EP4734932A1 - Organic compounds and their use for generating a fragrant alcohol - Google Patents

Organic compounds and their use for generating a fragrant alcohol

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Publication number
EP4734932A1
EP4734932A1 EP24737408.5A EP24737408A EP4734932A1 EP 4734932 A1 EP4734932 A1 EP 4734932A1 EP 24737408 A EP24737408 A EP 24737408A EP 4734932 A1 EP4734932 A1 EP 4734932A1
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EP
European Patent Office
Prior art keywords
formula
compound
group
dimethylnon
consumer product
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Pending
Application number
EP24737408.5A
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German (de)
French (fr)
Inventor
Felix Flachsmann
Lijun Zhou
Julie CHARPENTIER
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Givaudan SA
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Givaudan SA
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Publication of EP4734932A1 publication Critical patent/EP4734932A1/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
    • C07C69/738—Esters of keto-carboxylic acids or aldehydo-carboxylic acids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34—Alcohols
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34—Alcohols
    • A61K8/342—Alcohols having more than seven atoms in an unbroken chain
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/14—Unsaturated ethers
    • C07C43/178—Unsaturated ethers containing hydroxy or O-metal groups
    • C07C43/1787—Unsaturated ethers containing hydroxy or O-metal groups containing six-membered aromatic rings and having unsaturation outside the aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/215—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring having unsaturation outside the six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
    • C07C47/277—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms containing ether groups, groups, groups, or groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/52—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings
    • C07C47/575—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings containing ether groups, groups, groups, or groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/20—Unsaturated compounds containing keto groups bound to acyclic carbon atoms
    • C07C49/255—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing ether groups, groups, groups, or groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
    • C07C49/84—Ketones containing a keto group bound to a six-membered aromatic ring containing ether groups, groups, groups, or groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
    • C07C69/22—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety
    • C07C69/24—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety esterified with monohydroxylic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C07C69/84—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B9/00—Essential oils; Perfumes

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Birds (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Epidemiology (AREA)
  • Emergency Medicine (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Fats And Perfumes (AREA)

Abstract

Compound of formula (I) being an ether or an ester as precursor for generating a fragrant alcohol according to formula (II); its use as fragrance precursor, and fragrance compositions and consumer products comprising the compound.

Description

ORGANIC COMPOUNDS AND THEIR USE FOR GENERATING A FRAGRANT ALCOHOL
TECHNICAL FIELD
The present invention relates generally to fragrance precursors, which are able to release fragrant alcohols. The invention also relates to perfume preparations and consumer products containing said precursors. The invention further relates to methods of making said perfume precursors, perfume preparations and consumer products, as well as the use of said perfume precursors and perfume preparations in consumer products, such as personal care and household care products.
BACKGROUND
Perfumed consumer products such as personal care, cleaning or laundry products comprising fragrances are well-known in the art. However, it is known that fragrances can be altered through degradation caused by interaction with air or when incorporated in certain consumer product bases, where alkalinity, acidity, the presence of oxidizing agents, such as hypochlorite salts, or other base components may lead to chemical degradation of the fragrance. In addition, volatile fragrances tend to be dissipated with time. Furthermore, when used in the perfumed consumer products mentioned above, the deposition of the fragrance on a treated substrate is diminished by the washing and/or rinsing procedure.
Nevertheless, it is desired by consumers to have products that can be stored overtime and still giving a constant perfume impression. In particular, the impact of volatile components is to be retained. Furthermore, it is desired that such products create a long-lasting pleasing fragrance slowly emitting from the treated substrate over time.
To address these needs, fragrance precursors can be used, which are substances that are essentially odorless themselves, but which, in particular circumstances, will decompose to release the fragrant molecule.
There are several classes of known precursors which release fragrant molecules upon activation, such as hydrolysis, temperature change, oxygen, action of light and enzymes. For example, WO2012085287 reports a group of precursors able to release a fragrance by spontaneous air oxidation. In W02007143873 another group of precursors is described which can be cleaved by hydrolysis. All precursors do show different stability, and they release the fragrant molecule under different conditions. There is still need to provide precursors able to release fragrant alcohols over an extended time period and which can be easily incorporated into a variety of consumer products.
SUMMARY
In accordance with a first aspect of the present invention there is provided a compound of formula (I) wherein
- is indicating a carbon-carbon single or double bond between C2 and C3;
R1, R3, R4, R5 and R6 is independently selected from the group consisting of H, Me and Et;
R2 is selected from the group consisting of H, Me and Et, or forms together with the carbon atoms C2 and C3 a 3 membered ring; and
X is selected from the group consisting of aryl bearing up to two substituents selected from the group consisting of hydroxy, methoxy, ethoxy, formyl, allyl, oxoalkyl, oxoalkenyl and alkyl alkenoate; benzyl bearing a substituent selected from the group consisting of hydroxymethyl, formyl, vinyl, (C=O)Me, (C=O)Et, (C=O)OMe, (C=O)OEt, (C=O)Ph at the benzylic position; propan-2-yl substituted with phenyl, naphthalen-1-yl or naphthalen-2-yl at position 2; dimethyl 2-malonate and diethyl 2-malonate; and alkanoyl (C(O)-R10), with R10 selected from linear or branched C4 to Ci8 alkyl, linear or branched C4 to Cis alkenyl with one or two double bonds, linear or branched C4 to Ci8 ether and oxoalkyl, and hydroxyphenyl, with the proviso that the compound is not nona-2,6-dien-1-yl palmitate, as precursor for generating a fragrant alcohol of formula (II) In accordance with a second aspect of the present invention there is provided a use of a compound of formula (I) as fragrance precursor which is capable of releasing fragrant alcohols of formula (II) over an extended time period.
In accordance with a third aspect of the present invention there are provided fragrance compositions and consumer products comprising said compounds of formula (I).
In accordance with a fourth aspect of the present invention there is provided a method to release a fragrant alcohol of formula (II).
In accordance with a fifth aspect of the present invention there are provided methods of making said perfume precursors, perfume preparations and consumer products.
In accordance with a sixth aspect of the present invention there is provided the use of said perfume precursors of formula (I) and perfume preparations in consumer products, such as fabric care, personal care and household care products.
In accordance with a seventh aspect of the present invention there is provided a method to confer, enhance, improve or modify the hedonic properties of a fragrance composition or a consumer product.
Certain embodiments of any aspect of the present invention may provide one or more of the following advantages:
• release of fragrant alcohols,
• efficient delivery of the odors of fragrant alcohols in consumer products, and
• stability of fragrance precursors in consumer product bases as well as after their deposition on substrates.
The details, examples and preferences provided in relation to any particular one or more of the stated aspects of the present invention will be further described herein and apply equally to all aspects of the present invention. Any combination of the embodiments, examples and preferences described herein in all possible variations thereof is encompassed by the present invention unless otherwise indicated herein, or otherwise clearly contradicted by context.
DETAILED DESCRIPTION The present invention is based on the surprising finding that ethers and esters of fragrant alcohols can serve as fragrance precursors able to release said fragrant alcohols. These fragrance precursors provide a high substantivity of the fragrant alcohols and are robust in different consumer products.
There is therefore provided a compound of formula (I) wherein
- is indicating a carbon-carbon single or double bond between C2 and C3;
R1, R3, R4, R5 and R6 is independently selected from the group consisting of H, Me and Et;
R2 is selected from the group consisting of H, Me and Et, or forms together with the carbon atoms C2 and C3 a 3 membered ring; and
X is selected from the group consisting of aryl bearing up to two substituents selected from the group consisting of hydroxy, methoxy, ethoxy, formyl, allyl, oxoalkyl, oxoalkenyl and alkyl alkenoate; benzyl bearing a substituent selected from the group consisting of formyl, vinyl, (C=O)Me, (C=O)Et, (C=O)OMe, (C=O)OEt, (C=O)Ph at the benzylic position; propan-2-yl substituted with phenyl, naphthalen-1-yl or naphthalen-2-yl at position 2; dimethyl 2-malonate and diethyl 2-malonate; and alkanoyl (C(O)-R10), with R10 selected from linear or branched C4 to Ci8 alkyl, linear or branched C4 to Cis alkenyl with one or two double bonds, linear or branched C4 to Ci8 ether and oxoalkyl, and hydroxyphenyl, with the proviso that the compound is not nona-2,6-dien-1-yl palmitate, as precursor for generating a fragrant alcohol of formula (II)
The substituents R1 - R6 and the bond with the dotted line in the compound of formula (II) are defined as in the compound of formula (I).
The term aryl means for example phenyl or napthyl. The term alkyl alkenoate means for example methyl or ethyl acrylate.
The term linear or branched C4 to Ci8 alkyl means all linear or branched alkyl chains having between 4 and 18 carbon atoms, for example C5, C6, C7, C8, C9, C10, Cn, C12, C13, C14 C15, C16 or C17 alkyl etc.
The term linear or branched C4 to Ci8 alkenyl with one or two double bonds means all linear or branched alkenyl chains having one or two double bonds, for example C5, C6, C7, C8, C9, C10, C11 , C12, C13, Ci4 C15, C16 or Ci7 alkenyl. In case of two double bonds, they can be isolated or conjugated.
The term linear or branched C4 to Ci8 ether and oxoalkyl, oxoalkenyl means all linear or branched alkyl or alkenyl chains having between 4 and 18 carbon atoms as mentioned above and bearing an ether group or an oxo group in the chain, for example 3-oxobutyl.
The term benzyl bearing a substituent selected from the group consisting of hydroxymethyl, formyl, (C=O)Me, (C=O)Et, (C=O)OMe, (C=O)OEt, (C=O)Ph at the benzylic position means for example 2-phenyl-ethanal, 2-phenyl-ethanol, (2-oxopropyl)-1 -phenyl, methyl 2-phenyl ethanoate and 2-oxo-1 ,2-diphenyl-1-ethyl.
The term propan-2-yl substituted with phenyl, naphthalen-1-yl or naphthalen-2-yl at position 2 means for example 2-(naphthalen-2-yl)propan-2-yl, 2-phenylpropan-2-yl.
If not further specified, the CC double bond(s) in the compound of formula (I) and the compound of formula (II) has either E- orZ- configuration, or the compound is a mixture of E and Z isomers. If more double bonds are present, each of them has either E- or Z- configuration, and the compound can be present as a pure or enriched isomer, for example as 2E,6Z-nonadienol, or as a mixture of double bond isomers.
The compounds of formula (I) and formula (II) can have one or more stereo centers and in consequence exist as different stereoisomers (e.g. diastereomers or enantiomers), all of which are encompassed by the present invention. Chiral compounds of formula (I) or formula (II) can be enantiomerically pure, enriched or racemic. If more than one stereo centre is present, the compounds are either diastereomeric mixtures, diastereomerically enriched or pure diastereomers. The fragrant alcohols according to formula (II) and their corresponding fragment in the compound of formula (I) vary in the substituents R1 to R6, wherein R1, R3, R4, R5 and R6 is independently selected from the group consisting of H, Me and Et, and R2 is selected from the group consisting of H, Me and Et, or forms together with the carbon atoms C2 and C3 a 3 membered ring, and - is indicating a carbon-carbon single or double bond between C2 and C3.
For example, there is provided a compound of formula (I) wherein
- is indicating a carbon-carbon single or double bond between C2 and C3;
R1, R3, R4, R5 and R6 is independently selected from the group consisting of H, Me and Et;
R2 is selected from the group consisting of H, Me and Et, or forms together with the carbon atoms C2 and C3 a 3 membered ring; and
X is selected from the group consisting of aryl bearing up to two substituents selected from the group consisting of hydroxy, methoxy, ethoxy, formyl, allyl, oxoalkyl, oxoalkenyl and alkyl alkenoate; benzyl bearing a substituent selected from the group consisting of formyl, vinyl, (C=O)Me, (C=O)Et, (C=O)OMe, (C=O)OEt, (C=O)Ph at the benzylic position; propan-2-yl substituted with phenyl, naphthalen-1-yl or naphthalen-2-yl at position 2; dimethyl 2-malonate and diethyl 2-malonate; and alkanoyl (C(O)-R10), with R10 selected from linear or branched C4 to Ci8 alkyl, linear or branched C4 to Cis alkenyl with one or two double bonds, linear or branched C4 to Cis ether and oxoalkyl, and hydroxyphenyl, with the proviso that the compound is not nona-2,6-dien-1-yl palmitate, as precursor for generating a fragrant alcohol of formula (II) wherein the fragrant alcohol of formula (II) that is released from the compound of formula (I) is selected from the group consisting of 3,7-dimethylnon-6-en-1-ol, 2,4,7-trimethyloct-6-en-1-ol, 6-nonenol, 6-ethyl-3-methyloct-6-en-1-ol, (1-methyl-2-(5-methylhex-4-en-2- yl)cyclopropyl)methanol, and 2,6-nonadienol.
The fragrant alcohol of formula (II) show a good perception threshold when slowly released from the compound of formula (I). In contrast, other alcohols, for example citronellol (3,7- dimethyloct-6-en-1-ol) or geraniol (3,7-dimethylocta-2,6-dien-1-ol) have higher threshold which are making it difficult to work with in slow release mode, when released from the corresponding compound of formula (I).
For example, in the compounds of formula (I) and formula (II) the configuration of the double bond between C6 and C7 is Z. Alternatively, the configuration of said double bond can be E, or the compound can be an E/Z mixture.
For example, the fragrant alcohol of formula (II) can be selected from the group consisting of (Z)-3,7-dimethylnon-6-en-1-ol, (S,Z)-3,7-dimethylnon-6-en-1-ol, 2,4,7-trimethyloct-6-en-1-ol, (Z)-6-nonenol, (Z)-6-ethyl-3-methyloct-6-en-1-ol, (1-methyl-2-(5-methylhex-4-en-2- yl)cyclopropyl)methanol, and (2E,6Z) -nonadienol.
In one embodiment of the present invention there is provided a compound of formula (I) as defined above, wherein the sum of carbon atoms provided by R1 - R6 must not exceed 8. In other words, the fragrant alcohol (compound of formula (II)) which can be generated from the compound of formula (I) has a total number of carbon atoms between 9 and 15.
In one embodiment of the present invention there is provided a compound of formula (I) as defined above, with the proviso that if R2 is Me, then at least one of R5 and R6 is H or Et, while the other substituent is independently selected from the group consisting of H, Me and Et.
In one embodiment of the present invention there is provided a compound of formula (I) wherein is indicating a carbon-carbon single or double bond between C2 and C3; R1, R3, R4, R5 and R6 is independently selected from the group consisting of H, Me and Et;
R2 is selected from the group consisting of H, Me and Et, or forms together with the carbon atoms C2 and C3 a 3 membered ring; and
X is selected from the group consisting of aryl bearing up to two substituents selected from the group consisting of hydroxy, methoxy, ethoxy, formyl, allyl, oxoalkyl, oxoalkenyl and alkyl alkenoate; benzyl bearing a substituent selected from the group consisting of formyl, vinyl, (C=O)Me, (C=O)Et, (C=O)OMe, (C=O)OEt, (C=O)Ph at the benzylic position; propan-2-yl substituted with phenyl, naphthalen-1-yl or naphthalen-2-yl at position 2; dimethyl 2-malonate and diethyl 2-malonate, as precursor for generating a fragrant alcohol according to formula (II) wherein the fragrant alcohol of formula (II) that is released from the compound of formula (I) is selected from the group consisting of 3,7-dimethylnon-6-en-1-ol, 2,4,7-trimethyloct-6-en-1-ol, 6-nonenol, 6-ethyl-3-methyloct-6-en-1-ol, (1-methyl-2-(5-methylhex-4-en-2- yl)cyclopropyl)methanol, and 2,6-nonadienol.
Said compounds can be referred to as ether type compounds of formula (I).
In one embodiment of the present invention there is provided an ether type compound of formula (I), wherein the sum of carbon atoms provided by R1 - R6 must not exceed 8. In other words, the fragrant alcohol (compound of formula (II)) which can be generated from the compound of formula (I) has a total number of carbon atoms between 9 and 15.
In one embodiment of the present invention there is provided an ether type compound of formula (I) as defined above, with the proviso that if R2 is Me, then at least one of R5 and R6 is H or Et, while the other substituent is independently selected from the group consisting of H, Me and Et.
In one embodiment of the present invention there is provided an ether type compound of formula (I), wherein the sum of carbon atoms provided by R1 - R6 must not exceed 8, with the proviso that if R2 is Me, then at least one of R5 and R6 is H or Et, while the other substituent is independently selected from the group consisting of H, Me and Et.
For example, the compound of formula (I) can be selected from the group consisting of 1 -((3,7- dimethylnon-6-en-1-yl)oxy)naphthalene, 2-((3,7-dimethylnon-6-en-1-yl)oxy)naphthalene, 4- ((3,7-dimethylnon-6-en-1-yl)oxy)phenol, ethyl 3-(4-((3,7-dimethylnon-6-en-1- yl)oxy)phenyl)acrylate, 1-((3,7-dimethylnon-6-en-1-yl)oxy)-4-methoxybenzene, 2-((3,7- dimethylnon-6-en-1-yl)oxy)benzaldehyde, 1-((3,7-dimethylnon-6-en-1-yl)oxy)-2- methoxybenzene, 2-((3,7-dimethylnon-6-en-1-yl)oxy)-2-phenylacetaldehyde, 2-((3,7- dimethylnon-6-en-1-yl)oxy)phenol, 3-((3,7-dimethylnon-6-en-1-yl)oxy)phenol, 1 -((3,7- dimethylnon-6-en-1-yl)oxy)-3-methoxybenzene, 1-(non-6-en-1-yloxy)naphthalene, 2-(non-6- en-1-yloxy)naphthalene, 4-(non-6-en-1-yloxy)phenol, ethyl 3-(4-((non-6-en-1- yl)oxy)phenyl)acrylate, 1-methoxy-4-(non-6-en-1-yloxy)benzene, 2-(non-6-en-1- yloxy)benzaldehyde, 1-methoxy-2-(non-6-en-1-yloxy)benzene, 3-methoxy-4-(non-6-en-1- yloxy)benzaldehyde, 2-(non-6-en-1-yloxy)phenol, 3-(non-6-en-1-yloxy)phenol, 1-methoxy-3- (non-6-en-1-yloxy)benzene, 3-ethoxy-4-(non-6-en-1-yloxy)benzaldehyde, 4-((2,4,7- trimethyloct-6-en-1-yl)oxy) phenol, 4-((1-methyl-2-(5-methylhex-4-en-2- yl)cyclopropyl)methoxy)phenol, 1-methoxy-2-((nona-2,6-dien-1-yl)oxy)benzene, 1-((6-ethyl-3- methyloct-6-en-1-yl)oxy)naphthalene, 3-ethoxy-4-((nona-2,6-dien-1-yl)oxy)benzaldehyde, 4- (4-((nona-2,6-dien-1-yl)oxy)phenyl)butan-2-one, 4-allyl-2-methoxy-1-((nona-2,6-dien-1- yl)oxy)benzene, methyl 2-((3,7-dimethylnon-6-en-1-yl)oxy)-2-phenylacetate, 2-((3,7- dimethylnon-6-en-1-yl)oxy)-1 ,2-diphenylethan-1-one, (2-((3,7-dimethylnon-6-en-1- yl)oxy)propan-2-yl)benzene, and 2-(2-((3,7-dimethylnon-6-en-1-yl)oxy)propan-2- yl)naphthalene.
In a further embodiment of the present invention there is provided a compound of formula (I) wherein - is indicating a carbon-carbon single or double bond between C2 and C3; R1, R3, R4, R5 and R6 is independently selected from the group consisting of H, Me and Et; R2 is selected from the group consisting of H, Me and Et, or forms together with the carbon atoms C2 and C3 a 3 membered ring; and X is selected from the group consisting of alkanoyl (C(O)-R10), with R10 selected from linear or branched C4 to Ci8 alkyl, linear or branched C4 to Ci8 alkenyl with one or two double bonds, linear or branched C4 to Ci8 ether and oxoalkyl, and hydroxyphenyl, with the proviso that the compound is not nona-2,6-dien-1-yl palmitate, as precursor for generating a fragrant alcohol according to formula (II) wherein the fragrant alcohol of formula (II) that is released from the compound of formula (I) is selected from the group consisting of 3,7-dimethylnon-6-en-1-ol, 2,4,7-trimethyloct-6-en-1-ol, 6-nonenol, 6-ethyl-3-methyloct-6-en-1-ol, (1-methyl-2-(5-methylhex-4-en-2- yl)cyclopropyl)methanol, and 2,6-nonadienol.
The fragrant alcohol of formula (II) show a good perception threshold when slowly released from the compound of formula (I). In contrast, other alcohols, for example citronellol (3,7- dimethyloct-6-en-1-ol) or geraniol (3,7-dimethylocta-2,6-dien-1-ol) have higher threshold which are making it difficult to work with in slow release mode, when released from the corresponding compound of formula (I).
Said compounds can be referred to as ester type compounds of formula (I).
In one embodiment of the present invention there is provided an ester type compound of formula (I) as defined above, wherein the sum of carbon atoms provided by R1 - R6 must not exceed 8. In other words, the fragrant alcohol (compound of formula (II)) which can be generated from the compound of formula (I) has a total number of carbon atoms between 9 and 15.
In one embodiment of the present invention there is provided an ester type compound of formula (I) as defined above, with the proviso that if R2 is Me, then at least one of R5 and R6 is H or Et, while the other substituent is independently selected from the group consisting of H, Me and Et.
In one embodiment of the present invention there is provided an ester type compound of formula (I), wherein the sum of carbon atoms provided by R1 - R6 must not exceed 8, with the proviso that if R2 is Me, then at least one of R5 and R6 is H or Et, while the other substituent is independently selected from the group consisting of H, Me and Et.
For example, the compound of formula (I) can be selected from the group consisting of 3,7- dimethylnon-6-en-1-yl palmitate, 3,7-dimethylnon-6-en-1-yl 4-oxopentanoate, 2,4,7- trimethyloct-6-en-1-yl palmitate, 2,4,7-trimethyloct-6-en-1-yl 4-oxopentanoate, (1-methyl-2-(5- methylhex-4-en-2-yl)cyclopropyl)methyl palmitate, (1-methyl-2-(5-methylhex-4-en-2- yl)cyclopropyl)methyl 4-oxopentanoate, 6-ethyl-3-methyloct-6-en-1-yl palmitate, 6-ethyl-3- methyloct-6-en-1-yl 4-oxopentanoate, non-6-en-1-yl palmitate, non-6-en-1-yl 4-oxopentanoate, nona-2,6-dien-1-yl 4-oxopentanoate, non-6-en-1-yl 2-hydroxybenzoate, and nona-2,6-dien-1- yl 2-hydroxybenzoate.
The precursor effect of compounds of formula (I) is surprising, since esters are expected to be stable on dry fibers. Thus, the release of fragrant alcohols from esters of formula (I) at a sufficiently high rate to generate a perceivable odour signal is surprising. Furthermore, ethers are considered stable in consumer products and their applications. Thus, the release of perceivable amounts fragrance alcohols from ethers under ambient conditions is surprising.
The compound of formula (I) typically has low odour or is odourless, and is able to release fragrant alcohols of formula (II), which is the dominant odor compound generated by the presented precursor. Typically, the remaining part of the compound of formula (I) is either not contributing to the overall odor at all, or its contribution is relatively small, so that the main odor characteristics of the fragrant alcohols of formula (II) is perceived, and only side aspects of the odor are altered.
However, in some embodiments of the present invention, the compound of formula (I) might have an own odor.
In a further embodiment of the present invention there is provided the use of a compound of formula (I) wherein is indicating a carbon-carbon single or double bond between C2 and C3; R1, R3, R4, R5 and R6 is independently selected from the group consisting of H, Me and Et;
R2 is selected from the group consisting of H, Me and Et, or forms together with the carbon atoms C2 and C3 a 3 membered ring; and
X is selected from the group consisting of aryl bearing up to two substituents selected from the group consisting of hydroxy, methoxy, ethoxy, formyl, allyl, oxoalkyl, oxoalkenyl and alkyl alkenoate; benzyl bearing a substituent selected from the group consisting of hydroxymethyl, formyl, vinyl, (C=O)Me, (C=O)Et, (C=O)OMe, (C=O)OEt, (C=O)Ph at the benzylic position; propan-2-yl substituted with phenyl, naphthalen-1-yl or naphthalen-2-yl at position 2; dimethyl 2-malonate and diethyl 2-malonate; and alkanoyl (C(O)-R10), with R10 selected from linear or branched C4 to Ci8 alkyl, linear or branched C4 to Cis alkenyl with one or two double bonds, linear or branched C4 to Ci8 ether and oxoalkyl, and hydroxyphenyl, with the proviso that the compound is not nona-2,6-dien-1-yl palmitate, as precursor for generating a fragrant alcohol of formula (II)
For example, there is provided the use the use of a compound of formula (I) as described above as as precursor for generating a fragrant alcohol of formula (II), wherein the fragrant alcohol of formula (II) that is released from the compound of formula (I) is selected from the group consisting of 3,7-dimethylnon-6-en-1-ol, 2,4,7-trimethyloct-6-en-1-ol, 6-nonenol, 6-ethyl-3-methyloct-6-en-1-ol, (1-methyl-2-(5-methylhex-4-en-2- yl)cyclopropyl)methanol, and 2,6-nonadienol.
By the use of the compound of formula (I) instead of the fragrant alcohols as such, it is possible to provide the odor of the fragrant alcohols over prolonged time. Furthermore, it is possible to incorporate the precursor into different consumer products. In addition, compounds of formula (I) release the potent odour of the fragrant alcohols of formula (II) gradually in low concentrations. As some compounds of formula (II) have a high odour impact, they can only be used in very low amounts in fragrance compositions, e.g. below 0.5%. It is thus not possible to dose such fragrant alcohols in sufficient amounts to impact the dry down odour of a rinse-off application such as a laundry detergent application. Compounds of formula (I) solve that technical challenge.
The compounds of formula (I) described above release fragrant alcohols upon exposure to ambient air and/or humidity (by oxidation and/or hydrolysis) over a long period of time (e.g. several days such as 2-7 days or even longer).
Exposure of the precursor compound to ambient air means exposure to molecular oxygen which might be responsible for the cleavage of the compound of formula (I) and the release of the compound of formula (II). The concentration of oxygen in the air is sufficient for cleaving the compound of formula (I) so that the cleavage products can be detected in the ambient air, e.g. by olfaction or GC-MS analysis of headspace samples.
Exposure of the precursor compound to humidity means exposure to water which might be responsible for the cleavage of the compound of formula (I) and the release of the compound of formula (II). Already traces of water are sufficient to allow for cleavage of the compound of formula (I).
The compound of formula (I) is finely dispersed on fibers such as cotton fabric fiber, synthetic textile fiber, hair or hard surfaces such as ceramic or plastic, thereby maximizing the surface and allowing the exposure to air and humidity.
The compounds of formula (I) are very stable when not exposed to ambient air and/or humidity. Thus the compounds of formula (I) may find use in a broad range of consumer products in which a prolonged and defined release of fragrant compounds is desired.
The compound of formula (I) may be used alone, or in combination with known odorant molecules selected from the extensive range of natural products, and synthetic molecules currently available, such as essential oils, alcohols, aldehydes and ketones, ethers and acetals, esters and lactones, macrocycles and heterocycles, and/or in admixture with one or more ingredients or excipients conventionally used in conjunction with odorants in fragrance compositions, for example, carrier materials, and other auxiliary agents commonly used in the art.
For example, the compound of formula (I) may be used in combination with the free fragrant alcohol of formula (II). Such a combination ensures a continuous perception of the fragrant alcohol with time.
In a further aspect, the compound of formula (I) may be used in combination with other fragrance precursors, either with further compounds of formula (I) or with precursors possessing a different chemical structure. A combination of precursors allows releasing a perfume accord.
In a further aspect, there is provided a fragrance composition comprising at least one compound of formula (I). For example, the fragrance composition is further comprising one or more known odorant molecules or fragrance precursors, and/or one or more ingredients or excipients conventionally used in conjunction with odorants in fragrance compositions
As used herein, "carrier material" means a material which is practically neutral from an odourant point of view, i.e. a material that does not significantly alter the organoleptic properties of odorants.
The term "auxiliary agent" refers to ingredients that might be employed in a fragrance composition for reasons not specifically related to the olfactive performance of said composition. For example, an auxiliary agent may be an ingredient that acts as an aid to processing a fragrance ingredient or ingredients, ora composition containing said ingredient(s), or it may improve handling or storage of a fragrance ingredient or composition containing same. It might also be an ingredient that provides additional benefits such as imparting color or texture. It might also be an ingredient that imparts light resistance or chemical stability to one or more ingredients contained in a perfume composition. A detailed description of the nature and type of adjuvants commonly used in perfume compositions containing same cannot be exhaustive, but it has to be mentioned that said ingredients are well known to a person skilled in the art.
As used herein, "fragrance composition" means any composition comprising the compound of formula (I) and a base material, e.g. a diluent conventionally used in conjunction with odourants, such as diethyl phthalate (DEP), dipropylene glycol (DPG), isopropyl myristate (IPM), pentane- 1 ,2-diol, triethyl citrate (TEC) and alcohol (e.g. ethanol). Optionally, the composition may comprise an anti-oxidant adjuvant. Said anti-oxidant may be selected from Tinogard® TT (BASF), Tinogard® Q (BASF), Tocopherol (including its isomers, CAS 59-02-9; 364-49-8; 18920-62-2; 121854-78-2), 2,6-bis(1 ,1-dimethylethyl)-4-methylphenol (BHT, CAS 128-37-0) and related phenols, hydroquinones (CAS 121-31-9).
The following non limiting list comprises examples of known odourant molecules, which may be combined with the compound of formula (I) in a fragrance composition:
• Essential oils and extracts, e.g. castoreum, costus root oil, oak moss absolute, geranium oil, tree moss absolute, basil oil, fruit oils, such as bergamot oil and mandarine oil, myrtle oil, palmarose oil, patchouli oil, petitgrain oil, jasmine oil, rose oil, sandalwood oil, wormwood oil, lavender oil and/ or ylang-ylang oil;
• Alcohols, e.g. cinnamic alcohol ((E)-3-phenylprop-2-en-1-ol); cis-3-hexenol ((Z)-hex-3- en-1-ol); Citronellol (3,7-dimethyloct-6-en-1-ol); dihydro myrcenol (2,6-dimethyloct-7- en-2-ol); Ebanol™ ((E)-3-methyl-5-(2,2,3-trimethylcyclopent-3-en-1-yl)pent-4-en-2-ol); eugenol (4-allyl-2-methoxyphenol); ethyl linalool ((E)-3,7-dimethylnona-1 ,6-dien-3-ol); farnesol ((2E,6Z)-3,7,11-trimethyldodeca-2,6,10-trien-1-ol); geraniol ((E)-3,7- dimethylocta-2,6-dien-1-ol); Super Muguet™ ((E)-6-ethyl-3-methyloct-6-en-1-ol); linalool (3,7-dimethylocta-1 ,6-dien-3-ol); menthol (2-isopropyl-5-methylcyclohexanol); Nerol (3,7-dimethyl-2,6-octadien-1-ol); phenyl ethyl alcohol (2-phenylethanol); Rhodinol™ (3,7-dimethyloct-6-en-1-ol); Sandalore™ (3-methyl-5-(2,2,3- trimethylcyclopent-3-en-1-yl)pentan-2-ol); terpineol (2-(4-methylcyclohex-3-en-1- yl)propan-2-ol); or Timberol™ (1-(2,2,6-trimethylcyclohexyl)hexan-3-ol); 2,4,7- trimethylocta-2,6-dien-1-ol, and/or [1-methyl-2(5-methylhex-4-en-2-yl)cyclopropyl]- methanol;
• Aldehydes and ketones, e.g. anisaldehyde (4-methoxybenzaldehyde); alpha amyl cinnamic aldehyde (2-benzylideneheptanal); Georgywood™ (1-(1 ,2,8,8-tetramethyl- 1 ,2,3,4,5,6,7,8-octahydronaphthalen-2-yl)ethanone); Hydroxycitronellal (7-hydroxy- 3,7-dimethyloctanal); Iso E Super® (1-(2,3,8,8-tetramethyl-1 ,2,3,4,5,6,7,8- octahydronaphthalen-2-yl)ethanone); Isoraldeine® ((E)-3-methyl-4-(2,6,6- trimethylcyclohex-2-en-1-yl)but-3-en-2-one); Hedione® (methyl 3-oxo-2- pentylcyclopentaneacetate); Nympheal (3-(4-isobutyl-2-methylphenyl)propanal); Mahonial (5,9-dimethyl-9-hydroxy-decen-4-al); maltol; methyl cedryl ketone; methylionone; verbenone; and/or vanillin; • Ether and acetals, e.g. Ambrox® (3a,6,6,9a-tetramethyl-2,4,5,5a,7,8,9,9b-octahydro- 1/7-benzo[e][1]benzofuran); geranyl methyl ether ((2E)-1-methoxy-3,7-dimethylocta- 2,6-diene); rose oxide (4-methyl-2-(2-methylprop-1-en-1-yl)tetrahydro-2/7-pyran); and/ or Spirambrene® (2',2',3,7,7-pentamethylspiro[bicyclo[4.1 ,0]heptane-2,5'- [1 ,3]dioxane]);
• Esters and lactones, e.g. benzyl acetate; cedryl acetate ((1S,6/?,8a/?)-1 ,4,4,6- tetramethyloctahydro-1 /7-5,8a-methanoazulen-6-yl acetate); y-decalactone (6- pentyltetrahydro-2/7-pyran-2-one); Helvetolide® (2-(1-(3,3-dimethylcyclohexyl)ethoxy)- 2-methyl propyl propionate); y-undecalactone (5-heptyloxolan-2-one); and I or vetiveryl acetate ((4,8-dimethyl-2-propan-2-ylidene-3,3a,4,5,6,8a-hexahydro-1 /7-azulen-6-yl) acetate
• Macrocycles, e.g. Ambrettolide ((Z)-oxacycloheptadec-10-en-2-one); ethylene brassylate (1 ,4-dioxacycloheptadecane-5, 17-dione); and I or Exaltolide® (16- oxacyclohexadecan-1-one); and
• Heterocycles, e.g. isobutylquinoline (2-isobutylquinoline).
Overall, the compounds of formula (I) can be used alone, as a mixture thereof, or in combination with other fragrance ingredients and/or precursors thereof. Such other fragrance ingredients are also described, for example, in "Perfume and Flavor Chemicals", S. Arctander, Ed., Vol. I & II, Allured Publishing Corporation, Carol Stream, USA, 2003 and include fragrance compounds of natural or synthetic origin and essential oils.
In a further aspect, there is provided a consumer product comprising at least one compound of formula (I) and a consumer product base.
The consumer product for example is selected from fine fragrance, personal care products (body care products, hair care products, cosmetic products) fabric care products, home care products and air care products. As used herein, "consumer product base" means a composition for use as a consumer product to fulfill specific actions, such as cleaning, softening, and caring or the like.
Personal care products to which the compound of formula (I) can be added include for example all kinds of body care products. Especially interesting products are hair care products, for example shampoos, conditioners and hairsprays, and skin care products, like lotions or creams. Furthermore, the compound of formula (I) may be added to soaps, bath and shower gels and deodorants. The compound of formula (I) can be added to cosmetic products.
Home care products to which the compound of formula (I) can be added include all kinds of detergents, window cleaners, hard surface cleaners, all-purpose cleaners and furniture polishes. Preferably, the products are liquids, e.g. fabric detergent or conditioner compositions.
For example, the compounds of formula (I) can act as fragrance precursors in consumer products which further comprise enzymes.
The compound according to formula (I) may be used in a broad range of perfumed consumer products, e.g. in any field of fine and functional perfumery, such as perfumes, air care products, household products, laundry products, body care products and cosmetics. The compound can be employed in widely varying amounts, depending upon the specific consumer product and on the nature and quantity of other odourant ingredients. The proportion of the formula (I) is typically from 0.0001 to 5 weight% of the consumer product. In one embodiment, the compound of formula (I) may be employed in a fabric softener in an amount from 0.001 to 0.3 weight % (e.g. 0.01 to 0.1 including 0.05 weight%). In another embodiment, the compound of formula (I) may be used in fine perfumery but also in consumer products like shampoo, fabric softener or fabric detergents, in amounts from 0.001 to 30 weight% (e.g. up to about 10 or up to 20 weight%), more preferably between 0.01 and 5 weight%. However, these values are given only by way of example, since the experienced perfumer may also achieve effects or may create novel accords with lower or higher concentrations.
In one embodiment there is provided a consumer product comprising an acceptable amount of the compound of formula (I). For example, the fragranced consumer product may comprise 0.000001 weight% to 90 weight% (including 0.00001 weight %; 0.0001 weight%, 0.001 weight%, 0.01 weight%, 0.05 weight%, 0.1 weight%, 0.5 weight%, 1 weight%, 5 weight%, 8 weight%, 10 weight%, 15 weight%, 20 weight%, 25 weight%, 30 weight%, 50 weight%, 60 weight%, 65 weight%) of the compound of formula (I) based on the total amount of the consumer product.
The compound of formula (I) may be employed in a consumer product base simply by directly mixing the compound of the present invention, or a fragrance composition comprising the compound of formula (I), with the consumer product base, or it may, in an earlier step, be entrapped with an entrapment material, for example, polymers, capsules, microcapsules and nanocapsules, liposomes, film formers, absorbents such as carbon or zeolites, cyclic oligosaccharides and mixtures thereof, and then mixed with the consumer product base. The consumer base might further contain entrapment material able to release other fragrant compounds.
Thus, the invention additionally provides a method of manufacturing a consumer product, comprising the incorporation of a compound of formula (I) either by directly admixing it to the consumer product base or by admixing a fragrance composition comprising the compound of formula (I), which may then be mixed with a consumer product base, using conventional techniques and methods. Through the addition of an acceptable amount of the compound of the present invention as hereinabove described, the odour notes of an applied consumer product will be improved, conferred, enhanced, or modified.
As used herein, ‘consumer product base’ means a composition for use as a consumer product to fulfil specific actions, such as cleaning, softening, and caring or the like.
In a further aspect of the present invention, there is provided a method to release a a fragrant alcohol of formula (II), wherein a compound of formula (I) according to claim 1 is exposed to ambient air and/or humidity.
The compounds of the current invention can be prepared by methods known to the person skilled in the art of organic synthesis. For the purpose of illustration, descriptions of general methods are provided in the following. In all cases, isolation and purification of the product is effected according to suitable workup and purification methods known to the person skilled in the art.
For example, compounds of formula (I) of the ether type, wherein X is selected from the group consisting of aryl bearing up to two substituents selected from the group consisting of hydroxy, methoxy, ethoxy, formyl, allyl, oxoalkyl, oxoalkenyl and alkyl alkenoate, may be prepared by reaction of a phenol or hydroxynaphtalene (Aryl-OH) with substituted alkyl “R-CH2-B”, B being a chloride, bromide, iodide, tosylate or a mesylate, in the presence of a base, such as potassium carbonate, in a solvent, such as dimethyl formamide (DMF), at a temperature between 25°C and 150°C, for a time period between 1 and 24 h. base, solvent
Aryl-OH R-CH2-B Aryl-O-CH2-R For example, compounds of formula (I) of the ester type, wherein X is selected from the group consisting of alkanoyl (C(O)-R10), with R10 selected from linear or branched C4 to Ci8 alkyl, linear or branched C4 to Ci8 alkenyl with one or two double bonds, linear or branched C4 to Ci8 ether and oxoalkyl, and hydroxyphenyl may be prepared by reaction of a carboxylic acid chloride “R’-C(O)-CI” with an alcohol “R-CH2-OH” in the presence of a base, such as pyridine, triethyl amine, potassium carbonate or sodium hydroxide, optionally in the presence of 1-10 mol% of a catalyst, such as 4-(N,N-dimethylamino)pyridine, in a solvent, such as dichloromethane, toluene or heptane, at a temperature between 0°C and 100°C, for a time period between 1-48 h. base, solvent,
, catalyst
R-C(O)-CI + R-CH2-OH - - - *- R-C(O)-O-CH2-R
Alternatively, compounds of formula (I) of the ester type, R’-C(O)-O-CH2-R may be prepared by a transesterification reaction between a carboxylic acid ester “R’-C(O)-O(Me, Et)” and an alcohol “R-CH2-OH” in the presence of 1-20 mol% of a catalyst such as titanium tetraisopropoxide, under reduced pressure and distillation of the alcohol MeOH or EtOH, preferably without solvent, at a temperature between 50-200°C. catalyst
R-C(O)-OMe + R-CH2-OH - >► R-C(O)-O-CH2-R
-MeOH
The invention furthermore provides in another aspect a method to confer, enhance, improve or modify the hedonic properties of a fragrance composition or a consumer product, which method comprises adding to said composition or consumer product at least one compound of formula (I).
The invention is now further described with reference to the following non-limiting examples. These examples are for the purpose of illustration only and it is understood that variations and modifications can be made by one skilled in the art.
EXAMPLES General: All reagents and reaction solvents were analytical grade, purchased from commercial suppliers and used without further purification. Reactions were monitored by GO-FID (Zebron ZB-5 GO capillary column, 12 m x, 0.32 mm x 0.25 pm, or Zebron ZB-wax, 15 m x , 0.32 mm x 0.25 pm). Flash column chromatography was performed on Biotage silica gel prepacked columns (particle size 20 pm) with the indicated eluents, flow 50 mL/min. All reported yields, unless otherwise specified, refer to spectroscopically and chromatographically pure isolated compounds; isomeric ratios are indicated if appropriate. Routine NMR spectra were recorded on BrukerAvance III HD (500 MHZ) and AW 400 MHz Bruker, 2D NMR spectra were recorded on Bruker Avance-lll 600 MHz with 1.7 mm TCI-microcryoprobe). Proton chemical shifts are reported in ppm (5) relative to tetramethylsilane (TMS) with the solvent resonance employed as the internal standard (CDCk 6 7.27 ppm). Data are reported as follows: chemical shift, multiplicity (s = singlet, d = doublet, t = triplet, q = quartet, p = pentet, sext = sextet, h = heptet, m = multiplet, br = broad), coupling constants (Hz) and integration. 13C chemical shifts are reported in ppm from tetramethylsilane (TMS) with the solvent resonance as the internal standard (CDCI3 5 77.0 ppm;).
Example 1 : 3,7-dimethylnon-6-en-1-yl 4-oxopentanoate
The mixture of 3,7-dimethylnon-6-en-1-ol (E/Z mixture, 6.39 g, 37.5 mmol, 1.5 equiv.), methyl 4-oxopentanoate (3.25 g, 25.0 mmol, 1 equiv.) and titanium(IV) isopropoxide (355 mg, 1.25 mmol, 5 mol%) was placed in a 2-necked 25 mL glass flask, which was equipped with a distillation apparatus with a 6 cm Vigreux column. The mixture was heated under stirring to 110°C under reduced pressure (500 mbar) for 40 min, then at 130°C at 350 mbar for 2.5 h. After cooling to RT, the crude product was purified by FC (heptane/EtOAc, gradient from 0% to 100% EtOAc). The resulting product was subjected to bulb-to-bulb distillation (100°C/0.11 mbar) to remove excess 3,7-dimethylnon-6-en-1-ol. The residue consisted of 3,7-dimethylnon- 6-en-1-yl 4-oxopentanoate (colourless liquid, 4.79 g, 69%, E/Z 69:31 , purity >97%).
1H-NMR (500 MHz, CDCI3) 5.04 - 5.12 (m, 1 H), 4.07 - 4.15 (m, 2 H), 2.73 - 2.77 (m, 2 H), 2.56 - 2.59 (m, 2 H), 2.20 (s, 3 H), 1 .91 - 2.07 (m, 3 H), 1 .68 (q, J = 1.2 Hz, 0.5 H), 1.62 - 1 .73 (m, 1 H), 1.60 (br. s, 2.5 H), 1.50 - 1.59 (m, 1 H), 1.31 - 1.48 (m, 3 H), 1.14 - 1.23 (m, 1 H), 0.98 (q, J = 7.6 Hz, 3H), 0.91 (dd, J = 6.7, 2.1 Hz, 3H). 13C-NMR (126 MHz, CDCI3) 206.6 (s), 172.8 (s), 137.1 ,136.8 (s), 124.2,122.9 (d), 63.3, 63.2 (d), 38.0 (t), 37.3, 37.0 (t), 35.4 (t), 32.3 (t), 29.9, 29.5 (d), 28.0 (t), 25.2, 24.7 (t), 22.9 (q), 19.4, 19.4 (q), 15.9 (q), 12.8, 12.8 (q).
Example 2: (E/Z)-3,7-dimethylnon-6-en-1-yl palmitate The procedure described in Example 1 was repeated with 3,7-dimethylnon-6-en-1-ol (E/Z mixture, 3.8 g, 23 mmol, 1.5 equiv.), methyl palmitate (4.1 g, 15.0 mmol, 1 equiv.) and titanium(IV) isopropoxide (210 mg, 0.75 mmol, 5 mol%) to yield after chromatographic purification the product as a colourless liquid (4.2 g, 66%, E/Z 62:35).
1H-NMR (500 MHz, CDCI3) 5.07 - 5.12 (m, 1 H), 4.09 - 4.15 (m, 2 H), 2.30 (t, J=7.6 Hz, 2 H), 1.96 - 2.06 (m, 4 H), 1.55 - 1.71 (m, 5 H), 1.62 (br. s, 3H), 1.43 - 1.48 (m, 1 H), 1.19 - 1.41 (m, 25 H), 0.99 (q, J=7.6 Hz, 3 H), 0.92 - 0.95 (m, 3 H), 0.90 (t, J=7.3 Hz, 3 H). 13C-NMR (126 MHz, CDCh) 174.0 (s), 137.1 , 136.8 (s), 124.2, 123.0 (d), 62.8 (t), 37.3 (t), 37.0 (t), 35.5 (t), 34.5 (t),
32.4 (t), 31.9 (t), 29.7 (4t), 29.6 (t), 29.5 (d), 29.5 (t), 29.4 (t), 29.3 (t), 29.2 (t), 25.3, 25.0 (t), 25.0, 24.8 (t), 22.7 (t), 19.5, 19.4 (q), 15.9 (q), 14.1 (q), 12.9, 12.8 (q).
Example 3: 2,4,7-trimethyloct-6-en-1-yl 4-oxopentanoate
The procedure described in Example 1 was repeated with 2,4,7-trimethyloct-6-en-1-ol (5.1 g, 30 mmol, 1.5 equiv.), 4-oxopentanoate (2.6 g, 20.0 mmol, 1 equiv.) and titanium(IV) isopropoxide (284 mg, 1 .0 mmol, 5 mol%) to yield after chromatographic purification the product as a colourless liquid (3.6 g, 67%, 2 diastereomers, d.r. 56:43).
1H-NMR (500 MHz, CDCI3) 5.10 - 5.15 (m, 1 H), 3.91 - 4.00 (m, 1 H), 3.81 - 3.87 (m, 1 H), 2.75
- 2.78 (m, 2 H), 2.58 - 2.62 (m, 2 H), 2.21 (s, 3 H), 1 .83 - 2.00 (m, 2 H), 1.71 (br. s, 3 H), 1 .60 (br. s, 3 H), 1.55 (dq, J = 13.4, 6.7 Hz, 1 H), 1.33 (dt, J = 13.7, 6.9 Hz, 1 H), 1.12 - 1.16 (m, 1 H), 0.95 - 1.02 (m, 1 H), 0.93 (d, J = 6.7 Hz, 1 H), 0.89 (dd,J = 8.9, 6.7 Hz, 3 H), 0.85 (d, J =
6.4 Hz, 2 H). 13C-NMR (126 MHz, CDCh) 206.6 (2s), 172.8 (2s), 132.2 (s), 123.1 , 122.9 (d), 70.2, 69.6 (t), 40.8, 40.4 (t), 38.0 (t), 36.1 , 35.0 (t), 30.9, 30.8 (d), 30.1 (2d), 29.9 (q), 28.0 (t), 25.8, 25.8 (q), 20.1 , 19.2 (q), 17.9, 17.7 (q), 16.6 (q).
Example 4: (1-methyl-2-(5-methylhex-4-en-2-yl)cvclopropyl)methyl 4-oxopentanoate
The procedure described in Example 1 was repeated with (1-methyl-2-(5-methylhex-4-en-2- yl)cyclopropyl)methanol (4.1 g, 22.5 mmol, 1.5 equiv.), 4-oxopentanoate (2.0 g, 15.0 mmol, 1 equiv.) and titanium(IV) isopropoxide (213 mg, 0.75 mmol, 5 mol%) to yield after chromatographic purification the product as a colourless liquid (2.3 g, 54%, 2 diastereomers, d.r. 61 :32).
1H-NMR (500 MHz, CDCI3) 5.10 - 5.19 (m, 1 H), 3.78 - 3.88 (m, 2 H), 2.73 - 2.78 (m, 2 H), 2.57
- 2.65 (m, 2 H), 2.19 (s, 3 H), 2.01 - 2.14 (m, 1 H), 1.90 - 1.99 (m, 1 H), 1.69 - 1.72 (m, 3 H), 1.61 (s, 3 H), 1.13 - 1.15 (m, 1 H), 1.12 (s, 2 H), 0.99 - 1.10 (m, 2 H), 0.92 - 0.98 (m, 2 H), 0.47
- 0.62 (m, 2 H), -0.01 - 0.12 (m, 1 H). 13C-NMR (126 MHz, CDCh) 206.6 (2s), 172.9 (2s), 132.0,
The procedure described in Example 1 was repeated with (Z)-non-6-en-1-ol (4.3 g, 30.0 mmol, 1.5 equiv.), 4-oxopentanoate (2.6 g, 20.0 mmol, 1 equiv.) and titanium(IV) isopropoxide (284 mg, 1.0 mmol, 5 mol%) to yield after chromatographic purification the product as a colourless liquid (3.4 g, 70%).
1H-NMR (500 MHz, CDCI3) 5.27 - 5.39 (m, 2 H), 4.06 (t, J=6.7 Hz, 2 H), 2.74 (t, J=6.4 Hz, 2 H), 2.57 (t, J=6.7 Hz, 2 H), 2.19 (s, 3 H), 1.97 - 2.06 (m, 4 H), 1.59 - 1.66 (m, 2 H), 1.31 - 1.40 (m, 4 H), 0.95 (t, J=7.6 Hz, 3 H). 13C-NMR (126 MHz, CDCI3) 206.6 (s), 172.8 (s), 131.8 (d), 128.8 (d), 64.8 (t), 37.9 (t), 29.9 (q), 29.3 (t), 28.5 (t), 28.0 (t), 26.9 (t), 25.5 (t), 20.5 (t), 14.4 (q).
Example 6: 2-((3,7-dimethylnon-6-en-1-yl)oxy)naphthalene a) 9-bromo-3,7-dimethylnon-3-ene
Tribromophosphane (55.6 g, 0.21 mol, 0.35 equiv.) was added dropwise at 5°C to the stirred mixture of 3,7-dimethylnon-6-en-1-ol (E/Z mixture, 100 g, 0.59 mol, 1.5 equiv.) and pyridine (9.3 g, 0.12 mol, 0.2 equiv.). Stirring was continued at 2-10°C for 1 h, then the mixture was poured on water (300 mL). The organic layer was washed with water and brine and dried over MgSO4. The crude product (126 g of a slightly turbid liquid) was distilled over a 10 cm Vigreux column (bath 160°C, head 100°C) to yield a colourless oil (78.8 g, 58%). b) 2-((3,7-dimethylnon-6-en-1-yl)oxy)naphthalene
To the solution of naphtalene-2-ol (2.0 g, 14 mmol, 1 equiv.) in N,N-dimethyl formamide (DMF, 50 mL) was added potassium carbonate (3.8 g, 28 mmol, 2 equiv.) and the mixture was stirred at RT for 20 min. The above prepared 9-bromo-3,7-dimethylnon-3-ene (3.9 g, 17 mmol, 1.2 equiv.) was added and the resulting mixture was stirred at 95°C for 6 h. Workup was effected as described above in part a). The crude product was purified by FC on SiO2 (heptane/MTBE 60:1) to the product as a colourless oil (0.8 g, 20%, 3 isomers 50:36:12).
1H-NMR (500 MHz, CDCI3) 7.75 - 7.82 (m, 3 H), 7.47 (ddd, J=8.1 , 6.9, 1.3 Hz, 1 H), 7.34 - 7.39 (m, 1 H), 7.18 (s, 1 H), 7.19 (d, J=8.6 Hz, 1 H), 5.13 - 5.29 (m, 1 H), 4.10 - 4.20 (m, 2 H), 1.89 - 2.14 (m, 4 H), 1.60 - 1.84 (m, 7 H), 1.38 - 1.55 (m, 2 H), 1.22 - 1.36 (m, 1 H), 0.95 - 1.08 (m, 4 H).
Example 7: 2-((3,7-dimethylnon-6-en-1-yl)oxy)phenol The mixture of 1 ,2-dihdroxybenzene (2.0 g, 18 mmol, 1 equiv.), potassium carbonate (5.0 g, 36 mmol, 2 equiv.) and 9-bromo-3,7-dimethylnon-3-ene (as prepared in Example 6a, 5.1 g, 22 mmol, 1.2 equiv.) in DMF (50 mL) was heated to 80°C under stirring for 20 h. The mixture was poured on water (100 mL), acidified with 2M aq. HCI-solution and extracted with heptane. After drying over MgSO4 and evaporation of the solvent, a clear brown liquid was obtained (3.7 g), which was purified by FC on SiO2 (heptane/MTBE 30:1) to yield the product as a colourless oil (1.8 g, 36%, mixture of E/Z-isomers).
1H-NMR (500 MHz, CDCI3) 6.96 - 6.99 (m, 1 H), 6.85 - 6.94 (m, 3 H), 5.70 (s, 1 H), 5.02 - 5.42 (m, 1 H), 4.07 - 4.15 (m, 2 H), 1.99 - 2.11 (m, 2 H), 1.87 - 1.94 (m, 1 H), 1.60 - 1.76 (m, 6 H), 1.21 - 1.51 (m, 3 H), 0.98 - 1.06 (m, 6 H).
Example 8: 2-((3,7-dimethylnon-6-en-1-yl)oxy)benzaldehyde
The procedure described for Example 7 was repeated with salicylaldehyde (2.0 g, 16 mmol, 1 equiv.), potassium carbonate (4.5 g, 32 mmol, 2 equiv.) and 9-bromo-3,7-dimethylnon-3-ene (as prepared in Example 6a, 4.6 g, 20 mmol, 1.2 equiv.) in DMF (50 mL). After purification of the crude by FC on SiO2 (heptane/MTBE 30:1) the product was isolated as a colourless oil (4.0 g, 88%, mixture of E/Z-isomers).
1H-NMR (500 MHz, CDCI3) 10.52 (s, 1 H), 7.84 (dd, J=7.7, 1.8 Hz, 1 H), 7.54 (ddd, J=8.3, 7.5, 1.8 Hz, 1 H), 6.98 - 7.04 (m, 2 H), 5.03 - 5.30 (m, 1 H), 4.10 - 4.16 (m, 2 H), 1.88 - 2.08 (m, 4 H), 1.56 - 1.77 (m, 6 H), 1.19 - 1.48 (m, 2 H), 0.96 - 1 .02 (m, 6 H).
Example 9: 2-((3,7-dimethylnon-6-en-1-yl)oxy)-2-phenylethan-1-ol
To the mixture of styrene oxide (10.0 g, 83 mmol, 1 equiv., added in 2 portions after 0 and 24 h) and (E,Z)-3,7-dimethylnon-6-en-1-ol (14.2 g, 83 mmol, 1 equiv) was added FeCI3 (0.63 g, 4.1 mmol, 5 mol% added in 2 portions after 0 and 24 h). The mixture was stirred for 48 hours at 60°C, then poured on sat. aq. NaHCO3-solution (100 mL) and extracted with MTBE. The organic layer was washed with water and brine and dried over MgSO4. After removal of the solvent, a clear dark brown liquid was obtained (13.1 g), which was bulb-to-bulb distilled (180°C, 0.05 mbar) and purified by FC on SiO2 (heptane/MTBE 3:1) to obtain the product as a slightly yellow liquid (2.98 g, 27%, mixture of E and Z isomers).
1H-NMR (400 MHz, CDCI3) 7.27 - 7.43 (m, 5 H), 5.05 - 5.14 (m, 1 H), 4.42 (dd, J=8.4, 4.0 Hz, 1 H), 3.57 - 3.75 (m, 2 H), 3.35 - 3.56 (m, 2 H), 2.36 (dd, =9.4, 3.1 Hz, 1 H), 1.93 - 2.08 (m, 3 H), 1.54 - 1.73 (m, 5 H), 1.26 - 1.49 (m, 3 H), 1.10 - 1.24 (m, 1 H), 0.84 - 1.05 (m, 6 H).
Example 10: 2-((3,7-dimethylnon-6-en-1-yl)oxy)-2-phenylacetaldehyde The product of Example 9 (1.0 g, 3.4 mmol) was oxidized with Dess-Martin-periodinane (1.1 equiv.) in dichloromethane (50 mL) to yield, after FC on SiO2 (heptane/MTBE 9:1), the product as a colourless liquid (0.27 g, 27%, mixture of E and Z isomers).
1H-NMR (400 MHz, CDCI3) 9.62 (d, J=2.2 Hz, 1 H), 7.28 - 7.68 (m, 5 H), 5.01 - 5.14 (m, 1 H), 4.71 - 4.75 (m, 1 H), 3.45 - 3.75 (m, 2 H), 1 .83 - 2.07 (m, 3 H), 1.79 (br. s, 3 H), 1 .63 - 1 .81 (m, 2 H), 1.45 - 1.60 (m, 1 H), 1.13 - 1.43 (m, 3 H), 0.80 - 1.04 (m, 6 H).
Example 11 : (2E,6Z)-nona-2,6-dien-1-yl 2-hydroxybenzoate
The mixture of methyl salicylate (4.0 g, 26.3 mmol, 1 equiv), 2E,6Z-nona-2,6-dien-1-ol (18.4 g, 131 mmol, 5 equiv) und sodium methoxide (0.14 g, 2.6 mmol, 0.1 equiv.) was stirred for 3 h at 85°C. The mixture was poured on 2 N aq. HCI-solution (100 mL), then extracted with MTBE. The organic layer was washed with water and brine and dried over MgSO4. The residue obtained after removal of the solvent was bulb-to-bulb distilled (100°C/0.08 mbar) to yield the product as a clear, colourless liquid (3.81 g, 56%).
1H-NMR (400 MHz, CDCI3) 10.83 (s, 1 H), 7.89 (dd, J=8.2, 1.6 Hz, 1 H), 7.47 (ddd, J=8.5, 7.2, 1.7 Hz, 1 H), 7.00 (dd, J=8.3, 1.0 Hz, 1 H), 6.90 (t, J=7.6 Hz, 1 H), 5.87 - 5.95 (m, 1 H), 5.67 - 5.77 (m, 1 H), 5.31 - 5.54 (m, 2 H), 4.82 (dd, J=6.5, 0.9 Hz, 2 H), 1.99 - 2.26 (m, 6 H), 0.98 (t, J=7.5 Hz, 3 H). 13C-NMR (100 MHz, CDCI3) 170.0 (s), 161.7 (s), 136.7 (d), 135.6 (d), 132.4 (d), 130.0 (d), 127.8 (d), 123.5 (d), 119.1 (d), 117.5 (d), 112.6 (s), 66.0 (t), 32.4 (t), 26.5 (t), 20.6 (t), 14.3 (q).
Example 12: 4-allyl-2-methoxy-1-(((2E,6Z)-nona-2,6-dien-1-yl)oxy)benzene a) (2E,6Z)-1-bromonona-2,6-diene
Tetrabromomethane (92.2 g, 0.28 mol, 1.3 equiv.) was added dropwise at 5°C to the stirred solution of (2E,6Z)-nona-2,6-dien-1-ol (30 g, 0.21 mol, 1 equiv.) and triphenylphosphane (72.9 g, 0.28 mol, 1.3 equiv.) in dichloromethane (400 mL). Stirring was continued at room temperature for 1 h, then the solvent was evaporated and pentane (250 mL) was added. The mixture was placed in a refrigerator over night, then the formed precipitate was filtered off and the filtrate was concentrated to yield (2E,6Z)-1-bromonona-2,6-diene as a yellow liquid (45.1 g, >99%). b) 4-allyl-2-methoxy-1-(((2E,6Z)-nona-2,6-dien-1-yl)oxy)benzene
The mixture of eugenol (5.0 g, 28 mmol, 1 equiv.), (2E,6Z)-1-bromonona-2,6-diene (as prepared above, 6.3 g, 31 mmol, 1.1 equiv.), potassium carbonate (9.7 g, 70 mmol, 2.5 equiv.) and DMF (70 mL) was stirred at 80°C for 7 h. Usual workup and chromatography (heptane/MTBE 30:1) yielded the product as a yellow liquid (1.75 g, 39%).
1H-NMR (400 MHz, CDCI3) 6.81 (d, J=7.9 Hz, 1 H), 6.67 - 6.72 (m, 2 H), 5.96 (ddt, J=16.9, 10.1 , 6.7, 6.7 Hz, 1 H), 5.69 - 5.87 (m, 2 H), 5.24 - 5.44 (m, 2 H), 5.03 - 5.13 (m, 2 H), 4.51 (d, J=5.4 Hz, 2 H), 3.85 (s, 3 H), 3.33 (d, J=6.6 Hz, 2 H), 1.98 - 2.20 (m, 6 H), 0.95 (t, J=7.5 Hz, 3 H). 13C-NMR (101 MHz, CDCI3) 149.4 (s), 146.5 (s), 137.7 (d), 135.0 (d), 132.9 (s), 132.2 (d), 128.1 (d), 125.4 (d), 120.3 (d), 115.6 (t), 113.5 (d), 112.1 (d), 69.9 (t), 55.8 (d), 39.8 (t), 32.4 (t), 26.6 (t), 20.6 (t), 14.3 (q).
Example 13: 4-(4-(((2E,6Z)-nona-2,6-dien-1-yl)oxy)phenyl)butan-2-one
The procedure described in Example 12 was repeated with 4-(4-hydroxyphenyl)butan-2-one (5.0 g, 28 mmol, 1 equiv.), (2E,6Z)-1-bromonona-2,6-diene (6.3 g, 31 mmol, 1.1 equiv.), potassium carbonate (9.7 g, 70 mmol, 2.5 equiv.) and DMF (70 mL) to yield the product as a clear, yellow liquid (2.15 g, 43%).
1H-NMR (400 MHz, CDCI3) 6.99 - 7.10 (m, 2 H), 6.77 - 6.88 (m, 2 H), 5.78 - 5.93 (m, 1 H), 5.67 - 5.76 (m, 1 H), 5.26 - 5.44 (m, 2 H), 4.42 - 4.46 (m, 2 H), 2.80 - 2.86 (m, 2 H), 2.69 - 2.74 (m, 2 H), 1.94 - 2.22 (m, 9 H), 0.96 (t, J=7.5 Hz, 3 H). 13C-NMR (101 MHz, CDCI3) 208.2 (s), 157.1 (s), 134.9 (d), 133.1 (s), 132.3 (d), 129.2 (2d), 128.0 (d), 125.3 (d), 114.8 (2d), 68.8 (t), 45.5 (t), 32.4 (t), 30.1 (q), 28.9 (t), 26.6 (t), 20.6 (t), 14.32 (q).
Example 14: (Z)-3-ethoxy-4-(non-6-en-1-yloxy)benzaldehyde
(Z)-9-bromonon-3-ene was prepared from (Z)-non-6-en-1-ol according to the procedure described in Example 12a. The title compound was prepared from ethylvanillin and (Z)-9- bromonon-3-ene according to the procedure described in Example 12b. Purification by FC (heptane/MTBE 6:1) yielded a clear, slightly yellow liquid (4.44 g).
1H-NMR (400 MHz, CDCI3) 9.84 (s, 1 H), 7.43 (d, J=8.1 Hz, 1 H), 7.41 (s, 1 H), 6.97 (d, J=8.3 Hz, 1 H), 5.32 - 5.45 (m, 2 H), 4.08 - 4.18 (m, 4 H), 1.99 - 2.11 (m, 4 H), 1.85 - 1.93 (m, 2 H), 1.48 (t, J=7.1 Hz, 5 H), 1.41-1.55 (m, 1 H), 1.27 - 1.32 (m, 1 H), 0.92 - 0.99 (m, 3 H). 13C-NMR (101 MHz, CDCk) 190.9 (d), 154.5 (s), 149.2 (s), 131.9 (d), 129.9 (s), 128.8 (d), 126.6 (d), 111.8 (d), 110.9 (d), 69.1 (t), 64.6 (t), 29.4 (t), 28.8 (t), 27.0 (t), 25.5 (t), 20.5 (t), 14.7 (q), 14.4 (q).
Example 15: (Z)-2-(non-6-en-1-yloxy)naphthalene The procedure described in Example 14 was repeated with (Z)-9-bromonon-3-ene (17 mmol) and naphthalen-2-ol (14 mmol). The product was obtained as a clear colourless liquid (3.1 g, 77%) after column chromatographic purification (heptane/MTBE 60:1).
1H-NMR (400 MHz, CDCI3) 7.80 - 7.86 (m, 3 H), 7.52 (ddd, J=8.3, 6.9, 1.2 Hz, 1 H), 7.39 - 7.44 (m, 1 H), 7.24 - 7.28 (m, 1 H), 7.21 (d, J=2.4 Hz, 1 H), 5.43 - 5.54 (m, 2 H), 4.14 (t, J=6.6 Hz, 2 H), 2.12 - 2.22 (m, 4 H), 1.91 - 1.98 (m, 2 H), 1.51 - 1.66 (m, 4 H), 1 .08 (t, J=7.6 Hz, 3 H). 13C- NMR (101 MHz, CDCI3) 157.2 (s), 134.7 (s), 131.9 (d), 129.4 (d), 129.0 (d), 129.0 (s), 127.7 (d), 126.8 (d), 126.3 (d), 123.5 (d), 119.1 (d), 106.6 (d), 68.0 (t), 29.6 (t), 29.3 (t), 27.1 (t), 25.9 (t), 20.7 (t), 14.5 (q).
Example 16: methyl 2-((3,7-dimethylnon-6-en-1-yl)oxy)-2-phenylacetate
The solution of methyl 2-hydroxy-2-phenylacetate (1.8 g, 11 mmol, 1.3 equiv.) in DMF (50 mL) was added sodium hydride (0.45 g, 60% Wt, 11 mmol, 1.3 equiv.) at 0 °C and continued to stir at rt for 1 h, and 9-bromo-3,7-dimethylnon-3-ene (2.0 g, 8.6 mmol, 1.0 equiv.) in DMF (10 mL) was added and stirred at rt for 16 h. The mixture was poured on saturated ammonium chloride (100 mL) and extracted with ethyl acetate. After drying over MgSO4 and evaporation of the solvent, a clear brown liquid was obtained, which was purified by FC on SiO2 (heptane/MTBE 10:1) to yield the product as a colourless oil (0.20 g, 7%, mixture of E/Z-isomers).
1H-NMR (400 MHz, CDCI3) 6 7.48 - 7.42 (m, 2H), 7.40 - 7.29 (m, 3H), 5.22 - 5.00 (m, 1 H), 4.87 (s, 1 H), 3.71 (s, 3H), 3.63 - 3.38 (m, 2H), 2.06 - 1.88 (m, 4H), 1.79 - 1.07 (m, 8H), 1.01 - 0.82 (m, 6H) ppm.13C-NMR (101 MHz, CDCI3) 5 171.5, 171.5, 136.9, 136.8, 136.7, 128.6, 127.1 , 127.1 , 124.4, 123.2, 81.1 , 68.4, 52.2, 37.5, 37.4, 37.2, 37.1 , 36.5, 36.5, 32.3, 29.5, 29.5, 25.3, 25.3, 25.0, 25.0, 24.7, 22.9, 19.5, 19.5, 19.5, 15.9, 12.9, 12.8 ppm.
Example 17: 2-((3,7-dimethylnon-6-en-1-yl)oxy)-1 ,2-diphenylethan-1-one
The procedure described for Example 16 was repeated with 2-hydroxy-1 ,2-diphenylethan-1- one (2.4 g, 11 mmol, 1.3 equiv.), sodium hydride (0.45 g, 60% Wt, 11 mmol, 1.3 equiv.) and 9- bromo-3,7-dimethylnon-3-ene (2.0 g, 8.6 mmol, 1 equiv.) in DMF (50 mL). After purification of the crude by FC on SiO2 (heptane/MTBE 20:1) the product was isolated as a colourless oil (0.85 g, 27%, mixture of E/Z-isomers).
1H-NMR (400 MHz, CDCI3) 5 8.10 - 7.92 (m, 2H), 7.65 - 7.18 (m, 8H), 5.52 (s, 1 H), 5.24 - 4.98 (m, 1 H), 3.70 - 3.51 (m, 2H), 2.12 - 1 .86 (m, 4H), 1.82 - 1.05 (m, 8H), 1.03 - 0.90 (m, 3H), 0.89 - 0.78 (m, 3H) ppm. 13C-NMR (101 MHz, CDCI3) 5 198.1 , 198.0, 136.9, 136.8, 136.7, 136.7, 135.0, 133.1 , 129.3, 128.7, 128.6, 128.4, 128.2, 128.1 , 127.1 , 127.1 , 127.1 , 124.4, 123.2, 85.8, 68.5, 68.5, 37.4, 37.1 , 36.7, 32.4, 29.5, 29.5, 25.3, 25.0, 24.7, 22.9, 19.6, 19.5, 19.5, 15.9, 12.9, 12.8 ppm.
Example 18: (2-((3,7-dimethylnon-6-en-1-yl)oxy)propan-2-yl)benzene
The mixture of 2-phenylpropan-2-ol (1.1 g, 8.1 mmol, 1 equiv.), 3,7-dimethylnon-6-en-1-ol (2.75 g, 16 mmol, 2 equiv.), (hexafluoro-l7-stibaneyl)silver (0.28 g, 0.80 mmol, 0.1 equiv.) and platinum(ll) chloride (0.086 g, 0.32 mmol, 0.04 equiv.) in dichloromethane (100 mL) was stirred at rt for 4h, The mixture was poured on water (100 mL), and extracted with ethyl acetate. After drying over MgSO4 and evaporation of the solvent, and the crude oil was purified by FC on SiO2 (heptane/MTBE 50:1) to yield the product as a colourless oil (1.8 g, 76%, mixture of E/Z- isomers).
1H-NMR (400 MHz, CDCI3) 6 7.48 - 7.38 (m, 2H), 7.37 - 7.30 (m, 2H), 7.27 - 7.18 (m, 1 H), 5.32 - 4.96 (m, 1 H), 3.30 - 3.06 (m, 2H), 2.08 - 1.84 (m, 3H), 1.73 - 0.91 (m, 18H), 0.88 - 0.70 (m, 3H) ppm. 13C-NMR (101 MHz, CDCI3) 5 146.8, 137.8, 136.8, 136.6, 136.3, 136.1 , 128.1 , 126.7, 125.7, 124.5, 123.3, 118.7, 118.0, 76.3, 61.0, 39.9, 37.6, 37.5, 37.2, 37.0, 36.7, 32.4, 31.6, 29.8, 29.6, 29.6, 28.5, 25.3, 25.3, 25.1 , 24.7, 23.4, 22.9, 19.8, 19.7, 19.7, 19.7, 15.9, 15.6, 13.3,
13.2, 12.9, 12.8 ppm.
Example 19: 2-(2-((3,7-dimethylnon-6-en-1-yl)oxy)propan-2-yl)naphthalene
The mixture of 2-(naphthalen-2-yl)propan-2-ol (2, 0 g, 10.7 mmol, 1 equiv.), 3,7-dimethylnon- 6-en-1-ol (3.66 g, 21.5 mmol, 2 equiv.), (hexafluoro-l7-stibaneyl)silver (0.37 g, 1.1 mmol, 0.1 equiv.) and platinum(ll) chloride (0.114 g, 0.43 mmol, 0.04 equiv.) in dichloromethane (100 mL) was stirred at rt for 4h, The mixture was poured on water (100 mL), and extracted with ethyl acetate. After drying over MgSO4 and evaporation of the solvent, and the crude oil was purified by FC on SiO2 (heptane/MTBE 50:1) to yield the product as a colourless oil (2.9g, 80%, mixture of E/Z-isomers).
1H-NMR (400 MHz, CDCI3) 57.74 - 7.66 (m, 4H), 7.56 - 7.48 (m, 1 H), 7.38 - 7.31 (m, 2H), 5.01 - 4.91 (m, 1 H), 3.15 - 3.04 (m, 2H), 1.95-1.13 (m, 17H), 1.05 - 0.82 (m, 4H), 0.77 - 0.66 (m, 3H) ppm. 13C-NMR (101 MHz, CDCI3) 5 143.2, 135.7, 135.5, 132.1 , 131.4, 127.0, 126.8,
126.4, 124.9, 124.6, 123.5, 123.1 , 122.2, 75.3, 60.1 , 36.5, 36.2, 31.3, 28.5, 28.5, 27.3, 27.3,
24.3, 24.0, 23.7, 21.8, 18.6, 18.6, 14.8, 11.8, 11.8 ppm.
Example 20: Application in liquid detergent
A 40°C machine wash cycle was performed using 55 g of unperformed liquid detergent prepared with 0.2 % wt/wt of a) 2-((3,7-dimethylnon-6-en-1-yl)oxy)naphthalene (Compound of Example 6) and b) (E/Z)-3,7-dimethylnon-6-en-1-yl palmitate (Compound of Example 2) and a washload of odour-neutral cotton/elastan mixed fabric T-shirts. The wet and line-dried fabric (1 and 3 days) was assessed by a panel of 9 experts with regard to odour intensity and quality. The odour intensity was recorded on an intensity scale of 0 (odourless) to 5 (extremely strong). As can be seen from the table below, the odour on dry fabric increased from day 1 to day 3. The scent of the dry fabric was floral, fresh and clean.
This illustrates that precursors of the invention release fragrance in a consumer noticeable way.
Example 21 : Assessment of biodegradability
Representative results of the biodegradability assessment of compounds of the present invention by the manometric respirometry test (OECD10 guideline for the testing of materials No. 301 F, Paris 1992) are summarized below.
The results show that compounds of the present invention with varying phenol moieties and side chains are biodegradable.
A compound can be classified biodegradable, if it reaches the pass level of 60% oxygen consumption of theory required for complete mineralization.
It is readily biodegradable, if the pass level is reached within 10 days within the 28-day period of the test. The 10-day window begins when the degree of biodegradation has reached 10%.
If the pass level is obtained after 28-day period of the test, the compound can be classified as inherently biodegradable.

Claims

Claims
1 . A compound of formula (I) wherein
- is indicating a carbon-carbon single or double bond between C2 and C3;
R1, R3, R4, R5 and R6 is independently selected from the group consisting of H, Me and Et;
R2 is selected from the group consisting of H, Me and Et, or forms together with the carbon atoms C2 and C3 a 3 membered ring; and
X is selected from the group consisting of aryl bearing up to two substituents selected from the group consisting of hydroxy, methoxy, ethoxy, formyl, allyl, oxoalkyl, oxoalkenyl and alkyl alkenoate; benzyl bearing a substituent selected from the group consisting of hydroxymethyl, formyl, vinyl, (C=O)Me, (C=O)Et, (C=O)OMe, (C=O)OEt, (C=O)Ph at the benzylic position; propan-2-yl substituted with phenyl, naphthalen-1-yl or naphthalen-2-yl at position 2; dimethyl 2-malonate and diethyl 2-malonate; and alkanoyl (C(O)-R10), with R10 selected from linear or branched C4 to Ci8 alkyl, linear or branched C4 to Ci8 alkenyl with one or two double bonds, linear or branched C4 to Ci8 ether and oxoalkyl, and hydroxyphenyl, with the proviso that the compound is not nona-2,6-dien-1-yl palmitate as precursor for generating a fragrant alcohol of formula (II)
2. The compound of formula (I) according to claim 1 , wherein the fragrant alcohol of formula (II) that is released from the compound of formula (I) is selected from the group consisting of 3,7-dimethylnon-6-en-1-ol, 2,4,7-trimethyloct-6-en-1-ol, 6-nonenol, 6-ethyl-3- methyloct-6-en-1-ol, (1-methyl-2-(5-methylhex-4-en-2-yl)cyclopropyl)methanol, and 2,6- nonadienol.
3. The compound of formula (I) according to claim 1 or 2, wherein X is selected from the group consisting of aryl bearing up to two substituents selected from the group consisting of hydroxy, methoxy, ethoxy, formyl, allyl, oxoalkyl, oxoalkenyl and alkyl alkenoate; benzyl bearing a substituent selected from the group consisting of hydroxymethyl, formyl, vinyl, (C=O)Me, (C=O)Et, (C=O)OMe, (C=O)OEt, (C=O)Ph at the benzylic position; propan-2-yl substituted with phenyl, naphthalen-1-yl or naphthalen-2-yl at position 2; dimethyl 2-malonate and diethyl 2-malonate; and wherein the fragrant alcohol of formula (II) that is released from the compound of formula (I) is selected from the group consisting of 3,7-dimethylnon-6-en-1-ol, 2,4,7- trimethyloct-6-en-1-ol, 6-nonenol, 6-ethyl-3-methyloct-6-en-1-ol, (1-methyl-2-(5- methylhex-4-en-2-yl)cyclopropyl)methanol, and 2,6-nonadienol.
4. Use of a compound of formula (I) according to any of claims 1 through 3 as precursor for generating a fragrant alcohol of formula (II) according to claim 1.
5. A fragrance composition comprising at least one compound of formula (I) according to any of claims 1 through 3.
6. A consumer product comprising at least one compound of formula (I) according any of claims 1 through 3 and a consumer product base.
7. A method to release a fragrant alcohol of formula (II) as defined in any of claims 1 through 3, wherein a compound of formula (I) as defined in any of claims 1 through 3is exposed to ambient air and/or humidity.
8. A method of manufacturing a consumer product, comprising the steps of a) provision of a compound of formula (I) according to any of claims 1 through 3, or a fragrance composition according to claim 5; and b) admixing it to a consumer product base.
9. Use of a compound of formula (I) according to any of claims 1 through 3 or a fragrance composition according to claim 5 in consumer products.
10. A method to confer, enhance, improve or modify the hedonic properties of a fragrance composition or a consumer product, which method comprises adding to said composition or consumer product at least one compound of formula (I) according to any of claims 1 through 3.
EP24737408.5A 2023-06-27 2024-06-26 Organic compounds and their use for generating a fragrant alcohol Pending EP4734932A1 (en)

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