阅读说明：本技术 气味剂和包含气味剂的组合物 (Odorants and compositions comprising odorants ) 是由 F.波斯特 L.多斯察克 N.乔杜里 于 2018-10-16 设计创作，主要内容包括：本发明涉及新的类别的有气味的肟及其酮中间体(气味剂),其可用作香味或风味物质,特别是在向香料、芳香或除臭/掩蔽组合物提供黑醋栗、猫香、热带、绿香、松柏、金钟柏、花香和/或果香的嗅觉香韵方面。(The present invention relates to a new class of odorous oximes and their ketone intermediates (odorants) useful as aroma or flavor substances, in particular in providing olfactory notes of blackcurrant, cat, tropical, green, pine, thuja, flowery and/or fruity notes to perfumery, aroma or deodorizing/masking compositions.)

1. Fragrance, flavour and/or deodorant/masking composition comprising an oxime selected from a compound of formula (7) or a compound of formula (8)

Wherein R is an alkyl group having 1 to 9 carbon atoms, an alkenyl group having only one carbon-carbon double bond (which is preferably not conjugated to an oxime C ═ N bond) and having up to 9 carbon atoms, a (substituted) aryl group having up to 8 carbon atoms, an oxo-alkyl group having up to 9 carbon atoms or an alkoxyaryl group comprising up to 9 carbon atoms or a (substituted) benzyl group having up to 9 carbon atoms.

2. A flavour, flavour and/or odor/masking composition according to claim 1, wherein R is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-pentyl, 3-pentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 1- (cyclohexylmethyl), (methoxy) methyl, (ethoxy) methyl, 3-butenyl, 5- (2-methylpent-2-ene) yl, 4-pent-2-enyl, 4-pent-1-enyl, 5- (2, 5-dimethylhex-2-ene) yl, benzyl, phenyl or 4-methoxyphenyl.

3. A flavour, fragrance and/or deodorizing/masking composition according to claim 1, wherein said oxime is selected from

And/or a mixture of two or more of said oximes.

4. A flavour, flavour and/or deodorizing/masking composition according to any one of the preceding claims, wherein said compound of formula (7) and/or compound of formula (8) is comprised in a content of between 0.00001% and 99.9% by weight, such as between 0.0001% and 95% by weight.

5. A flavour, flavour and/or odor eliminating/masking composition according to any one of the preceding claims, further comprising at least one ester and/or one alcohol, preferably a mixture of at least an ester and an alcohol.

6. A flavour, flavour and/or deodorizing/masking composition according to the preceding claim, wherein the total content of the compounds of formula (7) and/or compounds of formula (8) and the esters and/or alcohols is more than 25 wt.%, preferably more than 50 wt.%, such as more than 75 wt.%, or even more than 90 wt.%.

7. A flavour, flavour and/or odor eliminating/masking composition according to any one of the preceding claims, comprising a mixture of oxime compounds of formula (7) and/or (8), wherein the weight ratio comprised between the oxime present in the highest weight and the oxime present in the second highest weight in said mixture is comprised between 99.9% and 50%, such as between 99% and 70%.

8. The fragrance, flavor and/or deodorizing/masking composition according to any one of the preceding claims, further comprising at least one ketone compound of formula (5) and/or (6)

Wherein R is an alkyl group having 1 to 9 carbon atoms, an alkenyl group having up to 9 carbon atoms with only one carbon-carbon double bond, a (substituted) aryl group having up to 9 carbon atoms, an oxo-alkyl group having up to 9 carbon atoms, an alkoxyaryl group containing up to 9 carbon atoms or a (substituted) benzyl group having up to 9 carbon atoms.

9. The fragrance, flavor and/or odor/masking composition of claim 8 wherein the group R of the oxime compound is the same as the group R of the ketone compound.

10. A flavour, fragrance and/or deodorizing/masking composition according to any one of claims 8 or 9, wherein the weight ratio between oxime and ketone comprised is between 0.01% and 99.99%, such as between 80% and 99%.

11. An oxime for use in a flavour, fragrance and/or deodorizing/masking composition according to any one of the preceding claims, wherein said oxime is selected from compounds of formula (7) or formula (8)

Wherein R is an alkyl group having 2 to 9 carbon atoms, an alkenyl group having only one carbon-carbon double bond (which is preferably not conjugated to an oxime C ═ N bond) and having up to 9 carbon atoms, a (substituted) aryl group having up to 9 carbon atoms, an oxo-alkyl group having up to 9 carbon atoms, an alkoxyaryl group having up to 9 carbon atoms or a (substituted) benzyl group having up to 9 carbon atoms.

12. An oxime according to claim 11 wherein R is ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-pentyl, 3-pentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 1- (cyclohexylmethyl), (methoxy) methyl, (ethoxy) methyl, 3-butenyl, 5- (2-methylpent-2-enyl), 4-pent-2-enyl, 4-pent-1-enyl, 5- (2, 5-dimethylhex-2-enyl), benzyl, phenyl or 4-methoxyphenyl.

13. An oxime according to any one of claims 11 to 12 wherein the compound of formula (8) excludes those wherein R is phenyl.

14. The oxime of claim 11 wherein said oxime is selected from

15. Mixture of oxime compounds according to claims 11-14 wherein the weight ratio comprised between the oxime present in the highest weight and the oxime present in the second highest weight in the mixture is comprised between 99.9% and 50%, such as between 99% and 70%.

16. A process for the preparation of an oxime of formula (7) and/or (8) according to any one of claims 11 to 15 by reacting a ketone of formula (5) and/or (6) with a hydroxylamine salt (e.g. hydroxylamine hydrochloride) in the presence of an amine (e.g. pyridine, imidazole) and at a temperature below 80 ℃, preferably below 70 ℃ to form an oxime of formula (7) and/or (8)

Wherein R is an alkyl group having 2 to 9 carbon atoms, an alkenyl group having only one carbon-carbon double bond and having up to 9 carbon atoms, a (substituted) aryl group having up to 9 carbon atoms, an oxo-alkyl group having up to 9 carbon atoms, an alkoxyaryl group comprising up to 9 carbon atoms or a (substituted) benzyl group having up to 9 carbon atoms.

17. A method of producing an oxime according to claim 16 wherein the reaction time is more than 1 day, preferably more than 3 days, such as more than 7 days.

18. The method for producing an oxime according to any one of claims 16 to 17 wherein the compound of formulae (5), (6), (7) and (8) is characterized in that R is an alkyl group having 3 to 9 carbon atoms or an aryl group having 6 to 9 carbon atoms.

19. The method for producing an oxime according to any one of claims 16 to 18 wherein

Preparing a compound of formula (5) by subjecting 2, 3-dimethylbutene to an acylation reaction step, optionally followed by an alkylation or aldol condensation step, and/or

The compound of formula (6) is prepared by subjecting 2, 3-dimethylbutene to an acylation reaction step, optionally followed by an alkylation or aldol condensation step, to form a compound of formula (5), and subjecting said compound of formula (5) to a hydrogenation reaction step to form a compound of formula (6).

20. Use of a fragrance, flavor and/or deodorizing/masking composition according to any one of claims 1 to 10 in perfuming or flavoring products.

21. Use of an oxime according to any one of claims 11 to 15 in a perfuming or flavoring product.

Technical Field

The present invention relates to a new class of odorous oximes useful as aroma or flavor substances, in particular in providing olfactory notes of blackcurrant, cat, tropical and/or green notes, and to the corresponding odorous ketones (intermediates), which ketones may also be used as aroma or flavor substances, in particular in providing pine, thuja, floral and/or fruity notes to a perfumery, perfuming or deodorizing/masking composition, and also to confer on said composition one or more of the following advantages/properties: lack of sulfur off-flavors, complex odor profiles, natural impression, high volatility (affecting top notes), and/or solubility. The invention also relates to flavour, flavour and/or deodorant/masking compositions comprising said novel class of odorants oximes and the corresponding parent ketones (intermediates). The invention also relates to said odorants, which can be used in the novel aroma, flavor and/or deodorizing/masking compositions of the invention. The invention also relates to methods for producing said odorants/compounds and for producing corresponding aroma, flavor and/or deodorizing/masking compositions containing said odorants/compounds.

Background

In general, many of the odorants currently used in the perfumery industry and/or the flavor industry are synthetic molecules. In particular, there is a high need and a demand for new odorants/compounds and/or new aroma, flavor and/or deodorizing/masking compositions comprising said odorants/compounds.

For industrial applications, it is beneficial if various products can be obtained from one basic framework/raw material. This will become even more beneficial if the raw materials are exclusive in some respects. 2, 3-dimethylbutene 1 and 2 are almost exclusively used for the production of substituted tetralins (3), in particular for the production of Tonalid (4).

Therefore, during their research and development activities, the applicant began to develop products for novel odorants using 2, 3-dimethylbutene 1 and 2 as raw materials. An advantage of one or more embodiments of the present invention is that the claimed odorant/compound derived from 2, 3-dimethylbutene can impart and/or accentuate specific olfactory notes, in particular those that provide a fragrance, flavor and/or deodorizing/masking composition with black currant, cat scent, tropical, green scent, conifer, thuja, floral and/or fruity notes, and also impart one or more of the following advantages/properties to said composition: lack of sulfur off-flavors, complex odor profiles, natural impression, high volatility (affecting top notes), and/or solubility.

Brief description of the invention

Disclosed are novel fragrance, flavor and/or deodorizing/masking compositions comprising oximes selected from compounds of formula (7) or formula (8)

Wherein R is an alkyl group having 1 to 9 carbon atoms, an alkenyl group having only one carbon-carbon double bond (which is preferably not conjugated to an oxime C ═ N bond) and having up to 9 carbon atoms, a (substituted) aryl group having up to 9 carbon atoms, an oxo-alkyl group having up to 9 carbon atoms, an alkoxyaryl group having up to 9 carbon atoms or a (substituted) benzyl group having up to 9 carbon atoms.

In one embodiment according to the invention R is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-pentyl, 3-pentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 1- (cyclohexylmethyl), (methoxy) methyl, (ethoxy) methyl, 3-butenyl, 5- (2-methylpent-2-ene) yl, 4-pent-2-enyl, 4-pent-1-enyl, 5- (2, 5-dimethylhex-2-ene) yl, benzyl, phenyl or 4-methoxyphenyl.

In another embodiment, the compounds of the present invention may be present as stereoisomers, for example, as compounds having the Z and E configurations of C ═ N bonds, or as mixtures thereof.

In one embodiment, when the R group comprises a chiral center, the compounds of the present invention may exist as stereoisomers, for example, as compounds having R or S configuration or as mixtures thereof.

In another embodiment, when R is an alkenyl group containing only one carbon-carbon double bond (which is preferably not conjugated to an oxime C ═ N bond) and having up to 9 carbon atoms, the compounds of the invention may be present as stereoisomers, for example as compounds having the Z or E configuration of the C ═ C bond or as mixtures thereof.

In another embodiment, the compounds of the invention may be chiral, for example, they may exist as stereoisomeric mixtures (more specifically as mixtures of enantiomers), R isomers, S isomers, racemic and/or non-racemic mixtures of R and S isomers, and they may also be advantageously used in pure form or as mixtures.

Detailed Description

The term "odorant" characterizing a compound according to the invention means that, in humans, it triggers an odor sensation, which sensation is preferably pleasant; it is therefore commonly used in perfuming industrial and hygiene articles, detergents, cleaning agents, personal care products, cosmetics and the like. For the purposes of the present invention and appended claims, the term "odorant" includes "aroma". Aroma is a term commonly used to refer to substances that provide an aroma and/or flavor to food products.

The oxime compounds of the formula (7) or (8) can be used alone, in a mixture thereof, or in combination with a base material.

As explained and detailed below, the intermediate ketone compounds of formula (5) or (6) can also be used alone, in mixtures thereof, or in combination with a base material.

As used herein, "base material" includes all known aroma/flavor materials selected from a wide range of natural products such as: essential oils, extracts, resinous materials or isolates and synthetic materials currently available, such as: hydrocarbons, alcohols, aldehydes and ketones, ethers and acetals, esters and lactones, nitriles, oximes or heterocycles, and/or with one or more ingredients or excipients/adjuvants commonly used in conjunction with odorants in aroma and/or flavor compositions (e.g., solvents/diluents, stabilizers, carrier materials and other adjuvants commonly used in the art).

The oxime compounds according to formula (7) or formula (8) and/or the ketone compounds of formula (5) or formula (6) can be used in a wide range of fragrance applications, for example in the field of any fine and functional fragrance, such as fragrances, air care products, household products, laundry products, body care products and cosmetics. The compounds may be used in widely varying amounts depending on the particular application and the nature and amount of the other odorant components.

According to a preferred embodiment of the present invention, the flavour, flavour and/or deodorizing/masking composition according to the invention contains at least one oxime compound according to formula (7) or formula (8) as described before and/or at least one ketone compound according to formula (5) or formula (6) as described further below in an amount of in each case between 0.00001 and 99.9% by weight, for example between 0.0001 and 95% by weight, for example between 0.001 and 25% by weight, preferably between 0.01 and 15% by weight, more advantageously between 0.1 and 10% by weight, in particular between 1 and 5% by weight, relative to the total composition. In a particular embodiment of the present invention, the flavour, taste and/or deodorizing/masking composition according to the invention comprises a mixture of at least one oxime compound of formula (7) and at least one corresponding ketone compound of formula (5) [ i.e. ketones having the same group R ]. In a particular embodiment of the present invention, the flavour, taste and/or deodorizing/masking composition according to the invention comprises a mixture of at least one oxime compound of formula (8) and at least one corresponding ketone compound of formula (6) [ i.e. ketones having the same group R ].

The use of more than one oxime compound according to formula (7) or formula (8) in a flavour, fragrance and/or deodorant/masking composition according to the invention may be particularly advantageous when the difference in the number of carbon atoms of the respective oximes of the same general formula is between 1 and 9, for example between 1 and 5, preferably between 1 and 4, more advantageously between 1 and 3, in particular between 1 and 2. When mixtures of oximes are used, the weight ratio between the oxime present in the highest weight and the oxime present in the second highest weight in the mixture comprised is between 99.9% and 50%, for example between 99% and 70%, preferably between 98% and 80%, more advantageously between 98% and 90%, in particular between 98% and 95%.

The use of more than one ketone compound according to formula (5) or formula (6) in the flavour, fragrance and/or deodorant/masking composition according to the invention may be particularly advantageous when the difference in the number of carbon atoms of the respective ketones of the same general formula is between 1 and 9, for example between 1 and 5, preferably between 1 and 4, more advantageously between 1 and 3, in particular between 1 and 2. When a mixture of ketones is used, the weight ratio between the ketone present in the highest weight and the ketone present in the second highest weight in the mixture comprised is between 99.9% and 50%, for example between 99% and 70%, preferably between 98% and 80%, more advantageously between 98% and 90%, in particular between 98% and 95%.

According to a particularly preferred embodiment of the present invention, the flavour, taste and/or deodorizing/masking composition according to the invention comprises, in addition to the compound of formula (7) or (8) and/or the compound of formula (5) or (6) according to the invention, a further odorant, for example in an amount of 0.1 to 99.9% by weight, preferably 5 to 90% by weight, in particular 15 to 70% by weight, relative to the total flavour and/or taste composition.

A compound of formula (7) or formula (8) as described above and/or a compound of formula (5) or formula (6) as described below can be used in a consumer product base simply by directly mixing at least one compound of formula (7) or formula (8) and/or at least one compound of formula (5) or formula (6), or a flavour composition comprising said compound of formula (7) or formula (8) and/or said compound of formula (5) or formula (6) with the consumer product base; or they may be encapsulated in an earlier step with an encapsulating material such as polymers, capsules, microcapsules and/or nanocapsules, liposomes, film formers, absorbents such as activated carbon or zeolites, cyclic oligosaccharides, cyclic glycolurils (glycourils), and mixtures of two or more thereof, or they may be chemically bonded to a substrate suitable for releasing flavor molecules upon application of an external stimulus such as light, enzymes, air, water, etc., and then mixed with the consumer product matrix.

Thus, the present invention can be used in existing processes for the preparation of flavour, fragrance and/or deodorant/masking compositions comprising the incorporation of a compound of formula (7) or formula (8) and/or a compound of formula (5) or formula (6) as a flavour, fragrance and/or deodorant/masking ingredient, either by directly mixing the compound with a consumer product base, or by mixing a flavour, fragrance and/or deodorant/masking composition comprising said compound of formula (7) or formula (8) and/or said compound of formula (5) or formula (6), which composition can then be mixed with a consumer product base, using conventional techniques and methods. The odor note of the consumer product substrate may be modified, enhanced and/or altered by the addition of an olfactory acceptable amount of at least one compound of formula (7) or formula (8) and/or at least one compound of formula (5) or formula (6) of the present invention as described above/below.

The present invention provides a flavour, fragrance and/or deodorant/masking composition comprising an oxime selected from a compound of formula (7) or formula (8)

Wherein R is an alkyl group having 1 to 9 carbon atoms, an alkenyl group having only one carbon-carbon double bond (which is preferably not conjugated to an oxime C ═ N bond) and having up to 9 carbon atoms, a (substituted) aryl group having up to 8 carbon atoms, an oxo-alkyl group having up to 9 carbon atoms or an alkoxyaryl group comprising up to 9 carbon atoms or a (substituted) benzyl group having up to 9 carbon atoms.

In one embodiment according to the invention R is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-pentyl, 3-pentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 1- (cyclohexylmethyl), (methoxy) methyl, (ethoxy) methyl, 3-butenyl, 5- (2-methylpent-2-ene) yl, 4-pent-2-enyl, 4-pent-1-enyl, 5- (2, 5-dimethylhex-2-ene) yl, benzyl, phenyl or 4-methoxyphenyl.

In one embodiment according to the present invention, the flavour, fragrance and/or deodorant/masking composition comprises a compound of formula (7) or formula (8) selected from

And/or mixtures of two or more of said compounds.

The applicant has also found that the compounds of formula (7) or (8) have a distinctive blackcurrant, cat-fragrance, tropical and/or green fragrance character from an olfactory point of view, which makes them directly usable in fruit fragrance compositions, such as blackcurrants, grapefruit, peach, strawberry, grape and/or passion fruit. In fact, the compounds of formula (7) or (8) exhibit a blackcurrant-type note and a green note with an isobutyl thiazole-like note, without a sulphur odour. It also has more uses, with easily identifiable applications to tomato leaves, basil, sage and/or mint herbs and notes such as citrus, lily of the valley and/or sea breeze. Furthermore, the compounds of formula (7) or (8) have greater diffusivity and presence than other odorants, such as the bulk blackcurrants (Corps casis), without a sulphur odour, which makes them very valuable. They have greater stability and volatility in various application media, especially in the base media.

For example, when R is chosen to be propyl, isopropyl and/or sec-butyl in the compounds of formula (7) or formula (8), the applicant has found that it is possible to obtain a very diffuse olfactory note with characteristics of green, blackcurrant, cat and/or peach notes.

Oxime compounds

In one embodiment, the present invention also provides novel compounds of formula (7) useful in the fragrance, fragrance and/or deodorizing/masking compositions of the present invention

Wherein R is an alkyl group having 2 to 9 carbon atoms, an alkenyl group having only one carbon-carbon double bond (which is preferably not conjugated to an oxime C ═ N bond) and having up to 9 carbon atoms, a phenyl group, a substituted aryl group having up to 9 carbon atoms, an oxo-alkyl group having up to 9 carbon atoms, an alkoxyaryl group having up to 9 carbon atoms or a (substituted) benzyl group having up to 9 carbon atoms.

In one embodiment according to the invention R is ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-pentyl, 3-pentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 1- (cyclohexylmethyl), (methoxy) methyl, (ethoxy) methyl, 3-butenyl, 5- (2-methylpent-2-ene) yl, 4-pent-2-enyl, 4-pent-1-enyl, 5- (2, 5-dimethylhex-2-ene) yl, benzyl, phenyl or 4-methoxyphenyl.

In one embodiment, the present invention also provides novel compounds of formula (8) useful in the fragrance, fragrance and/or deodorizing/masking compositions of the present invention

Wherein R is an alkyl group having 2-9 carbon atoms, an alkenyl group containing only one carbon-carbon double bond and having up to 9 carbon atoms, a substituted aryl group having up to 9 carbon atoms, an oxo-alkyl group having up to 9 carbon atoms, an alkoxyaryl group containing up to 9 carbon atoms or a (substituted) benzyl group having up to 9 carbon atoms.

In one embodiment according to the invention R is ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-pentyl, 3-pentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 1- (cyclohexylmethyl), (methoxy) methyl, (ethoxy) methyl, 3-butenyl, 5- (2-methylpent-2-ene) yl, 4-pent-2-enyl, 4-pent-1-enyl, 5- (2, 5-dimethylhex-2-ene) yl, benzyl or 4-methoxyphenyl.

In one embodiment according to the present invention, the novel compounds of formula (7) and/or formula (8) useful in the perfume, fragrance and/or deodorizing/masking composition according to the present invention are selected from

And/or mixtures of two or more of said compounds.

Preparation of

In a preferred embodiment according to the present invention, the compounds of formula (7) and/or formula (8) may advantageously be prepared from 2, 3-dimethylbutene, as described hereinafter.

Oximation of

In one embodiment, the compounds of formula (7) may be advantageously prepared from the compounds of formula (5) by using an oximation synthesis procedure

Wherein R is an alkyl group having 1 to 9 carbon atoms, an alkenyl group containing only one carbon-carbon double bond and having up to 9 carbon atoms, a (substituted) aryl group having up to 9 carbon atoms, an oxo-alkyl group having up to 9 carbon atoms, an alkoxyaryl group having up to 9 carbon atoms or a (substituted) benzyl group having up to 9 carbon atoms, for example by reacting a compound of said formula (5) with hydroxylamine, hydroxylamine in the presence of an acid or a base, a hydroxylamine salt in the presence of a base (e.g. sodium acetate, sodium carbonate, potassium hydroxide, ammonium acetate, pyridine, triethylamine, etc.) (e.g. hydroxylamine hydrochloride, etc.), another oxime in the presence of an acid (e.g. sulfuric acid, perchloric acid, trifluoromethanesulfonic acid, etc.) or a base (e.g. potassium hydroxide, pyridine, triethylamine, etc.), or a masked hydroxylamine (e.g. N in the presence of a strong base (e.g. potassium hydride, bis (trimethylsilyl) amino potassium, etc.), o-bis (trimethylsilyl) hydroxylamine) to form the compound of formula (7). In alternative embodiments, the compound of formula (5) may be subjected to an intermediate alkylation or aldol condensation synthesis step prior to the oximation step.

In one embodiment, the compounds of formula (8) may be advantageously prepared as follows

-is prepared from a compound of formula (7) by using a hydrogenation synthesis step, e.g. by reacting said compound of formula (7) with hydrogen, preferably in the presence of a catalyst, to form a compound of formula (8),

or from a compound of formula (5) as defined above, by using a hydrogenation synthesis step followed by an oximation synthesis step, for example by reacting said compound of formula (5) with hydrogen, preferably in the presence of a catalyst, to form a compound of formula (6)

Wherein R is an alkyl group having 1 to 9 carbon atoms, an alkenyl group containing only one carbon-carbon double bond and having up to 9 carbon atoms, a (substituted) aryl group having up to 9 carbon atoms, an oxo-alkyl group having up to 9 carbon atoms, an alkoxyaryl group containing up to 9 carbon atoms or a (substituted) benzyl group having up to 9 carbon atoms;

and forming a compound of formula (8) by reacting the compound of formula (6) with hydroxylamine in the presence of an acid, a hydroxylamine salt (e.g., hydroxylamine hydrochloride or the like) in the presence of a base (e.g., sodium acetate, sodium carbonate, potassium hydroxide, ammonium acetate, pyridine, triethylamine or the like), another oxime in the presence of an acid (e.g., sulfuric acid, perchloric acid, trifluoromethanesulfonic acid or the like) or a base (e.g., potassium hydroxide, pyridine, triethylamine or the like), or a masked hydroxylamine (e.g., N, O-bis (trimethylsilyl) hydroxylamine) in the presence of a strong base (e.g., potassium hydride, potassium bis (trimethylsilyl) amide or the like). In an alternative embodiment, the compound of formula (6) may be subjected to an intermediate alkylation or aldol condensation synthesis step prior to the oximation step.

In a preferred embodiment according to the invention, the compounds of formula (7) and/or (8) can advantageously be prepared from compounds of formula (5) and/or (6) [ preferably the corresponding ketone compounds, i.e. ketones having the same group R ], the preparation process being characterized in that the compounds of formula (5) and/or (6) are reacted with hydroxylamine salts (e.g. hydroxylamine hydrochloride) in the presence of amines (e.g. pyridine, imidazole) and at temperatures below 80 ℃, preferably below 70 ℃. In fact, we have found that the synthesis of oximes involving the reaction of hydroxylamine with the corresponding ketone is not effective for the synthesis of sterically hindered oximes such as 2,4,4, 5-tetramethylhex-5-en-3-one oxime (i.e. when R ═ isopropyl).

For the synthesis of, in particular, sterically hindered compounds of formulae (7) and (8), for example those in which the R group is a branched or cyclic alkyl group, it is advantageous to maintain the reaction temperature in the range from 60 ℃ to 80 ℃. We have found that when the temperature of the reaction mixture exceeds 80 ℃, the simultaneous decomposition of hydroxylamine leads to a drastic decrease in the yield of the desired oxime and the formation of impurities, which complicates the purification process.

For example, when 0.25g of 2,4,4, 5-tetramethylhex-5-en-3-one (i.e., R ═ i-Pr) is reacted with two equivalents (0.225g) of hydroxylamine hydrochloride in the presence of eight equivalents (1m L) of pyridine used as a base and 1m L of ethanol, it becomes apparent that it is more advantageous to increase the reaction time while keeping the temperature low (for illustrative purposes, see figure 1, which is a graphical representation of oxime GC yield versus time).

For example, when the temperature of the reaction mixture was set to 92 ℃, the GC yield of the desired 2,4,4, 5-tetramethylhex-5-en-3-one oxime reached a peak of 38% after 7 days of reaction, after which it began to decrease due to decomposition. This is accompanied by the formation of various impurities. However, when the oximation reaction was carried out at a lower temperature for 14 days, a steady increase in the yield was observed, and the desired oximes were obtained at 76 ℃,60 ℃ and 40 ℃ in 45%, 21% and 5% GC yields, respectively.

In addition, we have found that the use of a nitrogen heterocyclic base, particularly pyridine, as the base is more effective in the synthesis of hindered ketones than the use of, for example, sodium acetate or sodium hydroxide in combination with hydroxylamine in water, for example, when 5.0g of 2,4,4, 5-tetramethylhex-5-en-3-one is reacted at 60 ℃ with two equivalents (4.5g) of hydroxylamine hydrochloride in the presence of two equivalents (5g) of sodium acetate used as the base and 20m L ethanol for 7 days, 2,4,4, 5-tetramethylhex-5-en-3-one oxime is formed at 4% GC yield, and when 5.0g of 2,4,4, 5-tetramethylhex-5-en-3-one is reacted at 60 ℃ with three equivalents (6.42g) of a 50% aqueous solution of hydroxylamine in the presence of 3.4 equivalents (4.4g) of sodium hydroxide and 32.4m L ethanol for 7 days, 2,4,4, 5-tetramethylhex-5-3-en-3-one is formed at 5% GC equivalent, 4 equivalent, 5-5 g of pyridine in the presence of pyridine, 5g of 3.5 g of ethanol and 5g of octa-5 g of hydroxylamine in the presence of 635.5 g of ethanol.

Thus, in a preferred embodiment according to the present invention, the compounds of formula (7) and/or (8) can advantageously be prepared from compounds of formula (5) and/or (6) [ preferably the corresponding ketone compounds, i.e. ketones having the same group R ], said preparation process being characterized in that the compounds of formula (5) and/or (6) are reacted with hydroxylamine salts, such as hydroxylamine hydrochloride, in the presence of aromatic amines, such as pyridine, imidazole or aniline, and at a temperature below 80 ℃, preferably below 70 ℃, wherein the compounds of formulae (5), (6), (7) and (8) are characterized in that R is an alkyl group having 3 to 9 carbon atoms or an aryl group having 6 to 9 carbon atoms. In one embodiment according to the invention, the oximation reaction is carried out for more than one day, more preferably for more than 3 days, for example for more than 7 days. The molar ratio of aromatic amine (e.g. pyridine, imidazole) or aniline to hydroxylamine salt (e.g. hydroxylamine hydrochloride, hydroxylamine sulphate) is preferably 1: 1 to 50: 1, more preferably 4: 1 to 20: 1. the oximation reaction can be carried out using various amounts of additional solvents (e.g., methanol, ethanol), but can also be carried out without the use of additional solvents. The volume ratio of aromatic amine (e.g. pyridine, imidazole) or aniline to solvent (e.g. methanol, ethanol) is preferably higher than 1: 4, more preferably higher than 1: 2, even more preferably higher than 1: 1.

in one embodiment according to the present invention, the compound of formula (5) as defined above may be advantageously synthesized from 2, 3-dimethylbutene by using an acylation synthesis step.

2, 3-dimethylbutene

The 2, 3-dimethylbutene compound according to the invention can be selected from 2, 3-dimethyl-1-butene, 2, 3-dimethyl-2-butene or mixtures thereof; preferably selected from 2, 3-dimethyl-2-butene or from a mixture of 2, 3-dimethyl-2-butene and 2, 3-dimethyl-1-butene.

Optional isomerization step

In one embodiment according to the present invention, an isomerization step is preferably carried out to convert 2, 3-dimethyl-1-butene to 2, 3-dimethyl-2-butene. The isomerization step is preferably carried out, for example, when the starting material is 2, 3-dimethyl-1-butene or when the starting material is a mixture of 2, 3-dimethyl-2-butene and 2, 3-dimethyl-1-butene (the content of 2, 3-dimethyl-1-butene is higher than that of 2, 3-dimethyl-2-butene). Any suitable olefin isomerization process may be used; as an illustrative and non-limiting example, base catalyzed and/or acid catalyzed isomerization processes may be advantageously employed. In one embodiment according to the invention, it is advantageous to use an ion exchange resin acid catalyst, such as Amberlyst catalyst in acid form.

Acylation Synthesis procedure

Thus, in one embodiment of the present invention, 2, 3-dimethylbutene is subjected to an acylation synthesis step to form a compound of formula (5) which can be represented by the following formula

Wherein R is an alkyl group having 1 to 9 carbon atoms, an alkenyl group having only one carbon-carbon double bond and having up to 9 carbon atoms, a (substituted) aryl group having up to 9 carbon atoms, an oxo-alkyl group having up to 9 carbon atoms, an alkoxyaryl group comprising up to 9 carbon atoms or a (substituted) benzyl group having up to 9 carbon atoms.

In one embodiment of the invention, the product is obtained by reacting 2, 3-dimethylbutene with an acyl anhydride or acid chloride, followed by conventional work-up (e.g., washing with water, removal of unreacted reactants and/or solvent, and distillation).

Acceptable alternatives describing the compound of formula (5) are 1-substituted 3,3, 4-trimethyl-pent-4-en-2-ones wherein the substituent in position 1 is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-pentyl, 3-pentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 1- (cyclohexylmethyl), (methoxy) methyl, (ethoxy) methyl, 1-propenyl, 1-isobutenyl, 3-butenyl, 5- (2-methylpent-2-en) yl, 4-pent-2-enyl, 4-pent-1-enyl, 4- (4-methylpent-1-en) yl, 2-pentenyl, 4-penten-1-enyl, 4-penten-yl, 2,5- (2, 5-dimethylhex-2-ene) group, benzyl group, phenyl group, 4-methoxyphenyl group.

Any suitable acylation procedure that results in the production of a compound of formula (5) may be used; as an illustrative and non-limiting example, the acylation reaction is carried out in the presence of 2, 3-dimethylbutene and a carboxylic acid anhydride, such as acetic anhydride. The process step can advantageously be carried out in the presence of a Lewis acid orIn the presence of an acid catalyst such as zinc chloride, methanesulfonic acid, trifluoromethanesulfonic acid, etc. This process step can be advantageously carried out neat or by using a suitable aprotic polar solvent (e.g. dichloromethane).

In one embodiment according to the present invention, the acylation step is preferably followed by an alkylation step; for example, 2, 3-dimethylbutene is subjected to an acylation synthesis step to form a compound represented by the formula (5a, i.e., wherein R ═ CH₃) A compound of the formula (5a)

Then converting it into a compound of formula (5b) represented by the following formula

Wherein R is¹Selected from alkyl having 1-8 carbon atoms, alkenyl comprising only one carbon-carbon double bond and having at most 8 carbon atoms, oxo-alkyl having at most 8 carbon atoms or (substituted) benzyl having at most 8 carbon atoms.

The compound of formula (5b) which may be obtained by subjecting 2, 3-dimethylbutene to an acylation synthesis step to form the compound of formula (5b) directly or by subjecting the compound of formula (5a) to an alkylation step may be further alkylated to form the compound of formula (5c)

Wherein R is¹Selected from the group consisting of alkyl having 1 to 7 carbon atoms, alkenyl comprising only one carbon-carbon double bond and having up to 7 carbon atoms, aryl having up to 7 carbon atoms, oxo-alkyl having up to 7 carbon atoms, alkoxyaryl comprising up to 7 carbon atoms or (substituted) benzyl having up to 7 carbon atoms, and R²Selected from alkyl having 1 to 7 carbon atoms, alkenyl comprising only one carbon-carbon double bond and having at most 7 carbon atoms, (substituted) aryl having at most 7 carbon atoms, oxo-alkyl having at most 7 carbon atoms, alkoxyaryl comprising at most 7 carbon atoms or (substituted) benzyl having at most 7 carbon atoms, and R is¹And R²The total number of carbon atoms present in the group is no greater than 8.

The compound of formula (5c) which may be obtained by subjecting 2, 3-dimethylbutene to an acylation synthesis step to form the compound of formula (5c) directly or by subjecting the compound of formula (5b) to an alkylation step or by subjecting compound (5a) to a double alkylation step, may be further alkylated to form the compound of formula (5d)

Wherein R is¹Is alkyl having 1 to 6 carbon atoms, alkenyl comprising only one carbon-carbon double bond and having up to 6 carbon atoms, aryl having up to 6 carbon atoms, oxo-alkyl having up to 6 carbon atoms, and R²Selected from alkyl having 1 to 6 carbon atoms, alkenyl comprising only one carbon-carbon double bond and having up to 6 carbon atoms or oxo-alkyl having up to 6 carbon atoms, R³Selected from alkyl having 1 to 6 carbon atoms, alkenyl comprising only one carbon-carbon double bond and having up to 6 carbon atoms or oxo-alkyl having up to 6 carbon atoms, and R¹、R²And R³The total number of carbon atoms present in the group is no greater than 8.

When the compounds of the formulae (5c) and (5d) have R¹、R²Or R³Where at least two of the radicals are identical, the introduction of these identical radicals may be effectedTo be carried out in a single alkylation step.

When 2, 3-dimethyl-2-butene is the starting material, the acylation step of the synthetic process of the present invention has the advantage that it can tolerate the presence of 2, 3-dimethyl-1-butene. Thus, although the present invention preferentially uses pure 2, 3-dimethyl-2-butene for the acylation step, it can advantageously tolerate, as starting material, a molar ratio of 2, 3-dimethyl-2-butene to 2, 3-dimethyl-1-butene of less than 99%, for example less than 95%, said molar ratio being preferably higher than 50%, for example higher than 75%, or even higher than 85%.

In an alternative embodiment according to the invention, the acylation step is preferably followed by an aldol condensation step; for example, subjecting 2, 3-dimethylbutene to an acylation synthesis step to form a compound represented by the formula (5a, i.e., wherein R ═ CH₃) A compound of the formula (5a)

And then converted into a compound of formula (5e) represented by the following formula

Wherein R is¹Selected from hydrogen, alkyl having 1 to 7 carbon atoms, aryl having up to 7 carbon atoms, oxo-alkyl having up to 7 carbon atoms, alkoxyaryl comprising up to 7 carbon atoms or (substituted) benzyl having up to 7 carbon atoms, and R²Selected from hydrogen, alkyl having 1 to 7 carbon atoms, (substituted) aryl having up to 7 carbon atoms, oxo-alkyl having up to 7 carbon atoms, alkoxyaryl comprising up to 7 carbon atoms or (substituted) benzyl having up to 7 carbon atoms, and R¹And R²The total number of carbon atoms present in the group is no greater than 7.

In one embodiment of the invention, the aldol condensation step may be carried out to form the compound of formula (5f) by subjecting 2, 3-dimethylbutene to an acylation synthesis step to form the compound of formula (5b) directly or the compound of formula (5b) obtained by subjecting the compound of formula (5a) to an alkylation step

Wherein R is¹Selected from alkyl having 1 to 7 carbon atoms, aryl having up to 7 carbon atoms, oxo-alkyl having up to 7 carbon atoms, alkoxyaryl comprising up to 7 carbon atoms or (substituted) benzyl having up to 7 carbon atoms, and R²Selected from the group consisting of hydrogen, alkyl having 1 to 6 carbon atoms, (substituted) aryl having up to 6 carbon atoms, oxo-alkyl having up to 6 carbon atoms, and R³Selected from the group consisting of hydrogen, alkyl having 1 to 6 carbon atoms, (substituted) aryl having up to 6 carbon atoms, oxo-alkyl having up to 6 carbon atoms, and R¹And R²And R³The total number of carbon atoms present in the group is no greater than 7.

In one embodiment according to the present invention, the acylation step is preferably followed by a hydrogenation step and an alkylation step; for example, 2, 3-dimethylbutene is subjected to an acylation synthesis step followed by a hydrogenation synthesis step to form a compound represented by the formula (6a, i.e., wherein R ═ CH₃) A compound of the formula (6a)

And then converted into a compound of formula (6b) represented by the following formula

Wherein R is¹Selected from alkyl having 1-8 carbon atoms, alkenyl comprising only one carbon-carbon double bond and having at most 8 carbon atoms, oxo-alkyl having at most 8 carbon atoms or (substituted) benzyl having at most 8 carbon atoms.

In one embodiment of the invention, the compound of formula (5b) which may be obtained by subjecting 2, 3-dimethylbutene to an acylation synthesis step to form the compound of formula (5b) directly or by subjecting the compound of formula (6a) to an alkylation step, may be further alkylated to form the compound of formula (6c)

Wherein R is¹Selected from the group consisting of alkyl having 1 to 7 carbon atoms, alkenyl comprising only one carbon-carbon double bond and having up to 7 carbon atoms, aryl having up to 7 carbon atoms, oxo-alkyl having up to 7 carbon atoms, alkoxyaryl comprising up to 7 carbon atoms or (substituted) benzyl having up to 7 carbon atoms, and R²Selected from alkyl having 1 to 7 carbon atoms, alkenyl comprising only one carbon-carbon double bond and having at most 7 carbon atoms, (substituted) aryl having at most 7 carbon atoms, oxo-alkyl having at most 7 carbon atoms, alkoxyaryl comprising at most 7 carbon atoms or (substituted) benzyl having at most 7 carbon atoms, and R is¹And R²The total number of carbon atoms present in the group is no greater than 8.

In one embodiment of the invention, a compound of formula 6c, obtainable by subjecting 2, 3-dimethylbutene to an acylation synthesis step to directly form a compound of formula (6c), or to an alkylation step of a compound of formula (6b), or to a double alkylation step of compound (6a), may be further alkylated to form a compound of formula (6d)

Wherein R is¹Is alkyl having 1 to 6 carbon atoms, alkenyl comprising only one carbon-carbon double bond and having up to 6 carbon atoms, aryl having up to 6 carbon atoms, oxo-alkyl having up to 6 carbon atoms, and R²Selected from alkyl having 1 to 6 carbon atoms, alkenyl comprising only one carbon-carbon double bond and having up to 6 carbon atoms or oxo-alkyl having up to 6 carbon atoms, R³Selected from alkyl groups having 1 to 6 carbon atoms, alkenes containing only one carbon-carbon double bond and having up to 6 carbon atomsOr oxo-alkyl having up to 6 carbon atoms, and R¹、R²And R³The total number of carbon atoms present in the group is no greater than 8.

When the compounds of the formulae (6c) and (6d) have R¹、R²Or R³Where at least two of the groups are the same, the introduction of these same groups may be carried out in a single alkylation step.

In one embodiment according to the present invention, it is preferred to carry out the hydrogenation step after the acylation step, followed by the aldol condensation step; for example, 2, 3-dimethylbutene is subjected to an acylation synthesis step followed by a hydrogenation step to form a compound represented by the formula (6a, i.e., wherein R ═ CH₃) A compound of the formula (6a)

And then converted into a compound of formula (6e) represented by the following formula

Wherein R is¹Selected from hydrogen, alkyl having 1 to 7 carbon atoms, aryl having up to 7 carbon atoms, oxo-alkyl having up to 7 carbon atoms, alkoxyaryl comprising up to 7 carbon atoms or (substituted) benzyl having up to 7 carbon atoms, and R²Selected from hydrogen, alkyl having 1 to 7 carbon atoms, (substituted) aryl having up to 7 carbon atoms, oxo-alkyl having up to 7 carbon atoms, alkoxyaryl comprising up to 7 carbon atoms or (substituted) benzyl having up to 7 carbon atoms, and R¹And R²The total number of carbon atoms present in the group is no greater than 7.

In one embodiment according to the invention, the aldol condensation step may be carried out to form the compound of formula (6f) by subjecting 2, 3-dimethylbutene to an acylation synthesis step to form the compound of formula (6b) directly or to a compound of formula (6b) obtained by subjecting the compound of formula (6a) to an alkylation step

Wherein R is¹Selected from alkyl having 1 to 7 carbon atoms, aryl having up to 7 carbon atoms, oxo-alkyl having up to 7 carbon atoms, alkoxyaryl comprising up to 7 carbon atoms or (substituted) benzyl having up to 7 carbon atoms, and R²Selected from the group consisting of hydrogen, alkyl having 1 to 6 carbon atoms, (substituted) aryl having up to 6 carbon atoms, oxo-alkyl having up to 6 carbon atoms, and R³Selected from the group consisting of hydrogen, alkyl having 1 to 6 carbon atoms, (substituted) aryl having up to 6 carbon atoms, oxo-alkyl having up to 6 carbon atoms, and R¹And R²And R³The total number of carbon atoms present in the group is no greater than 7.

Thus, the synthesis of ketones (5) and (6) can be advantageously achieved according to the following scheme:

any suitable alkylation method that results in the production of compounds of formulae 5b-d and 6b-d, respectively, may be used; by way of illustrative and non-limiting example, alkylation is carried out in the presence of a base (potassium hydroxide, potassium tert-butoxide, etc.) in the presence of an acylation product of 2, 3-dimethylbutene having the general structure 5 or 6 and an alkyl halide or alkyl sulfate (methyl iodide, dimethyl sulfate, etc.).

Any suitable aldol condensation method that results in the production of compounds of formulas 5e-f and 6e-f, respectively, can be used; as an illustrative and non-limiting example, aldol condensation is carried out in the presence of an acylation product of 2, 3-dimethylbutene having the general structure 5 or 6 and an aldehyde or ketone, in the presence of a base (potassium hydroxide, potassium tert-butoxide, etc.) or in the presence of an acid (hydrochloric acid, sulfuric acid, etc.).

Compositions comprising ketones

According to a further embodiment of the present invention, the applicant has found that some intermediate compounds of formula (5) or (6) can also be used as odorants, and that they can be advantageously incorporated in perfume, fragrance or deodorant/masking compositions, either because of their effective olfactive properties imparted to said compositions or because of their following advantages/properties: top note impact, biodegradability, solubility, safety of use, and/or stability.

Thus, the present invention also discloses novel flavour, fragrance and/or deodorant/masking compositions comprising a ketone selected from compounds of formula (5) or (6)

Wherein R is an alkyl group having 1 to 9 carbon atoms, an alkenyl group having only one carbon-carbon double bond and having up to 9 carbon atoms, a (substituted) aryl group having up to 9 carbon atoms, an oxo-alkyl group having up to 9 carbon atoms, an alkoxyaryl group comprising up to 9 carbon atoms or a (substituted) benzyl group having up to 9 carbon atoms.

In one embodiment according to the invention R is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-pentyl, 3-pentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 1- (cyclohexylmethyl), (methoxy) methyl, (ethoxy) methyl, 1-propenyl, 1-isobutenyl, 3-butenyl, 5- (2-methylpent-2-ene) yl, 4-pent-2-enyl, 4-pent-1-enyl, 4- (4-methylpent-1-ene) yl, 5- (2, 5-dimethylhex-2-ene) yl, benzyl, phenyl or 4-methoxyphenyl.

In one embodiment according to the present invention, the flavour, fragrance and/or deodorant/masking composition comprises a compound of formula (5) or formula (6) selected from

And/or mixtures of two or more of said compounds.

The use of more than one ketone compound according to formula (5) or (6) as described above in the flavour, fragrance and/or deodorant/masking composition according to the invention may be particularly advantageous when the difference in the number of carbon atoms of the respective ketones of the same general formula is between 1 and 9, for example between 1 and 5, preferably between 1 and 4, more advantageously between 1 and 3, in particular between 1 and 2. When a mixture of ketones is used, the weight ratio between the ketone present in the highest weight and the ketone present in the second highest weight in the mixture comprised is between 99.9% and 50%, for example between 99% and 70%, preferably between 98% and 80%, more advantageously between 98% and 90%, in particular between 98% and 95%.

According to one embodiment of the present invention, the flavour, flavour and/or deodorizing/masking composition according to the invention contains at least one ketone compound of formula (5) or formula (6) as described above, in an amount of in each case between 0.00001 and 99.9% by weight, for example between 0.0001 and 95% by weight, for example between 0.001 and 25% by weight, preferably between 0.01 and 15% by weight, more advantageously between 0.1 and 10% by weight, in particular between 1 and 5% by weight, relative to the total composition.

According to a preferred embodiment of the present invention, the flavour, flavour and/or deodorant/masking composition according to the invention comprises at least one ketone compound according to formula (5) as described above and at least one corresponding ketone compound [ i.e. a ketone having the same group R ] according to formula (6) as described above in an amount of in each case between 0.00001 and 99.9% by weight, for example between 0.0001 and 95% by weight, for example between 0.001 and 25% by weight, preferably between 0.01 and 15% by weight, more advantageously between 0.1 and 10% by weight, in particular between 1 and 5% by weight, relative to the total composition.

According to a particularly preferred embodiment of the present invention, the flavour, fragrance and/or deodorant/masking composition according to the present invention comprises, in addition to the compound of formula (5) or formula (6) as described above, an additional odorant, for example in an amount of 0.1 to 99.9% by weight, preferably 5-90% by weight, in particular 15-70% by weight, relative to the total flavour and/or fragrance composition.

Ketones

In a particular embodiment according to the invention, the compounds of formula (5) and/or formula (6) useful in the perfume, fragrance and/or deodorizing/masking composition according to the invention are selected from

And/or mixtures of two or more of said compounds.

In one embodiment according to the present invention, the compound of formula (7) can be advantageously prepared by the following successive steps:

subjecting 2, 3-dimethylbutene to an acylation synthesis step, optionally followed by an alkylation or aldol condensation step, to form a compound of formula (5), and

subjecting the compound of formula (5) to an oximation synthesis step to form the compound of formula (7).

In one embodiment according to the present invention, the compound of formula (8) can be advantageously prepared by the following successive steps:

subjecting 2, 3-dimethylbutene to an acylation synthesis step, optionally followed by an alkylation or aldol condensation step, to form a compound of formula (5), and

subjecting the compound of formula (5) to a hydrogenation step to form a compound of formula (6), which is then subjected to an oximation synthesis step to form a compound of formula (8).

The advantage of the oximation step of the synthetic process of the invention is that it can tolerate the presence of the reactants of the previous synthetic steps (i.e. the reactants from the acylation step and/or from the combined acylation/alkylation or acylation/aldol condensation step, as described above).

Thus, in one embodiment of the invention, the oximation step may advantageously be carried out when:

-the molar ratio of 2, 3-dimethyl-2-butene to the compounds of formula (5) and (6) is greater than 0, for example greater than 0.05; and/or

-the molar ratio of carboxylic anhydride from the acylation step to the compounds of formula (5) and (6) is greater than 0, for example greater than 0.05; and/or

The molar ratio of catalyst residues from the acylation step to the compounds of formula (5) and (6) is greater than 0, for example greater than 0.05.

In one embodiment of the invention, the oximation step can also be advantageously carried out when:

-the molar ratio of 2, 3-dimethyl-2-butene to the compounds of formula (5) and (6) is less than 0.2, for example less than 0.15; and/or

-the molar ratio of carboxylic anhydride from the acylation step to the compounds of formula (5) and (6) is less than 0.2, for example less than 0.15; and/or

The molar ratio of catalyst residues from the acylation step to the compounds of formula (5) and (6) is less than 0.2, for example less than 0.15.

An illustrative scheme for the synthesis of compounds of formula (7) and/or formula (8) according to the invention is shown below:

wherein R is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-pentyl, 3-pentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 1- (cyclohexylmethyl), (methoxy) methyl, (ethoxy) methyl, 3-butenyl, 5- (2-methylpent-2-enyl) group, 4-pent-2-enyl, 4-pent-1-enyl, 5- (2, 5-dimethylhex-2-enyl) group, benzyl, phenyl or 4-methoxyphenyl.

In one embodiment of the present invention, the desired fragrance, flavor and/or deodorizing/masking composition is advantageously used as a fragrance composition. Perfume compositions according to the present invention typically comprise perfume, cologne (cologne), eau dutoliette and/or eau de parfum. In one embodiment of the present invention, the desired fragrance, flavor and/or deodorizing/masking composition is advantageously used in cosmetic formulations, personal care products, cleaning products, fabric softeners and/or air fresheners and the like. Furthermore, it is within the scope of embodiments of the present invention that the novel flavour, flavour and/or deodorant/masking compositions described herein and/or the novel compounds of formula (7) or formula (8) or formula (5) or formula (6) may be incorporated into building materials, wall and floor coverings, vehicle parts and the like.

In general, suitable aroma, flavor, or deodorizing compositions can advantageously include conventional ingredients such as solvents, carriers, stabilizers, emulsifiers, humectants, dispersants, diluents, thickeners, thinning agents, other odorants and/or adjuvants, and the like, in addition to the novel odorant and/or aroma, flavor, and/or deodorizing/masking compositions described herein.

The compounds of formula (5), (6), (7) or (8) are combined with a number of known natural or synthetic aroma, flavour and/or deodorizing/masking materials, whereby the range of natural ingredients may include not only volatile ingredients, but also semi-volatile and slightly volatile ingredients, and the range of synthetic ingredients may include representatives from a variety of substances, as will be apparent from the following non-limiting compilation:

natural products such as:

essential oil (Ajowan oil), Balsam (sweet oil), sage oil (sweet oil), olive oil (sweet oil), sage oil (sweet oil), sage oil (sweet oil).

Synthetic starting materials, for example:

esters such as C16 aldehyde, galbanum ester, allyl caproate, allyl cyclohexylpropionate, allyl heptanoate, allyl phenoxyacetate, isoamyl acetate, amyl benzoate, amyl butyrate, amyl caproate, amyl cinnamate, amyl isovalerate, phenyl acetate, amyl propionate, isoamyl salicylate, acetylated balsam (Amyritis acetate), fennel acetate, benzyl benzoate, benzyl butyrate, benzyl cinnamate, benzyl formate, benzyl isobutyrate, benzyl isoeugenol, benzyl propionate, benzyl salicylate, benzyl tiglate, butyl acetate, butyl butyrate, butyl butyryl lactate, Caryophyllene acetate, Cedryl acetate, cinnamyl butyrate, cis-3-hexenyl acetate, cis-3-hexenyl benzoate, cis-3-hexenyl hexanoate, cis-3-hexenyl formate, cis-3-hexenyl benzoate, allyl butyrate, Methyl methacrylate, Ethyl methacrylate, jasmonate (Methyl methacrylate, Ethyl methacrylate, Methyl methacrylate, Ethyl methacrylate, Methyl methacrylate, Ethyl methacrylate, Methyl methacrylate, Ethyl methacrylate (Methyl methacrylate, Ethyl methacrylate, Methyl methacrylate, Ethyl methacrylate, Methyl methacrylate, Ethyl methacrylate, Methyl methacrylate, Ethyl methacrylate, Methyl methacrylate, Ethyl methacrylate, Methyl methacrylate, Ethyl methacrylate, Methyl methacrylate, Ethyl methacrylate, Methyl methacrylate, Ethyl methacrylate, Methyl methacrylate, Ethyl methacrylate, Methyl methacrylate, Ethyl methacrylate, Methyl methacrylate, Ethyl methacrylate, Methyl methacrylate, Ethyl methacrylate, Methyl methacrylate, Ethyl methacrylate, Methyl methacrylate, Ethyl methacrylate, Methyl methacrylate, Ethyl methacrylate, Methyl methacrylate, Ethyl methacrylate, Methyl methacrylate, Ethyl methacrylate, Methyl methacrylate, Ethyl methacrylate, Methyl methacrylate, Ethyl methacrylate, Methyl.

Lactones, such as: pelargonide (Ambrettolide), Arova N, 3-propylenylidene-1-isobenzofuranone (Celeriax), -decalactone, γ -decalactone, -dodecalactone, γ -dodecalactone, ethylene brassylate (Ethylenebrassylate), cyclopentadecanolide (Exaltolide), γ -heptalactone, -caprolactone, γ -caprolactone, methylketolide (Methyl laitone), methyloctalactone, -nonalactone, γ -nonalactone, octahydrocoumarin, -octalactone, γ -octalactone, Rootylone, cyclohexadecanolide (Silvanone surra), -undecalactone, γ -valerolactone, 10-oxahexadecanolide (OHD musk), Coumarin (Coumarin), cyclopentadecanolide (kabanolide), Jasmolactone (jasmolide).

Aldehydes such as acetaldehyde, Adoxal (Adoxal), C10 Aldehyde, iso-C11 Aldehyde (Aldehyde C11 iso), C11 moa Aldehyde, undecaenal C11(Aldehyde C11undecylic), undecaenal C11(Aldehyde C11undecylic), lauraldehyde C12, Aldehyde C12 MNA, Anisaldehyde (Ananalyde), amyl cinnamaldehyde, benzaldehyde (Bourgel), camphorenal (Camphoraldehyde), Canonal, violet (Cetolal), cinnamaldehyde, cis-4-decenal, cis-6-nonenal, citral, citronellal, citronyloxyl acetaldehyde (citronellyl Aldehyde), citral (citronellal, cinnamic Aldehyde (citral), citral (citral), citral, citralylacetylenal (citral), citral.

Ketones such as hawthorn ketone (acetoanisol), Acetoin (Acetoin), acetophenone, Aldron, allylionone (Allyl Ionone), benzophenone, benzyl acetone, watermelon ketone (Calone), Camphor (Camphor), d-carvone, l-carvone, cashmeratone (Cashmeran), Cedryl methyl ketone (Cedriyl methyl ketone), dihydrojasmonate (Cepionate), Claritone, Cosmone, salidiolide (Cryssolide), Cyclotene, Damascenone (Damascenone), Damascenone (Medamascenone α, Damascenone β, Damascenone gamma, Diacetyl (Diacetyl), Dihydro- β -Ionone, dihydrojasmonate (Didroisosmo josterone), jasmonate (Jambosone, acetone, Jasmone (Jambosone), Jasmone (Jambopoganone), Jasmone (Jambosone), keton-methyl ketone), Jasmone (Jambosone), ketoprofen ketone, acetone (Iressone), ketoximolone (Iressone), ketoprofen ketone (E-methyl ketone), ketone (E-methyl ketone (E), ketone (E-35367-methyl ketone, ketone), ketone (E-methyl ketone (E), ketone (E-methyl ketone), ketone (E-methyl ketone (E-ketone (E), ketone (E-35367-methyl ketone, ketone (E), ketone (E-ketone, ketone (E-methyl ketone), ketone (E-methyl ketone (E-35367-ketone, ketone (E), ketone (E-ketone (E), ketone (E-ketone (E), ketone (E-ketone), ketone (E-methyl ketone, ketone (E), ketone (E-E), ketone (E-ketone (E), ketone (E-methyl ketone (E), ketone (E-35367-ketone (E), ketone (E-ketone, ketone (E), ketone (E-ketone (E), ketone (E-ketone (E), ketone (E-35367-E-methyl ketone (E-.

Alcohols, such as oxo-C13 Alcohol (Alcooxo C13), Amber core (Ambercore), Ambermax, ambergris octahydronaphthalenol (Ambrinol), Amyl vinyl carbinol (Amylvinyl carbinol), anisyl Alcohol (Anasicalcohol), santalol (Bacdanol), benzyl Alcohol, butanol, crystalline Cedrol (Cedrol crystals), cinnamyl Alcohol, Citronellol, coronal (Coranol), Decanol (Decanol), dimethylbenzyl carbinol, dimethyl octanol, dimethylphenylethyl carbinol, dimethyl heptanol (Dimethol), Fenchol (Fenchol), hexanol, isobornenol, isobornyl cyclohexanol, Java sandalwood (Javanol), Keflo, tetramethyl-4-methylene-2-heptanol (Koholhinol), Dilauryl Alcohol, Styloxylenol, linalool (Camphorol), linalool oxide, menthol (Ocolol), menthol (Ocalol), menthol (Neocinnamool), menthol (Neocinnamoyl Alcohol), menthol (Neodecanol), menthol (Neodecanol (cis-2-dihydrodecanol), menthol (Neodecanol), menthol (Neodecanol, cis-2-D-E), menthol (Neodecanol), menthol (Neodecano.

Phenols, such as: butylated hydroxyanisole, Dihydroeugenol (Dihydroeugenol), dimethylhydroquinone, dimethylresorcinol, Eugenol (Eugenol pure), guaiacol, isoeugenol, m-cresol, methyldanshensis (Methyl dianiliis), p-cresol, Propenyl ethylguaiacol (Propenyl guaethol), Thymol (Thymol), and vanillin (Ultravanil).

Ethers, such as ambroxol (Ambroxan), Anethole (Anethole), Anther (Anther), benzyl isoamyl ether, benzyl isopropyl ether, benzyl isovalerate, Iris (Boisiris), cedarwood methyl ether (Cedramber), ambrox (Cetalox), decyl methyl ether, dibenzyl ether, dihydrorose oxide, Diphenyl ether (Diphenyl oxide), Doremox (Doremox), Estragole (Estragol), ethyl linalool, eucalyptol, Galaxolide (Galaxolide), Geranian (Gyrane), Herbavert, acid orange oxide (L imine oxide), Madrox, methyl isobutyl phenol, naphthyl isobutyl ether β, Nerol ether (Neroline oxide), naphthyl ether (Nerolin britin bromide), p-tolyl butyl ether, p-tolyl methyl ether, peonitol, 2, 4-dimethyl-4-phenyl-butyl ether (Rose oxide), rose oxide (Rolba), Royal methyl ether (Royal).

Acetals as follows: acetal CD, acetal R, ambroxol acetal (Amberketal), ethoxycyclododecyl methane (Boisambrene forte), citral diethyl acetal (Citrathal), 1-diethoxyethane, Emeraldine (Emeraldine), Freshopal, lavandin dioxane (Herboxane), indoflo, Jacinthaflor, Magnolan, spicery ether (Spirambrene), phenylacetaldehyde dimethyl acetal (viridin), irinotecan (elinal), graciloborane (glycorolil), Karanal (Karanal), and Methyl grapefruit methane (Methyl palmlemouse).

Hydrocarbons such as Bisabolene (Bisabolene), camphene, Carene 3(Carene delta 3), Caryophyllene (caryophylene), Cedrene (Cedrene), p-Cymene (Cymene para), Dipentene (Dipentene), diphenylmethane, Isolongifolene (Isolongifolene), d-limonene, longifolene (L longifolene), Myrcene (Myrcene), naphthalene, Ocimene (Ocimene), pinene α, pinene β, styrene, terpinene γ, Terpinolene (Terpinolene), 1,3, 5-undecene, and isopropyl graticum (Verdoracine).

Sulfur compounds, such as: main body blackcurrants (Corps cassis), dibutyl sulfide, dimethyl sulfide, methyl 2-hexyl-3-oxocyclopentanecarboxylate (Exovert), Grapefruit mercaptan (Grapefruit thiol), oxanes (oxanes), mercaptomaleates (Ribes captan), thiothiazoles (sulflurol), eucalyptus sulfide (Thiocineol).

Nitriles, such as cinnamonitrile (Cinnamyl nitrile), Citronellyl nitrile (Citronellyl nitrile), 3, 7-dimethyl-6-octenenitrile (Citronellyl nitrile), Clonal, cuminuronitrile (Cumin nitrile), hexylcyclopentanone, irinitryl, 3, 7-dimethyl-2, 6-octadienenitrile (L emonium), peoronitrile (peonium), tridecyl nitrile, Agrumen nitrile, n-decylnitrile.

Oximes, such as dimethylbicyclooctanone oxime (Buccoxime), Rapinoxacin (L abienoxime), and elenolide (Stemone).

Nitrogen heterocycles, such as: 2-acetylpyrazine, 2-acetylpyridine, sec-butylquinoline, Corps racine, 2-ethyl-3, 5 (or 6) -dimethylpyrazine, furfurylpyrrole, indole, isobutylquinoline, 2-isobutyl-3 (or 6) -methoxypyrazine, isopropylquinoline, Maritima, p-methylquinoline, 3-methylindole (Skotol), 2,3, 5-trimethylpyrazine.

Nitro compounds such as: muscone (Musk Ketone).

Schiff bases, such as nervone (Aurantiol), labdanol (Helianthrol), privet acetal (L igintaal), and linganin (Verdantoil).

Other materials such as: acetanilide, cyclic amine (Gardamide), terephthalamide, dimethyl anthranilate, methyl anthranilate, n-butyric acid, capric acid, caproic acid, caprylic acid, phenylacetic acid, caryophyllene oxide, cedryl oxide (Cedroxyde), Tobacanol.

Thus, the compounds of formula (5), (6), (7) or (8) can be used to produce compositions and, as is evident from the above compilation, a wide range of known odorants/aromas, flavors and/or deodorizing/masking materials. In the production of such compositions, the known fragrance, flavour and/or deodorising/masking materials mentioned earlier may be used according to methods known to perfumers, e.g. according to w.a. poucher, Perfumes, Cosmetics and Soaps 2, 7 th edition, Chapman and hall, london 1974.

The invention also relates to mixtures useful in fragrance, flavor and/or deodorizing/masking compositions, wherein the mixtures comprise at least one oxime compound of the formula (7) and/or (8) and at least one ketone compound of the formula (5) and/or (6), wherein R is an alkyl radical having 1 to 9 carbon atoms, an alkenyl radical having only one carbon-carbon double bond (which is preferably not conjugated to an oxime C ═ N bond) and having up to 9 carbon atoms, a (substituted) aryl radical having up to 9 carbon atoms, an oxo-alkyl radical having up to 9 carbon atoms, an alkoxyaryl radical having up to 9 carbon atoms or a (substituted) benzyl radical having up to 9 carbon atoms. In one embodiment of the invention, the group R of the oxime compound is the same as the group R of the ketone compound. In one embodiment of the invention, the mixture comprises oxime and ketone in a weight ratio between 0.01% and 99.99%, such as 0.1% and 99.9%, such as 1% and 99%, such as 1% and 20%, such as 80% and 99%.

The invention also relates to a fragrance, flavor and/or deodorizing/masking composition comprising at least one oxime compound of the formula (7) and/or (8) and at least one ketone compound of the formula (5) and/or (6), wherein R is an alkyl radical having 1 to 9 carbon atoms, an alkenyl radical having only one carbon-carbon double bond (which is preferably not conjugated to an oxime C ═ N bond) and having up to 9 carbon atoms, a (substituted) aryl radical having up to 9 carbon atoms, an oxo-alkyl radical having up to 9 carbon atoms, an alkoxyaryl radical having up to 9 carbon atoms or a (substituted) benzyl radical having up to 9 carbon atoms. In one embodiment of the invention, the group R of the oxime compound is the same as the group R of the ketone compound. In one embodiment of the invention, the weight ratio between oxime and ketone comprised is comprised between 0.01% and 99.99%, such as between 0.1% and 99.9%, such as between 1% and 99%, such as between 1% and 20%, such as between 80% and 99%.

In one embodiment of the present invention, the desired flavour, flavor and/or deodorizing/masking composition comprises, in addition to the oxime/ketone, at least one ester and/or one alcohol, preferably at least a mixture of ester and alcohol; the ester and/or alcohol is preferably selected from the list defined herein above. In one embodiment of the invention, the claimed odorant composition is characterized by a total content of compounds of formula (7) or formula (8) or formula (5) or formula (6) together with ester and/or alcohol of more than 25 wt.%, preferably more than 50 wt.%, such as more than 75 wt.%, or even more than 90 wt.%.

The disclosure is further illustrated by the following examples, which should not be construed as further limiting in any way. Those skilled in the art will readily appreciate that the specific methods and results described are merely illustrative.

All stereoisomers of the compounds of the present disclosure, whether mixtures or pure or substantially pure forms, are contemplated. The compounds of the present disclosure may have asymmetric centers at any carbon atom, and thus, the desired compounds may exist in enantiomeric forms or diastereomeric forms, or as mixtures thereof. The preparation processes can utilize racemates, (pure) enantiomers, non-racemic mixtures of enantiomers, diastereomers or mixtures of diastereomers as starting materials. When the diastereomeric or enantiomeric products are obtained as mixtures, they may be separated by conventional methods such as chromatographic separation or fractional crystallization, or by formation of diastereomeric salts. Where desired, the desired enantiomer or diastereomer may also be obtained by following an appropriate enantioselective or diastereoselective reaction.

Synthetic examples

Example 1:

synthesis of 3,3, 4-trimethylpent-4-en-2-one:

2, 3-dimethyl-2-butene (510g, 5.94mol, 1 equiv.) was added to a solution of zinc chloride (243g, 1.78mol, 0.3 equiv.) in acetic anhydride (1.04kg, 10.2mol, 1.71 equiv.) at 5 ℃ under nitrogen atmosphere with stirring the mixture was stirred in an ice bath and left to stand to reach 20 ℃ in 24 hours then water (1.50L) was added and the mixture was extracted with methyl tert-butyl ether (3 × 500m L) water (2 × 750m L), saturated Na in turn₂CO₃The combined organic phases were washed with aqueous solution (to pH 7) and brine (750m L.) the organic phase was washed with Na₂SO₄Dried and volatiles removed under reduced pressure. The residue (960g) was distilled in vacuo (57 ℃/55 mbar) to give 3,3, 4-trimethylpent-4-en-2-one (501g, 66%).

¹H NMR(400MHz,CDCl₃):1.15(s,6H),1.58(s,3H),1.98(s,3H),4.89(s,2H).¹³CNMR(100MHz,CDCl₃):19.2,22.2,23.9,53.0,110.6,146.8,210.9。