

The following chemicals and abbreviations were used:

Amberlyst® 131: Acid ion exchange resin from Rohm and Haas

Isoprenol: 3-methyl-3-buten-1-ol

Isopulegol: 2-isopropenyl-5-methylcyclohexanol

Ketene: ethenone (H ₂ C = C = 0)

DMAP: 4- (dimethylamino) pyridine

Gas chromatographic analysis

Gas chromatographic analyzes (GC) were carried out according to the following method:

Column: DB WAX 30 m x 0.32 mm; FD 0.25 μηη

Flow rate: 1 .5 mL / min N2

Method A: Start at 50 ° C, then at 3 ° C / min to 170 ° C, then at 20 ° C / min to 230 ° C Method B: Start 60 ° C, then at 2 ° C / min to 120 ° C , then at 20 ° C / min to 230 ° C Method C: Start 80 ° C, then at 2 ° C / min to 140 ° C, then at 20 ° C / min to 230 ° C.

Aroma-determination

The smell of the respective substances was evaluated on a smelling strip. If indicated, the intensity is between 1 (very weak) and 6 (very strong).

Example 1: Preparation of compounds (IA.1)

Benzaldehyde (1961 g, 18.5 mol) and an acidic ion exchange resin (Amberlyst® 131, 375 g) were initially charged at 40 ° C. Isoprenol (1591 g, 18.5 mol) was metered in with stirring within 3 h, during which the internal temperature rose to about 60.degree. After completion of the addition, stirring was continued at 60 ° C. for 3 h and then filtered off hot from the acidic ion exchanger. 2913 g of crude product were obtained with a purity of 67% (yield about 55% by gas chromatography, GC method A, R _t = 44.4 min).

The product can be purified by fractional distillation (head temperature 106 to 130 ° C at 3 mbar). cis -tetrahydro-4-methyl-2-phenyl-pyranol, cis- (1-Ac.1)

3C-NMR (125 MHz, CDCl ₃ ): δ = 25.1, 40.1, 48.2, 65.8, 68.9, 77.6, 125.9 (2x), 127.6, 128.4 (2x), 141.9 ppm. trans -tetrahydro-4-methyl-2-phenyl-pyranol, trans- (I-Ac.l)

3C NMR (125 MHz, CDC): δ = 31.6, 38.2, 46.4, 64.0, 67.9, 75.2, 125.9 (2x), 127.4, 128.3 (2x) 142.6 ppm.

Tetrahydro-4-methyl-2-phenyl-pyranol (as a cis / trans mixture, 10.3 g, 53.5 mmol) was initially charged in 80 ml of toluene at 60 ° C. Keten was obtained by pyrolysis of acetone at 700 ° C and the pyrolysis gas stream passed through the reaction mixture with vigorous stirring for 8 h. Sales were> 98%. It was then allowed to cool and the solvent removed on a rotary evaporator.

The crude product was purified by column chromatography (cyclohexane with 0 to 20% ethyl acetate in 30 min). The product was obtained in 96% purity as a mixture of two diastereomers with a cis: trans ratio of 1.4: 1.

Odor: green (Int 4), dill (Int 4) cis-Tetrahydro-4-methyl-2-phenyl-pyranylacetate, cis- (IA.I)

Rt = 34.8 min (GC method B). ³ C-NMR (125 MHz, CDCl ₃ ): δ = 21 .6, 22.4, 37.4, 45.2, 65.0, 76.7, 79.9, 125.8 (2x), 127.6, 128.4 (2x), 141 .8, 170.2 ppm. Trans -tetrahydro-4-methyl-2-phenyl-pyranylacetate, trans (IA.1)

Rt = 34, 1 min (GC method B). ³ C-NMR (125 MHz, CDCl ₃ ): δ = 22.4, 26.1, 35.7, 44.2, 63.8, 74.9, 79.2, 125.8 (2x), 127.5, 128.3 (2x), 142.1, 170.4 ppm. Example 2: Preparation of compounds (IA.2)

The preparation was carried out analogously to Example 1. The product was obtained after column chromatography (cyclohexane / ethyl acetate) in 86% purity as a cis / trans mixture with a cis: trans ratio of 1 .7: 1.

Odor: flowery, grape hyacinth (int.3), sweet (int.3), coumarin (int.2)

Intensity: 2 - 3 cis- (l-A.2)

R _t = 43.4 min (GC method C). MS (El): m / z (%) = 264 [M] ⁺ (15), 204 (35), 189 (100), 173 (10), 137 (39), 135 (35), 69 (11 ), 43 (13). ³ C-NMR (125 MHz, CDCl ₃ ): δ = 170.4, 159.0, 134.0, 127.2, 1 13.7, 80.0, 76.4, 65.0, 55.3, 45.0, 37.4, 22.5, 21 .6 ppm. trans- (lA.2)

Rt = 41.2 min (GC Method C). MS (El): m / z (%) = 264 [M] ⁺ (2), 204 (37), 189 (100), 137 (16), 135 (28), 77 (4), 69 (5) , 43 (8). ³ C-NMR (125 MHz, CDC): δ = 171.1, 158.9, 134.3, 127.1, 1 13.7, 79.3, 74.5, 63.9, 55.3, 44.0, 35.7, 26.2, 22.5 ppm. Example 3: Preparation of compounds (IA.3)

The preparation was carried out analogously to Example 1. The product was obtained after column chromatography (cyclohexane / ethyl acetate) in 80% purity as cis / trans mixture with a cis: trans ratio of 1.2: 1.

Odor: phenolic (Int.3), leather (Int.2), technical (Int.3)

Intensity: 3 cis- (l-A.3)

Rt = 42.4 min (GC Method C). MS (El): m / z (%) = 264 [M] ⁺ (29), 204 (24), 189 (100), 173 (17), 135 (32), 121 (6), 109 (6) , 77 (6), 69 (11), 43 (17). ³ C-NMR (125 MHz, CDCl 3): δ = 170.4, 159.6, 143.8, 129.4, 118.1, 113.2, 111.0, 79.2, 74.8, 63.8, 55.2, 44.2, 35.6, 22.4, 21.6 ppm. trans- (lA.3)

Rt = 40.5 min (GC Method C). MS (El): m / z (%) = 264 [M] ⁺ (2), 204 (38), 189 (100), 173 (7), 135 (21), 43 (8). ³ C-NMR (125 MHz, CDC): δ = 170.3, 159.6, 143.4, 129.4, 118.1, 113.4, 111.1, 79.9, 76.6, 64.9, 55.2, 45.1, 37.4, 26.1, 22.4 ppm.

Example 4: Preparation of compounds (I-A.4)

(IA.4) The preparation was carried out analogously to Example 1. The product was obtained after column chromatography (cyclohexane / ethyl acetate) in 74% purity as a cis / trans mixture with a cis: trans ratio of 4: 1. Odor: Cresol, technical (Int 3)

Intensity: 3 cis- (l-A.4)

Rt = 39.8 min (GC method C). MS (El): m / z (%) = 264 [M] ⁺ (18), 204 (35), 189 (100), 173 (13), 159 (10), 135 (39), 1 19 (18 ), 107 (14), 91 (17), 69 (17), 43 (28). ³ C-NMR (125 MHz, CDCIs): δ = 170.3, 155.4, 130.3, 128.3, 126.2, 120.8, 1 10.1, 80.3, 71.0, 65.2, 55.4, 44.1, 37.7, 22.5, 21 .5 ppm. trans- (lA.4)

R _t = 38.1 min (GC method C). MS (El): m / z (%) = (264) [M] ⁺ (1), 204 (48), 189 (100), 173 (8), 159 (7), 135 (35), 1 19 (1 1), 107 (8), 91 (12), 69 (9), 43 (16). ³ C-NMR (125 MHz, CDCIs): δ = 170.5, 155.6, 130.7, 128.2, 126.0, 120.7, 1 10.2, 80.3, 71.0, 64.1, 55.4, 42.6, 36.3, 26.2, 22.5 ppm. Example 5: Preparation of compounds (IA.5)

The preparation was carried out analogously to Example 1. The product was obtained after column chromatography (cyclohexane / ethyl acetate) in 96% purity as a cis / trans mixture with a cis: trans ratio of 5: 1.

Odor: not determined. cis- (l-A.5)

Rt = 41.6 min (GC method C). MS (El): m / z (%) = 294 [M] ⁺ (73), 234 (24), 219 (89), 206 (83), 191 (28), 165 (100), 152 (21) , 139 (15), 69 (24), 43 (40). ³ C NMR (125 MHz, CDCIs): δ = 170.2, 160.7, 144.2, 103.6, 99.7, 79.8, 76.7, 64.8, 55.3, 45.1, 37.4, 22.4, 21.6 ppm. trans- (lA.5)

Rt = 41.2 min (GC method C). MS (El): m / z (%) = 294 [M] ⁺ (14), 234 (37), 219 (100), 206 (12), 165 (20), 152 (6), 43 (1 1 ). ³ C-NMR (125 MHz, CDC): δ = 170.4, 160.7, 144.7, 103.6, 99.6, 79.2, 74.9, 63.8, 55.3, 44.3, 35.5, 26.1, 22.4 ppm.

Example 6: Preparation of compounds (I-A.6)

The preparation was carried out analogously to Example 1. The product was obtained after column chromatography (cyclohexane / ethyl acetate) in 97% purity as a cis / trans mixture with a cis: trans ratio of 45: 1. Odor: floral (int.2), honey (int.2), iris (int.2)

Intensity: 1 - 2 cis- (l-A.6)

Rt = 37.9 min (GC method C). MS (El): m / z (%) = 248 [M] ⁺ (2), 188 (40), 173 (100), 159 (3), 145 (5), 1 19 (22), 91 (1 1), 69 (10), 43 (14). ³ C-NMR (125 MHz, CDCl 3): δ = 170.2, 138.8, 137.2, 129.0, 125.8, 80.0, 76.6, 65.0, 45.1, 37.4, 22.4, 21.5, 21 .1 ppm. trans- (lA.6)

Rt = 36.8 min (GC method C). MS (El): m / z (%) = 188 (40), 173 (100), 159 (2), 145 (4), 1 19 (21), 91 (9), 69 (6), 43 ( 9).

Example 7: Preparation of Compounds (IA.7)

The preparation was carried out analogously to Example 1. The product was obtained after column chromatography (cyclohexane / ethyl acetate) in 84% purity as a cis / trans mixture with a cis: trans ratio of 2.8: 1.

Odor: lily of the valley (int.1), cresol / smoke (int.2), technical (int.2) cis- (l-A.7)

Rt = 37.7 min (GC method C). MS (El): m / z (%) = 248 [M] ⁺ (2), 188 (46), 173 (100), 145 (7), 1 19 (27), 91 (16), 69 (16 ), 43 (25). ³ C-NMR (125 MHz, CDCl ₃ ): δ = 170.3, 141.6, 138.0, 128.4, 128.3, 126.5, 122.9, 79.9, 76.8, 65.0, 45.1, 37.4, 22.5, 21.5,

21.4 ppm. trans- (l-A.7)

R _t = 36.7 min (GC method C). MS (El): m / z (%) = 248 [M] ⁺ (<1), 188 (41), 173 (100), 145 (6), 1 19 (23), 91 (12), 69 ( 8), 43 (15). ³ C-NMR (125 MHz, CDC): δ = 170.4, 142.0, 138.0, 129.4, 128.24, 128.22, 126.4, 79.2, 74.9, 63.9, 44.2, 35.7, 26.1, 22.4,

21.5 ppm. Example 8: Preparation of compounds (I-A.8)

(IA.8) The preparation was carried out analogously to Example 1. The product was obtained after column chromatography (cyclohexane / ethyl acetate) in 86% purity as a cis / trans mixture with a cis: trans ratio of 3.8: 1.

Odor: solvent (int.3), rubber (int.4), hot angle grinder cis- (l-A.8)

Rt = 37.7 min (GC method C). MS (El): m / z (%) = 248 [M] ⁺ (4), 188 (54), 173 (100), 143 (14), 1 19 (34), 91 (21), 69 (26 ), 43 (31). ³ C-NMR (125 MHz, CDCl ₃ ): δ = 170.2, 139.8, 134.0, 130.2, 127.3, 126.3, 125.2, 80.0, 73.6, 65.2, 44.0, 37.5, 22.5, 21 .4, 18.9 ppm. trans- (lA.8)

Rt = 36.5 min (GC Method C). MS (El): m / z (%) = 248 [M] ⁺ (<1), 188 (50), 173 (100), 145 (10), 1 19 (25), 91 (15), 69 ( 14), 43 (18). ³ C-NMR (125 MHz, CDC): δ = 170.4, 140.2, 134.1, 130.2, 127.1, 126.2, 125.0, 79.4, 73.8, 64.0, 42.8, 36.1, 26.1, 22.4, 18.8 ppm.

Example 9: Preparation of compounds (I-A.9)

The preparation was carried out analogously to Example 1. The product was obtained after column chromatography (cyclohexane / ethyl acetate) in 70% purity as a cis / trans mixture with a cis: trans ratio of 3: 1.

Odor: not determined. cis- (l-A.9)

Rt = 38.8 min (GC method C). MS (El): m / z (%) = 262 [M] ⁺ (4), 202 (41), 187 (100), 159 (8), 133 (32), 1 19 (6), 105 (9 ), 91 (9), 69 (1 1), 43 (18). ³ C NMR (125 MHz, CDC): δ = 170.2, 141.6, 137.9, 129.2, 123.6, 80.0, 76.9, 65.0, 45.0, 37.4, 22.4, 21.5,

21 .3 ppm. trans- (lA.9)

Rt = 37.7 min (GC method C). MS (El): m / z (%) = 262 [M] ⁺ (1), 202 (39), 187 (100), 159 (6), 133 (25), 1 19 (4), 105 (7 ), 91 (6), 69 (6), 43 (1 1). ³ C-NMR (125 MHz, CDCl ₃ ): δ = 170.4, 142.0, 137.8, 129.2, 123.5, 79.3, 75.0, 65.0, 45.0, 37.4, 26.1, 22.3,

21 .3 ppm.

Example 10: Preparation of compounds (I-B.3)

n-Butanal (120 g, 1.66 mol) was initially charged with an acidic ion exchange resin (Amberlyst® 131, 50 g) at room temperature and isopulegol (240 g, 1.56 mol) was metered in within 20 minutes. During the addition, the temperature rose to about 65 ° C. After completion of the addition, the mixture was stirred at 70 ° C for 8 h, allowed to cool and the mixture was diluted with 300 ml of water and filtered from the acidic ion exchanger. The phases were separated, the organic phase diluted with toluene and washed with saturated aqueous NaHCO 3 solution and NaCl solution. Subsequently, the solvent was removed on a rotary evaporator.

The product was fractionated by distillation as a diastereomeric mixture of the alcohols with an (alpha) - (l-Bc.3): (beta) - (l-Bc.3) ratio of 1: 4 as a viscous liquid (1.104 g, 30 %) receive.

(Alpha) - (l-Bc.3)

Rt = 32.6 (GC method B). MS (El): m / z (%) = 225 [MH] ⁺ (<1), 208 (56), 193 (52), 183 (27), 165 (43), 139 (100), 121 (19 ), 1 1 1 (13), 95 (24), 81 (53), 71 (29), 55 (23), 43 (50). ³ C-NMR (125 MHz, CDCl ₃ ): δ = 75.0, 72.1, 69.0, 50.3, 47.0, 42.0, 38.8, 35.0, 31 .5, 28.4, 22.9, 22.5, 19.2, 14.5 ppm.

(Beta) - (l-Bc.3)

Rt = 33.3 (GC method B). MS (El): m / z (%) = 225 [MH] ⁺ (<1), 208 (4), 183 (45), 165 (8), 139 (100), 131 (24), 121 (13 ), 13 (27), 95 (25), 81 (53), 71 (24), 55 (19), 43 (51). ³ C-NMR (125 MHz, CDC): δ = 76.8, 74.4, 70.8, 52.3, 48.4, 41 .6, 38.4, 34.4, 31 .4, 23.0, 22.2, 21 .4, 18.7, 14.1 ppm.

The alcohol (as a mixture of diastereomers, 10.2 g, 42 mmol) was initially charged in toluene at 60 ° C. Keten was obtained by pyrolysis of acetone at 700 ° C and the pyrolysis gas stream for 8.5 h with vigorous stirring passed through the reaction mixture. Sales were> 90%. It was then allowed to cool and the solvent removed on a rotary evaporator.

The product was obtained after column chromatography (cyclohexane / ethyl acetate) in a purity of 96% as a mixture of two diastereomers with a

(alpha) - (l-B.3) :( beta) - (l-B.3) ratio of 1:10.

Odor: not determined.

(Alpha) - (l-B.3)

Rt = 31 .5 min (GC method B). MS (El): m / z (%) = 267 [MH] ⁺ (<1), 208 (39), 193 (64), 180 (15), 165 (100), 139 (8), 121 (18 ), 107 (15), 93 (23), 81 (46), 67 (9), 55 (17), 43 (32). ³ C-NMR (125 MHz, CDCl ₃ ): δ = 170.4, 80.5, 74.6, 72.2, 51 .4, 41 .4, 40.3, 37.9, 34.4, 31 .1, 23.4, 22.5, 22.2, 22.1, 18.7, 14.0 ppm.

Rt = 32.8 min (GC method B). MS (El): m / z (%) = 208 (27), 193 (22), 179 (9), 165 (100), 147 (7) 136 (12), 121 (25), 107 (13) , 93 (20), 81 (40), 67 (7), 55 (12), 43 (24). 3C-NMR (125 MHz, CDC): δ = 170.1, 82.5, 75.9, 73.6, 50.0, 43.9, 41.6, 38.4, 34.2, 31.3, 23.3, 22.5, 22.2, 18.8, 18.4, 14.1 ppm.

Example 1 1: Preparation of compounds (I-B.1)

The preparation was carried out analogously to Example 10. The product was after column chromatography (cyclohexane / ethyl acetate) in a purity of 84% as a mixture of two isomers with an (alpha) - (lB.1): (beta) - (lB.1) Ratio of 1:16 obtained.

Odor: not determined.

(alpha) - (I-B.I)

Rt = 30.2 min (GC method C). MS (El): m / z (%) = 180 (45), 165 (100), 151 (22), 137 (24), 122 (15), 107 (14), 95 (16), 81 (37 ), 67 (9), 55 (1 1), 43 (33).

(beta) - (I-B.I)

Rt = 32.3 min (GC method C). MS (El): m / z (%) = 239 [MH] ⁺ (<1), 180 (65), 165 (100), 151 (31), 137 (36), 121 (44), 107 (17 ), 95 (23), 81 (58), 67 (12), 55 (14), 43 (49) 3C-NMR (125 MHz, CDCl ₃ ): δ = 170.5, 82.3, 75.8, 69.9, 49.6, 45.5 , 41 .6, 34.2, 31 .3, 23.2, 22.5, 22.2, 21 .9, 18.3 ppm. Example 12: Preparation of compounds (IB.2)

The preparation was carried out analogously to Example 10. The product was after column chromatography (cyclohexane / ethyl acetate) in a purity of 91% as a mixture of two isomers with an (alpha) - (lB.2): (beta) - (lB.2) Ratio of 1: 6.5. Odor: not determined.

(Alpha) - (l-B.2)

Rt = 31 .5 min (GC method C). MS (El): m / z (%) = 194 (47), 179 (81), 165 (100), 151 (18), 139 (6), 121 (10), 107 (9), 95 (12 ), 81 (25), 67 (5), 55 (9), 43 (20). ³ C-NMR (125 MHz, CDCIs): δ = 170.4, 80.5, 74.6, 73.7, 51.5, 41.4, 40.0, 34.4, 31.2, 28.7, 23.4, 22.6, 22.3, 22.2, 9.9 ppm.

(Beta) - (l-B.2)

Rt = 33.0 min (GC Method C). MS (El): m / z (%) = 194 (32), 179 (29), 165 (100), 151 (1 1), 137 (10), 121 (22), 107 (8), 95 ( 1 1), 81 (25), 67 (5), 55 (7), 43 (19). ¹³ C-NMR (125 MHz, CDCIs): δ = 170.5, 82.5, 75.8, 75.2, 50.0, 43.4, 41.6, 34.2, 31 .3, 29.1, 23.3, 22.5, 22.2, 18.4, 10.0 ppm.

Example 13: Preparation of compounds (I-B.4)

(IB.4) The preparation was carried out analogously to Example 10. The product was obtained after column chromatography (cyclohexane / ethyl acetate) in a purity of 70% as an isomer. A low-boiling by-product could be removed in vacuo and the purity increased to> 90%.

Odor: not determined.

(Beta) - (l-B.4)

Rt = 35.1 min (GC Method C). MS (El): m / z (%) = 266 [M] ⁺ (1), 206 (68), 191 (100), 178 (49), 165 (23), 149 (9), 136 (47) , 121 (52), 107 (30), 95 (41), 81 (58), 69 (18), 55 (16), 43 (53). ³ C-NMR (125 MHz, CDCl ₃ ): δ = 170.5, 82.2, 78.7, 75.8, 49.9, 43.7, 41.6, 34.2, 31 .3, 23.3, 22.5, 22.2, 18.2, 16.2, 3.5, 2.0 ppm.

Example 14: Preparation of compound (I-A.10)

4-methyl-2- (p-tolyl) tetrahydropyran-4-ol (4.13 g, 20 mmol, 1.0 eq.), Et ₃ N (2.23 g;

22 mmol; 1.1 eq.) And DMAP (240 mg, 2 mmol, 0.1 eq.) Were initially charged in toluene (40 mL) at RT. The reaction was warmed to 60 ° C and butyric acid chloride (2.24 g, 21 mmol, 1.05 eq.) Was added dropwise with stirring. After complete addition, stirring was continued for 6 h. It was then allowed to cool to rt, water added to the batch (10 g) and the phases separated. The solvent of the organic phase was removed on a rotary evaporator and the product purified by column chromatography (cyclohexane / ethyl acetate) to> 90% purity. Odor: natural (5), green (5), herbaceous (5), spearmint (4), cumin (4), fresh (4). Intensity 3. cis-isomer

Rt = 39.7 min (GC method C). MS (El): m / z (%) = 276 (1) [M] ⁺ , 188 (36), 173 (100), 145 (6), 121 (17), 1 19 (18), 105 (4 ), 91 (10), 71 (12), 69 (15), 43 (16). ³ C-NMR (125 MHz, CDCIs): δ = 172.8, 138.9, 137.2, 129.0, 125.8, 79.7, 76.6, 65.0, 45.3, 37.5, 37.4, 21.6, 21.1, 18.5, 13.6 ppm.

Comparative Examples: General preparation of the tetrahydropyranol derivatives from benzaldehydes

To prepare the various tetrahydropyranol derivatives, the respective benzaldehyde was initially charged at room temperature with Amberlyst 131 wet® (10% by weight, based on the sum of the masses of benzaldehyde and isoprenol) and an equimolar amount of isoprenol was rapidly added. If necessary, especially if the respective benzaldehyde was solid at room temperature, toluene was used as the solvent. Then the reaction mixture was stirred for 5 h at 60 ° C, then cooled, filtered off the acidic ion exchanger and washed with toluene. Any solvents were removed on a rotary evaporator. Fragrance samples were obtained either by purification by distillation, column chromatography or by recrystallization.

Comparative Example 1 Preparation of Compounds (I-Ac.2)

The preparation was carried out analogously to the general preparation of tetra hydropyran nolderivate from benzaldehydes. The product was obtained after column chromatography (cyclohexane / ethyl acetate) in a purity of 99% as cis / trans mixture with a cis: trans ratio of 2: 1.

The alcohol was odorless. cis isomer

R _t = 44.8 min (GC method C). MS (El): m / z (%) = 222 [M] ⁺ (24), 204 (32), 189 (100), 135 (55), 43 (13). ³ C-NMR (125 MHz, CDCl ₃ ): δ = 159.0, 134.2, 127.3, 1 13.7, 77.2, 69.0, 65.8, 55.2, 48.0, 40.2, 25.2 ppm. trans isomer

R _t = 43.7 min (GC method C). MS (El): m / z (%) = 222 [M] ⁺ (22), 204 (31), 189 (100), 135 (49), 43 (1 1). ³ C-NMR (125 MHz, CDC): δ = 158.8, 134.8, 127.3, 1 13.7, 74.8, 68.0, 64.1, 55.2, 46.3, 38.3, 31 .7 ppm.

Comparative Example 2 Preparation of Compounds (I-Ac.3)

The preparation was carried out analogously to the general preparation of tetra hydropyran nolderivate from benzaldehydes. The product was obtained after column chromatography (cyclohexane / ethyl acetate) in a purity of 99% as a cis / trans mixture with a cis: trans ratio of 1.1: 1.

Odor: technical. cis isomer

R _t = 44.1 min (GC method C). MS (El): m / z (%) = 222 [M] ⁺ (22), 204 (37), 189 (100), 177 (9), 135 (48), 109 (12), 77 (10) , 43 (17). ³ C-NMR (125 MHz, CDC): δ = 159.6, 143.6, 129.4, 1 18.2, 1 13.3, 1 1 1.2, 77.5, 69.1, 65.8, 55.2, 48.3, 40.2, 25.3 ppm. trans isomer Rt = 43.2 min (GC method C). MS (El): m / z (%) = 222 [M] ⁺ (26), 204 (35), 189 (100), 135 (55), 119 (13), 108 (11), 77 (10) , 43 (20). ³ C-NMR (125 MHz, CDCl ₃ ): δ = 159.6, 144.3, 129.3, 118.1, 113.1, 111.1, 75.1, 68.64, 55.2, 46.6, 38.4, 31.7 ppm. Comparative Example 3 Preparation of Compounds (I-Ac.4)

The preparation was carried out analogously to the general preparation of the Tetrahydropyran- nolderivate from benzaldehydes. The product was obtained after column chromatography (cyclohexane / ethyl acetate) in a purity of 96% as a cis / trans mixture with a cis: trans ratio of 1.4: 1.

Odor: technical. cis isomer

Rt = 40.7 min (GC method C). MS (El): m / z (%) = 222 [M] ⁺ (23), 204 (31), 189 (100), 177 (6), 135 (54), 119 (22), 107 (17) , 91 (19), 77 (11), 43 (18). ³ C-NMR (125 MHz, CDCl ₃ ): 5 = 155.4, 130.5, 128.2, 126.1, 120.7, 110.1, 71.7, 69.2, 66.0, 55.3, 47.40, 25.1 ppm. trans isomer

Rt = 39.7 min (GC method C); MS (El): m / z (%) = 222 [M] ⁺ (18), 204 (35), 189 (100), 135 (46), 121 (10), 119 (18), 107 (14) , 91 (15), 43 (13); ³ C-NMR (125 MHz, CDC): δ = 155.5, 131.1, 128.0, 126.2, 120.7, 110.1, 69.4, 68.2, 64.2, 55.3, 45.4, 38.4, 31.6 ppm.

Comparative Example 4 Preparation of Compounds (I-Ac.5)

(I-Ac.5) The preparation was carried out analogously to the general preparation of tetra hydropyran nolderivate from benzaldehydes. The product was obtained after column chromatography (cyclohexane / ethyl acetate) in a purity of 98% as a cis / trans mixture with a cis: trans ratio of 2.1: 1.

The product was odorless. cis isomer

Rt = 60.1 min (GC method C). MS (El): m / z (%) = 252 [M] ⁺ (27), 219 (15), 206 (8), 191 (4), 165 (100), 152 (14), 139 (10) , ³ C-NMR (125 MHz, acetone-D ₆ ): δ = 161.6, 146.8, 104.3, 99.6, 78.0, 68.4, 66.2, 55.5, 50.0, 41.3, 25.6 ppm. trans isomer

Rt = 58.3 min (GC Method C). MS (El): m / z (%) = 252 [M] ⁺ (66), 219 (69), 206 (10), 191 (7), 165 (100), 152 (13), 139 (15) , 43 (1 1). ¹³ C-NMR (125 MHz, acetone-D ₆ ): δ = 161.6, 146.8, 104.3, 99.4, 75.7, 67.5, 64.5, 55.5, 48.0, 39.2, 31 .9 ppm.

Comparative Example 5 Preparation of Compounds (I-Ac.6)

The preparation was carried out analogously to the general preparation of tetra hydropyran nolderivate from benzaldehydes. The crude product was recrystallized from n-heptane. The cis-isomer was obtained in a purity of 99%.

The product was odorless. cis isomer

Rt = 38.6 min (GC Method C). MS (El): m / z (%) = 206 [M] ⁺ (5), 188 (52), 173 (100), 1 19 (36), 103 (4), 91 (18), 71 (9 ), 43 (14). ³ C-NMR (125 MHz, CDCl ₃ ): δ = 139.0, 137.2, 129.0, 125.9, 77.5, 69.0, 65.8, 48.2, 40.2, 25.2, 21 .1 ppm. trans isomer

Rt = 38.1 min (GC Method C). Comparative Example 6 Preparation of Compounds (I-Ac.7)

The preparation was carried out analogously to the general preparation of the Tetrahydropyran- nolderivate from benzaldehydes. The product was obtained after column chromatography (cyclohexane / ethyl acetate) in a purity of 97% as a cis / trans mixture with a cis: trans ratio of 9: 1. The product was odorless. cis isomer

Rt = 38.5 min (GC Method C). MS (El): m / z (%) = 206 [M] ⁺ (4), 188 (58), 173 (100), 1 19 (35), 91 (19), 71 (10), 43 (16 ). ³ C-NMR (125 MHz, acetone-D ₆ ): δ = 144.2, 138.2, 128.8, 128.4, 127.1, 123.6, 78.0, 68.4, 66.2, 50.0, 41 .3, 25.5, 21 .4 ppm. trans isomer

Rt = 38.0 min (GC method C). MS (El): m / z (%) = 206 [M] ⁺ (2), 188 (60), 173 (100), 1 19 (31), 91 (15), 71 (8), 58 (6 ), 43 (12).

Comparative Example 7 Preparation of Compounds (I-Ac.8)

The preparation was carried out analogously to the general preparation of tetra hydropyran nolderivate from benzaldehydes. The product was obtained after column chromatography (cyclohexane / ethyl acetate) in a purity of 98%.

Odor: balsamic (2), cresol (2). cis isomer

Rt = 38.6 min (GC method C). MS (El): m / z (%) = 206 [M] ⁺ (4), 188 (53), 173 (100), 118 (64), 91 (37), 71 (24), 58 (16) , 43 (37). ³ C-NMR (125 MHz, acetone-D ₆ ): δ = 142.1, 134.7, 130.8, 127.6, 126.7, 126.1, 75.1, 68.5, 66.4, 48.4, 41.4, 25.4, 18.9 ppm. trans isomer

Rt = 37.8 min (GC method C). MS (El): m / z (%) = 206 [M] ⁺ (8), 188 (49), 173 (100), 118 (49), 91 (32), 71 (18), 58 (14) , 43 (29). ³ C-NMR (125 MHz, CDCl ₃ ): δ = 140.6, 134.5, 130.1, 127.1, 126.1, 125.3, 71.9, 68.2, 64.2, 45.1, 38.5, 31.7, 19.0 ppm.

Comparative Example 8 Preparation of Compounds (I-Ac.9)

The preparation was carried out analogously to the general preparation of the tetrahydropyranol derivatives of benzaldehydes. The product was obtained after column chromatography (cyclohexane / ethyl acetate) as a cis isomer in a purity of 95%.

The product was odorless. cis isomer: R _t = 39.7 min (GC Method C); MS (El): m / z (%) = 220 [M] ⁺ (13), 202 (53), 187 (100), 159 (6), 133 (45), 117 (15), 107 (17) , 91 (14), 71 (12), 43 (15); ³ C-NMR (125 MHz, acetone-De): δ = 144.2, 138.1, 129.3, 124.3, 78.1, 68.4, 66.2, 50.1, 41.4, 25.6, 21.4 ppm. trans isomer: R _t = 39.2 min (GC Method C); MS (El): m / z (%) = 220 [M] ⁺ (10), 202 (51), 187 (100), 159 (6), 133 (41), 117 (12), 107 (14) , 91 (14), 71 (11), 58 (5), 43 (15); 3C-NMR (125 MHz, CDC): δ = 142.5, 137.9, 129.0, 123.6, 75.3, 68.2, 64.1, 46.5, 38.4, 31.8, 21.3 ppm.

Comparative Examples: General preparation of the tetrahydropyranol derivatives from aliphatic aldehydes To prepare the various tetrahydropyranol derivatives of the respective aldehyde at room temperature with Amberlyst 131 wet® (10 wt .-%, based on the sum of the masses of the corresponding aldehyde and isopulegol), if necessary, submitted with toluene as a solvent, and an equimolar amount of isopulegol quickly added , Then the reaction mixture was stirred for 5 h at 60 ° C, then cooled, filtered off the acidic ion exchanger and washed with toluene. Any solvents were removed on a rotary evaporator. Fragrance samples were obtained either by purification by distillation, column chromatography or by recrystallization.

Comparative Example 9 Preparation of Compounds (I-Bc.1)

The preparation was carried out analogously to the general preparation of the tetrahydropyranol derivatives from aliphatic aldehydes. The product was after column chromatography (cyclohexane / ethyl acetate) in a purity of 97% as an isomer mixture with an (alpha) - (l-Bc.1): (beta) - (l-Bc.1) ratio of 1: 5.5 received. Odor: no specific smell.

(alpha) - (l-Bd)

(alpha) - (l-Bc.l)

Rt = 32.2 min (GC Method C). MS (El): m / z (%) = 198 [M] ⁺ (1), 180 (71), 165 (100), 151 (32), 137 (31), 121 (10), 95 (24) , 81 (65), 71 (30), 55 (18), 43 (52). ³ C-NMR (125 MHz, CDCIs): δ = 75.0, 69.3, 68.5, 49.4, 47.9, 41.4, 34.4, 31.3, 28.2, 22.5, 22.3, 21.7 ppm. (beta) - (l-Bd)

Rt = 33.1 min (GC method C). MS (El): m / z (%) = 198 [M] ⁺ (<1), 183 (10), 165 (7), 139 (15), 103 (100), 95 (26), 81 (77 ), 71 (34), 55 (19), 43 (59). ³ C NMR (125 MHz, CDCIs): δ = 76.9, 70.7, 70.5, 51.9, 50.2, 41.6, 34.4, 31.5, 23.0, 22.3, 22.0, 21.4 ppm.

Comparative Example 10 Preparation of Compounds (I-Bc.2)

The preparation was carried out analogously to the general preparation of tetra hydropyran- nolderivate from aliphatic aldehydes. The product was obtained after column chromatography (cyclohexane / ethyl acetate) in a purity of 92% as an isomer mixture with an (alpha) - (l-Bc.1): (beta) - (l-Bc.1) ratio of 1: 5.6 ,

Odor: no specific smell.

(Alpha) - (l-Bc.2)

Rt = 33.0 min (GC Method C). MS (El): m / z (%) = 212 [M] ⁺ (1), 194 (83), 179 (81), 165 (59), 151 (26), 139 (100), 121 (19) , 1 1 1 (14), 95 (26), 71 (23), 55 (18), 81 (56), 43 (42). 3C-NMR (125 MHz, CDCIs): δ = 75.0, 73.8, 69.3, 49.7, 45.7, 41.4, 34.4, 31.3, 28.9, 28.3, 22.6, 22.2, 10.0 ppm.

(Beta) - (l-Bc.2)

Rt = 33.8 min (GC method C). MS (El): m / z (%) = 197 (6), 183 (53), 165 (6), 139 (100), 1 17 (34), 99 (29), 81 (50), 43 ( 41). ³ C-NMR (125 MHz, CDCl ₃ ): δ = 76.9, 75.9, 70.8, 52.3, 48.0, 41.6, 34.4, 31 .5, 29.1, 23.1, 22.3, 21 .5, 10.0 ppm.

Comparative Example 1 1: Preparation of Compounds (I-Bc.4)

The preparation was carried out analogously to the general preparation of tetra hydropyran- nolderivate from aliphatic aldehydes. The product was recrystallized from n-heptane and obtained as a pure isomer. Odor: no specific smell.

(Beta) - (l-Bc.4)

R _t = 35.6 min (GC method C). MS (El): m / z (%) = 224 [M] ⁺ (2), 109 (39), 191 (58), 165 (82), 139 (84), 1 1 1 (91), 95 ( 47), 81 (85), 71 (100), 43 (99). ³ C-NMR (125 MHz, CDCl 3): δ = 77.1, 70.8, 59.6, 52.3, 48.2, 41 .8, 34.5, 31.6, 23.2, 22.4, 21.4, 16.3, 3.7, 2.0 ppm.

Claims

claims

Compounds of the formula (Γ)

wherein

R ^{1 is} hydrogen,

R ^{2 is} unsubstituted or mono- or polysubstituted phenyl, where the substituents are independently selected from C 1 -C 6 -alkyl and C 1 -C ₄ -alkoxy,

R ³ represents hydrogen, Ci-C ₆ alkyl or C ₃ -C ₆ cycloalkyl,

R ^{4 is} hydrogen or methyl,

R ^{6 is} Ci-Cs-alkyl,

or

2. Compounds according to claim 1 of the formula (I)

wherein

R is hydrogen,

R ^{3 is} hydrogen, C ₁ -C ₆ -alkyl or C ₃ -C ₆ -cycloalkyl,

R ^{4 is} hydrogen or methyl, or

3. Compounds according to claim 1 of the formula (Ι-Α ')

wherein

R ^{1 is} hydrogen,

R ^{3 is} hydrogen or methyl,

R ^{4 is} hydrogen or methyl,

R ^Ph1 , R ^Ph2 , R ^Ph3 , R ^Ph4 and R ^Ph5 are each independently hydrogen,

Ci-C6-alkyl or Ci-C4-alkoxy,

R ^{6 is} Ci-C ₃ alkyl.

Compounds according to any one of claims 1 to 3 of the formula (I-A)

wherein

R ^{1 is} hydrogen,

R ^{3 is} hydrogen or methyl,

R ^{4 is} hydrogen or methyl,

R ^Ph1 , R ^Ph2 , R ^Ph3 , R ^Ph4 and R ^Ph5 are each independently hydrogen,

Ci-C6-alkyl or Ci-C4-alkoxy.

5. Compounds according to claim 3 or 4 of the formula (Ι-Α ') or (IA) in which 2, 3, 4 or 5 of the radicals R ^Ph1 , R ^Ph2 , R ^Ph3 , R ^Ph4 and R ^{Ph5 are} hydrogen and the other radicals R ^Ph1 , R ^Ph2 , R ^Ph3 , R ^Ph4 and R ^{Ph5 are} independently selected from methyl and methoxy.

6. A compound according to any one of claims 1 to 5 selected from compounds of the formulas (IA.1), (IA.2), (IA.3) (IA.4), (IA.5), (IA.6), (IA.7), (IA.8), (IA.9) u

7. Compounds according to claim 1 or 2 of the formula (I-B)

wherein

R ^{3 is} hydrogen or C ₁ -C ₆ -alkyl or C ₃ -C ₆ -cycloalkyl, R ^{4 is} hydrogen, R ^{5 is} hydrogen or methyl.

Compounds according to Claim 1, 2 or 7 of the formula (I-B),

R ³ is Ci-C ₄ alkyl or C ₃ -C ₄ cycloalkyl,

R ^{4 is} hydrogen,

R ^{5 is} hydrogen or methyl.

9. Compounds according to any one of claims 1, 2, 7 or 8 selected from compounds of the formulas (I-B.1), (I-B.2), (I-B.3) and (I-B.4).

10. Process for the preparation of compounds of the formula (I)

wherein

R ^{1 is} hydrogen,

R ³ represents hydrogen, Ci-C ₆ alkyl or C ₃ -C ₆ cycloalkyl,

R ^{4 is} hydrogen or methyl, or

R ¹ and R ² together with the atoms to which they are attached form a cyclohexane ring which is unsubstituted or monosubstituted or polysubstituted by methyl, in which a) at least one compound of the formula (Ic)

and b) the compound of the formula (Ic) with a ketene of the formula (K)

^ C = C = 0

^H (K)

to give compounds of formula (I).

1 1. Use of compounds of formula (Γ) or (I) as defined in any one of claims 1 to 9 or obtainable by a process as defined in claim 10, as an aroma chemical. 12. Use of compounds of formula (Γ) or (I) according to claim 1 1 in agents selected from perfumes, detergents and cleaners, cosmetics, personal care products, hygiene articles, products for oral and dental hygiene, fragrance dispensers, fragrances and pharmaceutical agents , Use of compounds of formula (Γ) or (I) as defined in any of claims 1 to 9 or obtainable by a process as defined in claim 10, as an aroma chemical, in particular

i) of compounds of formula (I-A.1) for producing a fragrance with a green and / or dill note, and / or

ii) of compounds of formula (I-A.2) for the preparation of a fragrance with a

Note of flowery and / or grape hyacinth and / or sweet and / or coumarin, and / or

iii) of compounds of the formula (IA.3) for the production of a fragrance with a note of phenolic and / or leather and / or technically, and / or technically iv) of compounds of formula (IA.4) for the production of a fragrance with a rating of cresol and / or technically, and / or

vi) of compounds of the formula (IA.6) for producing a fragrance with a note of flowery and / or honey and / or iris, and / or vii) of compounds of the formula (IA.10) for producing a fragrance with a note of natural and / or green and / or herbaceous and / or spearmint and / or cumin and / or fresh.

Flavoring and / or perfume composition containing

i) at least one compound of formula (Γ) or (I) as defined in any one of claims 1 to 9 or obtainable by a process as defined in claim 10,

ii) optionally at least one further aromatic chemical other than compounds of the formula (Γ) or (I) and

iii) optionally at least one diluent,

with the proviso that the composition contains at least one component ii) or iii).

A perfumed or flavored product containing at least one compound of formula (Γ) or (I) as defined in any one of claims 1 to 9 or obtainable by a process as defined in claim 10.

A method of scenting, in particular lending and / or enhancing an odor or flavor, a product in which at least one compound of formula (Γ) or (I) is used which is as defined in any one of claims 1 to 9 or which a method as defined in claim 10 is obtainable.

Method according to claim 16,

i) in which one or more compounds of formula (I-A.1) is used to scent a product with a green and / or dill rating, and / or

ii) in which one or more compounds of the formula (I-A.2) is used to perfume a product with a note of flowery and / or grape hyaine the and / or sweet and / or coumarin, and / or

iii) in which one or more compounds of the formula (IA.3) is used for scenting a product with a phenolic and / or leather grade and / or technical, and / or iv) in which one or more compounds of formula (IA.4) is used for scenting a product with a rating of cresol and / or technically, and / or

vi) in which one or more compounds of the formula (I-A.6) is used to scent a product with a note of flowery and / or honey and / or iris, and / or

vii in which one or more compounds of formula (I-A.10) is used to scent a product with a note of natural and / or green and / or herbaceous and / or spearmint and / or cumin and / or fresh